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Sample records for resolved photoelectron spectra

  1. Revealing Deactivation Pathways Hidden in Time-Resolved Photoelectron Spectra

    Science.gov (United States)

    Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2016-10-01

    Time-resolved photoelectron spectroscopy is commonly employed with the intention to monitor electronic excited-state dynamics occurring in a neutral molecule. With the help of theory, we show that when excited-state processes occur on similar time scales the different relaxation pathways are completely obscured in the total photoionization signal recorded in the experiment. Using non-adiabatic molecular dynamics and Dyson norms, we calculate the photoionization signal of cytosine and disentangle the transient contributions originating from the different deactivation pathways of its tautomers. In the simulations, the total signal from the relevant keto and enol tautomers can be decomposed into contributions either from the neutral electronic state populations or from the distinct mechanistic pathways across the multiple potential surfaces. The lifetimes corresponding to these contributions cannot be extracted from the experiment, thereby illustrating that new experimental setups are necessary to unravel the intricate non-adiabatic pathways occurring in polyatomic molecules after irradiation by light.

  2. Imaging plasmonic fields near gold nanospheres in attosecond time-resolved streaked photoelectron spectra

    Science.gov (United States)

    Li, Jianxiong; Thumm, Uwe

    2016-05-01

    To study time-resolved photoemission from gold nanospheres, we introduce a quantum-mechanical approach, including the plasmonic near-field-enhancement of the streaking field at the surface of the nanosphere. We use Mie theory to calculate the plasmonically enhanced fields near 10 to 200 nm gold nanospheres, driven by incident near infrared (NIR) or visible laser pulses. We model the gold conduction band in terms of a spherical square well potential. Our simulated streaked photoelectron spectra reveal a plasmonic amplitude enhancement and phase shift related to calculations that exclude the induced plasmonic field. The phase shift is due to the plasma resonance. This suggests the use of streaked photoelectron spectroscopy for imaging the dielectric response and plasmonic field near nanoparticles. Supported by the NSD-EPSCoR program, NSF, and the USDoE.

  3. Is the Separable Propagator Perturbation Approach Accurate in Calculating Angle Resolved Photoelectron Diffraction Spectra?

    Science.gov (United States)

    Ng, C. N.; Chu, T. P.; Wu, Huasheng; Tong, S. Y.; Huang, Hong

    1997-03-01

    We compare multiple scattering results of angle-resolved photoelectron diffraction spectra between the exact slab method and the separable propagator perturbation method. In the slab method,footnote C.H. Li, A.R. Lubinsky and S.Y. Tong, Phys. Rev. B17, 3128 (1978). the source wave and multiple scattering within the strong scattering atomic layers are expanded in spherical waves while interlayer scattering is expressed in plane waves. The transformation between spherical waves and plane waves is done exactly. The plane waves are then matched across the solid-vacuum interface to a single outgoing plane wave in the detector's direction. The separable propagator perturbation approach uses two approximations: (i) A separable representation of the Green's function propagator and (ii) A perturbation expansion of multiple scattering terms. Results of c(2x2) S-Ni(001) show that this approximate method fails to converge due to the very slow convergence of the separable representation for scattering angles less than 90^circ. However, this method is accurate in the backscattering regime and may be applied to XAFS calculations.(J.J. Rehr and R.C. Albers, Phys. Rev. B41, 8139 (1990).) The use of this method for angle-resolved photoelectron diffraction spectra is substantially less reliable.

  4. Attosecond electronic and nuclear quantum photodynamics of ozone monitored with time and angle resolved photoelectron spectra

    CERN Document Server

    Decleva, P; Perveaux, A; Lauvergnat, D; Gatti, F; Lasorne, B; Halász, G J; Vibók, Á

    2016-01-01

    Recently we reported a series of numerical simulations proving that it is possible in principle to create an electronic wave packet and subsequent electronic motion in a neutral molecule photoexcited by a UV pump pulse within a few femtoseconds. We considered the ozone molecule: for this system the electronic wave packet leads to a dissociation process. In the present work, we investigate more specifically the time-resolved photoelectron angular distribution of the ozone molecule that provides a much more detailed description of the evolution of the electronic wave packet. We thus show that this experimental technique should be able to give access to observing in real time the creation of an electronic wave packet in a neutral molecule and its impact on a chemical process.

  5. Attosecond electronic and nuclear quantum photodynamics of ozone monitored with time and angle resolved photoelectron spectra

    Science.gov (United States)

    Decleva, Piero; Quadri, Nicola; Perveaux, Aurelie; Lauvergnat, David; Gatti, Fabien; Lasorne, Benjamin; Halász, Gábor J.; Vibók, Ágnes

    2016-11-01

    Recently we reported a series of numerical simulations proving that it is possible in principle to create an electronic wave packet and subsequent electronic motion in a neutral molecule photoexcited by a UV pump pulse within a few femtoseconds. We considered the ozone molecule: for this system the electronic wave packet leads to a dissociation process. In the present work, we investigate more specifically the time-resolved photoelectron angular distribution of the ozone molecule that provides a much more detailed description of the evolution of the electronic wave packet. We thus show that this experimental technique should be able to give access to observing in real time the creation of an electronic wave packet in a neutral molecule and its impact on a chemical process.

  6. Vibrationally high-resolved electronic spectra of MCl2 (M = C, Si, Ge, Sn, Pb) and photoelectron spectra of MCl2-

    Science.gov (United States)

    Ran, Yibin; Pang, Min; Shen, Wei; Li, Ming; He, Rongxing

    2016-10-01

    We systematically studied the vibrational-resolved electronic spectra of group IV dichlorides using the Franck-Condon approximation combined with the Duschinsky and Herzberg-Teller effects in harmonic and anharmonic frameworks (only the simulation of absorption spectra includes the anharmonicity). Calculated results showed that the band shapes of simulated spectra are in accordance with those of the corresponding experimental or theoretical ones. We found that the symmetric bend mode in progression of absorption is the most active one, whereas the main contributor in photoelectron spectra is the symmetric stretching mode. Moreover, the Duschinsky and anharmonic effects exert weak influence on the absorption spectra, except for PbCl2 molecule. The theoretical insights presented in this work are significant in understanding the photophysical properties of MCl2 (M = C, Si, Ge, Sn, Pb) and studying the Herzberg-Teller and the anharmonic effects on the absorption spectra of new dichlorides of this main group.

  7. Application of high-resolution photoelectron spectroscopy: Vibrational resolved C 1s and O 1s spectra of CO adsorbed on Ni(100)

    Energy Technology Data Exchange (ETDEWEB)

    Foehlisch, A.; Nilsson, A.; Martensson, N. [Uppsala Univ. (Sweden)] [and others

    1997-04-01

    There are various effects which determine the line shape of a core-level electron spectrum. These are due to the finite life-time of the core hole, inelastic scattering of the outgoing photoelectron, electronic shake-up and shake-off processes and vibrational excitations. For free atoms and molecules the different contributions to the observed line shapes can often be well separated. For solids, surfaces and adsorbates the line shapes are in general much broader and it has in the past been assumed that no separation of the various contributions can be made. In the present report the authors will show that this is indeed not the case. Surprisingly, the vibrational fine structure of CO adsorbed on Ni(100) can be resolved in the C 1s and O 1s electron spectra. This was achieved by the combination of highly monochromatized soft X-rays from B18.0 with a high resolution Scienta 200 mm photoelectron spectrometer. X-ray photoelectron spectroscopy (XPS) with tunable excitation energy yields as a core level spectroscopy atomic and site-specific information. The presented measurements allow for a determination of internuclear distances and potential energy curves in corehole ionized adsorbed molecules. The authors analysis of the c(2x2) phase CO/Ni(100) on {open_quotes}top{close_quotes} yielded a vibrational splitting of 217 +/- 2 meV for C 1s ionization. For O 1s ionization a splitting of 173 +/- 8 meV was found.

  8. A spin- and angle-resolving photoelectron spectrometer

    CERN Document Server

    Berntsen, M H; Leandersson, M; Hahlin, A; hlund, J \\AA; Wannberg, B; nsson, M M\\aa; Tjernberg, O

    2010-01-01

    A new type of hemispherical electron energy analyzer that permits angle and spin resolved photoelectron spectroscopy has been developed. The analyzer permits standard angle resolved spectra to be recorded with a two-dimensional detector in parallel with spin detection using a mini-Mott polarimeter. General design considerations as well as technical solutions are discussed and test results from the Au(111) surface state are presented.

  9. Cation profiling of passive films on stainless steel formed in sulphuric and acetic acid by deconvolution of angle-resolved X-ray photoelectron spectra

    Energy Technology Data Exchange (ETDEWEB)

    Högström, Jonas, E-mail: jhogstrom@gmail.com; Fredriksson, Wendy, E-mail: wendy.fredriksson@kemi.uu.se; Edstrom, Kristina, E-mail: kristina.edstrom@kemi.uu.se; Björefors, Fredrik, E-mail: fredrik.bjorefors@kemi.uu.se; Nyholm, Leif, E-mail: leif.nyholm@kemi.uu.se; Olsson, Claes-Olof A., E-mail: drclabbe@kth.se

    2013-11-01

    An approach for determining depth gradients of metal-ion concentrations in passive films on stainless steel using angle-resolved X-ray photoelectron spectroscopy (ARXPS) is described. The iterative method, which is based on analyses of the oxidised metal peaks, provides increased precision and hence allows faster ARXPS measurements to be carried out. The method was used to determine the concentration depth profiles for molybdenum, iron and chromium in passive films on 316L/EN 1.4432 stainless steel samples oxidised in 0.5 M H{sub 2}SO{sub 4} and acetic acid diluted with 0.02 M Na{sub 2}B{sub 4}O{sub 7} · 10H{sub 2}O and 1 M H{sub 2}O, respectively. The molybdenum concentration in the film is pin-pointed to the oxide/metal interface and the films also contained an iron-ion-enriched surface layer and a chromium-ion-dominated middle layer. Although films of similar composition and thickness (i.e., about 2 nm) were formed in the two electrolytes, the corrosion currents were found to be three orders of magnitude larger in the acetic acid solution. The differences in the layer composition, found for the two electrolytes as well as different oxidation conditions, can be explained based on the oxidation potentials of the metals and the dissolution rates of the different metal ions.

  10. Inversion of Strong Field Photoelectron Spectra for Molecular Orbital Imaging

    CERN Document Server

    Puthumpally-Joseph, R; Peters, M; Nguyen-Dang, T T; Atabek, O; Charron, E

    2016-01-01

    Imaging structures at the molecular level is a fast developing interdisciplinary research field that spans across the boundaries of physics and chemistry. High spatial resolution images of molecules can be obtained with photons or ultrafast electrons. In addition, images of valence molecular orbitals can be extracted via tomographic techniques based on the coherent XUV radiation emitted by a molecular gas exposed to an intense ultra-short infrared laser pulse. In this paper, we demonstrate that similar information can be obtained by inverting energy resolved photoelectron spectra using a simplified analytical model.

  11. Theoretical Investigation of Femtosecond-Resolved Photoelectron Spectrum of NaI Molecules

    Institute of Scientific and Technical Information of China (English)

    LIU Yu-Fang; ZHAI Hong-Sheng; GAO Ya-Li; LIU Rui-Qiong

    2008-01-01

    The time-resolved photoelectron spectra (TRPES) of Ned molecules are calculated by using the time-dependent wave packet method. Two different potential energy curves (adiabatic and diabatic) are adopted in the simulation. The third peak of the photoelectron spectra presented in the adiabatic calculation is induced by the reflection of the wave packet. The oscillating of the wave packet onto the diabatic energy curve is a decreasing process. The comparison of the photoelectron spectra between the two different calculations (adiabatic and diabatic) is presented.

  12. Imaging electron dynamics with time- and angle-resolved photoelectron spectroscopy

    CERN Document Server

    Popova-Gorelova, Daria; Santra, Robin

    2016-01-01

    We theoretically study how time- and angle-resolved photoemission spectroscopy can be applied for imaging coherent electron dynamics in molecules. We consider a process in which a pump pulse triggers coherent electronic dynamics in a molecule by creating a valence electron hole. An ultrashort extreme ultraviolet (XUV) probe pulse creates a second electron hole in the molecule. Information about the electron dynamics is accessed by analyzing angular distributions of photoemission probabilities at a fixed photoelectron energy. We demonstrate that a rigorous theoretical analysis, which takes into account the indistinguishability of transitions induced by the ultrashort, broadband probe pulse and electron hole correlation effects, is necessary for the interpretation of time- and angle-resolved photoelectron spectra. We show how a Fourier analysis of time- and angle-resolved photoelectron spectra from a molecule can be applied to follow its electron dynamics by considering photoelectron distributions from an indol...

  13. Quantum optimal control of photoelectron spectra and angular distributions

    CERN Document Server

    Goetz, R Esteban; Santra, Robin; Koch, Christiane P

    2016-01-01

    Photoelectron spectra and photoelectron angular distributions obtained in photoionization reveal important information on e.g. charge transfer or hole coherence in the parent ion. Here we show that optimal control of the underlying quantum dynamics can be used to enhance desired features in the photoelectron spectra and angular distributions. To this end, we combine Krotov's method for optimal control theory with the time-dependent configuration interaction singles formalism and a splitting approach to calculate photoelectron spectra and angular distributions. The optimization target can account for specific desired properties in the photoelectron angular distribution alone, in the photoelectron spectrum, or in both. We demonstrate the method for hydrogen and then apply it to argon under strong XUV radiation, maximizing the difference of emission into the upper and lower hemispheres, in order to realize directed electron emission in the XUV regime.

  14. Ultrafast dynamics of o-fluorophenol studied with femtosecond time-resolved photoelectron and photoion spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The ultrafast dynamics of o-fluorophenol via the excited states has been studied by femtosecond time-resolved photoelectron imaging. The photoion and photoelectron spectra taken with a time delay between 267 nm pump laser and 800 nm probe laser provide a longer-lived S1 electronic state of about ns timescale. In comparison,the spectra obtained by exciting the S2 state with femtosecond laser pulses at 400 nm and ionizing with pulses at 800 nm suggest that the S2 state has an ultrashort lifetime about 102 fs and reflects the internal conversion dynamics of the S2 state to the S1 state.

  15. Photoelectron spectra with Qprop and t-SURFF

    CERN Document Server

    Mosert, Volker

    2016-01-01

    Calculating strong-field, momentum-resolved photoelectron spectra (PES) from numerical solutions of the time-dependent Schr\\"odinger equation (TDSE) is a very demanding task due to the large spatial excursions and drifts of electrons in intense laser fields. The time-dependent surface flux (t-SURFF) method for the calculation of PES [L. Tao, A. Scrinzi, New Journal of Physics 14, 013021 (2012)] allows to keep the numerical grid much smaller than the space over which the wavefunction would be spread at the end of the laser pulse. We present an implementation of the t-SURFF method in the well established TDSE-solver Qprop [D. Bauer, P. Koval, Comput. Phys. Commun. 174, 396 (2006)]. Qprop efficiently propagates wavefunctions for single-active electron systems with spherically symmetric binding potentials in classical, linearly (along $z$) or elliptically (in the $xy$-plane) polarized laser fields in dipole approximation. Its combination with t-SURFF makes the simulation of PES feasible in cases where it is just ...

  16. Interatomic scattering in energy dependent photoelectron spectra of Ar clusters

    Energy Technology Data Exchange (ETDEWEB)

    Patanen, M.; Benkoula, S.; Nicolas, C.; Goel, A. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex (France); Antonsson, E. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex (France); Physikalische und Theoretische Chemie Institut für Chemie und Biochemie, Fachbereich Biologie, Chemie, Pharmazie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin (Germany); Neville, J. J. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex (France); Department of Chemistry, University of New Brunswick, Fredericton, New Brunswick E3B 6E2 (Canada); Miron, C., E-mail: Catalin.Miron@synchrotron-soleil.fr [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex (France); Extreme Light Infrastructure - Nuclear Physics (ELI-NP), ‘Horia Hulubei’ National Institute for Physics and Nuclear Engineering, 30 Reactorului Street, RO-077125 Măgurele, Jud. Ilfov (Romania)

    2015-09-28

    Soft X-ray photoelectron spectra of Ar 2p levels of atomic argon and argon clusters are recorded over an extended range of photon energies. The Ar 2p intensity ratios between atomic argon and clusters’ surface and bulk components reveal oscillations similar to photoelectron extended X-ray absorption fine structure signal (PEXAFS). We demonstrate here that this technique allows us to analyze separately the PEXAFS signals from surface and bulk sites of free-standing, neutral clusters, revealing a bond contraction at the surface.

  17. Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

    DEFF Research Database (Denmark)

    Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.

    2014-01-01

    comparing time-resolved photoelectron spectroscopy (TRPES) with ab initio multiple spawning (AIMS) simulations on the MS-MR-CASPT2 level of theory. We disentangle the relationship between two phenomena that dominate the immediate molecular response upon light absorption: a spectrally dependent delay...... replaced by ‘‘hydrogen atoms’’ having mass 15 and TRPES spectra were calculated. These showed an induction time of (108 10) fs which could directly be assigned to progress along a torsional mode leading to the intersection seam with the molecular ground state. In a stepladder-type approach, the close...

  18. Rotationally resolved state-to-state photoelectron study of niobium carbide radical

    Science.gov (United States)

    Luo, Zhihong; Huang, Huang; Zhang, Zheng; Chang, Yih-Chung; Ng, C. Y.

    2014-07-01

    By employing the two-color visible (VIS)-ultraviolet (UV) laser photoexcitation scheme and the pulsed field ionization-photoelectron (PFI-PE) detection, we have obtained rovibronically selected and resolved photoelectron spectra for niobium carbide cation (NbC+). The fully rotationally resolved state-to-state VIS-UV-PFI-PE spectra thus obtained allow the unambiguous assignments of rotational photoionization transitions, indicating that the electronic configuration and term symmetry of NbC+(tilde X) ground state are …10σ2 5π4 11σ2 (tilde X1Σ+). Furthermore, the rotational analysis of these spectra yields the ionization energy of NbC [IE(NbC)] to be 56 369.2 ± 0.8 cm-1 (6.9889 ± 0.0001 eV) and the rotation constant B0+ = 0.5681 ± 0.0007 cm-1. The latter value allows the determination of the bond distance r0+ = 1.671 ± 0.001 Å for NbC+(tilde X1Σ+). Based on conservation of energy, the IE(NbC) determined in the present study along with the known IE(Nb) gives the difference of 0 K bond dissociation energies (D0's) for NbC+ and NbC, D0(NbC+) - D0(NbC) = -1855.4 ± 0.9 cm-1 (-0.2300 ± 0.0001 eV). The energetic values and the B0+ constant determined in this work are valuable for benchmarking state-of-the-art ab initio quantum calculations of 4d transition metal-containing molecules.

  19. Rotationally resolved state-to-state photoelectron study of niobium carbide radical

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Zhihong; Huang, Huang; Zhang, Zheng; Chang, Yih-Chung; Ng, C. Y., E-mail: cyng@ucdavis.edu [Department of Chemistry, University of California, Davis, California 95616 (United States)

    2014-07-14

    By employing the two-color visible (VIS)-ultraviolet (UV) laser photoexcitation scheme and the pulsed field ionization-photoelectron (PFI-PE) detection, we have obtained rovibronically selected and resolved photoelectron spectra for niobium carbide cation (NbC{sup +}). The fully rotationally resolved state-to-state VIS-UV-PFI-PE spectra thus obtained allow the unambiguous assignments of rotational photoionization transitions, indicating that the electronic configuration and term symmetry of NbC{sup +}(X{sup ~}) ground state are …10σ{sup 2} 5π{sup 4} 11σ{sup 2} (X{sup ~1}Σ{sup +}). Furthermore, the rotational analysis of these spectra yields the ionization energy of NbC [IE(NbC)] to be 56 369.2 ± 0.8 cm{sup −1} (6.9889 ± 0.0001 eV) and the rotation constant B{sub 0}{sup +} = 0.5681 ± 0.0007 cm{sup −1}. The latter value allows the determination of the bond distance r{sub 0}{sup +} = 1.671 ± 0.001 Å for NbC{sup +}(X{sup ~1}Σ{sup +}). Based on conservation of energy, the IE(NbC) determined in the present study along with the known IE(Nb) gives the difference of 0 K bond dissociation energies (D{sub 0}’s) for NbC{sup +} and NbC, D{sub 0}(NbC{sup +}) − D{sub 0}(NbC) = −1855.4 ± 0.9 cm{sup −1} (−0.2300 ± 0.0001 eV). The energetic values and the B{sub 0}{sup +} constant determined in this work are valuable for benchmarking state-of-the-art ab initio quantum calculations of 4d transition metal-containing molecules.

  20. Photoelectron spectra with QPROP and t-SURFF

    Science.gov (United States)

    Mosert, Volker; Bauer, Dieter

    2016-10-01

    Calculating strong-field, momentum-resolved photoelectron spectra (PES) from numerical solutions of the time-dependent Schrödinger equation (TDSE) is a very demanding task due to the large spatial excursions and drifts of electrons in intense laser fields. The time-dependent surface flux (t-SURFF) method for the calculation of PES [Tao and Scrinzi (2012)] allows to keep the numerical grid much smaller than the space over which the wavefunction would be spread at the end of the laser pulse. We present an implementation of the t-SURFF method in the well established TDSE-solver QPROP [Bauer and Koval (2006)]. QPROP efficiently propagates wavefunctions for single-active electron systems with spherically symmetric binding potentials in classical, linearly (along z) or elliptically (in the xy-plane) polarized laser fields in dipole approximation. Its combination with t-SURFF makes the simulation of PES feasible in cases where it is just too expensive to keep the entire wavefunction on the numerical grid, e.g., in the long-wavelength or long-pulse regime. Catalogue identifier: ADXB_v2_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADXB_v2_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License, version 3 No. of lines in distributed program, including test data, etc.: 12458 No. of bytes in distributed program, including test data, etc.: 86258 Distribution format: at.gz Programming language: C++. Computer: x86_64. Operating system: Linux. RAM: The memory requirements for calculating PES are determined by the maximum ℓ in the spherical harmonics expansion of the wave function and the number of momentum (or energy) values for which the PES are to be calculated. The example with the largest memory demand (large-clubs) uses approximately 6GB of RAM. The size of the numerical representation of a wavefunction during propagation is modest for the examples included (53 MB for the large

  1. 4f heavy femion photoelectron spectra do not exhibit the Kondo scale

    Energy Technology Data Exchange (ETDEWEB)

    Arko, A.J.; Joyce, J.J.; Andrews, A.B.; Blyth, I.R.; Barlett, R.J.; Fisk, Z. [Los Alamos National Laboratory, NM (United States); Canfield, P.C.; Olson, C.G.; Benning, P.J. [Iowa Sate Univ., Ames, IA (United States); Poirier, D.M.; Weaver, J.H. [Univ. of Minnesota, Minneapolis, MN (United States); Riseborough, P.S. [Polytechnic Univ., Brookyln, NY (United States)

    1994-12-31

    It has been the authors contention for some time that the Single Impurity Anderson Model (SIAM), as extended by Gunnarsson and Schonhammer (GS), or the non-crossing approximation (NCA), does not correctly describe the 4f photoelectron spectra of heavy fermions. Recently they have concentrated on Yb heavy fermions since in these materials the Kondo resonance (KR) is fully occupied and thus accessible via photoemission. In particular, they have repeatedly pointed out that the width, position, spectral weight, lineshape, and temperature dependence of the features assumed to be the KR and its sidebands, are nearly independent of the Kondo temperature, T{sub K}, while at the same time bearing a striking resemblance to the simple 4f core level spectra of pure Yb metal, or of Lu isostructural Lu compounds. It is important to resolve these issues in view of the fundamental nature of the problem.

  2. 4f heavy fermion photoelectron spectra do not exhibit the Kondo scale

    Energy Technology Data Exchange (ETDEWEB)

    Arko, A.J.; Joyce, J.J.; Andrews, A.B.; Blyth, R.I.R.; Bartlett, R.J.; Fisk, Z. [Los Alamos National Lab., NM (United States); Canfield, P.C.; Olson, C.G.; Benning, P.J. [Iowa State Univ., Ames, IA (United States); Poirier, D.M.; Weaver, J.H. [Univ. of Minnesota, Minneapolis, MN (United States); Riseborough, P.S. [Polytechnic Univ., Brooklyn, NY (United States)

    1994-02-01

    It has been the authors contention for some time that the Single Impurity Anderson Model (SIAM), as extended by Gunnarsson and Schonhammer (GS), or the non-crossing approximation (NCA), does not correctly describe the 4f photoelectron spectra of heavy fermions. Recently, they have concentrated on Yb heavy fermions since in these materials the Kondo resonance (KR) is fully occupied and thus accessible via photoemission. In particular, they have repeatedly pointed out that the width, position, spectral weight, lineshape, and temperature dependence of the features assumed to be the KR and its sidebands, are nearly independent of the Kondo temperature, T{sub K}, while at the same time bearing a striking resemblance to the simple 4f core level spectra of pure Yb metal, or of Lu in isostructural Lu compounds. It is important to resolve these issues in view of the fundamental nature of the problem. Here, the authors chose to test the bulk vs. surface hypothesis by performing measurements on YbCu{sub 2}Si{sub 2} and YbAl{sub 3} single crystals at hv {approx} 120 eV (UPS) and hv {approx} 1,500 eV(XPS) to see if the n{sub f}, hole occupancy, values increase markedly at XPS energies as the electron escape depth increases by about a factor of 3--5. Measurements were performed at both 300K and 20K using single crystals cleaved in-situ, with photoelectrons collected in normal emission for maximum bulk sensitivity. UPS measurements were performed at NSLS and the University of Wisconsin SRC, while XPS measurements were done at the University of Minnesota. The UPS, ultraviolet photoelectron spectra, and the L{sub III} edge x-ray absorption and photoemission measurements are in fundamental disagreement.

  3. Real-time analysis for MBE by time-resolved core-level photoelectron spectroscopy.

    Science.gov (United States)

    Maeda, F; Watanabe, Y; Oshima, M; Taguchi, M; Oiwa, R

    1998-05-01

    A system has been developed for the real-time analysis of surface reactions during molecular beam epitaxial growth which uses photoelectron spectroscopy with VUV light taken from synchrotron radiation. This system consists of a synchrotron radiation beamline and growth/analysis apparatus in which photoelectron spectroscopy is performed with sub-second time resolution. In this system, photoelectron spectra are measured in sequence by a 'non-scanning' measurement method that enables the acquisition of snapshot photoelectron spectra using a multi-channel detector. This non-scanning measurement method was enabled by equipping an electric field correction grid. This system was used to monitor the photoelectron spectra of a GaSb(001) surface.

  4. Time-resolved photoelectron spectroscopy and ab initio multiple spawning studies of hexamethylcyclopentadiene

    DEFF Research Database (Denmark)

    Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.

    2014-01-01

    Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom....

  5. Time-resolved photoelectron spectroscopy of non-adiabatic dynamics in polyatomic molecules

    CERN Document Server

    Stolow, Albert

    2015-01-01

    This review article discusses advances in the use of time-resolved photoelectron spectroscopy for the study of non-adiabatic processes in molecules. A theoretical treatment of the experiments is presented together with a number of experimental examples.

  6. Assignment of benzodiazepine UV absorption spectra by the use of photoelectron spectroscopy

    Science.gov (United States)

    Khvostenko, O. G.; Tzeplin, E. E.; Lomakin, G. S.

    2002-04-01

    Correlations between singlet transition energies and energy gaps of corresponding pairs of occupied and unoccupied molecular orbitals were revealed in a series of benzodiazepines. The occupied orbital energies were taken from the photoelectron spectra of the compound investigated, the unoccupied ones were obtained from MNDO/d calculations, and the singlet energies were taken from the UV absorption spectra. The correspondence of the singlet transitions to certain molecular orbitals was established using MNDO/d calculations and comparing between UV and photoelectron spectra. It has been concluded that photoelectron spectroscopy can be applied for interpretation of UV absorption spectra of various compounds on the basis of similar correlations.

  7. Symmetry adapted cluster-configuration interaction calculation of the photoelectron spectra of famous biological active steroids

    Science.gov (United States)

    Abyar, Fatemeh; Farrokhpour, Hossein

    2014-11-01

    The photoelectron spectra of some famous steroids, important in biology, were calculated in the gas phase. The selected steroids were 5α-androstane-3,11,17-trione, 4-androstane-3,11,17-trione, cortisol, cortisone, corticosterone, dexamethasone, estradiol and cholesterol. The calculations were performed employing symmetry-adapted cluster/configuration interaction (SAC-CI) method using the 6-311++G(2df,pd) basis set. The population ratios of conformers of each steroid were calculated and used for simulating the photoelectron spectrum of steroid. It was found that more than one conformer contribute to the photoelectron spectra of some steroids. To confirm the calculated photoelectron spectra, they compared with their corresponding experimental spectra. There were no experimental gas phase Hesbnd I photoelectron spectra for some of the steroids of this work in the literature and their calculated spectra can show a part of intrinsic characteristics of this molecules in the gas phase. The canonical molecular orbitals involved in the ionization of each steroid were calculated at the HF/6-311++g(d,p) level of theory. The spectral bands of each steroid were assigned by natural bonding orbital (NBO) calculations. Knowing the electronic structures of steroids helps us to understand their biological activities and find which sites of steroid become active when a modification is performing under a biological pathway.

  8. Crystal structures and photoelectron spectra of some trimethanoanthracenes, tetramethanonaphthacenes, and pentamethanopentacenes. Experimental evidence for laticyclic hyperconjugation

    DEFF Research Database (Denmark)

    Paddon-Row, Michael N.; Englehardt, Lutz M.; Skelton, Brian W.

    1987-01-01

    Photoelectron (p.e.) spectra of the series of dienes (), (), ()-(), and crystal structures for the dodecachlorodienes()-() are reported. The spectra revealed large [small pi]-splitting energies of 0.32 and 0.52 eV for () and () respectively. The value of () is attributed to the presence of orbita...

  9. Calculation of photoelectron spectra within the time-dependent configuration interaction singles scheme

    CERN Document Server

    Karamatskou, Antonia; Chen, Yi-Jen; Santra, Robin

    2014-01-01

    We present the extension of the time-dependent configuration interaction singles (TDCIS) method to the computation of the electron kinetic-energy spectrum in photoionization processes. Especially for strong and long ionizing light pulses the detection of the photoelectron poses a computational challenge because propagating the outgoing photoelectron wavepacket requires large grid sizes. Two different methods which allow for the extraction of the asymptotic photoelectron momentum are compared regarding their methodological and computational performance. The first method follows the scheme of Tong et al. \\cite{tong} where the photoelectron wavefunction is absorbed by a real splitting function. The second method after Tao and Scrinzi \\cite{scrinzi} measures the flux of the electron wavepacket through a surface at a fixed radius. With both methods the full angle- and energy-resolved photoelectron spectrum is obtained. Combined with the TDCIS scheme it is possible to analyze the dynamics of the outgoing electron i...

  10. Photoelectron Spectra of Aqueous Solutions from First Principles

    Energy Technology Data Exchange (ETDEWEB)

    Gaiduk, Alex P.; Govoni, Marco; Seidel, Robert; Skone, Jonathan H.; Winter, Bernd; Galli, Giulia

    2016-06-08

    We present a combined computational and experimental study of the photoelectron spectrum of a simple aqueous solution of NaCl. Measurements were conducted on microjets, and first-principles calculations were performed using hybrid functionals and many-body perturbation theory at the G0W0 level, starting with wave functions computed in ab initio molecular dynamics simulations. We show excellent agreement between theory and experiments for the positions of both the solute and solvent excitation energies on an absolute energy scale and for peak intensities. The best comparison was obtained using wave functions obtained with dielectric-dependent self-consistent and range-separated hybrid functionals. Our computational protocol opens the way to accurate, predictive calculations of the electronic properties of electrolytes, of interest to a variety of energy problems.

  11. Pseudo-bimolecular [2+2] cycloaddition studied by time-resolved photoelectron spectroscopy

    DEFF Research Database (Denmark)

    Brogaard, Rasmus Y; Boguslavskiy, Andrey E; Schalk, Oliver

    2011-01-01

    The first study of pseudo-bimolecular cycloaddition reaction dynamics in the gas phase is presented. We used femtosecond time-resolved photoelectron spectroscopy (TRPES) to study the [2+2] photocycloaddition in the model system pseudo-gem-divinyl[2.2]paracyclophane. From X-ray crystal diffraction...

  12. Photoelectron spectra and structures of three cyclic dipeptides

    DEFF Research Database (Denmark)

    Wickrama Arachchilage, A.P.; Wang, F.; Feyer, V.;

    2012-01-01

    chemical properties associated with the central diketopiperazine ring, and with the additional functional groups. The valence spectra are generally characterized by a restricted set of outer valence orbitals separated by a gap from most other valence orbitals. The theoretically simulated core and valence...

  13. Capturing interfacial photoelectrochemical dynamics with picosecond time-resolved X-ray photoelectron spectroscopy.

    Science.gov (United States)

    Neppl, Stefan; Shavorskiy, Andrey; Zegkinoglou, Ioannis; Fraund, Matthew; Slaughter, Daniel S; Troy, Tyler; Ziemkiewicz, Michael P; Ahmed, Musahid; Gul, Sheraz; Rude, Bruce; Zhang, Jin Z; Tremsin, Anton S; Glans, Per-Anders; Liu, Yi-Sheng; Wu, Cheng Hao; Guo, Jinghua; Salmeron, Miquel; Bluhm, Hendrik; Gessner, Oliver

    2014-01-01

    Time-resolved core-level spectroscopy using laser pulses to initiate and short X-ray pulses to trace photoinduced processes has the unique potential to provide electronic state- and atomic site-specific insight into fundamental electron dynamics in complex systems. Time-domain studies using transient X-ray absorption and emission techniques have proven extremely valuable to investigate electronic and structural dynamics in isolated and solvated molecules. Here, we describe the implementation of a picosecond time-resolved X-ray photoelectron spectroscopy (TRXPS) technique at the Advanced Light Source (ALS) and its application to monitor photoinduced electron dynamics at the technologically pertinent interface formed by N3 dye molecules anchored to nanoporous ZnO. Indications for a dynamical chemical shift of the Ru3d photoemission line originating from the N3 metal centre are observed ∼30 ps after resonant HOMO-LUMO excitation with a visible laser pump pulse. The transient changes in the TRXPS spectra are accompanied by a characteristic surface photovoltage (SPV) response of the ZnO substrate on a pico- to nanosecond time scale. The interplay between the two phenomena is discussed in the context of possible electronic relaxation and recombination pathways that lead to the neutralisation of the transiently oxidised dye after ultrafast electron injection. A detailed account of the experimental technique is given including an analysis of the chemical modification of the nano-structured ZnO substrate during extended periods of solution-based dye sensitisation and its relevance for studies using surface-sensitive spectroscopy techniques.

  14. Electronic spectra of radical cations and their correlation with photoelectron spectra—III. Perylenes and coronenes

    Science.gov (United States)

    Khan, Zahid H.

    Radical cations of perylene, 1,12-benzoperylene, coronene, 1,2-benzocoronene, and naphtho-(2',3':1,2)coronene are produced by photooxidation in boric acid matrix and their electronic absorption spectra are measured. The results are discussed in terms of Longuet-Higgins-Pople and Wasilewski type Open-Shell SCF-MO calculations and the u.v. photoelectron spectra of the parent molecules. The correspondence between optical and photoelectron spectra is found to be fairly good. A correlation diagram for the electronic transitions for some of the molecular ions is presented to demonstrate their movement from one system to another. Finally, an expression showing the relationship between the first ionization potentials of the parent molecules and A-type electronic band energies in the cation spectra is given from which the first IP's of the hydrocarbons may be estimated.

  15. Pump laser-induced space-charge effects in HHG-driven time- and angle-resolved photoelectron spectroscopy

    Science.gov (United States)

    Oloff, L.-P.; Hanff, K.; Stange, A.; Rohde, G.; Diekmann, F.; Bauer, M.; Rossnagel, K.

    2016-06-01

    With the advent of ultrashort-pulsed extreme ultraviolet sources, such as free-electron lasers or high-harmonic-generation (HHG) sources, a new research field for photoelectron spectroscopy has opened up in terms of femtosecond time-resolved pump-probe experiments. The impact of the high peak brilliance of these novel sources on photoemission spectra, so-called vacuum space-charge effects caused by the Coulomb interaction among the photoemitted probe electrons, has been studied extensively. However, possible distortions of the energy and momentum distributions of the probe photoelectrons caused by the low photon energy pump pulse due to the nonlinear emission of electrons have not been studied in detail yet. Here, we systematically investigate these pump laser-induced space-charge effects in a HHG-based experiment for the test case of highly oriented pyrolytic graphite. Specifically, we determine how the key parameters of the pump pulse—the excitation density, wavelength, spot size, and emitted electron energy distribution—affect the measured time-dependent energy and momentum distributions of the probe photoelectrons. The results are well reproduced by a simple mean-field model, which could open a path for the correction of pump laser-induced space-charge effects and thus toward probing ultrafast electron dynamics in strongly excited materials.

  16. Caveats in the interpretation of time-resolved photoionization measurements: A photoelectron imaging study of pyrrole

    Science.gov (United States)

    Crane, Stuart W.; Zawadzki, Magdalena M.; Thompson, James O. F.; Kotsina, Nikoleta; Ghafur, Omair; Townsend, Dave

    2016-12-01

    We report time-resolved photoelectron imaging studies of gas-phase pyrrole over the 267-240 nm excitation region, recorded in conjunction with a 300 nm probe. Of specific interest is the lowest-lying (3 s /π σ* ) state, which exhibits very weak oscillator strength but is thought to be excited directly at wavelengths ≤254 nm. We conclude, however, that the only significant contribution to our photoelectron data at all wavelengths investigated is from non-resonant ionization. Our findings do not rule out (3 s /π σ* ) state excitation (as appears to be confirmed by supporting time-resolved ion-yield measurements) but do potentially highlight important caveats regarding the use and interpretation of photoreactant ionization measurements to interrogate dynamical processes in systems exhibiting significant topological differences between the potential energy surfaces of the neutral and cation states.

  17. An instrument for the investigation of actinides with spin resolved photoelectron spectroscopy and bremsstrahlung isochromat spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yu, S.-W. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Tobin, J. G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Chung, B. W. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2011-01-01

    A new system for spin resolved photoelectron spectroscopy and bremsstrahlung isochromat spectroscopy has been built and commissioned at Lawrence Livermore National Laboratory for the investigation of the electronic structure of the actinides.Actinide materials are very toxic and radioactive and therefore cannot be brought to most general user facilities for spectroscopic studies. The technical details of the new system and preliminary data obtained therein will be presented and discussed.

  18. Excited state dynamics in SO2. I. Bound state relaxation studied by time-resolved photoelectron-photoion coincidence spectroscopy.

    Science.gov (United States)

    Wilkinson, Iain; Boguslavskiy, Andrey E; Mikosch, Jochen; Bertrand, Julien B; Wörner, Hans Jakob; Villeneuve, David M; Spanner, Michael; Patchkovskii, Serguei; Stolow, Albert

    2014-05-28

    The excited state dynamics of isolated sulfur dioxide molecules have been investigated using the time-resolved photoelectron spectroscopy and time-resolved photoelectron-photoion coincidence techniques. Excited state wavepackets were prepared in the spectroscopically complex, electronically mixed (B̃)(1)B1/(Ã)(1)A2, Clements manifold following broadband excitation at a range of photon energies between 4.03 eV and 4.28 eV (308 nm and 290 nm, respectively). The resulting wavepacket dynamics were monitored using a multiphoton ionisation probe. The extensive literature associated with the Clements bands has been summarised and a detailed time domain description of the ultrafast relaxation pathways occurring from the optically bright (B̃)(1)B1 diabatic state is presented. Signatures of the oscillatory motion on the (B̃)(1)B1/(Ã)(1)A2 lower adiabatic surface responsible for the Clements band structure were observed. The recorded spectra also indicate that a component of the excited state wavepacket undergoes intersystem crossing from the Clements manifold to the underlying triplet states on a sub-picosecond time scale. Photoelectron signal growth time constants have been predominantly associated with intersystem crossing to the (c̃)(3)B2 state and were measured to vary between 750 and 150 fs over the implemented pump photon energy range. Additionally, pump beam intensity studies were performed. These experiments highlighted parallel relaxation processes that occurred at the one- and two-pump-photon levels of excitation on similar time scales, obscuring the Clements band dynamics when high pump beam intensities were implemented. Hence, the Clements band dynamics may be difficult to disentangle from higher order processes when ultrashort laser pulses and less-differential probe techniques are implemented.

  19. Rotationally Resolved Photoelectron Spectroscopic Study of the tilde{A}^+ State of H_2O^+

    Science.gov (United States)

    Lauzin, Clément; Gans, Berenger; Jacovella, Ugo; Merkt, Frederic

    2016-06-01

    This talk will present the analysis of the rotationally resolved pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectrum of H_2O and will be focussed on the tilde{A}^+←tilde{X} transitions. H_2O^+ in the tilde{A}^+ state is predicted to be linear. The sensitivity and the high resolution of PFI- ZEKE photoelectron spectroscopy allowed us to observe the rotational structure of low bending vibrational levels of the tilde{A}^+ state of H_2O^+ from the tilde{X} ground electronic state of H_2O. The assignment of the rotational structure of ionic levels previously observed by optical spectroscopy of the tilde{A}^+ - tilde{X}^+ band system of H_2O^+ will be presented and the intensity distribution of the photoelectron spectrum will be discussed in terms of the even or odd nature of the orbital angular momentum quantum number l of the photoelectron. Tentative assignments will be presented for several low-lying vibrational levels of the tilde{A}^+ state and compared with theoretical predictions ^c. They will also be discussed in terms of the rotational structure of higher tilde{A}^+ vibrational levels of the same symmetry. M. Brommer, B. Weis, B. Follmeg, P. Rosmus, S. Carter, N. C. Handy, H. J. Werner, and P. J. Knowles, J. Chem. Phys. 98, 5222 (1993) H. Lew, Can. J. Phys. 54, 2028 (1976).

  20. High-resolution photoelectron spectra of the pyrimidine-type nucleobases.

    Science.gov (United States)

    Fulfer, K D; Hardy, D; Aguilar, A A; Poliakoff, E D

    2015-06-14

    High-resolution photoelectron spectra of the gas phase pyrimidine-type nucleobases, thymine, uracil, and cytosine, were collected using synchrotron radiation over the photon energy range 17 ≤ hν ≤ 150 eV. These data provide the highest resolution photoelectron spectra of thymine, uracil, and cytosine published to date. By comparing integrated regions of the energy dependent photoelectron spectra of thymine, the ionization potentials of the first four ionic states of thymine were estimated to be 8.8, 9.8, 10.3, and 10.8 eV. The thymine data also show evidence for low energy shape resonances in three of the outermost valence electronic states. Comparing the uracil spectrum with the thymine spectrum, the four outermost valence electronic states of uracil likely begin at binding energies 9.3, 9.9, 10.5, and 11.0 eV. High-resolution spectra indicate only one tautomeric form of cytosine contributes significantly to the spectrum with the four outermost valence electronic states beginning at binding energies 8.9, 9.9, 10.4, and 10.85 eV.

  1. High-resolution photoelectron spectra of the pyrimidine-type nucleobases

    Energy Technology Data Exchange (ETDEWEB)

    Fulfer, K. D.; Hardy, D.; Poliakoff, E. D., E-mail: epoliak@lsu.edu [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Aguilar, A. A. [Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2015-06-14

    High-resolution photoelectron spectra of the gas phase pyrimidine-type nucleobases, thymine, uracil, and cytosine, were collected using synchrotron radiation over the photon energy range 17 ≤ hν ≤ 150 eV. These data provide the highest resolution photoelectron spectra of thymine, uracil, and cytosine published to date. By comparing integrated regions of the energy dependent photoelectron spectra of thymine, the ionization potentials of the first four ionic states of thymine were estimated to be 8.8, 9.8, 10.3, and 10.8 eV. The thymine data also show evidence for low energy shape resonances in three of the outermost valence electronic states. Comparing the uracil spectrum with the thymine spectrum, the four outermost valence electronic states of uracil likely begin at binding energies 9.3, 9.9, 10.5, and 11.0 eV. High-resolution spectra indicate only one tautomeric form of cytosine contributes significantly to the spectrum with the four outermost valence electronic states beginning at binding energies 8.9, 9.9, 10.4, and 10.85 eV.

  2. Interference stabilization of autoionizing states in molecular $N_2$ studied by time- and angular-resolved photoelectron spectroscopy

    CERN Document Server

    Eckstein, Martin; Yang, Chung-Hsin; Sansone, Giuseppe; Vrakking, Marc J J; Ivanov, Misha; Kornilov, Oleg

    2016-01-01

    An autoionizing resonance in molecular N$_2$ is excited by an ultrashort XUV pulse and probed by a subsequent weak IR pulse, which ionizes the contributing Rydberg states. Time- and angular-resolved photoelectron spectra recorded with a velocity map imaging spectrometer reveal two electronic contributions with different angular distributions. One of them has an exponential decay rate of $20\\pm5$ fs, while the other one is shorter than 10 fs. This observation is interpreted as a manifestation of interference stabilization involving the two overlapping discrete Rydberg states. A formalism of interference stabilization for molecular ionization is developed and applied to describe the autoionizing resonance. The results of calculations reveal, that the effect of the interference stabilization is facilitated by rotationally-induced couplings of electronic states with different symmetry.

  3. Single-State Electronic Structure Measurements Using Time-Resolved X-Ray Laser Induced Photoelectron Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A J; Dunn, J; van Buuren, T; Hunter, J

    2004-11-11

    We demonstrate single-shot x-ray laser induced time-of-flight photoelectron spectroscopy on semiconductor and metal surfaces with picosecond time resolution. The LLNL COMET compact tabletop x-ray laser source provides the necessary high photon flux (>10{sup 12}/pulse), monochromaticity, picosecond pulse duration, and coherence for probing ultrafast changes in the city, chemical and electronic structure of these materials. Static valence band and shallow core-level photoemission spectra are presented for ambient temperature Ge(100) and polycrystalline Cu foils. Surface contamination was removed by UV ozone cleaning prior to analysis. In addition, the ultrafast nature of this technique lends itself to true single-state measurements of shocked and heated materials. Time-resolved electron time-of-flight photoemission results for ultra-thin Cu will be presented.

  4. Disentangling Multichannel Photodissociation Dynamics in Acetone by Time-Resolved Photoelectron-Photoion Coincidence Spectroscopy.

    Science.gov (United States)

    Maierhofer, Paul; Bainschab, Markus; Thaler, Bernhard; Heim, Pascal; Ernst, Wolfgang E; Koch, Markus

    2016-08-18

    For the investigation of photoinduced dynamics in molecules with time-resolved pump-probe photoionization spectroscopy, it is essential to obtain unequivocal information about the fragmentation behavior induced by the laser pulses. We present time-resolved photoelectron-photoion coincidence (PEPICO) experiments to investigate the excited-state dynamics of isolated acetone molecules triggered by two-photon (269 nm) excitation. In the complex situation of different relaxation pathways, we unambiguously identify three distinct pump-probe ionization channels. The high selectivity of PEPICO detection allows us to observe the fragmentation behavior and to follow the time evolution of each channel separately. For channels leading to fragment ions, we quantitatively obtain the fragment-to-parent branching ratio and are able to determine experimentally whether dissociation occurs in the neutral molecule or in the parent ion. These results highlight the importance of coincidence detection for the interpretation of time-resolved photochemical relaxation and dissociation studies if multiple pathways are present.

  5. Magnetic dichroism in angular resolved hard X-ray photoelectron spectroscopy from buried magnetic layers

    Energy Technology Data Exchange (ETDEWEB)

    ViolBarbosa, Carlos E.; Ouardi, Siham [Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, 01187 Dresden (Germany); Fecher, Gerhard H., E-mail: fecher@cpfs.mpg.de [Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, 01187 Dresden (Germany); Ebke, Daniel; Felser, Claudia [Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, 01187 Dresden (Germany)

    2013-08-15

    Highlights: ► We show the feasibility of angular resolved MCD in photospectroscopy. ► Wide-acceptance lens system allows a fixed incident light angle in the experiment. ► Bulk-sensitive HAXPES-MCDAD was used to study buried layers. ► Performance tools as Scalasca and Paraver are used to debug the applications. -- Abstract: This work reports on the measurement of magnetic dichroism in angular-resolved photoelectron spectroscopy from in-plane magnetized buried thin films. The high bulk sensitivity of hard X-ray photoelectron spectroscopy (HAXPES) in combination with circularly polarized radiation enables the investigation of the magnetic properties of buried layers. Angular distributions of high kinetic energy (7–8 keV) photoelectrons in a range of about 60° were recorded in parallel to the energy distribution. Depending on purpose, energy and angular resolutions of 150–250 meV and 0.17–2° can be accomplished simultaneously in such experiments. Experiments were performed on exchange-biased magnetic layers covered by thin oxide films. More specifically, the angular distribution of photoelectrons from the ferromagnetic layer Co{sub 2}FeAl layer grown on MnIr exchange-biasing layer was investigated where the magnetic structure is buried beneath a MgO layer. Pronounced magnetic dichroism is found in the Co and Fe 2p states for all angles of emission. A slightly increased magnetic dichroism was observed for normal emission in agreement with theoretical considerations.

  6. Electron momentum distributions and photoelectron spectra of atoms driven by intense spatially inhomogeneous field

    CERN Document Server

    Ciappina, M F; Shaaran, T; Roso, L; Lewenstein, M

    2013-01-01

    We use three dimensional time-dependent Schr\\"odinger equation (3D--TDSE) to calculate angular electron momentum distributions and photoelectron spectra of atoms driven by spatially inhomogeneous fields. An example for such inhomogeneous fields is the locally enhanced field induced by resonant plasmons, appearing at surfaces of metallic nanoparticles, nanotips and gold bow-tie shape nanostructures. Our studies show that the inhomogeneity of the laser electric field plays an important role in the above threshold ionization process in the tunneling regime, causing significant modifications to the electron momentum distributions and photoelectron spectra, while its effects in the multiphoton regime appear to be negligible. Indeed, through tunneling ATI process, one can obtain higher energy electrons as well as high degree of asymmetry in the momentum space map. In this study we consider near infrared laser fields with intensities in the mid-$10^{14}$ W/cm$^{2}$ range and we use linear approximation to describe t...

  7. Time-resolved photoelectron imaging of the iodide-thymine and iodide-uracil binary cluster systems.

    Science.gov (United States)

    King, Sarah B; Yandell, Margaret A; Neumark, Daniel M

    2013-01-01

    The energetics and dynamics of thymine and uracil transient negative ions were examined using femtosecond time-resolved photoelectron imaging. The vertical detachment energies (VDEs) of these systems were found to be 4.05 eV and 4.11 eV for iodide-thymine (I(-) x T) and iodide-uracil (I(-) x U) clusters, respectively. An ultraviolet pump pulse was used to promote intracluster charge transfer from iodide to the nucleobase. Subsequent electron detachment using an infrared probe pulse monitored the dynamics of the resulting transient negative ion. Photoelectron spectra reveal two primary features: a near-zero electron kinetic energy signal attributed to autodetachment and a transient feature representing photodetachment from the excited anion state. The transient state exhibits biexponential decay in both thymine and uracil complexes with short and long decay time constants ranging from 150-600 fs and 1-50 ps, respectively, depending on the excitation energy. However, both time constants are systematically shorter for I(-) x T. Vibrational autodetachment and iodine loss are identified as the primary decay mechanisms of the transient negative ions of thymine and uracil.

  8. Double photo-electron momentum spectra of Helium at infrared wavelength

    CERN Document Server

    Zielinski, Alejandro; Scrinzi, Armin

    2015-01-01

    Double photo-electron momentum spectra of the Helium atom are calculated \\textit{ab initio} at extreme ultra-violet and near infrared wavelengths. At short wavelengths two-photon double ionization yields, two-electron energy spectra, and triply differential cross sections agree with results from recent literature. At the near infrared wavelength of $780\\,nm$ the experimental single-to-double ionization ratio is reproduced up to intensities of $4\\times 10^{14}W/cm^2$, and two-electron energy spectra and joint angular distributions are presented. The time-dependent surface flux (tSurff) approach is extended to full 3+3 spatial dimensions and systematic error control is demonstrated. We analyze our differential spectra in terms of an experimentally accessible quantitative measure of correlation.

  9. Excited state non-adiabatic dynamics of pyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Guorong [National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Neville, Simon P.; Worth, Graham A., E-mail: g.a.worth@bham.ac.uk [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Schalk, Oliver [National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Physics, AlbaNova University Center, Stockholm University, Roslagstullsbacken 21, 109 61 Stockholm (Sweden); Sekikawa, Taro [National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Applied Physics, Hokkaido University, Kita-13 Nishi-8, Kita-ku, Sapporo 060-8628 (Japan); Ashfold, Michael N. R. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Stolow, Albert, E-mail: astolow@uottawa.ca [National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Departments of Chemistry and Physics, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada)

    2015-02-21

    The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole’s electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A{sub 2}(πσ{sup ∗}) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths has previously been assumed to result predominantly in population of the bright A{sub 1}(ππ{sup ∗}) and B{sub 2}(ππ{sup ∗}) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole’s electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B{sub 1}(πσ{sup ∗}) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B{sub 1}(πσ{sup ∗}) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A{sub 2}(πσ{sup ∗}) state.

  10. Expansion dynamics of supercritical water probed by picosecond time-resolved photoelectron spectroscopy.

    Science.gov (United States)

    Gladytz, Thomas; Abel, Bernd; Siefermann, Katrin R

    2015-02-21

    Vibrational excitation of liquid water with femtosecond laser pulses can create extreme states of water. Yet, the dynamics directly after initial sub-picosecond delocalization of molecular vibrations remain largely unclear. We study the ultrafast expansion dynamics of an accordingly prepared supercritical water phase with a picosecond time resolution. Our experimental setup combines vacuum-compatible liquid micro-jet technology and a table top High Harmonic light source driven by a femtosecond laser system. An ultrashort laser pulse centered at a wavelength of 2900 nm excites the OH-stretch vibration of water molecules in the liquid. The deposited energy corresponds to a supercritical phase with a temperature of about 1000 K and a pressure of more than 1 GPa. We use a time-delayed extreme ultraviolet pulse centered at 38.6 eV, and obtained via High Harmonic generation (HHG), to record valence band photoelectron spectra of the expanding water sample. The series of photoelectron spectra is analyzed with noise-corrected target transform fitting (cTTF), a specifically developed multivariate method. Together with a simple fluid dynamics simulation, the following picture emerges: when a supercritical phase of water expands into vacuum, temperature and density of the first few nanometers of the expanding phase drop below the critical values within a few picoseconds. This results in a supersaturated phase, in which condensation seeds form and grow from small clusters to large clusters on a 100 picosecond timescale.

  11. TIME—RESOLVED X—RAY SPECTRA AND ATOMIC PROCESSES

    Institute of Scientific and Technical Information of China (English)

    TakakoKATO

    1990-01-01

    In this article we will discuss time-resolved He-like X-ray spectra of titanium ions from a TFTR tokamak plasma[1] and of iron ions from solar flares[2] in particular attention to a presence of high energy electrons which affect the spectra and ionization balances.We consider a model that a hot component interacts with a bulk plasma.With this model,the time evolution of the spectra and ionization balaces derived therefrom can be described consistently.

  12. Time-resolved luminescence spectra of porous Si

    OpenAIRE

    Miyoshi, Tadaki; Lee, Kyu-Seok; Aoyagi, Yoshinobu

    1992-01-01

    Time-resolved luminescence spectra of porous Si were measured under an N_2 laser excitation. The luminescence shows a nonexponential decay with an initial time constant of less than 5 ns and more than 200 ns for the secondary decay. The luminescence is considered to be associated with localized states, which are probably conduction and valence sublevels in Si microstructures.

  13. Multiple-plateau structure and scaling relation in photoelectron spectra of high-order above-threshold ionization

    Institute of Scientific and Technical Information of China (English)

    Wu Yan; Ye Hui-Liang; Zhang Jing-Tao; Guo Dong-Sheng

    2012-01-01

    By developing a full quantum scattering theory of high-order above-threshold ionization,we study the energy spectra and the angular distributions of photoelectrons from atoms with intense laser fields shining on them.We find that real rescattering can occur many times,and even infinite times.The photoelectrons from the rescattering process form a broad plateau in the kinetic-energy spectrum.We further disclose a multiple-plateau structure formed by the high-energy photoelectrons,which absorb many photons during the rescattering process.Moreover,we find that both the angular distributions and the kinetic-energy spectra of photoelectrons obey the same scaling law as that for directly emitted photoelectrons.

  14. Laser-Induced Electron Diffraction: Inversion of Photoelectron Spectra for Molecular Orbital Imaging

    CERN Document Server

    Puthumpally-Joseph, R; Peters, M; Nguyen-Dang, T T; Atabek, O; Charron, E

    2016-01-01

    In this paper, we discuss the possibility of imaging molecular orbitals from photoelectron spectra obtained via Laser Induced Electron Diffraction (LIED) in linear molecules. This is an extension of our work published recently in Physical Review A \\textbf{94}, 023421 (2016) to the case of the HOMO-1 orbital of the carbon dioxide molecule. We show that such an imaging technique has the potential to image molecular orbitals at different internuclear distances in a sub-femtosecond time scale and with a resolution of a fraction of an Angstr\\"om.

  15. Advancements in time-resolved x-ray laser induced time-of-flight photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A J; Dunn, J; Widmann, K; Ao, T; Ping, Y; Hunter, J; Ng, A

    2005-07-28

    Time-resolved soft x-ray photoelectron spectroscopy is used to probe the non-steady-state evolution of the valence band electronic structure of laser heated ultra-thin (50 nm) metal foils and bulk semiconductors. Single-shot soft x-ray laser induced time-of-flight photoelectron spectroscopy with picosecond time resolution was used in combination with optical measurements of the disassembly dynamics that have shown the existence of a metastable liquid phase in fs-laser heated metal foils persisting 4-5 ps. This metastable phase is studied using a 527 nm wavelength 400 fs laser pulse containing 0.3-2.5 mJ laser energy focused in a large 500 x 700 {micro}m{sup 2} spot to create heated conditions of 0.2-1.8 x 10{sup 12} W cm{sup -2} intensity. The unique LLNL COMET compact tabletop soft x-ray laser source provided the necessary high photon flux, highly monoenergetic, picosecond pulse duration, and coherence for observing the evolution of changes in the valence band electronic structure of laser heated metals and semiconductors with picosecond time resolution. This work demonstrates the continuing development of a powerful new technique for probing reaction dynamics and changes of local order on surfaces on their fundamental timescales including phenomena such as non-thermal melting, chemical bond formation, intermediate reaction steps, and the existence of transient reaction products.

  16. A novel approach to angular-resolved X-ray photoelectron spectroscopy depth-profiling

    Energy Technology Data Exchange (ETDEWEB)

    Stanchev, A.; Ignatova, V.; Ghelev, Ch. E-mail: chghelev@ie.bas.bg

    2000-05-02

    The angular-resolved-X-ray photoelectron spectroscopy (AR-XPS) technique is chosen to investigate the O redistribution on the surface of yttria-stabilized ZrO{sub 2} crystals during 10 keV He{sup +} ion bombardment. The data processing is performed by means of a newly-developed version of the 'Box-car' function method. An energy correction of the inelastic mean free paths (IMFP) of the elements present is performed and the elements peak areas are normalized with respect to surface carbon layer. An algorithm is described, which is tested and applied to the angular-dependent XPS data, and the true elements' depth-profiles are thus obtained.

  17. Multiple isomers in the photoelectron spectra of small mono-niobium carbide clusters

    Science.gov (United States)

    Iordanov, Ivan; Sofo, Jorge O.

    2011-05-01

    We calculate the photoelectron spectrum of small mono-niobium carbide clusters (NbCn) using density functional theory for clusters with n = 2-7 and the symmetry adapted cluster configuration interaction method for the smallest clusters (n = 2-4). Theoretical spectra of a single structure cannot explain all peaks present in the spectrum measured by Zhai et al. [J. Chem. Phys. 115, 5170 (2001)]. However, we can match all peaks in the experimental spectra if we assume that the beam contains a combination of cyclic and linear structures. This finding is even more surprising given the fact that some of the excited metastable geometries have energies as large as 0.5 eV above the ground state. Our result is confirmed by both theoretical approaches. We suggest further experiments, using additional beam cooling, to corroborate this observation.

  18. Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling

    CERN Document Server

    Grell, Gilbert; Winter, Bernd; Seidel, Robert; Aziz, Emad F; Aziz, Saadullah G; Kühn, Oliver

    2015-01-01

    X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the Restricted Active Space Self-Consistent Field method including spin-orbit coupling is used to cope with this challenge and to calculate valence and core photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the $\\text{[Fe(H}_2\\text{O)}_6\\text{]}^{2+}$ complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approx...

  19. Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling

    Energy Technology Data Exchange (ETDEWEB)

    Grell, Gilbert; Bokarev, Sergey I., E-mail: sergey.bokarev@uni-rostock.de; Kühn, Oliver [Institut für Physik, Universität Rostock, D-18051 Rostock (Germany); Winter, Bernd; Seidel, Robert [Helmholtz-Zentrum Berlin für Materialien und Energie, Methods for Material Development, Albert-Einstein-Strasse 15, D-12489 Berlin (Germany); Aziz, Emad F. [Helmholtz-Zentrum Berlin für Materialien und Energie, Methods for Material Development, Albert-Einstein-Strasse 15, D-12489 Berlin (Germany); Department of Physics, Freie Universität Berlin, Arnimalle 14, D-14159 Berlin (Germany); Aziz, Saadullah G. [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah (Saudi Arabia)

    2015-08-21

    X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the restricted active space self-consistent field method including spin-orbit coupling is used to cope with this challenge and to calculate valence- and core-level photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the [Fe(H{sub 2}O){sub 6}]{sup 2+} complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments.

  20. Dynamics of dipole- and valence bound anions in iodide-adenine binary complexes: A time-resolved photoelectron imaging and quantum mechanical investigation.

    Science.gov (United States)

    Stephansen, Anne B; King, Sarah B; Yokoi, Yuki; Minoshima, Yusuke; Li, Wei-Li; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M

    2015-09-14

    Dipole bound (DB) and valence bound (VB) anions of binary iodide-adenine complexes have been studied using one-color and time-resolved photoelectron imaging at excitation energies near the vertical detachment energy. The experiments are complemented by quantum chemical calculations. One-color spectra show evidence for two adenine tautomers, the canonical, biologically relevant A9 tautomer and the A3 tautomer. In the UV-pump/IR-probe time-resolved experiments, transient adenine anions can be formed by electron transfer from the iodide. These experiments show signals from both DB and VB states of adenine anions formed on femto- and picosecond time scales, respectively. Analysis of the spectra and comparison with calculations suggest that while both the A9 and A3 tautomers contribute to the DB signal, only the DB state of the A3 tautomer undergoes a transition to the VB anion. The VB anion of A9 is higher in energy than both the DB anion and the neutral, and the VB anion is therefore not accessible through the DB state. Experimental evidence of the metastable A9 VB anion is instead observed as a shape resonance in the one-color photoelectron spectra, as a result of UV absorption by A9 and subsequent electron transfer from iodide into the empty π-orbital. In contrast, the iodide-A3 complex constitutes an excellent example of how DB states can act as doorway state for VB anion formation when the VB state is energetically available.

  1. Changes in X-ray photoelectron spectra of yttria-tetragonal zirconia polycrystal by ion sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Eiko; Yoshinari, Masao [Tokyo Dental College, Oral Health Science Center, Tokyo, Chiyoda-ku (Japan)

    2016-04-15

    This paper reports changes in X-ray photoelectron spectroscopy spectra of yttria-tetragonal zirconia polycrystal (Y-TZP) brought about by Ar ion sputtering. The changes in the core-level spectra of Y-TZP suggest that preferential sputtering of oxygen occurred. A new peak was observed near 0 eV binding energy accompanied with changes in the core-level spectra by the sputtering. After 18 h in a high vacuum following the sputtering, the spectra changed by the sputtering were returned to their original shapes. In contrast, the color of Y-TZP was changed from white to pale brown by X-ray irradiation and was changed from pale brown to dark gray by ion sputtering. However, when the new peak near 0 eV decreased after 18 h, no color change was observed. Therefore, it is thought that the new peak was mainly derived from electrons trapped in various kinds of oxygen vacancies created by the sputtering in other than color centers. (orig.)

  2. Ultrafast Dynamics Through Conical Intersections in 2,6-dimethylpyridine Studied with Time-resolved Photoelectron Imaging

    Institute of Scientific and Technical Information of China (English)

    Xue-jun Qiu; Rong-shu Zhu; Yan-qi Xu; Abulimiti Bumaliya; Song Zhang; Bing Zhang

    2011-01-01

    The ultrafast dynamics through conical intersections in 2,6-dimethylpyridine has been studied by femtosecond time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy.Upon absorption of 266 nm pump laser,2,6-dimethylpyridine is excited to the S2 state with a ππ* character from So state.The time evolution of the parent ion signals consists of two exponential decays.One is a fast component on a timescale of 635 fs and the other is a slow component with a timescale of 4.37 ps.Time-dependent photoelectron angular distributions and energy-resolved photoelectron spectroscopy are extracted from time-resolved photoelectron imaging and provide the evolutive information of S2 state.In brief,the ultrafast component is a population transfer from S2 to S1 through the S2/S1 conical intersections,the slow component is attributed to simultaneous IC from the S2 state and the higher vibrational levels of S1 state to S0 state,which involves the coupling of S2/S0 and S1/S0 conical intersections.Additionally,the observed ultrafast S2→S1 transition occurs only with an 18% branching ratio.

  3. Interpretation of the photoelectron spectra of FeS(2)(-) by a multiconfiguration computational approach.

    Science.gov (United States)

    Clima, Sergiu; Hendrickx, Marc F A

    2007-11-01

    The ground states of FeS(2) and FeS(2)(-), and several low-lying excited electronic states of FeS(2) that are responsible for the FeS(2)(-) photoelectron spectrum, are calculated. At the B3LYP level an open, quasi-linear [SFeS](-) conformation is found as the most stable structure, which is confirmed at the ab initio CASPT2 computational level. Both the neutral and the anionic unsaturated complexes possess high-spin electronic ground states. For the first time a complete assignment of the photoelectron spectrum of FeS(2)(-) is proposed. The lowest energy band in this spectrum is ascribed to an electron detachment from the two highest-lying 3dpi antibonding orbitals (with respect to the iron-sulfur bonding) of iron. The next-lowest experimental band corresponds to an electron removal from nonbonding, nearly pure sulfur orbitals. The two highest bands in the spectra are assigned as electron detachments from pi and sigma bonding mainly sulfur orbitals.

  4. [Photoelectron Spectra of CCl2-: Ab Initio Calculation and Franck-Condon Analysis].

    Science.gov (United States)

    Wu, Jun

    2015-12-01

    Geometry optimization and harmonic vibrational frequency calculations were performed on the X¹A₁ state of CCl₂ and X²B₁ state of CCl₂⁻ at the B3LYP, MP2, CCSD levels. Franck-Condon analysis and spectral simulations were carried out on the photoelectron band of CCl₂⁻ including Duschinsky effects. The simulated spectra obtained are in excellent agreement with the experiment. Note that Duschinsky effect between bending vibration and the symmetric stretch modes should be considered in the CCl₂ (X¹A₁)-CCl₂⁻ (X²B₁) photodetachment process. By combining ab initio calculations with Franck-Condon analyses, the assignment of spectrum observed is firmly established to the X¹A₁-X²B₁ photodetachment process of the CCl₂⁻ radical, and the recommended geometric parameters of which in the literature are confirmed again base on ab initio theory and IFCA process.

  5. Valence photoelectron spectra of an electron-beam-irradiated C60 film

    Science.gov (United States)

    Onoe, Jun; Nakao, Aiko; Hida, Akira

    2004-10-01

    Valence photoelectron spectra of an electron-beam (EB) irradiated C60 film, which exhibited metallic electron-transport properties in air at room temperature, are presented. The electronic structure of the C60 film became closer to that of graphite as the EB-irradiation time increased, and its density of states around the Fermi level was eventually greater than for the graphite. This suggests that the electronic structure of the C60 film changed from a semiconductor to a semimetal and/or metal by EB irradiation. Interestingly, the electronic structure remained metallic even after five days of air exposure, which is the reason for the metallic electron-transport property in our previous report [Appl. Phys. Lett. 82, 595 (2003)].

  6. Spectra-resolved technique of a sensitive time-resolved fluorescence immunoassay instrument

    Science.gov (United States)

    Guo, Zhouyi; Tian, Zhen; Jia, Yali

    2004-07-01

    The lanthanide trivalence ion and its chelates are used for marking substance in time-resolved fluorescence immunoassay (TRFIA), marking the protein, hormone, antibody, nucleic acid probe or biologica alive cell, to measure the concentration of the analysis substance inside the reaction system with time-resolved fluorometry after the reaction system occurred, and attain the quantitative analysis's purpose. TRFIA has been become a kind of new and more sensitive measure method after radioisotope marking, enzymatic marking, chemiluminescence, electrochemiluminescence, it primarily is decided by the special physics and chemistry characteristic of lanthanide trivalence ion and its chelates. In this paper, the result of spectroscopic evaluation of europium trivalence ion and its chelate, and the principle of spectra-resolved technology and a sensitive time-resolved fluorescence immunoassay instrument made by ourselves are reported. In the set, a high frequency Xenon pulsed-light was adopted as exciting light, and two special filters was utilized according to spectra-resolved technique. Thus the influence of scattering light and short-lifetime fluorescence was removed. And the sensitivity is 10-12mol/L (when Eu3+ was used for marking substance), examination repeat is CV = 95% (p < 0.01).

  7. Initial processes of proton transfer in salicylideneaniline studied by time-resolved photoelectron spectroscopy.

    Science.gov (United States)

    Sekikawa, Taro; Schalk, Oliver; Wu, Guorong; Boguslavskiy, Andrey E; Stolow, Albert

    2013-04-11

    Excited-state intramolecular proton transfer (ESIPT) in salicylideneaniline (SA) and selected derivatives substituted in the para position of the anilino group have been investigated by femtosecond time-resolved photoelectron spectroscopy (TRPES) and time-dependent density functional theory (TDDFT). SA has a twisted structure at the energetic minimum of the ground state, but ESIPT is assumed to take place through a planar structure, although this has not been fully established. The TRPES studies revealed that the excited-state dynamics within the S1 band varied significantly with excitation wavelength. At finite temperatures, the ground state was found to sample a broad range of torsional angles, from planar to twisted. At lower photon energies (370 nm), only the planar ground-state molecules were excited, and the excited-state reaction took place within 50 fs. At higher energies (350 and 330 nm), predominantly twisted ground-state molecules were excited: they had to planarize before ESIPT could occur. This process was found to be slower in methylated SA but did not change significantly in the brominated and nitrated SAs. These substitution effects on the decay dynamics can be explained by modifications of the potential barriers, as predicted by the TDDFT calculations, and support the mechanism of a twisting motion of the anilino ring prior to ESIPT. The contribution of another pathway leading to internal conversion within the enol form was found to be minor at the excitation wavelengths considered here.

  8. Electronic states localized at surface defects on Cu(755) studied by angle-resolved ultraviolet photoelectron spectroscopy using synchrotron radiation

    CERN Document Server

    Ogawa, K; Namba, H

    2003-01-01

    'Regularly stepped' and 'defective' surfaces of Cu(755) were prepared by low- and high-temperature annealing, respectively, of a clean specimen. Electronic states on both surfaces were studied by angle-resolved ultraviolet photoelectron spectroscopy using synchrotron radiation. On the defective Cu(755), we found a new photoelectron peak due to surface defects just below the Fermi level. The dispersion profile of the defect state is derived to be almost flat, which demonstrates the localized nature of the defects. High activity to oxygen adsorption of the defect state was revealed. (author)

  9. Complex structure of spatially resolved high-order-harmonic spectra

    Science.gov (United States)

    Catoire, F.; Ferré, A.; Hort, O.; Dubrouil, A.; Quintard, L.; Descamps, D.; Petit, S.; Burgy, F.; Mével, E.; Mairesse, Y.; Constant, E.

    2016-12-01

    We investigate the spatiospectral coupling appearing in the spatially resolved high-order-harmonic spectra generated in gases. When ionization is weak, harmonic generation in the far field often exhibits rings surrounding a central spot centered on each odd harmonics in the spatiospectral domain. The nature of these structures is debated. They could stem from interferences between the emission of short and long trajectories, or could be the signature of the temporal and spatial dependence of the longitudinal phase matching of long trajectories (Maker fringes). We conducted spectrally and spatially resolved measurements of the harmonic spectra as a function of pressure, intensity, and ellipticity. In addition, we performed calculations where only a single emission plane is included (i.e., omitting deliberately the longitudinal phase matching), reproducing the features experimentally observed. This study has been completed by the spatiospectral coupling when strong ionization occurs leading to complex patterns which have been compared to calculations using the same model and also show good agreement. We conclude that many spatiospectral structures of the harmonic spectrum can be interpreted in terms of spatial and temporal transverse coherence of the emitting medium without resorting to longitudinal phase matching or quantum phase interference between short and long trajectories.

  10. X-ray photoelectron spectra structure and chemical bonding in AmO2

    Directory of Open Access Journals (Sweden)

    Teterin Yury A.

    2015-01-01

    Full Text Available Quantitative analysis was done of the X-ray photoelectron spectra structure in the binding energy range of 0 eV to ~35 eV for americium dioxide (AmO2 valence electrons. The binding energies and structure of the core electronic shells (~35 eV-1250 eV, as well as the relativistic discrete variation calculation results for the Am63O216 and AmO8 (D4h cluster reflecting Am close environment in AmO2 were taken into account. The experimental data show that the many-body effects and the multiplet splitting contribute to the spectral structure much less than the effects of formation of the outer (0-~15 eV binding energy and the inner (~15 eV-~35 eV binding energy valence molecular orbitals. The filled Am 5f electronic states were shown to form in the AmO2 valence band. The Am 6p electrons participate in formation of both the inner and the outer valence molecular orbitals (bands. The filled Am 6p3/2 and the O 2s electronic shells were found to make the largest contributions to the formation of the inner valence molecular orbitals. Contributions of electrons from different molecular orbitals to the chemical bond in the AmO8 cluster were evaluated. Composition and sequence order of molecular orbitals in the binding energy range 0-~35 eV in AmO2 were established. The experimental and theoretical data allowed a quantitative scheme of molecular orbitals for AmO2, which is fundamental for both understanding the chemical bond nature in americium dioxide and the interpretation of other X-ray spectra of AmO2.

  11. Band structures of 4f and 5f materials studied by angle-resolved photoelectron spectroscopy

    Science.gov (United States)

    Fujimori, Shin-ichi

    2016-04-01

    Recent remarkable progress in angle-resolved photoelectron spectroscopy (ARPES) has enabled the direct observation of the band structures of 4f and 5f materials. In particular, ARPES with various light sources such as lasers (hν ∼ 7~\\text{eV} ) or high-energy synchrotron radiations (hν ≳ 400~\\text{eV} ) has shed light on the bulk band structures of strongly correlated materials with energy scales of a few millielectronvolts to several electronvolts. The purpose of this paper is to summarize the behaviors of 4f and 5f band structures of various rare-earth and actinide materials observed by modern ARPES techniques, and understand how they can be described using various theoretical frameworks. For 4f-electron materials, ARPES studies of \\text{Ce}M\\text{I}{{\\text{n}}5} (M=\\text{Rh} , \\text{Ir} , and \\text{Co} ) and \\text{YbR}{{\\text{h}}2}\\text{S}{{\\text{i}}2} with various incident photon energies are summarized. We demonstrate that their 4f electronic structures are essentially described within the framework of the periodic Anderson model, and that the band-structure calculation based on the local density approximation cannot explain their low-energy electronic structures. Meanwhile, electronic structures of 5f materials exhibit wide varieties ranging from itinerant to localized states. For itinerant \\text{U}~5f compounds such as \\text{UFeG}{{\\text{a}}5} , their electronic structures can be well-described by the band-structure calculation assuming that all \\text{U}~5f electrons are itinerant. In contrast, the band structures of localized \\text{U}~5f compounds such as \\text{UP}{{\\text{d}}3} and \\text{U}{{\\text{O}}2} are essentially explained by the localized model that treats \\text{U}~5f electrons as localized core states. In regards to heavy fermion \\text{U} -based compounds such as the hidden-order compound \\text{UR}{{\\text{u}}2}\\text{S}{{\\text{i}}2} , their electronic structures exhibit complex behaviors. Their overall band structures

  12. Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations

    Energy Technology Data Exchange (ETDEWEB)

    Palmer, Michael H., E-mail: m.h.palmer@ed.ac.uk; Ridley, Trevor, E-mail: t.ridley@ed.ac.uk, E-mail: vronning@phys.au.dk, E-mail: nykj@phys.au.dk, E-mail: marcello.coreno@elettra.eu, E-mail: desimone@iom.cnr.it, E-mail: malgorzata.biczysko@sns.it, E-mail: kipeters@wsu.edu [School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Scotland (United Kingdom); Hoffmann, Søren Vrønning, E-mail: t.ridley@ed.ac.uk, E-mail: vronning@phys.au.dk, E-mail: nykj@phys.au.dk, E-mail: marcello.coreno@elettra.eu, E-mail: desimone@iom.cnr.it, E-mail: malgorzata.biczysko@sns.it, E-mail: kipeters@wsu.edu; Jones, Nykola C., E-mail: t.ridley@ed.ac.uk, E-mail: vronning@phys.au.dk, E-mail: nykj@phys.au.dk, E-mail: marcello.coreno@elettra.eu, E-mail: desimone@iom.cnr.it, E-mail: malgorzata.biczysko@sns.it, E-mail: kipeters@wsu.edu [ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus C (Denmark); Coreno, Marcello, E-mail: t.ridley@ed.ac.uk, E-mail: vronning@phys.au.dk, E-mail: nykj@phys.au.dk, E-mail: marcello.coreno@elettra.eu, E-mail: desimone@iom.cnr.it, E-mail: malgorzata.biczysko@sns.it, E-mail: kipeters@wsu.edu [CNR-IMIP, Montelibretti, c/o Laboratorio Elettra, Trieste (Italy); Simone, Monica de, E-mail: t.ridley@ed.ac.uk, E-mail: vronning@phys.au.dk, E-mail: nykj@phys.au.dk, E-mail: marcello.coreno@elettra.eu, E-mail: desimone@iom.cnr.it, E-mail: malgorzata.biczysko@sns.it, E-mail: kipeters@wsu.edu [CNR-IOM Laboratorio TASC, Trieste (Italy); Grazioli, Cesare [CNR-IOM Laboratorio TASC, Trieste (Italy); Department of Chemical and Pharmaceutical Sciences, University of Trieste, Trieste (Italy); Zhang, Teng [Department of Physics and Astronomy, University of Uppsala, Uppsala (Sweden); and others

    2015-10-28

    New photoelectron, ultraviolet (UV), and vacuum UV (VUV) spectra have been obtained for bromobenzene by synchrotron study with higher sensitivity and resolution than previous work. This, together with use of ab initio calculations with both configuration interaction and time dependent density functional theoretical methods, has led to major advances in interpretation. The VUV spectrum has led to identification of a considerable number of Rydberg states for the first time. The Franck-Condon (FC) analyses including both hot and cold bands lead to identification of the vibrational structure of both ionic and electronically excited states including two Rydberg states. The UV onset has been interpreted in some detail, and an interpretation based on the superposition of FC and Herzberg-Teller contributions has been performed. In a similar way, the 6 eV absorption band which is poorly resolved is analysed in terms of the presence of two ππ* states of {sup 1}A{sub 1} (higher oscillator strength) and {sup 1}B{sub 2} (lower oscillator strength) symmetries, respectively. The detailed analysis of the vibrational structure of the 2{sup 2}B{sub 1} ionic state is particularly challenging, and the best interpretation is based on equation-of-motion-coupled cluster with singles and doubles computations. A number of equilibrium structures of the ionic and singlet excited states show that the molecular structure is less subject to variation than corresponding studies for iodobenzene. The equilibrium structures of the 3b{sub 1}3s and 6b{sub 2}3s (valence shell numbering) Rydberg states have been obtained and compared with the corresponding ionic limit structures.

  13. Study of the photoelectron and electron momentum spectra of cyclopentene using benchmark Dyson orbital theories.

    Science.gov (United States)

    Huang, Yan R; Ning, Chuan G; Deng, Jing K; Deleuze, Michael S

    2008-05-07

    A complete study of the valence electronic structure and related electronic excitation properties of cyclopentene in its C(s) ground state geometry is presented. Ionization spectra obtained from this compound by means of photoelectron spectroscopy (He I and He II) and electron momentum spectroscopy have been analyzed in details up to electron binding energies of 30 eV using one-particle Green's function (1p-GF) theory along with the outer-valence (OVGF) and the third-order algebraic diagrammatic construction [ADC(3)] schemes. The employed geometries derive from DFT/B3LYP calculations in conjunction with the aug-cc-pVTZ basis set, and closely approach the structures inferred from experiments employing microwave spectroscopy or electron diffraction in the gas phase. The 1p-GF/ADC(3) calculations indicate that the orbital picture of ionization breaks down at electron binding energies larger than approximately 17 eV in the inner-valence region, and that the outer-valence 7a' orbital is also subject to a significant dispersion of the ionization intensity over shake-up states. This study confirms further the rule that OVGF pole strengths smaller than 0.85 foretell a breakdown of the orbital picture of ionization at the ADC(3) level. Spherically averaged (e, 2e) electron momentum distributions at an electron impact energy of 1200 eV that were experimentally inferred from an angular analysis of EMS intensities have been interpreted by comparison with accurate simulations employing ADC(3) Dyson orbitals. Very significant discrepancies were observed with momentum distributions obtained from several outer-valence ionization bands using standard Kohn-Sham orbitals.

  14. Relaxation Dynamics in Photoexcited Chiral Molecules Studied by Time-Resolved Photoelectron Circular Dichroism: Toward Chiral Femtochemistry

    CERN Document Server

    Comby, Antoine; Boggio-Pasqua, Martial; Descamps, Dominique; Légaré, Francois; Nahon, Laurent; Petit, Stéphane; Pons, Bernard; Fabre, Baptiste; Mairesse, Yann; Blanchet, Valérie

    2016-01-01

    Unravelling the main initial dynamics responsible for chiral recognition is a key stepin the understanding of many biological processes. However this challenging task requires a sensitive enantiospecic probe to investigate molecular dynamics on their natural femtosecond timescale. Here we show that, in the gas phase, the ultrafast relaxationdynamics of photoexcited chiral molecules can be tracked by recording Time-ResolvedPhotoElectron Circular Dichroism (TR-PECD) resulting from the photoionisation bya circularly polarized probe pulse. A large forward/backward asymmetry along theprobe propagation axis is observed in the photoelectron angular distribution. Its evolution with pump-probe delay reveals ultrafast dynamics that are inaccessible in theangle-integrated photoelectron spectrum nor via the usual electron emission anisotropyparameter ($\\beta$). PECD, which originates from the electron scattering in the chiral molecular potential, appears as a new sensitive observable for ultrafast molecular dynamicsin ch...

  15. Angle resolved photoelectron distribution of the 1{pi} resonance of CO/Pt(111)

    Energy Technology Data Exchange (ETDEWEB)

    Haarlammert, Thorben; Wegner, Sebastian; Tsilimis, Grigorius; Zacharias, Helmut [Physikalisches Institut, Westfaelische Wilhelms Universitaet, Muenster (Germany); Golovin, Alexander [Institute of Physics, St. Petersburg State University (Russian Federation)

    2009-07-01

    The CO 1{pi} level of a c(4 x 2)-2CO/Pt(111) reconstruction shows a significant resonance when varying the photon energy between h{nu}=23 eV and h{nu}=48 e V. This resonance has not been observed in gas phase measurements or on the Pt(1 10) surface. To investigate the photoelectron distribution of the 1{pi} level high harmonic radiaton has been used. By conversion in rare gases like argon, neon, or helium photon energies of up to 100 eV have been generated at repetition r ates of up to 10 kHz. The single harmonics have been separated and focused by a toroidal grating and directed to the sample surface. A time-of-flight detector with multiple anodes registers the kinetic energies of the emitted photoelectrons and enables the simultaneous detection of multiple emission angles. The angular distributions of photoelectrons emitted from the CO 1{pi} level have been measured for a variety of initial photon energies. Further the angular distributions of the CO 1{pi} level photoelectrons emitted from a CO-Pt{sub 7} cluster have been calculated using the MSX{alpha}-Method which shows good agreement with the ex perimental data.

  16. Relativistic calculation of the SeH{sub 2} and TeH{sub 2} photoelectron spectra

    Energy Technology Data Exchange (ETDEWEB)

    Pernpointner, Markus [Theoretische Chemie, Universitaet Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg (Germany)], E-mail: Markus.Pernpointner@pci.uni-heidelberg.de

    2006-10-26

    Photoelectron (PE) spectra provide detailed insight into the electronic structure of atoms, molecules and solids. Hereby electron correlation and relativistic effects influence the structure of the PE spectrum in a complicated way necessitating a consistent theoretical treatment. By embedding the one-particle propagator technique in a four-component framework the interplay between relativistic and correlation effects can be described correctly. In this article the Dirac-Hartree-Fock algebraic diagrammatic construction scheme (DHF-ADC) together with recent applications is reviewed and fully relativistic PE spectra of SeH{sub 2} and TeH{sub 2} in combination with basis set studies are presented.

  17. Highly polarized emission in spin resolved photoelectron spectroscopy of alpha-Fe(001)/GaAs(001)

    Energy Technology Data Exchange (ETDEWEB)

    Tobin, James; Yu, Sung Woo; Morton, Simon; Waddill, George; Thompson, Jamie; Neal, James; Spangenberg, Matthais; Shen, T.H.

    2009-05-19

    Highly spin-polarized sources of electrons, Integrated into device design, remain of great interest to the spintronic and magneto-electronic device community Here, the growth of Fe upon GaAs(001) has been studied with photoelectron spectroscopy (PES), including Spin Resolved PES. Despite evidence of atomic level disorder such as intermixing, an over-layer with the spectroscopic signature of alpha-Fe(001), with a bcc real space ordering, Is obtained The results will be discussed in light of the possibility of using such films as a spin-polarized source in device applications.

  18. Depth-resolved soft x-ray photoelectron emission microscopy in nanostructures via standing-wave excited photoemission

    Energy Technology Data Exchange (ETDEWEB)

    Kronast, F.; Ovsyannikov, R.; Kaiser, A.; Wiemann, C.; Yang, S.-H.; Locatelli, A.; Burgler, D.E.; Schreiber, R.; Salmassi, F.; Fischer, P.; Durr, H.A.; Schneider, C.M.; Eberhardt, W.; Fadley, C.S.

    2008-11-24

    We present an extension of conventional laterally resolved soft x-ray photoelectron emission microscopy. A depth resolution along the surface normal down to a few {angstrom} can be achieved by setting up standing x-ray wave fields in a multilayer substrate. The sample is an Ag/Co/Au trilayer, whose first layer has a wedge profile, grown on a Si/MoSi2 multilayer mirror. Tuning the incident x-ray to the mirror Bragg angle we set up standing x-ray wave fields. We demonstrate the resulting depth resolution by imaging the standing wave fields as they move through the trilayer wedge structure.

  19. Dual analyzer system for surface analysis dedicated for angle-resolved photoelectron spectroscopy at liquid surfaces and interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Niedermaier, Inga; Kolbeck, Claudia; Steinrück, Hans-Peter; Maier, Florian, E-mail: florian.maier@fau.de [Lehrstuhl für Physikalische Chemie II, FAU Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen (Germany)

    2016-04-15

    The investigation of liquid surfaces and interfaces with the powerful toolbox of ultra-high vacuum (UHV)-based surface science techniques generally has to overcome the issue of liquid evaporation within the vacuum system. In the last decade, however, new classes of liquids with negligible vapor pressure at room temperature—in particular, ionic liquids (ILs)—have emerged for surface science studies. It has been demonstrated that particularly angle-resolved X-ray Photoelectron Spectroscopy (ARXPS) allows for investigating phenomena that occur at gas-liquid and liquid-solid interfaces on the molecular level. The results are not only relevant for IL systems but also for liquids in general. In all of these previous ARXPS studies, the sample holder had to be tilted in order to change the polar detection angle of emitted photoelectrons, which restricted the liquid systems to very thin viscous IL films coating a flat solid support. We now report on the concept and realization of a new and unique laboratory “Dual Analyzer System for Surface Analysis (DASSA)” which enables fast ARXPS, UV photoelectron spectroscopy, imaging XPS, and low-energy ion scattering at the horizontal surface plane of macroscopically thick non-volatile liquid samples. It comprises a UHV chamber equipped with two electron analyzers mounted for simultaneous measurements in 0° and 80° emission relative to the surface normal. The performance of DASSA on a first macroscopic liquid system will be demonstrated.

  20. GAMMA-RAY LIGHT CURVE AND PHASE-RESOLVED SPECTRA FROM GEMINGA PULSAR

    Institute of Scientific and Technical Information of China (English)

    ZHANG LI; BIAN XIA; MEI DONG-CHENG

    2001-01-01

    We calculate the light curve and phase-resolved spectra of Geminga in a three-dimensional pulsar magnetosphere model. The light curve of gamma-rays is consistent with that observed if the magnetic inclination and viewing angle are~50° and~86° respectively. We also model the phase-resolved spectra of the Geminga pulsar.

  1. Phase-Resolved Spectra of PSR B0525+21 and PSR B2020+28

    Indian Academy of Sciences (India)

    J. L. Chen; H. G. Wang; N. Wang

    2011-03-01

    Using the published data of multi-frequency time-aligned pulse profiles from Kuzmin et al. (1998), we calculate the phase-resolved spectra of PSRs B0525+21 and B2020+28. The results reveal that conaldouble pulsars have common `M’-shaped phase-resolved spectra.

  2. Vibrationally resolved high-resolution NEXAFS and XPS spectra of phenanthrene and coronene

    Energy Technology Data Exchange (ETDEWEB)

    Fronzoni, Giovanna; Baseggio, Oscar; Stener, Mauro, E-mail: stener@univ.trieste.it [Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste, Via L. Giorgieri 1, I-34127 Trieste (Italy); Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, INSTM, Unita’ di Trieste, I-34127 Trieste (Italy); Hua, Weijie; Tian, Guangjun [Department of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, S-106 91 Stockholm (Sweden); Luo, Yi [Department of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, S-106 91 Stockholm (Sweden); National Synchrotron Radiation Laboratory and Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Apicella, Barbara; Alfé, Michela [Istituto di Ricerche sulla Combustione, IRC-CNR, P.le Tecchio, 80, 80125 Napoli (Italy); Simone, Monica de; Kivimäki, Antti [CNR-IOM, Laboratorio TASC, 34149 Trieste (Italy); Coreno, Marcello [CNR-IMIP, 00016 Montelibretti (Italy)

    2014-07-28

    We performed a combined experimental and theoretical study of the C1s Near-Edge X-ray Absorption Fine-Structure (NEXAFS) spectroscopy and X-ray Photoelectron Spectroscopy in the gas phase of two polycyclic aromatic hydrocarbons (phenanthrene and coronene), typically formed in combustion reactions. In the NEXAFS of both molecules, a double-peak structure appears in the C1s → LUMO region, which differ by less than 1 eV in transition energies. The vibronic coupling is found to play an important role in such systems. It leads to weakening of the lower-energy peak and strengthening of the higher-energy one because the 0 − n (n > 0) vibrational progressions of the lower-energy peak appear in nearly the same region of the higher-energy peak. Vibrationally resolved theoretical spectra computed within the Frank-Condon (FC) approximation and linear coupling model agree well with the high-resolution experimental results. We find that FC-active normal modes all correspond to in-plane vibrations.

  3. Franck-Condon profiles in photodetachment-photoelectron spectra of ? and ? based on vibrational configuration interaction wavefunctions

    Science.gov (United States)

    Huh, Joonsuk; Neff, Michael; Rauhut, Guntram; Berger, Robert

    2010-02-01

    Explicitly electron correlating coupled cluster calculations, CCSD(T)-F12a, were performed to determine three-dimensional potential energy hypersurfaces of disulphanide and disulphanyl in an automated approach. Surfaces for different electronic states were used in a Watson rovibrational Hamiltonian ansatz to obtain the correlated anharmonic vibrational wavefunctions. Subsequently the anharmonic Franck-Condon overlap integrals were evaluated. The computed Franck-Condon profiles were compared to experimental photodetachment-photoelectron spectra and confirm essentially the assignments made previously. The profiles indicate, however, additional weaker, and as of yet unresolved, additional features.

  4. He(I) and He(II) Photoelectron Spectra of Some Mixed Sandwich Compounds of Titanium, Zirconium and Hafnium

    NARCIS (Netherlands)

    Andréa, R.R.; Oskam, A.; Bruin, P.; Teuben, J.H.

    1986-01-01

    The He(I) and He(II) photoelectron spectra are reported for two series of transition metal mixed sandwich complexes of general formula LaMLb (M = Ti, La = η5-C5H5, η5-CH3C5H4, η5-C5(CH3)5; M = Zr, Hf, La = η5-C5(CH3)5; Lb = η7-C7H7 (series I); M = Ti, La = η5-CH3C5H4, η5-C5(CH3)5; M = Zr, La =

  5. Time-resolved photoelectron nano-spectroscopy of individual silver particles: Perspectives and limitations

    DEFF Research Database (Denmark)

    Rohmer, Martin; Bauer, Michael; Leissner, Till

    2010-01-01

    Simultaneous time- and energy-resolved two-photon photoemission with nanometer resolution is demonstrated for the first time. We monitor the energy dependence of the decay dynamics of electron excitations in individual silver particles, which were deposited from a gas aggregation cluster source o...

  6. Photoelectron spectroscopy at a free-electron laser. Investigation of space-charge effects in angle-resolved and core-level spectroscopy and realizaton of a time-resolved core-level photoemission experiment

    Energy Technology Data Exchange (ETDEWEB)

    Marczynski-Buehlow, Martin

    2012-01-30

    The free-electron laser (FEL) in Hamburg (FLASH) is a very interesting light source with which to perform photoelectron spectroscopy (PES) experiments. Its special characteristics include highly intense photon pulses (up to 100 J/pulse), a photon energy range of 30 eV to 1500 eV, transverse coherence as well as pulse durations of some ten femtoseconds. Especially in terms of time-resolved PES (TRPES), the deeper lying core levels can be reached with photon energies up to 1500 eV with acceptable intensity now and, therefore, element-specific, time-resolved core-level PES (XPS) is feasible at FLASH. During the work of this thesis various experimental setups were constructed in order to realize angle-resolved (ARPES), core-level (XPS) as well as time-resolved PES experiments at the plane grating monochromator beamline PG2 at FLASH. Existing as well as newly developed systems for online monitoring of FEL pulse intensities and generating spatial and temporal overlap of FEL and optical laser pulses for time-resolved experiments are successfully integrated into the experimental setup for PES. In order to understand space-charge effects (SCEs) in PES and, therefore, being able to handle those effects in future experiments using highly intense and pulsed photon sources, the origin of energetic broadenings and shifts in photoelectron spectra are studied by means of a molecular dynamic N-body simulation using a modified Treecode Algorithm for sufficiently fast and accurate calculations. It turned out that the most influencing parameter is the ''linear electron density'' - the ratio of the number of photoelectrons to the diameter of the illuminated spot on the sample. Furthermore, the simulations could reproduce the observations described in the literature fairly well. Some rules of thumb for XPS and ARPES measurements could be deduced from the simulations. Experimentally, SCEs are investigated by means of ARPES as well as XPS measurements as a function of

  7. Time-resolved photoelectron nano-spectroscopy of individual silver particles: Perspectives and limitations

    DEFF Research Database (Denmark)

    Rohmer, Martin; Bauer, Michael; Leissner, Till

    2010-01-01

    Simultaneous time- and energy-resolved two-photon photoemission with nanometer resolution is demonstrated for the first time. We monitor the energy dependence of the decay dynamics of electron excitations in individual silver particles, which were deposited from a gas aggregation cluster source o...... onto a silicon substrate. We show furthermore that the near-field enhancement due to plasmon-resonant excitation is an efficient means to address individual nanometer-sized particles using photoemission electron microscopy. (C) 2010 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim......Simultaneous time- and energy-resolved two-photon photoemission with nanometer resolution is demonstrated for the first time. We monitor the energy dependence of the decay dynamics of electron excitations in individual silver particles, which were deposited from a gas aggregation cluster source...

  8. Charge-transfer-to-solvent reactions from I(-) to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids.

    Science.gov (United States)

    Okuyama, Haruki; Suzuki, Yoshi-Ichi; Karashima, Shutaro; Suzuki, Toshinori

    2016-08-21

    The charge-transfer-to-solvent (CTTS) reactions from iodide (I(-)) to H2O, D2O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H2O and D2O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field created for I(-). The photoelectron spectra for CTTS in H2O and D2O-measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]-indicate that internal conversion yields from the photoexcited I(-*) (CTTS) state are less than 10%, while alcohols provide 2-3 times greater yields of internal conversion from I(-*). The overall geminate recombination yields are found to be in the order of H2O > D2O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.

  9. Charge-transfer-to-solvent reactions from I- to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids

    Science.gov (United States)

    Okuyama, Haruki; Suzuki, Yoshi-Ichi; Karashima, Shutaro; Suzuki, Toshinori

    2016-08-01

    The charge-transfer-to-solvent (CTTS) reactions from iodide (I-) to H2O, D2O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H2O and D2O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field created for I-. The photoelectron spectra for CTTS in H2O and D2O—measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]—indicate that internal conversion yields from the photoexcited I-* (CTTS) state are less than 10%, while alcohols provide 2-3 times greater yields of internal conversion from I-*. The overall geminate recombination yields are found to be in the order of H2O > D2O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.

  10. Development of a high resolution laser based angle-resolving time-of-flight photoelectron spectrometer

    CERN Document Server

    Berntsen, M H; Tjernberg, O

    2011-01-01

    We present the design and performance of a novel Laser-based Angle-Resolving Time-of-Flight (LARTOF) system for photoemission from solids in the vacuum ultraviolet (VUV) energy range. A pulsed laser provides photons which through a third harmonic generation (THG) process performed in a xenon filled gas cell generates VUV photons of energy 10.5 eV. The time-of-flight analyzer is able to collect all electrons that are emitted from the sample within a circular cone of up to +/-15 degrees. By simultaneously measuring the energy and emission angle along two spatial directions for the electrons the analyzer provides three-dimensional detection capability. Data from a test measurement performed on the Au(111) surface state is presented along with some more advanced measurements of the Fermi surface of the high-temperature superconductor Bi2212.

  11. Assignment of Photoelectron Spectra of MC2 (M= V, Cr, Fe, and Co)

    Institute of Scientific and Technical Information of China (English)

    YUAN Yong-Bo; DENG Kai-Ming; LIU Yu-Zhen; TANG Chun-Mei

    2006-01-01

    @@ Hybrid density functional theory (DFT) calculations are performed to study MC2 (M= V, Cr, Fe and Co) clusters in the neutral and anionic charge states. We find that the equilibrium geometries of MC2 and their anions are all cyclic structures with C2v symmetry, which agrees well with the previous theoretical studies. The Mulliken charge and spin populations of MC2 clusters and their anions are also calculated, and it is found that the electron charge transformations from anions to neutral molecules mainly take place on the M atoms. Time-dependent DFT is used to calculate the excited states, and a theoretical assignment for the features in the experimental photoelectron spectrum is given, which are in good agreement with the available experimental data.

  12. Spin-resolved photoelectron spectroscopy using femtosecond extreme ultraviolet light pulses from high-order harmonic generation

    Science.gov (United States)

    Plötzing, M.; Adam, R.; Weier, C.; Plucinski, L.; Eich, S.; Emmerich, S.; Rollinger, M.; Aeschlimann, M.; Mathias, S.; Schneider, C. M.

    2016-04-01

    The fundamental mechanism responsible for optically induced magnetization dynamics in ferromagnetic thin films has been under intense debate since almost two decades. Currently, numerous competing theoretical models are in strong need for a decisive experimental confirmation such as monitoring the triggered changes in the spin-dependent band structure on ultrashort time scales. Our approach explores the possibility of observing femtosecond band structure dynamics by giving access to extended parts of the Brillouin zone in a simultaneously time-, energy- and spin-resolved photoemission experiment. For this purpose, our setup uses a state-of-the-art, highly efficient spin detector and ultrashort, extreme ultraviolet light pulses created by laser-based high-order harmonic generation. In this paper, we present the setup and first spin-resolved spectra obtained with our experiment within an acquisition time short enough to allow pump-probe studies. Further, we characterize the influence of the excitation with femtosecond extreme ultraviolet pulses by comparing the results with data acquired using a continuous wave light source with similar photon energy. In addition, changes in the spectra induced by vacuum space-charge effects due to both the extreme ultraviolet probe- and near-infrared pump-pulses are studied by analyzing the resulting spectral distortions. The combination of energy resolution and electron count rate achieved in our setup confirms its suitability for spin-resolved studies of the band structure on ultrashort time scales.

  13. Phase-resolved spectra of burst oscillations in Neutron Stars

    Science.gov (United States)

    Zoghbi, Abderahmen; Miller, Jon M.

    2017-08-01

    Millisecond oscillations have been observed during thermonuclear bursts from many neutron stars (NS) in LMXBs. Their periods are comparable to the rotational period of the NS, and are thought to be produced by temperature anisotropies on the NS surface. Understanding and correcly modeling these oscillation is a powerful tool to constrain the NS interior. Studying these oscillations has thus far focused on modeling the oscillation profile form these pulsations using mostly XTE data. Here, we take a different approach and extract spectra at different phases of the oscillations. This allows us track the observed spectrum as the NS rotates. We are able to measure temperature changes as the star rotates. The temperature profiles from some bursts show asymetries likely due to Doppler effects. Here, we present detailed results from the phase spectra and discuss their implications on measurements of NS masses and radii.

  14. Valence photoelectron spectra of alkali bromides calculated within the propagator theory

    DEFF Research Database (Denmark)

    Karpenko, Alexander; Iablonskyi, Denys; Aksela, Helena

    2013-01-01

    The valence ionization spectra covering the binding energy range 0-45 eV of alkali bromide XBr (X = Li, Na, K, Rb) vapors are studied within the framework of the propagator theory. Relativistic Algebraic Diagrammatic Construction calculations have been carried out in order to investigate photoion......The valence ionization spectra covering the binding energy range 0-45 eV of alkali bromide XBr (X = Li, Na, K, Rb) vapors are studied within the framework of the propagator theory. Relativistic Algebraic Diagrammatic Construction calculations have been carried out in order to investigate...

  15. The effect of the dipole bound state on AgF{sup −} vibrationally resolved photodetachment cross sections and photoelectron angular distributions

    Energy Technology Data Exchange (ETDEWEB)

    Dao, Diep Bich; Mabbs, Richard, E-mail: mabbs@wustl.edu [Department of Chemistry, Washington University in St. Louis, One Brookings Drive, St. Louis 63130 (United States)

    2014-10-21

    The first photoelectron spectra of AgF{sup −} are recorded over the energy range 1.61–1.85 eV using the velocity map imaging technique. The resolved vibrational structure of the AgF X′, v′ ← AgF{sup −} X″, v″ = 0 band yields an AgF electron affinity of 1.46 ± 0.01 eV and vibrational frequency of 500 ± 40 cm{sup −1}. For the v′ = 2, 3, 4 channels, the photodetachment cross sections and angular distributions undergo rapid changes over a narrow electron kinetic energy range in the region of 50 meV (approximately 13 meV below the opening of the next vibrational channel). This is consistent with Fano-like behavior indicating autodetachment following excitation to a resonant anion state lying in the detachment continuum. EOM-CCSD calculations reveal this to be a dipole bound state. The consistency of the detachment data with the vibrational autodetachment propensity rule Δv = −1 shows that the autodetachment results from breakdown of the Born-Oppenheimer approximation, coupling the vibrational and electronic degrees of freedom.

  16. Valence photoelectron spectra of alkali bromides calculated within the propagator theory.

    Science.gov (United States)

    Karpenko, Alexander; Iablonskyi, Denys; Aksela, Helena

    2013-04-28

    The valence ionization spectra covering the binding energy range 0-45 eV of alkali bromide XBr (X = Li, Na, K, Rb) vapors are studied within the framework of the propagator theory. Relativistic Algebraic Diagrammatic Construction calculations have been carried out in order to investigate photoionization processes and to describe molecular electronic structure. Theoretical results are compared with available experimental data.

  17. Angle-resolved X-ray photoelectron spectroscopy (ARXPS) and a modified Levenberg-Marquardt fit procedure: a new combination for modeling thin layers

    NARCIS (Netherlands)

    Aarnink, W.A.M.; Weishaupt, A.; Silfhout, van A.

    1990-01-01

    The combination of angle-resolved X-ray photoelectron spectroscopy (ARXPS) and a modified Levenberg-Marquardt (LM) fit procedure has been used to study a native oxide layer on a clean Si(100) substrate. Numerical calculations show that with an aperture of 3° or 9° of the electron analyser, the photo

  18. Theoretical characterization of X-ray absorption, emission, and photoelectron spectra of nitrogen doped along graphene edges.

    Science.gov (United States)

    Wang, Xianlong; Hou, Zhufeng; Ikeda, Takashi; Oshima, Masaharu; Kakimoto, Masa-aki; Terakura, Kiyoyuki

    2013-01-24

    K-edge X-ray absorption (XAS), emission (XES), and photoelectron (XPS) spectra of nitrogen doped along graphene edges are systematically investigated by using first-principles methods. In this study we considered pyridinium-like, pyridine-like, cyanide-like, and amine-like nitrogens at armchair and zigzag edges and pyrrole-like nitrogen at armchair edge as well as graphite-like nitrogen at graphene interior site. Our results indicate that nitrogen configuration and its location (armchair or zigzag edge) in nitrogen-doped graphene can be identified via the spectral analysis. Furthermore, some controversial spectral features observed in experiment for N-doped graphene-like materials are unambiguously assigned. The present analysis gives an explanation to the reason why the peak assignment is usually made differently between XPS and XAS.

  19. Spatially-resolved spectra of the accretion disc of the novalike UU Aquarii

    CERN Document Server

    Baptista, R; Steiner, J E; Horne, K; Baptista, Raymundo; Horne, Keith

    2000-01-01

    Time-resolved spectroscopy of the novalike variable UU Aquarii is analyzedwith eclipse mapping techniques to produce spatially resolved spectra of itsaccretion disc and gas stream as a function of distance from disc centre in therange 3600-6900 \\AA. The spatially-resolved spectra show that the continuumemission becomes progressively fainter and redder for increasing disc radius --reflecting the radial temperature gradient -- and reveal that the HI and HeIlines appear as deep, narrow absorption features in the inner disc regionstransitioning to emission with P Cygni profiles for intermediate and large discradii. The spectrum of the uneclipsed component has strong HI and HeI emissionlines plus a Balmer jump in emission and is explained as optically thinemission from a vertically extended disc chromosphere + wind. Most of the lineemission probably arises from the wind. The spatially-resolved spectra alsosuggest the existence of gas stream ``disk-skimming'' overflow in UU Aqr, whichcan be seen down to R \\simeq 0....

  20. Derivation of dielectric function and inelastic mean free path from photoelectron energy-loss spectra of amorphous carbon surfaces

    Science.gov (United States)

    David, Denis; Godet, Christian

    2016-11-01

    Photoelectron Energy Loss Spectroscopy (PEELS) is a highly valuable non destructive tool in applied surface science because it gives access to both chemical composition and electronic properties of surfaces, including the near-surface dielectric function. An algorithm is proposed for real materials to make full use of experimental X-ray photoelectron spectra (XPS). To illustrate the capabilities and limitations of this algorithm, the near-surface dielectric function ε(ℏω) of a wide range of amorphous carbon (a-C) thin films is derived from energy losses measured in XPS, using a dielectric response theory which relates ε(ℏω) and the bulk plasmon (BP) loss distribution. Self-consistent separation of bulk vs surface plasmon excitations, deconvolution of multiple BP losses and evaluation of Bethe-Born sensitivity factors for bulk and surface loss distributions are crucial to obtain several material parameters: (1) energy loss function for BP excitation, (2) dielectric function of the near-surface material (3-5 nm depth sensitivity), (3) inelastic mean free path, λP (E0), for plasmon excitation, (4) surface excitation parameter, (5) effective number NEFF of valence electrons participating in the plasma oscillation. This photoelectron energy loss spectra analysis has been applied to a-C and a-C:H films grown by physical and chemical methods with a wide range of (sp3/sp2 + sp3) hybridization, optical gap and average plasmon energy values. Different methods are assessed to accurately remove the photoemission peak tail at low loss energy (0-10 eV) due to many-body interactions during the photo-ionization process. The σ + π plasmon excitation represents the main energy-loss channel in a-C; as the C atom density decreases, λP (970 eV) increases from 1.22 nm to 1.6 nm, assuming a cutoff plasmon wavenumber given by a free electron model. The π-π* and σ-σ* transitions observed in the retrieved dielectric function are discussed as a function of the average (sp3/sp

  1. Resolving nanophotonic spectra with quasi-normal modes (Conference Presentation)

    Science.gov (United States)

    Powell, David A.

    2016-09-01

    Many nanophotonic systems are strongly coupled to radiating waves, or suffer significant dissipative losses. Furthermore, they may have complex shapes which are not amenable to closed form calculations. This makes it challenging to determine their modes without resorting to quasi-static or point dipole approximations. To solve this problem, the quasi-normal modes (QNMs) are found from an integral equation model of the particle. These give complex frequencies where excitation can be supported without any incident field. The corresponding eigenvectors yield the modal distributions, which are non-orthogonal due to the non-Hermitian nature of the system. The model based on quasi-normal modes is applied to plasmonic and dielectric particles, and compared with a spherical multipole decomposition. Only with the QNMs is it possible to resolve all features of the extinction spectrum, as each peak in the spectrum can be attributed to a particular mode. In contrast, many of the multipole coefficient have multiple peaks and dips. Furthermore, by performing a multipolar decomposition of each QNM, the spectrum of multipole coefficients is explained in terms of destructive interference between modes of the same multipole order.

  2. Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Guorong [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Neville, Simon P. [Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Schalk, Oliver [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Physics, AlbaNova University Center, Stockholm University, Roslagstullsbacken 21, 106 91 Stockholm (Sweden); Sekikawa, Taro [Department of Applied Physics, Hokkaido University, Kita-13 Nishi-8, Kita-ku, Sapporo 060-8628 (Japan); Ashfold, Michael N. R. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Worth, Graham A. [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Stolow, Albert, E-mail: astolow@uottawa.ca [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, Ontario K1N 6N5 (Canada)

    2016-01-07

    The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A{sub 2}(πσ{sup ∗}) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B{sub 1}(π3p{sub y}) Rydberg state, followed by prompt internal conversion to the A{sub 2}(πσ{sup ∗}) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A{sub 2}(πσ{sup ∗}) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A{sub 2}(πσ{sup ∗}) state, facilitating wavepacket motion around the potential barrier in the N–CH{sub 3} dissociation coordinate.

  3. Inconsistencies with the single-impurity Anderson model in photoelectron spectra of cerium heavy fermion compounds

    Energy Technology Data Exchange (ETDEWEB)

    Joyce, J.J.; Arko, A.J.; Lawrence, J.; Canfield, P.C.; Fisk, Z.; Bartlett, R.J.; Thompson, J.D.; Smith, J.L. (Los Alamos National Lab., NM (United States))

    1992-04-03

    A series of cerium heavy fermion compounds have been studied in order to check for the systematics with T{sub K} and the temperature dependence of the Kondo resonance predicted by the Kondo model. Neither the systematics nor the temperature dependence is found, the latter primarily determined from a detailed study in CeSi{sub 2}. The qualitative shapes of the features at E{sub F} remain nearly constant irrespectively of T{sub K}, while all the temperature dependence can be explained as resulting from phonon broadening of core-like states as well as Fermi function broadening. In addition, if the d electron contribution to the spectra is subtracted, one obtains a symmetric, lorentzian line shape for the ''main'' 4f peak. (orig.).

  4. First-principles approach to excitons in time-resolved and angle-resolved photoemission spectra

    Science.gov (United States)

    Perfetto, E.; Sangalli, D.; Marini, A.; Stefanucci, G.

    2016-12-01

    In this work we put forward a first-principles approach and propose an accurate diagrammatic approximation to calculate the time-resolved (TR) and angle-resolved photoemission spectrum of systems with excitons. We also derive an alternative formula to the TR photocurrent which involves a single time-integral of the lesser Green's function. The diagrammatic approximation applies to the relaxed regime characterized by the presence of quasistationary excitons and vanishing polarization. The nonequilibrium self-energy diagrams are evaluated using excited Green's functions; since this is not standard, the analytic derivation is presented in detail. The final result is an expression for the lesser Green's function in terms of quantities that can all be calculated in a first-principles manner. The validity of the proposed theory is illustrated in a one-dimensional model system with a direct gap. We discuss possible scenarios and highlight some universal features of the exciton peaks. Our results indicate that the exciton dispersion can be observed in TR and angle-resolved photoemission.

  5. Extracting Time-Resolved Information from Time-Integrated Laser-Induced Breakdown Spectra

    Directory of Open Access Journals (Sweden)

    Emanuela Grifoni

    2014-01-01

    Full Text Available Laser-induced breakdown spectroscopy (LIBS data are characterized by a strong dependence on the acquisition time after the onset of the laser plasma. However, time-resolved broadband spectrometers are expensive and often not suitable for being used in portable LIBS instruments. In this paper we will show how the analysis of a series of LIBS spectra, taken at different delays after the laser pulse, allows the recovery of time-resolved spectral information. The comparison of such spectra is presented for the analysis of an aluminium alloy. The plasma parameters (electron temperature and number density are evaluated, starting from the time-integrated and time-resolved spectra, respectively. The results are compared and discussed.

  6. Comparison between X-ray photoelectron and X-ray absorption spectra of an environmental aerosol sample measured by synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Kawai, J.; Yamamoto, T. [Department of Materials Science and Engineering, Kyoto University, Sakyo-ku, Kyoto (Japan); Tohno, S. [Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University, Uji, Kyoto (Japan); Kitajima, Y. [Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba (Japan)

    1999-01-04

    Sulfur X-ray photoelectron spectra (XPS) and X-ray absorption spectra (XAS) of an aerosol sample collected by an Andersen sampler were measured using a synchrotron beam line. While the XPS was more surface sensitive than XAS, the detection limit of XAS was better than that of XPS. It was concluded that the XAS was more suitable for the chemical state analysis of sulfur in aerosol samples than XPS. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  7. Angle resolved x-ray photoelectron spectroscopy (ARXPS) analysis of lanthanum oxide for micro-flexography printing

    Energy Technology Data Exchange (ETDEWEB)

    Hassan, S., E-mail: suhaimihas@uthm.edu.my; Yusof, M. S., E-mail: mdsalleh@uthm.edu.my; Maksud, M. I., E-mail: midris1973@gmail.com [Faculty of Mechanical and Manufacturing Engineering, Universiti Tun Hussein Onn Malaysia, 86400 Batu Pahat, Johor (Malaysia); Embong, Z., E-mail: zaidi@uthm.edu.my [Faculty of Science, Technology and Human Development, Universiti Tun Hussein Onn Malaysia, 86400 Batu Pahat, Johor (Malaysia)

    2016-01-22

    Micro-flexography printing was developed in patterning technique from micron to nano scale range to be used for graphic, electronic and bio-medical device on variable substrates. In this work, lanthanum oxide (La{sub 2}O{sub 3}) has been used as a rare earth metal candidate as depositing agent. This metal deposit was embedded on Carbon (C) and Silica (Si) wafer substrate using Magnetron Sputtering technique. The choose of Lanthanum as a target is due to its wide application in producing electronic devices such as thin film battery and printed circuit board. The La{sub 2}O{sub 3} deposited on the surface of Si wafer substrate was then analyzed using Angle Resolve X-Ray Photoelectron Spectroscopy (ARXPS). The position for each synthetic component in the narrow scan of Lanthanum (La) 3d and O 1s are referred to the electron binding energy (eV). The La 3d narrow scan revealed that the oxide species of this particular metal is mainly contributed by La{sub 2}O{sub 3} and La(OH){sub 3}. The information of oxygen species, O{sup 2-} component from O 1s narrow scan indicated that there are four types of species which are contributed from the bulk (O{sup 2−}), two chemisorb component (La{sub 2}O{sub 3}) and La(OH){sub 3} and physisorp component (OH). Here, it is proposed that from the adhesive and surface chemical properties of La, it is suitable as an alternative medium for micro-flexography printing technique in printing multiple fine solid lines at nano scale. Hence, this paper will describe the capability of this particular metal as rare earth metal for use in of micro-flexography printing practice. The review of other parameters contributing to print fine lines will also be described later.

  8. Theoretical studies on the photoelectron and absorption spectra of MnO4(-) and TcO4(-).

    Science.gov (United States)

    Su, Jing; Xu, Wen-Hua; Xu, Chao-Fei; Schwarz, W H E; Li, Jun

    2013-09-03

    The tetraoxo pertechnetate anion (TcO4(-)) is of great interest for nuclear waste management and radiopharmceuticals. To elucidate its electronic structure and to compare with that of its lighter congener MnO4(-), the photoelectron and electronic absorption spectra of MnO4(-) and TcO4(-) are investigated with density functional theory (DFT) and ab initio wave function theory (WFT). The vertical electron detachment energies (VDEs) of MnO4(-) obtained with the CR-EOM-CCSD(T) method are in good agreement with the lowest two experimental VDEs; the differences are less than 0.1 eV, representing a significant improvement over the IP-EOM-CCSD(T) result in the literature. Combining our CCSD(T) and CR-EOM-CCSD(T) results, the first five VDEs of TcO4(-) are estimated between 5 and 10 eV with an estimated accuracy of about ±0.2 eV. The vertical excitation energies are determined by using TD-DFT, CR-EOM-CCSD(T), and RAS-PT2 methods. The excitation energies and the assignments of the spectra are analyzed and partly improved. They are compared with reported SAC-CI results and available experimental data. Both dynamic and nondynamic electron correlations are important in the ground and excited states of MnO4(-) and TcO4(-). Nondynamical correlations are particularly relevant in TcO4(-) for reliable prediction of excitation energies. In TcO4(-) one Rydberg state interlaces but does not mix with the valence excited states, and it disappears in the condensed phase.

  9. Electron-hole recombination on ZnO(0001) single-crystal surface studied by time-resolved soft X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yukawa, R.; Yamamoto, S.; Ogawa, M.; Yamamoto, Sh.; Fujikawa, K.; Hobara, R.; Matsuda, I., E-mail: imatsuda@issp.u-tokyo.ac.jp [Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581 (Japan); Ozawa, K. [Department of Chemistry and Materials Science, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551 (Japan); Emori, M.; Sakama, H. [Department of Physics, Sophia University, Chiyoda-ku, Tokyo 102-8554 (Japan); Kitagawa, S.; Daimon, H. [Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192 (Japan)

    2014-10-13

    Time-resolved soft X-ray photoelectron spectroscopy (PES) experiments were performed with time scales from picoseconds to nanoseconds to trace relaxation of surface photovoltage on the ZnO(0001) single crystal surface in real time. The band diagram of the surface has been obtained numerically using PES data, showing a depletion layer which extends to 1 μm. Temporal evolution of the photovoltage effect is well explained by a recombination process of a thermionic model, giving the photoexcited carrier lifetime of about 1 ps at the surface under the flat band condition. This lifetime agrees with a temporal range reported by the previous time-resolved optical experiments.

  10. Self-consistent modelling of X-ray photoelectron spectra from air-exposed polycrystalline TiN thin films

    Science.gov (United States)

    Greczynski, G.; Hultman, L.

    2016-11-01

    We present first self-consistent modelling of x-ray photoelectron spectroscopy (XPS) Ti 2p, N 1s, O 1s, and C 1s core level spectra with a cross-peak quantitative agreement for a series of TiN thin films grown by dc magnetron sputtering and oxidized to different extent by varying the venting temperature Tv of the vacuum chamber before removing the deposited samples. So-obtained film series constitute a model case for XPS application studies, where certain degree of atmosphere exposure during sample transfer to the XPS instrument is unavoidable. The challenge is to extract information about surface chemistry without invoking destructive pre-cleaning with noble gas ions. All TiN surfaces are thus analyzed in the as-received state by XPS using monochromatic Al Kα radiation (hν = 1486.6 eV). Details of line shapes and relative peak areas obtained from deconvolution of the reference Ti 2p and N 1 s spectra representative of a native TiN surface serve as an input to model complex core level signals from air-exposed surfaces, where contributions from oxides and oxynitrides make the task very challenging considering the influence of the whole deposition process at hand. The essential part of the presented approach is that the deconvolution process is not only guided by the comparison to the reference binding energy values that often show large spread, but in order to increase reliability of the extracted chemical information the requirement for both qualitative and quantitative self-consistency between component peaks belonging to the same chemical species is imposed across all core-level spectra (including often neglected O 1s and C 1s signals). The relative ratios between contributions from different chemical species vary as a function of Tv presenting a self-consistency check for our model. We propose that the cross-peak self-consistency should be a prerequisite for reliable XPS peak modelling as it enhances credibility of obtained chemical information, while relying

  11. Electronic structure and spectroscopy of nucleic acid bases: Ionization energies, ionization-induced structural changes, and photoelectron spectra

    Energy Technology Data Exchange (ETDEWEB)

    Bravaya, Ksenia B.; Kostko, Oleg; Dolgikh, Stanislav; Landau, Arie; Ahmed, Musahid; Krylov, Anna I.

    2010-08-02

    We report high-level ab initio calculations and single-photon ionization mass spectrometry study of ionization of adenine (A), thymine (T), cytosine (C) and guanine (G). For thymine and adenine, only the lowest-energy tautomers were considered, whereas for cytosine and guanine we characterized five lowest-energy tautomeric forms. The first adiabatic and several vertical ionization energies were computed using equation-of-motion coupled-cluster method for ionization potentials with single and double substitutions. Equilibrium structures of the cationic ground states were characterized by DFT with the {omega}B97X-D functional. The ionization-induced geometry changes of the bases are consistent with the shapes of the corresponding molecular orbitals. For the lowest-energy tautomers, the magnitude of the structural relaxation decreases in the following series G > C > A > T, the respective relaxation energies being 0.41, 0.32, 0.25 and 0.20 eV. The computed adiabatic ionization energies (8.13, 8.89, 8.51-8.67 and 7.75-7.87 eV for A,T,C and G, respectively) agree well with the onsets of the photoionization efficiency (PIE) curves (8.20 {+-} 0.05, 8.95 {+-} 0.05, 8.60 {+-} 0.05 and 7.75 {+-} 0.05 eV). Vibrational progressions for the S{sub 0}-D{sub 0} vibronic bands computed within double-harmonic approximation with Duschinsky rotations are compared with previously reported experimental photoelectron spectra.

  12. Electronic structure of ThRu2Si2 studied by angle-resolved photoelectron spectroscopy: Elucidating the contribution of U 5 f states in URu2Si2

    Science.gov (United States)

    Fujimori, Shin-ichi; Kobata, Masaaki; Takeda, Yukiharu; Okane, Tetsuo; Saitoh, Yuji; Fujimori, Atsushi; Yamagami, Hiroshi; Matsumoto, Yuji; Yamamoto, Etsuji; Tateiwa, Naoyuki; Haga, Yoshinori

    2017-09-01

    The electronic structure of ThRu2Si2 was studied using angle-resolved photoelectron spectroscopy (ARPES) with incident photon energies of h ν =655 -745 eV. Detailed band structure and the three-dimensional shapes of Fermi surfaces were derived experimentally, and their characteristic features were mostly explained by means of band-structure calculations based on density-functional theory. Comparison of the experimental ARPES spectra of ThRu2Si2 with those of URu2Si2 shows that they have considerably different spectral profiles, particularly in the energy range of 1 eV from the Fermi level, suggesting that U 5 f states are substantially hybridized in these bands. The relationship between the ARPES spectra of URu2Si2 and ThRu2Si2 is very different from the one between the ARPES spectra of CeRu2Si2 and LaRu2Si2 , where the intrinsic difference in their spectra is limited only in the very vicinity of the Fermi energy. The present result suggests that the U 5 f electrons in URu2Si2 have strong hybridization with ligand states and have an essentially itinerant character.

  13. Correlations Between Variations in Solar EUV and Soft X-Ray Irradiance and Photoelectron Energy Spectra Observed on Mars and Earth

    Science.gov (United States)

    Peterson, W. K.; Brain, D. A.; Mitchell, D. L.; Bailey, S. M.; Chamberlin, P. C.

    2013-01-01

    Solar extreme ultraviolet (EUV; 10-120 nm) and soft X-ray (XUV; 0-10 nm) radiation are major heat sources for the Mars thermosphere as well as the primary source of ionization that creates the ionosphere. In investigations of Mars thermospheric chemistry and dynamics, solar irradiance models are used to account for variations in this radiation. Because of limited proxies, irradiance models do a poor job of tracking the significant variations in irradiance intensity in the EUV and XUV ranges over solar rotation time scales when the Mars-Sun-Earth angle is large. Recent results from Earth observations show that variations in photoelectron energy spectra are useful monitors of EUV and XUV irradiance variability. Here we investigate photoelectron energy spectra observed by the Mars Global Surveyor (MGS) Electron Reflectometer (ER) and the FAST satellite during the interval in 2005 when Earth, Mars, and the Sun were aligned. The Earth photoelectron data in selected bands correlate well with calculations based on 1 nm resolution observations above 27 nm supplemented by broadband observations and a solar model in the 0-27 nm range. At Mars, we find that instrumental and orbital limitations to the identifications of photoelectron energy spectra in MGS/ER data preclude their use as a monitor of solar EUV and XUV variability. However, observations with higher temporal and energy resolution obtained at lower altitudes on Mars might allow the separation of the solar wind and ionospheric components of electron energy spectra so that they could be used as reliable monitors of variations in solar EUV and XUV irradiance than the time shifted, Earth-based, F(10.7) index currently used.

  14. Correlation and relativistic effects in 2p photoelectron spectra of sodium atoms from the initial state 2{p}^{6}3p

    Science.gov (United States)

    Liu, Xiaobin; Shi, Yinglong; Xing, Yongzhong; Lu, Feiping; Chen, Zhanbin

    2017-02-01

    We investigate the 2p photoelectron spectra of sodium atoms with the initial state 2{p}63p at a photon energy of 54 eV. The analysis is performed based on the multi-configuration Dirac–Fock method. Special attention is given to the influences of correlation and relativistic effects on the spectra structures. To explore the nature and importance of such influences, calculations were performed based on detailed analyses of the thresholds, relative intensities and corresponding data calculated in the nonrelativistic limit.

  15. Hemoglobin concentration determination based on near infrared spatially resolved transmission spectra

    Science.gov (United States)

    Zhang, Linna; Li, Gang; Lin, Ling

    2016-10-01

    Spatially resolved diffuse reflectance spectroscopy method has been proved to be more effective than single point spectroscopy method in the experiment to predict the concentration of the Intralipid diluted solutions. However, Intralipid diluted solution is simple, cannot be the representative of turbid liquids. Blood is a natural and meaningful turbid liquid, more complicate. Hemoglobin is the major constituent of the whole blood. And hemoglobin concentration is commonly used in clinical medicine to diagnose many diseases. In this paper, near infrared spatially resolved transmission spectra (NIRSRTS) and Partial Least Square Regression (PLSR) were used to predict the hemoglobin concentration of human blood. The results showed the prediction ability for hemoglobin concentration of the proposed method is better than single point transmission spectroscopy method. This paper demonstrated the feasibility of the spatially resolved diffuse reflectance spectroscopy method for practical liquid composition analysis. This research provided a new thinking of practical turbid liquid composition analysis.

  16. Application of normalized spectra in resolving a challenging Orphenadrine and Paracetamol binary mixture

    Science.gov (United States)

    Yehia, Ali M.; Abd El-Rahman, Mohamed K.

    2015-03-01

    Normalized spectra have a great power in resolving spectral overlap of challenging Orphenadrine (ORP) and Paracetamol (PAR) binary mixture, four smart techniques utilizing the normalized spectra were used in this work, namely, amplitude modulation (AM), simultaneous area ratio subtraction (SARS), simultaneous derivative spectrophotometry (S1DD) and ratio H-point standard addition method (RHPSAM). In AM, peak amplitude at 221.6 nm of the division spectra was measured for both ORP and PAR determination, while in SARS, concentration of ORP was determined using the area under the curve from 215 nm to 222 nm of the regenerated ORP zero order absorption spectra, in S1DD, concentration of ORP was determined using the peak amplitude at 224 nm of the first derivative ratio spectra. PAR concentration was determined directly at 288 nm in the division spectra obtained during the manipulation steps in the previous three methods. The last RHPSAM is a dual wavelength method in which two calibrations were plotted at 216 nm and 226 nm. RH point is the intersection of the two calibration lines, where ORP and PAR concentrations were directly determined from coordinates of RH point. The proposed methods were applied successfully for the determination of ORP and PAR in their dosage form.

  17. Virtual detector methods for efficiently computing momentum-resolved dissociation and ionization spectra

    Science.gov (United States)

    Kramer, Alex; Thumm, Uwe

    2016-05-01

    We discuss a class of window-transform-based ``virtual detector'' methods for computing momentum-resolved dissociation and ionization spectra by numerically analyzing the motion of nuclear or electronic quantum-mechanical wavepackets at the periphery of their numerical grids. While prior applications of such surface-flux methods considered semi-classical limits to derive ionization and dissociation spectra, we systematically include quantum-mechanical corrections and extensions to higher dimensions, discussing numerical convergence properties and the computational efficiency of our method in comparison with alternative schemes for obtaining momentum distributions. Using the example of atomic ionization by co- and counter-rotating circularly polarized laser pulses, we scrutinize the efficiency of common finite-difference schemes for solving the time-dependent Schrödinger equation in virtual detection and standard Fourier-transformation methods for extracting momentum spectra. Supported by the DoE, NSF, and Alexander von Humboldt foundation.

  18. Rotationally resolved state-to-state photoionization and photoelectron study of titanium carbide and its cation (TiC/TiC⁺).

    Science.gov (United States)

    Luo, Zhihong; Huang, Huang; Chang, Yih-Chung; Zhang, Zheng; Yin, Qing-Zhu; Ng, C Y

    2014-10-14

    Titanium carbide and its cation (TiC/TiC(+)) have been investigated by the two-color visible (VIS)-ultraviolet (UV) resonance-enhanced photoionization and pulsed field ionization-photoelectron (PFI-PE) methods. Two visible excitation bands for neutral TiC are observed at 16,446 and 16,930 cm(-1). Based on rotational analyses, these bands are assigned as the respective TiC((3)Π1) ← TiC(X(3)Σ(+)) and TiC((3)Σ(+)) ← TiC(X(3)Σ(+)) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ(2)8σ(1)9σ(1)3π(4) (X(3)Σ(+)). The rotational constant and the corresponding bond distance of TiC(X(3)Σ(+); v″ = 0) are determined to be B0″ = 0.6112(10) cm(-1) and r0″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC(+)(X; v(+) = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC(+) ground state are …7σ(2)8σ(1)3π(4) (X(2)Σ(+)) with the v(+) = 0 → 1 vibrational spacing of 870.0(8) cm(-1) and the rotational constants of B(e)(+) = 0.6322(28) cm(-1), and α(e)(+) = 0.0085(28) cm(-1). The latter rotational constants yield the equilibrium bond distance of r(e)(+) = 1.667(4) Å for TiC(+)(X(2)Σ(+)). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm(-1) [6.5960(1) eV] for the adiabatic ionization energy (IE) of TiC. This IE(TiC) value along with the known IE(Ti) has made possible the determination of the difference between the 0 K bond dissociation energy (D0) of TiC(+)(X(2)Σ(+)) and that of TiC(X(3)Σ(+)) to be D0(Ti(+)-C) - D0(Ti-C) = 0.2322(2) eV. Similar to previous experimental observations, the present state-to-state PFI-PE study of the photoionization transitions, TiC(+)(X(2)Σ(+); v(+) = 0 and 1, N(+)) ← TiC((3)Π1; v', J'), reveals a strong decreasing trend for the photoionization cross section as |ΔN(+)| = |N

  19. Rotationally resolved state-to-state photoionization and photoelectron study of titanium carbide and its cation (TiC/TiC+)

    Science.gov (United States)

    Luo, Zhihong; Huang, Huang; Chang, Yih-Chung; Zhang, Zheng; Yin, Qing-Zhu; Ng, C. Y.

    2014-10-01

    Titanium carbide and its cation (TiC/TiC+) have been investigated by the two-color visible (VIS)-ultraviolet (UV) resonance-enhanced photoionization and pulsed field ionization-photoelectron (PFI-PE) methods. Two visible excitation bands for neutral TiC are observed at 16 446 and 16 930 cm-1. Based on rotational analyses, these bands are assigned as the respective TiC(3Π1) ← TiC(X3Σ+) and TiC(3Σ+) ← TiC(X3Σ+) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ28σ19σ13π4 (X3Σ+). The rotational constant and the corresponding bond distance of TiC(X3Σ+; v″ = 0) are determined to be B0″ = 0.6112(10) cm-1 and r0″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC+(X; v+ = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC+ ground state are …7σ28σ13π4 (X2Σ+) with the v+ = 0 → 1 vibrational spacing of 870.0(8) cm-1 and the rotational constants of Be+ = 0.6322(28) cm-1, and αe+ = 0.0085(28) cm-1. The latter rotational constants yield the equilibrium bond distance of re+ = 1.667(4) Å for TiC+(X2Σ+). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm-1 [6.5960(1) eV] for the adiabatic ionization energy (IE) of TiC. This IE(TiC) value along with the known IE(Ti) has made possible the determination of the difference between the 0 K bond dissociation energy (D0) of TiC+(X2Σ+) and that of TiC(X3Σ+) to be D0(Ti+-C) - D0(Ti-C) = 0.2322(2) eV. Similar to previous experimental observations, the present state-to-state PFI-PE study of the photoionization transitions, TiC+(X2Σ+; v+ = 0 and 1, N+) ← TiC(3Π1; v', J'), reveals a strong decreasing trend for the photoionization cross section as |ΔN+| = |N+ - J'| is increased. The maximum |ΔN+| change of 7 observed here is also consistent with the previous

  20. Time-resolved photoelectron signals from bifurcating electron wavepackets propagated across conical intersection in path-branching dynamics

    Science.gov (United States)

    Arasaki, Yasuki; Takatsuka, Kazuo

    2017-08-01

    A computational scheme of energy- and geometry-dependent photoelectron signals from the dynamics near a conical intersection based on a simplified path-branching representation of nonadiabatic electron wavepacket dynamics is proposed. Taking the NO2 X / A conical intersection as an example, the results of the present scheme compared to those from previous study based on the method of full quantum vibrational wavepacket shows qualitative agreement suggesting promising application to computation in larger systems intractable to full quantum exact methods.

  1. Photoelectron spectrometer for attosecond spectroscopy of liquids and gases

    Energy Technology Data Exchange (ETDEWEB)

    Jordan, I.; Huppert, M.; Wörner, H. J., E-mail: hwoerner@ethz.ch [Laboratory of Physical Chemistry, ETH Zurich, Vladimir-Prelog-Weg 2, 8093 Zurich (Switzerland); Brown, M. A. [Laboratory for Surface Science and Technology, Department of Materials, ETH Zurich, Vladimir-Prelog-Weg 5, 8093 Zurich (Switzerland); Bokhoven, J. A. van [Institute for Chemical and Bioengineering, ETH Zurich, Vladimir-Prelog-Weg 1, 8093 Zurich (Switzerland); Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institute, 5232 Villigen (Switzerland)

    2015-12-15

    A new apparatus for attosecond time-resolved photoelectron spectroscopy of liquids and gases is described. It combines a liquid microjet source with a magnetic-bottle photoelectron spectrometer and an actively stabilized attosecond beamline. The photoelectron spectrometer permits venting and pumping of the interaction chamber without affecting the low pressure in the flight tube. This pressure separation has been realized through a sliding skimmer plate, which effectively seals the flight tube in its closed position and functions as a differential pumping stage in its open position. A high-harmonic photon spectrometer, attached to the photoelectron spectrometer, exit port is used to acquire photon spectra for calibration purposes. Attosecond pulse trains have been used to record photoelectron spectra of noble gases, water in the gas and liquid states as well as solvated species. RABBIT scans demonstrate the attosecond resolution of this setup.

  2. Femtosecond time-resolved photoelectron spectroscopy with a vacuum-ultraviolet photon source based on laser high-order harmonic generation.

    Science.gov (United States)

    Wernet, Philippe; Gaudin, Jérôme; Godehusen, Kai; Schwarzkopf, Olaf; Eberhardt, Wolfgang

    2011-06-01

    A laser-based tabletop approach to femtosecond time-resolved photoelectron spectroscopy with photons in the vacuum-ultraviolet (VUV) energy range is described. The femtosecond VUV pulses are produced by high-order harmonic generation (HHG) of an amplified femtosecond Ti:sapphire laser system. Two generations of the same setup and results from photoelectron spectroscopy in the gas phase are discussed. In both generations, a toroidal grating monochromator was used to select one harmonic in the photon energy range of 20-30 eV. The first generation of the setup was used to perform photoelectron spectroscopy in the gas phase to determine the bandwidth of the source. We find that our HHG source has a bandwidth of 140 ± 40 meV. The second and current generation is optimized for femtosecond pump-probe photoelectron spectroscopy with high flux and a small spot size at the sample of the femtosecond probe pulses. The VUV radiation is focused into the interaction region with a toroidal mirror to a spot smaller than 100 × 100 μm(2) and the flux amounts to 10(10) photons/s at the sample at a repetition rate of 1 kHz. The duration of the monochromatized VUV pulses is determined to be 120 fs resulting in an overall pump-probe time resolution of 135 ± 5 fs. We show how this setup can be used to map the transient valence electronic structure in molecular dissociation. © 2011 American Institute of Physics

  3. The effect of autoionization on the N2+ X 2Σg+ state vibrationally resolved photoelectron anisotropy parameters and branching ratios

    Science.gov (United States)

    Holland, D. M. P.; Seddon, E. A.; Daly, S.; Alcaraz, C.; Romanzin, C.; Nahon, L.; Garcia, G. A.

    2013-05-01

    Vibrationally resolved photoelectron anisotropy parameters and branching ratios for the N2+ X 2Σg+ state have been measured between the ionization threshold and ˜16.7 eV to study the influence of autoionization on the photoionization dynamics. In this energy range the ion yield curve exhibits extensive structure due to autoionizing Rydberg or valence states. Some of these Rydberg states belong to series converging onto the A 2Πu limit but, close to the ionization threshold, states belonging to series converging onto vibrationally excited levels of the X 2Σg+ state are also observed. At photon energies free from the influence of neutral excited states, the measured vibrational branching ratios correlate with the Franck-Condon factors for direct ionization. However, strong deviations are observed when the excitation energy corresponds with a transition into an autoionizing state. An attempt to interpret these variations using Franck-Condon factors connecting the neutral excited state and the final ionic state proved unsuccessful. This failure suggests that the intermediate states might not be pure Rydberg states. Electronic and, close to threshold, vibrational autoionization affects the vibrationally resolved photoelectron anisotropy parameters, leading to a significant reduction in the fairly high β-values determined for non-resonant ionization. Photoelectron images of the N2+ X 2Σg+ state recorded close to the v+ = 1 or the v+ = 2 ionization thresholds suggest that electronic autoionization results in rotational branch populations that differ from those due to direct, non-resonant, photoionization.

  4. Spatially-Resolved Spectra of the "Teacup" AGN: Tracing the History of a Dying Quasar

    CERN Document Server

    Gagne, J P; Kraemer, S B; Schmitt, H R; Keel, W C; Rafter, S; Fischer, T C; Bennert, V N; Schawinski, K

    2014-01-01

    The Sloan Digital Sky Survey (SDSS) Galaxy Zoo project has revealed a number of spectacular galaxies possessing Extended Emission-Line Regions (EELRs), the most famous being Hanny's Voorwerp galaxy. We present another EELR object discovered in the SDSS endeavor: the Teacup Active Galactic Nucleus (AGN), nicknamed for its EELR, which has a handle like structure protruding 15 kpc into the northeast quadrant of the galaxy. We analyze physical conditions of this galaxy with long-slit ground based spectroscopy from Lowell, Lick, and KPNO observatories. With the Lowell 1.8m Perkin's telescope we took multiple observations at different offset positions, allowing us to recover spatially resolved spectra across the galaxy. Line diagnostics indicate the ionized gas is photoionized primarily by the AGN. Additionally we are able to derive the hydrogen density from the [S II] 6716/6731 ratio. We generated two-component photoionization models for each spatially resolved Lowell spectrum. These models allow us to calculate t...

  5. Cervical cancer detection by time-resolved spectra of blood components

    Science.gov (United States)

    Kalaivani, Rudran; Masilamani, Vadivel; AlSalhi, Mohamad Saleh; Devanesan, Sandhanasamy; Ramamurthy, P.; Palled, Siddanna R.; Ganesh, K. M.

    2014-05-01

    Fluorescence spectral techniques are very sensitive, and hence they are gaining importance in cancer detection. The biomarkers indicative of cancer could be identified and quantified by spectral or time domain fluorescence spectroscopy. The results of an investigation of time-resolved spectra of cellular components of blood obtained from cervical cancer patients and normal controls are given. The cancer indicative biomarker in this paper is porphyrin; it has a fluorescence decay time of 60% more in samples of cancer patients than those of normal controls. Based on such measurements, a randomized set comprising samples from cancer patients and controls (N=27 in total) could be classified with sensitivity (92%) and specificity (86%).

  6. Resolving the bulk ion region of millimeter-wave collective Thomson scattering spectra at ASDEX Upgrade

    Energy Technology Data Exchange (ETDEWEB)

    Stejner, M., E-mail: mspe@fysik.dtu.dk; Nielsen, S.; Jacobsen, A. S.; Korsholm, S. B.; Leipold, F.; Meo, F.; Michelsen, P. K.; Rasmussen, J.; Salewski, M. [Department of Physics, Association EURATOM-DTU, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Moseev, D. [Max-Planck-Institut für Plasmaphysik, EURATOM-Association, Boltzmannstr. 2, 85748 Garching (Germany); Association Euratom-FOM Institute DIFFER, 3430 BE Nieuwegein (Netherlands); Schubert, M.; Stober, J.; Wagner, D. H. [Max-Planck-Institut für Plasmaphysik, EURATOM-Association, Boltzmannstr. 2, 85748 Garching (Germany)

    2014-09-15

    Collective Thomson scattering (CTS) measurements provide information about the composition and velocity distribution of confined ion populations in fusion plasmas. The bulk ion part of the CTS spectrum is dominated by scattering off fluctuations driven by the motion of thermalized ion populations. It thus contains information about the ion temperature, rotation velocity, and plasma composition. To resolve the bulk ion region and access this information, we installed a fast acquisition system capable of sampling rates up to 12.5 GS/s in the CTS system at ASDEX Upgrade. CTS spectra with frequency resolution in the range of 1 MHz are then obtained through direct digitization and Fourier analysis of the CTS signal. We here describe the design, calibration, and operation of the fast receiver system and give examples of measured bulk ion CTS spectra showing the effects of changing ion temperature, rotation velocity, and plasma composition.

  7. Time-Resolved Measurement of Radiatively Heated Iron 2p-3d Transmission Spectra

    Institute of Scientific and Technical Information of China (English)

    ZHAO Yang; SHANG Wan-Li; XIONG Gang; JIN Feng-Tao; HU Zhi-Min; WEI Min-Xi; YANG Guo-Hong; ZHANG Ji-Yan; YANG Jia-Min

    2010-01-01

    @@ An experimental measurement of radiatively heated iron plasma transmission spectra was performed on Shenguang Ⅱ laser facility.In the measurement,the self-emission spectrum,the backlighting spectrum,and the absorption spectrum were imaged with a fiat filed grating and recorded on a gated micro channel plate detector to obtain the time-resolved transmission spectra in the range 10-20 A (approximately 0.6-1.3 keV).Experimental results are compared with the calculation results of an unsolved transition array (UTA) code.The time-dependent relative shift in the positions of the 2p-3d transmission array is interpreted in terms of the plasma temperature variations.

  8. Structural and time resolved emission spectra of Er 3+: Silver lead borate glass

    Science.gov (United States)

    Coelho, João; Hungerford, Graham; Hussain, N. Sooraj

    2011-08-01

    The structural properties of Er 3+: silver lead borate glass is assessed by means of SEM, X-ray mapping, EDS and Raman analysis. In order to verify the time dependency of emission spectra, steady-state luminescence spectroscopy (SSLS) and time-resolved emission spectroscopy (TRES) studies have been performed. The stimulated emission cross-sections for the NIR emission transition 4I 13/2 → 4I 15/2 (1535 nm) at 970 nm excitation are reported. The decay times were obtained by fitting one ( τm = 0.301 ms) and two ( τm1 = 0.141 ms, τm2 = 0.368 ms) distributions for the NIR transition. Furthermore, by making use of TRES measurements the decay associated spectra were obtained allowing the time dependency for the different emission bands to be elucidated.

  9. Spatially and momentum resolved energy electron loss spectra from an ultra-thin PrNiO{sub 3} layer

    Energy Technology Data Exchange (ETDEWEB)

    Kinyanjui, M. K., E-mail: michael.kinyanjui@uni-ulm.de; Kaiser, U. [Central Facility of Electron Microscopy, University of Ulm, Albert-Einstein Allee 11, 89081 Ulm (Germany); Benner, G.; Pavia, G. [Carl Zeiss Microscopy GmbH, Carl-Zeiss-Str. 22, 73447 Oberkochen (Germany); Boucher, F. [Institut des Matériaux Jean Rouxel, UMR6502, CNRS - Université de Nantes, 2 rue de la Houssinière, B.P.32229, 44322 Nantes Cedex (France); Habermeier, H.-U.; Keimer, B. [Max Planck Institute for Solid State Research, Heisenbergstrasse 1, D-70579 Stuttgart (Germany)

    2015-05-18

    We present an experimental approach which allows for the acquisition of spectra from ultra-thin films at high spatial, momentum, and energy resolutions. Spatially and momentum (q) resolved electron energy loss spectra have been obtained from a 12 nm ultra-thin PrNiO{sub 3} layer using a nano-beam electron diffraction based approach which enabled the acquisition of momentum resolved spectra from individual, differently oriented nano-domains and at different positions of the PrNiO{sub 3} thin layer. The spatial and wavelength dependence of the spectral excitations are obtained and characterized after the analysis of the experimental spectra using calculated dielectric and energy loss functions. The presented approach makes a contribution towards obtaining momentum-resolved spectra from nanostructures, thin film, heterostructures, surfaces, and interfaces.

  10. Photoelectron spectra of V/sub 3/Si, a high I/sub c/ superconductor with A15 structure

    Energy Technology Data Exchange (ETDEWEB)

    Riley, J.; Azoulay, J.; Ley, L.

    1976-08-01

    A high resolution (0.55 eV FWHM) overview of the valence band of V/sub 3/Si by x-ray induced photoelectron spectroscopy is presented. A comparison of the spectrum with band structure calculations allows the determination of band energies at points of high symmetry. A new correlation between the core line asymmetry and the superconducting transition temperature has been established for Ti, V and V/sub 3/Si (11 references).

  11. Measurement of the time-resolved spectrum of photoelectrons from ZnS:Mn, Cu luminescent material

    CERN Document Server

    Dong Guo Yi; Wei Zh; Yang Shao Peng; Fu Guang Sheng

    2003-01-01

    The process of decay of photoelectrons in the conduction band of ZnS:Mn, Cu luminescent materials after excitation with a short-pulse laser has been investigated in this paper by means of measurements made using the microwave absorption dielectric spectrum detection technique. Exponential decay processes were observed for the electrons in the conduction band and the shallow-trapped electrons; the lifetimes of the electrons were found to be 1177 and 1703 ns, respectively. The processes of decay of the luminescence from ZnS:Mn, Cu were investigated and exponential decay processes were found for blue Cu sup + , green Cu sup + and Mn sup 2 sup + luminescent centres with lifetimes of the excited state of 139, 140 and 680 mu s, respectively.

  12. Detection of radionuclides from weak and poorly resolved spectra using Lasso and subsampling techniques

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Er-Wei, E-mail: er-wei-bai@uiowa.edu [Department of Electrical and Computer Engineering, University of Iowa, Iowa City, IA 52242 (United States); Chan, Kung-sik, E-mail: kung-sik-chan@uiowa.edu [Department of Statistical and Actuarial Science, University of Iowa, Iowa City, IA 52242 (United States); Eichinger, William, E-mail: william-eichinger@uiowa.edu [Department of Civil and Environmental Engineering, University of Iowa, Iowa City, IA 52242 (United States); Kump, Paul [Department of Electrical and Computer Engineering, University of Iowa, Iowa City, IA 52242 (United States)

    2011-10-15

    We consider a problem of identification of nuclides from weak and poorly resolved spectra. A two stage algorithm is proposed and tested based on the principle of majority voting. The idea is to model gamma-ray counts as Poisson processes. Then, the average part is taken to be the model and the difference between the observed gamma-ray counts and the average is considered as random noise. In the linear part, the unknown coefficients correspond to if isotopes of interest are present or absent. Lasso types of algorithms are applied to find non-vanishing coefficients. Since Lasso or any prediction error based algorithm is inconsistent with variable selection for finite data length, an estimate of parameter distribution based on subsampling techniques is added in addition to Lasso. Simulation examples are provided in which the traditional peak detection algorithms fail to work and the proposed two stage algorithm performs well in terms of both the False Negative and False Positive errors. - Highlights: > Identification of nuclides from weak and poorly resolved spectra. > An algorithm is proposed and tested based on the principle of majority voting. > Lasso types of algorithms are applied to find non-vanishing coefficients. > An estimate of parameter distribution based on sub-sampling techniques is included. > Simulations compare the results of the proposed method with those of peak detection.

  13. Radio Phase-Resolved Spectra of the Conal-Double Pulsar B1133+16

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Based on dividing the profile into a number of absolute phase intervals, the phase-resolved spectra (PHRS) are derived from published time-aligned average profiles at radio frequencies over two decades for the classic conal-double pulsar B1133+16. The relative spectral index, defined as the difference between the spectral indices of a reference and the given arbitrary phase interval, is obtained by power-law fit at each phase interval. The derived phase-resolved spectra show an "M-like" shape, of which the leading part and trailing part are approximately symmetrical. The basic feature of the PHRS is that the spectrum first flattens then steepens as the pulse phase sweeps from the profile center to the profile edges. The PHRS provide a coherent explanation of the major features of profile evolution of B1133+16, namely, the pulse width shrinkage with increasing frequency and the frequency evolution of the relative intensity between the leading and trailing conal components, and the bridge emission. The PHRS may be an indicator for emission spectral variation across the pulsar magnetosphere. Possible mapping from PHRS to emission-location-dependent spectral variation is presented, and some intrinsic mechanisms are discussed.

  14. Ultrafast α -CC bond cleavage of acetone upon excitation to 3p and 3d Rydberg states by femtosecond time-resolved photoelectron imaging

    Science.gov (United States)

    Hüter, O.; Temps, F.

    2016-12-01

    The radiationless electronic relaxation and α -CC bond fission dynamics of jet-cooled acetone in the S1 (n π* ) state and in high-lying 3p and 3d Rydberg states have been investigated by femtosecond time-resolved mass spectrometry and photoelectron imaging. The S1 state was accessed by absorption of a UV pump photon at selected wavelengths between λ = 320 and 250 nm. The observed acetone mass signals and the S1 photoelectron band decayed on sub-picosecond time scales, consistent with a recently proposed ultrafast structural relaxation of the molecules in the S1 state away from the Franck-Condon probe window. No direct signatures could be observed by the experiments for CC dissociation on the S1 potential energy hypersurface in up to 1 ns. The observed acetyl mass signals at all pump wavelengths turned out to be associated with absorption by the molecules of one or more additional pump and/or probe photons. In particular, absorption of a second UV pump photon by the S1 (n π* ) state was found to populate a series of high-lying states belonging to the n = 3 Rydberg manifold. The respective transitions are favored by much larger cross sections compared to the S1 ← S0 transition. The characteristic energies revealed by the photoelectron images allowed for assignments to the 3p and 3dyz states. At two-photon excitation energies higher than 8.1 eV, an ultrafast reaction pathway for breaking the α -CC bond in 50-90 fs via the 3dyz Rydberg state and the elusive π π* state was observed, explaining the formation of acetyl radicals after femtosecond laser excitation of acetone at these wavelengths.

  15. Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

    Science.gov (United States)

    Winghart, Marc-Oliver; Yang, Ji-Ping; Vonderach, Matthias; Unterreiner, Andreas-Neil; Huang, Dao-Ling; Wang, Lai-Sheng; Kruppa, Sebastian; Riehn, Christoph; Kappes, Manfred M.

    2016-02-01

    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt2(μ-P2O5H2)4 + 2H]2- after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet 1A2u state and concomitant rise in population of the triplet 3A2u state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet 1A2u state takes only a few picoseconds, ESETD from the triplet 3A2u state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt2(μ-P2O5H2)4 + 2H]2- is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

  16. Fourier-resolved energy spectra of the Narrow Line Seyfert 1 Mkn 766

    CERN Document Server

    Arevalo, P; Markowitz, A; Papadakis, I E; Turner, T J; Miller, L; Reeves, J

    2008-01-01

    We compute Fourier-resolved X-ray spectra of the Seyfert 1 Markarian 766 to study the shape of the variable components contributing to the 0.3-10 keV energy spectrum and their time-scale dependence. The fractional variability spectra peak at 1-3 keV, as in other Seyfert 1 galaxies, consistent with either a constant contribution from a soft excess component below 1 keV and Compton reflection component above 2 keV, or variable warm absorption enhancing the variability in the 1-3 keV range. The rms spectra, which shows the shape of the variable components only, is well described by a single power law with an absorption feature around 0.7 keV, which gives it an apparent soft excess. This spectral shape can be produced by a power law varying in normalisation, affected by an approximately constant (within each orbit) warm absorber, with parameters similar to those found by Turner et al. for the warm-absorber layer covering all spectral components in their scattering scenario. The total soft excess in the average sp...

  17. Ultrafast electron relaxation in superconducting Bi(2)Sr(2)CaCu(2)O(8+delta) by time-resolved photoelectron spectroscopy.

    Science.gov (United States)

    Perfetti, L; Loukakos, P A; Lisowski, M; Bovensiepen, U; Eisaki, H; Wolf, M

    2007-11-09

    Time-resolved photoelectron spectroscopy is employed to study the dynamics of photoexcited electrons in optimally doped Bi{2}Sr{2}CaCu{2}O{8+delta} (Bi-2212). Hot electrons thermalize in less than 50 fs and dissipate their energy on two distinct time scales (110 fs and 2 ps). These are attributed to the generation and subsequent decay of nonequilibrium phonons, respectively. We conclude that 20% of the total lattice modes dominate the coupling strength and estimate the second momentum of the Eliashberg coupling function lambdaOmega{0}{2}=360+/-30 meV{2}. For the typical phonon energy of copper-oxygen bonds (Omega{0} approximately 40-70 meV), this results in an average electron-phonon coupling lambda<0.25.

  18. Rotationally resolved state-to-state photoionization and photoelectron study of titanium carbide and its cation (TiC/TiC{sup +})

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Zhihong; Huang, Huang; Chang, Yih-Chung; Zhang, Zheng; Ng, C. Y., E-mail: cyng@ucdavis.edu [Department of Chemistry, University of California, Davis, California 95616 (United States); Yin, Qing-Zhu [Department of Earth and Planetary Sciences, University of California, Davis, California 95616 (United States)

    2014-10-14

    Titanium carbide and its cation (TiC/TiC{sup +}) have been investigated by the two-color visible (VIS)-ultraviolet (UV) resonance-enhanced photoionization and pulsed field ionization-photoelectron (PFI-PE) methods. Two visible excitation bands for neutral TiC are observed at 16 446 and 16 930 cm{sup −1}. Based on rotational analyses, these bands are assigned as the respective TiC({sup 3}Π{sub 1}) ← TiC(X{sup 3}Σ{sup +}) and TiC({sup 3}Σ{sup +}) ← TiC(X{sup 3}Σ{sup +}) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ{sup 2}8σ{sup 1}9σ{sup 1}3π{sup 4} (X{sup 3}Σ{sup +}). The rotational constant and the corresponding bond distance of TiC(X{sup 3}Σ{sup +}; v″ = 0) are determined to be B{sub 0}″ = 0.6112(10) cm{sup −1} and r{sub 0}″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC{sup +}(X; v{sup +} = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC{sup +} ground state are …7σ{sup 2}8σ{sup 1}3π{sup 4} (X{sup 2}Σ{sup +}) with the v{sup +} = 0 → 1 vibrational spacing of 870.0(8) cm{sup −1} and the rotational constants of B{sub e}{sup +} = 0.6322(28) cm{sup −1}, and α{sub e}{sup +} = 0.0085(28) cm{sup −1}. The latter rotational constants yield the equilibrium bond distance of r{sub e}{sup +} = 1.667(4) Å for TiC{sup +}(X{sup 2}Σ{sup +}). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm{sup −1} [6.5960(1) eV] for the adiabatic ionization energy (IE) of TiC. This IE(TiC) value along with the known IE(Ti) has made possible the determination of the difference between the 0 K bond dissociation energy (D{sub 0}) of TiC{sup +}(X{sup 2}Σ{sup +}) and that of TiC(X{sup 3}Σ{sup +}) to be D{sub 0}(Ti{sup +}−C) − D{sub 0}(Ti−C) = 0.2322(2) eV. Similar to previous experimental

  19. Photoelectron spectra and structures of three cyclic dipeptides: PhePhe, TyrPro, and HisGly

    Science.gov (United States)

    Wickrama Arachchilage, Anoja P.; Wang, Feng; Feyer, Vitaliy; Plekan, Oksana; Prince, Kevin C.

    2012-03-01

    We have investigated the electronic structure of three cyclic dipeptides: cyclo(Histidyl-Glycyl) (cHisGly), cyclo(Tyrosyl-Prolyl) (cTyrPro), and cyclo(Phenylalanyl-Phenylalanyl) (cPhePhe) in the vapor phase, by means of photoemission spectroscopy and theoretical modeling. The last compound was evaporated from the solid linear dipeptide, but cyclised, losing water to form cPhePhe in the gas phase. The results are compared with our previous studies of three other cyclopeptides. Experimental valence and core level spectra have been interpreted in the light of calculations to identify the basic chemical properties associated with the central diketopiperazine ring, and with the additional functional groups. The valence spectra are generally characterized by a restricted set of outer valence orbitals separated by a gap from most other valence orbitals. The theoretically simulated core and valence spectra of all three cyclic dipeptides agree reasonably well with the experimental spectra. The central ring and the side chains act as independent chromophores whose spectra do not influence one another, except for prolyl dipeptides, where the pyrrole ring is fused with the central ring. In this case, significant changes in the valence and core level spectra were observed, and explained by stronger hybridization of the valence orbitals.

  20. New method for measuring time-resolved spectra of lanthanide emission using square-wave excitation

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Feng [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150080 (China); Zhao, Hua; Cai, Wei, E-mail: weicai@hit.edu.cn [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China); Duan, Qianqian [College of Information Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Zhang, Zhiguo, E-mail: zhangzhiguo@hit.edu.cn [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150080 (China); Laboratory of Sono- and Photo-Theranostic Technologies, Harbin Institute of Technology, Harbin 150080 (China); Cao, Wenwu, E-mail: dzk@psu.edu [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150080 (China); Laboratory of Sono- and Photo-Theranostic Technologies, Harbin Institute of Technology, Harbin 150080 (China); Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

    2013-11-15

    A method using modulated continuous wave (CW) visible laser to measure time-resolved fluorescence spectra of trivalent rare-earth ions has been developed. Electro-optic modulator was used to modulate the CW pumping laser with a rise time of 2 μs. CW Nd{sup 3+} lasers were used as examples to present the method. Upconversion dynamic process of Ho{sup 3+} was studied utilizing a 532 nm CW laser. Quantum cutting dynamic process from Tb{sup 3+} to Yb{sup 3+} was analyzed by a 473 nm CW laser. This method can be applied to any CW laser such as He-Ne laser, Ar{sup +} laser, Kr{sup +} laser, Ti:sapphire laser, etc.

  1. Theoretical simulations for vibrationally-resolved absorption spectra of naphthalenediimide cyclophane derivatives

    Science.gov (United States)

    Song, Ce; Li, Li; Duan, Sai; Luo, Yi; Tian, Guangjun

    2017-08-01

    In the present work we systematically investigated the vibrationally-resolved absorption spectra of three core substituted naphthalenediimide cyclophane derivatives. It has been performed by time-dependent density functional theory calculations using three different exchange-correlation functionals, including the conventional B3LYP functional and two long-range corrected functionals: CAM-B3LYP and ωB97XD. The solvent effects were also considered with the polarizable continuum model. Calculation results showed that long range corrections are needed to correctly describe the optical properties of the three molecules because of the strong charge transfer characteristic of the excited states. The core substitution induced red shift to the first absorption band is nicely explained by the theoretical calculations. It is found that this band mainly involves the transitions within the core substituted naphthalenediimide chromophore. The high energy absorption band, on the other hand, is generated mainly from the un-substituted chromophore. These characters result in different substitution dependence for those two main absorption bands. Furthermore, the simulated vibrational profiles of the first two absorption bands nicely reproduce the observed vibrational features in the measured spectra. The accuracy of the calculated results from different functionals and basis sets has been discussed.

  2. Time-resolved Photoluminescence Spectra of Nominally Disordered GaInP Alloy

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Luminescence decay and time-resolved photoluminescence(TRPL) spectra are used for study on the transient luminescence process of the nominally disordered GaInP alloy. The luminescence decay of GaInP alloy shows the temperature and excitation-intensity dependent characters. At 77K and under high excitation intensity, the luminescence decay shows single exponential time dependence, while under low excitation intensity or at 300K, the luminescence decay shows double exponential time dependence. The analysis indicates that this nominally disordered GaInP alloy actually exhibits a very weak degree of order. The blue-shift of PL peak is observed in the TRPL spectra at 77K, which is derived from the transfer of the carriers from the ordered domain to the disordered region of the alloy. At 300K, due to the thermal quenching, the transfer is too weak to be observed. However, The recombination of the carriers between the ordered domain and the disordered region is still devoted to luminesce.

  3. Development of a single-shot CCD-based data acquisition system for time-resolved X-ray photoelectron spectroscopy at an X-ray free-electron laser facility.

    Science.gov (United States)

    Oura, Masaki; Wagai, Tatsuya; Chainani, Ashish; Miyawaki, Jun; Sato, Hiromi; Matsunami, Masaharu; Eguchi, Ritsuko; Kiss, Takayuki; Yamaguchi, Takashi; Nakatani, Yasuhiro; Togashi, Tadashi; Katayama, Tetsuo; Ogawa, Kanade; Yabashi, Makina; Tanaka, Yoshihito; Kohmura, Yoshiki; Tamasaku, Kenji; Shin, Shik; Ishikawa, Tetsuya

    2014-01-01

    In order to utilize high-brilliance photon sources, such as X-ray free-electron lasers (XFELs), for advanced time-resolved photoelectron spectroscopy (TR-PES), a single-shot CCD-based data acquisition system combined with a high-resolution hemispherical electron energy analyzer has been developed. The system's design enables it to be controlled by an external trigger signal for single-shot pump-probe-type TR-PES. The basic performance of the system is demonstrated with an offline test, followed by online core-level photoelectron and Auger electron spectroscopy in 'single-shot image', 'shot-to-shot image (image-to-image storage or block storage)' and `shot-to-shot sweep' modes at soft X-ray undulator beamline BL17SU of SPring-8. In the offline test the typical repetition rate for image-to-image storage mode has been confirmed to be about 15 Hz using a conventional pulse-generator. The function for correcting the shot-to-shot intensity fluctuations of the exciting photon beam, an important requirement for the TR-PES experiments at FEL sources, has been successfully tested at BL17SU by measuring Au 4f photoelectrons with intentionally controlled photon flux. The system has also been applied to hard X-ray PES (HAXPES) in `ordinary sweep' mode as well as shot-to-shot image mode at the 27 m-long undulator beamline BL19LXU of SPring-8 and also at the SACLA XFEL facility. The XFEL-induced Ti 1s core-level spectrum of La-doped SrTiO3 is reported as a function of incident power density. The Ti 1s core-level spectrum obtained at low power density is consistent with the spectrum obtained using the synchrotron source. At high power densities the Ti 1s core-level spectra show space-charge effects which are analysed using a known mean-field model for ultrafast electron packet propagation. The results successfully confirm the capability of the present data acquisition system for carrying out the core-level HAXPES studies of condensed matter induced by the XFEL.

  4. Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

    Energy Technology Data Exchange (ETDEWEB)

    Winghart, Marc-Oliver, E-mail: marc-oliver.winghart@kit.edu; Unterreiner, Andreas-Neil [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Yang, Ji-Ping [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); School of Sciences, Hefei University of Technology, Hefei 230009 (China); Vonderach, Matthias [Centre for Proteome Research, Institute of Integrative Biology, University of Liverpool, Liverpool L69 7ZB (United Kingdom); Huang, Dao-Ling; Wang, Lai-Sheng [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States); Kruppa, Sebastian; Riehn, Christoph [Fachbereich Chemie und Landesforschungszentrum OPTIMAS, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Kappes, Manfred M., E-mail: manfred.kappes@kit.edu [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe (Germany)

    2016-02-07

    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet {sup 1}A{sub 2u} state and concomitant rise in population of the triplet {sup 3}A{sub 2u} state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet {sup 1}A{sub 2u} state takes only a few picoseconds, ESETD from the triplet {sup 3}A{sub 2u} state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

  5. Spin-orbit ab initio curves of 80Se+2 ion and the assignment of photoelectron spectra of 80Se2 molecule

    Institute of Scientific and Technical Information of China (English)

    Yan Bing; Pan Shou-Fu; Guo Qing-Qun

    2008-01-01

    This paper carries out ab initio calculations to study the 80Se2(X3∑-g)state and 80Se+2(X2∏g),80Se+2(a4∏g)states by using completed active space self-consistent field and multi-reference second order perturbation theory.The electronic curves of these states including spin-orbit coupling are calculated,and then the spectroscopic parameters are obtained.The photoelectron spectra of 80Se2 molecule in gas phase are assigned according to Franck-Condon analysis based on calculated potential energy curves.The ionization energies of 80Se2 molecule are determined by the present calculation.

  6. Resolved Ultraviolet Reflectance Spectra of Mercury from the Third MESSENGER Flyby

    Science.gov (United States)

    Holsclaw, G. M.; McClintock, W. E.; Blewett, D. T.; Denevi, B. W.; Domingue, D. L.; Izenberg, N. R.; Jensen, E. A.; Robinson, M. S.; Solomon, S. C.; Sprague, A. L.; Vilas, F.

    2009-12-01

    Reflectance spectroscopy at ultraviolet wavelengths is a valuable remote sensing tool for studying the chemical makeup of planetary surfaces. The MESSENGER spacecraft instrument payload includes the Mercury Atmospheric and Surface Composition Spectrometer (MASCS), which contains the Ultraviolet and Visible Spectrometer (UVVS), capable of acquiring point-reflectance spectra from the far to near ultraviolet (115-350 nm). The first disk-integrated reflectance spectrum of Mercury at middle-ultraviolet wavelengths (220-300 nm) was obtained by MASCS-UVVS during the first flyby of the planet on 14 January 2008. A comparison of this spectrum with the reflectance of the Moon obtained with the same instrument showed that an inflection, interpreted as a volume absorption due to an electronic charge-transfer between oxygen and a transition-metal cation, was present in the Mercury data but absent in the lunar spectrum. Given the intense space weathering environment at Mercury, it was expected that such volume absorptions might be obscured by even small amounts of nanophase metallic iron within vapor-deposited coatings. During the second Mercury flyby on 6 October 2008, several spatially resolved middle-ultraviolet spectra were acquired. These spectra were found to have spectral characteristics similar to those of the disk-integrated spectrum. However, it was not possible to discern subtle spectral variations because of the spatial-spectral coupling of the data. The UVVS operates as a scanning-grating monochromator. Consequently, during acquisition of a spectrum (obtained one wavelength at a time) the instrument field of view is carried across the planet’s surface by spacecraft motion. Therefore, variations in albedo, composition, maturity, topography, and shadowing all contribute to structure in the spectrum. During MESSENGER’s third flyby of Mercury on 29 September 2009, a specialized observing strategy was implemented. From multispectral images obtained during the

  7. Direct asymmetry measurement of temperature and density spatial distributions in inertial confinement fusion plasmas from pinhole space-resolved spectra

    CERN Document Server

    Nagayama, T; Florido, R; Mayes, D; Tommasini, R; Koch, J A; Delettrez, J A; Regan, S P; Smalyuk, V A

    2014-01-01

    Two-dimensional space-resolved temperature and density images of an inertial confinement fusion (ICF) implosion core have been diagnosed for the first time. Argon-doped, direct-drive ICF experiments were performed at the Omega Laser Facility and a collection of two-dimensional space-resolved spectra were obtained from an array of gated, spectrally resolved pinhole images recorded by a multi-monochromatic x-ray imager. Detailed spectral analysis revealed asymmetries of the core not just in shape and size but in the temperature and density spatial distributions, thus characterizing the core with an unprecedented level of detail.

  8. Two Bathointermediates of the Bacteriorhodopsin Photocycle, from Time-Resolved Nanosecond Spectra in the Visible

    Science.gov (United States)

    Lanyi, Janos K.

    2013-01-01

    Time-resolved measurements were performed on wild-type bacteriorhodopsin with an optical multi-channel analyzer in the spectral range of 350–735 nm, from 100 ns to the photocycle completion, at four temperatures in the 5–30 °C range. The intent was to examine the possibility of two K-like bathochromic intermediates and to obtain their spectra and kinetics in the visible. The existence of a second K-like intermediate, termed KL, had been postulated (Shichida et al., BBA 723:240–246, 1983) to reconcile inconsistencies in data in the pico- and microsecond time-domains. However, introduction of KL led to a controversy since neither its visible spectrum nor its kinetics could be confirmed. Infra-red data (Dioumaev & Braiman, J. Phys. Chem., B, 101:1655–1662, 1997), revealed a state, which might have been considered a homologue to KL but it had a kinetic pattern different from that of the earlier proposed KL. Here we characterize two distinct K-like intermediates, KE (“early”) and KL (“late”), by their spectra and kinetics in the visible as revealed by global kinetic analysis. The KE-to-KL transition has a time constant of ~250 ns at 20 °C, and describes a shift from KE with λmax at ~600 nm and extinction of ~56,000 M−1·cm−1 to KL with λmax at ~590 nm and extinction of ~50,000 M−1·cm−1. The temperature dependence of this transition is characterized by an enthalpy of activation ΔH# ~ 40 kJ/mol, and a positive entropy of activation ΔS#/R = ~4. The consequences of multiple K-like states for interpreting the spectral evolution in the early stages of the photocycle are discussed. PMID:19994879

  9. Evaluation of intrinsic chemical kinetics and transient product spectra from time-resolved spectroscopic data.

    Science.gov (United States)

    Dioumaev, A K

    1997-09-01

    This communication is devoted to the evaluation of true spectra and intrinsic (microscopic) rate constants from apparent kinetics measured in time-resolved spectroscopic experiments monitoring complex relaxation dynamics of multi-intermediate systems. Retinal proteins, cytochrom c oxidase, phytochrome, hemoglobin, and photoactive yellow protein are examples of natural systems in which several transient states (intermediates) overlap so strongly, both in time and spectral domains, that their isolation and full characterization by classical biochemical methods is impossible, and mathematical evaluation of their true spectra and microscopic kinetic constants is required. Most of the popular methods for analysis of kinetic data, global fitting (GF), singular value decomposition (SVD), principal component analysis (PCA) and factor analysis (FA), are applicable to two-dimensional (2D, in time and spectral domains) arrays of data. All these methods produce only a phenomenological description of data, that approximates the measured data only with apparent kinetics. A fundamental limitation, namely, insufficient information in 2D data, does not allow any of these methods to reach the final goal: to recalculate from apparent to intrinsic values in any but the most trivial cases. A strategy was proposed (J.F. Nagle, Biophys. J.. 59 (1991) 476-487) to include an additional (third) information-rich dimension, temperature, into the simultaneous computer analysis. A simultaneous direct fitting of 3D data arrays to systems of differential rate equations allows recalculation of apparent kinetics into true spectra and intrinsic rate constants. In spite of its evident theoretical advantages, this strategy has not been successful on real data. Here we describe another custom-built program, SCHEMEFIT, developed for the same purpose: to fit measured kinetics directly to the system of coupled differential rate equations describing the photochrome's relaxation dynamics. Though sharing the

  10. High-resolution soft X-ray beamline ADRESS at the Swiss Light Source for resonant inelastic X-ray scattering and angle-resolved photoelectron spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Strocov, V. N., E-mail: vladimir.strocov@psi.ch; Schmitt, T.; Flechsig, U.; Schmidt, T.; Imhof, A.; Chen, Q.; Raabe, J. [Swiss Light Source, Paul Scherrer Institut, CH-5232 Villigen-PSI (Switzerland); Betemps, R.; Zimoch, D.; Krempasky, J. [Paul Scherrer Institut, CH-5232 Villigen-PSI (Switzerland); Wang, X. [Swiss Light Source, Paul Scherrer Institut, CH-5232 Villigen-PSI (Switzerland); Institut de Physique de la Matiére Condensé, Ecole Polytechnique Fédéderale de Lausanne (Switzerland); Grioni, M. [Institut de Physique de la Matiére Condensé, Ecole Polytechnique Fédéderale de Lausanne (Switzerland); Piazzalunga, A. [Swiss Light Source, Paul Scherrer Institut, CH-5232 Villigen-PSI (Switzerland); Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milano (Italy); Patthey, L. [Swiss Light Source, Paul Scherrer Institut, CH-5232 Villigen-PSI (Switzerland)

    2010-09-01

    Concepts and technical realization of the high-resolution soft X-ray beamline ADRESS at the Swiss Light Source are described. Optimization of the optical scheme for high resolution and photon flux as well as diagnostics tools and alignment strategies are discussed. The concepts and technical realisation of the high-resolution soft X-ray beamline ADRESS operating in the energy range from 300 to 1600 eV and intended for resonant inelastic X-ray scattering (RIXS) and angle-resolved photoelectron spectroscopy (ARPES) are described. The photon source is an undulator of novel fixed-gap design where longitudinal movement of permanent magnetic arrays controls not only the light polarization (including circular and 0–180° rotatable linear polarizations) but also the energy without changing the gap. The beamline optics is based on the well established scheme of plane-grating monochromator operating in collimated light. The ultimate resolving power E/ΔE is above 33000 at 1 keV photon energy. The choice of blazed versus lamellar gratings and optimization of their profile parameters is described. Owing to glancing angles on the mirrors as well as optimized groove densities and profiles of the gratings, the beamline is capable of delivering high photon flux up to 1 × 10{sup 13} photons s{sup −1} (0.01% BW){sup −1} at 1 keV. Ellipsoidal refocusing optics used for the RIXS endstation demagnifies the vertical spot size down to 4 µm, which allows slitless operation and thus maximal transmission of the high-resolution RIXS spectrometer delivering E/ΔE > 11000 at 1 keV photon energy. Apart from the beamline optics, an overview of the control system is given, the diagnostics and software tools are described, and strategies used for the optical alignment are discussed. An introduction to the concepts and instrumental realisation of the ARPES and RIXS endstations is given.

  11. Phonon-assisted indirect transitions in angle-resolved photoemission spectra of graphite and graphene

    Science.gov (United States)

    Ayria, Pourya; Tanaka, Shin-ichiro; Nugraha, Ahmad R. T.; Dresselhaus, Mildred S.; Saito, Riichiro

    2016-08-01

    Indirect transitions of electrons in graphene and graphite are investigated by means of angle-resolved photoemission spectroscopy (ARPES) with several different incident photon energies and light polarizations. The theoretical calculations of the indirect transition for graphene and for a single crystal of graphite are compared with the experimental measurements for highly-oriented pyrolytic graphite and a single crystal of graphite. The dispersion relations for the transverse optical (TO) and the out-of-plane longitudinal acoustic (ZA) phonon modes of graphite and the TO phonon mode of graphene can be extracted from the inelastic ARPES intensity. We find that the TO phonon mode for k points along the Γ -K and K -M -K' directions in the Brillouin zone can be observed in the ARPES spectra of graphite and graphene by using a photon energy ≈11.1 eV. The relevant mechanism in the ARPES process for this case is the resonant indirect transition. On the other hand, the ZA phonon mode of graphite can be observed by using a photon energy ≈6.3 eV through a nonresonant indirect transition, while the ZA phonon mode of graphene within the same mechanism should not be observed.

  12. PHASE-RESOLVED X-RAY SPECTRA OF MAGNETARS AND THE CORONAL OUTFLOW MODEL

    Energy Technology Data Exchange (ETDEWEB)

    Hascoët, Romain; Beloborodov, Andrei M. [Physics Department and Columbia Astrophysics Laboratory, Columbia University, 538 West 120th Street, New York, NY 10027 (United States); Den Hartog, Peter R., E-mail: hascoet@astro.columbia.edu [Stanford University HEPL/KIPAC, 452 Lomita Mall, Stanford, CA 94305-4085 (United States)

    2014-05-01

    We test a model recently proposed for the persistent hard X-ray emission from magnetars. In the model, hard X-rays are produced by a decelerating electron-positron flow in the closed magnetosphere. The flow decelerates as it radiates its energy away via resonant scattering of soft X-rays, then it reaches the top of the magnetic loop and annihilates there. We test the model against observations of three magnetars: 4U 0142+61, 1RXS J1708-4009, and 1E 1841-045. We find that the model successfully fits the observed phase-resolved spectra. We derive constraints on the angle between the rotational and magnetic axes of the neutron star, the object inclination to the line of sight, and the size of the active twisted region filled with the plasma flow. Using the fit of the hard X-ray component of the magnetar spectrum, we revisit the remaining soft X-ray component. We find that it can be explained by a modified two-temperature blackbody model. The hotter blackbody is consistent with a hot spot covering 1%-10% of the neutron star surface. Such a hot spot is expected at the base of the magnetospheric e {sup ±} outflow, as some particles created in the e {sup ±} discharge flow back and bombard the stellar surface.

  13. Time-resolved GRB spectra in the complex radiation of synchrotron and Compton processes

    Science.gov (United States)

    Jiang, Y. G.; Hu, S. M.; Chen, X.; Li, K.; Guo, D. F.; Li, Y. T.; Li, H. Z.; Zhao, Y. Y.; Lin, H. N.; Chang, Z.

    2016-03-01

    Under the steady-state condition, the spectrum of electrons is investigated by solving the continuity equation under the complex radiation of both the synchrotron and Compton processes. The resulted gamma-ray burst (GRB) spectrum is a broken power law in both the fast and slow cooling phases. On the basis of this electron spectrum, the spectral indices of the Band function in four different phases are presented. In the complex radiation frame, the detail investigation on physical parameters reveals that three models can answer the α ˜ -1 problem, which are the synchrotron plus synchrotron self-Compton in the internal and the external shock models, and the synchrotron plus the external Compton processes in the external shock model. A possible marginal to fast cooling phase transition in GRB 080916C is discussed. The time-resolved spectra in different main pulses of GRB 100724B, GRB 100826A and GRB 130606B are investigated. We found that the flux is proportional to the peak energy in almost all main pulses. A significant (5σ) correlation for Fp ˜ Ep is evident the first main pulse of GRB 100826A, and three marginally significant (3σ) correlations Fp ˜ Ep are found in main pulses of GRB 100826A and GRB 130606B. The correlation between spectral index and Ep at 3 ˜ 4σ level are observed in the first main pulse of GRB 100826A. Such correlations are possible explained in the complex radiation scenario.

  14. Phase-resolved X-ray spectra of magnetars and the coronal outflow model

    CERN Document Server

    Hascoet, R; Hartog, P R den

    2014-01-01

    We test a model recently proposed for the persistent hard X-ray emission from magnetars. In the model, hard X-rays are produced by a decelerating electron-positron flow in the closed magnetosphere. The flow decelerates as it radiates its energy away via resonant scattering of soft X-rays, then it reaches the top of the magnetic loop and annihilates there. We test the model against observations of three magnetars: 4U 0142+61, 1RXS J1708-4009, and 1E 1841-045. We find that the model successfully fits the observed phase-resolved spectra. We derive constraints on the angle between the rotational and magnetic axes of the neutron star, the object inclination to the line of sight, and the size of the active twisted region filled with the plasma flow. Using the fit of the hard X-ray component of the magnetar spectrum, we revisit the remaining soft X-ray component. We find that it can be explained by a modified two-temperature blackbody model. The hotter blackbody is consistent with a hot spot covering 1-10% of the ne...

  15. Influence of surface hydroxylation on 3-aminopropyltriethoxysilane growth mode during chemical functionalization of GaN Surfaces: an angle-resolved X-ray photoelectron spectroscopy Study.

    Science.gov (United States)

    Arranz, A; Palacio, C; García-Fresnadillo, D; Orellana, G; Navarro, A; Muñoz, E

    2008-08-19

    A comparative study of the chemical functionalization of undoped, n- and p-type GaN layers grown on sapphire substrates by metal-organic chemical vapor deposition was carried out. Both types of samples were chemically functionalized with 3-aminopropyltriethoxysilane (APTES) using a well-established silane-based approach for functionalizing hydroxylated surfaces. The untreated surfaces as well as those modified by hydroxylation and APTES deposition were analyzed using angle-resolved X-ray photoelectron spectroscopy. Strong differences were found between the APTES growth modes on n- and p-GaN surfaces that can be associated with the number of available hydroxyl groups on the GaN surface of each sample. Depending on the density of surface hydroxyl groups, different mechanisms of APTES attachment to the GaN surface take place in such a way that the APTES growth mode changes from a monolayer to a multilayer growth mode when the number of surface hydroxyl groups is decreased. Specifically, a monolayer growth mode with a surface coverage of approximately 78% was found on p-GaN, whereas the formation of a dense film, approximately 3 monolayers thick, was observed on n-GaN.

  16. Stark-assisted population control of coherent CS(2) 4f and 5p Rydberg wave packets studied by femtosecond time-resolved photoelectron spectroscopy.

    Science.gov (United States)

    Knappenberger, Kenneth L; Lerch, Eliza-Beth W; Wen, Patrick; Leone, Stephen R

    2007-09-28

    A two-color (3+1(')) pump-probe scheme is employed to investigate Rydberg wave packet dynamics in carbon disulfide (CS(2) (*)). The state superpositions are created within the 4f and 5p Rydberg manifolds by three photons of the 400 nm pump pulse, and their temporal evolution is monitored with femtosecond time-resolved photoelectron spectroscopy using an 800 nm ionizing probe pulse. The coherent behavior of the non-stationary superpositions are observed through wavepacket revivals upon ionization to either the upper (12) or lower (32) spin-orbit components of CS(2) (+). The results show clearly that the composition of the wavepacket can be efficiently controlled by the power density of the excitation pulse over a range from 500 GWcm(2) to 10 TWcm(2). The results are consistent with the anticipated ac-Stark shift for 400 nm light and demonstrate an effective method for population control in molecular systems. Moreover, it is shown that Rydberg wavepackets can be formed in CS(2) with excitation power densities up to 10 TWcm(2) without significant fragmentation. The exponential 1e population decay (T(1)) of specific excited Rydberg states are recovered by analysis of the coherent part of the signal. The dissociation lifetimes of these states are typically 1.5 ps. However, a region exhibiting a more rapid decay ( approximately 800 fs) is observed for states residing in the energy range of 74 450-74 550 cm(-1), suggestive of an enhanced surface crossing in this region.

  17. Are carboxyl groups the most acidic sites in amino acids? Gas-phase acidities, photoelectron spectra, and computations on tyrosine, p-hydroxybenzoic acid, and their conjugate bases.

    Science.gov (United States)

    Tian, Zhixin; Wang, Xue-Bin; Wang, Lai-Sheng; Kass, Steven R

    2009-01-28

    Deprotonation of tyrosine in the gas phase was found to occur preferentially at the phenolic site, and the conjugate base consists of a 70:30 mixture of phenoxide and carboxylate anions at equilibrium. This result was established by developing a chemical probe for differentiating these two isomers, and the presence of both ions was confirmed by photoelectron spectroscopy. Equilibrium acidity measurements on tyrosine indicated that deltaG(acid)(o) = 332.5 +/- 1.5 kcal mol(-1) and deltaH(acid)(o) = 340.7 +/- 1.5 kcal mol(-1). Photoelectron spectra yielded adiabatic electron detachment energies of 2.70 +/- 0.05 and 3.55 +/- 0.10 eV for the phenoxide and carboxylate anions, respectively. The H/D exchange behavior of deprotonated tyrosine was examined using three different alcohols (CF3CH2OD, C6H5CH2OD, and CH3CH2OD), and incorporation of up to three deuterium atoms was observed. Two pathways are proposed to account for these results, and all of the experimental findings are supplemented with B3LYP/aug-cc-pVDZ and G3B3 calculations. In addition, it was found that electrospray ionization of tyrosine from a 3:1 (v/v) CH3OH/H2O solution using a commercial source produces a deprotonated [M-H]- anion with the gas-phase equilibrium composition rather than the structure of the ion that exists in aqueous media. Electrospray ionization from acetonitrile, however, leads largely to the liquid-phase (carboxylate) structure. A control molecule, p-hydroxybenzoic acid, was found to behave in a similar manner. Thus, the electrospray conditions that are employed for the analysis of a compound can alter the isomeric composition of the resulting anion.

  18. Quantum chemical study of conformational fingerprints in the photoelectron spectra and (e, 2e) electron momentum distributions of n-hexane.

    Science.gov (United States)

    Morini, F; Knippenberg, S; Deleuze, M S; Hajgató, B

    2010-04-01

    The main purpose of the present work is to simulate from many-body quantum mechanical calculations the results of experimental studies of the valence electronic structure of n-hexane employing photoelectron spectroscopy (PES) and electron momentum spectroscopy (EMS). This study is based on calculations of the valence ionization spectra and spherically averaged (e, 2e) electron momentum distributions for each known conformer by means of one-particle Green's function [1p-GF] theory along with the third-order algebraic diagrammatic construction [ADC(3)] scheme and using Kohn-Sham orbitals derived from DFT calculations employing the Becke 3-parameters Lee-Yang-Parr (B3LYP) functional as approximations to Dyson orbitals. A first thermostatistical analysis of these spectra and momentum distributions employs recent estimations at the W1h level of conformational energy differences, by Gruzman et al. [J. Phys. Chem. A 2009, 113, 11974], and of correspondingly obtained conformer weights using MP2 geometrical, vibrational, and rotational data in thermostatistical calculations of partition functions beyond the level of the rigid rotor-harmonic oscillator approximation. Comparison is made with the results of a focal point analysis of these energy differences using this time B3LYP geometries and the corresponding vibrational and rotational partition functions in the thermostatistical analysis. Large differences are observed between these two thermochemical models, especially because of strong variations in the contributions of hindered rotations to relative entropies. In contrast, the individual ionization spectra or momentum profiles are almost insensitive to the employed geometry. This study confirms the great sensitivity of valence ionization bands and (e, 2e) momentum distributions on the molecular conformation and sheds further light on spectral fingerprints of through-space methylenic hyperconjugation, in both PES and EMS experiments.

  19. Sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy setup for pulsed and constant wave X-ray light sources.

    Science.gov (United States)

    Shavorskiy, Andrey; Neppl, Stefan; Slaughter, Daniel S; Cryan, James P; Siefermann, Katrin R; Weise, Fabian; Lin, Ming-Fu; Bacellar, Camila; Ziemkiewicz, Michael P; Zegkinoglou, Ioannis; Fraund, Matthew W; Khurmi, Champak; Hertlein, Marcus P; Wright, Travis W; Huse, Nils; Schoenlein, Robert W; Tyliszczak, Tolek; Coslovich, Giacomo; Robinson, Joseph; Kaindl, Robert A; Rude, Bruce S; Ölsner, Andreas; Mähl, Sven; Bluhm, Hendrik; Gessner, Oliver

    2014-09-01

    An apparatus for sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy studies with pulsed and constant wave X-ray light sources is presented. A differentially pumped hemispherical electron analyzer is equipped with a delay-line detector that simultaneously records the position and arrival time of every single electron at the exit aperture of the hemisphere with ~0.1 mm spatial resolution and ~150 ps temporal accuracy. The kinetic energies of the photoelectrons are encoded in the hit positions along the dispersive axis of the two-dimensional detector. Pump-probe time-delays are provided by the electron arrival times relative to the pump pulse timing. An average time-resolution of (780 ± 20) ps (FWHM) is demonstrated for a hemisphere pass energy E(p) = 150 eV and an electron kinetic energy range KE = 503-508 eV. The time-resolution of the setup is limited by the electron time-of-flight (TOF) spread related to the electron trajectory distribution within the analyzer hemisphere and within the electrostatic lens system that images the interaction volume onto the hemisphere entrance slit. The TOF spread for electrons with KE = 430 eV varies between ~9 ns at a pass energy of 50 eV and ~1 ns at pass energies between 200 eV and 400 eV. The correlation between the retarding ratio and the TOF spread is evaluated by means of both analytical descriptions of the electron trajectories within the analyzer hemisphere and computer simulations of the entire trajectories including the electrostatic lens system. In agreement with previous studies, we find that the by far dominant contribution to the TOF spread is acquired within the hemisphere. However, both experiment and computer simulations show that the lens system indirectly affects the time resolution of the setup to a significant extent by inducing a strong dependence of the angular spread of electron trajectories entering the hemisphere on the retarding ratio. The scaling of the angular spread with

  20. Three-dimensional factorization of size-resolved organic aerosol mass spectra from Mexico City

    Directory of Open Access Journals (Sweden)

    I. M. Ulbrich

    2012-01-01

    Full Text Available A size-resolved submicron organic aerosol composition dataset from a high-resolution time-of-flight mass spectrometer (HR-ToF-AMS collected in Mexico City during the MILAGRO campaign in March 2006 is analyzed using 3-dimensional (3-D factorization models. A method for estimating the precision of the size-resolved composition data for use with the factorization models is presented here for the first time. Two 3-D models are applied to the dataset. One model is a 3-vector decomposition (PARAFAC model, which assumes that each chemical component has a constant size distribution over all time steps. The second model is a vector-matrix decomposition (Tucker 1 model that allows a chemical component to have a size distribution that varies in time. To our knowledge, this is the first report of an application of 3-D factorization models to data from fast aerosol instrumentation, and the first application of this vector-matrix model to any ambient aerosol dataset. A larger number of degrees of freedom in the vector-matrix model enable fitting real variations in factor size distributions, but also make the model susceptible to fitting noise in the dataset, giving some unphysical results. For this dataset and model, more physically meaningful results were obtained by partially constraining the factor mass spectra using a priori information and a new regularization method. We find four factors with each model: hydrocarbon-like organic aerosol (HOA, biomass-burning organic aerosol (BBOA, oxidized organic aerosol (OOA, and a locally occurring organic aerosol (LOA. These four factors have previously been reported from 2-dimensional factor analysis of the high-resolution mass spectral dataset from this study. The size distributions of these four factors are consistent with previous reports for these particle types. Both 3-D models produce useful results, but the vector-matrix model captures real variability in the size distributions that cannot be captured by the

  1. Three-dimensional factorization of size-resolved organic aerosol mass spectra from Mexico City

    Directory of Open Access Journals (Sweden)

    I. M. Ulbrich

    2011-07-01

    Full Text Available A size-resolved submicron organic aerosol composition dataset from a high-resolution time-of-flight mass spectrometer (HR-ToF-AMS collected in Mexico City during the MILAGRO campaign in March 2006 is analyzed using 3-dimensional (3-D factorization models. A method for estimating the precision of the size-resolved composition data for use with the factorization models is presented here for the first time. Two 3-D models are applied to the dataset. One model is a 3-vector decomposition (PARAFAC model, which assumes that each chemical component has a constant size distribution over all time steps. The second model is a vector-matrix decomposition (Tucker 1 model that allows a chemical component to have a size distribution that varies in time. To our knowledge, this is the first report of an application of 3-D factorization models to data from fast aerosol instrumentation; it is also the first application of this vector-matrix model to any ambient aerosol dataset. A larger number of degrees of freedom in the vector-matrix model enable fitting real variations in factor size distributions, but also make the model susceptible to fitting noise in the dataset, giving some unphysical results. For this dataset and model, more physical results were obtained by partially constraining the factor mass spectra using a priori information and a new regularization method. We find four factors with each model: hydrocarbon-like organic aerosol (HOA, biomass-burning organic aerosol (BBOA, oxidized organic aerosol (OOA, and a locally occurring organic aerosol (LOA. These four factors have previously been reported from 2-dimensional factor analysis of the high-resolution mass spectral dataset from this study. The size distributions of these four factors are consistent with previous reports for these particle types. Both 3-D models produce useful results, but the vector-matrix model captures real variability in the size distributions that cannot be captured by the 3

  2. Assessment of the. pi. -acceptor capability of selected ligands based on the photoelectron spectra of ruthenium ammine complexes

    Energy Technology Data Exchange (ETDEWEB)

    Shepherd, R. E.; Proctor, A.; Henderson, W.W.; Myser, T.K.

    1987-07-29

    ESCA spectra have been recorded for a series of Ru/sup II/ and Ru/sup III/ ammine complexes of general formula ((NH/sub 3/)/sub 5/RuL)X/sub n/ (X/sup -/ = PF/sub 6//sup -/, Cl/sup -/). Binding energy regions of the C/sub 1s/, Ru/sub 3d3/s/, and Ru/sub 3d5/s/, and Ru/sub 3p3/2/ photopeaks were studied. Binding energies were determined by using nonlinear-least-squares curve fitting. ..delta.. equal to the binding energy difference for (C/sub 1s/ - Ru/sub 3d5/2/) has been used to assign a fractional increase in charge at the Ru/sup II/ center when L = a series of ..pi..-acceptor ligands: N-methylpyrazinium (CH/sub 3/pz/sup +/), CO dimethyl acetylenedicarboxylate ester (dmad), CO, pyrazine (pz), pyridine (py), and CH/sub 3/CN. Authentic Ru/sup II/ and Ru/sup III/ oxidation states were assumed for (Ru(en)/sub 3/)ZnCl/sub 4/, ..delta.. = 5.1 eV, and (Ru(NH/sub 3/)/sub 6/)Cl/sub 3/, ..delta.. = 2.5 eV, respectively. The ..pi..-acceptor order and effective Ru oxidation state were determined to be as follows: CH/sub 3/pz/sup +/, 3.01 > CO, 2.88 > dmad, 2.73 > pz, 2.51 > CH/sub 3/CN, 2.31 > py, 2.20. ..delta.. was also found to be linear in the value of E/sub 1/2/ for the (NH/sub 3/)/sub 5/RuL/sup 3+/2+/ couple. ..pi..-Donor ligands exhibit little influence on ..delta.. for Ru/sup III/ derivatives; ..delta.. = 2.4 +/- 0.1 eV for 3,5-dimethylpyrazole, 4-(dimethylamino)pyridine, and 4-aminopyridine.

  3. Computational study on the molecular structures and photoelectron spectra of bimetallic oxide clusters MW2O9(-/0) (M=V, Nb, Ta).

    Science.gov (United States)

    Chen, Wen-Jie; Zhang, Chang-Fu; Zhang, Xian-Hui; Zhang, Yong-Fan; Huang, Xin

    2013-05-15

    Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are carried out to investigate the electronic and structural properties of a series of bimetallic oxide clusters MW2O9(-/0) (M=V, Nb, Ta). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level yield singlet and doublet ground states for the bimetallic anionic and neutral clusters, respectively. All the clusters present the six-membered ring structures with different symmetries, except that the TaW2O9(-) cluster shows a chained style with a penta-coordinated tantalum atom. Spin density analyses reveal oxygen radical species in all neutral clusters, consistent with their structural characteristics. Moreover, additional calculations are performed to study the oxidation reaction of CO molecule with the W3O9(+) cation and the isoelectronic VW2O9 cluster, and results indicate that the introduction of vanadium at tungsten site can efficiently improve the oxidation reactivity. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Computational study on the molecular structures and photoelectron spectra of bimetallic oxide clusters MWO9-/0 (M = V, Nb, Ta)

    Science.gov (United States)

    Chen, Wen-Jie; Zhang, Chang-Fu; Zhang, Xian-Hui; Zhang, Yong-Fan; Huang, Xin

    2013-05-01

    Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are carried out to investigate the electronic and structural properties of a series of bimetallic oxide clusters MWO9-/0 (M = V, Nb, Ta). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level yield singlet and doublet ground states for the bimetallic anionic and neutral clusters, respectively. All the clusters present the six-membered ring structures with different symmetries, except that the TaWO9- cluster shows a chained style with a penta-coordinated tantalum atom. Spin density analyses reveal oxygen radical species in all neutral clusters, consistent with their structural characteristics. Moreover, additional calculations are performed to study the oxidation reaction of CO molecule with the WO9+ cation and the isoelectronic VW2O9 cluster, and results indicate that the introduction of vanadium at tungsten site can efficiently improve the oxidation reactivity.

  5. Theoretical studies on the electronic structures and photoelectron spectra of tri-rhenium oxide clusters: Re3On- and Re3On (n = 1-6)

    Science.gov (United States)

    Zhou, Qi; Gong, Wei-Chao; Xie, Lu; Zheng, Cun-Gong; Zhang, Wei; Wang, Bin; Zhang, Yong-Fan; Huang, Xin

    2014-01-01

    Density functional theory (DFT) calculations are performed to study the structural and electronic properties of tri-rhenium oxide clusters Re3On-/0 (n = 1-6). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level are carried out to search for the global minima for both the anions and the neutrals. For the anions, the first two O atoms prefer the same corner position of a Re3 triangle. Whereas, Re3O3- possesses a C2v symmetry with one bridging and two terminal O atoms. The next three O atoms (n = 4-6) are adding sequentially on the basis of Re3O3- motif, i.e., adding one terminal O atom for Re3O4-, one terminal and one bridging O atoms for Re3O5-, and one terminal and two bridging O atoms for Re3O6-, respectively. Their corresponding neutral species are similar to the anions in geometry except Re3O4 and Re3O5. Molecular orbital analyses are employed to investigate the chemical bonding and structural evolution in these tri-rhenium oxide clusters.

  6. Theoretical characterization of four distinct isomer types in hydrated-electron clusters, and proposed assignments for photoelectron spectra of water cluster anions.

    Science.gov (United States)

    Jacobson, Leif D; Herbert, John M

    2011-12-14

    Water cluster anions, (H(2)O)(N)(-), are examined using mixed quantum/classical molecular dynamics based on a one-electron pseudopotential model that incorporates many-body polarization and predicts vertical electron detachment energies (VDEs) with an accuracy of ~0.1 eV. By varying the initial conditions under which the clusters are formed, we are able to identify four distinct isomer types that exhibit different size-dependent VDEs. On the basis of a strong correlation between the electron's radius of gyration and its optical absorption maximum, and extrapolating to the bulk limit (N → ∞), our analysis supports the assignment of the "isomer Ib" data series, observed in photoelectron spectra of very cold clusters, as arising from cavity-bound (H(2)O)(N)(-) cluster isomers. The "isomer I" data reported in warmer experiments are assigned to surface-bound isomers in smaller clusters, transitioning to partially embedded isomers in larger clusters. The partially embedded isomers are characterized by a partially formed solvent cavity at the cluster surface, and they are spectroscopically quite similar to internalized cavity isomers. These assignments are consistent with various experimental data, and our theoretical characterization of these isomers sheds new light on a long-standing assignment problem. © 2011 American Chemical Society

  7. Photoelectron Spectroscopy of Substituted Phenylnitrenes

    Science.gov (United States)

    Wijeratne, Neloni R.; Fonte, Maria Da; Wenthold, Paul G.

    2009-06-01

    Nitrenes are unusual molecular structures with unfilled electronic valences that are isoelectronic with carbenes. Although, both can be generated by either thermal or photochemical decomposition of appropriate precursors they usually exhibit different reactivities. In this work, we carry out spectroscopic studies of substituted phenylnitrene to determine how the introduction of substituents will affect the reactivity and its thermochemical properties. All studies were carried out by using the newly constructed time-of-flight negative ion photoelectron spectrometer (NIPES) at Purdue University. The 355 nm photoelectron spectra of the o-, m-, and p-chlorophenyl nitrene anions are fairly similar to that measured for phenylnitrene anion. All spectra show low energy triplet state and a high energy singlet state. The singlet state for the meta isomer is well-resolved, with a well defined origin and observable vibrational structure. Whereas the singlet states for the ortho and para isomers have lower energy onsets and no resolved structure. The isomeric dependence suggests that the geometry differences result from the resonance interaction between the nitrogen and the substituent. Quinoidal resonance structures are possible for the open-shell singlet states of the o- and p-chlorinated phenyl nitrenes. The advantages of this type of electronic structures for the open-shell singlet states is that the unpaired electrons can be more localized on separate atoms in the molecules, minimizing the repulsion between. Because the meta position is not in resonance with the nitrenes, substitution at that position should not affect the structure of the open-shell singlet state. The measured electron affinities (EA) of the triplet phenylnitrenes are in excellent agreement with the values predicted by electronic structure calculations. The largest EA, 1.82 eV is found for the meta isomer, with para being the smallest, 1.70 eV.

  8. Core-level spectra and binding energies of transition metal nitrides by non-destructive x-ray photoelectron spectroscopy through capping layers

    Science.gov (United States)

    Greczynski, G.; Primetzhofer, D.; Lu, J.; Hultman, L.

    2017-02-01

    We present the first measurements of x-ray photoelectron spectroscopy (XPS) core level binding energies (BE:s) for the widely-applicable group IVb-VIb polycrystalline transition metal nitrides (TMN's) TiN, VN, CrN, ZrN, NbN, MoN, HfN, TaN, and WN as well as AlN and SiN, which are common components in the TMN-based alloy systems. Nitride thin film samples were grown at 400 °C by reactive dc magnetron sputtering from elemental targets in Ar/N2 atmosphere. For XPS measurements, layers are either (i) Ar+ ion-etched to remove surface oxides resulting from the air exposure during sample transfer from the growth chamber into the XPS system, or (ii) in situ capped with a few nm thick Cr or W overlayers in the deposition system prior to air-exposure and loading into the XPS instrument. Film elemental composition and phase content is thoroughly characterized with time-of-flight elastic recoil detection analysis (ToF-E ERDA), Rutherford backscattering spectrometry (RBS), and x-ray diffraction. High energy resolution core level XPS spectra acquired with monochromatic Al Kα radiation on the ISO-calibrated instrument reveal that even mild etching conditions result in the formation of a nitrogen-deficient surface layer that substantially affects the extracted binding energy values. These spectra-modifying effects of Ar+ ion bombardment increase with increasing the metal atom mass due to an increasing nitrogen-to-metal sputter yield ratio. The superior quality of the XPS spectra obtained in a non-destructive way from capped TMN films is evident from that numerous metal peaks, including Ti 2p, V 2p, Zr 3d, and Hf 4f, exhibit pronounced satellite features, in agreement with previously published spectra from layers grown and analyzed in situ. In addition, the N/metal concentration ratios are found to be 25-90% higher than those obtained from the corresponding ion-etched surfaces, and in most cases agree very well with the RBS and ToF-E ERDA values. The N 1 s BE:s extracted from

  9. Time-Resolved Raman Spectra Measured with an Aerosol Raman Spectrometer

    Science.gov (United States)

    Videen, G.; Doughty, D., III; Hill, S. C.; Wetmore, A.; James, D.

    2016-12-01

    Raman spectroscopy yields information about the composition of atmospheric particles, but generally requires offline analysis. To examine temporal trends in aerosol composition we use an automated aerosol Raman spectrometer (Battelle, Columbus, OH) which semi-continuously samples aerosol particles onto a metallized tape and within a few minutes measures the Raman spectra of these. We collected particles (24 hr at 15 minute intervals), clustered their Raman spectra, noted particle composition of many of them, and examined the time variations of numbers of spectra indicating different particle types. We discuss contemporaneous aerosol measurements, the heterogeneity of many particles as indicated by their Raman spectra, and the prevalence of Raman spectra similar to humic-like substances or soot, which we suggest may be related to the relatively large Raman cross sections of materials with extensively conjugated sp2 bonds.

  10. The interfacial and surface properties of thin Fe and Gd films grown on W(110) as studied by scanning tunneling microscopy, site-resolved photoelectron diffraction, and spin polarized photoelectron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Tober, E.D. [Univ. of California, Davis, CA (US). Office of Graduate Studies

    1997-06-01

    Combined scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) measurements from Gd films grown on W(110) prepared with and without annealing have been used to provide a detailed picture of the growth of such films, permitting a quantitative structural explanation for previously-measured magnetic properties and the identification of a new two-dimensional structure for the first monolayer. The analysis of the film roughness of room-temperature-grown films as a function of coverage and lateral length scale reveals that the growing Gd surface follows scaling laws for a self-affine surface. Annealing these as-deposited films at elevated temperatures is found to drastically alter the morphology of the films, as seen by both STM and LEED. Nanometer-scale islands of relatively well-defined size and shape are observed under certain conditions. Finally, the first monolayer of Gd is observed to form a (7x14) superstructure with pseudo-(7x7) symmetry that is consistent with a minimally-distorted hexagonal two-dimensional Gd(0001) film. Furthermore, a new beamline and photoelectron spectrometer/diffractometer at the Advanced Light Source have been used to obtain full-solid-angle and site-specific photoelectron diffraction (PD) data from interface W atoms just beneath (1x1) Fe and (7x14) Gd monolayers on W(110) by utilizing the core level shift in the W 4f{sub 7/2} spectrum. A comparison of experiment with multiple scattering calculations permits determining the Fe adsorption site and the relative interlayer spacing to the first and second W layers. These Fe results are also compared to those from the very different Gd overlayer and from the clean W(110) surface. Such interface PD measurements show considerable promise for future studies. Finally, the rare-earth ferromagnetic system of Gd(0001) has been examined through the use of spin polarized photoelectron diffraction from the Gd 4s and 5s photoelectron multiplets.

  11. The interfacial and surface properties of thin Fe and Gd films grown on W(110) as studied by scanning tunneling microscopy, site-resolved photoelectron diffraction, and spin polarized photoelectron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Tober, Eric D. [Univ. of California, Davis, CA (United States)

    1997-06-01

    Combined scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) measurements from Gd films grown on W(110) prepared with and without annealing have been used to provide a detailed picture of the growth of such films, permitting a quantitative structural explanation for previously-measured magnetic properties and the identification of a new two-dimensional structure for the first monolayer. The analysis of the film roughness of room-temperature-grown films as a function of coverage and lateral length scale reveals that the growing Gd surface follows scaling laws for a self-affine surface. Annealing these as-deposited films at elevated temperatures is found to drastically alter the morphology of the films, as seen by both STM and LEED. Nanometer-scale islands of relatively well-defined size and shape are observed under certain conditions. Finally, the first monolayer of Gd is observed to form a (7x14) superstructure with pseudo-(7x7) symmetry that is consistent with a minimally-distorted hexagonal two-dimensional Gd(0001) film. Furthermore, a new beamline and photoelectron spectrometer/diffractometer at the Advanced Light Source have been used to obtain full-solid-angle and site-specific photoelectron diffraction (PD) data from interface W atoms just beneath (1x1) Fe and (7x14) Gd monolayers on W(110) by utilizing the core level shift in the W 4f7/2 spectrum. A comparison of experiment with multiple scattering calculations permits determining the Fe adsorption site and the relative interlayer spacing to the first and second W layers. These Fe results are also compared to those from the very different Gd overlayer and from the clean W(110) surface. Such interface PD measurements show considerable promise for future studies. Finally, the rare-earth ferromagnetic system of Gd(0001) has been examined through the use of spin polarized photoelectron diffraction from the Gd 4s and 5s photoelectron multiplets.

  12. Hard X-ray photoelectron spectra (HXPES) of bulk non-conductor vitreous SiO{sub 2}: Minimum linewidths and surface chemical shifts

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Y.F., E-mail: Yongfeng.hu@lightsource.ca [Canadian Light Source, Saskatoon, SK (Canada); Xiao, Q.; Wang, D.; Cui, X. [Canadian Light Source, Saskatoon, SK (Canada); Nesbitt, H.W. [Department of Earth Sciences, University of Western Ontario, London, ONT (Canada); Bancroft, G.M. [Department of Chemistry, University of Western Ontario, London, ONT (Canada)

    2015-07-15

    Highlights: • Electronic structure of non-conducting glass studied by hard X-ray photoelectron spectroscopy. • A thin film of Cr was deposited on the vitreous SiO{sub 2} glass to overcome the sample charging. • Excellent O 1s and Si 1s linewidths were obtained, matching those reported using the laboratory based Kratos Axis Ultra spectrometer equipped with a magnetic compensation system. • The bulk and interface states of non-conducting samples are studied as a function of photon energy. - Abstract: Hard X-ray photoelectron spectra (2200 eV to 5000 eV photon energies) have been obtained for the first time on a bulk non-conductor, vitreous SiO{sub 2}, on a high resolution (E/ΔE of 10,000) synchrotron beamline at the Canadian Light Source (CLS). To minimize charging and differential charging, the SiO{sub 2} was coated with very thin layers (0.5 to 1.5 nm) of Cr metal. The O 1s linewidth obtained at 2500 eV photon energy was 1.26 eV—the minimum linewidth for SiO{sub 2}—and in good agreement with that obtained at 1486 eV on a Kratos Axis Ultra spectrometer equipped with a magnetic charge compensation system. The Si 1s linewidth of 1.5 eV, somewhat broader than that previously obtained at 1486 eV on the Si 2p{sub 3/2} line of 1.16 eV, is mainly due to the much larger inherent Si 1s linewidth (0.5 eV) compared to the inherent Si 2p linewidth (<0.1 eV). Both linewidths are dominated by the large final state vibrational broadening previously described. The Cr coating produces surface monolayers of interfacial Cr “suboxide” (Cr-subox), Cr metal, and a surface Cr oxide (Cr-surfox). Cr-subox (Si−O−Cr) gives rise to the weak near-surface Si 1s peak, while both oxides give rise to both the weak surface O 1s peak and the Cr 2p oxide peak. Both the O 1s and Si 1s surface peaks are shifted by ∼2 eV relative to the large bulk Si 1s and O 1s peaks. The weak Si 1s and O 1s surface peaks along with the Cr 2p oxide peak decrease in intensity greatly as the photon

  13. Negative ion photoelectron spectroscopic studies of transition metal cluster

    Science.gov (United States)

    Marcy, Timothy Paul

    The studies reported in this thesis were performed using a negative ion photoelectron spectrometer consisting of a cold cathode DC discharge ion source, a flowing afterglow ion-molecule reactor, a magnetic sector mass analyzer, an argon ion laser for photodetachment and a hemispherical electron kinetic energy analyzer and microchannel plate detector for photoelectron spectrum generation. The 476.5 nm (2.601 eV), 488.0 nm (2.540 eV) and 514.5 nm (2.410 eV) negative ion photoelectron spectra of VMn are reported and compared to the previously studied spectra of isoelectronic Cr2.1 The photoelectron spectra are remarkably similar to those of Cr2 in electron affinity and vibrational frequencies. The 488.0 nm photoelectron spectra and electron affinities of Nb n- (n = 1 - 9) are reported with discussion of observed vibrational structure. There are transitions to several electronic states of Nb2 in the reported spectra with overlapping vibrational progressions. The spectra of Nb3, Nb4 and Nb6 show partially resolved vibrational structure in the transitions to the lowest observed electronic state of each cluster. There is a single distinct active vibrational mode in the transition to the ground state of Nb8. Spin-orbit energies of Nb- are also reported. The 488.0 nm negative ion photoelectron spectra of Nb3H(D) are reported and compared to those of Nb3. There is a single vibrational mode active in the spectra of Nb3H(D) which is very similar to the most distinct mode active in the spectrum of Nb3. The 488.0 nm photoelectron spectra of the NbxCyH(D) y- (x = 1, 2, 3, y = 2, 4, 6) dehydrogenated products of the reactions of ethylene with niobium cluster anions are reported. Temperature studies of some of these species give evidence for the presence of multiple isomers of each molecule in the ion beam. The spectra of NbC6H(D) 6 are identical to those obtained from the reactions of benzene with niobium clusters and indicate that benzene is being formed from ethylene in the flow

  14. X-ray diffraction, X-ray photoelectron spectra, crystal structure, and optical properties of centrosymmetric strontium borate Sr2B16O26.

    Science.gov (United States)

    Reshak, Ali Hussain; Auluck, S; Kityk, I V; Chen, Xuean

    2009-07-09

    We report results of X-ray diffraction (XRD) and valence band X- ray photoelectron (VB-XPS) spectra for strontium borate Sr(2)B(16)O(26). The X-ray structural analysis shows that the single crystals of Sr(2)B(16)O(26) crystallize in the monoclinic space group P2(1)/c with a = 8.408(1) A, b = 16.672(1) A, c = 13.901(2) A, beta = 106.33(1) degrees , and Z = 4. The crystal structure consists of a 3D network of the complex borate anion [B(16)O(20)O(12/2)](4-), formed by 12 BO(3) triangles and four BO(4) tetrahedra, which can be viewed as three linked [B(3)O(3)O(4/2)](-) triborate groups bonded to one pentaborate [B(5)O(6)O(4/2)](-) group and two BO(3) triangles. Using this structure, we have performed theoretical calculations using the all-electron full potential linearized augmented plane wave (FP-LAPW) method for the band structure, density of states, electron charge density, and the frequency-dependent optical properties. Our experimental VB-XPS of Sr(2)B(16)O(26) is compared with results of our FP-LAPW calculations. Our calculations show that the valence band maximum (VBM) and conduction band minimum (CBM) are located at Gamma of the Brillouin zone (BZ) resulting in a direct energy gap of about 5.31 eV. Our measured VB-XPS show reasonable agreement with our calculated total density of states for the valence band that is attributed to the use of the full potential method.

  15. Calculating time-resolved differential absorbance spectra for ultrafast pump-probe experiments with surface hopping trajectories

    Energy Technology Data Exchange (ETDEWEB)

    Petit, Andrew S.; Subotnik, Joseph E. [Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104 (United States)

    2014-10-21

    We report a surface hopping approach for modeling the full time- and frequency-resolved differential absorbance spectra (beyond the inhomogenous limit) obtained in ultrafast pump-probe experiments. In our approach, we combine dynamical information obtained from ensembles of classical trajectories propagated on the ground and on the excited potential energy surfaces to directly calculate optical response functions and hence spectral lineshapes. We demonstrate that our method is exact for the model problem of two shifted harmonic potentials with identical harmonic frequencies in the absence of electronic relaxation. We then consider a model three state system with electronic relaxation and show that our method is able to capture the effects of nonadiabatic excited state dynamics on the time-dependent differential absorbance spectra. Furthermore, by comparing our spectra against those spectra calculated with either an (1) inhomogenous expression, (2) ground-state Kubo theory, or (3) excited-state Kubo theory, we show that including dynamical information from both the ground and excited potential energy surfaces significantly improves the reliability of the semiclassical approximations. As such, our surface hopping method should find immediate use in modeling the time-dependent differential abosrbance spectra of ultrafast pump-probe experiments.

  16. FT-IR reflection spectra of single crystals: resolving phonons of different symmetry without using polarised radiation

    Directory of Open Access Journals (Sweden)

    METODIJA NAJDOSKI

    2000-07-01

    Full Text Available Fourier-transform infrared (FT-IR reflection spectra, asquired at nearnormal incidence, were recorded from single crystals belonging to six crystal systems: CsCr(SO42.12H2O (alum, cubic, K2CuCl2·2H2O (Mitscherlichite, tetragonal, CaCO3 (calcite, hexagonal, KHSO4 (mercallite, orthorhombic, CaSO4·2H2O (gypsum, monoclinic and CuSO4·5H2O (chalcantite, triclinic. The acquired IR reflection spectra were further transformed into absorption spectra, employing the Kramers-Kronig transformation. Except for the cubic alums, the spectra strongly depend on the crystal face from which they were recorded; this is a consequence of anisotropy. Phonons of a given symmetry (E-species, in tetragonal/hexagonal and B-species, in monoclinic crystals may be resolved without using a polariser. The spectrum may be simplified in the case of an orthorhombic crystal, as well. The longitudinal-optical (LO and transversal-optical (TO mode frequencies were calculated in the case of optically isotropic and the simplified spectra of optically uniaxial crystals.

  17. Maximum information photoelectron metrology

    CERN Document Server

    Hockett, P; Wollenhaupt, M; Baumert, T

    2015-01-01

    Photoelectron interferograms, manifested in photoelectron angular distributions (PADs), are a high-information, coherent observable. In order to obtain the maximum information from angle-resolved photoionization experiments it is desirable to record the full, 3D, photoelectron momentum distribution. Here we apply tomographic reconstruction techniques to obtain such 3D distributions from multiphoton ionization of potassium atoms, and fully analyse the energy and angular content of the 3D data. The PADs obtained as a function of energy indicate good agreement with previous 2D data and detailed analysis [Hockett et. al., Phys. Rev. Lett. 112, 223001 (2014)] over the main spectral features, but also indicate unexpected symmetry-breaking in certain regions of momentum space, thus revealing additional continuum interferences which cannot otherwise be observed. These observations reflect the presence of additional ionization pathways and, most generally, illustrate the power of maximum information measurements of th...

  18. Imaging molecular structure through femtosecond photoelectron diffraction on aligned and oriented gas-phase molecules.

    Science.gov (United States)

    Boll, Rebecca; Rouzée, Arnaud; Adolph, Marcus; Anielski, Denis; Aquila, Andrew; Bari, Sadia; Bomme, Cédric; Bostedt, Christoph; Bozek, John D; Chapman, Henry N; Christensen, Lauge; Coffee, Ryan; Coppola, Niccola; De, Sankar; Decleva, Piero; Epp, Sascha W; Erk, Benjamin; Filsinger, Frank; Foucar, Lutz; Gorkhover, Tais; Gumprecht, Lars; Hömke, André; Holmegaard, Lotte; Johnsson, Per; Kienitz, Jens S; Kierspel, Thomas; Krasniqi, Faton; Kühnel, Kai-Uwe; Maurer, Jochen; Messerschmidt, Marc; Moshammer, Robert; Müller, Nele L M; Rudek, Benedikt; Savelyev, Evgeny; Schlichting, Ilme; Schmidt, Carlo; Scholz, Frank; Schorb, Sebastian; Schulz, Joachim; Seltmann, Jörn; Stener, Mauro; Stern, Stephan; Techert, Simone; Thøgersen, Jan; Trippel, Sebastian; Viefhaus, Jens; Vrakking, Marc; Stapelfeldt, Henrik; Küpper, Jochen; Ullrich, Joachim; Rudenko, Artem; Rolles, Daniel

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray free-electron laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C(8)H(5)F) and dissociating, laser-aligned 1,4-dibromobenzene (C(6)H(4)Br(2)) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.

  19. Imaging Molecular Structure through Femtosecond Photoelectron Diffraction on Aligned and Oriented Gas-Phase Molecules

    CERN Document Server

    Boll, R; Adolph, M; Anielski, D; Aquila, A; Bari, S; Bomme, C; Bostedt, C; Bozek, J D; Chapman, H N; Christensen, L; Coffee, R; Coppola, N; De, S; Decleva, P; Epp, S W; Erk, B; Filsinger, F; Foucar, L; Gorkhover, T; Gumprecht, L; Hoemke, A; Holmegaard, L; Johnsson, P; Kienitz, J S; Kierspel, T; Krasniqi, F; Kuehnel, K -U; Maurer, J; Messerschmidt, M; Moshammer, R; Mueller, Nele L M; Rudek, B; Savelyev, E; Schlichting, I; Schmidt, C; Scholz, F; Schorb, S; Schulz, J; Seltmann, J; Stener, M; Stern, S; Techert, S; Thogersen, J; Trippel, S; Viefhaus, J; Vrakking, M; Stapelfeldt, H; Kuepper, J; Ullrich, J; Rudenko, A; Rolles, D

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laseraligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.

  20. Comparison of species-resolved energy spectra from ACE EPAM and Van Allen Probes RBSPICE

    Science.gov (United States)

    Patterson, J.; Manweiler, J. W.; Armstrong, T. P.; Lanzerotti, L. J.; Gerrard, A. J.; Gkioulidou, M.

    2013-12-01

    We present a comparison between energy spectra measured by the Advanced Composition Explorer (ACE) Electron Proton Alpha Monitor (EPAM) instrument and the Van Allen Probe Ion Composition Experiment (RBSPICE) for two significant and distinct events in early 2013. The first is an impulsive solar particle event on March 17th. While intense, this event presented no significant surprises in terms of its composition or anisotropy characteristics, thus providing a good baseline for response of the trapped radiation belts as observed by the Van Allen Probes. The second solar event occurred late May 22nd and early May 23rd. This event has a much greater concentration of medium and heavy ions than the St. Patrick's Day event, as well as having very peculiar energy spectra with evidence of two distinct populations. During the St. Patrick's Day Event, the energy spectra for helium, carbon, oxygen, neon, silicon, and iron all show the same spectral power law slope -3.1. The event shows strong anisotropy with intensities differing by a factor of four for both protons and Z>1 ions. The late May event also has strong anisotropy, and in the same directions as the St. Patrick's Day Event, but with very different composition and energy spectra. The spectra are much harder with power law spectral slopes of -0.5. Additionally, there is a significant spectral bump at 3 MeV/nuc for helium that is not present in the spectra of the heavier ions. The intensities of the heavier ions, however, show an increase that is an order of magnitude greater than the increase seen for helium. The March 17 RBSPICE observations show multiple injection events lasting for less than an hour each during the Van Allen Probes B apogees. These injections are seen in protons as well as Helium and only somewhat observed in Oxygen. Spectral slopes for the observations range from approximately -5 during quiet times to double peaked events with a spectral slope of approximately -2 at the beginning of the injection

  1. Hard x-ray photoelectron spectroscopy of chalcopyrite solar cell components

    Science.gov (United States)

    Gloskovskii, A.; Jenkins, C. A.; Ouardi, S.; Balke, B.; Fecher, G. H.; Dai, X.-F.; Gruhn, T.; Johnson, B.; Lauermann, I.; Caballero, R.; Kaufmann, C. A.; Felser, C.

    2012-02-01

    Hard x-ray photoelectron spectroscopy is used to examine the partial density of states of Cu(In,Ga)Se2 (CIGSe), a semiconducting component of solar cells. The investigated, thin Cu(In,Ga)Se2 films were produced by multi-stage co-evaporation. Details of the measured core level and valence band spectra are compared to the calculated density of states. The semiconducting type electronic structure of Cu(In,Ga)Se2 is clearly resolved in the hard x-ray photoelectron spectra.

  2. Modelling high-resolution spatially-resolved Supernova Remnant spectra with the Sardinia Radio Telescope

    CERN Document Server

    Loru, Sara; Egron, Elise; Iacolina, Noemi; Righini, Simona; Marongiu, Marco; Mulas, Sara; Murtas, Giulia; Simeone, Davide; Pilia, Maura; Bachetti, Matteo; Trois, Alessio; Ricci, Roberto; Melis, Andrea; Concu, Raimondo

    2016-01-01

    Supernova Remnants (SNRs) exhibit spectra featured by synchrotron radio emission arising from the relativistic electrons, and high-energy emission from both leptonic (Bremsstrahlung and Inverse Compton) and hadronic processes (${\\pi}^0$ mesons decay) which are a direct signature of cosmic rays acceleration. Thanks to radio single-dish imaging observations obtained in three frequency bands (1.6, 7, 22 GHz) with the Sardinia Radio Telescope (www.srt.inaf.it), we can model different SNR regions separately. Indeed, in order to disentangle interesting and peculiar hadron contributions in the high-energy spectra (gamma-ray band) and better constrain SNRs as cosmic rays emitters, it is crucial to fully constrain lepton contributions first through radio-observed parameters. In particular, the Bremsstrahlung and Inverse Compton bumps observed in gamma-rays are bounded to synchrotron spectral slope and cut-off in the radio domain. Since these parameters vary for different SNR regions and electron populations, spatially...

  3. Vibronic-structure tracking: A shortcut for vibrationally resolved UV/Vis-spectra calculations

    Energy Technology Data Exchange (ETDEWEB)

    Barton, Dennis; König, Carolin; Neugebauer, Johannes, E-mail: j.neugebauer@uni-muenster.de [Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster (Germany)

    2014-10-28

    The vibrational coarse structure and the band shapes of electronic absorption spectra are often dominated by just a few molecular vibrations. By contrast, the simulation of the vibronic structure even in the simplest theoretical models usually requires the calculation of the entire set of normal modes of vibration. Here, we exploit the idea of the mode-tracking protocol [M. Reiher and J. Neugebauer, J. Chem. Phys. 118, 1634 (2003)] in order to directly target and selectively calculate those normal modes which have the largest effect on the vibronic band shape for a certain electronic excitation. This is achieved by defining a criterion for the importance of a normal mode to the vibrational progressions in the absorption band within the so-called “independent mode, displaced harmonic oscillator” (IMDHO) model. We use this approach for a vibronic-structure investigation for several small test molecules as well as for a comparison of the vibronic absorption spectra of a truncated chlorophyll a model and the full chlorophyll a molecule. We show that the method allows to go beyond the often-used strategy to simulate absorption spectra based on broadened vertical excitation peaks with just a minimum of computational effort, which in case of chlorophyll a corresponds to about 10% of the cost for a full simulation within the IMDHO approach.

  4. Molecular component distribution imaging of living cells by multivariate curve resolution analysis of space-resolved Raman spectra.

    Science.gov (United States)

    Ando, Masahiro; Hamaguchi, Hiro-o

    2014-01-01

    Label-free Raman microspectroscopy combined with a multivariate curve resolution (MCR) analysis can be a powerful tool for studying a wide range of biomedical molecular systems. The MCR with the alternating least squares (MCR-ALS) technique, which retrieves the pure component spectra from complicatedly overlapped spectra, has been successfully applied to in vivo and molecular-level analysis of living cells. The principles of the MCR-ALS analysis are reviewed with a model system of titanium oxide crystal polymorphs, followed by two examples of in vivo Raman imaging studies of living yeast cells, fission yeast, and budding yeast. Due to the non-negative matrix factorization algorithm used in the MCR-ALS analysis, the spectral information derived from this technique is just ready for physical and/or chemical interpretations. The corresponding concentration profiles provide the molecular component distribution images (MCDIs) that are vitally important for elucidating life at the molecular level, as stated by Schroedinger in his famous book, "What is life?" Without any a priori knowledge about spectral profiles, time- and space-resolved Raman measurements of a dividing fission yeast cell with the MCR-ALS elucidate the dynamic changes of major cellular components (lipids, proteins, and polysaccharides) during the cell cycle. The MCR-ALS technique also resolves broadly overlapped OH stretch Raman bands of water, clearly indicating the existence of organelle-specific water structures in a living budding yeast cell.

  5. Data-driven signal-resolving approaches of infrared spectra to explore the macroscopic and microscopic spatial distribution of organic and inorganic compounds in plant.

    Science.gov (United States)

    Chen, Jian-bo; Sun, Su-qin; Zhou, Qun

    2015-07-01

    The nondestructive and label-free infrared (IR) spectroscopy is a direct tool to characterize the spatial distribution of organic and inorganic compounds in plant. Since plant samples are usually complex mixtures, signal-resolving methods are necessary to find the spectral features of compounds of interest in the signal-overlapped IR spectra. In this research, two approaches using existing data-driven signal-resolving methods are proposed to interpret the IR spectra of plant samples. If the number of spectra is small, "tri-step identification" can enhance the spectral resolution to separate and identify the overlapped bands. First, the envelope bands of the original spectrum are interpreted according to the spectra-structure correlations. Then the spectrum is differentiated to resolve the underlying peaks in each envelope band. Finally, two-dimensional correlation spectroscopy is used to enhance the spectral resolution further. For a large number of spectra, "tri-step decomposition" can resolve the spectra by multivariate methods to obtain the structural and semi-quantitative information about the chemical components. Principal component analysis is used first to explore the existing signal types without any prior knowledge. Then the spectra are decomposed by self-modeling curve resolution methods to estimate the spectra and contents of significant chemical components. At last, targeted methods such as partial least squares target can explore the content profiles of specific components sensitively. As an example, the macroscopic and microscopic distribution of eugenol and calcium oxalate in the bud of clove is studied.

  6. Molecular-orbital decomposition of the ionization continuum for a diatomic molecule by angle- and energy-resolved photoelectron spectroscopy. I. Formalism

    Science.gov (United States)

    Park, Hongkun; Zare, Richard N.

    1996-03-01

    A theoretical formalism is developed for the quantum-state-specific photoelectron angular distributions (PADs) from the direct photoionization of a diatomic molecule in which both the ionizing state and the state of the ion follow Hund's case (b) coupling. The formalism is based on the molecular-orbital decomposition of the ionization continuum and therefore fully incorporates the molecular nature of the photoelectron-ion scattering within the independent electron approximation. The resulting expression for the quantum-state-specific PADs is dependent on two distinct types of dynamical quantities, one that pertains only to the ionization continuum and the other that depends both on the ionizing state and the ionization continuum. Specifically, the electronic dipole-moment matrix element rlλ exp(iηlλ) for the ejection of a photoelectron with orbital angular momentum quantum number l making a projection λ on the internuclear axis is expressed as ΣαλŪlαλλ exp (iπτ¯αλλ) Mαλλ, where Ūλ is the electronic transformation matrix, τ¯αλλ is the scattering phase shift associated with the αλth continuum molecular orbital, and Mαλλ is the real electronic dipole-moment matrix element that connects the ionizing orbital to the αλth continuum molecular orbital. Because Ūλ and τ¯αλλ depend only on the dynamics in the ionization continuum, this formalism allows maximal exploitation of the commonality between photoionization processes from different ionizing states. It also makes possible the direct experimental investigation of scattering matrices for the photoelectron-ion scattering and thus the dynamics in the ionization continuum by studying the quantum-state-specific PADs, as illustrated in the companion article on the photoionization of NO.

  7. Vibrationally resolved translational energy release spectra from the ultraviolet photodissociation of methyl mercaptan

    Science.gov (United States)

    Segall, J.; Wen, Y.; Singer, R.; Dulligan, M.; Wittig, C.

    1993-11-01

    Product translational energy release spectra resulting from 248 and 193 nm photodissociation of methyl mercaptan are obtained for the hydrogen atom channels (CH3SH+hν→CH3S+H) by using the high-n Rydberg time-of-flight technique. The spectra exhibit vibrational structure that is assigned to a CH3-S stretch progression. At 248 nm, the progression extends only to v=2, while at 193 nm levels up to approximately v=17 are populated. The progression observed at 193 nm is bimodal, with the higher kinetic energy component showing greater spatial anisotropy than the lower energy component, suggesting that two different processes occurring on different time scales are responsible for the two components. The results at 248 nm are consistent with excitation to a repulsive electronic surface. For 193 nm excitation, the high kinetic energy component is consistent with direct photoexcitation to a repulsive surface and/or rapid intramolecular access to a repulsive surface. The lower kinetic energy component presumably derives from the molecule spending more time on an excited surface. A simple model is applied to estimate the extent of C-S bond extension for the various processes.

  8. Vibrationally resolved translational energy release spectra from the ultraviolet photodissociation of methyl mercaptan

    Energy Technology Data Exchange (ETDEWEB)

    Segall, J.; Wen, Y.; Singer, R.; Dulligan, M.; Wittig, C. (Department of Chemistry, University of Southern California, Los Angeles, California 90089 (United States))

    1993-11-01

    Product translational energy release spectra resulting from 248 and 193 nm photodissociation of methyl mercaptan are obtained for the hydrogen atom channels (CH[sub 3]SH+[ital h][nu][r arrow]CH[sub 3]S+H) by using the high-[ital n] Rydberg time-of-flight technique. The spectra exhibit vibrational structure that is assigned to a CH[sub 3]--S stretch progression. At 248 nm, the progression extends only to [ital v]=2, while at 193 nm levels up to approximately [ital v]=17 are populated. The progression observed at 193 nm is bimodal, with the higher kinetic energy component showing greater spatial anisotropy than the lower energy component, suggesting that two different processes occurring on different time scales are responsible for the two components. The results at 248 nm are consistent with excitation to a repulsive electronic surface. For 193 nm excitation, the high kinetic energy component is consistent with direct photoexcitation to a repulsive surface and/or rapid intramolecular access to a repulsive surface. The lower kinetic energy component presumably derives from the molecule spending more time on an excited surface. A simple model is applied to estimate the extent of C--S bond extension for the various processes.

  9. Time-resolved Absorption Spectra of the Laser-dressed Hydrogen Atom

    Science.gov (United States)

    Murakami, Mitsuko; Chu, Shih-I.

    2013-05-01

    A theoretical study of the transient absorption spectra for the laser-dressed hydrogen atom based on the accurate numerical solution of the time-dependent Schrödinger equation is presented. The timing of absorption is controlled by the time delay between an isolated extreme ultraviolet (XUV) pulse and a dressing infrared (IR) field. We identify two different kinds of physical processes in the spectra. One is the formation of dressed states, signified by the appearance of sidebands between the XUV absorption lines separated by one IR-photon energy. We show that their population is maximized when the XUV pulse coincides with the zero-crossing of the IR field, and that their energy can be manipulated by using a chirped IR field. The other process is the dynamical AC Stark shift induced by the IR field and probed by the XUV pulse. Our calculations indicate that the accidental degeneracy of the hydrogen atom leads to the multiple splittings of each XUV absorption line whose separations change in response to a slowly-varying IR envelope. Furthermore, we observe the Autler-Townes doublets for the n=2 and 3 states using the 656 nm dressing field, but their separation does not agree with the prediction by the conventional 3-level model that neglects the dynamical AC Stark effects.

  10. Synthesis and time-resolved absorption spectra of 1,3,3,5,2’-pentamethylspiro[indolinnaphthooxazine

    Institute of Scientific and Technical Information of China (English)

    张新宇; 金声; 明阳福; 梁永超; 于联合; 樊美公; 骆坚; 姚思德

    1995-01-01

    The title compound 1,3,3,5,2’-pentamethylspirooxazine (I) is synthesized and identified by 1R, 1H NMR and elemental analysis. The time-resolved transient absorption spectra of I are investigated by nanosecond laser flash photolysis. The photolysis of I in solution excited by 248 nm laser pulse results in two different colored species. One of them is a short-lived species (CT intermediate), which has two absorption maxima at 440 and 640 nm in acetonitrile, and 450 and 640 nm in cyclohexane. The corresponding lifetimes are 12 and 0.8 us, respectively. The absorption spectra of CT intermediate are not influenced by solvent polarity. This fact indicates that the structure of CT is between the zwitterionic and quinoidal ones. The much longer lifetime of CT in acetonitrile than in cyclohexane is due to the electron donating effect of methyl in position 5 of indolino ring. The long-lived colored species (>>80 us) proves a planar photomerocyanine (PMC) structure, whose absorption spectra in acetonitrile and cyc

  11. Time-resolved spectra of dense plasma focus using spectrometer, streak camera, and CCD combination

    Energy Technology Data Exchange (ETDEWEB)

    Goldin, F. J. [Livermore Operations, National Security Technologies, LLC, Livermore, California 94550 (United States); Meehan, B. T.; Hagen, E. C. [North Las Vegas Facility, National Security Technologies, LLC, North Las Vegas, Nevada 89030 (United States); Wilkins, P. R. [Lawrence Livermore National Laboratories, Livermore, California 94550 (United States)

    2010-10-15

    A time-resolving spectrographic instrument has been assembled with the primary components of a spectrometer, image-converting streak camera, and CCD recording camera, for the primary purpose of diagnosing highly dynamic plasmas. A collection lens defines the sampled region and couples light from the plasma into a step index, multimode fiber which leads to the spectrometer. The output spectrum is focused onto the photocathode of the streak camera, the output of which is proximity-coupled to the CCD. The spectrometer configuration is essentially Czerny-Turner, but off-the-shelf Nikon refraction lenses, rather than mirrors, are used for practicality and flexibility. Only recently assembled, the instrument requires significant refinement, but has now taken data on both bridge wire and dense plasma focus experiments.

  12. Time-Resolved Spectra of Dense Plasma Focus Using Spectrometer, Streak Camera, CCD Combination

    Energy Technology Data Exchange (ETDEWEB)

    F. J. Goldin, B. T. Meehan, E. C. Hagen, P. R. Wilkins

    2010-10-01

    A time-resolving spectrographic instrument has been assembled with the primary components of a spectrometer, image-converting streak camera, and CCD recording camera, for the primary purpose of diagnosing highly dynamic plasmas. A collection lens defines the sampled region and couples light from the plasma into a step index, multimode fiber which leads to the spectrometer. The output spectrum is focused onto the photocathode of the streak camera, the output of which is proximity-coupled to the CCD. The spectrometer configuration is essentially Czerny–Turner, but off-the-shelf Nikon refraction lenses, rather than mirrors, are used for practicality and flexibility. Only recently assembled, the instrument requires significant refinement, but has now taken data on both bridge wire and dense plasma focus experiments.

  13. Rotationally resolved infrared spectra of the explosive bouquet compounds associated with C-4 explosives

    Science.gov (United States)

    Clasp, Trocia N.; Johnson, Tiffani; Sullivan, Michael N.; Reeve, Scott W.

    2011-05-01

    The explosive material known as Composition C4, or simply C4, is an RDX based military grade explosive. RDX itself possesses a negligible vapor pressure at room temperature suggesting it is not a good target for conventional instruments designed to detect vapor phase chemical compounds. Recent research with canines has indicated that a better approach for detecting explosive vapors such as C4 is to focus on a characteristic mixture of impurities associated with the material. These characteristic mixtures of impurity vapors are referred to by canine researchers as the explosive bouquet and are fairly unique to the specific energetic material. In this paper, we will examine and report rotationally resolved infrared spectral signatures for the known compounds comprising the explosive bouquet for C4 based explosives including isobutylene, 2-ethyl-1-hexanol and cyclohexanone.

  14. Time-resolved fluorescence spectra of cis-stilbene in hexane and acetonitrile

    Science.gov (United States)

    Sajadi, M.; Dobryakov, A. L.; Garbin, E.; Ernsting, N. P.; Kovalenko, S. A.

    2010-04-01

    Transient fluorescence spectra from cis-stilbene in solution are recorded with 0.24 ps instrument response by a Kerr-Shutter upon excitation at 283 and 267 nm. The fluorescence decay shows no dependence on the excitation wavelength and proceeds monoexponentially with 0.21 ps in acetonitrile and 0.75 ps in hexane. No spectral shift or distortion of the fluorescence band is observed during the decay. Fluorescence contribution from 4a,4b-dihydrophenanthrene (DHP), produced in a competing reaction channel, was not detectable. From comparison with trans-fluorescence, the emission oscillator strength of cis-stilbene is determined to be 0.19 in hexane and 0.21 in acetonitrile.

  15. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  16. Time resolved spectra in the infrared absorption and emission from shock heated hydrocarbons. [in interstellar medium

    Science.gov (United States)

    Bauer, S. H.; Borchardt, D. B.

    1990-01-01

    The wavelength range of a previously constructed multichannel fast recording spectrometer was extended to the mid-infrared. With the initial configuration, light intensities were recorded simultaneously with a silicon-diode array simultaneously at 20 adjacent wavelengths, each with a 20-micron time resolution. For studies in the infrared, the silicon diodes were replaced by a 20-element PbSe array of similar dimensions, cooled by a three-stage thermoelectric device. It is proposed that infrared emissions could be due to shock-heated low molecular-weight hydrocarbons. The full Swan band system appeared in time-integrated emission spectra from shock-heated C2H2; no soot was generated. At low resolution, the profiles on the high-frequency side of the black body maximum show no distinctive features. These could be fitted to Planck curves, with temperatures that declined with time from an initial high that was intermediate between T5 (no conversion) and T5(eq).

  17. Exploring the effect of vibronic contributions on light harvesting efficiency of NKX-2587 derivatives through vibrationally resolved electronic spectra

    Science.gov (United States)

    Yang, Pan; Shen, Wei; Li, Ming; He, Rongxing

    2017-01-01

    The vibrationally resolved electronic spectra of five metal-free NKX-2587 derivatives containing heteroatom with different atomic sizes and electronegativity, were simulated within the Franck-Condon approximation including the Herzberg-Teller and Duschinsky effects, aimed at exploring the correlation of vibronic structure associated with the spectrum and efficiency of dye sensitized solar cells (DSSCs). The parameters of short-circuit current density (Jsc) and open circuit voltage (Voc) involving efficiency of DSSCs, such as total dipole moments (μnormal), the light harvesting efficiency (LHE), injection driving force (∆ Ginject), and the number of electrons in the conduction band (nc), were calculated and discussed in detail. Results showed that the heteroatoms in the same period with large size and weak electronegativity and the ones in the same main group with large size and weak electronegativity are beneficial to Voc. The sizes and electronegativity of the heteroatoms have a weak effect on Jsc. The low-frequency modes play important roles in enhancing the intensities of the electronic spectra and structures can affect light harvesting efficiency (LHE). In this sense, our results provided guidance for understanding the sources of spectral intensities of dye molecules, and a valuable help for rational design of new molecules to improve the energy conversion efficiency (η) of DSSCs.

  18. Site-resolved 2H relaxation experiments in solid materials by global line-shape analysis of MAS NMR spectra

    Science.gov (United States)

    Lindh, E. L.; Stilbs, P.; Furó, I.

    2016-07-01

    We investigate a way one can achieve good spectral resolution in 2H MAS NMR experiments. The goal is to be able to distinguish between and study sites in various deuterated materials with small chemical shift dispersion. We show that the 2H MAS NMR spectra recorded during a spin-relaxation experiment are amenable to spectral decomposition because of the different evolution of spectral components during the relaxation delay. We verify that the results are robust by global least-square fitting of the spectral series both under the assumption of specific line shapes and without such assumptions (COmponent-REsolved spectroscopy, CORE). In addition, we investigate the reliability of the developed protocol by analyzing spectra simulated with different combinations of spectral parameters. The performance is demonstrated in a model material of deuterated poly(methacrylic acid) that contains two 2H spin populations with similar chemical shifts but different quadrupole splittings. In 2H-exchanged cellulose containing two 2H spin populations with very similar chemical shifts and quadrupole splittings, the method provides new site-selective information about the molecular dynamics.

  19. Bayesian analysis of resolved stellar spectra: application to MMT/Hectochelle Observations of the Draco dwarf spheroidal

    CERN Document Server

    Walker, Matthew G; Mateo, Mario

    2015-01-01

    We introduce a Bayesian method for fitting faint, resolved stellar spectra in order to obtain simultaneous estimates of redshift and stellar-atmospheric parameters. We apply the method to thousands of spectra---covering 5160-5280 Angs. at resolution R~20,000---that we have acquired with the MMT/Hectochelle fibre spectrograph for red-giant and horizontal branch candidates along the line of sight to the Milky Way's dwarf spheroidal satellite in Draco. The observed stars subtend an area of ~4 deg^2, extending ~3 times beyond Draco's nominal `tidal' radius. For each spectrum we tabulate the first four moments---central value, variance, skewness and kurtosis---of posterior probability distribution functions representing estimates of the following physical parameters: line-of-sight velocity v_los, effective temperature (T_eff), surface gravity (logg) and metallicity ([Fe/H]). After rejecting low-quality measurements, we retain a new sample consisting of 2813 independent observations of 1565 unique stars, including ...

  20. Quantum-based Molecular Dynamics Simulations of Shock-induced Reactions with Time-resolved Raman Spectra

    Science.gov (United States)

    Cawkwell, Marc; Sanville, Edward; Coe, Joshua; Niklasson, Anders

    2012-02-01

    Shock-induced reactions in liquid hydrocarbons have been studied using quantum-based, self-consistent tight-binding (SC-TB) molecular dynamics simulations with an accurate and transferable model for interatomic bonding. Our SC-TB code LATTE enables explicit simulations of shock compression using the universal liquid Hugoniot. Furthermore, the effects of adiabatic shock heating are captured precisely using Niklasson's energy conserving extended Lagrangian Born-Oppenheimer Molecular Dynamics formalism. We have been able to perform relatively large-scale SC-TB simulations by either taking advantage of the sparsity of the density matrix to achieve O(N) performance or by using graphics processing units to accelerate O(N^3) algorithms. We have developed the capability for the on-the-fly computation of Raman spectra from the Fourier transform of the polarizability autocorrelation function via the density matrix perturbation theory of Niklasson and Challacombe. These time-resolved Raman spectra enable us compare the results of our simulations with identical diagnostics collected experimentally. We will illustrate these capabilities with a series of simulations of shock-induced reaction paths in a number of simple molecules.

  1. Automated charge state determination of complex isotope-resolved mass spectra by peak-target Fourier transform.

    Science.gov (United States)

    Chen, Li; Yap, Yee Leng

    2008-01-01

    This study describes a new algorithm for charge state determination of complex isotope-resolved mass spectra. This algorithm is based on peak-target Fourier transform (PTFT) of isotope packets. It is modified from the widely used Fourier transform method because Fourier transform may give ambiguous charge state assignment for low signal-to-noise ratio (S/N) or overlapping isotopic clusters. The PTFT algorithm applies a novel "folding" strategy to enhance peaks that are symmetrically spaced about the targeted peak before applying the FT. The "folding" strategy multiplies each point to the high-m/z side of the targeted peak by its counterpart on the low-m/z side. A Fourier transform of this "folded" spectrum is thus simplified, emphasizing the charge state of the "chosen" ion, whereas ions of other charge states contribute less to the transformed data. An intensity-dependent technique is also proposed for charge state determination from frequency signals. The performance of PTFT is demonstrated using experimental electrospray ionization Fourier transform ion cyclotron resonance mass spectra. The results show that PTFT is robust for charge state determination of low S/N and overlapping isotopic clusters, and also useful for manual verification of potential hidden isotopic clusters that may be missed by the current analysis algorithms, i.e., AID-MS or THRASH.

  2. Photoelectron spectroscopy and density functional theory study of ConO- (n = 1-3)

    Science.gov (United States)

    Li, Ren-Zhong; Liang, Jun; Xu, Xi-Ling; Xu, Hong-Guang; Zheng, Wei-Jun

    2013-06-01

    ConO- (n = 1-3) clusters were investigated with photoelectron spectroscopy and density functional calculations. The vertical detachment energies (VDEs) of ConO- (n = 1-3) were measured to be 1.54 ± 0.04, 1.43 ± 0.08, and 1.42 ± 0.08 eV respectively from their photoelectron spectra. The electron affinity and term energy of CoO were determined to be 1.54 ± 0.04 eV and 0.31 ± 0.04 eV respectively based on the vibrationally resolved photoelectron spectrum of CoO- and theoretical calculations. The structures of ConO- (n = 1-3) were determined by comparison of photoelectron experiments and calculations. The analysis of molecular orbitals shows that the HOMOs of ConO- (n = 1-3) cluster anions are mainly localized on the Co atoms.

  3. Mass spectra of benzaldehyde using time resolved ion trapping mass spectrometer. Jikan bunkai ion trapping shitsuryo bunsekikei ni yoru benzaldehyde no mass spector

    Energy Technology Data Exchange (ETDEWEB)

    Ishigane, M.; Isa, K. (Fukui Univ., Fukui (Japan). Faculty of Education); Nishioka, K. (Fukui Univ., Fukui (Japan). Faculty of Engineering)

    1991-12-28

    An ion trapping mass spectrometer for time resolved analysis has been set up. The time resolved analysis function of this system is excellent and the ion detecting sensitivity is also high. Benzaldehyde is used as the specimen for the measurement of the A group of the mass spectra (m/z 105 106 and 107) by this system and similar mass spectra are obtained at delay time zero to those reported by now. Big changes are observed in the spectra when the delay times are varied. It is found that mass spectra which are different from those reported already are obtained when the mass spectrometer is pulse operated. In other words it can be said that the time dependence of the data on ion decomposition ( fragmentation) and ion/molecule reactions can be obtained in the state where solvent has no influence if this new system is adopted. 6 refs. 12 figs.

  4. High-power, narrow-band, high-repetition-rate, 5.9 eV coherent light source using passive optical cavity for laser-based angle-resolved photoelectron spectroscopy.

    Science.gov (United States)

    Omachi, J; Yoshioka, K; Kuwata-Gonokami, M

    2012-10-08

    We demonstrate a scheme for efficient generation of a 5.9 eV coherent light source with an average power of 23 mW, 0.34 meV linewidth, and 73 MHz repetition rate from a Ti: sapphire picosecond mode-locked laser with an output power of 1 W. Second-harmonic light is generated in a passive optical cavity by a BiB(3)O(6) crystal with a conversion efficiency as high as 67%. By focusing the second-harmonic light transmitted from the cavity into a β-BaB(2)O(4) crystal, we obtain fourth-harmonic light at 5.9 eV. This light source offers stable operation for at least a week. We discuss the suitability of the laser light source for high-resolution angle-resolved photoelectron spectroscopy by comparing it with other sources (synchrotron radiation facilities and gas discharge lamp).

  5. Differences between GaAs/GaInP and GaAs/AlInP interfaces grown by movpe revealed by depth profiling and angle-resolved X-ray photoelectron spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    López-Escalante, M.C., E-mail: mclopez@uma.es [Nanotech Unit, Laboratorio de Materiales y Superficies, Departamento de Ingeniería Química, Facultad de Ciencias, Universidad de Málaga, 29071 Málaga (Spain); Gabás, M. [The Nanotech Unit, Depto. de Física Aplicada I, Andalucía Tech, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga Spain (Spain); García, I.; Barrigón, E.; Rey-Stolle, I.; Algora, C. [Instituto de Energía Solar, Universidad Politécnica de Madrid, Avda. Complutense 30, 28040 Madrid Spain (Spain); Palanco, S.; Ramos-Barrado, J.R. [The Nanotech Unit, Depto. de Física Aplicada I, Andalucía Tech, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga Spain (Spain)

    2016-01-01

    Graphical abstract: - Highlights: • GaAs, AlInP and GaInP epi-layers grown in a MOVPE facility. • GaAs/GaInP and GaAs/AlInP interfaces studied through the combination of angle resolved and depth profile X-ray photoelectros spectroscopies. • GaAs/GaInP interface shows no features appart from GaAs, GaInP and mixed GaInAs or GaInAsP phases. • GaAs/AlInP interface shows traces of an anomalous P environment, probably due to P-P clusters. - Abstract: GaAs/GaInP and GaAs/AlInP interfaces have been studied using photoelectron spectroscopy tools. The combination of depth profile through Ar{sup +} sputtering and angle resolved X-ray photoelectron spectroscopy provides reliable information on the evolution of the interface chemistry. Measurement artifacts related to each particular technique can be ruled out on the basis of the results obtained with the other technique. GaAs/GaInP interface spreads out over a shorter length than GaAs/AlInP interface. The former could include the presence of the quaternary GaInAsP in addition to the nominal GaAs and GaInP layers. On the contrary, the GaAs/AlInP interface exhibits a higher degree of compound mixture. Namely, traces of P atoms in a chemical environment different to the usual AlInP coordination were found at the top of the GaAs/AlInP interface, as well as mixed phases like AlInP, GaInAsP or AlGaInAsP, located at the interface.

  6. Quantum mechanics/molecular mechanics modeling of photoelectron spectra: the carbon 1s core-electron binding energies of ethanol-water solutions.

    Science.gov (United States)

    Löytynoja, T; Niskanen, J; Jänkälä, K; Vahtras, O; Rinkevicius, Z; Ågren, H

    2014-11-20

    Using ethanol-water solutions as illustration, we demonstrate the capability of the hybrid quantum mechanics/molecular mechanics (QM/MM) paradigm to simulate core photoelectron spectroscopy: the binding energies and the chemical shifts. An integrated approach with QM/MM binding energy calculations coupled to preceding molecular dynamics sampling is adopted to generate binding energies averaged over the solute-solvent configurations available at a particular temperature and pressure and thus allowing for a statistical assessment with confidence levels for the final binding energies. The results are analyzed in terms of the contributions in the molecular mechanics model-electrostatic, polarization, and van der Waals-with atom or bond granulation of the corresponding MM charge and polarizability force-fields. The role of extramolecular charge transfer screening of the core-hole and explicit hydrogen bonding is studied by extending the QM core to cover the first solvation shell. The results are compared to those obtained from pure electrostatic and polarizable continuum models. Particularly, the dependence of the carbon 1s binding energies with respect to the ethanol concentration is studied. Our results indicate that QM/MM can be used as an all-encompassing model to study photoelectron binding energies and chemical shifts in solvent environments.

  7. Multimode Surface Functional Group Determination: Combining Steady-State and Time-Resolved Fluorescence with X-ray Photoelectron Spectroscopy and Absorption Measurements for Absolute Quantification.

    Science.gov (United States)

    Fischer, Tobias; Dietrich, Paul M; Unger, Wolfgang E S; Rurack, Knut

    2016-01-19

    The quantitative determination of surface functional groups is approached in a straightforward laboratory-based method with high reliability. The application of a multimode BODIPY-type fluorescence, photometry, and X-ray photoelectron spectroscopy (XPS) label allows estimation of the labeling ratio, i.e., the ratio of functional groups carrying a label after reaction, from the elemental ratios of nitrogen and fluorine. The amount of label on the surface is quantified with UV/vis spectrophotometry based on the molar absorption coefficient as molecular property. The investigated surfaces with varying density are prepared by codeposition of 3-(aminopropyl)triethoxysilane (APTES) and cyanoethyltriethoxysilane (CETES) from vapor. These surfaces show high functional group densities that result in significant fluorescence quenching of surface-bound labels. Since alternative quantification of the label on the surface is available through XPS and photometry, a novel method to quantitatively account for fluorescence quenching based on fluorescence lifetime (τ) measurements is shown. Due to the complex distribution of τ on high-density surfaces, the stretched exponential (or Kohlrausch) function is required to determine representative mean lifetimes. The approach is extended to a commercial Rhodamine B isothiocyanate (RITC) label, clearly revealing the problems that arise from such charged labels used in conjunction with silane surfaces.

  8. Angle-resolved photoelectron spectroscopy studies of the many-body effects in the electronic structure of high-T{sub c} cuprates

    Energy Technology Data Exchange (ETDEWEB)

    Inosov, Dmytro S.

    2008-06-18

    In the present work some steps are done towards understanding the anomalous effects observed in the single-particle excitation spectra of cuprates. First, the electronic properties of BSCCO are considered. The main result of this part of the work is a model of the Green's function that is later used for calculating the two-particle excitation spectrum. Then, the matrix element effects in the photoemission spectra of cuprates are discussed. After a general introduction to the problem, the thesis focuses on the recently discovered anomalous behavior of the ARPES spectra that partially originates from the momentum-dependent photoemission matrix element. The momentum- and excitation energy dependence of the anomalous high-energy dispersion, termed ''waterfalls'', is covered in full detail. Understanding the role of the matrix element effects in this phenomenon proves crucial, as they obstruct the view of the underlying excitation spectrum that is of indisputable interest. For the optimally doped bilayer Bi-based cuprate, the renormalized two-particle correlation function in the superconducting state is calculated from ARPES data within an itinerant model based on the random phase approximation (RPA). (orig.)

  9. Calibrating stellar velocity dispersions based on spatially-resolved h-band spectra for improving the m-sigma relation

    CERN Document Server

    Kang, Wol-Rang; Schulze, Andreas; Riechers, Dominik A; Kim, Sang Chul; Park, Daeseong; Smolcic, Vernesa

    2013-01-01

    To calibrate stellar velocity dispersion measurements from optical and near-IR stellar lines, and to improve the black hole mass (MBH)- stellar velocity dispersion (sigma) relation, we measure stellar velocity dispersions based on high quality H-band spectra for a sample of 31 nearby galaxies, for which dynamical MBH is available in the literature. By comparing velocity dispersions measured from stellar lines in the H-band with those measured from optical stellar lines, we find no significant difference, suggesting that optical and near-IR stellar lines represent the same kinematics and that dust effect is negligible for early-type galaxies. Based on the spatially-resolved rotation and velocity dispersion measurements along the major axis of each galaxy, we find that a rotating stellar disk is present for 80% of galaxies in the sample. For galaxies with a rotation component, velocity dispersions measured from a single aperture spectrum can vary by up to ~20%, depending on the size of the adopted extraction ap...

  10. Spatially resolved spectroscopy across stellar surfaces. II. High-resolution spectra across HD 209458 (G0 V)

    Science.gov (United States)

    Dravins, Dainis; Ludwig, Hans-Günter; Dahlén, Erik; Pazira, Hiva

    2017-09-01

    Context. High-resolution spectroscopy across spatially resolved stellar surfaces aims at obtaining spectral-line profiles that are free from rotational broadening; the gradual changes of these profiles from disk center toward the stellar limb reveal properties of atmospheric fine structure, which are possible to model with 3D hydrodynamics. Aims: Previous such studies have only been carried out for the Sun but are now extended to other stars. In this work, profiles of photospheric spectral lines are retrieved across the disk of the planet-hosting star HD 209458 (G0 V). Methods: During exoplanet transit, stellar surface portions successively become hidden and differential spectroscopy provides spectra of small surface segments temporarily hidden behind the planet. The method was elaborated in Paper I, with observable signatures quantitatively predicted from hydrodynamic simulations. Results: From observations of HD 209458 with spectral resolution λ/ Δλ 80 000, photospheric Fe I line profiles are obtained at several center-to-limb positions, reaching adequately high S/N after averaging over numerous similar lines. Conclusions: Retrieved line profiles are compared to synthetic line profiles. Hydrodynamic 3D models predict, and current observations confirm, that photospheric absorption lines become broader and shallower toward the stellar limb, reflecting that horizontal velocities in stellar granulation are greater than vertical velocities. Additional types of 3D signatures will become observable with the highest resolution spectrometers at large telescopes.

  11. Absolute Time-Resolved Emission of Non-LTE L-Shell Spectra from Ti-Doped Aerogels

    Energy Technology Data Exchange (ETDEWEB)

    Back,C.; Feldman, U.; Weaver, J.; Seely, J.; Constantin, C.; Holland, G.; Lee, R.; Chung, H.; Scott, H.

    2006-01-01

    Outstanding discrepancies between data and calculations of laser-produced plasmas in recombination have been observed since the 1980s. Although improvements in hydrodynamic modeling may reduce the discrepancies, there are indications that non-LTE atomic kinetics may be the dominant cause. Experiments to investigate non-LTE effects were recently performed at the NIKE KrF laser on low-density Ti-doped aerogels. The laser irradiated a 2 mm diameter, cylindrical sample of various lengths with a 4-ns square pulse to create a volumetrically heated plasma. Ti L-shell spectra spanning a range of 0.47-3 keV were obtained with a transmission grating coupled to Si photodiodes. The diagnostic can be configured to provide 1-dimensional spatial resolution at a single photon energy, or 18 discrete energies with a resolving power, {gamma}/{delta}{gamma} of 3-20. The data are examined and compared to calculations to develop absolute emission measurements that can provide new tests of the non-LTE physics.

  12. Absolute, time-resolved emission of non-LTE L-shell spectra from Ti-doped aerogels

    Energy Technology Data Exchange (ETDEWEB)

    Back, C.A. [Lawrence Livermore National Laboratory, P.O. Box 808, L-21, Livermore, CA 94551 (United States)]. E-mail: tinaback@llnl.gov; Feldman, U. [Artep Inc. 2922 Excelsior Ct., Ellicott City, MD 21042 (United States); Weaver, J.L. [Naval Research Laboratory, 4555 Overlook Drive, SW, Washington DC 20375 (United States); Seely, J.F. [Naval Research Laboratory, 4555 Overlook Drive, SW, Washington DC 20375 (United States); Constantin, C. [Lawrence Livermore National Laboratory, P.O. Box 808, L-21, Livermore, CA 94551 (United States); Holland, G. [Naval Research Laboratory, 4555 Overlook Drive, SW, Washington DC 20375 (United States); Lee, R.W. [Lawrence Livermore National Laboratory, P.O. Box 808, L-21, Livermore, CA 94551 (United States); Chung, H.-K. [Lawrence Livermore National Laboratory, P.O. Box 808, L-21, Livermore, CA 94551 (United States); Scott, H.A. [Lawrence Livermore National Laboratory, P.O. Box 808, L-21, Livermore, CA 94551 (United States)

    2006-05-15

    Outstanding discrepancies between data and calculations of laser-produced plasmas in recombination have been observed since the 1980s. Although improvements in hydrodynamic modeling may reduce the discrepancies, there are indications that non-LTE atomic kinetics may be the dominant cause. Experiments to investigate non-LTE effects were recently performed at the NIKE KrF laser on low-density Ti-doped aerogels. The laser irradiated a 2mm diameter, cylindrical sample of various lengths with a 4-ns square pulse to create a volumetrically heated plasma. Ti L-shell spectra spanning a range of 0.47-3keV were obtained with a transmission grating coupled to Si photodiodes. The diagnostic can be configured to provide 1-dimensional spatial resolution at a single photon energy, or 18 discrete energies with a resolving power, {lambda}/{delta}{lambda} of 3-20. The data are examined and compared to calculations to develop absolute emission measurements that can provide new tests of the non-LTE physics.

  13. Use of photoelectron laser phase determination method for attosecond measurements with quantum-mechanical calculations

    Institute of Scientific and Technical Information of China (English)

    Ge Yu-Cheng

    2008-01-01

    This paper calculates quantum-mechanically the photoelectron energy spectra excited by attosecond x-rays in the presence of a few-cycle laser. A photoelectron laser phase determination method is used for precise measurements of the pulse natural properties of x-ray intensity and the instantaneous frequency profiles. As a direct procedure without any previous pulse profile assumptions and time-resolved measurements as well as data fitting analysis, this method can be used to improve the time resolutions of attosecond timing and measurements with metrological precision. The measurement range is half of a laser optical cycle.

  14. Magnetic field dependence of rotationally resolved excitation spectra of the 1B3u 000 transition of jet-cooled pyrazine

    NARCIS (Netherlands)

    Jonkman, Harry Th.; Drabe, Karel E.

    1991-01-01

    We report rotationally resolved excitation spectra of the 1B3u 000 transition of jet-cooled pyrazine in magnetic fields up to 50 kG. The emission intensity of every rotational line is found to decrease by a factor of three for magnetic fields larger than about 300 G. For still larger magnetic fields

  15. MAGNETIC-FIELD DEPENDENCE OF ROTATIONALLY RESOLVED EXCITATION-SPECTRA OF THE B-1(3U)0(0)(0) TRANSITION OF JET-COOLED PYRAZINE

    NARCIS (Netherlands)

    DELANGE, PJ; JONKMAN, HT; DRABE, KE

    1991-01-01

    We report rotationally resolved excitation spectra of the 1B3u 0(0)0 transition of jet-cooled pyrazine in magnetic fields up to 50 kG. The emission intensity of every rotational line is found to decrease by a factor of three for magnetic fields larger than about 300 G. For still larger magnetic fiel

  16. HST Spatially Resolved Spectra of the Accretion Disc and Gas Stream of the Nova-Like Variable UX Ursae Majoris

    Science.gov (United States)

    Baptista, Raymundo; Horne, Keith; Wade, Richard A.; Hubeny, Ivan; Long, Knox S.; Rutten, Rene G. M.

    1998-01-01

    Time-resolved eclipse spectroscopy of the nova-like variable UX UMa obtained with the Hubble Space Telescope/Faint Object Spectrograph (HST/FOS) on 1994 August and November is analysed with eclipse mapping techniques to produce spatially resolved spectra of its accretion disk and gas stream as a function of distance from the disk centre. The inner accretion disk is characterized by a blue continuum filled with absorption bands and lines, which cross over to emission with increasing disk radius, similar to that reported at optical wavelengths. The comparison of spatially resolved spectra at different azimuths reveals a significant asymmetry in the disk emission at ultraviolet (UV) wavelengths, with the disk side closest to the secondary star showing pronounced absorption by an 'iron curtain' and a Balmer jump in absorption. These results suggest the existence of an absorbing ring of cold gas whose density and/or vertical scale increase with disk radius. The spectrum of the infalling gas stream is noticeably different from the disc spectrum at the same radius suggesting that gas overflows through the impact point at the disk rim and continues along the stream trajectory, producing distinct emission down to 0.1 R(sub LI). The spectrum of the uneclipsed light shows prominent emission lines of Lyalpha, N v lambda1241, SiIV Lambda 1400, C IV Lambda 1550, HeII Lambda 1640, and MgII Lambda 2800, and a UV continuum rising towards longer wavelengths. The Balmer jump appears clearly in emission indicating that the uneclipsed light has an important contribution from optically thin gas. The lines and optically thin continuum emission are most probably emitted in a vertically extended disk chromosphere + wind. The radial temperature profiles of the continuum maps are well described by a steady-state disc model in the inner and intermediate disk regions (R greater than or equal to 0.3R(sub LI) ). There is evidence of an increase in the mass accretion rate from August to November

  17. Evolution of photoelectron-vibrational coupling with molecular complexity

    Energy Technology Data Exchange (ETDEWEB)

    Poliakoff, E D [Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803 (United States); Lucchese, R R [Department of Chemistry, Texas A and M University, College Station, TX 77843 (United States)

    2006-11-15

    We review how electronic and vibrational degrees of freedom become coupled in molecular photoionization, and describe effects that emerge as the molecular complexity increases. Molecular photoionization is frequently influenced by the temporary trapping of the continuum electron in the field of the target molecules, which is referred to as a shape resonance, as it depends on the shape of the potential experienced by the exiting photoelectron. Such resonances couple electronic and vibrational motion, and the nature of the coupling can vary widely for polyatomic molecules. We show how vibrationally resolved photoelectron spectra acquired as a function of energy can be used to elucidate such coupling. The experiments are analysed using physically realistic and computationally tractable Schwinger variational theory, and the systems studied to date can be well understood using an independent-particle, adiabatic nuclei framework. As a result, simple and intuitive pictures emerge, even when dealing with scattering phenomena involving complex molecular targets and potentials.

  18. Photoelectron Microscopy

    Science.gov (United States)

    King, Paul Lawrence

    1992-01-01

    This thesis describes the theory and first operations of a novel synchrotron-based imaging system allowing photoemission spectroscopy (XPS or ESCA) to be performed at lateral resolutions better than 10 microns. Originally developed in David Turner's group at Oxford, the MicroESCA^ {rm TM} relies on the diverging magnetic field from a 7 Tesla superconducting solenoid to project photoemitted electrons from a sample to an imaging detector located 1.5 meters away. The diverging magnetic field converts off-axis momentum to forward momentum and electrons form a magnified image at the detector while moving nearly parallel to one another. Because of this "parallelization", a planar gridded retarding field analyzer achieves excellent energy resolution with only minor impact on image quality. The thesis begins with an overview of the various techniques by which high lateral resolution photoelectron spectroscopy can be achieved. This is followed by a theoretical treatment of magnetic projection leading to predictions of lateral and energy resolution. Chapter 3 documents resolution tests and known deviations from ideality. Image forming capabilities and energy resolution of the retarding field analyzer are demonstrated at near-theoretical limits. Practical limitations of the microscope are recognized in the form of poor signal to noise ratios of core level images which originate from a combination of the narrow dynamic range of the imaging detector and the large backgrounds inherent in retarding field spectroscopy of solids. Chapter 4 describes an interactive image processing and interpretation scheme that relies on scatter plots and principal component analysis to reduce the dimensionality of retarding field image sets and improve image signal to noise. This procedure is generally applicable to all imaging spectroscopies and an example from SEM-based energy dispersive spectroscopy (EDS) is included. In a final results section, variations in the surface Fermi levels on cleaved

  19. Initial and steady-state Ru growth by atomic layer deposition studied by in situ Angle Resolved X-ray Photoelectron Spectroscopy

    Science.gov (United States)

    Egorov, Konstantin V.; Lebedinskii, Yury Yu.; Soloviev, Anatoly A.; Chouprik, Anastasia A.; Azarov, Alexander Yu.; Markeev, Andrey M.

    2017-10-01

    The clear substrate-dependent growth and delayed film continuity are essential challenges of Ru atomic layer deposition (ALD) demanding adequate and versatile approaches for their study. Here, we report on the application of in situ Angle Resolved X-ray Phototelectron Spectroscopy (ARXPS) for investigation of initial and steady-state ALD growth of Ru using Ru(EtCp)2 and O2 as precursors. Using ARXPS surface analysis technique we determine such parameters of Ru ALD initial growth as incubation period, fractional coverage and the thickness of islands/film depending on the substrate chemical state, governed by the presence/absence of NH3/Ar plasma pretreatment. It was demonstrated that NH3/Ar plasma pretreatment allows to obtain the lowest incubation period (∼7 ALD cycles) resulting in a continuous ultrathin (∼20 Å) and smooth Ru films after 70 ALD cycles. In situ XPS at UHV was used at steady state Ru growth for analysis of half-cycle reactions that revealed formation of RuOx (x ≈ 2) layer with thickness of ∼8 Å after O2 pulse (first half-cycle). It was also shown that oxygen of RuOx layer combusts Ru(EtCp)2 ligands in the second half-cycle reaction and the observed Ru growth of ∼0.34 Å per cycle is in a good agreement with the amount of oxygen in the RuOx layer.

  20. Photoelectron spectra of the late rare-earth misfit layer compounds (LnS)(1+x)TS2 (Ln=Tb, Dy, Ho; T=Nb, Ta)

    NARCIS (Netherlands)

    Fang, CM; Wiegers, GA; Haas, C

    1997-01-01

    Photoemission spectra (XPS and UPS) are presented for the valence band of misfit layer compounds (LnS)(1+x)TS2 with Ln = Dy, Ho or Tb; T = Nb or Ta. The Nb 4d(x)2 (or Ta 5d(x)2) conduction band is almost filled, which indicates a charge transfer of slightly less than one electron per T from the LnS

  1. H2CN+ and H2CNH+: New insight into the structure and dynamics from mass-selected threshold photoelectron spectra

    Science.gov (United States)

    Holzmeier, Fabian; Lang, Melanie; Hader, Kilian; Hemberger, Patrick; Fischer, Ingo

    2013-06-01

    In this paper, we reinvestigate the photoionization of nitrogen containing reactive intermediates of the composition H2CN and H2CNH, molecules of importance in astrochemistry and biofuel combustion. In particular, H2CN is also of considerable interest to theory, because of its complicated potential energy surface. The species were generated by flash pyrolysis, ionized with vacuum ultraviolet synchrotron radiation, and studied by mass-selected threshold photoelectron (TPE) spectroscopy. In the mass-selected TPE-spectrum of m/z = 28, contributions of all four isomers of H2CN were identified. The excitation energy to the triplet cation of the methylene amidogen radical H2CN was determined to be 12.32 eV. Considerable activity in the C-N mode of the cation is visible. Furthermore, we derived values for excitation into the triplet cations of 11.72 eV for cis-HCNH, 12.65 eV for trans-HCNH, and 11.21 eV for H2NC. The latter values are probably accurate to within one vibrational quantum. The spectrum features an additional peak at 10.43 eV that corresponds to excitation into the C2v-symmetric H2CN+. As this structure constitutes a saddle point, the peak is assigned to an activated complex on the singlet potential energy surface of the cation, corresponding to a hydrogen atom migration. For methanimine, H2CNH, the adiabatic ionization energy IEad was determined to be 9.99 eV and the vibrational structure of the spectrum was analyzed in detail. The uncertainty of earlier values that simply assigned the signal onset to the IEad is thus considerably reduced. The spectrum is dominated by the H-N-C bending mode ν1+ and the rocking mode ν3+. All experimental data were supported by calculations and Franck-Condon simulations.

  2. Photoelectronic characterization of heterointerfaces.

    Energy Technology Data Exchange (ETDEWEB)

    Brumbach, Michael Todd

    2012-02-01

    In many devices such as solar cells, light emitting diodes, transistors, etc., the performance relies on the electronic structure at interfaces between materials within the device. The objective of this work was to perform robust characterization of hybrid (organic/inorganic) interfaces by tailoring the interfacial region for photoelectron spectroscopy. Self-assembled monolayers (SAM) were utilized to induce dipoles of various magnitudes at the interface. Additionally, SAMs of molecules with varying dipolar characteristics were mixed into spatially organized structures to systematically vary the apparent work function. Polymer thin films were characterized by depositing films of varying thicknesses on numerous substrates with and without interfacial modifications. Hard X-ray photoelectron spectroscopy (HAXPES) was performed to evaluate a buried interface between indium tin oxide (ITO), treated under various conditions, and poly(3-hexylthiophene) (P3HT). Conducting polymer films were found to be sufficiently conducting such that no significant charge redistribution in the polymer films was observed. Consequently, a further departure from uniform substrates was taken whereby electrically disconnected regions of the substrate presented ideally insulating interfacial contacts. In order to accomplish this novel strategy, interdigitated electrodes were used as the substrate. Conducting fingers of one half of the electrodes were electrically grounded while the other set of electrodes were electronically floating. This allowed for the evaluation of substrate charging on photoelectron spectra (SCOPES) in the presence of overlying semiconducting thin films. Such an experiment has never before been reported. This concept was developed out of the previous experiments on interfacial modification and thin film depositions and presents new opportunities for understanding chemical and electronic changes in a multitude of materials and interfaces.

  3. A novel electronic configuration of the 5f states in {delta}-plutonium as revealed by the photo-electron spectra

    Energy Technology Data Exchange (ETDEWEB)

    Wills, J.M.; Eriksson, O. E-mail: olle.eriksson@fysik.uu.se; Delin, A.; Andersson, P.H.; Joyce, J.J.; Durakiewicz, T.; Butterfield, M.T.; Arko, A.J.; Moore, D.P.; Morales, L.A

    2004-04-01

    We present a theoretical model, the mixed-level model, aiming at describing metals with very complex, strongly correlated, electronic structures. As a demonstration, it is applied to the electronic structure of {delta}-Pu. The model reproduces the electronic-structure related properties of this complex metal; in particular, the theory is capable of reproducing the valence band photoemission spectrum of {delta}-Pu. We also report new experimental photoemission spectra at several photon energies. Taken together, our results provide strong evidence that the electronic structure of {delta}-Pu involves a 5f shell with four electrons in a localized multiplet hybridizing with valence states, and approximately one 5f electron forming a completely delocalized band state.

  4. A photoelectron spectroscopic investigation of vinyl fluoride (C{sub 2}H{sub 3}F): the HeI, threshold and CIS photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Locht, R; Leyh, B [Laboratoire de Dynamique Moleculaire, Departement de Chimie, Institut de Chimie, Bat.B6c, Universite de Liege, Sart-Tilman par B-4000 Liege 1 (Belgium); Dehareng, D [Centre d' Ingenierie des Proteines, Institut de Chimie, Bat.B6a, Universite de Liege, Sart-Tilman par B-4000 Liege 1 (Belgium); Hottmann, K; Baumgaertel, H, E-mail: robert.locht@ulg.ac.b [Institut fuer Physikalische und Theoretische Chemie, Freie Universitaet Berlin, Takustrasse 3, D-14195 Berlin (Germany)

    2010-01-14

    The threshold photoelectron spectrum (TPES) and the constant ion state (CIS) spectra of the individual ionic states of C{sub 2}H{sub 3}F have been recorded using synchrotron radiation. For comparison a well-resolved HeI photoelectron spectrum (HeI-PES) has also been measured and analysed in detail. The TPES has been measured between 9.5 eV and 35 eV photon energy. Numerous vibrational structures, reported for the first time, observed in the ground state and the six excited states of the cation are analysed. Quantum chemical calculations have been performed and provide strong support to the assignments. State-selected CIS spectra highlighted the major importance of autoionization for the production of almost all ionized states of C{sub 2}H{sub 3}F observed in this work.

  5. Radiationless S 1 → S 0 phenyl deactivation pathway: an investigation of iodine-marked bi-phenyl on a silicon surface by means of time resolved core-level photoelectron spectroscopy

    Science.gov (United States)

    Michelswirth, Martin; Dachraoui, Hatem; Mattay, Jochen; Heinzmann, Ulrich

    2012-02-01

    The S 1 → S 0 radiationless deactivation of iodine terminated bi-phenyl immobilized on a silicon surface was probed by analysing the I4d signature (BE: 45.6 eV, 47.3 eV) by means of High Harmonic Generation (HHG) based photoelectron spectroscopy. Modifications of the 4d5/2,3/2 spectroscopic contents spanning about 0.2 ps after UV activation (266 nm) were verified as showing a transient molecular response character. A localization to the terminated phenyl substructure in the complex structural environment on the surface was ensured according to the core-level nature of the recorded I4d. The activation of the bi-phenyl achieved by UV irradiation, corresponding to the UV absorption band-edge, was verified as being dominated by a Bπ → Bπ* phenyl excitation. Time-Dependent Density Functional Theory (TD-DFT) modellings were therefore performed. They were matched to Configuration Interaction semi-empirical calculations (CI-MNDO) verifying the Rustagi-Ducuing relation. The simulated singlet-singlet excitation spectrum was referenced to the spectra of an iodine terminated monomer and a linear oligophenyl chain (N = 8). Thus the deactivation response studied was assigned to a conical intersection promoted ? reaction pathway.

  6. FT-IR reflection spectra of single crystals: resolving phonons of different symmetry without using polarised radiation

    OpenAIRE

    METODIJA NAJDOSKI; VLADIMIR IVANOVSKI; VLADIMIR M. PETRUSEVSKI

    2000-01-01

    Fourier-transform infrared (FT-IR) reflection spectra, asquired at nearnormal incidence, were recorded from single crystals belonging to six crystal systems: CsCr(SO4)2.12H2O (alum, cubic), K2CuCl2·2H2O (Mitscherlichite, tetragonal), CaCO3 (calcite, hexagonal), KHSO4 (mercallite, orthorhombic), CaSO4·2H2O (gypsum, monoclinic) and CuSO4·5H2O (chalcantite, triclinic). The acquired IR reflection spectra were further transformed into absorption spectra, employing the Kramers-Kronig transformation...

  7. X-ray photoelectron spectroscopic investigation of conducting polymer blends.

    Science.gov (United States)

    Süzer, S; Toppare, L; Hallam, K R; Allen, G C

    1996-06-01

    Electrochemically prepared films of conducting polymers of polypyrrole and polythiophene and their blends with polyamide have been investigated by X-ray photoelectron spectroscopy. In the N1s region of the spectra of films containing polypyrrole the peak corresponding to N(+) at 402.0 eV is separated from that of neutral N. The intensity of the N(+) peak can be correlated with the electrical conductivity of the films and the spectroscopically derived ratio of F/N(+) is close to 4 indicating that one BF(-)(4) dopant ion is incorporated for every oxidized nitrogen center. In the spectra of films of polythiophene and its blends peaks corresponding to S and S(+) can not be resolved but again the F/C ratio correlates with the electrical conductivity.

  8. Time-Resolved Holography with Photoelectrons

    NARCIS (Netherlands)

    Huismans, Y.; Rouzee, A.; Gijsbertsen, A.; Jungmann, J. H.; Smolkowska, A. S.; Logman, Pswm; Lepine, F.; Cauchy, C.; Zamith, S.; Marchenko, T.; Bakker, J. M.; G. Berden,; Redlich, B.; van der Meer, A. F. G.; Muller, H. G.; Vermin, W.; Schafer, K. J.; Spanner, M.; Ivanov, M. Y.; Smirnova, O.; Bauer, D.; Popruzhenko, S. V.; Vrakking, M. J. J.

    2011-01-01

    Ionization is the dominant response of atoms and molecules to intense laser fields and is at the basis of several important techniques, such as the generation of attosecond pulses that allow the measurement of electron motion in real time. We present experiments in which metastable xenon atoms were

  9. Photoelectron spectroscopy of the hydroxymethoxide anion, H2C(OH)O-

    Science.gov (United States)

    Oliveira, Allan M.; Lehman, Julia H.; McCoy, Anne B.; Lineberger, W. Carl

    2016-09-01

    We report the negative ion photoelectron spectroscopy of the hydroxymethoxide anion, H2C(OH)O-. The photoelectron spectra show that 3.49 eV photodetachment produces two distinct electronic states of the neutral hydroxymethoxy radical (H2C(OH)Oṡ). The H2C(OH)Oṡ ground state (X ˜ 2A) photoelectron spectrum exhibits a vibrational progression consisting primarily of the OCO symmetric and asymmetric stretches, the OCO bend, as well as combination bands involving these modes with other, lower frequency modes. A high-resolution photoelectron spectrum aids in the assignment of several vibrational frequencies of the neutral H2C(OH)Oṡ radical, including an experimental determination of the H2C(OH)Oṡ 2ν12 overtone of the H-OCO torsional vibration as 220(10) cm-1. The electron affinity of H2C(OH)Oṡ is determined to be 2.220(2) eV. The low-lying A ˜ 2A excited state is also observed, with a spectrum that peaks ˜0.8 eV above the X ˜ 2A state origin. The A ˜ 2A state photoelectron spectrum is a broad, partially resolved band. Quantum chemical calculations and photoelectron simulations aid in the interpretation of the photoelectron spectra. In addition, the gas phase acidity of methanediol is calculated to be 366(2) kcal mol-1, which results in an OH bond dissociation energy, D0(H2C(OH)O-H), of 104(2) kcal mol-1, using the experimentally determined electron affinity of the hydroxymethoxy radical.

  10. HST spatially-resolved spectra of the accretion disc and gas stream of the nova-like variable UX Ursae Majoris

    CERN Document Server

    Baptista, R; Wade, R A; Hubeny, I; Long, K S; Rutten, R G M

    1998-01-01

    Time-resolved eclipse spectroscopy of the nova-like variable UX UMa obtained with the HST/FOS on 1994 August and November is analyzed with eclipse mapping techniques to produce spatially resolved spectra of its accretion disc and gas stream as a function of distance from disc centre. The inner accretion disc is characterized by a blue continuum filled with absorption bands and lines which cross over to emission with increasing disc radius, similar to that reported by Rutten et al (1994) at optical wavelengths. The comparison of spatially resolved spectra at different azimuths reveals a significant asymmetry in the disc emission at UV wavelengths, with the disc side closest to the secondary star showing pronounced absorption by an `iron curtain' and a Balmer jump in absorption. These results suggest the existence of an absorbing ring of cold gas whose density and/or vertical scale increase with disc radius. The spectrum of the infalling gas stream is noticeably different from the disc spectrum at the same radi...

  11. Locally resolved investigation of wedged Cu(In,Ga)Se{sub 2} films prepared by physical vapor deposition using hard X-ray photoelectron and X-ray fluorescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Calvet, Wolfram, E-mail: wolfram.calvet@helmholtz-berlin.de [Helmholtz-Zentrum Berlin, Hahn-Meitner-Platz 1, D-14109 Berlin (Germany); Ümsür, Bünyamin; Höpfner, Britta; Lauermann, Iver; Prietzel, Karsten; Kaufmann, Christan A.; Unold, Thomas [Helmholtz-Zentrum Berlin, Hahn-Meitner-Platz 1, D-14109 Berlin (Germany); Lux-Steiner, Martha C. [Helmholtz-Zentrum Berlin, Hahn-Meitner-Platz 1, D-14109 Berlin (Germany); Freie Universität Berlin, Department of Physics, Arnimallee 14, D-14195 Berlin (Germany)

    2015-05-01

    We have investigated a specially grown Cu(In,Ga)Se{sub 2} (CIGSe) absorber, which was deposited by co-evaporation of Cu, In, Ga, and Se using a modified three stage process. Prior to the growth, the molybdenum-coated glass substrate was covered by a bent shroud made from tantalum (Ta), leading to a wedged absorber structure with a width of about 2 mm where the film thickness varies from 0 to 2 μm. In this region of interest the thickness dependency of morphology, concentration ratios and electronic properties was studied with secondary electron microscopy (SEM), X-ray fluorescence (XRF) and hard X-ray photoelectron spectroscopy (HAXPES), probing the CIGSe sample along the thickness gradient. The evidence of the thickness gradient itself was proven with SEM measurements in cross section geometry. By using XRF it was found that with decreasing film thickness the Cu concentration decreases significantly. This finding was also verified by HAXPES measurements. Furthermore, an enrichment of Ga towards the Mo back contact was found using the same technique. Besides these results the formation of a molybdenum selenide (MoSe) phase was observed on the fully covered part of the Mo coated substrate indicating a high mobility of Se on Mo under the given temperature conditions of the modified three stage deposition process. - Highlights: • Growth of a CIGSe wedge • Application of HAXPES and XRF as local probing techniques • Good agreement with former studies • Wedged CIGSe structures can be used for further, locally resolved experiments.

  12. Surface and subsurface oxidation of Mo2C/Mo(100): low-energy ion-scattering, auger electron, angle-resolved X-ray photoelectron, and mass spectroscopy studies.

    Science.gov (United States)

    Ovári, László; Kiss, János; Farkas, Arnold P; Solymosi, Frigyes

    2005-03-17

    The interaction of oxygen with a carburized Mo(100) surface was investigated at different temperatures (300-1000 K). The different information depths of low-energy ion-scattering (LEIS) spectroscopy, with topmost layer sensitivity, Auger electron spectroscopy (AES), and angle-resolved X-ray photoelectron spectroscopy (ARXPS) allowed us to discriminate between reactions on the topmost layer and subsurface transformations. According to ARXPS measurements, a carbide overlayer was prepared by the high-temperature decomposition of C(2)H(4) on Mo(100), and the carbon distribution proved to be homogeneous with a Mo(2)C stoichiometry down to the information depth of XPS. O(2) adsorbs dissociatively on the carbide layer at room temperature. One part of the chemisorbed oxygen is bound to both C and Mo sites, indicated by LEIS. Another fraction of oxygen atoms probably resides in the hollow sites not occupied by C. The removal of C from the outermost layer by O(2), in the form of CO, detected by mass spectroscopy (MS), was observed at 500-600 K. The carbon-depleted first layer is able to adsorb more oxygen compared to the Mo(2)C/Mo(100) surface. Applying higher doses of O(2) at 800 K results in the inward diffusion of O and the partial oxidation of Mo atoms. This process, however, is not accompanied by the removal of C from subsurface sites. The depletion of C from the bulk starts only at 900 K (as shown by MS, AES, and XPS), very probably by the diffusion of C to the surface followed by its reaction with oxygen. At T(ads) = 1000 K, the carbon content of the sample, down to the information depth of XPS, decreased further, accompanied by the attenuation of the C concentration gradient and a substantially decreased amount of oxygen.

  13. Theoretical Studies on the Photoelectron and Absorption Spectra of MnO 4 and TcO 4

    Energy Technology Data Exchange (ETDEWEB)

    Su, Jing; Xu, Wen-Hua; Xu, Chao-Fei; Schwarz, W. H. E.; Li, Jun

    2013-09-03

    The tetraoxo pertechnetate anion (TcO4-) is of great interest for nuclear waste management and radiopharmceuticals. To elucidate its electronic structure and to compare with that of its lighter congener MnO4-, the photoelectron and electronic absorption spectra of MnO4 - and TcO4 - are investigated with density functional theory (DFT) and ab initio wave function theory (WFT). The vertical electron detachment energies (VDEs) of MnO4 - obtained with the CR-EOM-CCSD(T) method are in good agreement with the lowest two experimental VDEs; the differences are less than 0.1 eV, representing a significant improvement over the IP-EOMCCSD(T) result in the literature. Combining our CCSD(T) and CR-EOMCCSD( T) results, the first five VDEs of TcO4 - are estimated between 5 and 10 eV with an estimated accuracy of about ±0.2 eV. The vertical excitation energies are determined by using TD-DFT, CR-EOM-CCSD(T), and RASPT2 methods. The excitation energies and the assignments of the spectra are analyzed and partly improved. They are compared with reported SAC-CI results and available experimental data. Both dynamic and nondynamic electron correlations are important in the ground and excited states of MnO4 - and TcO4 -. Nondynamical correlations are particularly relevant in TcO4 - for reliable prediction of excitation energies. In TcO4 - one Rydberg state interlaces but does not mix with the valence excited states, and it disappears in the condensed phase.

  14. Theoretical studies on the electronic structures and photoelectron spectra of tri-rhenium oxide clusters: Re3O(n)(-) and Re3O(n) (n=1-6).

    Science.gov (United States)

    Zhou, Qi; Gong, Wei-Chao; Xie, Lu; Zheng, Cun-Gong; Zhang, Wei; Wang, Bin; Zhang, Yong-Fan; Huang, Xin

    2014-01-03

    Density functional theory (DFT) calculations are performed to study the structural and electronic properties of tri-rhenium oxide clusters Re3On(-/0) (n=1-6). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level are carried out to search for the global minima for both the anions and the neutrals. For the anions, the first two O atoms prefer the same corner position of a Re3 triangle. Whereas, Re3O3(-) possesses a C2v symmetry with one bridging and two terminal O atoms. The next three O atoms (n=4-6) are adding sequentially on the basis of Re3O3(-) motif, i.e., adding one terminal O atom for Re3O4(-), one terminal and one bridging O atoms for Re3O5(-), and one terminal and two bridging O atoms for Re3O6(-), respectively. Their corresponding neutral species are similar to the anions in geometry except Re3O4 and Re3O5. Molecular orbital analyses are employed to investigate the chemical bonding and structural evolution in these tri-rhenium oxide clusters. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Spin resolved photoelectron spectroscopy of [Mn{sub 6}{sup III}Cr{sup III}]{sup 3+} single-molecule magnets and of manganese compounds as reference layers

    Energy Technology Data Exchange (ETDEWEB)

    Helmstedt, Andreas; Mueller, Norbert; Gryzia, Aaron; Dohmeier, Niklas; Brechling, Armin; Sacher, Marc D; Heinzmann, Ulrich [Fakultaet fuer Physik, Universitaet Bielefeld, Universitaetsstrasse 25, 33615 Bielefeld (Germany); Hoeke, Veronika; Krickemeyer, Erich; Glaser, Thorsten [Fakultaet fuer Chemie, Universitaet Bielefeld, Universitaetsstrasse 25, 33615 Bielefeld (Germany); Bouvron, Samuel; Fonin, Mikhail [Fachbereich Physik, Universitaet Konstanz, Universitaetsstrasse 10, 78457 Konstanz (Germany); Neumann, Manfred, E-mail: andreas.helmstedt@uni-bielefeld.de [Fachbereich Physik, Universitaet Osnabrueck, Barbarastrasse 7, 49069 Osnabrueck (Germany)

    2011-07-06

    Properties of the manganese-based single-molecule magnet [Mn{sup III}{sub 6}Cr{sup III}]{sup 3+} are studied. It contains six Mn{sup III} ions arranged in two bowl-shaped trinuclear triplesalen building blocks linked by a hexacyanochromate and exhibits a large spin ground state of S{sub t} = 21/2. The dominant structures in the electron emission spectra of [Mn{sup III}{sub 6}Cr{sup III}]{sup 3+} resonantly excited at the L{sub 3}-edge are the L{sub 3}M{sub 2,3}M{sub 2,3}, L{sub 3}M{sub 2,3}V and L{sub 3}VV Auger emission groups following the decay of the primary p{sub 3/2} core hole state. Significant differences of the Auger spectra from intact and degraded [Mn{sup III}{sub 6}Cr{sup III}]{sup 3+} show up. First measurements of the electron spin polarization in the L{sub 3}M{sub 2,3}V and L{sub 3}VV Auger emission peaks from the manganese constituents in [Mn{sup III}{sub 6}Cr{sup III}]{sup 3+} resonantly excited at the L{sub 3}-edge near 640 eV by circularly polarized synchrotron radiation are reported. In addition spin resolved Auger electron spectra of the reference substances MnO, Mn{sub 2}O{sub 3} and Mn{sup II}(acetate){sub 2{center_dot}}4H{sub 2}O are given. The applicability of spin resolved electron spectroscopy for characterizing magnetic states of constituent atoms compared to magnetic circular dichroism (MCD) is verified: the spin polarization obtained from Mn{sup II}(acetate){sub 2{center_dot}}4H{sub 2}O at room temperature in the paramagnetic state compares to the MCD asymmetry revealed for a star-shaped molecule with a Mn{sub 4}{sup II}O{sub 6} core at 5 K in an external magnetic field of 5 T.

  16. Rotationally resolved water dimer spectra in atmospheric air and pure water vapour in the 188-258 GHz range.

    Science.gov (United States)

    Serov, E A; Koshelev, M A; Odintsova, T A; Parshin, V V; Tretyakov, M Yu

    2014-12-21

    New experimental results regarding "warm" water dimer spectra under equilibrium conditions are presented. An almost equidistant series of six peaks corresponding to the merged individual lines of the bound dimer with consecutive rotational quantum numbers is studied in the 188-258 GHz frequency range in water vapour over a broad range of pressures and temperatures relevant to the Earth's atmosphere. The series is a continuation of the sequence detected earlier at lower frequencies at room temperature. The signal-to-noise ratio of the observed spectra allowed investigating their evolution, when water vapour was diluted by atmospheric air with partial pressure from 0 up to 540 Torr. Analysis of the obtained spectra permitted determining the dimerization constant as well as the hydrogen bond dissociation energy and the dimer spectral parameters, including the average coefficient of collisional broadening of individual lines by water vapour and air. The manifestation of metastable states of the dimer in the observed spectra is assessed. The contribution of three possible pair states of water molecules to the second virial coefficient is evaluated over the broad range of temperatures. The work supports the significant role of the water dimer in atmospheric absorption and related processes.

  17. Potential energy surfaces of short polyenes in the state T1 : analysis of time resolved resonance Raman spectra

    NARCIS (Netherlands)

    Orlandi, G.; Negri, F.; Wilbrandt, R.; Langkilde, F.W.; Brouwer, A.M.

    1993-01-01

    The analysis of T1 resonance Raman spectra of some conjugated compounds is discussed making use of semiempirical quantum chemical calculations. Information obtained about T1 potential energy curve indicates that in short polyenes the perpendicular form is roughly degenerate with the trans isomer. Pr

  18. A comparative study of ICH validated novel spectrophotometric techniques for resolving completely overlapping spectra of quaternary mixtures

    Science.gov (United States)

    Ali, Nouruddin W.; Abdelwahab, Nada S.; Abdelkawy, M.; Emam, Aml A.

    2016-02-01

    A pharmaceutically marketed mixture of Yohimbine, Alpha-tocopheryl acetate, Niacin, and Caffeine co-formulated as a promising therapy for erectile dysfunction. Simultaneous determination of the aforementioned pharmaceutical formulation without prior separation steps was applied using mean centering of ratio spectra and triple divisor spectrophotometric methods. Mean centering of ratio spectra method depended on using the mean centered ratio spectra in three successive steps which eliminated the derivative steps and so the signal to noise ratio was improved. The absorption spectra of the prepared solutions were measured in the wavelength range of 215-300 nm in the concentration ranges of 1-15, 3-15, 1-20, and 3-15 μg mL- 1 for Yohimbine, Alpha-tocopheryl acetate, Niacin, and Caffeine, respectively. The amplitudes of the mean centered third ratio spectra were measured at 250 nm and 268 nm for Yohimbine and Alpha-tocopheryl acetate, respectively and at peak to peak 272-273 and 262-263 nm for Niacin and Caffeine, respectively. In triple divisor method each drug in the quaternary mixture was determined by dividing the spectrum of the quaternary mixture by a standard spectrum of a mixture containing equal concentrations of the other three drugs. First derivative of these ratio spectra was obtained where determination could be achieved without any interference from the other three drugs. Amplitudes of 1-15, 3-15, 1-15, and 3-15 μg mL- 1 were used for selective determination of Yohimbine, Alpha-tocopheryl acetate, Niacin, and Caffeine, respectively. Laboratory prepared mixtures were analyzed by the developed novel methods to investigate their selectivity also, Super Act® capsules were successfully analyzed to ensure absence of interference from additives. The developed methods were validated according to the ICH guidelines. The proposed methods were statistically compared with each other and with the reported methods; using student t-test, F-test, and one way ANOVA

  19. Threshold photoelectron spectroscopy of acetaldehyde and acrolein

    Energy Technology Data Exchange (ETDEWEB)

    Yencha, Andrew J., E-mail: ayencha@albany.edu [Department of Chemistry, University at Albany, State University of New York, Albany, NY 12222 (United States); Siggel-King, Michele R.F. [Cockcroft Institute, Sci-Tech Daresbury, Warrrington WA4 4AD (United Kingdom); Department of Physics, University of Liverpool, Liverpool L69 3BX (United Kingdom); King, George C. [Department of Physics and Astronomy and Photon Science Institute, Manchester University, Manchester M13 9PL (United Kingdom); Malins, Andrew E.R. [Cockcroft Institute, Sci-Tech Daresbury, Warrrington WA4 4AD (United Kingdom); Eypper, Marie [School of Chemistry, University of Southampton, Southampton SO17 1BJ (United Kingdom)

    2013-04-15

    Highlights: •High-resolution threshold photoelectron spectrum of acetaldehyde. •High-resolution threshold photoelectron spectrum of acrolein. •High-resolution total photoion yield spectrum of acetaldehyde. •High-resolution total photoion yield spectrum of acrolein. •Determination of vertical ionization potentials in acetaldehyde and acrolein. -- Abstract: High-resolution (6 meV and 12 meV) threshold photoelectron (TPE) spectra of acetaldehyde and acrolein (2-propenal) have been recorded over the valence binding energy region 10–20 eV, employing synchrotron radiation and a penetrating-field electron spectrometer. These TPE spectra are presented here for the first time. All of the band structures observed in the TPE spectra replicate those found in their conventional HeI photoelectron (PE) spectra. However, the relative band intensities are found to be dramatically different in the two types of spectra that are attributed to the different dominant operative formation mechanisms. In addition, some band shapes and their vertical ionization potentials are found to differ in the two types of spectra that are associated with the autoionization of Rydberg states in the two molecules.

  20. New fine structures resolved at the ELNES Ti-L{sub 2,3} edge spectra of anatase and rutile: Comparison between experiment and calculation

    Energy Technology Data Exchange (ETDEWEB)

    Cheynet, M., E-mail: marie.cheynet@simap.grenoble-inp.fr [SIMAP-PHELMA-CNRS, BP 75, 38402 Saint-Martin-d' Heres (France); Pokrant, S. [Carl Zeiss NTS GmbH, 73447 Oberkochen (Germany); Irsen, S. [TEM Group, Forschungszentrum Caesar, 53175 Bonn (Germany); Krueger, P. [ICB, UMR 5209 Universite de Bourgogne-CNRS, BP 47870, 21078 Dijon (France)

    2010-07-15

    Anatase and rutile Ti-L{sub 2,3} edge spectra were measured in electron energy loss spectroscopy (EELS) using a transmission electron microscope (TEM) coupled to a CEOS Cs-probe corrector, an omega-type monochromator and an in-column omega-type energy filter fully corrected for 2nd order aberrations. Thanks to the high energy resolution, high electron probe current and high stability achieved under this instrumental configuration, new fine structures, never reported before, were resolved at the L{sub 3} band of both rutile and anatase. The data suggest that new peaks also exist in the L{sub 2} e{sub g} band. The experimental spectra are compared with multichannel multiple scattering (MMS) calculations. Good agreement is found for number, energy position and intensity of the newly resolved spectral features. Up to now, the L{sub 3} e{sub g} band splitting could not be well described by theory not even through the crystal field multiplet approach. We show that the L{sub 3} e{sub g} band splitting is due to long range band structure effects, contrary to the usual interpretations in terms of local ligand field or near-neighbour hybridization effects.

  1. Negative ion photoelectron spectra of ISO3-, IS2O3-, and IS2O4- intermediates formed in interfacial reactions of ozone and iodide/sulfite aqueous microdroplets

    Science.gov (United States)

    Qin, Zhengbo; Hou, Gao-Lei; Yang, Zheng; Valiev, Marat; Wang, Xue-Bin

    2016-12-01

    Three short-lived, anionic intermediates, ISO3-, IS2O3-, and IS2O4-, are detected during reactions between ozone and aqueous iodine/sulfur oxide microdroplets. These species may play an important role in ozone-driven inorganic aerosol formation; however their chemical properties remain largely unknown. This is the issue addressed in this work using negative ion photoelectron spectroscopy (NIPES) and ab initio modeling. The NIPE spectra reveal that all of the three anionic species are characterized by high adiabatic detachment energies (ADEs) - 4.62 ± 0.10, 4.52 ± 0.10, and 4.60 ± 0.10 eV for ISO3-, IS2O3-, and IS2O4-, respectively. Vibrational progressions with frequencies assigned to the S-O symmetric stretching modes are discernable in the ground state transition features. Density functional theory calculations show the presence of several low-lying isomers involving different bonding scenarios. Further analysis based on high level CCSD(T) calculations reveal that the lowest energy structures are characterized by the formation of I-S and S-S bonds and can be structurally viewed as SO3 linked with I, IS, and ISO for ISO3-, IS2O3-, and IS2O4-, respectively. The calculated ADEs and vertical detachment energies are in excellent agreement with the experimental results, further supporting the identified minimum energy structures. The obtained intrinsic molecular properties of these anionic intermediates and neutral radicals should be useful to help understand their photochemical reactions in the atmosphere.

  2. A scintillator-based online detector for the angularly resolved measurement of laser-accelerated proton spectra

    Energy Technology Data Exchange (ETDEWEB)

    Metzkes, J.; Kraft, S. D.; Sobiella, M.; Stiller, N.; Zeil, K.; Schramm, U. [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstr. 400, 01328 Dresden (Germany); Karsch, L.; Schuerer, M. [OncoRay - National Center for Radiation Research in Oncology, TU Dresden, Fetscherstr. 74, 01307 Dresden (Germany); Pawelke, J.; Richter, C. [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstr. 400, 01328 Dresden (Germany); OncoRay - National Center for Radiation Research in Oncology, TU Dresden, Fetscherstr. 74, 01307 Dresden (Germany)

    2012-12-15

    In recent years, a new generation of high repetition rate ({approx}10 Hz), high power ({approx}100 TW) laser systems has stimulated intense research on laser-driven sources for fast protons. Considering experimental instrumentation, this development requires online diagnostics for protons to be added to the established offline detection tools such as solid state track detectors or radiochromic films. In this article, we present the design and characterization of a scintillator-based online detector that gives access to the angularly resolved proton distribution along one spatial dimension and resolves 10 different proton energy ranges. Conceived as an online detector for key parameters in laser-proton acceleration, such as the maximum proton energy and the angular distribution, the detector features a spatial resolution of {approx}1.3 mm and a spectral resolution better than 1.5 MeV for a maximum proton energy above 12 MeV in the current design. Regarding its areas of application, we consider the detector a useful complement to radiochromic films and Thomson parabola spectrometers, capable to give immediate feedback on the experimental performance. The detector was characterized at an electrostatic Van de Graaff tandetron accelerator and tested in a laser-proton acceleration experiment, proving its suitability as a diagnostic device for laser-accelerated protons.

  3. Franck-Condon 因子计算及甲醛光电子能谱的理论研究%Calculation of Franck-Condon factors and theoretical investigation on the photoelectron spectra of Formaldehyde

    Institute of Scientific and Technical Information of China (English)

    王双力; 梁军; 陶松涛; 崔执凤

    2015-01-01

    On the basis of the closed expression of the Franck-Condon overlap integrals between arbitrary multi-dimensional harmonic oscillators and considering influence of the Duschinsky effects, a more general algebraic expression for the calculation of the three -dimensional three -mode Franck -Condon factors was derived straightforwardly.This algebraic expression was applied to study the photoelectron spectra of H2 CO.Franck-Condon analyses and spectral simulations were carried out on the H2 CO+( B珘2 A1 )←H2 CO( X珘1 A1 ) photoionization processes.The spectral simulations of vibrational structures based on the computed Franck-Condon factors are in excellent agreement with the observed spectra.%本文凭借多振动模混合下任意维Franck-Condon 重叠积分封闭表示,推导出三维三振动模Franck-Condon重叠积分的解析表示式;基于厄米多项式的级数形式,得到计算三维三振动模Franck-Condon 因子的一般代数表示式。另外,应用Franck-Condon因子的代数表示,研究甲醛光电子能谱的强度分布及振动结构。对于H2 CO+(Β珟2 A1)←H2 CO( X珘1 A1)离子化过程,基于ab initio力常数及几何参数,计算Franck-Condon因子,得到光电子能谱的谱线相对强度。结果表明理论模拟得到的光电子能谱与实验上观测到的能谱达到较好的一致;基于光谱模拟使人们能够对实验谱给予合理解释以及对谱峰进行正确归属。

  4. Photoelectron spectroscopy of phthalocyanine vapors

    Energy Technology Data Exchange (ETDEWEB)

    Berkowitz, J.

    1979-01-01

    The He(I) photoelectron spectra of several metal phthalocyanines and metal-free phthalocyanine vapor shows that: a sharp peak at 4.99 eV is an artifact due to ionization of atomic He by He(II) radiation; the first phthalocyanine peak (metal-containing or metal-free) occurs at 6.4 eV; and the metal-like d orbitals lie at least 1 to 2 eV deeper, except in the case of Fe. (DLC)

  5. Polarization Effects in Attosecond Photoelectron Spectroscopy

    DEFF Research Database (Denmark)

    Baggesen, Jan Conrad; Madsen, Lars Bojer

    2010-01-01

    following the field instead. We show that polarization effects may lead to an apparent temporal shift that needs to be properly accounted for in the analysis. The effect may be isolated and studied by angle-resolved photoelectron spectroscopy from oriented polar molecules. We also show that polarization...

  6. Photoelectron spectroscopy of liquid water, some alcohols, and pure nonane in free micro jets

    Science.gov (United States)

    Faubel, Manfred; Steiner, Björn; Toennies, J. Peter

    1997-06-01

    The recently developed technique of accessing volatile liquids in a high vacuum environment by using a very thin liquid jet is implemented to carry out the first measurements of photoelectron spectra of pure liquid water, methanol, ethanol, 1-propanol, 1-butanol, and benzyl alcohol as well as of liquid n-nonane. The apparatus, which consists of a commercial hemispherical (10 cm mean radius) electron analyzer and a hollow cathode discharge He I light source is described in detail and the problems of the sampling of the photoelectrons in such an environment are discussed. For water and most of the alcohols up to six different electronic bands could be resolved. The spectra of 1-butanol and n-nonane show two weakly discernable peaks from which the threshold ionization potential could be determined. A deconvolution of the photoelectron spectra is used to extract ionization potentials of individual molecular bands of molecules near the surface of the liquid and shifts of the order of 1 eV compared to the gas phase are observed. A molecular orientation for water molecules at the surface of liquid water is inferred from a comparison of the relative band strengths with the gas phase. Similar effects are also observed for some of the alcohols. The results are discussed in terms of a simple "Born-solvation" model.

  7. Using Bulk Magnetic Susceptibility to Resolve Internal and External Signals in the NMR Spectra of Plant Tissues

    Science.gov (United States)

    Shachar-Hill, Yair; Befroy, Douglas E.; Pfeffer, Philip E.; Ratcliffe, R. George

    1997-07-01

    Internal and external NMR signals from a variety of plant cells and plant tissues can be resolved by changing the bulk magnetic susceptibility (BMS) of the perfusing medium with [Gd (EDTA)]-or Dy(DTPA-BMA). This separation is observed in samples consisting of cylindrical cells oriented along theB0field, and is consistent with established theoretical predictions about BMS effects. Evidence is presented that the shifted signals represent material outside the tissue as well as some contribution from intercellular spaces and cell walls, while intracellular signals are unshifted. The paramagnetic complexes used to separate the signals are shown to be nontoxic and to have no effect on a number of transport processes. The method has been applied to roots, shoots, and giant algal cells, facilitating the interpretation of thein vivospectra from a range of biologically important magnetic isotopes. The potential of the method for studies of transport is illustrated with experiments showing: (i)14N/15N isotopic exchange of nitrate in roots; (ii) the influx of HDO into root and shoot segments; and (iii) the use of saturation transfer to follow water movement into and out of plant cells.

  8. TIME-RESOLVED PROPERTIES AND GLOBAL TRENDS IN dMe FLARES FROM SIMULTANEOUS PHOTOMETRY AND SPECTRA

    Energy Technology Data Exchange (ETDEWEB)

    Kowalski, Adam F.; Hawley, Suzanne L.; Davenport, James R. A. [Astronomy Department, University of Washington, Box 351580, U.W. Seattle, WA 98195-1580 (United States); Wisniewski, John P. [HL Dodge Department of Physics and Astronomy, University of Oklahoma, 440 W Brooks Street, Norman, OK 73019 (United States); Osten, Rachel A. [Space Telescope Science Institute, 3700 San Martin Drive Baltimore, MD 21218 (United States); Hilton, Eric J. [Universe Sandbox, Seattle, WA (United States); Holtzman, Jon A. [Department of Astronomy, New Mexico State University, Box 30001, Las Cruces, NM 88003 (United States); Schmidt, Sarah J., E-mail: adam.f.kowalski@nasa.gov [Department of Astronomy, Ohio State University, 140 West 18th Avenue, Columbus, OH 43210 (United States)

    2013-07-15

    We present a homogeneous analysis of line and continuum emission from simultaneous high-cadence spectra and photometry covering near-ultraviolet and optical wavelengths for 20 M dwarf flares. These data were obtained to study the white-light continuum components at bluer and redder wavelengths than the Balmer jump. Our goals were to break the degeneracy between emission mechanisms that have been fit to broadband colors of flares and to provide constraints for radiative-hydrodynamic (RHD) flare models that seek to reproduce the white-light flare emission. The main results from the analysis are the following: (1) the detection of Balmer continuum (in emission) that is present during all flares and with a wide range of relative contributions to the continuum flux at bluer wavelengths than the Balmer jump; (2) a blue continuum at flare maximum that is linearly decreasing with wavelength from {lambda} = 4000-4800 A, indicative of hot, blackbody emission with typical temperatures of T{sub BB} {approx} 9000-14, 000 K; (3) a redder continuum apparent at wavelengths longer than H{beta} ({lambda} {approx}> 4900 A) which becomes relatively more important to the energy budget during the late gradual phase. The hot blackbody component and redder continuum component have been detected in previous studies of flares. However, we have found that although the hot blackbody emission component is relatively well-represented by a featureless, single-temperature Planck function, this component includes absorption features and has a continuum shape strikingly similar to the spectrum of an A-type star as directly observed in our flare spectra. New model constraints are presented for the time evolution among the hydrogen Balmer lines and between Ca II K and the blackbody continuum emission. We calculate Balmer jump flux ratios and compare to the solar-type flare heating predictions from RHD models. The model ratios are too large and the blue-optical ({lambda} = 4000-4800 A) slopes are too

  9. Spatially Resolved Spectra from a new X-ray Imaging Crystal Spectrometer for Measurements of Ion and Electron Temperature Profiles

    Energy Technology Data Exchange (ETDEWEB)

    Bitter, M; Stratton, B; Roquemore, A; Mastrovito, D; Lee, S; Bak, J; Moon, M; Nam, U; Smith, G; Rice, J; Beiersdorfer, P; Fraenkel, B

    2004-08-10

    A new type of high-resolution X-ray imaging crystal spectrometer is being developed to measure ion and electron temperature profiles in tokamak plasmas. The instrument is particularly valuable for diagnosing plasmas with purely Ohmic heating and rf heating, since it does not require the injection of a neutral beam - although it can also be used for the diagnosis of neutral-beam heated plasmas. The spectrometer consists of a spherically bent quartz crystal and a two-dimensional position-sensitive detector. It records spectra of helium-like argon (or krypton) from multiple sightlines through the plasma and projects a de-magnified image of a large plasma cross-section onto the detector. The spatial resolution in the plasma is solely determined by the height of the crystal, its radius of curvature, and the Bragg angle. This new X-ray imaging crystal spectrometer may also be of interest for the diagnosis of ion temperature profiles in future large tokamaks, such as KSTAR and ITER, where the application of the presently used charge-exchange spectroscopy will be difficult, if the neutral beams do not penetrate to the plasma center. The paper presents the results from proof-of-principle experiments performed with a prototype instrument at Alcator C-Mod.

  10. Time-Resolved Properties and Global Trends in dMe Flares from Simultaneous Photometry and Spectra

    CERN Document Server

    Kowalski, Adam F; Wisniewski, John P; Osten, Rachel A; Hilton, Eric J; Holtzman, Jon A; Schmidt, Sarah J; Davenport, James R A

    2013-01-01

    We present a homogeneous survey of line and continuum emission from near-ultraviolet (NUV) to optical wavelengths during twenty M dwarf flares with simultaneous, high cadence photometry and spectra. These data were obtained to study the white-light continuum components at bluer and redder wavelengths than the Balmer jump. Our goals were to break the degeneracy between emission mechanisms that have been fit to broadband colors of flares and to provide constraints for radiative-hydrodynamic (RHD) flare models that seek to reproduce the white-light flare emission. The main results from the continuum analysis are the following: 1) the detection of Balmer continuum (in emission) that is present during all flares and with a wide range of relative contributions to the continuum flux at bluer wavelengths than the Balmer jump; 2) a blue continuum at flare maximum that is linearly decreasing with wavelength from \\lambda = 4000-4800\\AA, matched by the spectral shape of hot, blackbody emission with typical temperatures o...

  11. Electronic spectra of 2- and 3-tolunitrile in the gas phase. I. A study of methyl group internal rotation via rovibronically resolved spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz-Santoyo, José Arturo; Álvarez-Valtierra, Leonardo, E-mail: leoav@fisica.ugto.mx [División de Ciencias e Ingenierías, Universidad de Guanajuato, León, Guanajuato 37150, México (Mexico); Wilke, Josefin; Wilke, Martin; Schmitt, Michael [Institut für Physikalische Chemie, Heinrich-Heine-Universität, 40225 Düsseldorf (Germany); Yi, John T. [Department of Chemistry, Winston-Salem State University, Winston-Salem, North Carolina 27110 (United States); Pratt, David W. [Department of Chemistry, University of Vermont, Burlington, Vermont 05405 (United States)

    2016-01-28

    Rotationally resolved fluorescence excitation spectra of the origin bands in the S{sub 1}←S{sub 0} transition of 2-tolunitrile (2TN) and 3-tolunitrile (3TN) have been recorded in the collision-free environment of a molecular beam. Analyses of these data provide the rotational constants of each molecule and the potential energy curves governing the internal rotation of the attached methyl groups in both electronic states. 2TN exhibits much larger barriers along this coordinate than 3TN. Interestingly, the electronic transition dipole moment in both molecules is markedly influenced by the position of the attached methyl group rather than the position of the cyano group; possible reasons for this intriguing behavior are discussed.

  12. Photoelectron spectroscopy and the dipole approximation

    Energy Technology Data Exchange (ETDEWEB)

    Hemmers, O.; Hansen, D.L.; Wang, H. [Univ. of Nevada, Las Vegas, NV (United States)] [and others

    1997-04-01

    Photoelectron spectroscopy is a powerful technique because it directly probes, via the measurement of photoelectron kinetic energies, orbital and band structure in valence and core levels in a wide variety of samples. The technique becomes even more powerful when it is performed in an angle-resolved mode, where photoelectrons are distinguished not only by their kinetic energy, but by their direction of emission as well. Determining the probability of electron ejection as a function of angle probes the different quantum-mechanical channels available to a photoemission process, because it is sensitive to phase differences among the channels. As a result, angle-resolved photoemission has been used successfully for many years to provide stringent tests of the understanding of basic physical processes underlying gas-phase and solid-state interactions with radiation. One mainstay in the application of angle-resolved photoelectron spectroscopy is the well-known electric-dipole approximation for photon interactions. In this simplification, all higher-order terms, such as those due to electric-quadrupole and magnetic-dipole interactions, are neglected. As the photon energy increases, however, effects beyond the dipole approximation become important. To best determine the range of validity of the dipole approximation, photoemission measurements on a simple atomic system, neon, where extra-atomic effects cannot play a role, were performed at BL 8.0. The measurements show that deviations from {open_quotes}dipole{close_quotes} expectations in angle-resolved valence photoemission are observable for photon energies down to at least 0.25 keV, and are quite significant at energies around 1 keV. From these results, it is clear that non-dipole angular-distribution effects may need to be considered in any application of angle-resolved photoelectron spectroscopy that uses x-ray photons of energies as low as a few hundred eV.

  13. Multiple Component Analysis of Time Resolved Spectra of GRB041006: A Clue to the Nature of Underlying Soft Component of GRBs

    CERN Document Server

    Shirasaki, Yuji; Kawai, Nobuyuki; Tamagawa, Toru; Sakamoto, Takanori; Suzuki, Motoko; Nakagawam, Yujin; Kobayashi, Akina; Sugita, Satoshi; Takahashi, Ichiro; Arimoto, Makoto; Shimokawabe, Takashi; Pazmino, Nicolas Vasquez; Ishimura, Takuto; Sato, Rie; Matsuoka, Masaru; Fenimore, Edward E; Galassi, Mark; Lamb, Donald Q; Graziani, Carlo; Donaghy, Timothy Q; Atteia, Jean-Luc; Pelangeon, Alexandre; Vanderspek, Roland; Crew, Geoffrey B; Doty, John P; Villasenor, Joel; Prigozhin, Gregory; Butler, Nat; Ricker, George R; Hurley, Kevin; Woosley, Stanford E; Pizzichini, Graziella

    2008-01-01

    GRB 041006 was detected by HETE-2 at 12:18:08 UT on 06 October 2004. This GRB displays a soft X-ray emission, a precursor before the onset of the main event, and also a soft X-ray tail after the end of the main peak. The light curves in four different energy bands display different features; At higher energy bands several peaks are seen in the light curve, while at lower energy bands a single broader bump dominates. It is expected that these different features are the result of a mixture of several components each of which has different energetics and variability. To reveal the nature of each component, we analysed the time resolved spectra and they are successfully resolved into several components. We also found that these components can be classified into two distinct classes; One is a component which has an exponential decay of $E_{p}$ with a characteristic timescale shorter than $\\sim$ 30 sec, and its spectrum is well represented by a broken power law function, which is frequently observed in many prompt ...

  14. CCl2-光电子能谱:Ab Initio计算与Franck-Condon分析%Photoelectron Spectra of CCl 2-:Ab Initio Calculation and Franck-Condon Analysis

    Institute of Scientific and Technical Information of China (English)

    吴军

    2015-01-01

    Geometry optimization and harmonic vibrational frequency calculations were performed on the ~X1 A1 state of CCl2 and~X2B1 state of CCl-2 at the B3LYP ,MP2 ,CCSD levels .Franck-Condon analysis and spectral simulations were carried out on the photoelectron band of CCl2- including Duschinsky effects .The simulated spectra obtained are in excellent agreement with the ex-periment .Note that Duschinsky effect between bending vibration and the symmetric stretch modes should be considered in the CCl2 (~X1 A1 )-CCl-2 (~X2 B1 ) photodetachment process .By combining ab initio calculations with Franck-Condon analyses ,the as-signment of spectrum observed is firmly established to the ~X1 A1-~X2 B1 photodetachment process of the CCl-2 radical ,and the rec-ommended geometric parameters of which in the literature are confirmed again base on ab initio theory and IFCA process .%在B3LYP ,M P2,CCSD水平理论下,分别对CCl2分子~X1 A1态和CCl2-分子~X2 B1态进行了几何结构优化和谐振频率分析。在考虑“Duschinsky效应”情况下,通过Franck-Condon因子计算模拟了CCl2-离子的光电子能谱带。计算表明弯曲振动模与对称伸缩模发生了模式混合,即“Duschinsky效应”在该体系中不能简单忽略。数值模拟的CCl2-在~X1 A1-~X2 B1电子态跃迁中振动分辨的理论谱与实验测量到的光电子能谱能够较好吻合,并对其中的振动谱线进行了归属和标识。结合 ab initio计算和 IFCA 方法,对 M urray , Leopold ,Miller和Lineberger推荐的CCl2-的几何构型参数进行了再确认。

  15. 二氧化铬阴离子光电子能谱的理论研究%Theoretical investigation on the photoelectron spectra of the photodetachmentprocess of the CrO2- anion

    Institute of Scientific and Technical Information of China (English)

    王茹; 崔方; 张浚贤; 梁军; 崔执凤

    2013-01-01

    凭借密度泛函理论,采用不同基组对中性分子CrO2的基态((X)3B1)以及阴离子CrO1-的基态((X)4B1)进行几何优化和振动频率分析;应用量化计算得到的力常数及结构和光谱参数,基于推得的两维四模Franck-Condon重叠积分的代数表示,对CrO2((X)3B1)-CrO2-((X)4B1)的光脱附过程进行Franck-Condon分析和光谱模拟,理论上得到光电子能谱的谱线相对强度及振动结构分布,理论谱与实验测得的二氧化铬阴离子光电子能谱达到一致,并对光电子能谱的振动结构进行归属及热带分析;另外,在光谱模拟过程中通过迭代Franck-Condon分析过程,推得CrO2-((X)4B1)与CrO2((X)3B1)平衡几何结构之差:△R(Cr-O)=0.05A,△∠(O-Cr-O)=12°.%Geometry optimization and harmonic vibrational frequency calculations were performed on the(X)3B1 state of CrO2 and (X)4B1 state of CrO2-by using the Density Functional Theory with various basis sets.The adiabatic electron affinity of CrO2 was investigated by using BPW91 and B3PW91 methods extrapolated to the complete basis set limit.Frank-Condon analyses and spectral simulations were carried out on the CrO2 ((X)3B1)-CrO2-((X)4B1) photodetachment process.The simulated photoelectron spectra of CrO2-are in excellent agreement with the observed ones.While the Duschinsky effect plays a minor role and can be neglected.In addition,the equilibrium geometry differences between the ion and neutral,△R(Cr-O)=0.05 (A) and △ ∠(O-Cr-O)=12°,were deduced by employing an iterative Franck-Condon analysis procedure in the spectral simulation.

  16. The Electron-Phonon Interaction as Studied by Photoelectron Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    D.W. Lynch

    2004-09-30

    With recent advances in energy and angle resolution, the effects of electron-phonon interactions are manifest in many valence-band photoelectron spectra (PES) for states near the Fermi level in metals.

  17. Vibrationally resolved ¹Lb (¹A')↔S0 (¹A') electronic spectra of benzimidazole and indene: Influence of Duschinsky and Herzberg-Teller effects on weak dipole-allowed transitions.

    Science.gov (United States)

    Yang, Pan; Pang, Min; Li, Ming; Shen, Wei; He, Rongxing

    2015-12-05

    Geometrical optimizations of the ground and first excited states of benzimidazole and indene were performed using the density functional theory (DFT) and its time-dependent extension methods (TD-DFT), respectively. Their vibrationally resolved (1)Lb ((1)A')↔S0 ((1)A') absorption and fluorescence spectra were simulated within the Franck-Condon approximation including the Herzberg-Teller (HT) and Duschinsky effects. Calculated results revealed that, with the HT and Duschinsky effects getting involved, the simulated weak (1)Lb ((1)A')↔S0 ((1)A') electronic spectra of the two molecules excellently reproduce the experimental findings. Based on the experimental data and other theoretical results, we tentatively assigned most of the vibrational normal modes which emerged in the experimental spectra of the two molecules. The present theoretical insights are expected to help us understand the nature of electronic transitions in the vibrationally resolved absorption and fluorescence spectra of benzimidazole and its analogues.

  18. Photoelectron-photoabsorption (PePa) database

    Science.gov (United States)

    Śmiałek, Małgorzata A.; Mason, Nigel J.

    2016-03-01

    In this paper a recently launched Photoelectron-Photoabsorption Database is presented. The database was developed in order to gather all the photoelectron and photoabsorption spectra measured by various collaborators over the years as well as to ease the access to the data to the potential users. In the paper the main features of the database were described and its outline explained. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  19. Accurate ab initio dipole moment surfaces of ozone: First principle intensity predictions for rotationally resolved spectra in a large range of overtone and combination bands

    Science.gov (United States)

    Tyuterev, Vladimir G.; Kochanov, Roman V.; Tashkun, Sergey A.

    2017-02-01

    Ab initio dipole moment surfaces (DMSs) of the ozone molecule are computed using the MRCI-SD method with AVQZ, AV5Z, and VQZ-F12 basis sets on a dense grid of about 1950 geometrical configurations. The analytical DMS representation used for the fit of ab initio points provides better behavior for large nuclear displacements than that of previous studies. Various DMS models were derived and tested. Vibration-rotation line intensities of 16O3 were calculated from these ab initio surfaces by the variational method using two different potential functions determined in our previous works. For the first time, a very good agreement of first principle calculations with the experiment was obtained for the line-by-line intensities in rotationally resolved ozone spectra in a large far- and mid-infrared range. This includes high overtone and combination bands up to Δ V = 6. A particular challenge was a correct description of the B-type bands (even Δ V3 values) that represented major difficulties for the previous ab initio investigations and for the empirical spectroscopic models. The major patterns of various B-type bands were correctly described without empirically adjusted dipole moment parameters. For the 10 μ m range, which is of key importance for the atmospheric ozone retrievals, our ab initio intensity results are within the experimental error margins. The theoretical values for the strongest lines of the ν3 band lie in general between two successive versions of HITRAN (HIgh-resolution molecular TRANsmission) empirical database that corresponded to most extended available sets of observations. The overall qualitative agreement in a large wavenumber range for rotationally resolved cold and hot ozone bands up to about 6000 cm-1 is achieved here for the first time. These calculations reveal that several weak bands are yet missing from available spectroscopic databases.

  20. Effects of symmetry on circular and linear magnetic dichroism in angle-resolved photoemission spectra of Gd/Y (0001) and Fe-Ni//Cu (001)

    Energy Technology Data Exchange (ETDEWEB)

    Goodman, K.W.; Tobin, J.G.; Schumann, F.O. [Pennsylvania State Univ., University Park, PA (United States); Willis, R.F. [Pennsylvania State Univ., University Park, PA (United States); Gammon, J.W. [Virginia Commonwealth Univ., Richmond, VA (United States); Pappas, D.P. [Virginia Commonwealth Univ., Richmond, VA (United States); Kortright, J.B. [Lawrence Berkeley National Lab., CA (United States); Denlinger, J.D. [Lawrence Berkeley National Lab., CA (United States); Rotenberg, E. [Lawrence Berkeley National Lab., CA (United States); Warwick, A. [Lawrence Berkeley National Lab., CA (United States); Smith, N.V. [Lawrence Berkeley National Lab., CA (United States)

    1997-03-26

    We have observed circular and linear magnetic dichroism in angle- resolved photoemission spectra of 50-monolayer Gd film grown on Y(0001) and 6-monolayer Fe-Ni alloy films grown on Cu(001). The 4f level of Gd and the Fe 3p level of the Fe-Ni alloy were measured. A different geometry was used for the magnetic circular dichroism than was used to measure the magnetic linear dichroism. The geometries were chosen so that the shape of the magnetic circular dichroism is predicted to be equal to the shape of the magnetic linear dichroism for four-fold symmetric Fe-Ni/Cu(001) but not for three-fold symmetric Gd/Y(0001). Experimental results are presented. In this paper we examine the effect of symmetry (experimental geometry and sample geometry) on magnetic linear and circular dichroism in angle- resolved photoemission. In particular we chose separate geometries for measuring magnetic circular and magnetic linear dichroism. The geometries were chosen such that samples with four-fold symmetry about the sample normal may have magnetic circular and magnetic linear dichroism of the same shape. But samples with three-fold symmetry should not exhibit circular and magnetic linear dichroism of the same shape. The samples studied are three-fold symmetric Gd films grown on Y(0001) and four-fold symmetric Fe-Ni alloy grown on Cu(001). After presenting the methods of the experiment, we briefly review parts of a model of magnetic dichroism developed by Venus and coworkers and our specialization and extension of it, particularly for FeNi/Cu(001). We then show the results of our measurements.

  1. Accurate ab initio dipole moment surfaces of ozone: First principle intensity predictions for rotationally resolved spectra in a large range of overtone and combination bands.

    Science.gov (United States)

    Tyuterev, Vladimir G; Kochanov, Roman V; Tashkun, Sergey A

    2017-02-14

    Ab initio dipole moment surfaces (DMSs) of the ozone molecule are computed using the MRCI-SD method with AVQZ, AV5Z, and VQZ-F12 basis sets on a dense grid of about 1950 geometrical configurations. The analytical DMS representation used for the fit of ab initio points provides better behavior for large nuclear displacements than that of previous studies. Various DMS models were derived and tested. Vibration-rotation line intensities of (16)O3 were calculated from these ab initio surfaces by the variational method using two different potential functions determined in our previous works. For the first time, a very good agreement of first principle calculations with the experiment was obtained for the line-by-line intensities in rotationally resolved ozone spectra in a large far- and mid-infrared range. This includes high overtone and combination bands up to ΔV = 6. A particular challenge was a correct description of the B-type bands (even ΔV3 values) that represented major difficulties for the previous ab initio investigations and for the empirical spectroscopic models. The major patterns of various B-type bands were correctly described without empirically adjusted dipole moment parameters. For the 10 μm range, which is of key importance for the atmospheric ozone retrievals, our ab initio intensity results are within the experimental error margins. The theoretical values for the strongest lines of the ν3 band lie in general between two successive versions of HITRAN (HIgh-resolution molecular TRANsmission) empirical database that corresponded to most extended available sets of observations. The overall qualitative agreement in a large wavenumber range for rotationally resolved cold and hot ozone bands up to about 6000 cm(-1) is achieved here for the first time. These calculations reveal that several weak bands are yet missing from available spectroscopic databases.

  2. Time courses and time-resolved spectra of firefly bioluminescence initiated by two methods of ATP injection and photolysis of caged ATP.

    Science.gov (United States)

    Yanagisawa, Yuki; Kageyama, Takeshi; Wada, Naohisa; Tanaka, Masatoshi; Ohno, Shin-Ya

    2013-01-01

    The time-dependent characteristics of firefly bioluminescence initiated by manual injection of adenosine triphosphate (ATP) into buffer solution containing luciferin (Ln), luciferase (Luc) and Mg(2+) were measured with a resolution of 10 ms, and compared with those obtained by photolysis of caged ATP. The time course depends on pH; both rise and decay rates decrease when pH is lowered from 7.8 to 6.8. In contrast, the parameter λ in the kinetic formula related to diffusion of ATP is almost independent of pH. The pH dependence of the time course of bioluminescence can be explained by the same pH tendency as the rate of ATP binding at the active site of Luc. The time-resolved spectra can be decomposed into two Gaussian components with maxima at 2.2 and 2.0 eV. At pH 7.8, the band at 2.2 eV is more intense than that at 2.0 eV for all three concentration conditions. At lower pH, the band at 2.2 eV becomes weaker than that at 2.0 eV. The intensity ratio of the 2.0 and 2.2 eV bands is constant for duration time of 600 s for both injection and photolysis experiments, and the above conclusions are unaffected by the concentration ratio [Ln]/[Luc].

  3. Photoelectron diffraction and holography: Some new directions

    Energy Technology Data Exchange (ETDEWEB)

    Fadley, C.S. [Lawrence Berkeley Lab., CA (United States)]|[California Univ., Davis, CA (United States). Dept. of Physics

    1993-08-01

    Photoelectron diffraction has by now become a versatile and powerful technique for studying surface structures, with special capabilities for resolving chemical and magnetic states of atoms and deriving direct structural information from both forward scattering along bond directions and back-scattering path length differences. Further fitting experiment to theory can lead to structural accuracies in the {plus_minus}0.03 ){Angstrom} range. Holographic inversions of such diffraction data also show considerable promise for deriving local three-dimensional structures around a given emitter with accuracies of {plus_minus}0.2--0.3 {Angstrom}. Resolving the photoelectron spin in some way and using circularly polarized radiation for excitation provide added dimensions for the study of magnetic systems and chiral experimental geometries. Synchrotron radiation with the highest brightness and energy resolution, as well as variable polarization, is crucial to the full exploitation of these techniques.

  4. Ultrafast Time-Resolved Emission and Absorption Spectra of meso-Pyridyl Porphyrins upon Soret Band Excitation Studied by Fluorescence Up-Conversion and Transient Absorption Spectroscopy.

    Science.gov (United States)

    Venkatesh, Yeduru; Venkatesan, M; Ramakrishna, B; Bangal, Prakriti Ranjan

    2016-09-08

    A comprehensive study of ultrafast molecular relaxation processes of isomeric meso-(pyridyl) porphyrins (TpyPs) has been carried out by using femtosecond time-resolved emission and absorption spectroscopic techniques upon pumping at 400 nm, Soret band (B band or S2), in 4:1 dichloromethane (DCM) and tetrahydrofuran (THF) solvent mixture. By combined studies of fluorescence up-conversion, time-correlated single photon counting, and transient absorption spectroscopic techniques, a complete model with different microscopic rate constants associated with elementary processes involved in electronic manifolds has been reported. Besides, a distinct coherent nuclear wave packet motion in Qy state is observed at low-frequency mode, ca. 26 cm(-1) region. Fluorescence up-conversion studies constitute ultrafast time-resolved emission spectra (TRES) over the whole emission range (430-710 nm) starting from S2 state to Qx state via Qy state. Careful analysis of time profiles of up-converted signals at different emission wavelengths helps to reveal detail molecular dynamics. The observed lifetimes are as indicated: A very fast decay component with 80 ± 20 fs observed at ∼435 nm is assigned to the lifetime of S2 (B) state, whereas being a rise component in the region of between 550 and 710 nm emission wavelength pertaining to Qy and Qx states, it is attributed to very fast internal conversion (IC) occurring from B → Qy and B → Qx as well. Two distinct components of Qy emission decay with ∼200-300 fs and ∼1-1.5 ps time constants are due to intramolecular vibrational redistribution (IVR) induced by solute-solvent inelastic collisions and vibrational redistribution induced by solute-solvent elastic collision, respectively. The weighted average of these two decay components is assigned as the characteristic lifetime of Qy, and it ranges between 0.3 and 0.5 ps. An additional ∼20 ± 2 ps rise component is observed in Qx emission, and it is assigned to the formation time of

  5. A photoelectron spectroscopy study of the electronic structure evolution in CuInSe{sub 2}-related compounds at changing copper content

    Energy Technology Data Exchange (ETDEWEB)

    Kuznetsova, T. V.; Grebennikov, V. I. [Institute of Metal Physics, UB RAS, 620041 Ekaterinburg (Russian Federation); Zhao, H. [Department of Materials Science and Engineering, Royal Institute of Technology, SE-100 44 Stockholm (Sweden); Derks, C.; Taubitz, C.; Neumann, M. [University of Osnabrueck, D-49069 Osnabrueck (Germany); Persson, C. [Department of Materials Science and Engineering, Royal Institute of Technology, SE-100 44 Stockholm (Sweden); Department of Physics, University of Oslo, P.O. Box 1048 Blindern, NO-0316 Oslo (Norway); Kuznetsov, M. V. [Institute of Solid State Chemistry, UB RAS, 620990 Ekaterinburg (Russian Federation); Urals Federal University, 19 Mira Str., Ekaterinburg 620002 (Russian Federation); Bodnar, I. V. [Department of Chemistry, Belarusian State University of Informatics and Radioelectronics, P. Brovka 6, 220027 Minsk (Belarus); Martin, R. W.; Yakushev, M. V. [Department of Physics, SUPA, Strathclyde University, G4 0NG Glasgow (United Kingdom)

    2012-09-10

    Evolution of the valence-band structure at gradually increasing copper content has been analysed by x-ray photoelectron spectroscopy (XPS) in In{sub 2}Se{sub 3}, CuIn{sub 5}Se{sub 8}, CuIn{sub 3}Se{sub 5}, and CuInSe{sub 2} single crystals. A comparison of these spectra with calculated total and angular-momentum resolved density-of-states (DOS) revealed the main trends of this evolution. The formation of the theoretically predicted gap between the bonding and non-bonding states has been observed in both experimental XPS spectra and theoretical DOS.

  6. Molecular dynamics and information on possible sites of interaction of intramyocellular metabolites in vivo from resolved dipolar couplings in localized 1H NMR spectra

    Science.gov (United States)

    Schröder, Leif; Schmitz, Christian; Bachert, Peter

    2004-12-01

    solutions of histidine and N-acetyl- L-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo 1H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle ( θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids.

  7. Photoelectronic properties of semiconductors

    CERN Document Server

    Bube, Richard H

    1992-01-01

    The interaction between light and electrons in semiconductors forms the basis for many interesting and practically significant properties. This book examines the fundamental physics underlying this rich complexity of photoelectronic properties of semiconductors, and will familiarise the reader with the relatively simple models that are useful in describing these fundamentals. The basic physics is also illustrated with typical recent examples of experimental data and observations. Following introductory material on the basic concepts, the book moves on to consider a wide range of phenomena, including photoconductivity, recombination effects, photoelectronic methods of defect analysis, photoeffects at grain boundaries, amorphous semiconductors, photovoltaic effects and photoeffects in quantum wells and superlattices. The author is Professor of Materials Science and Electrical Engineering at Stanford University, and has taught this material for many years. He is an experienced author, his earlier books having fo...

  8. Global nonresonant vibrational-photoelectron coupling in molecular photoionization

    Science.gov (United States)

    Poliakoff, Erwin; Das, Aloke; Hardy, David; Bozek, John; Aguilar, Alex; Lucchese, Robert

    2009-05-01

    Using photoelectron spectroscopy and Schwinger variational scattering theory, we have investigated the coupling between vibrational motion and the exiting photoelectron over extended ranges of photoelectron kinetic energy. Photoelectron spectroscopy is performed with vibrational resolution over uncommonly large ranges of energy (ca. 200 eV). We find clear and significant changes in vibrational branching ratios as a function of photon energy, in direct contradiction to predictions of the Franck-Condon principle. While it is well known that resonances lead to coupling between electronic and vibrational degrees of freedom, nonresonant mechanisms that result in such coupling are not expected or well-documented. Photoelectron spectra are presented for several electronic states of N2^+, CO^+, and NO^+, and we find that valence isoelectronic channels behave very differently, which is also surprising. Theoretical results indicate that Cooper minima are the underlying cause of these effects, and we are currently working to understand the reasons for the sensitivity of the Cooper minima on bond length.

  9. Imaging molecular structure with photoelectron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Boll, Rebecca

    2014-07-02

    The possibility to study the structure of polyatomic gas-phase molecules by photoelectron diffraction is investigated with the goal of developing a method capable of imaging ultrafast photochemical reactions with femtosecond temporal and sub-Angstroem spatial resolution. The fluorine 1s-level of adiabatically laser-aligned 1-ethynyl-4-fluorobenzene (C{sub 8}H{sub 5}F) molecules was ionized by X-ray pulses from the Linac Coherent Light Source Free-Electron Laser, and the angular distributions of photoelectrons with kinetic energies between 30 and 60 eV were recorded by velocity map imaging. Comparison with density functional theory calculations allows relating the measured distributions to the molecular structure. The results of an IR-pump, X-ray-probe experiment on aligned 1,4-dibromobenzene (C{sub 6}H{sub 4}Br{sub 2})molecules are presented to explore the potential of photoelectron diffraction for time-resolved imaging. The influence of the alignment laser pulse on the pumping and probing step is discussed. Laser-alignment is contrasted with determination of the molecular orientation by photoelectron-photoion coincidences for an exemplary data set on 1-ethynyl-4-fluorobenzene molecules recorded at the PETRA III synchrotron. Both methods are evaluated with respect to their applicability to record time-dependent snapshots of molecular structure. The results obtained in this work indicate possible future avenues for investigating ultrafast molecular dynamics using X-ray Free-Electron Lasers.

  10. Molecular structure and vibrational spectra of spin-crossover complexes in solution and colloidal media: resonance Raman and time-resolved resonance Raman studies.

    Science.gov (United States)

    Brady, Clare; Callaghan, Philip L; Ciunik, Zbigniew; Coates, Colin G; Døssing, Anders; Hazell, Alan; McGarvey, John J; Schenker, Sabine; Toftlund, Hans; Trautwein, Alfred X; Winkler, Heiner; Wolny, Juliusz A

    2004-07-12

    The spin-crossover system [Fe(btpa)](PF(6))(2) (btpa = N,N,N',N'-tetrakis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) and the predominantly low-spin species [Fe(b(bdpa))](PF(6))(2) ((b(bdpa) = N,N'-bis(benzyl)-N,N'-bis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) have been characterized by means of X-ray diffraction. The unit cell of [Fe(btpa)](PF(6))(2) contains two crystallographically independent molecules revealing octahedral low-spin and quasi-seven-coordinated high-spin structures. The unit cell of [Fe(b(bdpa))](PF(6))(2) contains two crystallographically independent molecules one of which corresponds to a low-spin structure, while the other reveals a disordering. On the basis of magnetic susceptibility and Mössbauer measurements, it has been proposed that this disorder involves low-spin and high-spin six-coordinated molecules. The structures of [Zn(btpa)](PF(6))(2) and [Ru(btpa)](PF(6))(2) have been determined also. Pulsed laser photoperturbation, coupled here with time-resolved resonance Raman spectroscopy (TR(3)), has been used to investigate, for the first time by this technique, the relaxation dynamics in solution on nanosecond and picosecond time scales of low-spin, LS ((1)A) --> high-spin, HS ((5)T) electronic spin-state crossover in these Fe(II) complexes. For the nanosecond experiments, use of a probe wavelength at 321 nm, falling within the pi-pi transition of the polypyridyl backbone of the ligands, enabled the investigation of vibrational modes of both LS and HS isomers, through coupling to spin-state-dependent angle changes of the backbone. Supplementary investigations of the spin-crossover (SCO) equilibrium in homogeneous solution and in colloidal media assisted the assignment of prominent features in the Raman spectra of the LS and HS isomers. The relaxation data from the nanosecond studies confirm and extend earlier spectrophotometric findings, (Schenker, S.; Stein, P. C.; Wolny, J. A.; Brady, C.; McGarvey, J. J

  11. Bonding in inorganic compounds: a study by x-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Avanzino, S.C.

    1978-10-01

    Core electron binding energies were measured for a variety of inorganic and organometallic compounds using gas-phase X-ray photoelectron spectroscopy (XPS). The atomic charge distributions in these molecules are deduced from the binding energies, often leading to a better understanding of the bonding in these compounds. The XPS spectra of fifteen volatile tin compounds were recorded. The data suggest that the metal d orbitals are not significantly involved in the bonding. The oxygen ls XPS spectra of gaseous CH/sub 3/Mn(CO)/sub 5/, (..pi..-C/sub 5/H/sub 5/Fe(CO)/sub 2/)/sub 2/, and Co/sub 4/(CO)/sub 12/ can be readily resolved into separate peaks due to bridging and terminal carbonyl groups. The C ls spectrum of Fe(CO)/sub 5/ consists of a single symmetric peak. The carbonyl ligand core binding energies of transition-metal carbonyl complexes are sensitive to differences in the metal-to-CO ligand bonding. Both C ls and O ls carbonyl binding energies correlate well with average C-O stretching force constants or average C-O stretching frequencies. The metal and carbonyl binding energies in a series of pentacarbonylmanganese complexes LMn(CO)/sub 5/ are a good measure of the relative electronegativities of the ligands L. High-quality X-ray photoelectron spectra have been obtained for compounds dissolved in glycerin solutions, and aqueous solutions were converted into glycerin solutions which gave good XRSspectra of the solutes. The technique appears promising as a future analytical application of X-ray photoelectron spectroscopy. The shifts in the binding energies of oxygen, chlorine, and carbon atoms in some isoelectronic isostructural compounds can be explained in terms of simple trends in atomic charges.

  12. Molecular design of DABNTf as a highly efficient resolving reagent for racemic Pd complex with Tropos biphenylphosphine (BIPHEP) ligand: circular dichroism (CD) spectra of enantiopure BIPHEP-Pd complex.

    Science.gov (United States)

    Mikami, Koichi; Yusa, Yukinori; Aikawa, Kohsuke; Hatano, Manabu

    2003-01-01

    The racemic Pd complexes with chirally flexible (tropos) biphenylphosphine (BIPHEP) ligands can be resolved but transformed into the enantio- and diastereo-pure complex. The enantiopure metal complex of BIPHEP ligand is thus obtained through enantiomer-selective complexation of a racemic BIPHEP-Pd complex with enantiopure 1,1'-binaphthyl-2,2'-di(triflyl)amide, DABNTf. The differential CD spectra of the enantiopure BIPHEP-Pd complex is also reported. Copyright 2002 Wiley-Liss, Inc.

  13. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    Energy Technology Data Exchange (ETDEWEB)

    Bradforth, S.E.

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound {yields} bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN{sup {minus}}, NCO{sup {minus}} and NCS{sup {minus}}. Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH{sub 3}0H,F + C{sub 2}H{sub 5}OH,F + OH and F + H{sub 2}. A time dependent framework for the simulation and interpretation of the bound {yields} free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH {yields} O({sup 3}P, {sup 1}D) + HF and F + H{sub 2}. The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H{sub 2} system, comparisons with three-dimensional quantum calculations are made.

  14. Vector potential photoelectron microscopy.

    Science.gov (United States)

    Browning, R

    2011-10-01

    A new class of electron microscope has been developed for the chemical microanalysis of a wide range of real world samples using photoelectron spectroscopy. Highly structured, three-dimensional samples, such as fiber mats and fracture surfaces can be imaged, as well as insulators and magnetic materials. The new microscope uses the vector potential field from a solenoid magnet as a spatial reference for imaging. A prototype instrument has demonstrated imaging of uncoated silk, magnetic steel wool, and micron-sized single strand tungsten wires.

  15. Photoelectron imaging spectroscopy of MoC{sup −} and NbN{sup −} diatomic anions: A comparative study

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Qing-Yu; Li, Zi-Yu; He, Sheng-Gui, E-mail: shengguihe@iccas.ac.cn, E-mail: chenh@iccas.ac.cn [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Hu, Lianrui; Chen, Hui, E-mail: shengguihe@iccas.ac.cn, E-mail: chenh@iccas.ac.cn [Beijing National Laboratory for Molecular Sciences, Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Ning, Chuan-Gang [Department of Physics, State Key Laboratory of Low-Dimensional Quantum Physics, Tsinghua University, Beijing 100084 (China); Ma, Jia-Bi [Key Laboratory of Cluster Science, The Institute for Chemical Physics, School of Chemistry, Beijing Institute of Technology, Beijing 100081 (China)

    2015-04-28

    The isoeletronic diatomic MoC{sup −} and NbN{sup −} anions have been prepared by laser ablation and studied by photoelectron imaging spectroscopy combined with quantum chemistry calculations. The photoelectron spectra of NbN{sup −} can be very well assigned on the basis of literature reported optical spectroscopy of NbN. In contrast, the photoelectron spectra of MoC{sup −} are rather complex and the assignments suffered from the presence of many electronically hot bands and limited information from the reported optical spectroscopy of MoC. The electron affinities of NbN and MoC have been determined to be 1.450 ± 0.003 eV and 1.360  ±  0.003 eV, respectively. The good resolution of the imaging spectroscopy provided a chance to resolve the Ω splittings of the X{sup 3}Σ{sup −} (Ω = 0 and 1) state of MoC and the X{sup 4}Σ{sup −} (Ω = 1/2 and 3/2) state of MoC{sup −} for the first time. The spin-orbit splittings of the X{sup 2}Δ state of NbN{sup −} and the a{sup 2}Δ state of MoC{sup −} were also determined. The similarities and differences between the electronic structures of the NbN and MoC systems were discussed.

  16. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lai-Sheng, E-mail: Lai-Sheng-Wang@brown.edu [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States)

    2015-07-28

    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

  17. Surface Reactions Studied by Synchrotron Based Photoelectron Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hrbek, J.

    1998-11-03

    The goal of this article is to illustrate the use of synchrotron radiation for investigating surface chemical reactions by photoelectron spectroscopy. A brief introduction and background information is followed by examples of layer resolved spectroscopy, oxidation and sulfidation of metallic, semiconducting and oxide surfaces.

  18. High-resolution photoelectron imaging spectroscopy of cryogenically cooled Fe4O- and Fe5O-

    Science.gov (United States)

    Weichman, Marissa L.; DeVine, Jessalyn A.; Neumark, Daniel M.

    2016-08-01

    We report high-resolution photodetachment spectra of the cryogenically cooled iron monoxide clusters Fe4O- and Fe5O- obtained with slow photoelectron velocity-map imaging (cryo-SEVI). Well-resolved vibrational progressions are observed in both sets of spectra, and transitions to low-lying excited states of both species are seen. In order to identify the structural isomers, electronic states, and vibrational modes that contribute to the cryo-SEVI spectra of these clusters, experimental results are compared with density functional theory calculations and Franck-Condon simulations. The main bands observed in the SEVI spectra are assigned to the 15A2←16B2 photodetachment transition of Fe4O- and the 17A'←18A″ photodetachment transition of Fe5O-. We report electron affinities of 1.6980(3) eV for Fe4O and 1.8616(3) eV for Fe5O, although there is some uncertainty as to whether the 15A2 state is the true ground state of Fe4O. The iron atoms have a distorted tetrahedral geometry in Fe4O0/- and a distorted trigonal-bipyramidal arrangement in Fe5O0/-. For both neutral and anionic species, the oxygen atom preferably binds in a μ2-oxo configuration along the cluster edge. This finding is in contrast to prior predictions that Fe5O0/- exhibits a μ3 face-bound structure.

  19. Ultrahigh spatiotemporal resolved spectroscopy

    Institute of Scientific and Technical Information of China (English)

    LI; Zhi

    2007-01-01

    We review the technique and research of the ultrahigh spatiotemporal resolved spectroscopy and its applications in the field of the ultrafast dynamics of mesoscopic systems and nanomaterials. Combining femtosecond time-resolved spectroscopy and scanning near-field optical microscopy (SNOM), we can obtain the spectra with ultrahigh temporal and spatial resolutions simultaneously. Some problems in doing so are discussed. Then we show the important applications of the ultrahigh spatiotemporal resolved spectroscopy with a few typical examples.……

  20. Ultrahigh spatiotemporal resolved spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    @@ We review the technique and research of the ultrahigh spatiotemporal resolved spectroscopy and its applications in the field of the ultrafast dynamics of mesoscopic systems and nanomaterials. Combining femtosecond time-resolved spectroscopy and scanning near-field optical microscopy (SNOM), we can obtain the spectra with ultrahigh temporal and spatial resolutions simultaneously. Some problems in doing so are discussed. Then we show the important applications of the ultrahigh spatiotemporal resolved spectroscopy with a few typical examples.

  1. Process the Experimental Data of Time-resolved Photoluminescence Lifetime Spectra on Cu2 O Nanowires by Origin%用Origin拟合Cu2 O纳米线时间分辨荧光光谱寿命

    Institute of Scientific and Technical Information of China (English)

    王鹏

    2015-01-01

    The time-resolved photoluminescence spectra of synthesized Cu2 O nanowires are fitted by the func-tion of exponential decay in Origin. The time-resolved photoluminescence lifetimes of the Cu2 O nanowires are obtained in the temperature region of 77-300 K.%基于用Origin软件的指数衰减拟合函数对制备得到的Cu2 O纳米线的时间分辨荧光光谱进行拟合,得到了Cu2 O纳米线在77-300 K温度范围内的瞬态荧光寿命值。

  2. Imaging Molecular Structure through Femtosecond Photoelectron Diffraction on Aligned and Oriented Gas-Phase Molecules

    DEFF Research Database (Denmark)

    Boll, Rebecca; Rouzee, Arnaud; Adolph, Marcus

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular...

  3. Spatially resolved quasiparticle tunneling spectra in the vortex state of optimally hole-doped YBa2Cu3Ox (Y-123)

    Science.gov (United States)

    Grinolds, M. S.; Beyer, A. D.; Teague, M. L.; Yeh, N.-C.

    2008-03-01

    We report cryogenic scanning tunneling spectroscopic (STS) studies of superconducting single crystalline Y-123 (Tc = 93 K) as a function of magnetic field. We study and model the influence of competing orders (COs), which coexist with superconductivity (SC), on the quasiparticle (QP) excitation spectra. The spatial dependence of the QP tunneling spectra is probed via STS to quantify the presence and spatial extent of SC and CO. Zero-field spatial maps of the QP spectra (100x100 nm^2) in Y-123 exhibit long-range spatial homogeneity of SC (δSC = 23±1 meV) associated with the spectral coherence peaks and the presence of CO (VCO = 33±2 meV) that gives rise to the spectral satellite features at δeff = [(δSC)^2+(VCO)^2]^1/2. Conductance maps of the Y-123 in finite fields demonstrate spatially varying spectra consistent with the periodicity a0 of the vortex lattice, with pseudogap (PG) like features at ˜VCO inside the vortex core and SC gap features remaining at ˜δSC outside the vortex core. Moreover, conductance histograms of the vortex state reveal that the ratio of the areas associated with δSC and VCO is comparable to (a0/ξab)^2, (ξab: in-plane SC coherence length). These results therefore suggest the important role of COs in the cuprate QP excitations. This work is supported by NSF Grant DMR-0405088.

  4. Internal energy dependence of the photodissociation dynamics of O3(-) using cryogenic photoelectron-photofragment coincidence spectroscopy.

    Science.gov (United States)

    Shen, Ben B; Benitez, Yanice; Lunny, Katharine G; Continetti, Robert E

    2017-09-07

    Photoelectron-photofragment coincidence (PPC) spectra of ozonide, O3(-), were measured at 388 nm (Ehν = 3.20 eV) using a newly constructed cryogenic octopole accumulation trap coupled to a PPC spectrometer. The photoelectron spectra reveal three processes consisting of a stable photodetachment channel, and two distinct photodissociation pathways yielding (1) O2 + O(-) or (2) O + O2(-). The first photodissociation pathway is observed in the PPC spectra by photodetachment of the O(-) product by a second photon, and produces electronically excited O2((1)Δg). The O2(-) product of the second photodissociation pathway undergoes autodetachment for O2(-)((2)Πg, v″ > 4), a process greatly enhanced by vibrational excitation of the precursor O3(-). Cooling anions thermalized at 300 K to cryogenic octopole accumulation trap essentially turns off this autodetachment pathway. The product kinetic energy distribution in coincidence with the autodetached electrons from O2(-)(v″ = 4) exhibits resolved features consistent with bend (ν2), asymmetric stretch (ν3) and a stretching combination band (ν1 + ν3) in the intermediate electronic state, illustrating the insights that can be gained from kinematically complete measurements. These results are discussed in the context of the low-lying excited states of O3(-).

  5. Photoelectron spectroscopy bulk and surface electronic structures

    CERN Document Server

    Suga, Shigemasa

    2014-01-01

    Photoelectron spectroscopy is now becoming more and more required to investigate electronic structures of various solid materials in the bulk, on surfaces as well as at buried interfaces. The energy resolution was much improved in the last decade down to 1 meV in the low photon energy region. Now this technique is available from a few eV up to 10 keV by use of lasers, electron cyclotron resonance lamps in addition to synchrotron radiation and X-ray tubes. High resolution angle resolved photoelectron spectroscopy (ARPES) is now widely applied to band mapping of materials. It attracts a wide attention from both fundamental science and material engineering. Studies of the dynamics of excited states are feasible by time of flight spectroscopy with fully utilizing the pulse structures of synchrotron radiation as well as lasers including the free electron lasers (FEL). Spin resolved studies also made dramatic progress by using higher efficiency spin detectors and two dimensional spin detectors. Polarization depend...

  6. Phase-resolved energy spectra of the Crab pulsar in the range of 50-400 GeV measured with the MAGIC telescopes

    Science.gov (United States)

    Aleksić, J.; Alvarez, E. A.; Antonelli, L. A.; Antoranz, P.; Asensio, M.; Backes, M.; Barrio, J. A.; Bastieri, D.; Becerra González, J.; Bednarek, W.; Berdyugin, A.; Berger, K.; Bernardini, E.; Biland, A.; Blanch, O.; Bock, R. K.; Boller, A.; Bonnoli, G.; Borla Tridon, D.; Braun, I.; Bretz, T.; Cañellas, A.; Carmona, E.; Carosi, A.; Colin, P.; Colombo, E.; Contreras, J. L.; Cortina, J.; Cossio, L.; Covino, S.; Dazzi, F.; de Angelis, A.; de Caneva, G.; de Cea Del Pozo, E.; de Lotto, B.; Delgado Mendez, C.; Diago Ortega, A.; Doert, M.; Domínguez, A.; Dominis Prester, D.; Dorner, D.; Doro, M.; Eisenacher, D.; Elsaesser, D.; Ferenc, D.; Fonseca, M. V.; Font, L.; Fruck, C.; García López, R. J.; Garczarczyk, M.; Garrido, D.; Giavitto, G.; Godinović, N.; Hadasch, D.; Häfner, D.; Herrero, A.; Hildebrand, D.; Höhne-Mönch, D.; Hose, J.; Hrupec, D.; Jogler, T.; Kellermann, H.; Klepser, S.; Krähenbühl, T.; Krause, J.; Kushida, J.; La Barbera, A.; Lelas, D.; Leonardo, E.; Lewandowska, N.; Lindfors, E.; Lombardi, S.; López, M.; López-Oramas, A.; Lorenz, E.; Makariev, M.; Maneva, G.; Mankuzhiyil, N.; Mannheim, K.; Maraschi, L.; Mariotti, M.; Martínez, M.; Mazin, D.; Meucci, M.; Miranda, J. M.; Mirzoyan, R.; Moldón, J.; Moralejo, A.; Munar-Adrover, P.; Niedzwiecki, A.; Nieto, D.; Nilsson, K.; Nowak, N.; Orito, R.; Paneque, D.; Paoletti, R.; Pardo, S.; Paredes, J. M.; Partini, S.; Perez-Torres, M. A.; Persic, M.; Peruzzo, L.; Pilia, M.; Pochon, J.; Prada, F.; Prada Moroni, P. G.; Prandini, E.; Puerto Gimenez, I.; Puljak, I.; Reichardt, I.; Reinthal, R.; Rhode, W.; Ribó, M.; Rico, J.; Rügamer, S.; Saggion, A.; Saito, K.; Saito, T. Y.; Salvati, M.; Satalecka, K.; Scalzotto, V.; Scapin, V.; Schultz, C.; Schweizer, T.; Shayduk, M.; Shore, S. N.; Sillanpää, A.; Sitarek, J.; Šnidarić, I.; Sobczynska, D.; Spanier, F.; Spiro, S.; Stamatescu, V.; Stamerra, A.; Steinke, B.; Storz, J.; Strah, N.; Surić, T.; Takalo, L.; Takami, H.; Tavecchio, F.; Temnikov, P.; Terzić, T.; Tescaro, D.; Teshima, M.; Tibolla, O.; Torres, D. F.; Treves, A.; Uellenbeck, M.; Vankov, H.; Vogler, P.; Wagner, R. M.; Weitzel, Q.; Zabalza, V.; Zandanel, F.; Zanin, R.; Hirotani, K.

    2012-04-01

    We use 73 h of stereoscopic data taken with the MAGIC telescopes to investigate the very high-energy (VHE) gamma-ray emission of the Crab pulsar. Our data show a highly significant pulsed signal in the energy range from 50 to 400 GeV in both the main pulse (P1) and the interpulse (P2) phase regions. We provide the widest spectra to date of the VHE components of both peaks, and these spectra extend to the energy range of satellite-borne observatories. The good resolution and background rejection of the stereoscopic MAGIC system allows us to cross-check the correctness of each spectral point of the pulsar by comparison with the corresponding (strong and well-known) Crab nebula flux. The spectra of both P1 and P2 are compatible with power laws with photon indices of 4.0 ± 0.8 (P1) and 3.42 ± 0.26 (P2), respectively, and the ratio P1/P2 between the photon counts of the two pulses is 0.54 ± 0.12. The VHE emission can be understood as an additional component produced by the inverse Compton scattering of secondary and tertiary e± pairs on IR-UV photons.

  7. Probing the structures and chemical bonding of boron-boronyl clusters using photoelectron spectroscopy and computational chemistry: B4(BO)(n)- (n = 1-3).

    Science.gov (United States)

    Chen, Qiang; Zhai, Hua-Jin; Li, Si-Dian; Wang, Lai-Sheng

    2012-07-28

    The electronic and structural properties of a series of boron oxide clusters, B(5)O(-), B(6)O(2)(-), and B(7)O(3)(-), are studied using photoelectron spectroscopy and density functional calculations. Vibrationally resolved photoelectron spectra are obtained, yielding electron affinities of 3.45, 3.54, and 4.94 eV for the corresponding neutrals, B(5)O, B(6)O(2), and B(7)O(3), respectively. Structural optimizations show that these oxide clusters can be formulated as B(4)(BO)(n)(-) (n = 1-3), which involve boronyls coordinated to a planar rhombic B(4) cluster. Chemical bonding analyses indicate that the B(4)(BO)(n)(-) clusters are all aromatic species with two π electrons.

  8. Probing the structures and chemical bonding of boron-boronyl clusters using photoelectron spectroscopy and computational chemistry: B4(BO)n- (n = 1-3)

    Science.gov (United States)

    Chen, Qiang; Zhai, Hua-Jin; Li, Si-Dian; Wang, Lai-Sheng

    2012-07-01

    The electronic and structural properties of a series of boron oxide clusters, B5O-, B6O2-, and B7O3-, are studied using photoelectron spectroscopy and density functional calculations. Vibrationally resolved photoelectron spectra are obtained, yielding electron affinities of 3.45, 3.54, and 4.94 eV for the corresponding neutrals, B5O, B6O2, and B7O3, respectively. Structural optimizations show that these oxide clusters can be formulated as B4(BO)n- (n = 1-3), which involve boronyls coordinated to a planar rhombic B4 cluster. Chemical bonding analyses indicate that the B4(BO)n- clusters are all aromatic species with two π electrons.

  9. PHOTOCONDUCTIVE PROPERTIES OF PVK:Alq3 BLEND FILMS STUDIED BY STEADY-STATE AND TIME-RESOLVED TRANSIENT PHOTOCURRENT SPECTRA

    Institute of Scientific and Technical Information of China (English)

    Hui Jin; Yan-bing Hou; Xian-guo Meng; Ai-wei Tang; Feng Teng

    2008-01-01

    The carrier transport properties of the blends of the hole transport material poly(N-vinylcarbazole) (PVK) and the electron transport material tris (8-hydroxyquinolinotato) aluminum Ⅲ (Alq3) are investigated at room temperature using steady-state and time-resolved transient photocurrent measurements as a function of doping concentration of Alq3. Due to lower LUMO and higher HOMO energy level of Alq3 than those of PVK, Alq3 molecules may act as carrier trap states in PVK films at low concentration. However, at high concentration of Alq3, phase separation reduces trap states to some extent,which leads to the rise of photocurrent. It is concluded that strong excitation transfer from PVK to Alq3 does harm to photocurrent, because strong fluorescence effect of Alq3 inhibits photogeneration of charge carriers. In time-resolved transient photocurrent measurements, it is found that the decay time is obviously shortened because the recombination rate increases and the electron mobility of Alq3 is higher than the hole mobility of PVK.

  10. Photoelectron spectroscopy principles and applications

    CERN Document Server

    Hüfner, Stefan

    1995-01-01

    Photoelectron Spectroscopy presents an up-to-date introduction to the field by treating comprehensively the electronic structures of atoms, molecules, solids and surfaces Brief descriptions are given of inverse photoemission, spin-polarized photoemission and photoelectron diffraction Experimental aspects are considered throughout the book, and the results are carefully interpreted by theory A wealth of measured data is presented in the form of tables for easy use by experimentalists

  11. Phase-resolved energy spectra of the Crab Pulsar in the range of 50-400 GeV measured with the MAGIC Telescopes

    CERN Document Server

    Aleksić, J; Antonelli, L A; Antoranz, P; Asensio, M; Backes, M; Barrio, J A; Bastieri, D; González, J Becerra; Bednarek, W; Berdyugin, A; Berger, K; Bernardini, E; Biland, A; Blanch, O; Bock, R K; Boller, A; Bonnoli, G; Tridon, D Borla; Braun, I; Bretz, T; Cañellas, A; Carmona, E; Carosi, A; Colin, P; Colombo, E; Contreras, J L; Cortina, J; Cossio, L; Covino, S; Dazzi, F; De Angelis, A; De Caneva, G; del Pozo, E De Cea; De Lotto, B; Mendez, C Delgado; Ortega, A Diago; Doert, M; Domínguez, A; Prester, D Dominis; Dorner, D; Doro, M; Eisenacher, D; Elsaesser, D; Ferenc, D; Fonseca, M V; Font, L; Fruck, C; López, R J García; Garczarczyk, M; Garrido, D; Giavitto, G; Godinović, N; Hadasch, D; Häfner, D; Herrero, A; Hildebrand, D; Höhne-Mönch, D; Hose, J; Hrupec, D; Jogler, T; Kellermann, H; Klepser, S; Krähenbühl, T; Krause, J; Kushida, J; La Barbera, A; Lelas, D; Leonardo, E; Lewandowska, N; Lindfors, E; Lombardi, S; López, M; López-Oramas, A; Lorenz, E; Makariev, M; Maneva, G; Mankuzhiyil, N; Mannheim, K; Maraschi, L; Marcote, B; Mariotti, M; Martínez, M; Mazin, D; Meucci, M; Miranda, J M; Mirzoyan, R; Moldón, J; Moralejo, A; Munar-Adrover, P; Niedzwiecki, A; Nieto, D; Nilsson, K; Nowak, N; Orito, R; Paneque, D; Paoletti, R; Pardo, S; Paredes, J M; Partini, S; Perez-Torres, M A; Persic, M; Peruzzo, L; Pilia, M; Pochon, J; Prada, F; Moroni, P G Prada; Prandini, E; Gimenez, I Puerto; Puljak, I; Reichardt, I; Reinthal, R; Rhode, W; Ribó, M; Rico, J; Rügamer, S; Saggion, A; Saito, K; Saito, T Y; Salvati, M; Satalecka, K; Scalzotto, V; Scapin, V; Schultz, C; Schweizer, T; Shayduk, M; Shore, S N; Sillanpää, A; Sitarek, J; Snidaric, I; Sobczynska, D; Spanier, F; Spiro, S; Stamatescu, V; Stamerra, A; Steinke, B; Storz, J; Strah, N; Surić, T; Takalo, L; Takami, H; Tavecchio, F; Temnikov, P; Terzić, T; Tescaro, D; Teshima, M; Tibolla, O; Torres, D F; Treves, A; Uellenbeck, M; Vankov, H; Vogler, P; Wagner, R M; Weitzel, Q; Zabalza, V; Zandanel, F; Zanin, R; Hirotani, K

    2011-01-01

    We use 73 h of stereoscopic data taken with the MAGIC telescopes to investigate the very high energy (VHE) gamma-ray emission of the Crab Pulsar. Our data show a highly significant pulsed signal in the energy range from 50 to 400 GeV, in both the main pulse (P1) and interpulse (P2) phase regions. We provide the widest spectra to date of the VHE components of both peaks, extending down to the energy range of satellite-borne observatories. The improved precision and background rejection of the stereoscopic technique leads to relatively low systematic uncertainties and allows us to cross-check the correctness of each spectral point of the pulsar by comparison with the corresponding (strong and well-known) Crab Nebula flux. The spectra of both P1 and P2 are compatible with power laws of photon indices 4.0\\pm0.8 (P1) and 3.42\\pm0.26 (P2), respectively, and the ratio P1/P2 between the pulses is 0.54\\pm 0.12. The VHE emission can be understood as an additional component produced by inverse Compton scattering of seco...

  12. A simple electron time-of-flight spectrometer for ultrafast vacuum ultraviolet photoelectron spectroscopy of liquid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Arrell, C. A., E-mail: christopher.arrell@epfl.ch; Ojeda, J.; Mourik, F. van; Chergui, M. [Laboratory of Ultrafast Spectroscopy, ISIC, Station 6, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Sabbar, M.; Gallmann, L.; Keller, U. [Physics Department, ETH Zurich, 8093 Zurich (Switzerland); Okell, W. A.; Witting, T.; Siegel, T.; Diveki, Z.; Hutchinson, S.; Tisch, J. W.G.; Marangos, J. P. [Department of Physics, The Blackett Laboratory, Imperial College, London SW7 2AZ (United Kingdom); Chapman, R. T.; Cacho, C.; Rodrigues, N.; Turcu, I. C.E.; Springate, E. [Central Laser Facility, STFC Rutherford Appleton Laboratory, Oxon OX11 0QX (United Kingdom)

    2014-10-01

    We present a simple electron time of flight spectrometer for time resolved photoelectron spectroscopy of liquid samples using a vacuum ultraviolet (VUV) source produced by high-harmonic generation. The field free spectrometer coupled with the time-preserving monochromator for the VUV at the Artemis facility of the Rutherford Appleton Laboratory achieves an energy resolution of 0.65 eV at 40 eV with a sub 100 fs temporal resolution. A key feature of the design is a differentially pumped drift tube allowing a microliquid jet to be aligned and started at ambient atmosphere while preserving a pressure of 10⁻¹ mbar at the micro channel plate detector. The pumping requirements for photoelectron (PE) spectroscopy in vacuum are presented, while the instrument performance is demonstrated with PE spectra of salt solutions in water. The capability of the instrument for time resolved measurements is demonstrated by observing the ultrafast (50 fs) vibrational excitation of water leading to temporary proton transfer.

  13. Optimal fitting of gaussian-apodized or under-resolved emission lines in Fourier Transform spectra providing new insights on the velocity structure of NGC 6720

    Science.gov (United States)

    Martin, Thomas B.; Prunet, Simon; Drissen, Laurent

    2016-09-01

    An analysis of the kinematics of NGC 6720 is performed on the commissioning data obtained with SITELLE, the Canada-France-Hawaii Telescope's new imaging Fourier transform spectrometer. In order to measure carefully the small broadening effect of a shell expansion on an unresolved emission line, we have determined a computationally robust implementation of the convolution of a Gaussian with a sinc instrumental line shape which avoids arithmetic overflows. This model can be used to measure line broadening of typically a few km s-1 even at low spectral resolution (R less than 5000). We have also designed the corresponding set of Gaussian apodizing functions that are now used by ORBS, the SITELLE's reduction pipeline. We have implemented this model in ORCS, a fitting engine for SITELLE's data, and used it to derive the [S II] density map of the central part of the nebula. The study of the broadening of the [N II] lines shows that the Main Ring and the Central Lobe are two different shells with different expansion velocities. We have also derived deep and spatially resolved velocity maps of the Halo in [N II] and Hα and found that the brightest bubbles are originating from two bipolar structures with a velocity difference of more than 35 km s-1 lying at the poles of a possibly unique Halo shell expanding at a velocity of more than 15 km s-1.

  14. A study of selective spectrophotometric methods for simultaneous determination of Itopride hydrochloride and Rabeprazole sodium binary mixture: Resolving sever overlapping spectra

    Science.gov (United States)

    Mohamed, Heba M.

    2015-02-01

    Itopride hydrochloride (IT) and Rabeprazole sodium (RB) are co-formulated together for the treatment of gastro-esophageal reflux disease. Three simple, specific and accurate spectrophotometric methods were applied and validated for simultaneous determination of Itopride hydrochloride (IT) and Rabeprazole sodium (RB) namely; constant center (CC), ratio difference (RD) and mean centering of ratio spectra (MCR) spectrophotometric methods. Linear correlations were obtained in range of 10-110 μg/μL for Itopride hydrochloride and 4-44 μg/mL for Rabeprazole sodium. No preliminary separation steps were required prior the analysis of the two drugs using the proposed methods. Specificity was investigated by analyzing the synthetic mixtures containing the two cited drugs and their capsules dosage form. The obtained results were statistically compared with those obtained by the reported method, no significant difference was obtained with respect to accuracy and precision. The three methods were validated in accordance with ICH guidelines and can be used for quality control laboratories for IT and RB.

  15. Differential reflectivity and angle-resolved photoemission of PbS(1 0 0)

    Science.gov (United States)

    Cricenti, A.; Tallarida, M.; Ottaviani, C.; Kowalski, B.; Gutievitz, E.; Szczerbakow, A.; Orlowski, B. A.

    2001-06-01

    The surface electronic structure of a PbS sample, cleaved in ultra-high-vacuum environment, has been studied with surface differential reflectivity (SDR) and angle-resolved photoelectron spectroscopy (ARUPS). The ARUPS spectra show the presence of two surface (resonance) states along the two angular directions [0 0 1] and [0 1 1]. SDR shows the existence of a gap of approximately 2.1 eV and two more optical transitions at energies of 2.7 and 3.1 eV. These transitions have been, tentatively, assigned to different points in the surface Brillouin zone.

  16. High pressure and time-resolved luminescence spectra of Ca3Y2(SiO4)3 doped with Eu2+ and Eu3+.

    Science.gov (United States)

    Baran, A; Mahlik, S; Grinberg, M; Zych, E

    2013-01-16

    Tricalcium diyttrium trisilicon oxide, Ca(3)Y(2)(SiO(4))(3) doped with Eu(2+) and Eu(3+) belongs to a very limited number of hosts able to accommodate both Eu(3+) and Eu(2+) ions, which might make it useful for white light emitting diodes (WLEDs) based on UV chip technology. In this contribution we present a detailed study of photoluminescence kinetics and high pressure spectroscopy of Eu(3+) and Eu(2+) doped Ca(3)Y(2)(SiO(4))(3). At ambient pressure and room temperature, under excitation with near-UV radiation, a broad emission band from 400 to 550 nm due to the 4f(6)5d(1)→4f(7)((8)S(7/2)) transition in Eu(2+) was observed, as well as several emission peaks in the region between 550 and 710 nm, ascribed to the (5)D(0)→ (7)F(J) (J = 0-4) transitions in Eu(3+). The bluish green luminescence related to Eu(2+) in the Ca(3)Y(2)(SiO(4))(3) exhibits a small red pressure-induced shift reaching -5.2 cm(-1)/kbar. The red shifts of the luminescence lines related to Eu(3+) ion emission vary from 0.15 to -0.54 cm(-1)/kbar. Time-resolved photoluminescence was measured at different temperatures and pressures. Luminescence decay traces were studied for the bluish green emission band of Eu(2+) and for the red emission peak due to the (5)D(0) →  (7)F(2) transition of Eu(3+). Decay times slightly decreased with increasing pressure.

  17. Photoelectron circular dichroism of isopropanolamine

    Science.gov (United States)

    Catone, D.; Turchini, S.; Contini, G.; Prosperi, T.; Stener, M.; Decleva, P.; Zema, N.

    2017-01-01

    Spectroscopies based on circular polarized light are sensitive to the electronic and structural properties of chiral molecules. Photoelectron circular dichroism (PECD) is a powerful technique that combines the chiral sensitivity of the circular polarized light and the electronic information obtained by photoelectron spectroscopy. An experimental and theoretical PECD study of the outer valence and C 1s core states of 1-amino-2-propanol in the gas phase is presented. The experimental dichroic dispersions in the photoelectron kinetic energy are compared with theoretical calculations employing a multicentric basis set of B-spline functions and a Kohn-Sham Hamiltonian. In order to understand analogies and differences in the dichroism of structural isomers bearing the same functional groups, a comparison with previous PECD study of valence band of 2-amino-1-propanol is carried out.

  18. On Interpreting the Photoelectron Spectra of MgO

    Science.gov (United States)

    Bauschlicher, Charles W., Jr.; Partridge, Harry; Arnold, James (Technical Monitor)

    2001-01-01

    The (sup 2)Sigma(+) and (sup 2)Pi states of MgO(-) and the (sup 1)Sigma(+), (sup 1)Pi, and (sup 3)Pi states of MgO are studied using the averaged coupled-pair functional (ACPF) approach. The computed spectroscopic constants are in good agreement with the available experimental data. The computed Franck-Condon factors and photodetachment overlaps are compared with experiment.

  19. Photoelectron photoion molecular beam spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Trevor, D.J.

    1980-12-01

    The use of supersonic molecular beams in photoionization mass spectroscopy and photoelectron spectroscopy to assist in the understanding of photoexcitation in the vacuum ultraviolet is described. Rotational relaxation and condensation due to supersonic expansion were shown to offer new possibilities for molecular photoionization studies. Molecular beam photoionization mass spectroscopy has been extended above 21 eV photon energy by the use of Stanford Synchrotron Radiation Laboratory (SSRL) facilities. Design considerations are discussed that have advanced the state-of-the-art in high resolution vuv photoelectron spectroscopy. To extend gas-phase studies to 160 eV photon energy, a windowless vuv-xuv beam line design is proposed.

  20. Intensity-Resolved Above Threshold Ionization of Xenon with Short Laser Pulses

    CERN Document Server

    Hart, Nathan A; Kaya, Gamze; Kaya, Necati; Kolomenskii, Alexandre A; Schuessler, Hans A

    2014-01-01

    We present intensity-resolved above threshold ionization (ATI) spectra of xenon using an intensity scanning and deconvolution technique. Experimental data were obtained with laser pulses of 58 fs and central wavelength of 800 nm from a chirped-pulse amplifier. Applying a deconvolution algorithm, we obtained spectra that have higher contrast and are in excellent agreement with characteristic 2 $U_p$ and 10 $U_p$ cutoff energies contrary to that found for raw data. The retrieved electron ionization probability is consistent with the presence of a second electron from double ionization. This recovered ionization probability is confirmed with a calculation based on the PPT tunneling ionization model [Perelomov, Popov, and Terent'ev, Sov. Phys. JETP 23, 924 (1966)]. Thus, the measurements of photoelectron yields and the proposed deconvolution technique allowed retrieval of more accurate spectroscopic information from the ATI spectra and ionization probability features that are usually concealed by volume averaging...

  1. Valence state of manganese and iron ions in La{sub 1−x}A{sub x}MnO{sub 3} (A = Ca, Sr) and Bi{sub 1−x}Sr{sub x}FeO{sub 3} systems from Mn2p, Mn3s, Fe2p and Fe3s X-ray photoelectron spectra. Effect of delocalization on Fe3s spectra splitting

    Energy Technology Data Exchange (ETDEWEB)

    Kozakov, A.T. [Scientific Research Institute of Physics at Southern Federal University, 194 Stachki, Rostov on Don 344090 (Russian Federation); Kochur, A.G., E-mail: agk@rgups.ru [Rostov State Transport University, 2 Narodnogo Opolcheniya, Rostov on Don 344038 (Russian Federation); Googlev, K.A.; Nikolskii, A.V. [Scientific Research Institute of Physics at Southern Federal University, 194 Stachki, Rostov on Don 344090 (Russian Federation); Torgashev, V.I.; Trotsenko, V.G. [Faculty of Physics, Southern Federal University, 344006, Rostov on Don (Russian Federation); Bush, A.A. [Moscow State Technical University of Radio Engineering, Electronics and Automation, 119454, Moscow (Russian Federation)

    2015-10-25

    La{sub 1−x}Ca{sub x}MnO{sub 3} (x = 0.5, 0.7, 0.85, 0.95) ceramic samples are synthesized by solid state reaction method. Mn3s and Mn2p X-ray photoelectron spectra (XPS) of La{sub 1−x}Ca{sub x}MnO{sub 3}, and Fe3s-spectra of Bi{sub 1−x}Sr{sub x}FeO{sub 3} (0 ≤ x ≤ 1) are measured at room temperature. Both Mn{sup 3+} and Mn{sup 4+} ions are discovered in La{sub 1−x}Ca{sub x}MnO{sub 3} similarly to the case of Fe{sup 3+} and Fe{sup 4+} found earlier in Bi{sub 1−x}Sr{sub x}FeO{sub 3} ceramics. Relative Mn{sup 3+}/Mn{sup 4+} contents are determined by fitting measured Mn2p spectra with combinations of Mn2p spectra of compounds containing tri- and quadrivalent Mn ions. Relative portion of Mn{sup 4+} is shown to increase with the increase of x. Fe3s spectrum splitting in Bi{sub 1−x}Sr{sub x}FeO{sub 3} increases with x in contrast to the Mn3s-spectrum splitting in La{sub 1−x}Ca{sub x}MnO{sub 3} and La{sub 1−x}Sr{sub x}MnO{sub 3}. Anomalous behavior of Fe3s splitting is explained in the frame of the model of partly itinerant 3d-electrons by strong effect of 3d electron delocalization on electron correlation interaction in final state of 3s photoabsorption. - Highlights: • Mn3s, Mn2p XPS of La{sub 1−x}Ca{sub x}MnO{sub 3}, and Fe3s XPS of Bi{sub 1−x}Sr{sub x}FeO{sub 3} are measured. • Relative Mn{sup 4+}/Mn{sup 3+} contents are determined by decomposition of Mn2p XPS. • Splitting of Fe3s XPS in Bi{sub 1−x}Sr{sub x}FeO{sub 3} grows with the increase of Fe{sup 4+} content. • 3d electrons in Bi{sub 1−x}Sr{sub x}FeO{sub 3} are partly itinerant. • Anomalous behavior of Fe3s in Bi{sub 1−x}Sr{sub x}FeO{sub 3}is due to 3d electrons delocalization.

  2. Photoelectron Spectroscopy Study of Quinonimides

    Energy Technology Data Exchange (ETDEWEB)

    Hossain, Ekram; Deng, Shihu; Gozem, Samer; Krylov, Anna; Wang, Xue-Bin; Wenthold, Paul G.

    2017-08-16

    Structures and energetics of o-, m- and p-quinonimide anions (OC6H4N) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, and it is shown that accurate predictions for the electronic structure of the para quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.

  3. A facility for the analysis of the electronic structures of solids and their surfaces by synchrotron radiation photoelectron spectroscopy

    Science.gov (United States)

    Hoesch, M.; Kim, T. K.; Dudin, P.; Wang, H.; Scott, S.; Harris, P.; Patel, S.; Matthews, M.; Hawkins, D.; Alcock, S. G.; Richter, T.; Mudd, J. J.; Basham, M.; Pratt, L.; Leicester, P.; Longhi, E. C.; Tamai, A.; Baumberger, F.

    2017-01-01

    A synchrotron radiation beamline in the photon energy range of 18-240 eV and an electron spectroscopy end station have been constructed at the 3 GeV Diamond Light Source storage ring. The instrument features a variable polarisation undulator, a high resolution monochromator, a re-focussing system to form a beam spot of 50 × 50 μm2, and an end station for angle-resolved photoelectron spectroscopy (ARPES) including a 6-degrees-of-freedom cryogenic sample manipulator. The beamline design and its performance allow for a highly productive and precise use of the ARPES technique at an energy resolution of 10-15 meV for fast k-space mapping studies with a photon flux up to 2 ṡ 1013 ph/s and well below 3 meV for high resolution spectra.

  4. A facility for the analysis of the electronic structures of solids and their surfaces by synchrotron radiation photoelectron spectroscopy.

    Science.gov (United States)

    Hoesch, M; Kim, T K; Dudin, P; Wang, H; Scott, S; Harris, P; Patel, S; Matthews, M; Hawkins, D; Alcock, S G; Richter, T; Mudd, J J; Basham, M; Pratt, L; Leicester, P; Longhi, E C; Tamai, A; Baumberger, F

    2017-01-01

    A synchrotron radiation beamline in the photon energy range of 18-240 eV and an electron spectroscopy end station have been constructed at the 3 GeV Diamond Light Source storage ring. The instrument features a variable polarisation undulator, a high resolution monochromator, a re-focussing system to form a beam spot of 50 × 50 μm(2), and an end station for angle-resolved photoelectron spectroscopy (ARPES) including a 6-degrees-of-freedom cryogenic sample manipulator. The beamline design and its performance allow for a highly productive and precise use of the ARPES technique at an energy resolution of 10-15 meV for fast k-space mapping studies with a photon flux up to 2 ⋅ 10(13) ph/s and well below 3 meV for high resolution spectra.

  5. Visible and ultraviolet photoelectron spectroscopy of fullerenes using femtosecond laser pulses

    OpenAIRE

    Campbell E. E. B.; Henderson G. G.; Johansson J. O.

    2013-01-01

    Photoelectron spectra are presented for C60 excited with fs pulses of wavelengths 532 and 267 nm. The spectra indicate a quick redistribution of the excitation energy. Excitation of SAMO states is observed with 532 nm excitation, but due to the relatively large photon energy of the 267 nm pulses, these orbitals are not populated for this wavelength.

  6. On the photoelectron velocity-map imaging of lutetium monoxide anion LuO(-).

    Science.gov (United States)

    Liu, Zhiling; Xie, Hua; Li, Quanjiang; Qin, Zhengbo; Cong, Ran; Wu, Xia; Tang, Zichao; Fan, Hongjun

    2014-01-21

    We report a combined photoelectron velocity-map imaging spectroscopy and density functional theory investigation on lutetium monoxide anion. Transition between the X (1)Σ(+) anion electronic ground state and the neutral X (2)Σ(+) electronic ground state is observed. Vibrationally resolved spectra were obtained at four different photon energies, providing a wealth of spectroscopic information for the electronic ground states of the anionic lutetium monoxide and corresponding neutral species. Franck-Condon simulations of the ground-state transition are performed to assign vibrational structure in the spectra and to assist in identifying the observed spectral bands. The electronic ground state of LuO(-) is found to have a vibrational frequency of 743 ± 10 cm(-1) and an equilibrium bond length of 1.841 Å. The electron affinity of LuO is measured to be 1.624 ± 0.002 eV. The fundamental frequency of ground-state LuO is estimated to be 839 ± 10 cm(-1).

  7. SiON metrology using angular and energy distributions of photoelectrons

    Science.gov (United States)

    Tasneem, G.; Tomastik, C.; Mroczyński, R.; Werner, W. S. M.

    2013-06-01

    Angle-resolved X-ray photoelectron spectroscopy (ARXPS) is a useful tool for non-destructive in-depth analysis of near surface regions. However, the reconstruction of depth profile from ARXPS data is an ill-posed mathematical problem. Thus, the main goal of this work was to develop a new, iterative algorithm based on the least square fitting which allows to solve this problem. The depth profiles were restored by dividing sample in thin virtual box shaped layers each with a different concentration. To extract information on the depth distribution, this algorithm is based on the analysis of the angular peak intensities along with the inelastic background. In addition, the physically trivial constraint of atomic fractions adding up to unity was imposed. The model takes into account the effect of elastic scattering and anisotropy of the photoelectric cross section. To test the algorithm, experimental spectrum for SiON samples on Si substrate were measured with a Thermo Theta Probe electron spectrometer for off-normal emission angles in the range between 25° and 75°. A very good agreement was found between the measured spectra and obtained spectra from the algorithm.

  8. Photoelectron Imaging of OXIDE.VOC Clusters

    Science.gov (United States)

    Patros, Kellyn M.; Mann, Jennifer; Chick Jarrold, Caroline

    2016-06-01

    Perturbations of the bare O2- and O4- electronic structure arising from VOC (VOC = hexane, isoprene, benzene and benzene.D6) interactions are investigated using anion photoelectron imaging at 2.33 and 3.49 eV photon energies. Trends observed from comparing features in the spectra include VOC-identity-dependent electron affinities of the VOC complexes relative to the bare oxide clusters, due to enhance stability in the anion complex relative to the neutral. Autodetachment is observed in all O4-.VOC spectra and only isoprene with O2-. In addition, the intensities of transitions to states correlated with the singlet states of O2 neutral via detachment from the O2-.VOC anion complexes show dramatic VOC-identity variations. Most notably, benzene as a complex partner significantly enhances these transitions relative to O2- and O2-.hexane. A less significant enhancement is also observed in the O2-.isoprene complex. This enhancement may be due to the presence of low-lying triplet states in the complex partners.

  9. Conformation-resolved UV spectra of Pb(II) complexes: a gas phase study of the sandwich structures [Pb(toluene)2]2+ and [Pb(benzene)2]2+.

    Science.gov (United States)

    Ma, Lifu; Takashima, Tsukiko; Koka, Joseph; Kimber, Helen J; Cox, Hazel; Stace, Anthony J

    2013-04-28

    Toxic heavy metals, such as Pb(2+), have become important targets for the development of efficient receptors that are capable of recognizing their presence as environmental and biological pollutants, and an important part of that receptor-metal characterization process is the provision of spectral evidence that identifies the presence of a metal ion. From results reported here on a combined experimental and theoretical study it is shown that, when complexed with aromatic ligands, Pb(2+) is capable of yielding structured UV spectra, which: (i) exhibit discrete electronic transitions that include significant contributions from the metal ion; (ii) are very sensitive to the electronic properties of coordinating ligands; and (iii) are sensitive to subtle changes in coordination geometry. Two aromatic sandwich complexes, [Pb(benzene)2](2+) and [Pb(toluene)2](2+) have been prepared in the gas phase and their UV action spectra recorded from ions held and cooled in an ion trap. Whilst [Pb(benzene)2](2+) exhibits a spectrum with very little detail, that recorded for [Pb(toluene)2](2+) reveals a rich structure in the wavelength range 220-280 nm. Theory in the form of density functional theory (DFT) shows that both types of complex take the form of hemidirected structures, and that [Pb(toluene)2](2+) can adopt three distinct conformers depending upon the relative positions of the two methyl groups. Further calculations, using adiabatic time-dependent DFT to assign electronic transitions, provide evidence of individual [Pb(toluene)2](2+) conformers having been resolved in the experimental spectrum. Of particular significance for the development of methods for identifying Pb(2+) as an environmental or biological pollutant, is the observation that there are distinct ligand-to-metal charge transfer transitions in the UV that are sensitive to both the geometry and the electronic characteristics of molecules that accommodate the metal ion.

  10. Imaging molecular structure through femtosecond photoelectron diffraction on aligned and oriented gas-phase molecules

    OpenAIRE

    Boll, Rebecca; Rouzée, Arnaud; Christensen, Lauge; Coffee, Ryan; Coppola, Niccola; Sankar,; Decleva, Piero; Epp, Sascha W.; Erk, Benjamin; Filsinger, Frank; Foucar, Lutz; Gorkhover, Tais; Adolph, Marcus; Gumprecht, Lars; Hömke, André

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump–probe setup combining optical lasers and an X-ray free-electron laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laser-aligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffrac...

  11. Monitoring Nonadiabatic Electron-Nuclear Dynamics in Molecules by Attosecond Streaking of Photoelectrons.

    Science.gov (United States)

    Kowalewski, Markus; Bennett, Kochise; Rouxel, Jérémy R; Mukamel, Shaul

    2016-07-22

    Streaking of photoelectrons has long been used for the temporal characterization of attosecond extreme ultraviolet pulses. When the time-resolved photoelectrons originate from a coherent superposition of electronic states, they carry additional phase information, which can be retrieved by the streaking technique. In this contribution we extend the streaking formalism to include coupled electron and nuclear dynamics in molecules as well as initial coherences. We demonstrate how streaked photoelectrons offer a novel tool for monitoring nonadiabatic dynamics as it occurs in the vicinity of conical intersections and avoided crossings. Streaking can provide high time resolution direct signatures of electronic coherences, which affect many primary photochemical and biological events.

  12. Monitoring Nonadiabatic Electron-Nuclear Dynamics in Molecules by Attosecond Streaking of Photoelectrons

    Science.gov (United States)

    Kowalewski, Markus; Bennett, Kochise; Rouxel, Jérémy R.; Mukamel, Shaul

    2016-07-01

    Streaking of photoelectrons has long been used for the temporal characterization of attosecond extreme ultraviolet pulses. When the time-resolved photoelectrons originate from a coherent superposition of electronic states, they carry additional phase information, which can be retrieved by the streaking technique. In this contribution we extend the streaking formalism to include coupled electron and nuclear dynamics in molecules as well as initial coherences. We demonstrate how streaked photoelectrons offer a novel tool for monitoring nonadiabatic dynamics as it occurs in the vicinity of conical intersections and avoided crossings. Streaking can provide high time resolution direct signatures of electronic coherences, which affect many primary photochemical and biological events.

  13. Time-Resolved Single-State Measurements of the Electronic Structure of Isochoric Heated Copper

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A J; Dunn, J; Widmann, K; Ao, T; Ping, Y; Hunter, J; Ng, A

    2004-10-22

    Time-resolved x-ray photoelectron spectroscopy is used to probe the non-steady-state evolution of the valence band electronic structure of laser heated ultra-thin (50 nm) Cu. Single-shot x-ray laser induced time-of-flight photoelectron spectroscopy with picosecond time resolution is used in conjunction with optical measurements of the disassembly dynamics that have shown the existence of a metastable liquid phase in fs-laser heated Cu foils persisting 4-5 ps. This metastable phase is studied using a 527 nm wavelength 400 fs laser pulse containing 0.1-2.5 mJ laser energy focused in a large 500 x 700 {micro}m{sup 2} spot to create heated conditions of 0.07-1.8 x 10{sup 12} W cm{sup -2} intensity. Valence band photoemission spectra showing the changing occupancy of the Cu 3d level with heating are presented. These are the first picosecond x-ray laser time-resolved photoemission spectra of laser-heated ultra-thin Cu foil showing changes in electronic structure. The ultrafast nature of this technique lends itself to true single-state measurements of shocked and heated materials.

  14. Laser-induced electron emission from a tungsten nanotip: identifying above threshold photoemission using energy-resolved laser power dependencies

    CERN Document Server

    Bionta, M R; Champeaux, J P; Faure, S; Masseboeuf, A; Moretto-Capelle, P; Chatel, B

    2013-01-01

    We present an experiment studying the interaction of a strongly focused 25 fs laser pulse with a tungsten nanotip, investigating the different regimes of laser-induced electron emission. We study the dependence of the electron yield with respect to the static electric field applied to the tip. Photoelectron spectra are recorded using a retarding field spectrometer and peaks separated by the photon energy are observed with a 45 % contrast. They are a clear signature of above threshold photoemission (ATP), and are confirmed by extensive spectrally resolved studies of the laser power dependence. Understanding these mechanisms opens the route to control experiment in the strong-field regime on nanoscale objects.

  15. Negative ion photoelectron spectra of ISO3, IS2O3, and IS2O4 intermediates formed in interfacial reactions of ozone and iodide/sulfite aqueous microdroplets

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Zhengbo; Hou, Gao-Lei; Yang, Zheng; Valiev, Marat; Wang, Xue-Bin

    2016-12-07

    Three short-lived, anionic intermediates, ISO3, IS2O3, and IS2O4, are detected during reactions between ozone and aqueous iodine/sulfur oxides microdroplets. These species may play an important role in ozone-driven inorganic aerosol formation; however their chemical properties remain largely unknown. This is the issue addressed in this work using negative ion photoelectron spectroscopy (NIPES) and ab-initio modeling. The NIPE spectra reveal that all of the three anionic species are characterized by high adiabatic detachment energies (ADEs) - 4.62 ± 0.10, 4.52 ± 0.10, and 4.60 ± 0.10 eV for ISO3, IS2O3, and IS2O4, respectively. Vibrational progressions with frequencies assigned to the S–O symmetric stretching modes are also discernable in the ground state transition features. Density functional theory (DFT) calculations show the presence of several low-lying isomers involving different bonding scenarios. Further analysis based on high level CCSD(T) calculations reveal that the lowest energy structures are characterized by formation of I–S and S–S bonds and can be structurally viewed as SO3 linked with I, IS, and ISO for ISO3, IS2O3, and IS2O4, respectively. The calculated ADEs and vertical detachment energies (VDEs) are in excellent agreement with the experimental results, further supporting the identified minimum energy structures. The obtained intrinsic molecular properties of these anionic intermediates and neutral radicals should be useful to help understand their photochemical reactions in the atmosphere.

  16. Angular distribution and atomic effects in condensed phase photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Davis, R.F.

    1981-11-01

    A general concept of condensed phase photoelectron spectroscopy is that angular distribution and atomic effects in the photoemission intensity are determined by different mechanisms, the former being determined largely by ordering phenomena such as crystal momentum conservation and photoelectron diffraction while the latter are manifested in the total (angle-integrated) cross section. In this work, the physics of the photoemission process is investigated in several very different experiments to elucidate the mechanisms of, and correlation between, atomic and angular distribution effects. Theoretical models are discussed and the connection betweeen the two effects is clearly established. The remainder of this thesis, which describes experiments utilizing both angle-resolved and angle-integrated photoemission in conjunction with synchrotron radiation in the energy range 6 eV less than or equal to h ..nu.. less than or equal to 360 eV and laboratory sources, is divided into three parts.

  17. Electronic structures of U X3 (X =Al , Ga, and In) studied by photoelectron spectroscopy

    Science.gov (United States)

    Fujimori, Shin-ichi; Kobata, Masaaki; Takeda, Yukiharu; Okane, Tetsuo; Saitoh, Yuji; Fujimori, Atsushi; Yamagami, Hiroshi; Haga, Yoshinori; Yamamoto, Etsuji; Ōnuki, Yoshichika

    2017-09-01

    The electronic structures of U X3 (X =Al , Ga , and In ) were studied by photoelectron spectroscopy to understand the relationship between their electronic structures and magnetic properties. The band structures and Fermi surfaces of UAl3 and UGa3 were revealed experimentally by angle-resolved photoelectron spectroscopy (ARPES), and they were compared with the result of band-structure calculations. The topologies of the Fermi surfaces and the band structures of UAl3 and UGa3 were explained reasonably well by the calculation, although bands near the Fermi level (EF) were renormalized owing to the finite electron correlation effect. The topologies of the Fermi surfaces of UAl3 and UGa3 are very similar to each other, except for some minor differences. Such minor differences in their Fermi surface or electron correlation effect might take an essential role in their different magnetic properties. No significant changes were observed between the ARPES spectra of UGa3 in the paramagnetic and antiferromagnetic phases, suggesting that UGa3 is an itinerant weak antiferromagnet. The effect of chemical pressure on the electronic structures of U X3 compounds was also studied by utilizing the smaller lattice constants of UAl3 and UGa3 than that of UIn3. The valence band spectrum of UIn3 is accompanied by a satellitelike structure on the high-binding-energy side. The core-level spectrum of UIn3 is also qualitatively different from those of UAl3 and UGa3. These findings suggest that the U 5 f states in UIn3 are more localized than those in UAl3 and UGa3.

  18. High-Resolution Infrared-Vacuum Ultraviolet Photoion and Pulsed Field Ionization-Photoelectron Methods for Spectroscopic Studies of Neutrals and Cations

    Institute of Scientific and Technical Information of China (English)

    Xi Xing; Beth Reed; Mi Kyung Bahng; Peng Wang; Hin Koo Woo; Sun Jong Baek; Chee Shine Lam; Cheuk Yiu Ng

    2008-01-01

    We show that by scanning the frequency of a single mode infrared (IR) optical parametric oscillator (IR- OPO) laser to excite the molecular species of interest and fixing the frequency of a vacuum ultraviolet (VUV) laser to photoionize the IR excited species, high-resolution IR spectra of polyatomic neutrals can be obtained with high sensitivity. The fact that this IR-VUV-photoion (IR-VUV-PI) method is based on VUV photoionization probe, and thus, allows the identification of the neutral IR absorber, makes it applicable for IR spectroscopy measurements of isotopemers, radicals, and clusters, which usually exist as impure samples. The highly resolved IR-VUV-PI measurements achieved using the single mode IR-OPO laser have made possible the selection of single rovibrational states of CH3X (X=Br and I), C2H4, and C3H4 for VUV-pulsed field ionization-photoelectron (VUV-PFI-PE) measurements, resulting in rovibrationally resolved photoelectron spectra for these polyatomic molecules. These experiments show that the signal- to-noise ratios of the IR-VUV-PI and IR-VUV-PFI-PE spectra obtained by employing the high-resolution IR-OPO laser are significantly higher than those observed in previous IR-VUV-PI and IR-VUV-PFI-PE studies using a low-resolution IR-OPO laser. Further improvement in sensitivity of IR-VUV-PI and IR- VUV-PFI-PE measurements by using the collinear arrangement of IR-VUV lasers and molecular beam is discussed.

  19. Structural origin of Si-2p core-level shifts from Si(100)-c[4x2] surface: A spectral x-ray photoelectron diffraction study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, X.; Tonner, B.P. [Univ. of Wisconsin, Milwaukee, WI (United States); Denlinger, J. [Univ. of Wisconsin, Milwaukee, WI (United States)][Ernest Orlando Lawrence Berkeley National Lab., CA (United States)] [and others

    1997-04-01

    The authors have performed angle-resolved x-ray photoelectron diffraction (XPD) from a Si(100)-c(4x2) surface to study the structural origin of Si-2p core-level shifts. In the experiment, the highly resolved surface Si-2p core-level spectra were measured as a fine grid of hemisphere and photon energies, using the SpectroMicroscopy Facility {open_quotes}ultraESCA{close_quotes} instrument. By carefully decomposing the spectra into several surface peaks, the authors are able to obtain surface-atom resolved XPD patterns. Using a multiple scattering analysis, they derived a detailed atomic model for the Si(100)-c(4x2) surface. In this model, the asymmetric dimers were found tilted by 11.5 plus/minus 2.0 degrees with bond length of 2.32 plus/minus 0.05{angstrom}. By matching model XPD patterns to experiment, the authors can identify which atoms in the reconstructed surface are responsible for specific photoemission lines in the 2p spectrum.

  20. Threshold photoelectron spectroscopy of the imidogen radical

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, Gustavo A., E-mail: gustavo.garcia@synchrotron-soleil.fr [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Gans, Bérenger [Institut des Sciences Moléculaires d’Orsay, Univ Paris-Sud, CNRS, Bât 210, Univ Paris-Sud, 91405 Orsay Cedex (France); Tang, Xiaofeng [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Ward, Michael; Batut, Sébastien [PC2A, Université de Lille 1, UMR CNRS-USTL 8522, Cité Scientifique Bât. C11, F-59655 Villeneuve d’Ascq (France); Nahon, Laurent [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Fittschen, Christa [PC2A, Université de Lille 1, UMR CNRS-USTL 8522, Cité Scientifique Bât. C11, F-59655 Villeneuve d’Ascq (France); Loison, Jean-Christophe [ISM, Université de Bordeaux, CNRS, 351 cours de la Libération, 33405 Talence Cedex (France)

    2015-08-15

    We present the threshold photoelectron spectroscopy of the imidogen radical (NH) recorded in the photon energy region up to 1 eV above its first ionization threshold. The radical was produced by reaction of NH{sub 3} and F in a microwave discharge flow-tube and photoionized using vacuum ultraviolet (VUV) synchrotron radiation. A double imaging coincidence spectrometer was used to record mass-selected spectra and avoid contributions from the byproducts present in the reactor and background gas. The energy region includes the ground X{sup +2}Π and first electronically excited a{sup +4}Σ{sup −} states of NH{sup +}. Strong adiabatic transitions and weak vibrational progressions up to v{sup +} = 2 are observed for both electronic states. The rotational profile seen in the origin band has been modeled using existing neutral and cationic spectroscopic constants leading to a precise determination of the adiabatic ionization energy at 13.480 ± 0.002 eV.

  1. Circular dichroism in photoelectron images from aligned nitric oxide molecules

    Science.gov (United States)

    Sen, Ananya; Pratt, S. T.; Reid, K. L.

    2017-07-01

    We have used velocity map photoelectron imaging to study circular dichroism of the photoelectron angular distributions (PADs) of nitric oxide following two-color resonance-enhanced two-photon ionization via selected rotational levels of the A 2Σ+, v'=0 state. By using a circularly polarized pump beam and a counter-propagating, circularly polarized probe beam, cylindrical symmetry is preserved in the ionization process, and the images can be reconstructed using standard algorithms. The velocity map imaging set up enables individual ion rotational states to be resolved with excellent collection efficiency, rendering the measurements considerably simpler to perform than previous measurements conducted with a conventional photoelectron spectrometer. The results demonstrate that circular dichroism is observed even when cylindrical symmetry is maintained, and serve as a reminder that dichroism is a general feature of the multiphoton ionization of atoms and molecules. The observed PADs are in good agreement with calculations based on parameters extracted from previous experimental results obtained by using a time-of-flight electron spectrometer.

  2. Photoelectron spectroscopy of several lanthanide β-diketonates

    Energy Technology Data Exchange (ETDEWEB)

    Westcott, Barry L., E-mail: westcottb@ccsu.edu [Department of Chemistry and Biochemistry, Central Connecticut State University, New Britain, CT 06053 (United States); Seguin, Trevor J. [Department of Chemistry and Biochemistry, Central Connecticut State University, New Britain, CT 06053 (United States); Gruhn, Nadine E. [Department of Chemistry, University of Washington, Seattle, WA 98195 (United States)

    2014-03-01

    The valence region electronic structure of Ln(acac){sub 3} complexes (Ln = Nd, Tm, Pr; acac = acetylacetonate) is investigated using, principally, gas-phase ultraviolet photoelectron (PE) spectroscopy. Analysis of PE spectra focuses on the 7–12 eV region containing the first several ionization bands which likely contain metal f-ionizations and acac-based ionizations. These correspond to oxygen 2p-type orbitals and carbon 2p-type orbitals, which are equivalent to oxygen lone pairs and electrons from the pi-bond system of the ligand.

  3. Electronic structures of AlMoO(y)(-) (y = 1-4) determined by photoelectron spectroscopy and density functional theory calculations.

    Science.gov (United States)

    Waller, Sarah E; Mann, Jennifer E; Hossain, Ekram; Troyer, Mary; Jarrold, Caroline C

    2012-07-14

    Vibrationally-resolved photoelectron spectra of AlMoO(y)(-) (y = 1-4) are presented and analyzed in conjunction with density functional theory computational results. The structures determined for the AlMoO(y) anion and neutral clusters suggest ionic bonding between Al(+) and a MoO(y)(-) or MoO(y)(-2) moiety, and point to the relative stability of Mo=O versus Al=O bonds. The highest occupied and partially occupied orbitals in the anions and neutrals can be described as Mo atomic-like orbitals, so while the Mo is in a higher oxidation state than Al, the most energetically accessible electrons are localized on the molybdenum center.

  4. Molecular photoionisation using synchrotron radiation. Photoelectron photoion coincidence and circular dichroism

    CERN Document Server

    Garcia-Macias, G A

    2002-01-01

    The first ionisation potential of the CF sub 3 radical has been determined in this work from the appearance potential of the CF sub 3 sup + fragment, formed in the photofragmentation of CF sub 3 Br. In obtaining this value special care has been taken in removing the contributions from second order light and internal energy of the fragmenting parent ion. The resulting ionisation potential was found to be in very good agreement with a number of recent theoretical calculations. The valence photoelectron spectra of three monoterpenes such as limonene, carvone and camphor have been recorded along with their mass spectra taken in coincidence with energy selected photoelectrons, providing information about state selected parent ion fragmentation channels. A new photoelectron spectrometer based on the Alien box design has been studied by ray-tracing simulations. It will include a two dimensional position sensitive detector system consisting in two micro channel plates in a chevron stack and a delay-line anode to enco...

  5. Electronic structures of WAlO(y) and WAlO(y)(-) (y = 2-4) determined by anion photoelectron spectroscopy and density functional theory calculations.

    Science.gov (United States)

    Mann, Jennifer E; Waller, Sarah E; Jarrold, Caroline Chick

    2012-07-28

    The anion photoelectron spectra of WAlO(y)(-) (y = 2-4) are presented and assigned based on results of density functional theory calculations. The WAlO(2)(-) and WAlO(3)(-) spectra are both broad, with partially resolved vibrational structure. In contrast, the WAlO(4)(-) spectrum features well-resolved vibrational structure with contributions from three modes. There is reasonable agreement between experiment and theory for all oxides, and calculations are in particular validated by the near perfect agreement between the WAlO(4)(-) photoelectron spectrum and a Franck-Condon simulation based on computationally determined spectroscopic parameters. The structures determined from this study suggest strong preferential W-O bond formation, and ionic bonding between Al(+) and WO(y)(-2) for all anions. Neutral species are similarly ionic, with WAlO(2) and WAlO(3) having electronic structure that suggests Al(+) ionically bound to WO(y)(-) and WAlO(4) being described as Al(+2) ionically bound to WO(4)(-2). The doubly-occupied 3sp hybrid orbital localized on the Al center is energetically situated between the bonding O-local molecular orbitals and the anti- or non-bonding W-local molecular orbitals. The structures determined in this study are very similar to structures recently determined for the analogous MoAlO(y)(-)/MoAlO(y) cluster series, with subtle differences found in the electronic structures [S. E. Waller, J. E. Mann, E. Hossain, M. Troyer, and C. C. Jarrold, J. Chem. Phys. 137, 024302 (2012)].

  6. Hard X-ray photoelectron spectroscopy: A few recent applications

    Energy Technology Data Exchange (ETDEWEB)

    Taguchi, M., E-mail: mtaguchi@spring8.or.jp [RIKEN SPring-8 Center, Sayo, Hyogo 679-5148 (Japan); Takata, Y.; Chainani, A. [RIKEN SPring-8 Center, Sayo, Hyogo 679-5148 (Japan)

    2013-10-15

    Highlights: ► We discuss recent applications of HAXPES carried out at BL29XU in SPring-8. ► We provide a brief description of the salient features of the instrument. ► The recoil effect of photoelectrons in core levels and valence band are discussed. ► We overview HAXPES studies of a series of 3d transition metal compounds. ► The extended cluster model for explaining well-screened feature is presented. -- Abstract: In this report, we discuss a few recent applications of hard X-ray photoelectron spectroscopy (HAXPES) carried out at the RIKEN beamline BL29XU in SPring-8. We first provide a brief description of the salient features of the instrument in operation at BL29 XU in SPring-8. HAXPES studies on the recoil effect of photoelectrons in core levels and valence band states are presented. The experiments show remarkable consistency with theoretical results and indicate the role of phonon excitations in the recoil effect of photoelectrons. We then overview HAXPES applied to the study of a series of 3d transition metal (TM) compounds. The HAXPES experimental results often show an additional well-screened feature in bulk sensitive electronic structure of strongly correlated compounds compared to surface sensitive spectra. The extended cluster model developed by us for explaining this well-screened feature is validated for a series of TM compounds. These results show that HAXPES is a valuable tool for the study of doping and temperature dependent electronic structure of solids with tremendous potential for future activities.

  7. X-ray photoelectron spectroscopy of FeP phosphide

    Energy Technology Data Exchange (ETDEWEB)

    Teterin, Yu. A.; Sobolev, A. V., E-mail: salex12@rambler.ru, E-mail: alex@radio.chem.msu.ru; Presnyakov, I. A.; Maslakov, K. I. [Moscow State University (Russian Federation); Teterin, A. Yu. [National Research Center “Kurchatov Institute,” (Russian Federation); Morozov, I. V.; Chernyavskii, I. O. [Moscow State University (Russian Federation); Ivanov, K. E. [National Research Center “Kurchatov Institute,” (Russian Federation); Shevel’kov, A. V. [Moscow State University (Russian Federation)

    2017-02-15

    The structure of the outer and inner electron spectra of iron (2p, 3p, 3s, and 3d) and phosphorus (3s and 3p) atoms in FeP monophosphide is studied in detail by the X-ray photoelectron spectroscopy (XPS) method. On the basis of the analysis of the binding energy of electrons, as well as the parameters characterizing the structure of experimental spectra, a conclusion is made that Fe{sup 3+} (d{sup 5}) cations in FeP are stabilized in a state with intermediate value of the total spin (IS, S = 3/2). The range of values of intra-atomic parameters (10Dq, J{sub H}) is established in which the consideration of the high degree of covalence of Fe–P bonds may lead to the stabilization of (FeP{sub 6}){sup 15–} clusters in the IS state.

  8. Monitoring Nonadiabatic Electron-Nuclear Dynamics in Molecules by Attosecond Streaking of Photoelectrons

    CERN Document Server

    Kowalewski, Markus; Rouxel, Jérémy R; Mukamel, Shaul

    2016-01-01

    Streaking of photoelectrons has long been used for the temporal characterization of attosecond extreme ultraviolet pulses. When the time-resolved photoelectrons originate from a coherent superposition of electronic states, they carry an additional phase information, which can be retrieved by the streaking technique. In this contribution we extend the streaking formalism to include coupled electron and nuclear dynamics in molecules as well as initial coherences and demonstrate how it offers a novel tool to monitor non-adiabatic dynamics as it occurs in the vicinity of conical intersections and avoided crossings. Streaking can enhance the time resolution and provide direct signatures of electronic coherences, which affect many primary photochemical and biological events.

  9. The design of double electrostatic-lens optics for resonance enhanced multiphoton ionization and photoelectron imaging experiments

    Energy Technology Data Exchange (ETDEWEB)

    Qu, Zehua; Li, Chunsheng; Qin, Zhengbo, E-mail: wave0403@163.com, E-mail: xfzheng@mail.ahnu.edu.cn; Zheng, Xianfeng, E-mail: wave0403@163.com, E-mail: xfzheng@mail.ahnu.edu.cn; Yao, Guanxin; Zhang, Xianyi; Cui, Zhifeng [Institute of Atomic and Molecular Physics, Anhui Normal University, Wuhu, Anhui 241000 (China)

    2015-06-15

    Compared to single ion/electron-optics for velocity-map imaging, a double-focusing lens assembly designed not only allows for mapping velocity imaging of photoelectrons but also allows for investigating the vibrational structure of the intermediate states of neutral species in resonance enhanced multiphoton ionization (REMPI) spectra. In this presentation, in order to record REMPI and photoelectron spectra separately, we have constructed a compact photoelectron velocity-map imaging (VMI) apparatus combined with an opposite linear Wiley-Mclaren time-of-flight mass spectrometer (TOFMS). A mass resolution (m/Δm) of ∼1300 for TOFMS and electron energy resolution (ΔE/E) of 2.4% for VMI have been achieved upon three-photon ionization of Xe atom at 258.00 nm laser wavelength. As a benchmark, in combination of one-color (1 + 1) REMPI and photoelectron imaging of benzene via 6{sup 1} and 6{sup 1}1{sup 1} vibronic levels in the S{sub 1} state, the vibrational structures of the cation and photoelectron angular anisotropy are unraveled. In addition, two-color (1 + 1′) REMPI and photoelectron imaging of aniline was used to complete the accurate measurement of ionization potential (62 271 ± 3 cm{sup −1}). The results suggest that the apparatus is a powerful tool for studying photoionization dynamics in the photoelectron imaging using vibrational-state selected excitation to the intermediate states of neutrals based on REMPI technique.

  10. Coherent Control of Photoelectron Wavepacket Angular Interferograms

    OpenAIRE

    Hockett, Paul; Wollenhaupt, Matthias; Baumert, Thomas

    2015-01-01

    Coherent control over photoelectron wavepackets, via the use of polarization-shaped laser pulses, can be understood as a time and polarization-multiplexed process. In this work, we investigate this multiplexing via computation of the observable photoelectron angular interferograms resulting from multi-photon atomic ionization with polarization-shaped laser pulses. We consider the polarization sensitivity of both the instantaneous and cumulative continuum wavefunction; the nature of the cohere...

  11. Near threshold studies of photoelectron satellites

    Energy Technology Data Exchange (ETDEWEB)

    Heimann, P.A.

    1986-11-01

    Photoelectron spectroscopy and synchrotron radiation have been used to study correlation effects in the rare gases: He, Ne, Ar, Kr, and Xe. Two kinds of time-of-flight electron analyzers were employed to examine photoionization very close to threshold and at higher kinetic energies. Partial cross sections and angular distributions have been measured for a number of photoelectron satellites. The shake-off probability has been determined at some inner-shell resonances. 121 refs., 28 figs., 13 tabs.

  12. Coherent Control of Photoelectron Wavepacket Angular Interferograms

    OpenAIRE

    Hockett, Paul; Wollenhaupt, Matthias; Baumert, Thomas

    2015-01-01

    Coherent control over photoelectron wavepackets, via the use of polarization-shaped laser pulses, can be understood as a time and polarization-multiplexed process. In this work, we investigate this multiplexing via computation of the observable photoelectron angular interferograms resulting from multi-photon atomic ionization with polarization-shaped laser pulses. We consider the polarization sensitivity of both the instantaneous and cumulative continuum wavefunction; the nature of the cohere...

  13. Forward-backward asymmetries of atomic photoelectrons.

    Energy Technology Data Exchange (ETDEWEB)

    Biheux, J. C.; Dunford, R. W.; Gemmell, D. S.; Hasegawa, S.; Kanter, E. P.; Krassig, B.; Southworth, S. H.; Young, L.

    1999-01-19

    When atomic photoionization is treated beyond the dipole approximation, photoelectron angular distributions are asymmetric forward and backward with respect to the direction of the photon beam. We have measured forward-backward asymmetries of Ar 1s and Kr 1s and 2s photoelectrons using 2-19 keV x-rays. The measured asymmetries compare well with calculations which include interference between electric-dipole and electric-quadrupole amplitudes within the nonrelativistic, independent-particle approximations.

  14. Photoelectron imaging and theoretical study on the structure and chemical binding of the mixed-ligand M(I) complexes, [HMSH]⁻ (M = Cu, Ag, and Au).

    Science.gov (United States)

    Qin, Zhengbo; Liu, Zhiling; Cong, Ran; Xie, Hua; Tang, Zichao; Fan, Hongjun

    2014-03-21

    We have reported a combined photoelectron imaging and theoretical study on gaseous mixed-ligand M(I) complexes of [HMSH](-) (M = Cu, Ag, and Au). With the aid of Franck-Condon simulations, vibrationally resolved photoelectron spectra yield accurate electron affinities of 3.269(6), 3.669(10), and 3.591(6) eV for [HCuSH], [HAgSH], and [HAuSH], respectively. And low-frequency modes are observed: 368(12) cm(-1) for [HCuSH], 286(12) cm(-1) for [HAgSH], and 327(12) cm(-1) for [HAuSH], respectively. Extensive theoretical calculations are performed to aid in the spectral assignments and the calculated values agree well with the experimental observations. Although the S and H atoms have little discrepancy in electronegativity (2.20 for H and 2.54 for S), distinct bonding properties are demonstrated between H-M and M-S bond. It is revealed that there exists significant ionic bonding between M-S in [HMSH](-) (M = Cu, Ag, and Au), while a gradual transition from ionic behavior between H-Cu in [HCuSH](-) to quite strong covalent bonding between H-Au in [HAuSH](-), supported by a variety of chemical bonding analyses.

  15. Photoelectron imaging and theoretical study on the structure and chemical binding of the mixed-ligand M(I) complexes, [HMSH]- (M = Cu, Ag, and Au)

    Science.gov (United States)

    Qin, Zhengbo; Liu, Zhiling; Cong, Ran; Xie, Hua; Tang, Zichao; Fan, Hongjun

    2014-03-01

    We have reported a combined photoelectron imaging and theoretical study on gaseous mixed-ligand M(I) complexes of [HMSH]- (M = Cu, Ag, and Au). With the aid of Franck-Condon simulations, vibrationally resolved photoelectron spectra yield accurate electron affinities of 3.269(6), 3.669(10), and 3.591(6) eV for [HCuSH], [HAgSH], and [HAuSH], respectively. And low-frequency modes are observed: 368(12) cm-1 for [HCuSH], 286(12) cm-1 for [HAgSH], and 327(12) cm-1 for [HAuSH], respectively. Extensive theoretical calculations are performed to aid in the spectral assignments and the calculated values agree well with the experimental observations. Although the S and H atoms have little discrepancy in electronegativity (2.20 for H and 2.54 for S), distinct bonding properties are demonstrated between H-M and M-S bond. It is revealed that there exists significant ionic bonding between M-S in [HMSH]- (M = Cu, Ag, and Au), while a gradual transition from ionic behavior between H-Cu in [HCuSH]- to quite strong covalent bonding between H-Au in [HAuSH]-, supported by a variety of chemical bonding analyses.

  16. Photoelectron spectroscopy of mono-niobium carbide clusters NbCn-(n=2-7): Evidence for a cyclic to linear structural transition

    Science.gov (United States)

    Zhai, Hua-Jin; Liu, Shu-Rong; Li, Xi; Wang, Lai-Sheng

    2001-09-01

    We investigated a series of mono-niobium carbide clusters, NbCn- (n=2-7), using anion photoelectron spectroscopy. Vibrationally resolved photoelectron spectra were observed for NbC2- and NbC3-, which were both shown to have cyclic C2v structures. Two isomers were observed for NbC4- and NbC5-. The weak and low electron binding energy isomers were shown to be cyclic structures forming a series with NbC2- and NbC3-, and all have similar and low electron binding energies. The main isomers of NbC4- and NbC5-, which possess much higher electron binding energies, were shown to be due to linear structures, which form a series with NbC6- and NbC7-. All the linear NbCn- clusters were observed to have high electron binding energies and exhibit an even-odd alternation, similar to that observed for pure linear carbon clusters in the same size range. A cyclic to linear structural transition was thus observed for the NbCn- clusters from NbC3- to NbC4-, with the cyclic structures favored for the smaller clusters and the linear isomers favored for the larger clusters.

  17. Photoelectrons and solar ionizing radiation at Mars: Predictions versus MAVEN observations

    Science.gov (United States)

    Peterson, W. K.; Thiemann, E. M. B.; Eparvier, Francis G.; Andersson, Laila; Fowler, C. M.; Larson, Davin; Mitchell, Dave; Mazelle, Christian; Fontenla, Juan; Evans, J. Scott; Xu, Shaosui; Liemohn, Mike; Bougher, Stephen; Sakai, Shotaro; Cravens, T. E.; Elrod, M. K.; Benna, M.; Mahaffy, P.; Jakosky, Bruce

    2016-09-01

    Understanding the evolution of the Martian atmosphere requires knowledge of processes transforming solar irradiance into thermal energy well enough to model them accurately. Here we compare Martian photoelectron energy spectra measured at periapsis by Mars Atmosphere and Volatile Evolution MissioN (MAVEN) with calculations made using three photoelectron production codes and three solar irradiance models as well as modeled and measured CO2 densities. We restricted our comparisons to regions where the contribution from solar wind electrons and ions were negligible. The two intervals examined on 19 October 2014 have different observed incident solar irradiance spectra. In spite of the differences in photoionization cross sections and irradiance spectra used, we find the agreement between models to be within the combined uncertainties associated with the observations from the MAVEN neutral density, electron flux, and solar irradiance instruments.

  18. Fine-structure-resolved laser-photodetachment electron spectroscopy of In{sup {minus}}

    Energy Technology Data Exchange (ETDEWEB)

    Williams, W.W.; Carpenter, D.L.; Covington, A.M.; Thompson, J.S. [Department of Physics and Chemical Physics Program, University of Nevada, Reno, Nevada, 89557-0058 (United States); Kvale, T.J. [Department of Physics and Astronomy, University of Toledo, Toledo, Ohio, 43606-3390 (United States); Seely, D.G. [Department of Physics, Albion College, Albion, Michigan, 49224 (United States)

    1998-11-01

    The electron affinity of indium has been measured using the laser-photodetachment electron spectroscopy technique. Fine-structure-resolved photoelectron kinetic energy spectra of In{sup {minus}} were analyzed and the electron affinity of In({sup 2}P{sub 1/2}) was determined to be 0.404{plus_minus}0.009 eV. The fine-structure splittings in the ground state of In{sup {minus}}({sup 3}P{sub 0,1,2}) were determined to be 0.076{plus_minus}0.009 eV (J=0{r_arrow}J=1) and 0.175{plus_minus}0.009 eV (J=0{r_arrow}J=2). This measurement is compared to several recent calculations of the electron affinity of indium. {copyright} {ital 1998} {ital The American Physical Society}

  19. Photoelectron and photodissociation studies of free atoms and molecules, using synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Medhurst, L.J.

    1991-11-01

    High resolution synchrotron radiation and Zero-Kinetic-Energy Photoelectron spectroscopy were used to study two-electron transitions in atomic systems at their ionization thresholds. Using this same technique the core-ionized mainline and satellite states of N{sub 2} and CO were studied with vibrational resolution. Vibrationally resolved synchrotron radiation was used to study the dissociation of N{sub 2}, C{sub 2}H{sub 4}, and CH{sub 3}Cl near the N 1s and C 1s thresholds. The photoelectron satellites of the argon 3s, krypton 4s and xenon 4d subshells were studied with zero kinetic energy photoelectron spectroscopy at their ionization thresholds. In all of these cases, satellites with lower binding energies are enhanced at their thresholds while those closer to the double ionization threshold are suppressed relative to their intensities at high incident light energies.

  20. Spatiotemporal steering of photoelectron emission in multiphoton above-threshold ionization

    CERN Document Server

    Gong, Xiaochun; Liu, Mingming; Song, Qiying; Lin, Kang; Ji, Qinying; Zhang, Wenbin; Ma, Junyang; Lu, Peifen; Liu, Yunquan; He, Feng; Zeng, Heping; Yang, Weifeng; Wu, Jian

    2016-01-01

    We experimentally demonstrate spatiotemporal steering of photoelectron emission in multiphoton above-threshold single ionization of atoms exposed to a phase-controlled orthogonally polarized two-color (OTC) laser pulse. Spatial and energy resolved photoelectron angular distributions are measured as a function of the laser phase, allowing us to look into the fine structures and emission dynamics. The slow and fast photoelectrons, distinguished by the energy larger or smaller than 2Up with Up being the ponderomotive energy of a free electron in the laser field, have distinct spatiotemporal dependences of the laser waveform. The phase-of-phase of the slow electron oscillates as functions of both the energy and emission direction, however, the fast electron present rather flat phase structure which merely depends on its emission direction. Three-dimensional generalized quantum trajectory Monte Carlo simulations are performed to explore the sub-cycle dynamics of the electron emission in the phase-controlled OTC pu...

  1. Determination of the photoelectron reference plane in nanostructured surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lobo-Checa, Jorge; Mugarza, Aitor [Centre d' Investigacio en Nanociencia i Nanotecnologia, CIN2 (CSIC-ICN), Esfera UAB, Campus de la UAB, 08193-Bellaterra (Spain); Ortega, Jose Enrique [Dpto Fisica Aplicada I, Universidad del PaIs Vasco, E-20018 San Sebastian (Spain); Michel, Enrique G, E-mail: jorge.lobo@cin2.es [Dpto de Fisica de la Materia Condensada and Instituto Universitario de Ciencia de Materiales ' Nicolas Cabrera' , Universidad Autonoma de Madrid, 28049 Madrid (Spain)

    2011-10-15

    In angle-resolved photoemission (ARPES) from crystalline solids, wave-vector conservation applies to the two-dimensional (2D) surface, which may thus be defined as the reference plane in ARPES. We investigate whether such reference varies for photoemitted electrons in nanometer-sized systems that expose different crystal planes. To this aim, we exploit the structural tunability of the Ag/Cu(223) system which is capable of offering surfaces with periodic arrays of nanofacets of varying size and orientation. A thorough, photon-energy-dependent analysis of the surface states confined to such nanostructures is performed comparing different reference planes for photoemitted electrons. Assuming the premise that k{sub ||} must be a good quantum number for 2D states, we conclude that the (final state) photoelectron reference direction is not the average optical direction but the local facet that confines the (initial state) surface electrons. Moreover, in the general case of nanostructured systems with uneven surfaces, we show how the photoelectron reference plane can be empirically determined through such a photon-energy-dependent ARPES analysis. (paper)

  2. Momentum imaging of photofragments and photoelectrons using fast ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Domesle, Christian

    2012-07-04

    Momentum imaging of photofragments and photoelectrons using fast ion beams - Within the framework of this thesis a method for break-up channel specific detection of the photoelectrons from photon-induced dissociation processes of fast moving molecular ion has been established. For this purpose, a novel saddlepoint electron spectrometer was commissioned while investigating the photodetachment dynamics on a fast moving beam of oxygen anions. For a complete detection of all outgoing reaction products emerging from the photolysis of small water clusters (H{sub 2}O){sub n}H{sup +}(n≤3) in the wavelength range of 13.5-40 nm a new fragment analyzing system has been developed and in combination with the novel saddle-point spectrometer applied, to investigate the dissociative photoionization of the hydronium (H{sub 3}O{sup +}) and the Zundel ion (H{sub 5}O{sub 2}{sup +}). In case of the hydronium ion, a binary H{sub 2}O{sup +}+H{sup +} and two three-body channels OH{sup +}+2H{sup +}, OH{sup +}+H{sup +}+H have been identified to be initiated by outer valence vacancies, where the binary channel is mainly triggered by the ionization of the 3a{sub 1} orbital and the three-body channels follow ionization from the 1e orbital. The photolysis of H{sub 5}O{sub 2}{sup +} is found to proceed via five prominent pathways, where for a large number of processes the hydronium ion is split off as a stable structural unit. Also here, the investigation of the photoelectron spectra revealed the prominent dissociation pathways to be initiated by outer valence vacancies.

  3. Strong-field photoelectron emission from metal nanotips

    Energy Technology Data Exchange (ETDEWEB)

    Bormann, Reiner; Gulde, Max; Yalunin, Sergey; Weismann, Alexander; Ropers, Claus [University of Goettingen (Germany). Courant Research Center Nano-Spectroscopy and X-Ray Imaging

    2010-07-01

    The generation of ultrashort, localized electron pulses is of fundamental interest for future applications in time-resolved electron imaging and diffraction. Femtosecond electron sources of great spatial coherence make use of a combination of local field enhancement at metal nanotips and nonlinear photoelectric effects. Previous studies have resulted in a controversial debate about the underlying physical processes. Here, we present our most recent theoretical and experimental results regarding ultrafast photoelectron emission from nanometric gold tips. For the first time, we conclusively show the transition between the multiphoton and the optical field emission (i.e. tunneling) regimes. Direct evidence for this transition is found from both the power dependence of the total current and the spatial characteristics of the resulting electron beam. The results are supported by theoretical modeling.

  4. SPIN POLARIZED PHOTOELECTRON SPECTROSCOPY AS A PROBE OF MAGNETIC SYSTEMS.

    Energy Technology Data Exchange (ETDEWEB)

    JOHNSON, P.D.; GUNTHERODT, G.

    2006-11-01

    Spin-polarized photoelectron spectroscopy has developed into a versatile tool for the study of surface and thin film magnetism. In this chapter, we examine the methodology of the technique and its recent application to a number of different problems. We first examine the photoemission process itself followed by a detailed review of spin-polarization measurement techniques and the related experimental requirements. We review studies of spin polarized surface states, interface states and quantum well states followed by studies of the technologically important oxide systems including half-metallic transition metal oxides, ferromagnet/oxide interfaces and the antiferromagnetic cuprates that exhibit high Tc Superconductivity. We also discuss the application of high-resolution photoemission with spin resolving capabilities to the study of spin dependent self energy effects.

  5. State-to-State Spectroscopy and Dynamics of Ions and Neutrals by Photoionization and Photoelectron Methods

    Science.gov (United States)

    Ng, Cheuk-Yiu

    2014-04-01

    Recent advances in high-resolution photoionization, photoelectron, and photodissociation studies based on single-photon vacuum ultraviolet (VUV) and two-color infrared (IR)-VUV, visible (Vis)-ultraviolet (UV), and VUV-VUV laser excitations are illustrated with selected examples. VUV laser photoionization coupled with velocity-map-imaging threshold photoelectron (VMI-TPE) detection can achieve comparable energy resolution but has higher-detection sensitivities than those observed in VUV laser pulsed field ionization photoelectron (PFI-PE) measurements. For molecules with known intermediate states, IR-VUV and Vis-UV excitation schemes are highly sensitive for rovibronically selected and resolved PFI-PE studies. The successful applications of the VUV-PFI-PE, VUV-VMI-TPE, and Vis-UV-PFI-PE methods to state-resolved and state-to-state photoelectron studies of transient radicals and transitional metal-containing molecules are highlighted. The most recently established VUV-VUV pump-probe time-slice VMI photoion method is shown to be promising for state-to-state photodissociation studies of small molecules relevant to planetary atmospheres and for the fundamental understanding of photodissociation dynamics.

  6. State-To Spectroscopy and Dynamics of Ions and Neutrals by Photoionization and Photoelectron Methods

    Science.gov (United States)

    Ng, Cheuk-Yiu

    2014-06-01

    Recent advances in high-resolution photoionization, photoelectron, and photodissociation studies based on single-photon vacuum ultraviolet (VUV) and two-color infrared (IR)-VUV, visible (VIS)-ultraviolet (UV), and VUV-VUV laser excitations are illustrated with selected examples. We show that VUV laser photoionization coupled with velocity-map-imaging (VMI)-threshold photoelectron (VMI-TPE) detection can achieve comparable energy resolutions, but higher detection sensitivities than those observed in VUV laser pulsed field ionization-photoelectron (PFI-PE) measurements. For molecules with known intermediate states, IR-VUV and VIS-UV excitation schemes are highly sensitive for rovibronically selected and resolved PFI-PE studies. The successful applications of the VUV-PFI-PE, VUV-VMI-TPE and VIS-UV-PFI-PE methods to state-resolved and state-to-state photoelectron studies of transient radicals and transitional metal-containing molecules are highlighted. The most recently established VUV-VUV pump-probe time-slice VMI-photoion method is shown to be promising for state-to-state photodissociation studies of small molecules relevant to planetary atmospheres and for the fundamental understanding of photodissociation dynamics.

  7. State-to-state spectroscopy and dynamics of ions and neutrals by photoionization and photoelectron methods.

    Science.gov (United States)

    Ng, Cheuk-Yiu

    2014-01-01

    Recent advances in high-resolution photoionization, photoelectron, and photodissociation studies based on single-photon vacuum ultraviolet (VUV) and two-color infrared (IR)-VUV, visible (Vis)-ultraviolet (UV), and VUV-VUV laser excitations are illustrated with selected examples. VUV laser photoionization coupled with velocity-map-imaging threshold photoelectron (VMI-TPE) detection can achieve comparable energy resolution but has higher-detection sensitivities than those observed in VUV laser pulsed field ionization photoelectron (PFI-PE) measurements. For molecules with known intermediate states, IR-VUV and Vis-UV excitation schemes are highly sensitive for rovibronically selected and resolved PFI-PE studies. The successful applications of the VUV-PFI-PE, VUV-VMI-TPE, and Vis-UV-PFI-PE methods to state-resolved and state-to-state photoelectron studies of transient radicals and transitional metal-containing molecules are highlighted. The most recently established VUV-VUV pump-probe time-slice VMI photoion method is shown to be promising for state-to-state photodissociation studies of small molecules relevant to planetary atmospheres and for the fundamental understanding of photodissociation dynamics.

  8. Comparative Study of Ultraviolet Laser-Based Time-Resolved Photoacoustic Fingerprint Spectra and Thermal Decomposition Mechanisms of Energetic 1,2,3-1H-Triazole Derivatives Under Controlled Pyrolysis.

    Science.gov (United States)

    Rao, Konda Srinivasa; Chaudhary, Anil Kumar

    2017-01-01

    We report the comparative study of photoacoustic (PA) fingerprint spectra, thermal decomposition, and stability mechanism of some phenyl and bis series energetic compounds named 1-(2-methoxy,-3,5-dinitrophenyl)-1H-1,2,3-triazole ( S5), 1-(3-methoxy, 2, 6 dinitrophenyl) 1H-1, 2, 3 triazole ( S10), 1-(4-nitrophenyl)-1H-1,2,3-triazole ( S8), and 2,6-bis ((4-(nitromethyl)-1H-1,2,3-triazol-1-yl)methyl) pyridine ( S9). Fourth harmonic wavelength, i.e., 266 nm of pulse duration 7 ns and 10 Hz repetition rate obtained from Q-switched Nd: YAG laser, was used to record the thermal PA spectra of these compounds under controlled pyrolysis condition in the range of 30-350 ℃. The PA fingerprint spectra are produced due to entire molecule vapor along with principal functional byproduct NO2 molecule. NO2 molecule is a major gas released during thermal decomposition due to weakest nature of C-NO2 bond. Further, NO2 molecules are involved in photodissociation process due to π*← n transition and converted into NO molecules inside the PA cell due to excitation by 266 nm wavelength. The combined results of PA and gas chromatography-mass spectrometry (GC-MS) spectra along with thermo gravimetric-differential thermal analysis (TG-DTA) data confirm the thermal decomposition mechanism process that can be completed in multiple steps. In addition, GC-MS spectra also confirm the release of NO and NO2 molecules. The effect of incident laser energy and data acquisition time has been carried out for understanding the behavior of acoustic modes. Finally, the thermal quality factor "Q" is measured to test the stability of compounds.

  9. Photoelectron spectroscopy and Auger electron spectroscopy of solids and surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Kowalczyk, S.P.

    1976-01-01

    The use of photoelectron spectroscopy, primarily x-ray photoelectron spectroscopy, to obtain information on the electronic structure of a wide variety of solids (especially the bulk electronic structure of solids) is covered. Both valence band and core-level spectra, as well as a few cases of photon excited Auger electron spectroscopy, are employed in the investigations to derive information on N(E). The effect of several modulations inherent in the measured I(E)'s, such as final state band structure, cross section, and relaxation, is discussed. Examples of many-electron interactions in PES are given. Some experimental aspects of PES and AES studies are given with emphasis on sample preparation techniques. Multiple splitting of core levels is examined using the Mn levels in MnF/sub 2/ as a detailed case study. Core level splittings in transition metals, rare earth metals, transition metal halides and several alloys are also reported. The application of PES to the study of the chemical bond in some crystalline semiconductors and insulators, A/sup N/B/sup 8-N/ and A/sup N/B/sup 10-N/ compounds is treated, and a spectroscopic scale of ionicity for these compounds is developed from the measured ''s-band'' splitting in the valence band density of states. (GHT)

  10. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics of H2CCO + and D2CCO +

    Science.gov (United States)

    Niu, Baohua; Bai, Ying; Shirley, David A.

    1993-08-01

    High resolution helium Iα (584 Å) photoelectron spectra of H2CCO and D2CCO are reported. The present spectra of the ground states of ketene cations show more vibrational fine structure than previously reported. The adiabatic ionization energies (AIEs) of the cations' first, second, and fifth excited states are determined unambiguously. The doubletlike fine structures present in the first excited states of ketene cations imply the excitation of a ``soft'' mode that was not observed before. It was assigned to the ν5 mode, which is characterized by the CH2 (CD2) group out-of-plane wagging motion. The complexity of the photoelectron spectra obtained for the ionic first excited states is attributed to the possible dissociation and predissociation of this state. Strong isotope effects are observed in the vibronic (vibrational) couplings in most of the ionic states. Vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra for four of the six ionic states observed. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum of the upper potential energy surfaces (PES). The decay dynamics of the ionic first and fifth excited states of ketene are characterized by ultrafast intramolecular processes such as dissociation and predissociation.

  11. Bond Stretching Phonon Softening And Kinks in the Angle-Resolved Photoemission Spectra of Optimally Doped Bi(2)Sr(1.6)La(0.4)Cu(2)O(6)+-Delta Superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Graf, J.; d' Astuto, M.; Jozwiak, C.; Garcia, D.R.; Saini, N.L.; Krisch, M.; Ikeuchi, K.; Baron, A.Q.R.; Eisaki, H.; Lanzara, A.

    2009-05-19

    We report the first measurement of the Cu-O bond stretching phonon dispersion in optimally doped Bi{sub 2}Sr{sub 1.6}La{sub 0.4}Cu{sub 2}O{sub 6+{delta}} using inelastic x-ray scattering. We found a softening of this phonon at q = ({approx} 0.25, 0, 0) from 76 to 60 meV, similar to the one reported in other cuprates. A comparison with angle-resolved photoemission data on the same sample revealed an excellent agreement in terms of energy and momentum between the angle-resolved photoemission nodal kink and the soft part of the bond stretching phonon. Indeed, we find that the momentum space where a 63 {+-} 5 meV kink is observed can be connected with a vector q = ({zeta}, 0, 0) with {zeta} {ge} 0.22, corresponding exactly to the soft part of the bond stretching phonon.

  12. Coherent control of photoelectron wavepacket angular interferograms

    Science.gov (United States)

    Hockett, P.; Wollenhaupt, M.; Baumert, T.

    2015-11-01

    Coherent control over photoelectron wavepackets, via the use of polarization-shaped laser pulses, can be understood as a time and polarization-multiplexed process, where the final (time-integrated) observable coherently samples all instantaneous states of the light-matter interaction. In this work, we investigate this multiplexing via computation of the observable photoelectron angular interferograms resulting from multi-photon atomic ionization with polarization-shaped laser pulses. We consider the polarization sensitivity of both the instantaneous and cumulative continuum wavefunction; the nature of the coherent control over the resultant photoelectron interferogram is thus explored in detail. Based on this understanding, the use of coherent control with polarization-shaped pulses as a methodology for a highly multiplexed coherent quantum metrology is also investigated, and defined in terms of the information content of the observable.

  13. Coherent Control of Photoelectron Wavepacket Angular Interferograms

    CERN Document Server

    Hockett, Paul; Baumert, Thomas

    2015-01-01

    Coherent control over photoelectron wavepackets, via the use of polarization-shaped laser pulses, can be understood as a time and polarization-multiplexed process. In this work, we investigate this multiplexing via computation of the observable photoelectron angular interferograms resulting from multi-photon atomic ionization with polarization-shaped laser pulses. We consider the polarization sensitivity of both the instantaneous and cumulative continuum wavefunction; the nature of the coherent control over the resultant photoelectron interferogram is thus explored in detail. Based on this understanding, the use of coherent control with polarization-shaped pulses as a methodology for a highly multiplexed coherent quantum metrology is also investigated, and defined in terms of the information content of the observable.

  14. Anion photoelectron imaging spectroscopy of glyoxal

    Science.gov (United States)

    Xue, Tian; Dixon, Andrew R.; Sanov, Andrei

    2016-09-01

    We report a photoelectron imaging study of the radical-anion of glyoxal. The 532 nm photoelectron spectrum provides the first direct spectroscopic determination of the adiabatic electron affinity of glyoxal, EA = 1.10 ± 0.02 eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy of the radical-anion is determined as VDE = 1.30 ± 0.04 eV. The reported EA and VDE values are attributed to the most stable (C2h symmetry) isomers of the neutral and the anion.

  15. Attosecond photoelectron spectroscopy of electron transport in solids

    Energy Technology Data Exchange (ETDEWEB)

    Magerl, Elisabeth

    2011-03-31

    Time-resolved photoelectron spectroscopy of condensed matter systems in the attosecond regime promises new insights into excitation mechanisms and transient dynamics of electrons in solids. This timescale became accessible directly only recently with the development of the attosecond streak camera and of laser systems providing few-cycle, phase-controlled laser pulses in the near-infrared, which are used to generate isolated, sub-femtosecond extreme-ultraviolet pulses with a well-defined timing with respect to the near-infrared pulse. Employing these pulses, the attosecond streak camera offers time resolutions as short as a few 10 attoseconds. In the framework of this thesis, a new, versatile experimental apparatus combining attosecond pulse generation in gases with state of the art surface science techniques is designed, constructed, and commissioned. Employing this novel infrastructure and the technique of the attosecond transient recorder, we investigate transport phenomena occurring after photoexcitation of electrons in tungsten and rhenium single crystals and show that attosecond streaking is a unique method for resolving extremely fast electronic phenomena in solids. It is demonstrated that electrons originating from different energy levels, i.e. from the conduction band and the 4f core level, are emitted from the crystal surface at different times. The origin of this time delay, which is below 150 attoseconds for all studied systems, is investigated by a systematic variation of several experimental parameters, in particular the photon energy of the employed attosecond pulses. These experimental studies are complemented by theoretical studies of the group velocity of highly-excited electrons based on ab initio calculations. While the streaking technique applied on single crystals can provide only information about the relative time delay between two types of photoelectrons, the absolute transport time remains inaccessible. We introduce a scheme of a reference

  16. Photoelectron Spectroscopy in Advanced Placement Chemistry

    Science.gov (United States)

    Benigna, James

    2014-01-01

    Photoelectron spectroscopy (PES) is a new addition to the Advanced Placement (AP) Chemistry curriculum. This article explains the rationale for its inclusion, an overview of how the PES instrument records data, how the data can be analyzed, and how to include PES data in the course. Sample assessment items and analysis are included, as well as…

  17. Photoelectron Spectroscopy in Advanced Placement Chemistry

    Science.gov (United States)

    Benigna, James

    2014-01-01

    Photoelectron spectroscopy (PES) is a new addition to the Advanced Placement (AP) Chemistry curriculum. This article explains the rationale for its inclusion, an overview of how the PES instrument records data, how the data can be analyzed, and how to include PES data in the course. Sample assessment items and analysis are included, as well as…

  18. Photoelectron spectroscopy of heavy atoms and molecules

    Energy Technology Data Exchange (ETDEWEB)

    White, M.G.

    1979-07-01

    The importance of relativistic interactions in the photoionization of heavy atoms and molecules has been investigated by the technique of photoelectron spectroscopy. In particular, experiments are reported which illustrate the effects of the spin-orbit interaction in the neutral ground state, final ionic states and continuum states of the photoionization target.

  19. Inequality spectra

    Science.gov (United States)

    Eliazar, Iddo

    2017-03-01

    Inequality indices are widely applied in economics and in the social sciences as quantitative measures of the socioeconomic inequality of human societies. The application of inequality indices extends to size-distributions at large, where these indices can be used as general gauges of statistical heterogeneity. Moreover, as inequality indices are plentiful, arrays of such indices facilitate high-detail quantification of statistical heterogeneity. In this paper we elevate from arrays of inequality indices to inequality spectra: continuums of inequality indices that are parameterized by a single control parameter. We present a general methodology of constructing Lorenz-based inequality spectra, apply the general methodology to establish four sets of inequality spectra, investigate the properties of these sets, and show how these sets generalize known inequality gauges such as: the Gini index, the extended Gini index, the Rényi index, and hill curves.

  20. Acid generation efficiency: EUV photons versus photoelectrons

    Science.gov (United States)

    Goldfarb, Dario L.; Afzali-Ardakani, Ali; Glodde, Martin

    2016-03-01

    EUV photoacid generation efficiency has been described primarily in terms of the EUV photon absorption by the PAG or the resist matrix and the production of low energy photoelectrons, which are reported as being ultimately responsible for the high quantum efficiencies reported in EUV resists (harvesting efficiency. However, such studies either did not disclose the PAG chemical structures, replaced the EUV source with an e-beam source, or lacked a fundamental discussion of the underlying physical mechanisms behind EUV PAG decomposition. In this work, we report the EUV photospeed of a methacrylatebased resist formulated with a battery of openly disclosed isostructural sulfonium PAGs covering a wide range of EA's and Ered's, to unveil any preferential photoelectron scavenging effect. In parallel, several iodonium PAGs are also tested in order to compare the direct EUV photon absorption route to the photoelectron-based decomposition path. Contrarily to what has been widely reported, we have found no direct correlation whatsoever between photospeed and the calculated EA's or experimental Ered's for the isostructural sulfonium PAGs studied. Instead, we found that iodonium PAGs make more efficient use of the available EUV power due to their higher photoabsorption cross-section. Additionally, we determined a cation size effect for both PAG groups, which is able to further modulate the acid generation efficiency. Finally, we present a formal explanation for the unselective response towards photoelectron harvesting based on the stabilization of the PAG cation by bulky substituent groups, the spatial and temporal range of the transient photoelectron and the differences in electron transfer processes for the different systems studied.

  1. Photo-electron momentum distribution and electron localization studies from laser-induced atomic and molecular dissociations

    Science.gov (United States)

    Ray, Dipanwita

    The broad objective of ultrafast strong-field studies is to be able to measure and control atomic and molecular dynamics on a femtosecond timescale. This thesis work has two major themes: (1) Study of high-energy photoelectron distributions from atomic targets. (2) Electron localization control in atomic and molecular reactions using shaped laser pulses. The first section focuses on the study of photoelectron diffraction patterns of simple atomic targets to understand the target structure. We measure the full vector momentum spectra of high energy photoelectrons from atomic targets (Xe, Ar and Kr) generated by intense laser pulses. The target dependence of the angular distribution of the highest energy photoelectrons as predicted by Quantitative Rescattering Theory (QRS) is explored. More recent developments show target structure information can be retrieved from photoelectrons over a range of energies, from 4Up up to 10Up, independent of the peak intensity at which the photoelectron spectra have been measured. Controlling the fragmentation pathways by manipulating the pulse shape is another major theme of ultrafast science today. In the second section we study the asymmetry of electron (and ion) emission from atoms (and molecules) by interaction with asymmetric pulses formed by the superposition of two colors (800 & 400 nm). Xe electron momentum spectra obtained as a function of the two-color phase exhibit a pronounced asymmetry. Using QRS theory we can analyze this asymmetric yield of the high energy photoelectrons to determine accurately the laser peak intensity and the absolute phase of the two-color electric field. This can be used as a standard pulse calibration method for all two-color studies. Experiments showing strong left-right asymmetry in D+ ion yield from D2 molecules using two-color pulses is also investigated. The asymmetry effect is found to be very ion-energy dependent.

  2. Electronic structure of AlCrN films investigated using various photoelectron spectroscopies and ab initio calculations

    Science.gov (United States)

    Tatemizo, N.; Imada, S.; Miura, Y.; Yamane, H.; Tanaka, K.

    2017-03-01

    The valence band (VB) structures of wurtzite AlCrN (Cr concentration: 0-17.1%), which show optical absorption in the ultraviolet-visible-infrared light region, were investigated via photoelectron yield spectroscopy (PYS), x-ray/ultraviolet photoelectron spectroscopy (XPS/UPS), and ab initio density of states (DOS) calculations. An obvious photoelectron emission threshold was observed ~5.3 eV from the vacuum level for AlCrN, whereas no emission was observed for AlN in the PYS spectra. Comparisons of XPS and UPS VB spectra and the calculated DOS imply that Cr 3d states are formed both at the top of the VB and in the AlN gap. These data suggest that Cr doping could be a viable option to produce new materials with relevant energy band structures for solar photoelectric conversion.

  3. Development of hard X-ray photoelectron SPLEED-based spectrometer applicable for probing of buried magnetic layer valence states

    Energy Technology Data Exchange (ETDEWEB)

    Kozina, Xeniya, E-mail: kozina@uni-mainz.de [Japan Synchrotron Radiation Research Institute, SPring-8, Hyogo 679-5198 (Japan); Ikenaga, Eiji [Japan Synchrotron Radiation Research Institute, SPring-8, Hyogo 679-5198 (Japan); Viol Barbosa, Carlos Eduardo; Ouardi, Siham; Karel, Julie [Max-Planck-Institut für Chemische Physik fester Stoffe, 01187 Dresden (Germany); Yamamoto, Masafumi [Division of Electronics for Informatics, Hokkaido University, Sapporo 060-0814 (Japan); Kobayashi, Keisuke [Japan Atomic Energy Agency, SPring-8, Hyogo 679-5148 (Japan); Elmers, Hans Joachim; Schönhense, Gerd [Institut für Physik, Johannes Gutenberg – Universität, 55099 Mainz (Germany); Felser, Claudia [Max-Planck-Institut für Chemische Physik fester Stoffe, 01187 Dresden (Germany)

    2016-08-15

    Highlights: • A high-voltage compatible spin-HAXPES detector based on SPLEED from W(001) has been developed. • Magnetic properties of a TMR device were studied by core-level photoemission on the Fe 2p{sub 3/2} states. • The developed instrument enabled probing of buried layers in the region of the valence states. - Abstract: A novel design of high-voltage compatible polarimeter for spin-resolved hard X-ray photoelectron spectroscopy (Spin-HAXPES) went into operation at beamline BL09XU of SPring-8 in Hyogo, Japan. The detector is based on the well-established principle of electron diffraction from a W(001) single-crystal at a scattering energy of 103.5 eV. It's special feature is that it can be operated at a high negative bias potential up to 10 kV, necessary to access the HAXPES range. The polarimeter is operated behind a large hemispherical analyzer (Scienta R-4000). It was optimized for high transmission of the transfer optics. A delay-line detector (20 mm dia.) is positioned at the exit plane of the analyzer enabling conventional multichannel intensity spectroscopy simultaneously with single-channel spin analysis. The performance of the combined setup is demonstrated by the spin-resolved data for the valence-region of a FeCo functional layer of a tunneling device, buried beneath 3 nm of oxidic material. The well-structured spin polarization spectrum validates Spin-HAXPES in the valence energy range as powerful method for bulk electronic structure analysis. The spin polarization spectrum exhibits a rich structure, originating from clearly discernible transitions in the majority and minority partial spin spectra.

  4. Electron spectra of radical cations of heteroanalogs

    Energy Technology Data Exchange (ETDEWEB)

    Petrushenko, K.B.; Turchaninov, V.K.; Vokin, A.I.; Ermikov, A.F.; Frolov, Yu.L.

    1985-12-01

    Radical cation spectra of indazole and benzothiophene in the visible region were obtained by laser photolysis during the reaction of photoexcited quinones with these compounds in acetonitrile. The charge transfer bands of the complexes of the test compounds with p-chloranil and 7,7,8,8-tetracyanoquinodimethane in dioxane were recorded on a Specord M-40. Photoelectron spectra were obtained on a ES-3201 electron spectrometer. The He(I) resonance band (21.21 eV) was used for excitation. Measurements were carried out in the 60-120/sup 0/C range. The energy scale was calibrated form the first ionization potentials of Ar (15.76 eV) and chlorobenzene (9.06 eV). The error in the determination of the ionization potentials for the first four photoelectron bands was 0.05 eV.

  5. Injection of photoelectrons into dense argon gas

    CERN Document Server

    Borghesani, A F

    2010-01-01

    The injection of photoelectrons in a gaseous or liquid sample is a widespread technique to produce a cold plasma in a weakly--ionized system in order to study the transport properties of electrons in a dense gas or liquid. We report here the experimental results of photoelectron injection into dense argon gas at the temperatureT=142.6 K as a function of the externally applied electric field and gas density. We show that the experimental data can be interpreted in terms of the so called Young-Bradbury model only if multiple scattering effects due to the dense environment are taken into account when computing the scattering properties and the energetics of the electrons.

  6. Analysis of multi-layer ERBS spectra

    Energy Technology Data Exchange (ETDEWEB)

    Marmitt, G.G. [Atomic and Molecular Physics Laboratories, Research School of Physics and Engineering, The Australian National University, Canberra 0200 (Australia); Instituto de Fisica da Universidade Federal do Rio Grande do Sul, Avenida Bento Goncalves 9500, 91501-970 Porto Alegre, RS (Brazil); Rosa, L.F.S. [Instituto de Fisica da Universidade Federal do Rio Grande do Sul, Avenida Bento Goncalves 9500, 91501-970 Porto Alegre, RS (Brazil); Nandi, S.K. [Electronic Materials Engineering Department, Research School of Physics and Engineering, The Australian National University, Canberra 0200 (Australia); Research School of Astronomy and Astrophysics, The Australian National University, Canberra, ACT 2611 (Australia); Department of Physics, University of Chittagong, Chittagong 4331 (Bangladesh); Vos, M., E-mail: maarten.vos@anu.edu.au [Atomic and Molecular Physics Laboratories, Research School of Physics and Engineering, The Australian National University, Canberra 0200 (Australia)

    2015-07-15

    Highlights: • Electron Rutherford backscattering (ERBS) spectra are presented. • The spectra are fitted based on physical meaningful quantities. • Very consistent results are obtained for spectra taken under different conditions. • This establishes that ERBS can be used to measure film thicknesses. - Abstract: A systematic way of analysis of multi-layer electron Rutherford backscattering spectra is described. The approach uses fitting in terms of physical meaningful parameters. Simultaneous analysis then becomes possible for spectra taken at different incoming energies and measurement geometries. Examples are given to demonstrate the level of detail that can be resolved by this technique.

  7. Nondipole effects in attosecond photoelectron streaking

    DEFF Research Database (Denmark)

    Spiewanowski, Maciek; Madsen, Lars Bojer

    2012-01-01

    The influence of nondipole terms on the time delay in photoionization by an extreme-ultraviolet attosecond pulse in the presence of a near-infrared femtosecond laser pulse from 1s, 2s, and 2p states in hydrogen is investigated. In this attosecond photoelectron streaking process, the relative...... to nondipole terms is found. The numerical calculations are supported by a theoretical analysis of the time delay....

  8. X-ray Photoelectron Spectroscopy Database (Version 4.1)

    Science.gov (United States)

    SRD 20 X-ray Photoelectron Spectroscopy Database (Version 4.1) (Web, free access)   The NIST XPS Database gives access to energies of many photoelectron and Auger-electron spectral lines. The database contains over 22,000 line positions, chemical shifts, doublet splittings, and energy separations of photoelectron and Auger-electron lines.

  9. Time-dependent wave packet approach to the pulse delay effect upon RbI photoelectron spectrum

    Institute of Scientific and Technical Information of China (English)

    LIU Chunhua; MENG Qingtian; ZHANG Qinggang

    2006-01-01

    The time-resolved photoelectron spectrum (TRPES) of Rbl molecule is simulated using the time-dependent wave-packet method. Both the normal three-photon ionization process and auto-ionization process are involved in the simulation. The calculated results show that the change of delay time will influence the shape of the photoelectron spectrum (PES), and the influence is substantially due to the existence of the crossing between excited states and the strong laser field which will change the position of relevant curves.

  10. Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection.

    Science.gov (United States)

    Lehmann, C Stefan; Ram, N Bhargava; Powis, Ivan; Janssen, Maurice H M

    2013-12-21

    Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations

  11. The Negative Ion Photoelectron Spectrum of meta -Benzoquinone Radical Anion (MBQ •– ): A Joint Experimental and Computational Study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Bo; Hrovat, David A.; Deng, S. H. M.; Zhang, Jian; Wang, Xue-Bin; Borden, Weston Thatcher

    2014-03-05

    Negative ion photoelectron (NIPE) spectra of the radical anion of meta-benzoquinone (MBQ, m-OC6H4O) have been obtained at 20 K, using both 355 and 266 nm lasers for electron photodetachment. The spectra show well-resolved peaks and complex spectral patterns. The electron affinity of MBQ is determined from the first resolved peak to be 2.875 ±17 0.010 eV. Single-point, CASPT2/aug-cc-pVTZ//CASPT2/ aug-cc-pVDZ calculations predict accurately the positions of the 0-0 bands in the NIPE spectrum for formation of the four lowest electronic states of neutral MBQ from the 2A2 state of MBQ•-. In addition, the Franck-Condon factors that are computed from the CASPT2/aug-cc-pVDZ optimized geometries,vibrational frequencies, and normal mode vectors, successfully simulate the intensities and frequencies of the vibrational peaks in the NIPE spectrum that are associated with each of these electronic states. The successful simulation of the NIPE spectrum of MBQ•- allows the assignment of 3B2 as the ground state of MBQ, followed by the 1B2 and 1A1 electronic states, respectively 9.0 ± 0.2 and 16.6 ± 0.2 kcal/mol higher in energy than the triplet. These experimental energy differences are in good agreement with the calculated values of 9.7 and 15.7 kcal/mol. The relative energies of these two singlet states in MBQ confirm the previous prediction that their relative energies would be reversed from those in meta-benzoquinodimethane (MBQDM, m-CH2C6H4CH2).

  12. High-resolution threshold photoelectron study of the propargyl radical by the vacuum ultraviolet laser velocity-map imaging method

    Science.gov (United States)

    Gao, Hong; Xu, Yuntao; Yang, Lei; Lam, Chow-Shing; Wang, Hailing; Zhou, Jingang; Ng, C. Y.

    2011-12-01

    By employing the vacuum ultraviolet (VUV) laser velocity-map imaging (VMI) photoelectron scheme to discriminate energetic photoelectrons, we have measured the VUV-VMI-threshold photoelectrons (VUV-VMI-TPE) spectra of propargyl radical [C3H3({tilde X}{}^2B_1)] near its ionization threshold at photoelectron energy bandwidths of 3 and 7 cm-1 (full-width at half-maximum, FWHM). The simulation of the VUV-VMI-TPE spectra thus obtained, along with the Stark shift correction, has allowed the determination of a precise value 70 156 ± 4 cm-1 (8.6982 ± 0.0005 eV) for the ionization energy (IE) of C3H3. In the present VMI-TPE experiment, the Stark shift correction is determined by comparing the VUV-VMI-TPE and VUV laser pulsed field ionization-photoelectron (VUV-PFI-PE) spectra for the origin band of the photoelectron spectrum of the {tilde X}^ + {- tilde X} transition of chlorobenzene. The fact that the FWHMs for this origin band observed using the VUV-VMI-TPE and VUV-PFI-PE methods are nearly the same indicates that the energy resolutions achieved in the VUV-VMI-TPE and VUV-PFI-PE measurements are comparable. The IE(C3H3) value obtained based on the VUV-VMI-TPE measurement is consistent with the value determined by the VUV laser PIE spectrum of supersonically cooled C3H3({tilde X}{}^2B_1) radicals, which is also reported in this article.

  13. Photoelectron imaging and theoretical study on the structure and chemical binding of the mixed-ligand M(I) complexes, [HMSH]{sup −} (M = Cu, Ag, and Au)

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Zhengbo; Liu, Zhiling; Cong, Ran; Xie, Hua; Tang, Zichao, E-mail: zctang@dicp.ac.cn, E-mail: fanhj@dicp.ac.cn; Fan, Hongjun, E-mail: zctang@dicp.ac.cn, E-mail: fanhj@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

    2014-03-21

    We have reported a combined photoelectron imaging and theoretical study on gaseous mixed-ligand M(I) complexes of [HMSH]{sup −} (M = Cu, Ag, and Au). With the aid of Franck-Condon simulations, vibrationally resolved photoelectron spectra yield accurate electron affinities of 3.269(6), 3.669(10), and 3.591(6) eV for [HCuSH], [HAgSH], and [HAuSH], respectively. And low-frequency modes are observed: 368(12) cm{sup −1} for [HCuSH], 286(12) cm{sup −1} for [HAgSH], and 327(12) cm{sup −1} for [HAuSH], respectively. Extensive theoretical calculations are performed to aid in the spectral assignments and the calculated values agree well with the experimental observations. Although the S and H atoms have little discrepancy in electronegativity (2.20 for H and 2.54 for S), distinct bonding properties are demonstrated between H–M and M–S bond. It is revealed that there exists significant ionic bonding between M–S in [HMSH]{sup −} (M = Cu, Ag, and Au), while a gradual transition from ionic behavior between H–Cu in [HCuSH]{sup −} to quite strong covalent bonding between H–Au in [HAuSH]{sup −}, supported by a variety of chemical bonding analyses.

  14. Investigation of coloration of SrLaGaO sub 4 single crystals by X-ray photoelectron spectroscopy

    CERN Document Server

    Novosselov, A; Talik, E; Pajaczkowska, A

    2003-01-01

    An investigation of the X-ray photoelectron spectra of single crystals of SrLaGaO sub 4 grown by the Czochralski method at various oxygen pressures is reported. Light yellow, yellow and red colored crystals were grown at an oxygen pressure lower than about 5x10 sup - sup 4 atm while the green colored crystals were grown at an oxygen pressure higher than 5x10 sup - sup 3 atm. The presence of Ga sup 1 sup + ions for green colored crystals was demonstrated and the existence of interstitial oxygen atoms in the green and red colored crystals was proposed by using X-ray photoelectron spectroscopy.

  15. Photoelectron emission as an alternative electron impact ionization source for ion trap mass spectrometry.

    Science.gov (United States)

    Gamez, Gerardo; Zhu, Liang; Schmitz, Thomas A; Zenobi, Renato

    2008-09-01

    Electron impact ionization has several known advantages; however, heated filament electron sources have pressure limitations and their power consumption can be significant for certain applications, such as in field-portable instruments. Herein, we evaluate a VUV krypton lamp as an alternative source for ionization inside the ion trap of a mass spectrometer. The observed fragmentation patterns are more characteristic of electron impact ionization than photoionization. In addition, mass spectra of analytes with ionization potentials higher than the lamp's photon energy (10.6 eV) can be easily obtained. A photoelectron impact ionization mechanism is suggested by the observed data allowed by the work function of the ion trap electrodes (4.5 eV), which is well within the lamp's photon energy. In this case, the photoelectrons emitted at the surface of the ion trap end-cap electrode are accelerated by the applied rf field to the ring electrode. This allows the photoelectrons to gain sufficient energy to ionize compounds with high ionization potentials to yield mass spectra characteristic of electron impact. In this manner, electron impact ionization can be used in ion trap mass spectrometers at low powers and without the limitations imposed by elevated pressures on heated filaments.

  16. X-ray photoelectron study of Si{sup +} ion implanted polymers

    Energy Technology Data Exchange (ETDEWEB)

    Tsvetkova, T; Balabanov, S; Bischoff, L; Krastev, V; Stefanov, P; Avramova, I, E-mail: tania_tsvetkova@yahoo.co.u

    2010-11-01

    X-ray photoelectron spectroscopy was used to characterize different polymer materials implanted with low energy Si{sup +} ions (E=30 keV, D= 1.10{sup 17} cm{sup -2}). Two kinds of polymers were studied - ultra-high-molecular-weight poly-ethylene (UHMWPE), and poly-methyl-methacrylate (PMMA). The non-implanted polymer materials show the expected variety of chemical bonds: carbon-carbon, carbon being three- and fourfold coordinated, and carbon-oxygen in the case of PMMA samples. The X-ray photoelectron and Raman spectra show that Si{sup +} ion implantation leads to the introduction of additional disorder in the polymer material. The X-ray photoelectron spectra of the implanted polymers show that, in addition to already mentioned bonds, silicon creates new bonds with the host elements - Si-C and Si-O, together with additional Si dangling bonds as revealed by the valence band study of the implanted polymer materials.

  17. Electron mean free path from angle-dependent photoelectron spectroscopy of aerosol particles

    CERN Document Server

    Goldmann, Maximilian; West, Adam H C; Yoder, Bruce L; Signorell, Ruth

    2015-01-01

    We propose angle-resolved photoelectron spectroscopy of aerosol particles as an alternative way to determine the electron mean free path of low energy electrons in solid and liquid materials. The mean free path is obtained from fits of simulated photoemission images to experimental ones over a broad range of different aerosol particle sizes. The principal advantage of the aerosol approach is twofold. Firstly, aerosol photoemission studies can be performed for many different materials, including liquids. Secondly, the size-dependent anisotropy of the photoelectrons can be exploited in addition to size-dependent changes in their kinetic energy. These finite size effects depend in different ways on the mean free path and thus provide more information on the mean free path than corresponding liquid jet, thin film, or bulk data. The present contribution is a proof of principle employing a simple model for the photoemission of electrons and preliminary experimental data for potassium chloride aerosol particles.

  18. Velocity map imaging of femtosecond laser induced photoelectron emission from metal nanotips

    Science.gov (United States)

    Bainbridge, A. R.; Bryan, W. A.

    2014-10-01

    A novel application of velocity-map imaging (VMI) is demonstrated, whereby the momentum distribution of photoelectrons ejected from a tungsten nanoscale metal tip (VMI instrument are optimized through finite element modelling, taking into account a physically realistic geometry including all conductive elements in the vicinity of the electron trajectories. The instrument is calibrated by observing above threshold ionization in krypton gas, and simultaneous electron emission from this gas and a tungsten nanotip is presented, illustrating that the velocity mapping condition is maintained. Realizing photoelectron VMI for femtosecond laser illuminated nanoscale objects will have a significant impact on the emerging field of ultrafast nanoplasmonics and will influence the development of such devices as a source of coherent pulses of electrons with applications in time-resolved microscopy, holography and diffractive imaging.

  19. Tracing attosecond electron motion inside a molecule by interferences from photoelectron emission

    Energy Technology Data Exchange (ETDEWEB)

    Xu Minghui; Peng Liangyou; Zhang Zheng; Gong Qihuang, E-mail: liangyou.peng@pku.edu.cn, E-mail: qhgong@pku.edu.cn [State Key Laboratory for Mesoscopic Physics and Department of Physics, Peking University, Beijing 100871 (China)

    2011-01-28

    We present a theoretical study of photoelectron emission of a homonuclear molecule by an attosecond xuv pulse, which can be regarded as a natural double-slit experiment. We show that attosecond electron motion inside the molecule opens one to two 'slits' for photoionization. Interference fringes in the angle-resolved photoelectron momentum distributions exhibit varying visibility (V), depending on the degree of which-path information (P). The complementarity relation, P{sup 2} + V{sup 2} {<=} 1, is verified in the time-dependent molecule double-slit experiment. Hence, the electron motion can be easily mapped out by measuring the interference visibility. This opens up the prospect of employing interferometric techniques to probe ultrafast intramolecular electronic motions. (fast track communication)

  20. Threshold photoelectron studies of isoxazole over the energy range 9.9-30 eV

    Energy Technology Data Exchange (ETDEWEB)

    Dampc, Marcin; Mielewska, Brygida [Department of Physics of Electronic Phenomena, Gdansk University of Technology, 80-233 Gdansk (Poland); Siggel-King, Michele R.F. [Daresbury Laboratory, Daresbury, Warrington WA4 4AD (United Kingdom); King, George C. [School of Physics and Astronomy, Manchester University, Manchester M13 9PL (United Kingdom); Sivaraman, Bhalamurugan; Ptasinska, Sylwia; Mason, Nigel [Department of Physics and Astronomy, The Open University, Milton Keynes MK7 6AA (United Kingdom); Zubek, Mariusz, E-mail: mazub@mif.pg.gda.pl [Department of Physics of Electronic Phenomena, Gdansk University of Technology, 80-233 Gdansk (Poland)

    2010-02-08

    The threshold photoelectron spectrum of the isoxazole molecule, C{sub 3}H{sub 3}NO has been measured over the photon energy range 9.9-30 eV with the use of synchrotron radiation. In the 9.9-10.8 eV range, corresponding to photoionization from the highest occupied molecular orbital 3a''({pi}{sub 3}), seven well resolved vibrational series have been observed and their modes are tentatively assigned. A strong adiabatic ionization, with an energy of 11.132 {+-} 0.003 eV corresponding to the 2a''({pi}{sub 2}) band, has also been observed. This is followed by a single vibrational series of the {nu}{sub C-H} stretching mode. Photoelectron bands in the energy region 13-30 eV have also been identified, some for the first time.

  1. High-throughput Toroidal Grating Beamline for Photoelectron Spectroscopy at CAMD

    Science.gov (United States)

    Kizilkaya, O; Jiles, R W; Patterson, M C; Thibodeaux, C A; Poliakoff, E D; Sprunger, P T; Kurtz, R L; Morikawa, E

    2016-01-01

    A 5 meter toroidal grating (5m-TGM) beamline has been commissioned to deliver 28 mrad of bending magnet radiation to an ultrahigh vacuum endstation chamber to facilitate angle resolved photoelectron spectroscopy. The 5m-TGM beamline is equipped with Au-coated gratings with 300, 600 and 1200 lines/mm providing monochromatized synchrotron radiation in the energy ranges 25-70 eV, 50–120 eV and 100–240 eV, respectively. The beamline delivers excellent flux (~1014-1017 photons/sec/100mA) and a combined energy resolution of 189 meV for the beamline (at 1.0 mm slit opening) and HA-50 hemispherical analyzer was obtained at the Fermi level of polycrystalline gold crystal. Our preliminary photoelectron spectroscopy results of phenol adsorption on TiO2 (110) surface reveals the metal ion (Ti) oxidation. PMID:27134636

  2. A flexible apparatus for attosecond photoelectron spectroscopy of solids and surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Magerl, E.; Stanislawski, M.; Uphues, Th. [Max-Planck-Institut fuer Quantenoptik, Hans-Kopfermann-Strasse 1, 85748 Garching (Germany); Neppl, S.; Barth, J. V.; Menzel, D.; Feulner, P. [Physik Department E20, Technische Universitaet Muenchen, James-Franck-Strasse, 85748 Garching (Germany); Cavalieri, A. L. [Max-Planck-Institut fuer Quantenoptik, Hans-Kopfermann-Strasse 1, 85748 Garching (Germany); Max-Planck Research Department for Structural Dynamics, Universitaet Hamburg, Notkestrasse 85, 22607 Hamburg (Germany); Bothschafter, E. M.; Ernstorfer, R.; Kienberger, R. [Max-Planck-Institut fuer Quantenoptik, Hans-Kopfermann-Strasse 1, 85748 Garching (Germany); Physik Department E11, Technische Universitaet Muenchen, James-Franck-Strasse, 85748 Garching (Germany); Hofstetter, M.; Kleineberg, U.; Krausz, F. [Max-Planck-Institut fuer Quantenoptik, Hans-Kopfermann-Strasse 1, 85748 Garching (Germany); Ludwig-Maximilians-Universitaet Muenchen, Fakultaet fuer Physik, Am Coulombwall 1, 85748 Garching (Germany)

    2011-06-15

    We describe an apparatus for attosecond photoelectron spectroscopy of solids and surfaces, which combines the generation of isolated attosecond extreme-ultraviolet (XUV) laser pulses by high harmonic generation in gases with time-resolved photoelectron detection and surface science techniques in an ultrahigh vacuum environment. This versatile setup provides isolated attosecond pulses with photon energies of up to 140 eV and few-cycle near infrared pulses for studying ultrafast electron dynamics in a large variety of surfaces and interfaces. The samples can be prepared and characterized on an atomic scale in a dedicated flexible surface science end station. The extensive possibilities offered by this apparatus are demonstrated by applying attosecond XUV pulses with a central photon energy of {approx}125 eV in an attosecond streaking experiment of a xenon multilayer grown on a Re(0001) substrate.

  3. Characterization of EUV irradiation effects on polystyrene derivatives studied by x-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS)

    Science.gov (United States)

    Yamamoto, Hiroki; Kozawa, Takahiro; Tagawa, Seiichi

    2011-04-01

    The trade-off among resolution, sensitivity, and line edge roughness (LER) is the most serious problem in actualization of extreme ultraviolet (EUV). As feature sizes are reduced, it becomes very strict to simultaneously meet these requirements. Also, reaction in resist materials induced by EUV photon is more complicate. In chemically amplified EUV resists, not acid generator but polymers mainly adsorbed EUV photons. The secondary electrons are generated from polymer upon exposure to ionizing radiation such as EUV radiation and electron beam. Therefore, the increase in secondary electrons generated by EUV photons adsorbed in resist film is very important factor in the resist design. Therefore, it is essential to know the ionization mechanisms of backbone polymers and understand the reaction mechanism in details in order to accomplish high sensitivity and ultra-fine pattern in EUV lithography. We investigated the photoelectron spectra of typical backbone polymers for chemically amplified EUV resists using ultraviolet photoelectron spectroscopy (UPS). Also, the structure degradations in polystyrene (PS) derivatives thin films induced by EUV radiation were analyzed by X-ray photoelectron spectroscopy (XPS) and UPS.

  4. X-Ray photoelectron Spectroscopy Applications

    Energy Technology Data Exchange (ETDEWEB)

    Engelhard, Mark H.; Droubay, Timothy C.; Du, Yingge

    2017-01-03

    With capability for obtaining quantitative elemental composition, chemical and electronic state, and overlayer thickness information from the top ~10 nm of a sample surface, X-ray Photoelectron Spectroscopy (XPS) or Electron Spectroscopy for Chemical Analysis (ESCA) is a versatile and widely used technique for analyzing surfaces. The technique is applied to a host of materials, from insulators to conductors in virtually every scientific field and sub-discipline. More recently, XPS has been extended under in-situ and operando conditions. Following a brief introduction to XPS principles and instrument components, this article exemplifies widely ranging XPS applications in material and life sciences.

  5. Coincident photoelectron spectroscopy on superconductors; Koinzidente Photoelektronenspektroskopie an Supraleitern

    Energy Technology Data Exchange (ETDEWEB)

    Voss, Stefan

    2011-07-01

    Aim of the performed experiments of this thesis was to attempt to detect Cooper pairs as carriers of the superconducting current directly by means of the photoelectric effect. The method of the coincident photoelectron spectroscopy aims thereby at the detection of two coherently emitted electrons by the interaction with a photon. Because electrostatic analyzers typically cover only a very small spatial angle, which goes along with very low coincidence rates, in connection with this thesis a time-of-flight projection system has been developed, which maps nearly the whole spatial angle on a position-resolving detector. The pulsed light source in form of special synchrotron radiation necessary for the measurement has been adjusted so weak, that only single photons could arrive at the sample. Spectroscoped were beside test measurements on silver layers both a lead monocrystal as representative of the classical BCS superconductors and monocrystalline Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} from the family of the high-temperature superconductors. With excitation energies up to 40 eV could be shown that sufficiently smooth and clean surfaces in the superconducting phase exhibit within the resolving power of about 0.5 eV no recognizable differences in comparison to the normally conducting phase. Beside these studies furthermore the simple photoemission at the different samples and especially in the case of the lead crystal is treated, because here no comparable results are known. Thereby the whole momentum space is discussed and the Fermi surface established as three-dimensional model, by means of which the measurement results are discussed. in the theoretical descriptions different models for the Cooper-pair production are presented, whereby to the momentum exchange with the crystal a special role is attributed, because this can only occur in direct excitations via discrete lattice vectors.

  6. Angle-resolved time delay in photoemission

    CERN Document Server

    Wätzel, Jonas; Pavlyukh, Yaroslav; Berakdar, Jamal

    2014-01-01

    We investigate theoretically the relative time delay of photoelectrons originating from different atomic subshells of noble gases. This quantity was measured via attosecond streaking and studied theoretically by Schultze et al. [Science 328, 1658 (2010)] for neon. A substantial discrepancy was found between the measured and the calculated values of the relative time delay. Several theoretical studies were put forward to resolve this issue, e.g., by including correlation effects. In the present paper we explore a further aspect, namely the directional dependence of time delay. In contrast to neon, for argon target a strong angular dependence of time delay is found near a Cooper minimum.

  7. The ionisation energy of cyclopentadienone: a photoelectron-photoion coincidence study

    Science.gov (United States)

    Ormond, Thomas K.; Hemberger, Patrick; Troy, Tyler P.; Ahmed, Musahid; Stanton, John F.; Ellison, G. Barney

    2015-08-01

    Imaging photoelectron photoion coincidence (iPEPICO) spectra of cyclopentadienone (C5H4=O and C5D4=O) have been measured at the Swiss Light Source Synchrotron (Paul Scherrer Institute, Villigen, Switzerland) at the Vacuum Ultraviolet (VUV) Beamline. Complementary to the photoelectron spectra, photoionisation efficiency curves were measured with tunable VUV radiation at the Chemical Dynamics Beamline at the Advanced Light Source Synchrotron (Lawrence Berkeley National Laboratory, Berkeley, CA, USA). For both experiments, molecular beams diluted in argon and helium were generated from the vacuum flash pyrolysis of o-phenylene sulphite in a resistively heated microtubular SiC flow reactor. The Franck-Condon profiles and ionisation energies were calculated at the CCSD(T) level of theory, and are in excellent agreement with the observed iPEPICO spectra. The ionisation energies of both cyclopentadienone-d0, IE(C5H4=O), and cyclopentadienone-d4, IE(C5D4=O), were observed to be the same: 9.41 ± 0.01 eV. The mass-selected threshold photoelectron spectrum (ms-TPES) of cyclopentadienone reveals that the C=C stretch in the ground state of the cation is excited upon ionisation, supporting computational evidence that the ground state of the cation is ? 2A2, and is in agreement with previous studies. However, the previously reported ionisation potential has been improved considerably in this work. In addition, since o-benzoquinone (o-O=C6H4=O and o-O=C6D4=O) is also produced in this process, its ms-TPES has been recorded. From the iPEPICO and photoionisation efficiency spectra, we infer an adiabatic ionisation energy of IE(o-O=C6H4=O) = 9.3 ± 0.1 eV, but the rather structureless spectrum indicates a strong change in geometry upon ionisation making this value less reliable.

  8. Photoelectron-Auger electron coincidence study for condensed matter

    Energy Technology Data Exchange (ETDEWEB)

    Stefani, G. [Department of Physics and Unita' INFM, University Roma Tre, Via della Vasca Navale 84, I-00146 Rome (Italy)]. E-mail: stefani@fis.uniroma3.it; Gotter, R. [National Laboratory TASC-INFM, Area Science Park, SS 14 Km 163.5, Basovizza, I-34012 Trieste (Italy); Ruocco, A. [Department of Physics and Unita INFM, University Roma Tre, Via della Vasca Navale 84, I-00146 Rome (Italy); Offi, F. [Department of Physics and Unita INFM, University Roma Tre, Via della Vasca Navale 84, I-00146 Rome (Italy); Pieve, F. Da [Department of Physics and Unita INFM, University Roma Tre, Via della Vasca Navale 84, I-00146 Rome (Italy); Iacobucci, S. [IMIP-CNR Area della Ricerca di Roma, via Salaria Km 29, 3 Montelibretti (Italy); Morgante, A. [National Laboratory TASC-INFM, Area Science Park, SS 14 Km 163.5, Basovizza, I-34012 Trieste (Italy); Verdini, A. [National Laboratory TASC-INFM, Area Science Park, SS 14 Km 163.5, Basovizza, I-34012 Trieste (Italy); Liscio, A. [IMIP-CNR Area della Ricerca di Roma, via Salaria Km 29, 3 Montelibretti (Italy); Yao, H. [Department of Physics and Astronomy and Laboratory of Surface Modification, Rutgers University, 136 Frelinghuysen Road, Piscataway, NJ 08855 (United States); Bartynski, R.A. [Department of Physics and Astronomy and Laboratory of Surface Modification, Rutgers University, 136 Frelinghuysen Road, Piscataway, NJ 08855 (United States)

    2004-12-01

    Advances in materials science have produced a wide array of new solid-state systems with tunable properties and previously unattainable combinations of phenomena that hold the promise of entirely new approaches to technological applications. Invariably, these new materials are increasingly complex and include a large number of constituents in a variety of chemical states. Entirely new theoretical and experimental approaches are needed to gain the insights necessary for intelligent engineering of these materials. In the past 20 years, a steadily increasing number of electron-electron coincidence experiments on atoms and molecules have demonstrated the capability of investigating complicated systems with sensitivity and specificity well beyond the limits imposed by conventional electron spectroscopies. Over the past decade or so, Auger-photoelectron coincidence spectroscopy (APECS) has emerged as a powerful technique for obtaining detailed information about complex materials systems. Moreover, the recent advent of angle-resolved (AR)-APECS has introduced a new level of discrimination in studying the distribution of electrons photoemitted from complex systems. In this review, we describe the basic ideas behind APECS and discuss a study of the SiO{sub 2} system as an example of the unique information this technique can provide. We then introduce the concept of AR-APECS, explain its novel state and angular momentum selectivity that can be used to disentangle information about complex systems that is hidden to conventional spectroscopies. Examples of AR-APECS measurements from Cu, Ge, and graphite that exemplify the capabilities of this technique are presented.

  9. Alignment of the photoelectron spectroscopy beamline at NSRL

    CERN Document Server

    Li, Chaoyang; Wen, Shen; Pan, Congyuan; An, Ning; Du, Xuewei; Zhu, Junfa; Wang, Qiuping

    2013-01-01

    The photoelectron spectroscopy beamline at National Synchrotron Radiation Laboratory (NSRL) is equipped with a spherical grating monochromator with the included angle of 174 deg. Three gratings with line density of 200, 700 and 1200 lines/mm are used to cover the energy region from 60 eV to 1000 eV. After several years operation, the spectral resolution and flux throughput were deteriorated, realignment is necessary to improve the performance. First, the wavelength scanning mechanism, the optical components position and the exit slit guide direction are aligned according to the design value. Second, the gratings are checked by Atomic Force Microscopy (AFM). And then the gas absorption spectrum is measured to optimize the focusing condition of the monochromator. The spectral resolving power is recovered to the designed value of 1000@244eV. The flux at the end station for the 200 lines/mm grating is about 10^10 photons/sec/200mA, which is in accordance with the design. The photon flux for the 700 lines/mm grati...

  10. Femtosecond photoelectron and photoion spectrometer with vacuum ultraviolet probe pulses

    CERN Document Server

    Koch, Markus; Grilj, Jakob; Sistrunk, Emily; Gühr, Markus

    2014-01-01

    We describe a setup to study ultrafast dynamics in gas-phase molecules using time-resolved photoelectron and photoion spectroscopy. The vacuum ultraviolet (VUV) probe pulses are generated via strong field high-order harmonic generation from infrared femtosecond laser pulses. The band pass characteristic in transmission of thin indium (In) metal foil is exploited to isolate the $9^{\\text{th}}$ harmonic of the 800 nm fundamental (H9, 14 eV, 89 nm) from all other high harmonics. The $9^{\\text{th}}$ harmonic is obtained with high conversion efficiencies and has sufficient photon energy to access the complete set of valence electron levels in most molecules. The setup also allows for direct comparison of VUV single-photon probe with 800 nm multi-photon probe without influencing the delay of excitation and probe pulse or the beam geometry. We use a magnetic bottle spectrometer with high collection efficiency for electrons, serving at the same time as a time of flight spectrometer for ions. Characterization measurem...

  11. Quantum dynamical study of low-energy photoelectron bands of 2-phenylethyl-,-dimethylamine

    Indian Academy of Sciences (India)

    Susana Gómez-Carrasco; Horst Köppel

    2012-01-01

    The first three photoelectron bands of 2-phenylethyl-,-dimethylamine (PENNA) are investigated theoretically, paying particular attention to the vibrational structure and to possible nonadiabatic coupling effects. A substantial vibronic interaction is established between the first and second excited cationic states (corresponding to the second and third photoelectron bands). Their coupling to the cationic ground state is found to be rather weak. This is tentatively attributed to the well-known fact that the latter carries a hole at the amine site, while the former two have the electron removed from benzene-type orbitals. The interaction between the two excited cationic states is characterized by a `hidden’ or local symmetry at the phenyl moiety. Preliminary dynamic calculations with two interacting electronic states and four vibrational modes are reported. The computed spectra are compared to experimental results of Weinkauf et al.

  12. Feasibility tests of transmission x-ray photoelectron emission microscopy of wet samples

    Science.gov (United States)

    De Stasio, Gelsomina; Gilbert, B.; Nelson, T.; Hansen, R.; Wallace, J.; Mercanti, D.; Capozi, M.; Baudat, P. A.; Perfetti, P.; Margaritondo, G.; Tonner, B. P.

    2000-01-01

    We performed feasibility tests of photoelectron emission spectromicroscopy of wet samples in the water window (285-532 eV) soft x-ray spectral region. Water was successfully confined in an ultrahigh vacuum compatible compartment with x-ray transparent sides. This water cell was placed in the MEPHISTO spectromicroscope in a transmission geometry, and complete x-ray absorption spectra of the water window region were acquired. We also show micrographs of test samples, mounted outside of the compartment, and imaged through the water. This technique can be used to study liquid chemistry and, at least to the micron level, the microstructure of wet samples. Possibilities include cells in water or buffer, proteins in solution, oils of tribological interest, liquid crystals, and other samples not presently accessible to the powerful x-ray photoelectron emission spectromicroscopy technique.

  13. High energy photoelectron emission from gases using plasmonics enhanced near-fields

    CERN Document Server

    Ciappina, M F; Guichard, R; Pérez-Hernández, J A; Roso, L; Arnold, M; Siegel, T; Zaïr, A; Lewenstein, M

    2013-01-01

    We study theoretically the photoelectron emission in noble gases using plasmonic enhanced near-fields. We demonstrate that these fields have a great potential to generate high energy electrons by direct mid-infrared laser pulses of the current femtosecond oscillator. Typically, these fields appear in the surroundings of plasmonic nanostructures, having different geometrical shape such as bow-ties, metallic waveguides, metal nanoparticles and nanotips, when illuminated by a short laser pulse. In here, we consider metal nanospheres, in which the spatial decay of the near-field of the isolated nanoparticle can be approximated by an exponential function according to recent attosecond streaking measurements. We establish that the strong nonhomogeneous character of the enhanced near-field plays an important role in the above threshold ionization (ATI) process and leads to a significant extension in the photoelectron spectra. In this work, we employ the time dependent Schr\\"odinger equation in reduced dimensions to ...

  14. Photoelectron momentum distributions of the hydrogen molecular ion driven by multicycle near-infrared laser pulses

    Science.gov (United States)

    Murakami, Mitsuko; Chu, Shih-I.

    2016-10-01

    The photoelectron momentum distributions (PMDs) of the hydrogen molecular ion H2+ driven by strong near-infrared laser pulses are studied based on the ab initio numerical solution of the time-dependent Schrödinger equation and the Volkov wave propagation. Both linear and circular polarization are considered, in accordance with the recent experiment by M. Odenweller et al. [Phys. Rev. A 89, 013424 (2014), 10.1103/PhysRevA.89.013424]. We will discuss the difference between the molecular (diatomic) and the atomic PMDs and the effect of molecular potential to the photoelectron energy. In particular, we demonstrate that the above-threshold ionization spectra of H2+ could upshift their energy when driven by a linearly polarized laser field parallel to the molecular axis.

  15. Vanadium-doped small silicon clusters: Photoelectron spectroscopy and density-functional calculations

    Science.gov (United States)

    Xu, Hong-Guang; Zhang, Zeng-Guang; Feng, Yuan; Yuan, Jinyun; Zhao, Yuchao; Zheng, Weijun

    2010-03-01

    Vanadium-doped small silicon clusters, VSin- and VSin- ( n = 3-6), have been studied by anion photoelectron spectroscopy. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) of these clusters were obtained from their photoelectron spectra. We have also conducted density-functional calculations of VSin- and VSin- clusters and determined their structures by comparison of theoretical calculations with experimental results. Our results show that two V atoms in VSin- clusters tend to form a strong V-V bond. VSi6- has D3d symmetry with the six Si atoms forming a chair like six-membered ring similar to the ring in cyclohexane and the two vanadium atoms are joined with a δ bond.

  16. Channel-resolved photo- and Auger-electron spectroscopy of halogenated hydrocarbons

    Science.gov (United States)

    Ablikim, Utuq; Kaderiya, B.; Kumarapan, V.; Kushawaha, R.; Rudenko, A.; Rolles, D.; Xiong, H.; Berrah, N.; Bomme, C.; Savelyev, E.; Kilcoyne, D.

    2016-05-01

    Inner-shell photoelectron and Auger electron spectra of polyatomic molecules such as halogenated hydrocarbons are typically hard to interpret and assign due to many overlapping states that form broad bands even in high-resolution measurements. With the help of electron-ion-ion coincidence measurements performed using the velocity map imaging technique, we are able to detect high-energy (ionic fragmentation channels. Such channel-resolved measurements allow disentangling the overlapping electronic structures and help assigning individual components of the electron spectra to specific potential surfaces and final states. In this work, we present measurements on CH3 I, CH2 IBr, and CH2 ICl molecules in the gas-phase using soft x-ray light provided by the Advanced Light Source at LBNL. This project is supported by the DOE, Office of Science, BES, Division of Chemical, Geological and Biological Sciences under Award Number DE-FG02-86ER13491 (U.A., B.K., V.K., A.R., D.R.) and Award Number DE-SC0012376 (H.X., N.B.).

  17. High-resolution angle-resolved photoemission study of the Fermi surface and the normal-state electronic structure of Bi sub 2 Sr sub 2 CaCu sub 2 O sub 8

    Energy Technology Data Exchange (ETDEWEB)

    Olson, C.G.; Liu, R.; Lynch, D.W. (Ames Laboratory, Ames, IA (USA) Physics Department, Iowa State University, Ames, IA (USA)); List, R.S.; Arko, A.J. (Los Alamos National Laboratory, Los Alamos, NM (USA)); Veal, B.W.; Chang, Y.C.; Jiang, P.Z.; Paulikas, A.P. (Argonne National Laboratory, Argonne, IL (USA))

    1990-07-01

    High-resolution angle-resolved photoelectron spectroscopic measurements were made of the Fermi edge of a single crystal of Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} at 90 K along several directions in the Brillouin zone. The resultant Fermi-level crossings are consistent with local-density band calculations, including a point calculated to be of Bi-O character. Additional measurements were made where bands crossed the Fermi level between 100 and 250 K, along with measurements on an adjacent Pt foil. The Fermi edges of both materials agree to within the noise. Below the Fermi level the spectra show correlation effects in the form of an increased effective mass, but the essence of the single-particle band structure is retained. The shape of the spectra can be explained by a lifetime-broadened photohole and secondary electrons. The effective inverse photohole lifetime is linear in energy.

  18. Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy.

    Science.gov (United States)

    Weatherup, Robert S; Eren, Baran; Hao, Yibo; Bluhm, Hendrik; Salmeron, Miquel B

    2016-05-05

    Atmospheric pressure X-ray photoelectron spectroscopy (XPS) is demonstrated using single-layer graphene membranes as photoelectron-transparent barriers that sustain pressure differences in excess of 6 orders of magnitude. The graphene serves as a support for catalyst nanoparticles under atmospheric pressure reaction conditions (up to 1.5 bar), where XPS allows the oxidation state of Cu nanoparticles and gas phase species to be simultaneously probed. We thereby observe that the Cu(2+) oxidation state is stable in O2 (1 bar) but is spontaneously reduced under vacuum. We further demonstrate the detection of various gas-phase species (Ar, CO, CO2, N2, O2) in the pressure range 10-1500 mbar including species with low photoionization cross sections (He, H2). Pressure-dependent changes in the apparent binding energies of gas-phase species are observed, attributable to changes in work function of the metal-coated grids supporting the graphene. We expect atmospheric pressure XPS based on this graphene membrane approach to be a valuable tool for studying nanoparticle catalysis.

  19. Analysis of microcapsule resin using the X-Ray photoelectron nitrogen 1s spectral method

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Chiaki; Kobayashi, Naoya; Ishiguro, Mamoru; Endo, Kazunaka [Mitsubishi Paper Mills, Ltd., Tsukuba, Ibaraki (Japan). Tsukuba Research Lab.

    1995-06-01

    X-Ray photoelectron N 1s spectra have been used to determine which material is involved in the microcapsule; melamine or non-melamine (gelatin, polyurea and polyurethane). The linewidth of the N 1s spectra of melamine-resin, 2.5 eV, is larger than that of non-melamine materials (polyurea (2.1 eV) and gelatin (1.9 eV)). This depends on the nitrogen functional groups: The melamine involves two functional groups, amino and triazine-ring nitrogens, while polyurea and gelatin have amino groups. The N 1s spectra of melamine-resin and polyurea were simulated by an ab initio MO method using the melamine and 1,3-dimethyl urea molecules, respectively. (author).

  20. Quantitative interpretation of molecular dynamics simulations for X-ray photoelectron spectroscopy of aqueous solutions

    Science.gov (United States)

    Olivieri, Giorgia; Parry, Krista M.; Powell, Cedric J.; Tobias, Douglas J.; Brown, Matthew A.

    2016-04-01

    Over the past decade, energy-dependent ambient pressure X-ray photoelectron spectroscopy (XPS) has emerged as a powerful analytical probe of the ion spatial distributions at the vapor (vacuum)-aqueous electrolyte interface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt to provide a complete description of the liquid interface. There is, however, no systematic protocol that permits a straightforward comparison of the two sets of results. XPS is an integrated technique that averages signals from multiple layers in a solution even at the lowest photoelectron kinetic energies routinely employed, whereas MD simulations provide a microscopic layer-by-layer description of the solution composition near the interface. Here, we use the National Institute of Standards and Technology database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to quantitatively interpret atom-density profiles from MD simulations for XPS signal intensities using sodium and potassium iodide solutions as examples. We show that electron inelastic mean free paths calculated from a semi-empirical formula depend strongly on solution composition, varying by up to 30% between pure water and concentrated NaI. The XPS signal thus arises from different information depths in different solutions for a fixed photoelectron kinetic energy. XPS signal intensities are calculated using SESSA as a function of photoelectron kinetic energy (probe depth) and compared with a widely employed ad hoc method. SESSA simulations illustrate the importance of accounting for elastic-scattering events at low photoelectron kinetic energies (hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquid interfaces are discussed.

  1. Multiphoton ionization photoelectron spectroscopy of xenon: Experiment and theory

    Energy Technology Data Exchange (ETDEWEB)

    Bajic, S.J.; Compton, R.N.; Tang, X.; L' Huiller, A.; Lambropoulos, P.

    1988-11-01

    Photoelectron energy and angular distributions for resonantly enhanced multiphoton ionization (REMPI) of xenon via the three-photon-allowed 7s(3/2)/sub 1//sup 0/ and 5d(3/2)/sub 1//sup 0/ states have been studied both experimentally and theoretically. The electron kinetic energy spectra give the probability of leaving Xe/sup +/ in either the /sup 2/P/sub 1/2/ or /sup 2/P/sub 3/2/ core. The measured branching ratio for leaving each ionic core is used to test the theoretical description of the REMPI process. Measurements of both the angular distributions and the (3+1) REMPI via the 5d state are adequately reproduced by multichannel quantum defect theory. However, measurements of angular distributions for the electrons resulting from (3+1) via the 7s(3/2)/sub 1//sup 0/ state into Xe/sup +/ /sup 2/P/sub 3/2/ (core preserving) or Xe/sup +/ /sup 2/P/sub 1/2/ (core changing) are in striking disagreement with theory. 1 ref., 2 figs.

  2. Electronic structure simulation of chromium aluminum oxynitride by discrete variational-X alpha method and X-ray photoelectron spectroscopy

    CERN Document Server

    Choi, Y; Lee, J D; Kim, E; No, K

    2002-01-01

    We use a first-principles discrete variational (DV)-X alpha method to investigate the electronic structure of chromium aluminum oxynitride. When nitrogen is substituted for oxygen in the Cr-Al-O system, the N2p level appears in the energy range between O2p and Cr3d levels. Consequently, the valence band of chromium aluminum oxynitride becomes broader and the band gap becomes smaller than that of chromium aluminum oxide, which is consistent with the photoelectron spectra for the valence band using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). We expect that this valence band structure of chromium aluminum oxynitride will modify the transmittance slope which is a requirement for photomask application.

  3. CRF-PEPICO: Double velocity map imaging photoelectron photoion coincidence spectroscopy for reaction kinetics studies

    Science.gov (United States)

    Sztáray, Bálint; Voronova, Krisztina; Torma, Krisztián G.; Covert, Kyle J.; Bodi, Andras; Hemberger, Patrick; Gerber, Thomas; Osborn, David L.

    2017-07-01

    Photoelectron photoion coincidence (PEPICO) spectroscopy could become a powerful tool for the time-resolved study of multi-channel gas phase chemical reactions. Toward this goal, we have designed and tested electron and ion optics that form the core of a new PEPICO spectrometer, utilizing simultaneous velocity map imaging for both cations and electrons, while also achieving good cation mass resolution through space focusing. These optics are combined with a side-sampled, slow-flow chemical reactor for photolytic initiation of gas-phase chemical reactions. Together with a recent advance that dramatically increases the dynamic range in PEPICO spectroscopy [D. L. Osborn et al., J. Chem. Phys. 145, 164202 (2016)], the design described here demonstrates a complete prototype spectrometer and reactor interface to carry out time-resolved experiments. Combining dual velocity map imaging with cation space focusing yields tightly focused photoion images for translationally cold neutrals, while offering good mass resolution for thermal samples as well. The flexible optics design incorporates linear electric fields in the ionization region, surrounded by dual curved electric fields for velocity map imaging of ions and electrons. Furthermore, the design allows for a long extraction stage, which makes this the first PEPICO experiment to combine ion imaging with the unimolecular dissociation rate constant measurements of cations to detect and account for kinetic shifts. Four examples are shown to illustrate some capabilities of this new design. We recorded the threshold photoelectron spectrum of the propargyl and the iodomethyl radicals. While the former agrees well with a literature threshold photoelectron spectrum, we have succeeded in resolving the previously unobserved vibrational structure in the latter. We have also measured the bimolecular rate constant of the CH2I + O2 reaction and observed its product, the smallest Criegee intermediate, CH2OO. Finally, the second

  4. Hard X-ray photoelectron spectroscopy of bulk and thin films of Heusler compounds

    Energy Technology Data Exchange (ETDEWEB)

    Kozina, Xeniya

    2012-03-26

    X-ray photoemission spectroscopy (XPS) is one of the most universal and powerful tools for investigation of chemical states and electronic structures of materials. The application of hard X-rays increases the inelastic mean free path of the emitted electrons within the solid and thus makes hard X-ray photoelectron spectroscopy (HAXPES) a bulk sensitive probe for solid state research and especially a very effective nondestructive technique to study buried layers. This thesis focuses on the investigation of multilayer structures, used in magnetic tunnel junctions (MTJs), by a number of techniques applying HAXPES. MTJs are the most important components of novel nanoscale devices employed in spintronics. The investigation and deep understanding of the mechanisms responsible for the high performance of such devices and properties of employed magnetic materials that are, in turn, defined by their electronic structure becomes feasible applying HAXPES. Thus the process of B diffusion in CoFeB-based MTJs was investigated with respect to the annealing temperature and its influence on the changes in the electronic structure of CoFeB electrodes that clarify the behaviour and huge TMR ratio values obtained in such devices. These results are presented in chapter 6. The results of investigation of the changes in the valence states of buried off-stoichiometric Co{sub 2}MnSi electrodes were investigated with respect to the Mn content {alpha} and its influence on the observed TMR ratio are described in chapter 7. Magnetoelectronic properties such as exchange splitting in ferromagnetic materials as well as the macroscopic magnetic ordering can be studied by magnetic circular dichroism in photoemission (MCDAD). It is characterized by the appearance of an asymmetry in the photoemission spectra taken either from the magnetized sample with the reversal of the photon helicity or by reversal of magnetization direction of the sample when the photon helicity direction is fixed. Though

  5. Electron band bending and surface sensitivity: X-ray photoelectron spectroscopy of polar GaN surfaces

    Science.gov (United States)

    Bartoš, I.; Romanyuk, O.; Paskova, T.; Jiříček, P.

    2017-10-01

    The role of electron band bending and surface sensitivity in determining the core level binding energies by X-ray photoelectron spectroscopy is investigated. A dominating contribution of surface atomic layers to photoemission intensity is confirmed for normal photoemission. The energy of the photoelectron core level peak does not deviate from core level peak energies of electrons photoemitted from the surface atomic layers of the crystal. The higher surface sensitivity regime, achieved e.g. at off-normal photoelectron detection angle, can be used to study the surface potential barrier in just a few topmost atomic layers. In addition, it is demonstrated that core level binding energy measured by angle-resolved X-ray photoelectron spectroscopy reflect the electron attenuation anisotropy. In particular, core level binding energy changes with emission angle and correlates with the forward focusing directions in a crystal. This effect is demonstrated by measuring the polar angle dependence of Ga 3d core levels on clean GaN(0001) and GaN(000 1 bar) surfaces with a higher and a lower band bending, respectively. The effect is explained by variation of emission depth in a crystal for normal and off-normal photoelectron emission angles.

  6. Photoelectron angular distributions from aligned molecules using the R-matrix method

    CERN Document Server

    Harvey, Alex G; Morales, Felipe; Smirnova, Olga

    2014-01-01

    We present a new extension of the UKRmol electron-molecule scattering code suite, which allows one to compute ab initio photoionization and photorecombination amplitudes for complex molecules, resolved both on the molecular alignment (orientation) and the emission angle and energy of the photoelectron. We illustrate our approach using CO$_2$ as an example, and analyze the importance of multi-channel effects by performing our calculations at different, increasing levels of complexity. We benchmark our method by comparing the results of our calculations with experimental data and with theoretical calculations available in the literature.

  7. A Photoelectron Spectroscopic Study of Di-t-butylphosphazene

    DEFF Research Database (Denmark)

    Elbel, S.; Ellis, A.; Niecke, E.

    1985-01-01

    Gaseous trans-ButPNBut, generated by mild gas-phase thermolysis of its more stable [2 + 1] cyclodimer, has been characterized by field-ionization mass spectrometry and U.V. photoelectron spectroscopy. The photoelectron spectrum has been assigned based on SCC-Xα model calculations for representat......Gaseous trans-ButPNBut, generated by mild gas-phase thermolysis of its more stable [2 + 1] cyclodimer, has been characterized by field-ionization mass spectrometry and U.V. photoelectron spectroscopy. The photoelectron spectrum has been assigned based on SCC-Xα model calculations...

  8. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    Energy Technology Data Exchange (ETDEWEB)

    Bradforth, S.E.

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound [yields] bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN[sup [minus

  9. An imaging photoelectron-photoion coincidence investigation of homochiral 2R,3R-butanediol clusters

    Science.gov (United States)

    Daly, Steven; Powis, Ivan; Garcia, Gustavo A.; Tia, Maurice; Nahon, Laurent

    2017-07-01

    We report an experimental investigation of homochiral cluster formation in seeded molecular beam expansions of (2R,3R)-butanediol. Synchrotron radiation vacuum ultraviolet photoionization measurements have been performed using a double imaging electron-ion spectrometer in various configurations and modes of operation. These include measurements of the cluster ion mass spectra, wavelength scanned ion yields, and threshold electron spectra. Protonated cluster ions ranging up to n = 7 have been observed and size-selected photoelectron spectra and photoelectron circular dichroism (PECD) have been recorded by velocity map imaging, recorded in coincidence with ions, at a number of fixed photon energies. Translation temperatures of the cluster ions have been further examined by ion imaging measurements. As well as the sequence of protonated clusters with integral numbers of butanediol monomer units, a second series with half-integral monomer masses is observed and deduced to result from a facile cleavage of a butanediol monomer moiety within the nascent cluster. This second sequence of half-integral masses displays quite distinct behaviours. PECD measurements are used to show that the half-integral mass cluster ions do not share a common parentage with whole integer masses. Using an analogy developed with simple theoretical calculations of butanediol dimer structures, it is inferred that the dissociative branching into integral and half-integral ion mass sequences is controlled by the presence of different butanediol monomer conformations within the hydrogen bonded clusters.

  10. Scanned-energy mode photoelectron diffraction measurements at beamline 7.0.1

    Energy Technology Data Exchange (ETDEWEB)

    Toomes, R.; Booth, N.A.; Woodruff, D.P. [Univ. of Warwick, Coventry (United Kingdom)] [and others

    1997-04-01

    This report covers the results of the authors first experimental run, in May 1996, conducted to explore the advantages offered by the high spectral resolution available at the SpectroMicroscopy Facility on beam line 7.0 to conduct scanned-energy mode photoelectron diffraction (PhD). This technique is now a well-established method for the determination of local structure of atomic and molecular adsorbates on well-characterised surfaces. The directly-emitted component of an adsorbate core-level photoelectron wavefield interferes coherently with components of the same wavefield elastically scattered by surrounding atoms, leading to a modulation in the photoemission intensity as a function of kinetic energy in any specific emission direction. A series of such PhD modulation spectra, each typically covering energies from 50-500 eV, for a series of different emission directions, provides the basis for a quantitative structure determination of the emitter-scatterer geometry. Within the last years the authors have developed an integrated approach to extract the structural information from these photoelectron diffraction (PhD) spectra in a quantitative way. A direct data inversion technique (the so-called Projection method) provides a first-order estimate of the local adsorbate geometry in the form of an `image` of the scatterer atoms which are nearest neighbours to the emitter. This information is then used as a starting model for optimisation of the structural parameters by comparing the experimental PhD spectra with the results of multiple scattering simulations using a code developed by Fritzsche. The optimisation uses an automated trial-and-error procedure by minimising a reliability factor which provides an objective measure of the quality of agreement between experiment and theory. The authors have successfully applied this approach to the structure determination of about 30 adsorption systems.

  11. Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO{sup +} and vibrational resolution in NCO{sup +}

    Energy Technology Data Exchange (ETDEWEB)

    Holzmeier, Fabian; Lang, Melanie; Fischer, Ingo, E-mail: ingo.fischer@uni-wuerzburg.de [Institute of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg (Germany); Tang, Xiaofeng [Synchrotron SOLEIL, l’Orme des Merisiers, Saint Aubin BP 48, F-91192 Gif sur Yvette Cedex (France); Cunha de Miranda, Barbara; Romanzin, Claire; Alcaraz, Christian [Laboratoire de Chimie-Physique, UMR 8000 CNRS and Université Paris-Sud 11, F-91405 Orsay Cedex (France); Hemberger, Patrick [Molecular Dynamics Group, Paul Scherrer Institute (PSI), CH-5232 Villigen (Switzerland)

    2015-05-14

    The threshold photoelectron spectra (TPES) of two unstable nitrogen-containing species, HNCO and NCO, were recorded utilizing vacuum ultraviolet synchrotron radiation. Both are intermediates in combustion processes and play a role in the removal of nitrogen oxides from exhaust gases. The rovibronic structure of the first band in the TPES of HNCO{sup +} was analyzed within the framework of an orbital ionization model, and the resolved structure of the origin band was assigned to ΔK subbands. An ionization energy of 11.602 ± 0.005 eV was determined and the vibrational structure of the cationic ground state was analyzed by a Franck-Condon fit. Low lying electronically excited states of HNCO{sup +} were also observed. In a second series of experiments, the NCO radical was generated by flash pyrolysis from chlorine isocyanate. The ionization energy to the X{sup +} {sup 3}Σ{sup −} ground state was determined to be 11.76 ± 0.02 eV, while for the a{sup +1}Δ state, a value of 12.93 ± 0.02 eV was obtained. Vibrational structure was observed for both states, and bands were assigned by Franck-Condon simulations.

  12. Coupled-cluster interpretation of the photoelectron spectrum of Ag3 (.).

    Science.gov (United States)

    Bauman, Nicholas P; Hansen, Jared A; Piecuch, Piotr

    2016-08-28

    We use the scalar relativistic ionized equation-of-motion coupled-cluster (IP-EOMCC) approaches to investigate the photoelectron spectrum of Ag3 (-), examining the effects of basis set, number of correlated electrons, level of applied theory including up to 3-hole-2-particle terms, and geometry relaxation. By employing an IP-EOMCC-based extrapolation scheme, we are able to provide an accurate interpretation and complete assignment of peaks and other key features in the experimentally observed spectra, including electron binding energies as high as about 6.5 eV.

  13. Short-range order in amorphous SiO{sub x} by x ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Novikov, Yu. N.; Gritsenko, V. A. [Institute of Semiconductor Physics, Novosibirsk 630090 (Russian Federation)

    2011-07-01

    The Si 2p x ray photoelectron spectra of SiO{sub x} with a different composition of 0 {<=} x {<=} 2 have been studied experimentally and theoretically. The SiO{sub x} films were prepared by low-pressure chemical vapor deposition from SiH{sub 4} and N{sub 2}O source at 750 deg. C. Neither random bonding nor random mixture models can adequately describe the structure of these compounds. The interpretation of the experimental results is discussed according to a large scale potential fluctuation due to the spatial variation of chemical composition in SiO{sub x}.

  14. Investigation of low-Z Coster-Kronig transitions by means of Auger and photoelectron spectroscopy

    Science.gov (United States)

    Yin, L. I.; Tsang, T.; Adler, I.

    1972-01-01

    Experimental intensity ratios of Auger transitions for Co, Ni, Cu, and Zn as well as the relative L sub 2 and L sub 3 level widths of Cu and Zn, derived from their photoelectron spectra, are presented. Evidence is presented that a great deal of vacancy reorganization took place following photoionization and prior to Auger emission. These reorganizations are assumed to be due to Coster-Kronig transitions f sub 23. These results are compared with theoretical calculations and agree with predicted discontinuity at Z = 30 where f sub 23 transitions become energetically impossible.

  15. Electronic structure effects in liquid water studied by photoelectron spectroscopy and density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Nordlund, Dennis; Odelius, Michael; Bluhm, Hendrik; Ogasawara, Hirohito; Pettersson, Lars G.M.; Nilsson, Anders

    2008-04-29

    We present valence photoelectron emission spectra of liquid water in comparison with gas-phase water, ice close to the melting point, low temperature amorphous and crystalline ice. All aggregation states have major electronic structure changes relative to the free molecule, with rehybridization and development of bonding and anti-bonding states accompanying the hydrogen bond formation. Sensitivity to the local structural order, most prominent in the shape and splitting of the occupied 3a{sub 1} orbital, is understood from the electronic structure averaging over various geometrical structures, and reflects the local nature of the orbital interaction.

  16. Low kinetic energy photoelectron diffractions for C 1s and O 1s electrons of free CO molecules in the EXAFS region

    Energy Technology Data Exchange (ETDEWEB)

    Adachi, Jun-ichi; Yamazaki, Masakazu; Kimura, Yasuyuki; Yagishita, Akira [Photon Factory, IMSS, KEK, 1-1 Oho, Tsukuba 305-0801 (Japan); Kazama, Misato; Ohori, Yusuke; Fujikawa, Takashi [Graduate School of Advanced Integration Science, Chiba University, 1-33 Yayoi-cho, Inage 263-8522 (Japan); Teramoto, Takahiro, E-mail: jun-ichi.adachi@kek.j [Graduate School of Science, University of Tokyo, Bunkyo-ku, Tokyo, 113-0033 (Japan)

    2009-11-15

    We have measured molecular-frame photoelectron angular distributions from carbon 1s and oxygen 1s levels of CO molecules up to a photoelectron kinetic energy (KE) of {approx}150 eV. The backward-scattering intensities exhibited a strong modulation as a function of the kinetic energy of the photoelectrons, whereas the intensities for the forward-scattering gradually increased and then became nearly constant over KE {approx}100 eV. Multiple scattering calculations with a muffin-tin potential qualitatively reproduced the experimental results. The present results may be considered as the observation of low-energy photoelectron diffraction patterns for gaseous free CO molecules, which are involved in modulations in extended X-ray absorption fine structure (EXAFS) spectra.

  17. Inner-valence states of N2(+) studied by UV photoelectron spectroscopy and configuration-interaction calculations

    Science.gov (United States)

    Baltzer, P.; Larsson, M.; Karlsson, L.; Wannberg, B.; Goethe, M. C.

    1992-11-01

    Spectrometric observations are conducted to examine the inner-valence photoelectron spectra of nitrogen molecules that are excited by He II. Spectra in the range 20-35 eV are studied by means of a UV source that provides high-resolution high-intensity readings for the radiation with a low photoionization cross section. Vibrational structures are reported in three electron bands related to cationic transitions, and a potential barrier towards dissociation is described. The three states of vibrational progression are given as C2Sigma(u)(+), D2Pi(g), and 3(2)Sigma(g)(+), and calculations of the same states are developed for comparison based on self-consistent-field and multireference configuration-interaction techniques. The present experimental and numerical results present data of interest in the interpretation of photoelectron spectroscopic astrophysical observations.

  18. Synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy of radicals produced in a flow tube: OH and OD

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, Gustavo A.; Tang, Xiaofeng; Gil, Jean-François; Nahon, Laurent [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Ward, Michael; Batut, Sebastien; Fittschen, Christa [PC2A, Université de Lille 1, UMR CNRS-USTL 8522, Cité Scientifique Bât. C11, F-59655 Villeneuve d’Ascq (France); Taatjes, Craig A.; Osborn, David L. [Combustion Research Facility, Mail Stop 9055, Sandia National Laboratories, Livermore, California 94551-0969 (United States); Loison, Jean-Christophe [ISM, Université Bordeaux 1, CNRS, 351 cours de la Libération, 33405 Talence Cedex (France)

    2015-04-28

    We present a microwave discharge flow tube coupled with a double imaging electron/ion coincidence device and vacuum ultraviolet (VUV) synchrotron radiation. The system has been applied to the study of the photoelectron spectroscopy of the well-known radicals OH and OD. The coincidence imaging scheme provides a high selectivity and yields the spectra of the pure radicals, removing the ever-present contributions from excess reactants, background, or secondary products, and therefore obviating the need for a prior knowledge of all possible byproducts. The photoelectron spectra encompassing the X{sup 3}Σ{sup −} ground state of the OH{sup +} and OD{sup +} cations have been extracted and the vibrational constants compared satisfactorily to existing literature values. Future advantages of this approach include measurement of high resolution VUV spectroscopy of radicals, their absolute photoionization cross section, and species/isomer identification in chemical reactions as a function of time.

  19. Synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy of radicals produced in a flow tube: OH and OD

    Science.gov (United States)

    Garcia, Gustavo A.; Tang, Xiaofeng; Gil, Jean-François; Nahon, Laurent; Ward, Michael; Batut, Sebastien; Fittschen, Christa; Taatjes, Craig A.; Osborn, David L.; Loison, Jean-Christophe

    2015-04-01

    We present a microwave discharge flow tube coupled with a double imaging electron/ion coincidence device and vacuum ultraviolet (VUV) synchrotron radiation. The system has been applied to the study of the photoelectron spectroscopy of the well-known radicals OH and OD. The coincidence imaging scheme provides a high selectivity and yields the spectra of the pure radicals, removing the ever-present contributions from excess reactants, background, or secondary products, and therefore obviating the need for a prior knowledge of all possible byproducts. The photoelectron spectra encompassing the X3Σ- ground state of the OH+ and OD+ cations have been extracted and the vibrational constants compared satisfactorily to existing literature values. Future advantages of this approach include measurement of high resolution VUV spectroscopy of radicals, their absolute photoionization cross section, and species/isomer identification in chemical reactions as a function of time.

  20. Attosecond dynamics through a Fano resonance: Monitoring the birth of a photoelectron

    Science.gov (United States)

    Gruson, V.; Barreau, L.; Jiménez-Galan, Á.; Risoud, F.; Caillat, J.; Maquet, A.; Carré, B.; Lepetit, F.; Hergott, J.-F.; Ruchon, T.; Argenti, L.; Taïeb, R.; Martín, F.; Salières, P.

    2016-11-01

    The dynamics of quantum systems are encoded in the amplitude and phase of wave packets. However, the rapidity of electron dynamics on the attosecond scale has precluded the complete characterization of electron wave packets in the time domain. Using spectrally resolved electron interferometry, we were able to measure the amplitude and phase of a photoelectron wave packet created through a Fano autoionizing resonance in helium. In our setup, replicas obtained by two-photon transitions interfere with reference wave packets that are formed through smooth continua, allowing the full temporal reconstruction, purely from experimental data, of the resonant wave packet released in the continuum. In turn, this resolves the buildup of the autoionizing resonance on an attosecond time scale. Our results, in excellent agreement with ab initio time-dependent calculations, raise prospects for detailed investigations of ultrafast photoemission dynamics governed by electron correlation, as well as coherent control over structured electron wave packets.

  1. Photoelectron Imaging as a Quantum Chemistry Visualization Tool

    Science.gov (United States)

    Grumbling, Emily R.; Pichugin, Kostyantyn; Mabbs, Richard; Sanov, Andrei

    2011-01-01

    An overview and simple example of photoelectron imaging is presented, highlighting its efficacy as a pedagogical tool for visualizing quantum phenomena. Specifically, photoelectron imaging of H[superscript -] (the simplest negative ion) is used to demonstrate several quantum mechanical principles. This example could be incorporated into an…

  2. Spectroscopy of transient neutral species via negative ion photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Weaver, A.

    1991-12-01

    Negative ion photoelectron spectroscopy has been used to study two types of transient neutral species: bound free radicals (NO{sub 2} and NO{sub 3}) and unstable neutral species ([IHI] and [FH{sub 2}]). The negative ion time-of-flight photoelectron spectrometer used for these experiments is described in detail.

  3. Spectroscopy of transient neutral species via negative ion photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Weaver, A.

    1991-12-01

    Negative ion photoelectron spectroscopy has been used to study two types of transient neutral species: bound free radicals (NO{sub 2} and NO{sub 3}) and unstable neutral species ((IHI) and (FH{sub 2})). The negative ion time-of-flight photoelectron spectrometer used for these experiments is described in detail.

  4. Study of selected benzyl azides by UV photoelectron spectroscopy and mass spectrometry

    Science.gov (United States)

    Pinto, R. M.; Olariu, R. I.; Lameiras, J.; Martins, F. T.; Dias, A. A.; Langley, G. J.; Rodrigues, P.; Maycock, C. D.; Santos, J. P.; Duarte, M. F.; Fernandez, M. T.; Costa, M. L.

    2010-09-01

    Benzyl azide and the three methylbenzyl azides were synthesized and characterized by mass spectrometry (MS) and ultraviolet photoelectron spectroscopy (UVPES). The electron ionization fragmentation mechanisms for benzyl azide and their methyl derivatives were studied by accurate mass measurements and linked scans at constant B/ E. For benzyl azide, in order to clarify the fragmentation mechanism, labelling experiments were performed. From the mass analysis of methylbenzyl azides isomers it was possible to differentiate the isomers ortho, meta and para. The abundance and nature of the ions resulting from the molecular ion fragmentation, for the three distinct isomers of substituted benzyl azides, were rationalized in terms of the electronic properties of the substituent. Concerning the para-isomer, IRC calculations were performed at UHF/6-31G(d) level. The photoionization study of benzyl azide, with He(I) radiation, revealed five bands in the 8-21 eV ionization energies region. From every photoelectron spectrum of methylbenzyl azides isomers it has been identified seven bands, on the same range as the benzyl azide. Interpretation of the photoelectron spectra was accomplished applying Koopmans' theorem to the SCF orbital energies obtained at HF/6-311++G(d, p) level.

  5. Ultraviolet photoelectron spectroscopy of the valence bands of some Au alloys

    Energy Technology Data Exchange (ETDEWEB)

    Nicholson, J.A.; Riley, J.D.; Leckey, R.C.G.; Jenkin, J.G.; Liesegang, J.; Azoulay, J.

    1978-09-15

    Ultraviolet photoelectron spectra taken with 40.81-eV photons are presented for three series of Au alloys: AuGa, AuIn, and AuCd. The results are discussed with reference to similar work on a series of Ag alloys previously reported and are also compared with x-ray photoelectron spectroscopy data. The results are consistent with the previous work on Ag alloys in that the Au 5d doublet width and splitting are (i) independent of the secondary or alloying metal, and (ii) strongly dependent on the mean number of nearest Au neighbors. The behavior of the Au 5d bandwidth, as a function of Au concentration, as measured here using He II radiation, differs significantly from that measured previously using x-ray photoelectron spectroscopy. This difference cannot be attributed wholly to the difference in linewidth of the two-photon sources or to surface enrichment of the samples. The similar variations of the Ga, In, and Cd d bands as a function of Au concentration are discussed with reference to previous work on the alloys of AgIn and AgCd.

  6. Electronic structure of the diatomic VO anion: A combined photoelectron-imaging spectroscopic and theoretical investigation

    Science.gov (United States)

    Cheng, Shi-Bo; Harmon, Christopher L.; Yang, Huan; Castleman, A. W.

    2016-12-01

    The electronic structure of the diatomic VO anion was explored by combining the photoelectron-imaging spectroscopy and high-level theoretical calculations. The electron affinity (EA) of VO is determined to be 1.244 ± 0.025 eV from the vibrationally resolved photoelectron spectrum acquired at 532 nm. The anisotropy parameter (β) for the EA defined peak is measured to be 1.59 ± 0.02, indicating that it is the 9σ electron attachment leading to the formation of the ground state of V O- . The present imaging experiment provides direct evidence that the ground state of V O- is X 3Σ- with a (3π ) 4(8σ ) 2(9σ ) 2(1δ ) 2 electron configuration, which resolves the significant discrepancy in previous experiment and theory. In addition, the molecular orbitals and bonding involved in the anionic VO cluster are also examined based on the present high-level theoretical calculations.

  7. Above-threshold ionization and photoelectron spectra in atomic systems driven by strong laser fields

    CERN Document Server

    Suárez, Noslen; Ciappina, Marcelo; Biegert, Jens; Lewenstein, Maciej

    2015-01-01

    Above-threshold ionization (ATI) results from strong field laser-matter interaction and it is one of the fundamental processes that may be used to extract electron structural and dynamical information about the atomic or molecular target. Moreover, it can also be used to characterize the laser field itself. Here, we develop an analytical description of ATI, which extends the theoretical Strong Field Approximation (SFA), for both the direct and re-scattering transition amplitudes in atoms. From a non-local, but separable potential, the bound-free dipole and the re-scattering transition matrix elements are analytically computed. In comparison with the standard approaches to the ATI process, our analytical derivation of the re-scattering matrix elements allows us to study directly how the re-scattering process depends on the atomic target and laser pulse features -we can turn on and off contributions having different physical origins or corresponding to different physical mechanisms. We compare SFA results with ...

  8. Temperature-invariant photoelectron spectra in cerium heavy-fermion compounds: Inconsistencies with the Kondo model

    Energy Technology Data Exchange (ETDEWEB)

    Joyce, J.J.; Arko, A.J.; Lawrence, J.; Canfield, P.C.; Fisk, Z.; Bartlett, R.J.; Thompson, J.D. (Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States))

    1992-01-13

    4{ital f} levels in Ce heavy-fermion compounds are examined using resonant photoemission. We find the following inconsistencies with the predictions of the Kondo model: (a) All temperature dependence can be accounted for simply by phonon broadening and the Fermi function; (b) the spectral weights of the features near {ital E}{sub {ital F}} do not scale with {ital T}{sub {ital K}}; and (c) the line shape of the feature previously identified as the Kondo resonance is Lorentzian and about an order of magnitude broader than predictions. Instrument resolution is not a limiting factor.

  9. Inconsistencies with the single impurity Undersign model in photoelectron spectra of cerium heavy fermion compounds

    Energy Technology Data Exchange (ETDEWEB)

    Joyce, J.J.; Arko, A.J; Canfield, P.C.; Fisk, Z.; Barlett, R.J.; Smith, J.L.; Thompson, J.D. (Los Alamos National Lab., NM (United States)); Lawrence, J. (California Univ., Irvine, CA (United States))

    1991-01-01

    We have re-examined the temperature-dependence of the valence band 4f features in Ce-based heavy fermions. We measured the phonon broadening of the Si-2p core levels in CeSi{sub 2} by determining the increase of the full width at half-maximum (FWHM) as a function of temperature. We discovered that all the temperature dependence is exactly accounted for, and there is none left over to attribute to any Kondo effects. We concluded that the feature of E{sub F} in Ce-based heavy fermions cannot be a Kondo resonance. 16 refs., 3 figs.

  10. Photoelectron spectroscopy of strongly correlated Yb compounds

    Energy Technology Data Exchange (ETDEWEB)

    Joyce, J.J.; Andrews, A.B.; Arko, A.J.; Bartlett, R.J.; Blythe, R.I. [Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Olson, C.G.; Benning, P.J.; Canfield, P.C. [Ames Laboratory, U. S. Department of Energy, Ames, Iowa 50011 (United States); Poirier, D.M. [Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455 (United States)

    1996-12-01

    The electronic properties of the Yb compounds YBCu{sub 2}Si{sub 2}, YBAgCu{sub 4}, and YbAl{sub 3} along with purely divalent Yb metal, have been investigated by means of high-resolution ultraviolet and x-ray photoelectron spectroscopy. We present the intrinsic characteristic features of the 4{ital f} levels of Yb while accounting for lattice vibrations and the manifestation of corelike energy levels degenerate with the valence states and modified by the temperature-dependent Fermi function. For these strongly correlated Yb-based compounds, the hole occupancy values ({ital n}{sub {ital f}}{approximately}0.6) directly obtained from integration of the divalent and trivalent portions of the 4{ital f} photoemission features indicate that these compounds are strongly mixed valent. The small intensity modulation with temperature in the divalent Yb 4{ital f} levels (0{endash}10{percent} over a {ital T}=20{minus}300 K range) is discussed within the conventional framework of the photoemission process and nominal allowances for lattice variations with temperature. Results from photoemission experiments on the divalent 4{ital f} levels of strongly correlated Yb compounds are remarkably similar to the 4{ital f} levels of purely divalent Yb metal. {copyright} {ital 1996 The American Physical Society.}

  11. X-ray Photoelectron Spectroscopy on Superconducting Tl2CaBa2Cu2O8 Thin Film

    Science.gov (United States)

    Zeng, Wensheng; Qiu, Ping; Yan, Shaolin; Li, Zengfa; Zhang, Guangyin

    1991-06-01

    We have prepared single-phase superconducting Tl2CaBa2Cu2O8 thin film by dc magnetron sputtering process and measured x-ray photoelectron spectra of the film at room and liquid nitrogen temperatures. From the relative intensities of the Ba3d, Tl4f. O1s and Cu2p spectra taken at different take-off angles, we have concluded that there is an adventitious contamination (nonsuperconducting phase) surface layer. After excluding contributions from these spurious phases, we have tentatively assigned which core-level shifts should be caused by the superconducting phase transition.

  12. X-Ray Photoelectron Spectroscopy and Reflection High Energy Electron Diffraction of Epitaxial Growth SiC on Si(100) Using C60 and Si

    Institute of Scientific and Technical Information of China (English)

    LIU Yan-Fang; LIU Jin-Feng; XU Peng-Shou; PAN Hai-Bin

    2007-01-01

    The formation of silicon carbide upon deposition of C60 and Si on Si(100) surface at 850 ℃ is studied via x-ray photoelectron spectroscopy and reflection high energy electron diffraction (RHEED). The C 1s, O 1s and Si 2p core-level spectra and the RHEED patterns indicate the formation of 3C-SiC.

  13. Structures of cycloserine and 2-oxazolidinone probed by X-ray photoelectron spectroscopy

    CERN Document Server

    Ahmed, Marawan; Acres, Robert G; Prince, Kevin C

    2013-01-01

    The electronic structures and properties of 2-oxazolidinone and the related compound cycloserine (CS) have been investigated using core and valence photoelectron spectroscopy and theoretical calculations. Isomerization of the central oxazolidine heterocycle and the addition of an amino group yields cycloserine. Theory correctly predicts the C, N and O 1s core spectra, and additionally we report theoretical natural bond orbital (NBO) charges. The valence ionization energies are also in agreement with theory and previous measurements. Although the lowest binding energy part of the spectra of the two compounds show superficial similarities, analysis of the charge densities of the frontier orbitals indicates substantial reorganization of the wave functions as a result of isomerization. The Highest Occupied Molecular Orbital of CS has leading carbonyl {\\pi} character with contributions from other heavy atoms in the molecule, while the Highest Occupied Molecular Orbital of 2-oxazolidinone has leading nitrogen, carb...

  14. Photoelectron imaging of tetrahydrofuran cluster anions (THF)n- (1<=n<=100)

    Science.gov (United States)

    Young, Ryan M.; Yandell, Margaret A.; Niemeyer, Markus; Neumark, Daniel M.

    2010-10-01

    Anionic tetrahydrofuran clusters (THF)n- (1≤n≤100) are studied with photoelectron imaging as gas-phase precursors for electrons solvated in THF. Photoelectron spectra of clusters up to n =5 show two peaks, one of which is attributed to a solvated open chain radical anion and the other to the closed THF ring. At n =6, the spectra change shape abruptly, which become more characteristic of (THF)n- clusters containing solvated electrons. From n =6-100, the vertical detachment energies (VDEs) of these solvated electron clusters increase from 1.96 to 2.71 eV, scaling linearly with n-1/3. For fully deuterated (THF-d8)n- clusters, the apparent transition to a solvated electron cluster is delayed to n =11. Extrapolation of the VDEs to infinite cluster size yields a value of 3.10 eV for the bulk photoelectric threshold. The relatively large VDEs at onset and small stabilization with increasing cluster size compared to other solvated electron clusters may reflect the tendency of the bulk solvent to form preexisting voids that can readily solvate a free electron.

  15. Photoelectron imaging of tetrahydrofuran cluster anions (THF)(n) (-) (1≤n≤100).

    Science.gov (United States)

    Young, Ryan M; Yandell, Margaret A; Niemeyer, Markus; Neumark, Daniel M

    2010-10-21

    Anionic tetrahydrofuran clusters (THF)(n) (-) (1≤n≤100) are studied with photoelectron imaging as gas-phase precursors for electrons solvated in THF. Photoelectron spectra of clusters up to n=5 show two peaks, one of which is attributed to a solvated open chain radical anion and the other to the closed THF ring. At n=6, the spectra change shape abruptly, which become more characteristic of (THF)(n) (-) clusters containing solvated electrons. From n=6-100, the vertical detachment energies (VDEs) of these solvated electron clusters increase from 1.96 to 2.71 eV, scaling linearly with n(-1/3). For fully deuterated (THF-d8)(n) (-) clusters, the apparent transition to a solvated electron cluster is delayed to n=11. Extrapolation of the VDEs to infinite cluster size yields a value of 3.10 eV for the bulk photoelectric threshold. The relatively large VDEs at onset and small stabilization with increasing cluster size compared to other solvated electron clusters may reflect the tendency of the bulk solvent to form preexisting voids that can readily solvate a free electron.

  16. Reactor Neutrino Spectra

    OpenAIRE

    Hayes, A. C.; Vogel, Petr

    2016-01-01

    We present a review of the antineutrino spectra emitted from reactors. Knowledge of these spectra and their associated uncertainties is crucial for neutrino oscillation studies. The spectra used to date have been determined either by converting measured electron spectra to antineutrino spectra or by summing over all of the thousands of transitions that make up the spectra, using modern databases as input. The uncertainties in the subdominant corrections to β-decay plague both methods, and we ...

  17. Zero kinetic energy photoelectron spectroscopy of pyrene.

    Science.gov (United States)

    Zhang, Jie; Han, Fangyuan; Kong, Wei

    2010-10-28

    We report zero kinetic energy photoelectron (ZEKE) spectroscopy of pyrene via resonantly enhanced multiphoton ionization. Our analysis centers on the symmetry of the first electronically excited state (S(1)), its vibrational modes, and the vibration of the ground cationic state (D(0)). From comparisons between the observed vibrational frequencies and those from ab initio calculations at the configuration interaction singles level using the 6-311G (d,p) basis set, and based on other previous experimental and theoretical reports, we confirm the (1)B(2u) symmetry for the S(1) state. This assignment represents a reversal in the energy order of the two closely spaced electronically excited states from our theoretical calculation, and extensive configuration interactions are attributed to this result. Among the observed vibrational levels of the S(1) state, three are results of vibronic coupling due to the nearby second electronically excited state. The ZEKE spectroscopy obtained via the vibronic levels of the S(1) state reveals similar modes for the cation as those of the intermediate state. Although we believe that the ground ionic state can be considered a single electron configuration, the agreement between theoretical and experimental frequencies for the cation is limited. This result is somewhat surprising based on our previous work on cata-condensed polycyclic aromatic hydrocarbons and small substituted aromatic compounds. Although a relatively small molecule, pyrene demonstrates its nonrigidity via several out-of-plane bending modes corresponding to corrugation of the molecular plane. The adiabatic ionization potential of neutral pyrene is determined to be 59 888 ± 7 cm(-1).

  18. Angle-Resolved Spectroscopy of Parametric Fluorescence

    CERN Document Server

    Hsu, Feng-kuo

    2013-01-01

    The parametric fluorescence from a nonlinear crystal forms a conical radiation pattern. We measure the angular and spectral distributions of parametric fluorescence in a beta-barium borate crystal pumped by a 405-nm diode laser employing angle-resolved imaging spectroscopy. The experimental angle-resolved spectra and the generation efficiency of parametric down conversion are compared with a plane-wave theoretical analysis. The parametric fluorescence is used as a broadband light source for the calibration of the instrument spectral response function in the wavelength range from 450 to 1000 nm.

  19. Disk-averaged synthetic spectra of Mars

    Science.gov (United States)

    Tinetti, Giovanna; Meadows, Victoria S.; Crisp, David; Fong, William; Velusamy, Thangasamy; Snively, Heather

    2005-01-01

    The principal goal of the NASA Terrestrial Planet Finder (TPF) and European Space Agency's Darwin mission concepts is to directly detect and characterize extrasolar terrestrial (Earthsized) planets. This first generation of instruments is expected to provide disk-averaged spectra with modest spectral resolution and signal-to-noise. Here we use a spatially and spectrally resolved model of a Mars-like planet to study the detectability of a planet's surface and atmospheric properties from disk-averaged spectra. We explore the detectability as a function of spectral resolution and wavelength range, for both the proposed visible coronograph (TPFC) and mid-infrared interferometer (TPF-I/Darwin) architectures. At the core of our model is a spectrum-resolving (line-by-line) atmospheric/surface radiative transfer model. This model uses observational data as input to generate a database of spatially resolved synthetic spectra for a range of illumination conditions and viewing geometries. The model was validated against spectra recorded by the Mars Global Surveyor-Thermal Emission Spectrometer and the Mariner 9-Infrared Interferometer Spectrometer. Results presented here include disk-averaged synthetic spectra, light curves, and the spectral variability at visible and mid-infrared wavelengths for Mars as a function of viewing angle, illumination, and season. We also considered the differences in the spectral appearance of an increasingly ice-covered Mars, as a function of spectral resolution, signal-to-noise and integration time for both TPF-C and TPFI/ Darwin.

  20. Disk-averaged synthetic spectra of Mars

    Science.gov (United States)

    Tinetti, Giovanna; Meadows, Victoria S.; Crisp, David; Fong, William; Velusamy, Thangasamy; Snively, Heather

    2005-01-01

    The principal goal of the NASA Terrestrial Planet Finder (TPF) and European Space Agency's Darwin mission concepts is to directly detect and characterize extrasolar terrestrial (Earthsized) planets. This first generation of instruments is expected to provide disk-averaged spectra with modest spectral resolution and signal-to-noise. Here we use a spatially and spectrally resolved model of a Mars-like planet to study the detectability of a planet's surface and atmospheric properties from disk-averaged spectra. We explore the detectability as a function of spectral resolution and wavelength range, for both the proposed visible coronograph (TPFC) and mid-infrared interferometer (TPF-I/Darwin) architectures. At the core of our model is a spectrum-resolving (line-by-line) atmospheric/surface radiative transfer model. This model uses observational data as input to generate a database of spatially resolved synthetic spectra for a range of illumination conditions and viewing geometries. The model was validated against spectra recorded by the Mars Global Surveyor-Thermal Emission Spectrometer and the Mariner 9-Infrared Interferometer Spectrometer. Results presented here include disk-averaged synthetic spectra, light curves, and the spectral variability at visible and mid-infrared wavelengths for Mars as a function of viewing angle, illumination, and season. We also considered the differences in the spectral appearance of an increasingly ice-covered Mars, as a function of spectral resolution, signal-to-noise and integration time for both TPF-C and TPFI/ Darwin.

  1. Laser induced threshold photoemission magnetic circular dichroism and its application to photoelectron microscope

    Energy Technology Data Exchange (ETDEWEB)

    Nakagawa, Takeshi, E-mail: nakagawa@ims.ac.jp [Institute for Molecular Science, Myodaiji-cho, Okazaki, 444-8585 (Japan); The Graduate University for Advanced Studies (Sokendai), Myodaiji-cho, Okazaki, 444-8585 (Japan); Yokoyama, Toshihiko, E-mail: yokoyama@ims.ac.jp [Institute for Molecular Science, Myodaiji-cho, Okazaki, 444-8585 (Japan); The Graduate University for Advanced Studies (Sokendai), Myodaiji-cho, Okazaki, 444-8585 (Japan)

    2012-10-15

    Highlights: Black-Right-Pointing-Pointer Threshold photoemission magnetic circular dichroism results are presented. Black-Right-Pointing-Pointer The enhanced MCD contrast is used to observe magnetic domains by PEEM. Black-Right-Pointing-Pointer Magnetization axis, probing depth and angle dependence of MCD are described. Black-Right-Pointing-Pointer Laser based measurements in this method expand the possibility of PEEM. -- Abstract: This work enlightens the threshold photoemission magnetic circular dichroism (MCD) and its adaption on photoemission electron microscopy (PEEM) using lasers. MCD is a simple and efficient way to investigate magnetic properties since it does not need any spin analyzers with low efficiency, and thus the MCD related techniques have developed to observe magnetic domains. Usually, MCD in a total yield measurement in the valence band with weak spin-orbit coupling (SOC) excited by low photon energy (h{nu}{<=} 6 eV) does not compete with the X-ray magnetic circular dichroism (XMCD) with strong SOC. XMCD PEEM observation of magnetic domains has been successfully established while MCD PEEM derived from valence bands has not been. However, using angle and energy resolved photoelectron, valence band MCD provides large asymmetry similar to that by XMCD. Threshold measurement of photoelectron in a total electron yield procedure can take advantage of the measurement of photoelectrons with a limited angle and energy mode. This restriction of the photoelectron makes the threshold MCD technique an efficient way to get magnetic information and gives more than 10% asymmetry for Ni/Cu(0 0 1), which is comparable to that obtained by angle resolved photoemission. Thus the threshold MCD technique is a suitable method to observe magnetic domains by PEEM. For threshold MCD, incident angle dependence and high sensitivity to out-of-plane magnetized films compared with in-plane ones are discussed. Ultrashort pulse lasers make it feasible to measure two photon

  2. Complex Spectra in Fusion Plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Hellermann, M.G. von; Jaspers, R. [FOM-Institute for Plasma Physics Rijnhuizen, Nieuwegein (Netherlands); Bertschinger, G.; Biel, W.; Marchuk, O. [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Plasmaphysik; Giroud, C.; Zastrow, K.D. [UKAEA Culham Laboratory Euratom Association, Abingdon (United Kingdom); Jupen, C. [Univ. of Lund (Sweden). Physics Dept.; O' Mullane, M.; Summers, H.P.; Whiteford, A. [Univ. of Strathclyde, Glasgow (United Kingdom). Applied Physics Dept.

    2005-12-15

    The need for quantitative evaluation of complex line emission spectra as observed in hot fusion plasmas initiated a challenging development of sophisticated interpretation tools based on integrating advanced atomic modelling with detailed treatment of the plasma environment. The successful merging of the two worlds has led to routine diagnostic procedures which have contributed enormously to the understanding of underlying plasma processes and also to a wide acceptance of spectroscopy as a reliable diagnostic method. In this paper three characteristic types of spectra of current and continuing interest are presented. The first is that of medium/heavy species with many ionisation stages revealed in survey VUV and XUV spectra. Such species occur as control gases, as wall materials, as ablated heavy species and possible as layered wall dopants for monitoring erosion. The spectra are complex with line-like and quasi-continuum regions and are amenable to advanced ?pattern recognition' methods. The second type is of few electron, highly ionised systems observed as line-of-sight integrated passive emission spectra in the soft X-ray region. They are analysed successfully in terms of plasma parameters through matching of observation with predicted synthetic spectra. Examples used here include highly resolved helium-like emission spectra of argon, iron and titanium observed on the tokamaks TEXTOR and Tore Supra. The third type, and the emphasis of this work, comprises spectra linked to active beam spectroscopy, that is, charge exchange recombination spectroscopy (CXRS) and beam emission spectroscopy (BES). In this case, a complex spectrum is again composed of a (usually) dominating active spectrum and an underlying passive emission spectrum. Its analysis requires modelling of both active and passive features. Examples used here are from the CXRS diagnostic at JET and TEXTOR. They display characteristic features of the main light impurity ions (C{sup +6}, He{sup +2}, N

  3. Photoelectron diffraction k-space volumes of the c(2x2) Mn/Ni(100) structure

    Energy Technology Data Exchange (ETDEWEB)

    Banerjee, S.; Denlinger, J.; Chen, X. [Univ. of Wisconsin, Milwaukee, WI (United States)] [and others

    1997-04-01

    Traditionally, x-ray photoelectron diffraction (XPD) studies have either been done by scanning the diffraction angle for fixed kinetic energy (ADPD), or scanning the kinetic energy at fixed exit angle (EDPD). Both of these methods collect subsets of the full diffraction pattern, or volume, which is the intensity of photoemission as a function of momentum direction and magnitude. With the high density available at the Spectromicroscopy Facility (BL 7.0) {open_quotes}ultraESCA{close_quotes} station, the authors are able to completely characterize the photoelectron diffraction patterns of surface structures, up to several hundred electron volts kinetic energy. This large diffraction `volume` can then be analyzed in many ways. The k-space volume contains as a subset the energy dependent photoelectron diffraction spectra along all emission angles. It also contains individual, hemispherical, diffraction patterns at specific kinetic energies. Other `cuts` through the data set are also possible, revealing new ways of viewing photoelectron diffraction data, and potentially new information about the surface structure being studied. In this article the authors report a brief summary of a structural study being done on the c(2x2) Mn/Ni(100) surface alloy. This system is interesting for both structural and magnetic reasons. Magnetically, the Mn/Ni(100) surface alloy exhibits parallel coupling of the Mn and Ni moments, which is opposite to the reported coupling for the bulk, disordered, alloy. Structurally, the Mn atoms are believed to lie well above the surface plane.

  4. A transient model to simulate HTPEM fuel cell impedance spectra

    DEFF Research Database (Denmark)

    Vang, Jakob Rabjerg; Andreasen, Søren Juhl; Kær, Søren Knudsen

    2012-01-01

    This paper presents a spatially resolved transient fuel cell model applied to the simulation of high temperature PEM fuel cell impedance spectra. The model is developed using a 2D finite volume method approach. The model is resolved along the channel and across the membrane. The model considers...

  5. Distant ionospheric photoelectron energy peak observations at Venus

    Science.gov (United States)

    Coates, A. J.; Wellbrock, A.; Frahm, R. A.; Winningham, J. D.; Fedorov, A.; Barabash, S.; Lundin, R.

    2015-08-01

    The dayside of the Venus ionosphere at the top of the planet's thick atmosphere is sustained by photoionization. The consequent photoelectrons may be identified by specific peaks in the energy spectrum at 20-30 eV which are mainly due to atomic oxygen photoionization. The ASPERA-4 electron spectrometer has an energy resolution designed to identify the photoelectron production features. Photoelectrons are seen not only in their production region, the sunlit ionosphere, but also at more distant locations on the nightside of the Venus environment. Here, we present a summary of the work to date on observations of photoelectrons at Venus, and their comparison with similar processes at Titan and Mars. We expand further by presenting new examples of the distant photoelectrons measured at Venus in the dark tail and further away from Venus than seen before. The photoelectron and simultaneous ion data are then used to determine the ion escape rate from Venus for one of these intervals. We compare the observed escape rates with other rates measured at Venus, and at other planets, moons and comets. We find that the escape rates are grouped by object type when plotted against body radius.

  6. Espectroscopia de fotoelétrons de limiares de átomos e moléculas Atomic and molecular threshold photoelectron spectroscopy

    Directory of Open Access Journals (Sweden)

    Maria Cristina Andreolli Lopes

    2006-02-01

    Full Text Available A threshold photoelectron spectrometer applied to the study of atomic and molecular threshold photoionization processes is described. The spectrometer has been used in conjunction with a toroidal grating monochromator at the National Synchrotron Radiation Laboratory (LNLS, Brazil. It can be tuned to accept threshold electrons (< 20 meV and work with a power resolution of 716 (~18 meV at 12 eV with a high signal/noise ratio. The performance of this apparatus and some characteristics of the TGM (Toroidal Grating Monochromator beam line of LNLS are described and discussed by means of argon, O2 and N2 threshold photoelectron spectra.

  7. Nanocrystalline tin oxide: Possible origin of its weak ferromagnetism deduced from nuclear magnetic resonance and X-ray photoelectron spectroscopies

    Science.gov (United States)

    Zhang, Feng; Lian, Yadong; Gu, Min; Yu, Ji; Tang, Tong B.; Sun, Jian; Zhang, Weiyi

    2016-09-01

    Nanocrystalline tin oxide was fabricated, with molar ratio O/Sn determined as 1.40, 1.55, 1.79, 1.92 and 1.96 from X-ray photoelectron spectroscopy. They displayed weak ferromagnetism, the sample with O/Sn = 1.55 showing the maximum saturation magnetization reaching almost 8 ×10-3 emu /g at room temperature. 119Sn nuclear magnetic resonance allowed the deduction, based on four resolved resonance peaks, that their Sn ions had four possible coordination numbers, namely 3, 4, 5 and 6. The relative fraction of 4-coordinated cations was the one found to bear positive linear correlation with saturation magnetization of the sample. It is surmised that magnetism in tin oxide results mainly from 4-coordination Sn ions, of valance about +3, as estimated from the binding energies of their 3d photoelectron emission levels.

  8. Microscopic solvation of NaBO2 in water: anion photoelectron spectroscopy and ab initio calculations.

    Science.gov (United States)

    Feng, Yuan; Cheng, Min; Kong, Xiang-Yu; Xu, Hong-Guang; Zheng, Wei-Jun

    2011-09-21

    We investigated the microscopic solvation of NaBO(2) in water by conducting photoelectron spectroscopy and ab initio studies on NaBO(2)(-)(H(2)O)(n) (n = 0-4) clusters. The vertical detachment energy (VDE) of NaBO(2)(-) is estimated to be 1.00 ± 0.08 eV. The photoelectron spectra of NaBO(2)(-)(H(2)O)(1) and NaBO(2)(-)(H(2)O)(2) are similar to that of bare NaBO(2)(-), except that their VDEs shift to higher electron binding energies (EBE). For the spectra of NaBO(2)(-)(H(2)O)(3) and NaBO(2)(-)(H(2)O)(4), a low EBE feature appears dramatically in addition to the features observed in the spectra of NaBO(2)(-)(H(2)O)(0-2). Our study shows that the water molecules mainly interact with the BO(2)(-) unit in NaBO(2)(-)(H(2)O)(1) and NaBO(2)(-)(H(2)O)(2) clusters to form Na-BO(2)(-)(H(2)O)(n) type structures, while in NaBO(2)(-)(H(2)O)(3) and NaBO(2)(-)(H(2)O)(4) clusters, the water molecules can interact strongly with the Na atom, therefore, the Na-BO(2)(-)(H(2)O)(n) and Na(H(2)O)(n)···BO(2)(-) types of structures coexist. That can be seen as an initial step of the transition from a contact ion pair (CIP) structure to a solvent-separated ion pair (SSIP) structure for the dissolution of NaBO(2).

  9. Spectroscopic analysis of time-resolved emission from detonating thin film explosive samples

    Science.gov (United States)

    Kay, Jeffrey J.; Wixom, Ryan R.; Jilek, Brook A.; Knepper, Robert; Tappan, Alexander S.; Damm, David L.

    2017-01-01

    We report a series of time-resolved spectroscopic measurements that aim to characterize the reactions that occur during shock initiation of high explosives. The experiments employ time- and wavelength-resolved emission spectroscopy to analyze light emitted from detonating thin explosive films. This paper presents analysis of optical emission spectra from hexanitrostilbene (HNS) and pentaerythritol tetranitrate (PETN) thin film samples. Both vibrationally resolved and broadband emission features are observed in the spectra and area as electronic transitions of intermediate species.

  10. High-resolution x-ray photoemission spectra of silver

    DEFF Research Database (Denmark)

    Barrie, A.; Christensen, N. E.

    1976-01-01

    An electron spectrometer fitted with an x-ray monochromator for Al Kα1,2 radiation (1486.6 eV) has been used to record high-resolution x-ray photoelectron spectra for the 4d valence band as well as the 3d spin doublet in silver. The core-level spectrum has a line shape that can be described...

  11. Ionospheric photoelectrons: Comparing Venus, Earth, Mars and Titan

    Science.gov (United States)

    Coates, A. J.; Tsang, S. M. E.; Wellbrock, A.; Frahm, R. A.; Winningham, J. D.; Barabash, S.; Lundin, R.; Young, D. T.; Crary, F. J.

    2011-08-01

    The sunlit portion of planetary ionospheres is sustained by photoionization. This was first confirmed using measurements and modelling at Earth, but recently the Mars Express, Venus Express and Cassini-Huygens missions have revealed the importance of this process at Mars, Venus and Titan, respectively. The primary neutral atmospheric constituents involved (O and CO 2 in the case of Venus and Mars, O and N 2 in the case of Earth and N 2 in the case of Titan) are ionized at each object by EUV solar photons. This process produces photoelectrons with particular spectral characteristics. The electron spectrometers on Venus Express and Mars Express (part of ASPERA-3 and 4, respectively) were designed with excellent energy resolution (Δ E/ E=8%) specifically in order to examine the photoelectron spectrum. In addition, the Cassini CAPS electron spectrometer at Saturn also has adequate resolution (Δ E/ E=16.7%) to study this population at Titan. At Earth, photoelectrons are well established by in situ measurements, and are even seen in the magnetosphere at up to 7 RE. At Mars, photoelectrons are seen in situ in the ionosphere, but also in the tail at distances out to the Mars Express apoapsis (˜3 RM). At both Venus and Titan, photoelectrons are seen in situ in the ionosphere and in the tail (at up to 1.45 RV and 6.8 RT, respectively). Here, we compare photoelectron measurements at Earth, Venus, Mars and Titan, and in particular show examples of their observation at remote locations from their production point in the dayside ionosphere. This process is found to be common between magnetized and unmagnetized objects. We discuss the role of photoelectrons as tracers of the magnetic connection to the dayside ionosphere, and their possible role in enhancing ion escape.

  12. Photoelectron spectroscopy and density functional study of Co(n)C2(-) (n = 1-5) clusters.

    Science.gov (United States)

    Yuan, Jin-Yun; Xu, Hong-Guang; Zheng, Wei-Jun

    2014-03-21

    ConC2(-) (n = 1-5) cluster anions were investigated using anion photoelectron spectroscopy. The adiabatic detachment energies (ADEs) and the vertical detachment energies (VDEs) of the ConC2(-) (n = 1-5) cluster anions were determined from their photoelectron spectra. Density functional calculations were performed for the ConC2 (n = 1-5) cluster anions and neutrals. Our studies show that the structures of ConC2(-) (n = 1-5) can be described as attaching C2 to the top sites, bridge sites, or hollow sites of the Con clusters. The C2 retains an integral structure unit in the ConC2 (n = 1-5) cluster anions and neutrals, rather than being separated by the Con clusters. The C2 unit in the ConC2 (n = 1-5) cluster anions and neutrals has the characteristics of a double-bond.

  13. Negative ion photoelectron spectroscopy of 2,2'-bithiophene cluster anions, (2T)n- (n = 1 100)

    Science.gov (United States)

    Mitsui, M.; Matsumoto, Y.; Ando, N.; Nakajima, A.

    2005-07-01

    Cluster anions of 2,2'-bithiophene, (2T){n}-, were produced up to n ˜ 500 in the gas-phase. The energetics of the excess electron in the (2T){n}- clusters with n =1{-}100 were explored by negative ion photoelectron spectroscopy. When the vertical detachment energies (VDEs) obtained from the photoelectron spectra were analyzed by a plot against n-1/3, it has been revealed that the excess electron trapping level thus extrapolated is located at ˜ 0.8 eV below the conduction band minimum (i.e. LUMO) of the 2T thin film. The large slope of the VDEs vs. n-1/3 plot suggests that the neutral 2T molecules surrounding the anion core take non-planar twisted conformations with permanent dipole moments, resulting in the exceedingly deep trapping of the excess electron in the 2T cluster anions.

  14. Disk-averaged synthetic spectra of Mars

    CERN Document Server

    Tinetti, G; Fong, W; Meadows, V S; Snively, H; Velusamy, T; Crisp, David; Fong, William; Meadows, Victoria S.; Snively, Heather; Tinetti, Giovanna; Velusamy, Thangasamy

    2004-01-01

    The principal goal of the NASA Terrestrial Planet Finder (TPF) and ESA Darwin mission concepts is to directly detect and characterize extrasolar terrestrial (Earth-sized) planets. This first generation of instruments is expected to provide disk-averaged spectra with modest spectral resolution and signal-to-noise. Here we use a spatially and spectrally resolved model of the planet Mars to study the detectability of a planet's surface and atmospheric properties from disk-averaged spectra as a function of spectral resolution and wavelength range, for both the proposed visible coronograph (TPF-C) and mid-infrared interferometer (TPF-I/Darwin) architectures. At the core of our model is a spectrum-resolving (line-by-line) atmospheric/surface radiative transfer model which uses observational data as input to generate a database of spatially-resolved synthetic spectra for a range of illumination conditions (phase angles) and viewing geometries. Results presented here include disk averaged synthetic spectra, light-cur...

  15. A Study on the Structure and Photodetachment Dynamics of Copper Based Molecular Anions Using Photoelectron Spectroscopy

    Science.gov (United States)

    Holtgrewe, Nicholas Stephen

    This dissertation represents a study of the effects of electron molecule interactions in the detachment and dissociation dynamics of copper based molecular anions. Results are presented on the photodetachment of small copper oxide CuOn-- (n = 1, 2) and copper fluoride CuFn-- (n = 1, 2) molecular anions. Effects of different resonances are explored using the photoelectron angular distributions (PADs) and the relative intensity variations in vibrational channel cross sections. The specific resonances studied include dipole bound resonances, in which the electric dipole moment of the neutral molecule captures the outgoing electron, and electronic Feshbach resonances, in which the anion undergoes absorption to an excited anion state (lying energetically above the neutral) followed by relaxation via autodetachment into the electronic continuum. In addition to electron scattering resonances, the effects of dissociation dynamics on linear CuO2-- are studied, wherein the linear anion isomer was found to dissociate to Cu-- fragments. This dissociation process is interpreted with experimental data acquired from nanosecond photoelectron images and a femtosecond time resolved study.

  16. Variable Mixed Orbital Character in the Photoelectron Angular Distribution of NO_{2}

    Science.gov (United States)

    Laws, Benjamin A.; Cavanagh, Steven J.; Lewis, Brenton R.; Gibson, Stephen T.

    2017-06-01

    NO_{2} a key component of photochemical smog and an important species in the Earth's atmosphere, is an example of a molecule which exhibits significant mixed orbital character in the HOMO. In photoelectron experiments the geometric properties of the parent anion orbital are reflected in the photoelectron angular distribution (PAD), an area of research that has benefited largely from the ability of velocity-map imaging (VMI) to simultaneously record both the energetic and angular information, with 100% collection efficiency. Photoelectron spectra of NO_{2}^{-}, taken over a range of wavelengths (355nm-520nm) with the ANU's VMI spectrometer, reveal an anomalous jump in the anisotropy parameter near threshold. Consequently, the orbital behavior of NO_{2}^{-} appears to be quite different near threshold compared to detachment at higher photon energies. This surprising effect is due to the Wigner Threshold law, which causes p orbital character to dominate the photodetachment cross-section near threshold, before the mixed s/d orbital character becomes significant at higher electron kinetic energies. By extending recent work on binary character models to form a more general expression, the variable mixed orbital character of NO_{2}^{-} is able to be described. This study provides the first multi-wavelength NO_{2} anisotropy data, which is shown to be in decent agreement with much earlier zero-core model predictions of the anisotropy parameter. K. J. Reed, A. H. Zimmerman, H. C. Andersen, and J. I. Brauman, J. Chem. Phys. 64, 1368, (1976). doi:10.1063/1.432404 D. Khuseynov, C. C. Blackstone, L. M. Culberson, and A. Sanov, J. Chem. Phys. 141, 124312, (2014). doi:10.1063/1.4896241 W. B. Clodius, R. M. Stehman, and S. B. Woo, Phys. Rev. A. 28, 760, (1983). doi:10.1103/PhysRevA.28.760 Research supported by the Australian Research Council Discovery Project Grant DP160102585

  17. Electronic structure and thermal decomposition of 5-aminotetrazole studied by UV photoelectron spectroscopy and theoretical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, Rui M., E-mail: ruipinto@fct.unl.pt [CFA, Centro de Fisica Atomica, Departamento de Fisica, Faculdade de Ciencias e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Dias, Antonio A.; Costa, Maria L. [CFA, Centro de Fisica Atomica, Departamento de Fisica, Faculdade de Ciencias e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)

    2011-03-18

    Graphical abstract: Gas-phase UV photoelectron spectrum of the thermal decomposition of 5-aminotetrazole (5ATZ), obtained at 245 {sup o}C, and mechanism underlying the thermal dissociation of 2H-5ATZ. Research highlights: {yields} Electronic structure of 5ATZ studied by photoelectron spectroscopy. {yields} Gas-phase 5-ATZ exists mainly as the 2H-tautomer. {yields} Thermal decomposition of 5ATZ gives N{sub 2}, NH{sub 2}CN, HN{sub 3} and HCN, at 245 {sup o}C. {yields} HCN can be originated from a carbene intermediate. - Abstract: The electronic properties and thermal decomposition of 5-aminotetrazole (5ATZ) are investigated using UV photoelectron spectroscopy (UVPES) and theoretical calculations. Simulated spectra of both 1H- and 2H-5ATZ, based on electron propagator methods, are produced in order to study the relative gas-phase tautomer population. The thermal decomposition results are rationalized in terms of intrinsic reaction coordinate (IRC) calculations. 5ATZ yields a HOMO ionization energy of 9.44 {+-} 0.04 eV and the gas-phase 5ATZ assumes mainly the 2H-form. The thermal decomposition of 5ATZ leads to the formation of N{sub 2}, HN{sub 3} and NH{sub 2}CN as the primary products, and HCN from the decomposition of a intermediate CH{sub 3}N{sub 3} compound. The reaction barriers for the formation of HN{sub 3} and N{sub 2} from 2H-5ATZ are predicted to be {approx}228 and {approx}150 kJ/mol, at the G2(MP2) level, respectively. The formation of HCN and HNNH from the thermal decomposition of a CH{sub 3}N{sub 3} carbene intermediate is also investigated.

  18. Tracking ultrafast relaxation dynamics of furan by femtosecond photoelectron imaging

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yuzhu, E-mail: yuzhu.liu@gmail.com [School of Physics and Optoelectronic Engineering, Nanjing University of Information Science and Technology, Nanjing 210044 (China); Knopp, Gregor [Paul Scherrer Institute, Villigen 5232 (Switzerland); Qin, Chaochao [Department of Physics, Henan Normal University, Xinxiang 453007 (China); Gerber, Thomas [Paul Scherrer Institute, Villigen 5232 (Switzerland)

    2015-01-13

    Graphical abstract: - Highlights: • Relaxation dynamics of furan are tracked by femtosecond photoelectron imaging. • The mechanism for ultrafast formation of α-carbene and β-carbene is proposed. • Ultrafast internal conversion from S{sub 2} to S{sub 1} is observed. • The transient characteristics of the fragment ions are obtained. • Single-color multi-photon ionization dynamics at 800 nm are also studied. - Abstract: Ultrafast internal conversion dynamics of furan has been studied by femtosecond photoelectron imaging (PEI) coupled with photofragmentation (PF) spectroscopy. Photoelectron imaging of single-color multi-photon ionization and two-color pump–probe ionization are obtained and analyzed. Photoelectron bands are assigned to the related states. The time evolution of the photoelectron signal by pump–probe ionization can be well described by a biexponential decay: two rapid relaxation pathways with time constants of ∼15 fs and 85 (±11) fs. The rapid relaxation is ascribed to the ultrafast internal conversion (IC) from the S{sub 2} state to the vibrationally hot S{sub 1} state. The second relaxation process is attributed to the redistributions and depopulation of secondarily populated high vibronic S{sub 1} state and the formation of α-carbene and β-carbene by H immigration. Additionally, the transient characteristics of the fragment ions are also measured and discussed as a complementary understanding.

  19. Insights from angle-resolved photoemission spectroscopy on the metallic states of YbB6(001): E(k) dispersion, temporal changes, and spatial variation

    NARCIS (Netherlands)

    Frantzeskakis, E.; de Jong, N.; Zhang, J.X.; Zhang, X.; Li, Z.; Liang, C.L.; Wang, Y.; Varykhalov, A.; Huang, Y.K.; Golden, M.S.

    2014-01-01

    We report high-resolution angle-resolved photoelectron spectroscopy (ARPES) results on the (001) cleavage surface of YbB6, a rare-earth compound that has been recently predicted to host surface electronic states with topological character. We observe two types of well-resolved metallic states, whose

  20. Atomic and Molecular Photoelectron and Auger Electron SpectroscopyStudies Using Synchrotron Radiation

    Energy Technology Data Exchange (ETDEWEB)

    Southworth, Stephen H.

    1982-01-01

    Electron spectroscopy, combined with synchrotron radiation, was used to measure the angular distributions of photoelectrons and Auger electrons from atoms and molecules as functions of photon energy. The branching ratios and partial cross sections were a 130 measured in certain cases. By comparison with theoretical calculations, the experimental results are interpreted in terms of the characteristic electronic structure and ionization dynamics of the atomic or molecular sample. The time structure of the synchrotron radiation source was used to record time-of-flight (TOF) spectra o f the ejected electrons. The ''a double-angle-TOF'' method for the measurement of photoelectron angular distributions is discussed. This technique offers the advantages of increased electron collect ion efficiency and the elimination of certain systematic errors. Several results were obtained for Xe using photon energies in the range hv {approx_equal} 60-190 eV, where excitation and ionization of the inner-subshell 4d electrons dominates. The 4d asymmetry parameter {beta} exhibits strong oscillations with energy, in agreement with several theoretical calculations. As predicted, the 5p asymmetry parameter was observed to deviate strongly from that calculated using the independent-electron model, due to intershell correlation with the 4d electrons.

  1. X-Ray photoelectron spectroscopic investigation of phenosafranine adsorbed onto micro and mesoporous materials

    Indian Academy of Sciences (India)

    S Easwaramoorthi; K Ananthanarayanan; B Sreedhar; P Natarajan

    2009-09-01

    The phenosafranine adsorbed onto the micro and mesoporous materials prepared by ion exchange method and interaction of the dye with host materials were studied by X-ray photoelectron spectroscopy to elucidate the influence of the host matrix on the binding energy of N 1s orbital. Core level N 1s X-ray photoelectron spectroscopy reveals the interaction between the dye and the solid surface through the hydrogen bonding between the hydrogen atoms of primary amino groups in dye molecule and the oxygen atom of surface hydroxyl groups. The strength of the hydrogen bonding depends on the nature of the solid surface. In the dye adsorbed onto the micro and mesoporous materials the interaction between adsorbed phenosafranine and the surfaces of the porous materials are found to modify the optical spectra and the excited state dynamics of the confined phenosafranine molecules. The change in photophysical properties of phenosafranine adsorbed on to the host materials on dehydration at elevated temperatures is attributed to the modification of host surface during dehydration process.

  2. Conformation-Selective Resonant Photoelectron Spectroscopy via Dipole-Bound States of Cold Anions.

    Science.gov (United States)

    Huang, Dao-Ling; Liu, Hong-Tao; Ning, Chuan-Gang; Wang, Lai-Sheng

    2015-06-18

    Molecular conformation is important in chemistry and biochemistry. Conformers connected by low energy barriers can only be observed at low temperatures and are difficult to be separated. Here we report a new method to obtain conformation-selective spectroscopic information about dipolar molecular radicals via dipole-bound excited states of the corresponding anions cooled in a cryogenic ion trap. We observed two conformers of cold 3-hydroxyphenoxide anions [m-HO(C6H4)O(-)] in high-resolution photoelectron spectroscopy and measured different electron affinities, 18,850(8) and 18,917(5) cm(-1), for the syn and anti 3-hydroxyphenoxy radicals, respectively. We also observed dipole-bound excited states for m-HO(C6H4)O(-) with different binding energies for the two conformers due to the different dipole moments of the corresponding 3-hydroxyphenoxy radicals. Excitations to selected vibrational levels of the dipole-bound states result in conformation-selective photoelectron spectra. This method should be applicable to conformation-selective spectroscopic studies of any anions with dipolar neutral cores.

  3. X-ray photoelectron spectroscopy of graphitic carbon nanomaterials doped with heteroatoms

    Directory of Open Access Journals (Sweden)

    Toma Susi

    2015-01-01

    Full Text Available X-ray photoelectron spectroscopy (XPS is one of the best tools for studying the chemical modification of surfaces, and in particular the distribution and bonding of heteroatom dopants in carbon nanomaterials such as graphene and carbon nanotubes. Although these materials have superb intrinsic properties, these often need to be modified in a controlled way for specific applications. Towards this aim, the most studied dopants are neighbors to carbon in the periodic table, nitrogen and boron, with phosphorus starting to emerge as an interesting new alternative. Hundreds of studies have used XPS for analyzing the concentration and bonding of dopants in various materials. Although the majority of works has concentrated on nitrogen, important work is still ongoing to identify its precise atomic bonding configurations. In general, care should be taken in the preparation of a suitable sample, consideration of the intrinsic photoemission response of the material in question, and the appropriate spectral analysis. If this is not the case, incorrect conclusions can easily be drawn, especially in the assignment of measured binding energies into specific atomic configurations. Starting from the characteristics of pristine materials, this review provides a practical guide for interpreting X-ray photoelectron spectra of doped graphitic carbon nanomaterials, and a reference for their binding energies that are vital for compositional analysis via XPS.

  4. Electronic structures of melatonin and related compounds studied by photoelectron spectroscopy

    CERN Document Server

    Kubota, M

    2003-01-01

    Melatonin is a hormone structurally regarded as being composed of a 5-methoxyindole group and an N-ethylacetamide group; its various physiological activities have attracted a great deal of attention recently. The gas phase He(I) photoelectron spectra of melatonin (M) and its related compounds including N-acetylserotonin have been studied with the aid of molecular orbital calculations. The first photoelectron spectral band group of compound M is ascribed to ionizations from the two pi orbitals localized on the methoxyindole group. The second band group is quite complicated and is regarded as being composed of several bands. The lower energy part of the second band group is ascribed to the three orbitals relevant to the third highest occupied pi orbital of 5-methoxyindole and the highest occupied pi and the n sub C sub = sub 0 orbitals of N-ethylacetamide. The interactions among the three orbitals have been found to operate on the basis of the molecular orbital calculations; these interactions depend strongly o...

  5. X-ray photoelectron spectroscopy of graphitic carbon nanomaterials doped with heteroatoms.

    Science.gov (United States)

    Susi, Toma; Pichler, Thomas; Ayala, Paola

    2015-01-01

    X-ray photoelectron spectroscopy (XPS) is one of the best tools for studying the chemical modification of surfaces, and in particular the distribution and bonding of heteroatom dopants in carbon nanomaterials such as graphene and carbon nanotubes. Although these materials have superb intrinsic properties, these often need to be modified in a controlled way for specific applications. Towards this aim, the most studied dopants are neighbors to carbon in the periodic table, nitrogen and boron, with phosphorus starting to emerge as an interesting new alternative. Hundreds of studies have used XPS for analyzing the concentration and bonding of dopants in various materials. Although the majority of works has concentrated on nitrogen, important work is still ongoing to identify its precise atomic bonding configurations. In general, care should be taken in the preparation of a suitable sample, consideration of the intrinsic photoemission response of the material in question, and the appropriate spectral analysis. If this is not the case, incorrect conclusions can easily be drawn, especially in the assignment of measured binding energies into specific atomic configurations. Starting from the characteristics of pristine materials, this review provides a practical guide for interpreting X-ray photoelectron spectra of doped graphitic carbon nanomaterials, and a reference for their binding energies that are vital for compositional analysis via XPS.

  6. Electronic structures of melatonin and related compounds studied by photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kubota, Mari. E-mail: marik@hc.cc.keio.ac.jp; Kobayashi, Tsunetoshi

    2003-02-01

    Melatonin is a hormone structurally regarded as being composed of a 5-methoxyindole group and an N-ethylacetamide group; its various physiological activities have attracted a great deal of attention recently. The gas phase He(I) photoelectron spectra of melatonin (M) and its related compounds including N-acetylserotonin have been studied with the aid of molecular orbital calculations. The first photoelectron spectral band group of compound M is ascribed to ionizations from the two {pi} orbitals localized on the methoxyindole group. The second band group is quite complicated and is regarded as being composed of several bands. The lower energy part of the second band group is ascribed to the three orbitals relevant to the third highest occupied {pi} orbital of 5-methoxyindole and the highest occupied {pi} and the n{sub C=0} orbitals of N-ethylacetamide. The interactions among the three orbitals have been found to operate on the basis of the molecular orbital calculations; these interactions depend strongly on the conformations. The high energy end of the second band group is relevant to the {pi} orbital mainly localized on the 5-methoxyindole group and is ascribed to the fourth highest occupied {pi} orbital of 5-methoxyindole.

  7. Examining the structural evolution of bicarbonate–water clusters: insights from photoelectron spectroscopy, basin-hopping structural search, and comparison with available IR spectral studies

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Hui [Chinese Academy of Sciences (CAS), Hefei (China). Lab. of Atmospheric Physico-Chemistry, Anhui Inst. of Optics & Fine Mechanics; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division; Hou, Gao-Lei [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division; Liu, Yi-Rong [Chinese Academy of Sciences (CAS), Hefei (China). Lab. of Atmospheric Physico-Chemistry, Anhui Inst. of Optics & Fine Mechanics; Wang, Xue-Bin [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division; Huang, Wei [Chinese Academy of Sciences (CAS), Hefei (China). Lab. of Atmospheric Physico-Chemistry, Anhui Inst. of Optics & Fine Mechanics; Univ. of Science and Technology of China, Hefei (China). School of Environmental Science & Optoelectronic Technology

    2016-05-31

    Bicarbonate serves a crucial biochemical role in the physiological pH buffering system and also has important atmospheric implications. In the current study, HCO3$-$(H2O)n (n = 0-13) clusters were successfully produced via electrospray ionization of corresponding bulk salt solution, and were characterized by combining negative ion photoelectron spectroscopy and theoretical calculations. The photoelectron spectra reveal that the electron binding energy monotonically increases with the cluster size up to n = 10 and remains largely the same after n > 10. The photo-detaching feature of the solute HCO3$-$itself, which dominates in the small clusters, diminishes with increase of water coverage. Based on the charge distribution and molecular orbital analyses, the universal high electron binding energy tail that dominates in the larger clusters can be attributed to ionization of water. Thus, the transition of ionization from solute to solvent at the size larger than n=10 has been observed. Extensive theoretical structural search based on the Basin-Hopping unbiased method was carried out, and a plethora of low energy isomers have been obtained for each medium and large size. By comparing the simulated photoelectron spectra and calculated electron binding energies with the experiments, as well as by comparing the simulated infrared spectra with previously reported IR spectra, the probable global minima and the structural evolutionary routes are presented. The nature of bicarbonate-water interactions are mainly electrostatic as implied by the electron localization function (ELF) analysis.

  8. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics of H[sub 2]CCO[sup +] and D[sub 2]CCO[sup +

    Energy Technology Data Exchange (ETDEWEB)

    Niu, B.; Bai, Y.; Shirley, D.A. (Department of Chemistry, The University of California at Berkeley, Chemical Science Division, Lawrence Berkeley Laboratory, One Cyclotron Road, Berkeley, California 94720 (United States))

    1993-08-15

    High resolution helium I[alpha] (584 A) photoelectron spectra of H[sub 2]CCO and D[sub 2]CCO are reported. The present spectra of the ground states of ketene cations show more vibrational fine structure than previously reported. The adiabatic ionization energies (AIEs) of the cations' first, second, and fifth excited states are determined unambiguously. The doubletlike fine structures present in the first excited states of ketene cations imply the excitation of a soft'' mode that was not observed before. It was assigned to the [nu][sub 5] mode, which is characterized by the CH[sub 2] (CD[sub 2]) group out-of-plane wagging motion. The complexity of the photoelectron spectra obtained for the ionic first excited states is attributed to the possible dissociation and predissociation of this state. Strong isotope effects are observed in the vibronic (vibrational) couplings in most of the ionic states. Vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra for four of the six ionic states observed. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum of the upper potential energy surfaces (PES). The decay dynamics of the ionic first and fifth excited states of ketene are characterized by ultrafast intramolecular processes such as dissociation and predissociation.

  9. A new photoelectron imager for X-ray astronomical polarimetry

    Energy Technology Data Exchange (ETDEWEB)

    La Monaca, A. [INFN, Laboratori Nazionali di Frascati, Rome (Italy); Costa, E; Soffitta, P.; Di Persio, G.; Manzan, M.; Martino, B.; Patria, G. [CNR, Rome (Italy). Ist. di Astrofisica Spaziale; Cappuccio, G. [CNR, Monterotondo (Italy). Ist. di Strutturistica Chimica]|[INFN, Laboratori Nazionali di Frascati, Rome (Italy); Zema, N. [CNR, Rome (Italy). Ist. di Struttura della Materia

    1998-04-01

    A new photoelectron imager for X-ray astronomical polarimetry (PIAP) has been developed and tested at the Frascati (Rome, Italy) National Laboratories of National Institute of Nuclear Physics (LNF-INFN). A charge-coupled device (CCD) is placed on one of the two conjugate foci of a Cassegrain reflective optics onto which are focused UV photons emitted by means of gas scintillation. This X-ray detector has been built to image the angular distribution of the photoelectron tracks, whose anisotropy measures the X-ray polarization. First tests, performed by using mixtures based on argon gas and benzene at low pressure, show events which are candidate tracks of photoelectrons and Auger electrons produced by a {sup 55}Fe source.

  10. Determination of band profiles in GaN films using hard X-ray photoelectron spectroscopy

    Science.gov (United States)

    Saito, Shinji; Yoshiki, Masahiko; Nunoue, Shinya; Sano, Nobuyuki

    2017-02-01

    We investigated band-profile control by introducing interlayers between a semiconductor and metal contact layers to improve the electrical properties of GaN-based semiconductor devices. We evaluated the electronic structure of the semiconductor surface and the metal/semiconductor interface by hard X-ray photoelectron spectroscopy. We also performed Monte Carlo simulations using the Boltzmann transport equation under the potential profile obtained using the Poisson equation. The band profile in the semiconductor substrate was then examined by comparing the energy spectra from the simulations with those from the experiments. We obtained good agreement between the two results. The present experimental and theoretical methods allow one to determine the band profile near the surface of a semiconductor as well as that in a metal interface. This approach may become a useful tool in the design and/or evaluation of processing conditions.

  11. Crystallographic orientation and induced potential effects in photoelectron emission from metal surfaces by ultrashort laser pulses

    CERN Document Server

    Rubiano, C A Rios; Mitnik, D M; Silkin, V M; Gravielle, M S

    2016-01-01

    The influence of the crystallographic orientation of a typical metal surface, like aluminum, on electron emission spectra produced by grazing incidence of ultrashort laser pulses is investigated by using the band-structure-based-Volkov (BSB-V) approximation. The present version of the BSB-V approach includes not only a realistic description of the surface interaction, accounting for band structure effects, but also effects due to the induced potential that originates from the collective response of valence-band electrons to the external electromagnetic field. The model is applied to evaluate differential electron emission probabilities from the valence band of Al(100) and Al(111). For both crystallographic orientations, the contribution of partially occupied surface electronic states and the influence of the induced potential are separately analyzed as a function of the laser carrier frequency. We found that the induced potential strongly affects photoelectron emission distributions, opening a window to scrut...

  12. X-Ray Laser Induced Photoelectron Spectroscopy for Single-State Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A J; Dunn, J; van Buuren, T; Hunter, J

    2004-07-14

    We demonstrate single-shot x-ray laser induced time-of-flight photoelectron spectroscopy on metal and semiconductor surfaces with picosecond time resolution. The LLNL COMET compact tabletop x-ray laser source provides the necessary high photon flux (>10{sup 12}/pulse), monochromaticity, picosecond pulse duration, and coherence for probing ultrafast changes in the chemical and electronic structure of these materials. Static valence band and shallow core-level photoemission spectra are presented for ambient temperature polycrystalline Cu foils and Ge(100). Surface contamination was removed by UV ozone cleaning prior to analysis. The ultrafast nature of this technique lends itself to true single-state measurements of shocked and heated materials.

  13. Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, D.W.

    1994-08-01

    Free radicals, elemental and van der Waals clusters and transition state species for bimolecular chemical reactions are investigated using anion photoelectron spectroscopy. Several low-lying electronic states of ozone have been identified via photoelectron spectroscopy of O{sub 3}{sup {minus}}. A characterization of these states is important to models for atmospheric ozone reaction kinetics. The fluoroformyloxyl radical, FCO{sub 2}, has been investigated, providing vibrational frequencies and energies for two electronic states. The technique has also been employed to make the first direct observation and characterization of the NNO{sub 2} molecule. Several electronic states are observed for this species which is believed to play a role as a reactive intermediate in the N + NO{sub 2} reaction. The experimental results for all three of these radicals are supplemented by ab initio investigations of their molecular properties. The clusters investigations include studies of elemental carbon clusters (C{sub 2}{sup {minus}} {minus} C{sub 11}{sup {minus}}), and van der Waals clusters (X{sup {minus}}(CO{sub 2}){sub n}, X = I, Br, Cl; n {le} 13 and I{sup {minus}} (N{sub 2}O){sub n=1--11}). Primarily linear clusters are observed for the smaller carbon clusters, while the spectra of the larger clusters contain contribution from cyclic anion photodetachment. Very interesting ion-solvent interactions are observed in the X{sup {minus}}(CO{sub 2})n clusters. The transition state regions for several bimolecular chemical reactions have also been investigated by photodetachment of a negative ion precursor possessing a geometry similar to that of the transition state species. These spectra show features which are assigned to motions of the unstable neutral complex existing between reactants and products.

  14. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics using supersonic molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Niu, B.

    1992-09-01

    High resolution He I[alpha] photoelectron spectroscopy of formaldehyde and ketene and their deuterated compounds, are reported. The combination of a (H2CO) double-pass high-resolution electron-energy analyzer and effective rotational cooling of the sample by supersonic expansion enable the spectroscopy of these molecular cations. The vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra, shedding light on the ultrafast intramolecular dynamics of the molecular cations. This study reveals much more vibrational structural detail in the first electronic excited state of H2CO cations. The first electronic excited state of H2CO cations may have nonplanar equilibrium geometry. Strong isotope effects on vibronic (vibrational) coupling are observed in the second electronic excited state of H2CO. Vibrational autocorrelation functions are calculated for all four observed electronic states of H2CO. The correlation function of the first electronic excited state of H2CO shows a slow decay rate on the femtosecond time scale. The ultrafast decay of the H2CO cations in the third electronic excited state implies that dissociation and intramolecular processes are the main decay pathways. The present spectra of the ground states of ketene cations have more fine structure than before. The AIEs of the first and fifth excited states are determined unambiguously more accurately. The doublet-like fine structures present in the lint excited state of ketene implies the excitation of a soft'' mode not observed before. The vibrational autocorrelation functions are calculated for 4 of the 6 observed electronic states. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum on the upper PES. The decay dynamics of the first and the fifth excited states of ketene are characterized by ultra-fast intramolecular processes like predissociation.

  15. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics using supersonic molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Niu, B.

    1992-09-01

    High resolution He I{alpha} photoelectron spectroscopy of formaldehyde and ketene and their deuterated compounds, are reported. The combination of a (H2CO) double-pass high-resolution electron-energy analyzer and effective rotational cooling of the sample by supersonic expansion enable the spectroscopy of these molecular cations. The vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra, shedding light on the ultrafast intramolecular dynamics of the molecular cations. This study reveals much more vibrational structural detail in the first electronic excited state of H2CO cations. The first electronic excited state of H2CO cations may have nonplanar equilibrium geometry. Strong isotope effects on vibronic (vibrational) coupling are observed in the second electronic excited state of H2CO. Vibrational autocorrelation functions are calculated for all four observed electronic states of H2CO. The correlation function of the first electronic excited state of H2CO shows a slow decay rate on the femtosecond time scale. The ultrafast decay of the H2CO cations in the third electronic excited state implies that dissociation and intramolecular processes are the main decay pathways. The present spectra of the ground states of ketene cations have more fine structure than before. The AIEs of the first and fifth excited states are determined unambiguously more accurately. The doublet-like fine structures present in the lint excited state of ketene implies the excitation of a ``soft`` mode not observed before. The vibrational autocorrelation functions are calculated for 4 of the 6 observed electronic states. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum on the upper PES. The decay dynamics of the first and the fifth excited states of ketene are characterized by ultra-fast intramolecular processes like predissociation.

  16. Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, Don Wesley [Univ. of California, Berkeley, CA (United States)

    1994-08-01

    Free radicals, elemental and van der Waals clusters and transition state species for bimolecular chemical reactions are investigated using anion photoelectron spectroscopy. Several low-lying electronic states of ozone have been identified via photoelectron spectroscopy of O3-. A characterization of these states is important to models for atmospheric ozone reaction kinetics. The fluoroformyloxyl radical, FCO2, has been investigated, providing vibrational frequencies and energies for two electronic states. The technique has also been employed to make the first direct observation and characterization of the NNO2 molecule. Several electronic states are observed for this species which is believed to play a role as a reactive intermediate in the N + NO2 reaction. The experimental results for all three of these radicals are supplemented by ab initio investigations of their molecular properties. The clusters investigations include studies of elemental carbon clusters (C2- - C11-), and van der Waals clusters (X-(CO2)n, X = I, Br, Cl; n {le} 13 and I- (N2O)n=1--11). Primarily linear clusters are observed for the smaller carbon clusters, while the spectra of the larger clusters contain contribution from cyclic anion photodetachment. Very interesting ion-solvent interactions are observed in the X-(CO2)n clusters. The transition state regions for several bimolecular chemical reactions have also been investigated by photodetachment of a negative ion precursor possessing a geometry similar to that of the transition state species. These spectra show features which are assigned to motions of the unstable neutral complex existing between reactants and products.

  17. Reactor Neutrino Spectra

    CERN Document Server

    Hayes, A C

    2016-01-01

    We present a review of the antineutrino spectra emitted from reactors. Knowledge of these and their associated uncertainties are crucial for neutrino oscillation studies. The spectra used to-date have been determined by either conversion of measured electron spectra to antineutrino spectra or by summing over all of the thousands of transitions that makeup the spectra using modern databases as input. The uncertainties in the subdominant corrections to beta-decay plague both methods, and we provide estimates of these uncertainties. Improving on current knowledge of the antineutrino spectra from reactors will require new experiments. Such experiments would also address the so-called reactor neutrino anomaly and the possible origin of the shoulder observed in the antineutrino spectra measured in recent high-statistics reactor neutrino experiments.

  18. Reinvestigation of the EXAFS and xanes spectra of ferrocene and nickelocene in the framework of the multiple scattering theory

    Science.gov (United States)

    Ruiz-Lopez, M. F.; Loos, M.; Goulon, J.; Benfatto, M.; Natoli, C. R.

    1988-04-01

    This paper produces direct evidences that even non-collinear scattering paths can give rise to well-detectable and interpretable signatures in EXAFS spectra. Ferrocene or nickelocene are most favourable examples to study these rather small signals because the shortest intermolecular distances are too large to interfer with them and add no significant contribution to the EXAFS spectrum. For the first time, we have been able to resolve in the R-space individual contributions of specific double and triple scattering paths and also to reproduce their relative amplitudes and phases using full ab initio simulations carried out in the general regime of spherical wave propagation of the ejected/scattered photoelectron. Due to considerable rotational disorder of the cyclopentadienyl (C p) rings, especially at room temperature, all multiple scattering paths involving carbon atoms located on different rings were found to vanish. Full multiple scattering XANES calculations have also been performed on the same systems and were shown to be identical in the staggered (D 5d) or eclipsed (D 5h) conformations of the C p rings. The experimental XANES spectra exhibit a shoulder which is better resolved in the case of ferrocene: our simulations have established the origin of this shoulder and that its resolution was sensitive to small variations of the metal…C bond lengths. The weak pre-edge structure can be explained either by a quadrupolar allowed transition to an antibonding (3d-like) excited state of symmetry 5e 1g if the rings have D 5d group symmetry, or by a disorder-allowed dipolar transition to the corresponding state if the group symmetry is reduced to D 5. In the case of ferrocene, there is also an additional "bump" at ≈ 12 eV past the main absorption peak, which is not reproduced by our single-electron calculations: a possible interpretation which, however, is not yet firmly established, is to assign this feature to a multielectron shakeup satellite.

  19. Angle-Resolved Photoemission of Solvated Electrons in Sodium-Doped Clusters

    CERN Document Server

    West, Adam H C; Luckhaus, David; Saak, Clara-Magdalena; Doppelbauer, Maximilian; Signorell, Ruth

    2015-01-01

    Angle-resolved photoelectron spectroscopy of the unpaired electron in sodium-doped water, methanol, ammonia, and dimethyl ether clusters is presented. The experimental observations and the complementary calculations are consistent with surface electrons for the cluster size range studied. Evidence against internally solvated electrons is provided by the photoelectron angular distribution. The trends in the ionization energies seem mainly determined by the degree of hydrogen bonding in the solvent and the solvation of the ion core. The onset ionization energies of water and methanol clusters do not level off at small cluster sizes, but decrease slightly with increasing cluster size.

  20. Newmark design spectra considering earthquake magnitudes and site categories

    Science.gov (United States)

    Li, Bo; Xie, Wei-Chau; Pandey, M. D.

    2016-09-01

    Newmark design spectra have been implemented in many building codes, especially in building codes for critical structures. Previous studies show that Newmark design spectra exhibit lower amplitudes at high frequencies and larger amplitudes at low frequencies in comparison with spectra developed by statistical methods. To resolve this problem, this study considers three suites of ground motions recorded at three types of sites. Using these ground motions, influences of the shear-wave velocity, earthquake magnitudes, source-to-site distances on the ratios of ground motion parameters are studied, and spectrum amplification factors are statistically calculated. Spectral bounds for combinations of three site categories and two cases of earthquake magnitudes are estimated. Site design spectrum coefficients for the three site categories considering earthquake magnitudes are established. The problems of Newmark design spectra could be resolved by using the site design spectrum coefficients to modify the spectral values of Newmark design spectra in the acceleration sensitive, velocity sensitive, and displacement sensitive regions.

  1. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111

    Directory of Open Access Journals (Sweden)

    A. Schuler

    2017-01-01

    Full Text Available Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3′,5,5′-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111 in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization.

  2. Intermediate state dependence of the photoelectron circular dichroism of fenchone observed via femtosecond resonance-enhanced multi-photon ionization

    Science.gov (United States)

    Kastner, Alexander; Ring, Tom; Krüger, Bastian C.; Park, G. Barratt; Schäfer, Tim; Senftleben, Arne; Baumert, Thomas

    2017-07-01

    The intermediate state dependence of photoelectron circular dichroism (PECD) in resonance-enhanced multi-photon ionization of fenchone in the gas phase is experimentally studied. By scanning the excitation wavelength from 359 to 431 nm, we simultaneously excite up to three electronically distinct resonances. In the PECD experiment performed with a broadband femtosecond laser, their respective contributions to the photoelectron spectrum can be resolved. High-resolution spectroscopy allows us to identify two of the resonances as belonging to the B- and C-bands, which involve excitation to states with 3s and 3p Rydberg character, respectively. We observe a sign change in the PECD signal, depending on which electronic state is used as an intermediate, and are able to identify two differently behaving contributions within the C-band. Scanning the laser wavelength reveals a decrease of PECD magnitude with increasing photoelectron energy for the 3s state. Combining the results of high-resolution spectroscopy and femtosecond experiment, the adiabatic ionization potential of fenchone is determined to be I PaF e n =(8.49 ±0.06 ) eV.

  3. Study on the ultrafast dynamics of o-xylene cation by combined fs-photoelectron imaging-photofragmentation spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yuzhu, E-mail: yuzhu.liu@psi.ch; Radi, Peter; Gerber, Thomas; Knopp, Gregor, E-mail: gregor.knopp@psi.ch

    2014-10-17

    Highlights: • Photoelectron imaging and photofragment spectroscopy are combined. • Photoelectron imaging has been measured to characterize the prepared cation states. • Ultrafast signal decay with time constant of 734 (±61) fs has been observed. - Abstract: Ultrafast dynamics of o-xylene cation has been studied by time resolved fs-photofragmentation (PF) spectroscopy in combination with photoelectron imaging (PEI). In the experiment, multiphoton ionization is used to prepare the o-xylene cation characterized by PEI. The ultrafast dynamics of o-xylene ions are measured by monitoring the time dependent parent-ion depletion and the fragment-ion formation, simultaneously. An ultrafast relaxation time of the parent ion of 734 (±61) fs has been observed. The PEI-PF measurements support the interpretation of this relaxation channel to a combination of internal conversion between the two ionic states (D{sub 0} and D{sub 1}) and intramolecular vibrational-energy redistribution process within the D{sub 0} state.

  4. Application of maximum-entropy spectral estimation to deconvolution of XPS data. [X-ray Photoelectron Spectroscopy

    Science.gov (United States)

    Vasquez, R. P.; Klein, J. D.; Barton, J. J.; Grunthaner, F. J.

    1981-01-01

    A comparison is made between maximum-entropy spectral estimation and traditional methods of deconvolution used in electron spectroscopy. The maximum-entropy method is found to have higher resolution-enhancement capabilities and, if the broadening function is known, can be used with no adjustable parameters with a high degree of reliability. The method and its use in practice are briefly described, and a criterion is given for choosing the optimal order for the prediction filter based on the prediction-error power sequence. The method is demonstrated on a test case and applied to X-ray photoelectron spectra.

  5. Double-Resonance Facilitated Decomposion of Emission Spectra

    Science.gov (United States)

    Kato, Ryota; Ishikawa, Haruki

    2016-06-01

    Emission spectra provide us with rich information about the excited-state processes such as proton-transfer, charge-transfer and so on. In the cases that more than one excited states are involved, emission spectra from different excited states sometimes overlap and a decomposition of the overlapped spectra is desired. One of the methods to perform a decomposition is a time-resolved fluorescence technique. It uses a difference in time evolutions of components involved. However, in the gas-phase, a concentration of the sample is frequently too small to carry out this method. On the other hand, double-resonance technique is a very powerful tool to discriminate or identify a common species in the spectra in the gas-phase. Thus, in the present study, we applied the double-resonance technique to resolve the overlapped emission spectra. When transient IR absorption spectra of the excited state are available, we can label the population of the certain species by the IR excitation with a proper selection of the IR wavenumbers. Thus, we can obtain the emission spectra of labeled species by subtracting the emission spectra with IR labeling from that without IR. In the present study, we chose the charge-transfer emission spectra of cyanophenyldisilane (CPDS) as a test system. One of us reported that two charge-transfer (CT) states are involved in the intramolecular charge-transfer (ICT) process of CPDS-water cluster and recorded the transient IR spectra. As expected, we have succeeded in resolving the CT emission spectra of CPDS-water cluster by the double resonance facilitated decomposion technique. In the present paper, we will report the details of the experimental scheme and the results of the decomposition of the emission spectra. H. Ishikawa, et al., Chem. Phys. Phys. Chem., 9, 117 (2007).

  6. Vibrational state-selective autodetachment photoelectron spectroscopy from dipole-bound states of cold 2-hydroxyphenoxide: o − HO(C{sub 6}H{sub 4})O{sup −}

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Dao-Ling; Wang, Lai-Sheng, E-mail: Lai-Sheng-Wang@brown.edu [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States); Liu, Hong-Tao [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States); Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Ning, Chuan-Gang [Department of Physics, State Key Laboratory of Low-Dimensional Quantum Physics, Tsinghua University, Beijing 100084 (China)

    2015-03-28

    We report a photodetachment and high-resolution photoelectron imaging study of cold 2-hydroxyphenoxide anion, o − HO(C{sub 6}H{sub 4})O{sup −}, cooled in a cryogenic ion trap. Photodetachment spectroscopy revealed a dipole-bound state (DBS) of the anion, 25 ± 5 cm{sup −1}, below the detachment threshold of 18784 ± 5 cm{sup −1} (2.3289 ± 0.0006 eV ), i.e., the electron affinity of the 2-hydroxyphenoxy radical o − HO(C{sub 6}H{sub 4})O{sup ⋅}. Twenty-two vibrational levels of the DBS are observed as resonances in the photodetachment spectrum. By tuning the detachment laser to these DBS vibrational levels, we obtain 22 high-resolution resonant photoelectron spectra, which are highly non-Franck-Condon due to mode-selective autodetachment and the Δv = − 1 propensity rule. Numerous Franck-Condon inactive vibrational modes are observed in the resonant photoelectron spectra, significantly expanding the vibrational information that is available in traditional high-resolution photoelectron spectroscopy. A total of 15 fundamental vibrational frequencies are obtained for the o − HO(C{sub 6}H{sub 4})O{sup ⋅}  radical from both the photodetachment spectrum and the resonant photoelectron spectra, including six symmetry-forbidden out-of-plane modes as a result of resonant enhancement.

  7. Photoelectron spectroscopy of cluster anions of naphthalene and related aromatic hydrocarbons

    Science.gov (United States)

    Ando, Naoto; Mitsui, Masaaki; Nakajima, Atsushi

    2008-04-01

    The electronic structures and structural morphologies of naphthalene cluster anions, (naphthalene)n- (n=3-150), and its related aromatic cluster anions, (acenaphthene)n- (n=4-100) and (azulene)n- (n=1-100), are studied using anion photoelectron spectroscopy. For (naphthalene)n- clusters, two isomers coexist over a wide size range: isomers I and II-1 (28⩽n⩽60) or isomers I and II-2 (n⩾˜60). Their contributions to the photoelectron spectra can be separated using an anion beam hole-burning technique. In contrast, such an isomer coexistence is not observed for (acenaphthene)n- and (azulene)n- clusters, where isomer I is exclusively formed throughout the whole size range. The vertical detachment energies (VDEs) of isomer I (7⩽n⩽100) in all the anionic clusters depend linearly on n-1/3 and their size-dependent energetics are quite similar to one another. On the other hand, the VDEs of isomers II-1 and II-2 produced in (naphthalene)n- clusters with n ⩾˜30 remain constant at 0.84 and 0.99eV, respectively, 0.4-0.6eV lower than those of isomer I. Based upon the ion source condition dependence and the hole-burning photoelectron spectra experiments for each isomer, the energetics and characteristics of isomers I, II-1, and II-2 are discussed: isomer I is an internalized anion state accompanied by a large change in its cluster geometry after electron attachment, while isomers II-1 and II-2 are crystal-like states with little structural relaxation. The nonappearance of isomers II-1 and II-2 for (acenaphthene)n- and (azulene)n- and a comparison with other aromatic cluster anions indicate that a highly anisotropic and symmetric π-conjugated molecular framework, such as found in the linear oligoacenes, is an essential factor for the formation of the crystal-like ordered forms (isomers II-1 and II-2). On the other hand, lowering the molecular symmetry makes their production unfavorable.

  8. Resolved SZE Cluster Count

    Institute of Scientific and Technical Information of China (English)

    Jia-Yu Tang; Zu-Hui Fan

    2003-01-01

    We study the counts of resolved SZE (Sunyaev-Zel'dovich effect) clus-ters expected from an interferometric survey in different cosmological models underdifferent conditions. The self-similar universal gas model and Press-Schechter massfunction are used. We take the observing frequency to be 90 GHz, and consider twodish diameters, 1.2 m and 2.5 m. We calculate the number density of the galaxyclusters dN/(dΩdz) at a high flux limit Slimv = 100mJy and at a relative lowSlimv = 10 mJy. The total numbers of SZE clusters N in two low-Ω0 models arecompared. The results show that the influence of the resolved effect depends notonly on D, but also on Slimv: at a given D, the effect is more significant for a highthan for a low Slim Also, the resolved effect for a flat universe is more impressivethan that for an open universe. For D = 1.2m and Slimv= 10mJy, the resolvedeffect is very weak. Considering the designed interferometers which will be used tosurvey SZE clusters, we find that the resolved effect is insignificant when estimatingthe expected yield of the SZE cluster surveys.

  9. Resolving-Power Quantization

    CERN Document Server

    Neuberger, Herbert

    2016-01-01

    Starting with a general discussion, a program is sketched for a quantization based on dilations. This resolving-power quantization is simplest for scalar field theories. The hope is to find a way to relax the requirement of locality so that the necessity to fine tune mass parameters is eliminated while universality is still preserved.

  10. Operation: Inherent Resolve

    DEFF Research Database (Denmark)

    Cramer-Larsen, Lars

    2015-01-01

    Kapitlet giver læseren indsigt i den internationale koalitions engagement mod IS igennem Operaton Inherent Resolve; herunder koalitionens strategi i forhold til IS strategi, ligesom det belyser kampagnens legalitet og folkeretlige grundlag, ligesom det giver et bud på overvejelser om kampagnens l...

  11. Resolving Disputes in Education.

    Science.gov (United States)

    Seeley, Kenneth R.; Schrant, Nancy E.

    Because of the increasing incidence of disputes in schools, educators need more knowledge about methods of dispute resolution. The adversary system of resolving disputes, on which the U.S. judicial system is founded, assumes that truth is best found through a struggle between two opposing parties. In the adversary system, due process plays a…

  12. Graphene defect formation by extreme ultraviolet generated photoelectrons

    NARCIS (Netherlands)

    Gao, An; Lee, Christopher James; Bijkerk, Frederik

    2014-01-01

    We have studied the effect of photoelectrons on defect formation in graphene during extreme ultraviolet (EUV) irradiation. Assuming the major role of these low energy electrons, we have mimicked the process by using low energy primary electrons. Graphene is irradiated by an electron beam with energy

  13. Photoelectron spectroscopy in heavy fermions: Inconsistencies with the Kondo model

    Energy Technology Data Exchange (ETDEWEB)

    Arko, A.J.; Joyce, J.J.; Blyth, R.R.; Canfield, P.C.; Thompson, J.D.; Bartlett, R.J.; Fisk, Z. [Los Alamos National Lab., NM (United States); Lawrence, J.; Tang, J. [California Univ., Irvine, CA (United States); Riseborough, P. [Polytechnic Univ., Brooklyn, NY (United States)

    1992-09-01

    We have investigated a number of Ce and Yb heavy fermion compounds via photoelectron spectroscopy and compared the results to the predictions of the Imurity Anderson Hamiltonian within the Gunnarson-Schonhammer approach. For the low T{sub K} materials investigated we find little or no correlation with T{sub K}, the only parameter that can be determined independent of photoemission.

  14. Graphene defect formation by extreme ultraviolet generated photoelectrons

    NARCIS (Netherlands)

    Gao, A.; Lee, C. J.; F. Bijkerk,

    2014-01-01

    We have studied the effect of photoelectrons on defect formation in graphene during extreme ultraviolet (EUV) irradiation. Assuming the major role of these low energy electrons, we have mimicked the process by using low energy primary electrons. Graphene is irradiated by an electron beam with energy

  15. Characterization of Ge-nanocrystal films with photoelectron spectroscopy

    CERN Document Server

    Bostedt, C; Willey, T M; Nelson, A J; Franco, N; Möller, T; Terminello, L J

    2003-01-01

    The Ge 3d core-levels of germanium nanocrystal films have been investigated by means of photoelectron spectroscopy. The experiments indicate bulk-like coordinated atoms in the nanocrystals and suggest structured disorder on the nanoparticle surface. The results underline the importance of the surface on the overall electronic structure of this class of nanostructured materials.

  16. A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO-

    Science.gov (United States)

    Roy, Soumendra K.; Jian, Tian; Lopez, Gary V.; Li, Wei-Li; Su, Jing; Bross, David H.; Peterson, Kirk A.; Wang, Lai-Sheng; Li, Jun

    2016-02-01

    The observation of the gaseous UFO- anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO- is linear with an O-U-F structure and a 3H4 spectral term derived from a U 7sσ25fφ15fδ1 electron configuration, whereas the ground state of neutral UFO has a 4H7/2 spectral term with a U 7sσ15fφ15fδ1 electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

  17. A study of the pressure profiles near the first pumping aperture in a high pressure photoelectron spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Kahk, J. Matthias; Villar-Garcia, Ignacio J. [Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Grechy, Lorenza; Bruce, Paul J.K.; Vincent, Peter E. [Department of Aeronautics, Imperial College London, London SW7 2AZ (United Kingdom); Eriksson, Susanna K. [Department of Chemistry-Ångström, Uppsala University, Box 523, 751 20 Uppsala (Sweden); Rensmo, Håkan; Hahlin, Maria [Department of Physics and Astronomy, Uppsala University, Box 516, 751 20 Uppsala (Sweden); Åhlund, John; Edwards, Mårten O.M. [VG Scienta AB, Box 15120, 750 15 Uppsala (Sweden); Payne, David J., E-mail: d.payne@imperial.ac.uk [Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom)

    2015-11-15

    Highlights: • We have examined pressure variations in a high pressure photoelectron spectrometer. • Pressure profiles have been simulated using computational fluid dynamics modelling. • The results are useful for determining the optimal sample position for measurements. - Abstract: In a high-pressure photoelectron spectrometer, the sample is positioned close to a differential pumping aperture, behind which the pressure is several orders of magnitude lower than the pressure in the analysis chamber. To find the optimal sample position, where the path length of the photoelectrons through the high pressure region is minimized as far as possible without compromising knowledge of the actual pressure at the sample surface, an understanding of the pressure variations near the sample and the aperture is required. A computational fluid dynamics study has been carried out to examine the pressure profiles, and the results are compared against experimental spectra whose intensities are analyzed using the Beer–Lambert law. The resultant pressure profiles are broadly similar to the one previously derived from a simplistic molecular flow model, but indicate that as the pressure in the analysis chamber is raised, the region over which the pressure drop occurs becomes progressively narrower.

  18. Ultrafast Molecular Photodissociation Dynamics Studied by Femtosecond Photoelectron-Photoion Coincidence Spectroscopy

    Science.gov (United States)

    Thaler, Bernhard; Heim, Pascal; Ernst, Wolfgang E.; Koch, Markus

    2017-06-01

    To completely characterize photodissociation mechanisms with time-resolved spectroscopy, it is essential to obtain unequivocal experimental information about the fragmentation dynamics induced by the laser pulse. We apply time-resolved photoelectron-photoion coincidence (PEPICO) detection in combination with different excitation schemes to obtain a mechanistic picture of the fragmentation process. For gas phase acetone molecules excited to high lying Rydberg states we are able to disentangle different ionization channels and investigate the fragmentation behavior of each channel separately. In particular, the high differentiability of PEPICO allows to distinguish channels where fragmentation proceeds after ionization from channels with fragmentation in the neutral. We show that excited Rydberg state population undergoes internal conversion due to coupling to valence states, which takes place within (150 ± 30) fs. The corresponding non-adiabatic, ultrafast relaxation dynamics to lower lying states causes conversion of electronic to vibrational energy and is found to play a crucial role in the fragmentation process (see figure 1). By studying the influence of photon energy, pulse duration, chirp and intensity of the laser pulses, we are able to determine the energy-threshold that is required for fragmentation, as well as corresponding fragmentation ratios. Surprisingly, for excitation with pulses possessing a strong negative chirp we observe significantly reduced fragmentation, indicating different internal conversion pathways and the associated intramolecular vibrational redistribution.

  19. Raman and photoelectron spectroscopic investigation of high-purity niobium materials: Oxides, hydrides, and hydrocarbons

    Science.gov (United States)

    Singh, Nageshwar; Deo, M. N.; Nand, Mangla; Jha, S. N.; Roy, S. B.

    2016-09-01

    We present investigations of the presence of oxides, hydrides, and hydrocarbons in high-purity (residual resistivity ratio, ˜300) niobium (Nb) materials used in fabrication of superconducting radio frequency (SRF) cavities for particle accelerators. Raman spectroscopy of Nb materials (as-received from the vendor as well as after surface chemical- and thermal processing) revealed numerous peaks, which evidently show the presence of oxides (550 cm-1), hydrides (1277 and 1385 cm-1: ˜80 K temperature), and groups of hydrocarbons (1096, 2330, 2710, 2830, 2868, and 3080 cm-1). The present work provides direct spectroscopic evidence of hydrides in the electropolished Nb materials typically used in SRF cavities. Raman spectroscopy thus can provide vital information about the near-surface chemical species in niobium materials and will help in identifying the cause for the performance degradation of SRF cavities. Furthermore, photoelectron spectroscopy was performed on the Nb samples to complement the Raman spectroscopy study. This study reveals the presence of C and O in the Nb samples. Core level spectra of Nb (doublet 3d5/2 and 3d3/2) show peaks near 206.6 and 209.4 eV, which can be attributed to the Nb5+ oxidation state. The core level spectra of C 1 s of the samples are dominated by graphitic carbon (binding energy, 284.6 eV), while the spectra of O 1 s are asymmetrically peaked near binding energy of ˜529 eV, and that indicates the presence of metal-oxide Nb2O5. The valence-band spectra of the Nb samples are dominated by a broad peak similar to O 2p states, but after sputtering (for 10 min) a peak appears at ˜1 eV, which is a feature of the elemental Nb atom.

  20. Database for Simulation of Electron Spectra for Surface Analysis (SESSA)Database for Simulation of Electron Spectra for Surface Analysis (SESSA)

    Science.gov (United States)

    SRD 100 Database for Simulation of Electron Spectra for Surface Analysis (SESSA)Database for Simulation of Electron Spectra for Surface Analysis (SESSA) (PC database for purchase)   This database has been designed to facilitate quantitative interpretation of Auger-electron and X-ray photoelectron spectra and to improve the accuracy of quantitation in routine analysis. The database contains all physical data needed to perform quantitative interpretation of an electron spectrum for a thin-film specimen of given composition. A simulation module provides an estimate of peak intensities as well as the energy and angular distributions of the emitted electron flux.