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Sample records for attosecond photoelectron spectroscopy

  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. 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......We study the influence of polarization effects in streaking by combined atto- and femtosecond pulses. The polarization-induced terms alter the streaking spectrum. The conventional streaking spectrum, which maps to the vector potential of the femtosecond pulse, is modified by a contribution...

  3. Attosecond photoelectron spectroscopy of electron transport in solids

    International Nuclear Information System (INIS)

    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

  4. 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

  5. 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.

  6. Attosecond Quantum-Beat Spectroscopy in Helium

    CERN Document Server

    Shivaram, Niranjan; Timmers, Henry; Sandhu, Arvinder

    2015-01-01

    The evolution of electron wavepackets determines the course of many physical and chemical phenomena and attosecond spectroscopy aims to measure and control such dynamics in real-time. Here, we investigate radial electron wavepacket motion in Helium by using an XUV attosecond pulse train to prepare a coherent superposition of excited states and a delayed femtosecond IR pulse to ionize them. Quantum beat signals observed in the high resolution photoelectron spectrogram allow us to follow the field-free evolution of the bound electron wavepacket and determine the time-dependent ionization dynamics of the low-lying 2p state.

  7. Theory of attosecond absorption spectroscopy in krypton

    DEFF Research Database (Denmark)

    Baggesen, Jan Conrad; Lindroth, Eva; Madsen, Lars Bojer

    2012-01-01

    A theory for time-domain attosecond pump–attosecond probe photoabsorption spectroscopy is formulated and related to the atomic response. The theory is illustrated through a study of attosecond absorption spectroscopy in krypton. The atomic parameters entering the formulation such as energies and...... Auger widths, as well as wave functions and dipole coupling matrix elements, are determined by accurate many-body structure calculations. We create a hole in a valence shell by an attosecond pump, couple an inner-shell electron to the hole by an attosecond probe, and then monitor the formation of the...

  8. Attosecond streaking of photoelectron emission from disordered solids

    CERN Document Server

    Okell, W A; Fabris, D; Arrell, C A; Hengster, J; Ibrahimkutty, S; Seiler, A; Barthelmess, M; Stankov, S; Lei, D Y; Sonnefraud, Y; Rahmani, M; Uphues, Th; Maier, S A; Marangos, J P; Tisch, J W G

    2014-01-01

    Attosecond streaking of photoelectrons emitted by extreme ultraviolet light has begun to reveal how electrons behave during their transport within simple crystalline solids. Many sample types within nanoplasmonics, thin-film physics, and semiconductor physics, however, do not have a simple single crystal structure. The electron dynamics which underpin the optical response of plasmonic nanostructures and wide-bandgap semiconductors happen on an attosecond timescale. Measuring these dynamics using attosecond streaking will enable such systems to be specially tailored for applications in areas such as ultrafast opto-electronics. We show that streaking can be extended to this very general type of sample by presenting streaking measurements on an amorphous film of the wide-bandgap semiconductor tungsten trioxide, and on polycrystalline gold, a material that forms the basis of many nanoplasmonic devices. Our measurements reveal the near-field temporal structure at the sample surface, and photoelectron wavepacket te...

  9. Real-Time Probing of Electron Dynamics Using Attosecond Time-Resolved Spectroscopy

    Science.gov (United States)

    Ramasesha, Krupa; Leone, Stephen R.; Neumark, Daniel M.

    2016-05-01

    Attosecond science has paved the way for direct probing of electron dynamics in gases and solids. This review provides an overview of recent attosecond measurements, focusing on the wealth of knowledge obtained by the application of isolated attosecond pulses in studying dynamics in gases and solid-state systems. Attosecond photoelectron and photoion measurements in atoms reveal strong-field tunneling ionization and a delay in the photoemission from different electronic states. These measurements applied to molecules have shed light on ultrafast intramolecular charge migration. Similar approaches are used to understand photoemission processes from core and delocalized electronic states in metal surfaces. Attosecond transient absorption spectroscopy is used to follow the real-time motion of valence electrons and to measure the lifetimes of autoionizing channels in atoms. In solids, it provides the first measurements of bulk electron dynamics, revealing important phenomena such as the timescales governing the switching from an insulator to a metallic state and carrier-carrier interactions.

  10. 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.

  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

    2016-07-01

    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.

  12. Photoelectron photoion molecular beam spectroscopy

    International Nuclear Information System (INIS)

    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

  13. 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)

  14. 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

  15. 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.

  16. Simultaneous observation of forward-backward attosecond photoelectron holography

    CERN Document Server

    Du, Hongchuan; Wang, Huiqiao; Yue, Shengjun; Hu, Bitao

    2015-01-01

    Photoelectron angular momentum distribution of He+ driven by a few-cycle laser is investigated numerically. We simultaneously observe two dominant interference patterns with one shot of lasers by solving the 3D time-dependent Schrodinger equation (TDSE). The analysis of a semiclassical model identi?es these two interference patterns as two kinds of photoelectron holography. The interference pattern with Pz > 0 is a kind of forward rescattering holography, which comes from the interference between direct (reference) and rescattered (signal) forward electrons ionized in the same quarter-cycle. The interference pattern with Pz < 0 is a kind of backward rescattering holography, which comes from the interference between direct electron ionized in the third quarter- cycle and rescattered backward electron ionized in the ?rst quarter-cycle. Moreover, we propose a method to distinguish this backward rescattering holography and intracycle interference patterns of direct electrons. This is an important step for dyna...

  17. Simulated Photoelectron-Based Imaging of Localized Surface Plasmons with Attosecond Resolution

    Science.gov (United States)

    Prell, James; Borja, Lauren; Gandman, Andrey; Whitmore, Desire; Neumark, Daniel; Leone, Stephen

    2013-03-01

    Simulations of proposed photoelectron streaking experiments in the presence of an oscillating plasmon field are presented. The results indicate that localized surface plasmon dephasing can be imaged with attosecond resolution using electron time-of-flight (TOF) or velocity map imaging (VMI) techniques. In the simulation, localized surface plasmons are excited in metal nanoparticles by a few-cycle infrared or visible laser pulse. Using time-delayed single, isolated attosecond x-ray pulses, electrons are photoemitted from the metallic nanoparticles and streaked by both the plasmon and laser electric fields. The effects of these two fields in the streaking spectra and images can be separated so that the temporal evolution of the plasmon electric field can be directly extracted. The plasmon electric field induces a broadening of the photoelectron speed distribution with an envelope directly proportional to that of the plasmon dipole moment. Plasmon-induced oscillation of the angular distribution in VMI is predicted to report the spatial distribution of the plasmon electric field for nanoparticles with high aspect ratios. The simulations indicate that these techniques can be used to map plasmon dynamics with unprecedented temporal resolution.

  18. Attosecond imaging.

    Science.gov (United States)

    Vrakking, Marc J J

    2014-02-21

    The natural timescale for electron dynamics reaches down to the attosecond domain. Following the discovery of attosecond laser pulses, about a decade ago, attosecond science has developed into a vibrant, new research field, where the motion of single or multiple electrons and, in molecules, the coupling of electronic and nuclear motion, can be investigated, on attosecond to few-femtosecond timescales. Attosecond experiments require suitable observables. This review describes how "attosecond imaging", basing itself on kinetic energy and angle-resolved detection of photoelectrons and fragment ions using a velocity map imaging (VMI) spectrometer, has been exploited in a number of pump-probe experiments. The use of a VMI spectrometer in attosecond experiments has allowed the characterization of attosecond pulse trains and isolated attosecond pulses, the elucidation of continuum electron dynamics and wave packet interferometry in atomic photoionization and the observation of electron localization in dissociative molecular photoionization. PMID:24398785

  19. State-of-the-art attosecond metrology

    Energy Technology Data Exchange (ETDEWEB)

    Schultze, M., E-mail: martin.schultze@mpq.mpg.de [Max-Planck-Institut fuer Quantenoptik, Hans-Kopfermann-Str. 1, D-85748 Garching (Germany); Department fuer Physik, Ludwig-Maximilians-Universitaet, Am Coulombwall 1, D-85748 Garching (Germany); Wirth, A.; Grguras, I.; Uiberacker, M.; Uphues, T.; Verhoef, A.J.; Gagnon, J. [Max-Planck-Institut fuer Quantenoptik, Hans-Kopfermann-Str. 1, D-85748 Garching (Germany); Hofstetter, M.; Kleineberg, U. [Department fuer Physik, Ludwig-Maximilians-Universitaet, Am Coulombwall 1, D-85748 Garching (Germany); Goulielmakis, E. [Max-Planck-Institut fuer Quantenoptik, Hans-Kopfermann-Str. 1, D-85748 Garching (Germany); Krausz, F. [Max-Planck-Institut fuer Quantenoptik, Hans-Kopfermann-Str. 1, D-85748 Garching (Germany); Department fuer Physik, Ludwig-Maximilians-Universitaet, Am Coulombwall 1, D-85748 Garching (Germany)

    2011-04-15

    Research highlights: {yields} We present a complete setup for investigations with attosecond temporal resoultion. {yields} Few-cycle visible laser pulses are used to generate xray pulses approaching the atomic unit of time. {yields} Attosecond XUV pulses explore ultrafast electronic dynamics in atoms. - Abstract: Tracking and controlling electron dynamics in the interior of atoms, molecules as well as in solids is at the forefront of modern ultrafast science . Time-resolved studies of these dynamics require attosecond temporal resolution that is provided by an ensemble of techniques consolidated under the term 'attosecond metrology'. This work reports the development and commissioning of what we refer to as next-generation attosecond beamline technology: the AS-1 attosecond beamline at the Max-Planck Institute of Quantum Optics. It consists of a phase-stabilized few-cycle laser system, for the generation of XUV radiation, and modules tailored for the spectral filtering and isolation of attosecond pulses as well as for their temporal characterization. The setup produces the shortest attosecond pulses demonstrated to date and combines them with advanced spectroscopic instrumentation (electron-, ion- and XUV-spectrometers). These pulses serve as temporally confined trigger events (attosecond streaking and tunneling spectroscopy) or probe pulses (attosecond absorption and photoelectron spectroscopy) enabling attosecond chronoscopy to be applied to a broad range of systems belonging to the microcosm.

  20. Two attosecond pulse transient absorption spectroscopy and extraction of the instantaneous AC Stark shift in helium

    Science.gov (United States)

    Bækhøj, Jens E.; Bojer Madsen, Lars

    2016-07-01

    In two attosecond pulse absorption spectroscopy (TAPAS) the use of two attosecond XUV pulses allows the extraction of atomic and molecular quantum mechanical dipole phases from spectroscopic measurements. TAPAS relies on interference between processes that individually only include a single XUV photon, and therefore does not rely on high intensity attosecond pulses. To show the usefulness and limitations of the TAPAS method we investigate its capability of capturing the instantaneous AC Stark shift induced by a midinfrared 3200 nm pulse in the | 1{{s}}2{{p}}> state of helium.

  1. 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.

  2. 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…

  3. Photoelectron spectroscopy of heavy atoms and molecules

    International Nuclear Information System (INIS)

    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

  4. 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.

  5. 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.

  6. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R.

    1999-12-16

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying {sup 2}{Sigma} and {sup 2}{Pi} states of C{sub 2n}H (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 C{sub 2}H and C{sub 4}H. Other radicals studied include NCN and I{sub 3}. 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 I{sub 3} 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.

  7. 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.

  8. 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...

  9. Nonlinear Fourier transformation spectroscopy of small molecules with intense attosecond pulse train

    International Nuclear Information System (INIS)

    We have developed an attosecond nonlinear molecular spectroscopic method called nonlinear Fourier transformation spectroscopy (NFTS) that uses an intense attosecond pulse train (APT) to induce multiphoton ionization processes. In the NFTS method, in addition to characterization of the temporal profile of attosecond pulses, the nonlinear molecular responses are encoded in the interferometric autocorrelation traces depending on the molecular species, their fragment ions and their kinetic energy distributions. The principle and applicability of the NFTS method are described in this paper along with the numerical simulations. The method is applied to diatomic molecules (N2 , D2 and O2) and polyatomic molecules (CO2, CH4 and SF6). Our results highlight the fact that nonlinear spectroscopic information of molecules in the short wavelength region can be obtained through the irradiation of intense APT by taking advantage of the broad spectral bandwidth of attosecond pulses. The development of the nonlinear spectroscopic method in attoseconds is expected to pave the way to investigate the ultrafast intramolecular electron motion such as ultrafast charge migration and electron correlation. (review article)

  10. Reconstruction of an excited-state molecular wave packet with attosecond transient absorption spectroscopy

    Science.gov (United States)

    Cheng, Yan; Chini, Michael; Wang, Xiaowei; González-Castrillo, Alberto; Palacios, Alicia; Argenti, Luca; Martín, Fernando; Chang, Zenghu

    2016-08-01

    Attosecond science promises to allow new forms of quantum control in which a broadband isolated attosecond pulse excites a molecular wave packet consisting of a coherent superposition of multiple excited electronic states. This electronic excitation triggers nuclear motion on the molecular manifold of potential energy surfaces and can result in permanent rearrangement of the constituent atoms. Here, we demonstrate attosecond transient absorption spectroscopy (ATAS) as a viable probe of the electronic and nuclear dynamics initiated in excited states of a neutral molecule by a broadband vacuum ultraviolet pulse. Owing to the high spectral and temporal resolution of ATAS, we are able to reconstruct the time evolution of a vibrational wave packet within the excited B'Σ1u+ electronic state of H2 via the laser-perturbed transient absorption spectrum.

  11. Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy.

    Science.gov (United States)

    Weatherup, Robert S; Eren, Baran; Hao, Yibo; Bluhm, Hendrik; Salmeron, Miquel B

    2016-05-01

    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.

  12. 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.

  13. Study of niobium oxidation by photoelectron spectroscopy

    International Nuclear Information System (INIS)

    The chemical composition of thin oxide layers, grown on clean niobium, in low oxygen pressure, was studied by a surface analysis method: X-ray Photoelectron Spectroscopy. The purpose of this study was to find the best conditions for the building of Nb/Nb oxide/Pb Josephson junctions, and particularly to minimise the interface thickness during the formation of the insulator film (Nb2O5) on the metal (Nb). This interface is essentially formed by the monoxide (NbO) and dioxide (NbO2). Nb 3d XPS core level peak positions and area ratios (obtained by the signal decomposition) of the components of the total peak, were used to determine the presence of the different oxidation states II, IV and V, their relative abundance, oxide thicknesses and their depth distribution. All this information was extracted by a special numerical procedure

  14. 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

  15. Theory of Attosecond Transient Absorption Spectroscopy of Krypton for Overlapping Pump and Probe Pulses

    OpenAIRE

    Pabst, Stefan; Sytcheva, Arina; Moulet, Antoine; Wirth, Adrian; Goulielmakis, Eleftherios; Santra, Robin

    2012-01-01

    We present the first fully ab initio calculations for attosecond transient absorption spectroscopy of atomic krypton with overlapping pump and probe pulses. Within the time-dependent configuration interaction singles (TDCIS) approach, we describe the pump step (strong-field ionization using a near-infrared pulse) as well as the probe step (resonant electron excitation using an extreme- ultraviolet pulse) from first principles. We extent our TDCIS model and account for the spin-orbit splitting...

  16. 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.

  17. Modelling the effect of nuclear motion on the attosecond time-resolved photoelectron spectra of ethylene

    CERN Document Server

    Crawford-Uranga, Alison; Mowbray, Duncan John; Kurth, Stefan; Rubio, Angel

    2014-01-01

    Using time dependent density functional theory (TDDFT) we examine the energy, angular and time-resolved photoelectron spectra (TRPES) of ethylene in a pump-probe setup. To simulate TRPES we expose ethylene to an ultraviolet (UV) femtosecond pump pulse, followed by a time delayed extreme ultraviolet (XUV) probe pulse. Studying the photoemission spectra as a function of this delay provides us direct access to the dynamic evolution of the molecule's electronic levels. Further, by including the nuclei's motion, we provide direct chemical insight into the chemical reactivity of ethylene. These results show how angular and energy resolved TRPES could be used to directly probe electron and nucleus dynamics in molecules.

  18. 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)

  19. Photoelectron spectroscopy and Auger electron spectroscopy of solids and surfaces

    International Nuclear Information System (INIS)

    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 MnF2 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

  20. 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.

  1. Tagging multiphoton ionization events by two-dimensional photoelectron spectroscopy

    OpenAIRE

    de Groot, Mattijs; Broos, Jaap; Buma, Wybren Jan

    2007-01-01

    Two-dimensional photoelectron spectroscopy has been used to supply process-specific labels to multiphoton ionization events. Employing these tags, the authors can construct excitation and photoelectron spectra along predefined excitation routes in the neutral manifold and ionization routes to the ionic manifold from one single two-dimensional photoelectron spectrum. These results offer a novel way to elucidate the vibronic and dynamic properties of excited and ionic states. (c) 2007 American ...

  2. Zero kinetic energy photoelectron spectroscopy of triphenylene

    Energy Technology Data Exchange (ETDEWEB)

    Harthcock, Colin; Zhang, Jie; Kong, Wei, E-mail: wei.kong@oregonstate.edu [Department of Chemistry, Oregon State University, Corvallis, Oregon 97331 (United States)

    2014-06-28

    We report vibrational information of both the first electronically excited state and the ground cationic state of jet-cooled triphenylene via the techniques of resonantly enhanced multiphoton ionization (REMPI) and zero kinetic energy (ZEKE) photoelectron spectroscopy. The first excited electronic state S{sub 1} of the neutral molecule is of A{sub 1}′ symmetry and is therefore electric dipole forbidden in the D{sub 3h} group. Consequently, there are no observable Franck-Condon allowed totally symmetric a{sub 1}′ vibrational bands in the REMPI spectrum. All observed vibrational transitions are due to Herzberg-Teller vibronic coupling to the E′ third electronically excited state S{sub 3}. The assignment of all vibrational bands as e′ symmetry is based on comparisons with calculations using the time dependent density functional theory and spectroscopic simulations. When an electron is eliminated, the molecular frame undergoes Jahn-Teller distortion, lowering the point group to C{sub 2v} and resulting in two nearly degenerate electronic states of A{sub 2} and B{sub 1} symmetry. Here we follow a crude treatment by assuming that all e′ vibrational modes resolve into b{sub 2} and a{sub 1} modes in the C{sub 2v} molecular frame. Some observed ZEKE transitions are tentatively assigned, and the adiabatic ionization threshold is determined to be 63 365 ± 7 cm{sup −1}. The observed ZEKE spectra contain a consistent pattern, with a cluster of transitions centered near the same vibrational level of the cation as that of the intermediate state, roughly consistent with the propensity rule. However, complete assignment of the detailed vibrational structure due to Jahn-Teller coupling requires much more extensive calculations, which will be performed in the future.

  3. Photoelectron spectroscopy as a tool of lignin chemistry

    International Nuclear Information System (INIS)

    Many efforts in systematic elucidation of lignin properties start from the properties of the lignin subunits. In this paper, the authors provide the vertical ionization potentials (IP) of a representative set of lignin model compound. Gas phase photoelectron spectroscopy enables them to determine ionization potentials and makes it possible to deduce the electron structure of molecules within the limitations of Koopman's theorem. They discuss reasons why photoelectron spectroscopy might be a valuable method for the study of lignin properties

  4. Attosecond Lighthouses

    CERN Document Server

    Vincenti, H

    2011-01-01

    Coherent light beams composed of ultrashort pulses are now increasingly used in different fields of Science, from time-resolved spectroscopy to plasma physics. Under the effect of even simple optical components, the spatial properties of these beams can vary over the duration of the light pulse. In this letter, we show how such spatio-temporally coupled electromagnetic fields can be exploited to produce an attosecond lighthouse, i.e. a source emitting a collection of isolated attosecond pulses, propagating in angularly well-separated light beams. This very general effect not only opens the way to a new generation of attosecond light sources, particularly suitable for pump-probe experiments, but also provides a powerful new tool for ultrafast metrology, for instance giving direct access to fluctuations in the phase of the laser field oscillations with respect to the pulse envelop, right at the focus of even the most intense ultrashort laser beams.

  5. 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.

  6. 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.

  7. Monitoring conical intersections in the ring opening of furan by attosecond stimulated X-ray Raman spectroscopy

    Directory of Open Access Journals (Sweden)

    Weijie Hua

    2016-03-01

    Full Text Available Attosecond X-ray pulses are short enough to capture snapshots of molecules undergoing nonadiabatic electron and nuclear dynamics at conical intersections (CoIns. We show that a stimulated Raman probe induced by a combination of an attosecond and a femtosecond pulse has a unique temporal and spectral resolution for probing the nonadiabatic dynamics and detecting the ultrafast (∼4.5 fs passage through a CoIn. This is demonstrated by a multiconfigurational self-consistent-field study of the dynamics and spectroscopy of the furan ring-opening reaction. Trajectories generated by surface hopping simulations were used to predict Attosecond Stimulated X-ray Raman Spectroscopy signals at reactant and product structures as well as representative snapshots along the conical intersection seam. The signals are highly sensitive to the changes in nonadiabatically coupled electronic structure and geometry.

  8. Photoelectron spectroscopy of boron aluminum hydride cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Haopeng; Zhang, Xinxing; Ko, Yeon Jae; Gantefoer, Gerd; Bowen, Kit H., E-mail: kbowen@jhu.edu, E-mail: kiran@mcneese.edu [Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Li, Xiang [Center for Space Science and Technology, University of Maryland–Baltimore County, Baltimore, Maryland 21250 (United States); Kiran, Boggavarapu, E-mail: kbowen@jhu.edu, E-mail: kiran@mcneese.edu [Department of Chemistry and Physics, McNeese State University, Lake Charles, Louisiana 70609 (United States); Kandalam, Anil K. [Department of Physics, West Chester University, West Chester, Pennsylvania 19383 (United States)

    2014-04-28

    Boron aluminum hydride clusters are studied through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations. Boron aluminum hydride cluster anions, B{sub x}Al{sub y}H{sub z}{sup −}, were generated in a pulsed arc cluster ionization source and identified by time-of-flight mass spectrometry. After mass selection, their photoelectron spectra were measured by a magnetic bottle-type electron energy analyzer. The resultant photoelectron spectra as well as calculations on a selected series of stoichiometries reveal significant geometrical changes upon substitution of aluminum atoms by boron atoms.

  9. Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy

    Science.gov (United States)

    Seidel, Robert; Winter, Bernd; Bradforth, Stephen E.

    2016-05-01

    The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

  10. AXSIS: Exploring the frontiers in attosecond X-ray science, imaging and spectroscopy

    Science.gov (United States)

    Kärtner, F. X.; Ahr, F.; Calendron, A.-L.; Çankaya, H.; Carbajo, S.; Chang, G.; Cirmi, G.; Dörner, K.; Dorda, U.; Fallahi, A.; Hartin, A.; Hemmer, M.; Hobbs, R.; Hua, Y.; Huang, W. R.; Letrun, R.; Matlis, N.; Mazalova, V.; Mücke, O. D.; Nanni, E.; Putnam, W.; Ravi, K.; Reichert, F.; Sarrou, I.; Wu, X.; Yahaghi, A.; Ye, H.; Zapata, L.; Zhang, D.; Zhou, C.; Miller, R. J. D.; Berggren, K. K.; Graafsma, H.; Meents, A.; Assmann, R. W.; Chapman, H. N.; Fromme, P.

    2016-09-01

    X-ray crystallography is one of the main methods to determine atomic-resolution 3D images of the whole spectrum of molecules ranging from small inorganic clusters to large protein complexes consisting of hundred-thousands of atoms that constitute the macromolecular machinery of life. Life is not static, and unravelling the structure and dynamics of the most important reactions in chemistry and biology is essential to uncover their mechanism. Many of these reactions, including photosynthesis which drives our biosphere, are light induced and occur on ultrafast timescales. These have been studied with high time resolution primarily by optical spectroscopy, enabled by ultrafast laser technology, but they reduce the vast complexity of the process to a few reaction coordinates. In the AXSIS project at CFEL in Hamburg, funded by the European Research Council, we develop the new method of attosecond serial X-ray crystallography and spectroscopy, to give a full description of ultrafast processes atomically resolved in real space and on the electronic energy landscape, from co-measurement of X-ray and optical spectra, and X-ray diffraction. This technique will revolutionize our understanding of structure and function at the atomic and molecular level and thereby unravel fundamental processes in chemistry and biology like energy conversion processes. For that purpose, we develop a compact, fully coherent, THz-driven attosecond X-ray source based on coherent inverse Compton scattering off a free-electron crystal, to outrun radiation damage effects due to the necessary high X-ray irradiance required to acquire diffraction signals. This highly synergistic project starts from a completely clean slate rather than conforming to the specifications of a large free-electron laser (FEL) user facility, to optimize the entire instrumentation towards fundamental measurements of the mechanism of light absorption and excitation energy transfer. A multidisciplinary team formed by laser

  11. Rotations of molecular photoelectron angular distributions in above threshold ionization of H2+ by intense circularly polarized attosecond UV laser pulses

    International Nuclear Information System (INIS)

    We present molecular photoelectron angular distributions (MPADs) in multi-photon ionization processes by circularly polarized attosecond UV laser pulses. Simulations are performed on the single electron aligned molecular ion H2+ by solving corresponding 3D time-dependent Schrödinger equations. Numerical results of molecular above threshold ionization (MATI) show that rotations of MPADs with respect to the molecular and polarization axes depend on pulse intensities and photoelectron kinetic energies. We attribute the rotation to Γ, the difference between parallel and perpendicular ionization probabilities. It is found that in a resonant ionization process, the rotation angle is also a function of the symmetry of intermediate electronic states. The coherent population transfer between the initial and the resonant electronic states is controlled by pulse intensities. Such dependence of rotations on the pulse intensity is absent in Rydberg resonant ionizations as well as in MATI at large energy photons ℏω > Ip, where ω is angular frequency of photons and Ip is the molecular ionization potential. We describe these processes by a multi-photon perturbation theory model. Effects of molecular alignment and pulse ellipticities on rotations are investigated, confirming the essence of the ionization parameter Γ in rotations of MPADs. (paper)

  12. Flexible attosecond beamline for high harmonic spectroscopy and XUV/near-IR pump probe experiments requiring long acquisition times

    Energy Technology Data Exchange (ETDEWEB)

    Weber, S. J., E-mail: sebastien.weber@cea.fr; Manschwetus, B.; Billon, M.; Bougeard, M.; Breger, P.; Géléoc, M.; Gruson, V.; Lin, N.; Ruchon, T.; Salières, P.; Carré, B. [Commissariat l’Energie Atomique, Laser, Interactions and Dynamics Laboratory (LIDyL), DSM/IRAMIS, CEA-Saclay, 91191 Gif sur Yvette (France); Böttcher, M.; Huetz, A.; Picard, Y. J. [ISMO, UMR 8214, Université Paris-Sud, Batiment 350, Orsay (France)

    2015-03-15

    We describe the versatile features of the attosecond beamline recently installed at CEA-Saclay on the PLFA kHz laser. It combines a fine and very complete set of diagnostics enabling high harmonic spectroscopy (HHS) through the advanced characterization of the amplitude, phase, and polarization of the harmonic emission. It also allows a variety of photo-ionization experiments using magnetic bottle and COLTRIMS (COLd Target Recoil Ion Momentum Microscopy) electron spectrometers that may be used simultaneously, thanks to a two-foci configuration. Using both passive and active stabilization, special care was paid to the long term stability of the system to allow, using both experimental approaches, time resolved studies with attosecond precision, typically over several hours of acquisition times. As an illustration, applications to multi-orbital HHS and electron-ion coincidence time resolved spectroscopy are presented.

  13. Angular distribution and atomic effects in condensed phase photoelectron spectroscopy

    International Nuclear Information System (INIS)

    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 ν less than or equal to 360 eV and laboratory sources, is divided into three parts

  14. Photoelectron spectroscopy beamline on Indus-1 synchrotron radiation source

    OpenAIRE

    Chaudhari, SM; Phase, DM; Wadikar, AD; Ramesh, GS; Hegde, MS; Dasannacharya, BA

    2002-01-01

    We describe here a photoelectron spectroscopy beamline installed on Indus-1 storage ring. Initially we give a brief description of optical and mechanical layout of beam-line. The beamline optics was designed to cover energy range from 10 eV to 200 eV and it consists of a pre-focusing mirror, a toroidal grating monochromator and a post-focusing mirror. We then discuss indigenously developed ultra high vacuum compatible work station to carry out angle integrated photoemission experiments. The b...

  15. 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.

  16. Ultrafast photoelectron spectroscopy of solutions: space-charge effect

    Science.gov (United States)

    Al-Obaidi, R.; Wilke, M.; Borgwardt, M.; Metje, J.; Moguilevski, A.; Engel, N.; Tolksdorf, D.; Raheem, A.; Kampen, T.; Mähl, S.; Kiyan, I. Yu; Aziz, E. F.

    2015-09-01

    The method of time-resolved XUV photoelectron spectroscopy is applied in a pump-probe experiment on a liquid micro-jet. We investigate how the XUV energy spectra of photoelectrons are influenced by the space charge created due to ionization of the liquid medium by the pump laser pulse. XUV light from high-order harmonic generation is used to probe the electron population of the valence shell of iron hexacyanide in water. By exposing the sample to a short UV pump pulse of 266 nm wavelength and ˜55 fs duration, we observe an energy shift of the spectral component associated with XUV ionization from the Fe 3d(t2g) orbital as well as a shift of the water spectrum. Depending on the sequence of the pump and probe pulses, the arising energy shift of photoelectrons acquires a positive or negative value. It exhibits a sharp positive peak at small time delays, which facilitates to determine the temporal overlap between pump and probe pulses. The negative spectral shift is due to positive charge accumulated in the liquid medium during ionization. Its dissipation is found to occur on a (sub)nanosecond time scale and has a biexponential character. A simple mean-field model is provided to interpret the observations. A comparison between the intensity dependencies of the spectral shift and the UV ionization yield shows that the space-charge effect can be significantly reduced when the pump intensity is attenuated below the saturation level of water ionization. For the given experimental conditions, the saturation intensity lies at 6× {10}10 W cm-2.

  17. Photoelectron imaging spectroscopy of niobium mononitride anion NbN(.).

    Science.gov (United States)

    Berkdemir, Cuneyt; Gunaratne, K Don Dasitha; Cheng, Shi-Bo; Castleman, A W

    2016-07-21

    In this gas-phase photoelectron spectroscopy study, we present the electron binding energy spectrum and photoelectron angular distributions of NbN(-) by the velocity-map imaging technique. The electron binding energy of NbN(-) is measured to be 1.42 ± 0.02 eV from the X band maximum which defines the 0-0 transition between ground states of anion and neutral. Theoretical binding energies which are the vertical and adiabatic detachment energies are computed by density functional theory to compare them with experiment. The ground state of NbN(-) is assigned to the (2)Δ3/2 state and then the electronic transitions originating from this state into X(3)ΔΩ (Ω = 1-3), a(1)Δ2, A(3)Σ1 (-), and b(1)Σ0 (+) states of NbN are reported to interpret the spectral features. As a prospective study for catalytic materials, spectral features of NbN(-) are compared with those of isovalent ZrO(-) and Pd(-). PMID:27448881

  18. 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.

  19. 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.

  20. Decoherence in Attosecond Photoionization

    OpenAIRE

    Pabst, Stefan; Greenman, L.; Ho, P; Mazziotti, D.; Santra, Robin

    2011-01-01

    The creation of superpositions of hole states via single-photon ionization using attosecond extreme-ultraviolet pulses is studied with the time-dependent configuration interaction singles (TDCIS) method. Specifically, the degree of coherence between hole states in atomic xenon is investigated. We find that interchannel coupling not only affects the hole populations, it also enhances the entanglement between the photoelectron and the remaining ion, thereby reducing the coherence within the ion...

  1. 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...

  2. Zero Kinetic Energy Photoelectron Spectroscopy of Benzo[h]quinoline.

    Science.gov (United States)

    Harthcock, Colin; Zhang, Jie; Kong, Wei

    2015-12-17

    We report zero kinetic energy (ZEKE) photoelectron spectroscopy of benzo[h]quinoline (BhQ) via resonantly enhanced multiphoton ionization (REMPI) through the first electronically excited state S1. From the simulated REMPI spectra with and without Herzberg-Teller coupling, we conclude that vibronic coupling plays a minor but observable role in the electronic excitation to the S1 state. We further compare the S1 state of BhQ with the first two electronically excited states of phenanthrene, noticing a similarity of the S1 state of BhQ with the second electronically excited state S2 of phenanthrene. In the ZEKE spectra of BhQ, the vibrational frequencies of the cationic state D0 are consistently higher than those of the intermediate neutral state, indicating enhanced bonding upon ionization. The sparse ZEKE spectra, compared with the spectrum of phenanthrene containing rich vibronic activities, further imply that the nitrogen atom has attenuated the structural change between S1 and D0 states. We speculate that the nitrogen atom can withdraw an electron in the S1 state and donate an electron in the D0 state, thereby minimizing the structural change during ionization. The origin of the first electronically excited state is determined to be 29,410 ± 5 cm(-1), and the adiabatic ionization potential is determined to be 65,064 ± 7 cm(-1). PMID:26039927

  3. Photoelectron spectroscopy investigation of the C60/calcium interface

    Energy Technology Data Exchange (ETDEWEB)

    Wetzstein, Holger; Schoell, Achim; Reinert, Friedrich [Experimental Physics VII, Julius-Maximilians-University of Wuerzburg, D-97074 Wuerzburg (Germany); Bunandar, Darius [Department of Physics, University of Texas at Austin, Austin, TX 78712-0264 (United States); Schafferhans, Julia; Deibel, Carsten [Experimental Physics VI, Julius-Maximilians-University of Wuerzburg, D-97074 Wuerzburg (Germany)

    2011-07-01

    Device lifetime is a crucial point for organic solar cells. Therefore it is important to understand the degradation mechanisms as well as their consequence on the performance of these photovoltaic devices. We observed a characteristic S-shape in the I/V-curves of P3HT/PCBM-bulk heterojunction cells with calcium contacts. A tentative origin of this behavior is a reaction of the calcium with oxygen, which leads to alterations in the regime of the anode interface. To shed more light on this issue we investigated the electronic structure of the Ca/C{sub 60} interface, which serves as a model for the PCBM/Ca contact. X-ray (XPS) and ultra-violet photoelectron spectroscopy (UPS) measurements were performed on C{sub 60} layers adsorbed on epitaxially grown Calcium as well as on Ca deposited on C{sub 60}. In both cases, the data clearly show the formation of an interface state due to the charge transfer from the Ca into the C{sub 60}, which is an indication for a chemical reaction. Moreover, we studied the effect of oxygen exposure on the interfacial chemical and electronic structure under conditions comparable to the conditions during device operation.

  4. Probing keto-enol tautomerism using photoelectron spectroscopy.

    Science.gov (United States)

    Capron, Nathalie; Casier, Bastien; Sisourat, Nicolas; Piancastelli, Maria Novella; Simon, Marc; Carniato, Stéphane

    2015-08-14

    We theoretically investigate the mechanism of tautomerism in the gas-phase acetylacetone molecule. The minimum energy path between the enolone and diketo forms has been computed using the Nudged-Elastic Band (NEB) method within the density-functional theory (DFT) using the projector augmented-wave method and generalized gradient approximation in Perdew-Wang (PW91) parametrization. The lowest transition state as well as several intermediate geometries between the two stable tautomers have been identified. The outer-valence ionization spectra for all determined geometries have been computed using the third-order non-Dyson algebraic diagrammatic construction technique. Furthermore, the oxygen core-shell ionization spectra for these geometries have been obtained using DFT and the Becke three-parameter Lee-Yang-Parr (B3LYP) functional. It is shown that all spectra depend strongly on the geometries demonstrating the possibility of following the proton-transfer dynamics using photoelectron spectroscopy in pump-probe experiments. PMID:26172609

  5. Insights into electrochemical reactions from ambient pressure photoelectron spectroscopy.

    Science.gov (United States)

    Stoerzinger, Kelsey A; Hong, Wesley T; Crumlin, Ethan J; Bluhm, Hendrik; Shao-Horn, Yang

    2015-11-17

    The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces. X-ray photoelectron spectroscopy (XPS), also known as ESCA (electron spectroscopy for chemical analysis), has been used as a quantitative spectroscopic technique that measures the elemental composition, as well as chemical and electronic state of a material. Building from extensive ex situ characterization of electrochemical systems, initial in situ studies were conducted at or near ultrahigh vacuum (UHV) conditions (≤10(-6) Torr) to probe solid-state electrochemical systems. However, through the integration of differential-pumping stages, XPS can now operate at pressures in the torr range, comprising a technique called ambient pressure XPS (AP-XPS). In this Account, we briefly review the working principles and current status of AP-XPS. We use several recent

  6. 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.

  7. Towards attosecond measurement in molecules and at surfaces

    Science.gov (United States)

    Marangos, Jonathan

    2015-05-01

    1) We will present a number of experimental approaches that are being developed at Imperial College to make attosecond timescale measurements of electronic dynamics in suddenly photoionized molecules and at surfaces. A brief overview will be given of some of the unanswered questions in ultrafast electron and hole dynamics in molecules and solids. These questions include the existence of electronic charge migration in molecules and how this process might couple to nuclear motion even on the few femtosecond timescale. How the timescale of photoemission from a surface may differ from that of an isolated atom, e.g. due to electron transport phenomena associated with the distance from the surface of the emitting atom and the electron dispersion relation, is also an open question. 2) The measurement techniques we are currently developing to answer these questions are HHG spectroscopy, attosecond pump-probe photoelectron/photoion studies, and attosecond pump-probe transient absorption as well as attosecond streaking for measuring surface emission. We will present recent advances in generating two synchronized isolated attosecond pulses at different colours for pump-probe measurements (at 20 eV and 90 eV respectively). Results on generation of isolated attosecond pulses at 300 eV and higher photon energy using a few-cycle 1800 nm OPG source will be presented. The use of these resources for making pump-probe measurements will be discussed. Finally we will present the results of streaking measurement of photoemission wavepackets from two types of surface (WO3 and a evaporated Au film) that show a temporal broadening of ~ 100 as compared to atomic streaks that is consistent with the electron mean free path in these materials. Work supported by ERC and EPSRC.

  8. High Resolution Photoelectron Spectroscopy of Au_2^- and Au_4^- by Photoelectron Imaging

    Science.gov (United States)

    Leon, Iker; Yang, Zheng; Wang, Lai-Sheng

    2013-06-01

    We report high resolution photoelectron spectra of Au_2^- and Au_4^- obtained with a newly-built photoelectron imaging apparatus. Gold anions are produced by laser vaporization and the desired specie is mass selected and focused into the collinear velocity-map imaging (VMI) lens assembly. The design of the imaging lens has allowed us to obtain less than 0.9% energy resolution for high kinetic energy electrons ( > 1eV) while maintaining wavenumber resolution for low kinetic energy electrons. Although gold dimer and tetramer have been studied in the past, we present spectroscopic results under high resolution. For Au_2^-, we report high resolution spectra with an accurate determination of the electron affinity together with a complete vibrational assignment, for both the anion and neutral ground states, while for Au_4^-, we are able to resolve a low frequency mode and obtain accurately the adiabatic detachment energy.

  9. 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....

  10. Photoelectron spectroscopy on doped organic semiconductors and related interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Olthof, Selina Sandra

    2010-06-08

    Using photoelectron spectroscopy, we show measurements of energy level alignment of organic semiconducting layers. The main focus is on the properties and the influence of doped layers. The investigations on the p-doping process in organic semiconductors show typical charge carrier concentrations up to 2.10{sup 20} cm{sup -3}. By a variation of the doping concentration, an over proportional influence on the position of the Fermi energy is observed. Comparing the number of charge carriers with the amount of dopants present in the layer, it is found that only 5% of the dopants undergo a full charge transfer. Furthermore, a detailed investigation of the density of states beyond the HOMO onset reveals that an exponentially decaying density of states reaches further into the band gap than commonly assumed. For an increasing amount of doping, the Fermi energy gets pinned on these states which suggests that a significant amount of charge carriers is present there. The investigation of metal top and bottom contacts aims at understanding the asymmetric current-voltage characteristics found for some symmetrically built device stacks. It can be shown that a reaction between the atoms from the top contact with the molecules of the layer leads to a change in energy level alignment that produces a 1.16 eV lower electron injection barrier from the top. Further detailed investigations on such contacts show that the formation of a silver top contact is dominated by diffusion processes, leading to a broadened interface. However, upon insertion of a thin aluminum interlayer this diffusion can be stopped and an abrupt interface is achieved. Furthermore, in the case of a thick silver top contact, a monolayer of molecules is found to oat on top of the metal layer, almost independent on the metal layer thickness. Finally, several device stacks are investigated, regarding interface dipoles, formation of depletion regions, energy alignment in mixed layers, and the influence of the built

  11. High resolution photoelectron spectroscopy of clusters of Group V elements

    International Nuclear Information System (INIS)

    High resolution HeI (580 angstrom) photoelectron spectra of As2, As4, and P4 were obtained with a newly-built high temperature molecular beam source. Vibrational structure was resolved in the photoelectron spectra of the three cluster species. The Jahn-Teller effect is discussed for the 2E and 2T2 states of P4+ and As4+. As a result of the Jahn-Teller effect, the 2E state splits into two bands, and the 2T2 state splits into three bands, in combination with the spin-orbit effect. It was observed that the ν2 normal vibrational mode was involved in the vibronic interaction of the 2E state, while both the ν2 and ν3 modes were active in the 2T2 state. 26 refs., 5 figs., 3 tabs

  12. High-order multiphoton ionization photoelectron spectroscopy of NO

    International Nuclear Information System (INIS)

    Photoelectron energy and angular distributions of NO following three different high-order multiphoton ionization (MPI) schemes have been measured. The 3+3 resonantly enhanced multiphoton ionization (REMPI) via the A2Σ+ (v=0) level yielded a distribution of electron energies corresponding to all accessible vibrational levels (v+=0--6) of the nascent ion. Angular distributions of electrons corresponding to v+=0 and v+=3 were significantly different. The 3+2 REMPI via the A2Σ+ (v=1) level produced only one low-energy electron peak (v+=1). Nonresonant MPI at 532 nm yielded a distribution of electron energies corresponding to both four- and five-photon ionization. Prominent peaks in the five-photon photoelectron spectrum (PES) suggest contributions from near-resonant states at the three-photon level

  13. Atomic and molecular photoelectron and Auger-electron-spectroscopy studies using synchrotron radiation

    International Nuclear Information System (INIS)

    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 also 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 of the ejected electrons. The double-angle-TOF method for the measurement of photoelectron angular distributions is discussed. This technique offers the advantages of increased electron collection efficiency and the elimination of certain systematic errors. An electron spectroscopy study of inner-shell photoexcitation and ionization of Xe, photoelectron angular distributions from H2 and D2, and photoionization cross sections and photoelectron asymmetries of the valence orbitals of NO are reported

  14. Beam-line systems for pump-probe photoelectron spectroscopy using SR and laser

    CERN Document Server

    Kamada, M; Takahashi, K; Doi, Y I; Fukui, K; Kinoshita, T; Haruyama, Y; Asaka, S; Fujii, Y; Itoh, M

    2001-01-01

    Combined systems for photoelectron spectroscopy using synchrotron radiation (SR) and laser have been constructed at BL5A and BL6A2 in the UVSOR facility, Okazaki. The systems consist of photoelectron spectrometers with high performance, mode-locked lasers, and timing electronic circuits. The laser pulses with repetition frequency of 90 MHz are synchronized with the SR pulses. An upgrade project to install a micro-ESCA at BL6A2, which is now in progress, is also reported.

  15. Development of the web-based NIST X-ray Photoelectron Spectroscopy (XPS) Database

    OpenAIRE

    Angela Y. Lee; Blakeslee, Dorothy M; Powell, Cedric J; Rumble, Jr., John

    2006-01-01

    The first Web-based version of the NIST X-ray Photoelectron Spectroscopy Database (XPSDB) is described. The current database, built from a relational database management system (RDBMS), contains critically evaluated data with over 19,000 line positions, chemical shifts, doublet splittings, and energy separations of photoelectron and Auger-electron lines. It is available free of charge to the public through the Internet at http://srdata.nist.gov/xps/.

  16. Photoelectron Holography

    Science.gov (United States)

    Huismans, Ymkje

    2011-05-01

    New techniques using High Harmonic Generation (HHG) or attosecond pulses have proven to be successful in following the ultrafast motion of electrons and holes inside a molecule,. We introduce a complementary technique; photoelectron holography. This uses the phase and amplitude of the rescattered electrons to encode the structure and dynamics of the studied atom or molecule. Since photoelectron holography benefits from longer wavelengths, i.e. small photon energies, it is very suitable for systems with a small ionization potential. To demonstrate photoelectron holography, both measurements and calculations on atomic Xenon will be shown. Metastable Xenon was ionized with 7 μm light from the FELICE-free electron laser. The three dimensional momentum distribution of the photoelectrons was recorded by a Velocity Map Imaging (VMI)-spectrometer. In these momentum maps interference structures are observed that can be identified as an interference of direct and scattered electrons; a hologram of Xenon. Semi-classical calculations have demonstrated that in the hologram dynamical information of the electron and the atom is stored with a femtosecond to attosecond time resolution. Supervisor: Prof. Dr. M.J.J. Vrakking

  17. Interlayer composition in Mo-Si multilayers using X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Molybdenum-silicon multilayers have been synthesized using electron beam evaporation method. The chemical nature of surfaces and interfaces are probed using a depth profile X-ray photoelectron spectroscopy. X-ray photoelectron spectroscopy results indicate the formation of MoSi2 phase on both the interfaces. The experimental results agree well with predicted results based on solid-state amorphizing reaction, as a result of large heat of mixing. The effective heat of formation model reveals the formation of MoSi2 as the first phase

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

    Science.gov (United States)

    Popova-Gorelova, Daria; Küpper, Jochen; Santra, Robin

    2016-07-01

    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 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 indole molecular cation with coherent electron dynamics.

  19. 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...

  20. FORTRAN program for x ray photoelectron spectroscopy data reformatting

    Science.gov (United States)

    Abel, Phillip B.

    1989-01-01

    A FORTRAN program has been written for use on an IBM PC/XT or AT or compatible microcomputer (personal computer, PC) that converts a column of ASCII-format numbers into a binary-format file suitable for interactive analysis on a Digital Equipment Corporation (DEC) computer running the VGS-5000 Enhanced Data Processing (EDP) software package. The incompatible floating-point number representations of the two computers were compared, and a subroutine was created to correctly store floating-point numbers on the IBM PC, which can be directly read by the DEC computer. Any file transfer protocol having provision for binary data can be used to transmit the resulting file from the PC to the DEC machine. The data file header required by the EDP programs for an x ray photoelectron spectrum is also written to the file. The user is prompted for the relevant experimental parameters, which are then properly coded into the format used internally by all of the VGS-5000 series EDP packages.

  1. Hydrogen bonds in the nucleobase-gold complexes: Photoelectron spectroscopy and density functional calculations

    Science.gov (United States)

    Cao, Guo-Jin; Xu, Hong-Guang; Li, Ren-Zhong; Zheng, Weijun

    2012-01-01

    The nucleobase-gold complexes were studied with anion photoelectron spectroscopy and density functional calculations. The vertical detachment energies of uracil-Au-, thymine-Au-, cytosine-Au-, adenine-Au-, and guanine-Au- were estimated to be 3.37 ± 0.08 eV, 3.40 ± 0.08 eV, 3.23 ± 0.08 eV, 3.28 ± 0.08 eV, and 3.43 ± 0.08 eV, respectively, based on their photoelectron spectra. The combination of photoelectron spectroscopy experiments and density functional calculations reveals the presence of two or more isomers for these nucleobase-gold complexes. The major isomers detected in the experiments probably are formed by Au anion with the canonical tautomers of the nucleobases. The gold anion essentially interacts with the nucleobases through N-H...Au hydrogen bonds.

  2. Structural and electronic characterization of self-assembled molecular nanoarchitectures by X-ray photoelectron spectroscopy.

    Science.gov (United States)

    Gulino, Antonino

    2013-02-01

    Molecular monolayers and similar nanoarchitectures are indicative of the promising future of nanotechnology. Therefore, many scientists recently devoted their efforts to the synthesis, characterization, and properties of mono- and multilayer-based systems. In this context, X-ray photoelectron spectroscopy is an important technique for the in-depth chemical and structural characterization of nanoscopic systems. In fact, it is a surface technique suitable for probing thicknesses of the same order of the photoelectron inelastic mean free paths (a few tens of ångströms) and allows one to immediately obtain qualitative and quantitative data, film thickness, surface coverage, molecule footprint, oxidation states, and presence of functional groups. Nevertheless, other techniques are important in obtaining a complete spectroscopic characterization of the investigated systems. Therefore, in the present review we report on X-ray photoelectron spectroscopy of self-assembled molecular mono- and multilayer materials including some examples on which other characterization techniques produced important results. PMID:23014858

  3. Photoelectron Spectroscopy under Ambient Pressure and Temperature Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Ogletree, D. Frank; Bluhm, Hendrik; Hebenstreit, Eleonore B.; Salmeron, Miquel

    2009-02-27

    We describe the development and applications of novel instrumentation for photoemission spectroscopy of solid or liquid surfaces in the presence of gases under ambient conditions or pressure and temperature. The new instrument overcomes the strong scattering of electrons in gases by the use of an aperture close to the surface followed by a differentially-pumped electrostatic lens system. In addition to the scattering problem, experiments in the presence of condensed water or other liquids require the development of special sample holders to provide localized cooling. We discuss the first two generations of Ambient Pressure PhotoEmission Spectroscopy (APPES) instruments developed at synchrotron light sources (ALS in Berkeley and BESSY in Berlin), with special focus on the Berkeley instruments. Applications to environmental science and catalytic chemical research are illustrated in two examples.

  4. Charge reorganization energy and small polaron binding energy of rubrene thin films by ultraviolet photoelectron spectroscopy.

    Science.gov (United States)

    Duhm, Steffen; Xin, Qian; Hosoumi, Shunsuke; Fukagawa, Hirohiko; Sato, Kazushi; Ueno, Nobuo; Kera, Satoshi

    2012-02-14

    The hole–phonon coupling of a rubrene monolayer on graphite is measured by means of angle resolved ultraviolet photoelectron spectroscopy. Thus, the charge reorganization energy λ and the small polaron binding energy is determined, which allows insight into the nature of charge transport in condensed rubrene. PMID:22403829

  5. X-ray photoelectron spectroscopy for the study of microbial cell surfaces

    NARCIS (Netherlands)

    van der Mei, Henderina C; de Vries, Jacob; Busscher, Hendrik J

    2000-01-01

    X-ray photoelectron spectroscopy (XPS) is well known for the characterisation of material surfaces, but at first glance, is an unexpected technique to study the composition of microbial cell surfaces. Despite the fact that intimate contact between materials and microbial cell surfaces occurs in many

  6. X-ray Photoelectron Spectroscopy Investigation on Electrochemical Degradation of Proton Exchange Membrane Fuel Cell Electrodes

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma; Dhiman, Rajnish; Skou, Eivind Morten

    2015-01-01

    X-ray photoelectron spectroscopy studies were systematically carried out on the electrodes before and after the electrochemical stress tests in an aqueous electrolyte at 20 °C and 70 °C. The electrodes have different ionomer structures (no ionomer, only ionomer, physically mixed ionomer and hot...

  7. 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 of the...

  8. Enzymatic Synthesis of Amylose Brushes Revisited : Details from X-Ray Photoelectron Spectroscopy and Spectroscopic Ellipsometry

    NARCIS (Netherlands)

    Mazzocchetti, Laura; Tsoufis, Theodorus; Rudolf, Petra; Loos, Katja

    2014-01-01

    The successful synthesis of amylose brushes via enzymatic ‘‘grafting from’’ polymerization and the detailed characterization of all synthetic steps by X-ray photoelectron spectroscopy (XPS) and spectroscopic ellipsometry measurements are reported. Au and Si surfaces are amino-functionalized with sel

  9. Accessing molecule-metal and hetero-molecular interfaces with direct and resonant photoelectron spectroscopy

    OpenAIRE

    Sauer, Christoph

    2015-01-01

    This thesis consists of two parts of original experimental work, its evaluation, and in- terpretation. Its final goal is to investigate dynamical charge transfer (CT) at a hetero- molecular interface with resonant photoelectron spectroscopy (RPES). In order to achieve this goal preliminary studies have been necessary. First two hetero-molecular inter- faces that exhibit adequate structural properties as well as an appropriate photoelec- tron spectroscopy (PES) spectrum of the valence regime h...

  10. Ultrafast Internal Conversion of Aromatic Molecules Studied by Photoelectron Spectroscopy using Sub-20 fs Laser Pulses

    Directory of Open Access Journals (Sweden)

    Toshinori Suzuki

    2014-02-01

    Full Text Available This article describes our recent experimental studies on internal conversion via a conical intersection using photoelectron spectroscopy. Ultrafast S2(ππ*–S1(nπ* internal conversion in pyrazine is observed in real time using sub-20 fs deep ultraviolet pulses (264 and 198 nm. While the photoelectron kinetic energy distribution does not exhibit a clear signature of internal conversion, the photoelectron angular anisotropy unambiguously reveals the sudden change of electron configuration upon internal conversion. An explanation is presented as to why these two observables have different sensitivities to internal conversion. The 198 nm probe photon energy is insufficient for covering the entire Franck-Condon envelopes upon photoionization from S2/S1 to D1/D0. A vacuum ultraviolet free electron laser (SCSS producing 161 nm radiation is employed to solve this problem, while its pulse-to-pulse timing jitter limits the time resolution to about 1 ps. The S2–S1 internal conversion is revisited using the sub-20 fs 159 nm pulse created by filamentation four-wave mixing. Conical intersections between D1(π−1 and D0(n−1 and also between the Rydberg state with a D1 ion core and that with a D0 ion core of pyrazine are studied by He(I photoelectron spectroscopy, pulsed field ionization photoelectron spectroscopy and one-color resonance-enhanced multiphoton ionization spectroscopy. Finally, ultrafast S2(ππ*–S1(ππ* internal conversion in benzene and toluene are compared with pyrazine.

  11. Observation of Strong Resonant Behavior in the Inverse Photoelectron Spectroscopy of Ce Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Tobin, J G; Yu, S W; Chung, B W; Waddill, G D; Damian, E; Duda, L; Nordgren, J

    2009-12-15

    X-ray Emission Spectroscopy (XES) and Resonant Inverse Photoelectron Spectroscopy (RIPES) have been used to investigate the photon emission associated with the Ce3d5/2 and Ce3d3/2 thresholds. Strong resonant behavior has been observed in the RIPES of Ce Oxide near the 5/2 and 3/2 edges. Inverse Photoelectron Spectroscopy (IPES) and its high energy variant, Bremstrahlung Isochromat Spectroscopy (BIS), are powerful techniques that permit a direct interrogation of the low-lying unoccupied electronic structure of a variety of materials. Despite being handicapped by counting rates that are approximately four orders of magnitude less that the corresponding electron spectroscopies (Photoelectron Spectroscopy, PES, and X-ray Photoelectron Spectroscopy, XPS) both IPES and BIS have a long history of important contributions. Over time, an additional variant of this technique has appeared, where the kinetic energy (KE) of the incoming electron and photon energy (hv) of the emitted electron are roughly the same magnitude as the binding energy of a core level of the material in question. Under these circumstances and in analogy to Resonant Photoelectron Spectroscopy, a cross section resonance can occur, giving rise to Resonant Inverse Photoelectron Spectroscopy or RIPES. Here, we report the observation of RIPES in an f electron system, specifically the at the 3d{sub 5/2} and 3d{sub 3/2} thresholds of Ce Oxide. The resonant behavior of the Ce4f structure at the 3d thresholds has been addressed before, including studies of the utilization of the technique as a probe of electron correlation in a variety of Ce compounds. Interestingly, the first RIPES work on rare earths dates back to 1974, although under conditions which left the state of the surface and near surface regions undefined. Although they did not use the more modern terminology of 'RIPES,' it is clear that RIPES was actually first performed in 1974 by Liefeld, Burr and Chamberlain on both La and Ce based

  12. Experimental evidence for extreme surface sensitivity in Auger-Photoelectron Coincidence Spectroscopy (APECS) from solids

    Energy Technology Data Exchange (ETDEWEB)

    Liscio, A.; Gotter, R.; Ruocco, A.; Iacobucci, S.; Danese, A.G.; Bartynski, R.A.; Stefani, G

    2004-07-01

    Core hole creation and subsequent Auger decay processes are studied with unprecedented discrimination by Auger-Photoelectron Coincidence Spectroscopy (APECS). Early works in this field have already pointed out the intrinsic surface sensitivity of these experiments. However, it was not until recently that a model calculation was developed to quantitatively evaluate it. Here we present the first attempt to experimentally establish an effective target thickness for such experiments. The angular distribution of 3p{sub 3/2} photoelectron with kinetic energy of 160 eV is measured in coincidence with the M{sub 3}VV Auger electron with kinetic energy of 55 eV on a Cu (1 1 1) surface. Coincidence and non-coincidence photoelectron angular distributions display differences that, to large extent, are explained by confining the source of the coincident signal within the first two layers of Cu target, thus establishing an experimental upper limit for the effective target thickness of the APECS experiment.

  13. Decoherence in attosecond photoionization.

    Science.gov (United States)

    Pabst, Stefan; Greenman, Loren; Ho, Phay J; Mazziotti, David A; Santra, Robin

    2011-02-01

    The creation of superpositions of hole states via single-photon ionization using attosecond extreme-ultraviolet pulses is studied with the time-dependent configuration-interaction singles (TDCIS) method. Specifically, the degree of coherence between hole states in atomic xenon is investigated. We find that interchannel coupling not only affects the hole populations, but it also enhances the entanglement between the photoelectron and the remaining ion, thereby reducing the coherence within the ion. As a consequence, even if the spectral bandwidth of the ionizing pulse exceeds the energy splittings among the hole states involved, perfectly coherent hole wave packets cannot be formed. For sufficiently large spectral bandwidth, the coherence can only be increased by increasing the mean photon energy. PMID:21405393

  14. 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

  15. Depth Profiling of the Passive Layer on Stainless Steel using Photoelectron Spectroscopy

    OpenAIRE

    Fredriksson, Wendy

    2012-01-01

    The physical properties of the protective passive films formed on the surface of stainless steels under electrochemical polarization in different electrolytes were studied. The structure of these films was analyzed as a function of depth using photoelectron spectroscopy (PES). Depth profiling (using PES) of the surface layer was achieved by either changing the angle of incidence to achieve different analysis depths (ARXPS), by argon ion etching, or by varying the energy of the incoming x-rays...

  16. Parent Anions of Iron, Manganese, and Nickel Tetraphenyl Porphyrins: Photoelectron Spectroscopy and Computations.

    Science.gov (United States)

    Buytendyk, Allyson M; Graham, Jacob D; Gould, Julian; Bowen, Kit H

    2015-08-13

    The singly charged, parent anions of three transition metal, tetraphenyl porphyrins, M(TPP) [Fe(TPP), Mn(TPP), and Ni(TPP)], were studied by negative ion photoelectron spectroscopy. The observed (vertical) transitions from the ground state anions of these porphyrins to the various electronic states of their neutral counterparts were modeled by density functional theory computations. Our experimental and theoretical results were in good agreement. PMID:26186172

  17. A Photoelectron Spectroscopy and ab initio Study of B3- and B4- Anions and Their Neutrals

    Energy Technology Data Exchange (ETDEWEB)

    Zhai, Hua-Jin; Wang, Lai S.; Alexandrova, A N.; Boldyrev, Alexander I.; Zakrzewski, V G.

    2003-11-06

    The two smallest boron clusters (B3 and B4) in their neutral and anionic forms were studied by photoelectron spectroscopy and ab initio calculations. Vibrationally resolved photoelectron spectra were observed for B3- at three photon energies (355, 266, and 193 nm) and the electron affinity of B3 was measured to be+0.02 eV.

  18. Pb 4f photoelectron spectroscopy on mass-selected anionic lead clusters at FLASH

    International Nuclear Information System (INIS)

    4f core level photoelectron spectroscopy has been performed on negatively charged lead clusters, in the size range of 10-90 atoms. We deploy 4.7 nm radiation from the free-electron laser FLASH, yielding sufficiently high photon flux to investigate mass-selected systems in a beam. A new photoelectron detection system based on a hemispherical spectrometer and a time-resolving delayline detector makes it possible to assign electron signals to each micro-pulse of FLASH. The resulting 4f binding energies show good agreement with the metallic sphere model, giving evidence for a fast screening of the 4f core holes. By comparing the present work with previous 5d and valence region data, the paper presents a comprehensive overview of the energetics of lead clusters, from atoms to bulk. Special care is taken to discuss the differences of the valence- and core-level anion cluster photoionizations. Whereas in the valence case the escaping photoelectron interacts with a neutral system near its ground state, core-level ionization leads to transiently highly excited neutral clusters. Thus, the photoelectron signal might carry information on the relaxation dynamics. (paper)

  19. X-ray photoelectron spectroscopy and positron annihilation spectroscopy analysis of surfactant affected FePt spintronic films

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Chun, E-mail: fengchun@ustb.edu.cn [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Li, Xujing; Liu, Fen; Wang, Qiang [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Yang, Meiyin [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); The Center for Micromagnetics and Information Technologies (MINT) and Department of Electrical and Computer Engineering, University of Minnesota, 200 Union St SE, Minneapolis, MN 55455 (United States); Zhao, Chongjun [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Gong, Kui [Centre for the Physics of Materials and Department of Physics, McGill University, Montreal, Quebec, H3A2T8 Canada (Canada); Zhang, Peng; Wang, Bao-Yi; Cao, Xing-Zhong [Key Laboratory of Nuclear Analysis Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Yu, Guanghua [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China)

    2014-07-01

    This paper reports the effects of surfactant Bi atomic diffusion on the microstructure evolution and resulted property manipulation in FePt spintronic films by the quantitative studies of X-ray photoelectron spectroscopy and positron annihilation spectroscopy. The defect density in the FePt layer, which was tunable by varying the thermal treatment temperatures, was found to be remarkably enhanced correlated with the Bi atomic diffusion behavior. The observed defect density evolution substantially favors Fe(Pt) atomic migrations and lowers the energy barrier for atomic ordering transition, resulting in a great improvement of hard magnet property of the films.

  20. Photoelectron yield spectroscopy and inverse photoemission spectroscopy evaluations of p-type amorphous silicon carbide films prepared using liquid materials

    Directory of Open Access Journals (Sweden)

    Tatsuya Murakami

    2016-05-01

    Full Text Available Phosphorus-doped amorphous silicon carbide films were prepared using a polymeric precursor solution. Unlike conventional polymeric precursors, this polymer requires neither catalysts nor oxidation for its synthesis and cross-linkage, providing semiconducting properties in the films. The valence and conduction states of resultant films were determined directly through the combination of inverse photoemission spectroscopy and photoelectron yield spectroscopy. The incorporated carbon widened energy gap and optical gap comparably in the films with lower carbon concentrations. In contrast, a large deviation between the energy gap and the optical gap was observed at higher carbon contents because of exponential widening of the band tail.

  1. X-ray and photoelectron spectroscopy of the structure, reactivity, and electronic structure of semiconductor nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Hamad, K.S.

    2000-05-01

    Semiconductor nanocrystals are a system which has been the focus of interest due to their size dependent properties and their possible use in technological applications. Many chemical and physical properties vary systematically with the size of the nanocrystal and thus their study enables the investigation of scaling laws. Due to the increasing surface to volume ratio as size is decreased, the surfaces of nanocrystals are expected to have a large influence on their electronic, thermodynamic, and chemical behavior. In spite of their importance, nanocrystal surfaces are still relatively uncharacterized in terms of their structure, electronic properties, bonding, and reactivity. Investigation of nanocrystal surfaces is currently limited by what techniques to use, and which methods are suitable for nanocrystals is still being determined. This work presents experiments using x-ray and electronic spectroscopies to explore the structure, reactivity, and electronic properties of semiconductor (CdSe, InAs) nanocrystals and how they vary with size. Specifically, x-ray absorption near edge spectroscopy (XANES) in conjunction with multiple scattering simulations affords information about the structural disorder present at the surface of the nanocrystal. X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS) probe the electronic structure in terms of hole screening, and also give information about band lineups when the nanocrystal is placed in electric contact with a substrate. XPS of the core levels of the nanocrystal as a function of photo-oxidation time yields kinetic data on the oxidation reaction occurring at the surface of the nanocrystal.

  2. X-ray photoelectron spectroscopy investigations of zinc-magnesium alloy coated steel

    International Nuclear Information System (INIS)

    The coating layer composition depth profiles and element chemical states of zinc-magnesium alloy coated steel were investigated by X-ray photoelectron spectroscopy depth profiling. Through the analysis of photoelectron signals and Auger signals of different elements on different depth planes of the coating layer, it can be found that the surface of the coating layer contains MgCO3, MgO, Mg(OH)2, metallic Mg, metallic Zn and some complex zinc compounds. Under the surface, there is a Zn2Mg alloy layer with the thickness of about 300 nm accompanied with MgO and Mg(OH)2 in the layer. There is a transitional layer with the thickness of about 200 nm between the Zn2Mg alloy layer and the pure Zn layer, whose components consist of zinc-magnesium alloy without fixed stoichiometry, a little MgO and a little Mg(OH)2.

  3. Study of low-lying electronic states of ozone by anion photoelectron spectroscopy of O - 3

    Science.gov (United States)

    Arnold, Don W.; Xu, Cangshan; Kim, Eun H.; Neumark, Daniel M.

    1994-07-01

    The low-lying electronic states of ozone are studied using anion photoelectron spectroscopy of O-3. The spectra show photodetachment transitions from O-3 to the X˜ 1A1 ground state and to the five lowest lying electronic states of the ozone molecule, namely the 3A2, 3B2, 1A2, 3B1, and 1B1 states. The geometry of the ozonide anion determined from a Franck-Condon analysis of the O3 X 1A1 ground state spectrum agrees reasonably well with previous work. The excited state spectra are dominated by bending vibrational progressions which, for some states, extend well above the dissociation asymptote without noticeable lifetime broadening effects. Preliminary assignments are based upon photoelectron angular distributions and comparison with ab initio calculations. None of the excited states observed lies below the ground state dissociation limit of O3 as suggested by previous experimental and theoretical results.

  4. 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.

  5. Electron mean free path from angle-dependent photoelectron spectroscopy of aerosol particles

    International Nuclear Information System (INIS)

    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. First, aerosol photoemission studies can be performed for many different materials, including liquids. Second, 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

  6. 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 (<300 eV) where the ad hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquid interfaces are discussed.

  7. In situ photoelectron spectroscopy of molecular-beam-epitaxy grown surfaces

    CERN Document Server

    Oshima, M; Okabayashi, J; Ono, K

    2003-01-01

    Two in situ high-resolution synchrotron radiation photoelectron spectroscopy (SRPES) systems combined with a molecular beam epitaxy (MBE) chamber for III-V compound semiconductors and a laser MBE chamber for strongly correlated oxide films, respectively, have been designed and fabricated to analyze intrinsic and surface/interface electronic structures of these unique materials. The importance of the in situ SRPES has been demonstrated by the results of 1) Si surface nanostructures, 2) GaAs surfaces/interfaces and nanostructures, 3) MnAs magnetic nanostructures, and 4) strongly-correlated La sub 1 sub - sub x Sr sub x MnO sub 3 surfaces/interfaces and superstructures.

  8. Chemical Reaction Between Polyvinyl Alcohol and Titanate Coupling Agent with X-Ray Photoelectron Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    LI Bei-xing; ZHANG Wen-sheng

    2003-01-01

    The chemical reaction between polyvinyl alcohol (PVA) and tri(dioctylpyrophosphoryloxy) isopropyl titanate (NDZ-201) was studied using X-ray photoelectron spectroscopy (XPS).The results show that some C-OH functional groups of PVA react with the titanate coupling agent to form CPVA-O-Ti-O-CPVA bond.The cross-linking of the PVA chains occurs through the formation of CPVA-O-Ti-O-CPVA bonds and produces a three dimensional hydrophobic polymer network.Accordingly,the mechanism is proposed that the titanate coupling agent improves the moisture sensitivity of high alumina cement/polyvinyl alcohol (HAC/PVA) based macro defect free (MDF) composite material.

  9. Study on RE-Al-Zr-C-N Coating by X-ray Photoelectron Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    韦永德; 马楠; 侯仰龙

    2001-01-01

    Thermal diffusion of coating on 45 steel with rare earths, zirconium, aluminum, carbon and nitrogen was reported. Through X-ray photoelectron spectrum, the binding energy of permeated elements and their existence states were analyzed. Their existence on the surface of treated steel was confirmed by scanning electronic microscopy and energy dispersive spectroscopy. The results show that the rare earth acts as an activator and accelerator of the permeating of other elements. The effect of rare earths on aluminum is greater than that on zirconium.

  10. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

    OpenAIRE

    Lu, Yi-Chun; Crumlin, Ethan J.; Veith, Gabriel M.; Harding, Jonathon R.; Mutoro, Eva; Baggetto, Loïc; Dudney, Nancy J.; LIU, ZHI; Shao-Horn, Yang

    2012-01-01

    The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+x Ti5O12/LiPON/Li x V2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, ...

  11. Adsorption of NO2 on WSe2: DFT and photoelectron spectroscopy studies.

    Science.gov (United States)

    Ovcharenko, R; Dedkov, Yu; Voloshina, E

    2016-09-14

    The electronic structure modifications of WSe2 upon NO2-adsorption at room and low temperatures were studied by means of photoelectron spectroscopy. We found only moderate changes in the electronic structure, which are manifested as an upward shift of the WSe2-related bands to the smaller binding energies. The observed effects are modelled within the density functional theory approach, where a small adsorption energy of gas molecules on the surface of WSe2 was deduced. The obtained experimental data are explained as a valence bands polarisation effect, which causes their energy shift depending on the adsorption geometry and the formed dipole moment. PMID:27392163

  12. X-ray Photoelectron Spectroscopy Studies of MgB2 for Valence State of Mg

    OpenAIRE

    Talapatra, A.; Bandyopadhyay, S K; Sen, Pintu; P. Barat; S. Mukherjee; Mukherjee, M.(Variable Energy Cyclotron Centre, Kolkata, India)

    2004-01-01

    Core level X-ray Photoelectron Spectroscopy (XPS) studies have been carried out on polycrystalline MgB_2 pellets over the whole binding energy range with a view to having an idea of the charge state of Magnesium (Mg). We observe 3 distinct peaks in Mg 2p spectra at 49.3 eV (trace), 51.3 eV (major) and 54.0 eV (trace), corresponding to metallic Mg, MgB_2 and MgCO_3 or, divalent Mg species respectively. Similar trend has been noticed in Mg 2s spectra. The binding energy of Mg in MgB_2 is lower ...

  13. Structural Investigation of SBGESE Glasses by High Resolution X-Ray Photoelectron Spectroscopy

    Directory of Open Access Journals (Sweden)

    R. Golovchak

    2011-01-01

    Full Text Available The evolution of the structure of Sb8Ge32Se60 (Z=2.72 and Sb20Ge20Se60 (Z=2.60 chalcogenide glasses is determined by high resolution X-ray photoelectron spectroscopy. Glasses with Z=2.60 the structure consists of deformed tetrahedra and pyramids, in which at least one Se atom is substituted by Ge or Sb atom. For the Z=2.72 structure consisting of shared pyramids and tetrahedra with two or more Se atoms substituted by the cations. At the same time, Se-Se dimers are present in both compositions.

  14. Attosecond delays in molecular photoionization

    CERN Document Server

    Huppert, Martin; Baykusheva, Denitsa; von Conta, Aaron; Wörner, Hans Jakob

    2016-01-01

    We report measurements of energy-dependent attosecond photoionization delays between the two outer-most valence shells of N$_2$O and H$_2$O. The combination of single-shot signal referencing with the use of different metal foils to filter the attosecond pulse train enables us to extract delays from congested spectra. Remarkably large delays up to 160 as are observed in N$_2$O, whereas the delays in H$_2$O are all smaller than 50 as in the photon-energy range of 20-40 eV. These results are interpreted by developing a theory of molecular photoionization delays. The long delays measured in N$_2$O are shown to reflect the population of molecular shape resonances that trap the photoelectron for a duration of up to $\\sim$110 as. The unstructured continua of H$_2$O result in much smaller delays at the same photon energies. Our experimental and theoretical methods make the study of molecular attosecond photoionization dynamics accessible.

  15. Diagrammatic approach to attosecond delays in photoionization

    CERN Document Server

    Dahlström, J M; Lindroth, E

    2012-01-01

    We study laser-assisted photoionization by attosecond pulses using a time-independent formalism based on diagrammatic many-body perturbation theory. Our aim is to provide an ab inito route to the "delays" for this above-threshold ionization process, which is essential for a quantitative understanding of attosecond metrology. We present correction curves for characterization schemes of attosecond pulses, such as "streaking", that account for the delayed atomic response in ionization from neon and argon. We also verify that photoelectron delays from many-electron atoms can be measured using similar schemes if, instead, the so-called continuum--continuum delay is subtracted. Our method is general and it can be extended also to more complex systems and additional correlation effects can be introduced systematically.

  16. In situ photoelectron spectroscopy study of water adsorption on model biomaterial surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Salmeron, Miquel; Ketteler, Guido; Ashby, Paul; Mun, B.S.; Ratera, I.; Bluhm, Hendrik; Kasemo, B.; Salmeron, Miquel

    2007-07-10

    Using in situ photoelectron spectroscopy at near ambient conditions, we compare the interaction of water with four different model biomaterial surfaces: self-assembled thiol monolayers on Au(111) that are functionalized with methyl, hydroxyl, and carboxyl groups, and phosphatidylcholine (POPC) lipid films on Silicon. We show that the interaction of water with biomaterial surfaces is mediated by polar functional groups that interact strongly with water molecules through hydrogen bonding, resulting in adsorption of 0.2-0.3 ML water on the polar thiol films in 700 mTorr water pressure and resulting in characteristic N1s and P2p shifts for the POPC films. Provided that beam damage is carefully controlled, in situ electron spectroscopy can give valuable information about water adsorption which is not accessible under ultra-high vacuum conditions.

  17. Photoelectron spectroscopy study of metallic nanocluster arrangement at the surface of reactively sputtered amorphous hydrogenated carbon

    International Nuclear Information System (INIS)

    We report on the results of the arrangement of isolated surface metallic nanoclusters embedded in amorphous hydrogenated carbon (a-C:H) thin films, studied by photoelectron spectroscopy. As a model system we used gold-containing amorphous hydrogenated carbon (a-C:H/Au), due to the lack of reactivity between carbon and gold. The a-C:H/Au samples are obtained by simultaneous magnetron sputtering of Au target by argon and plasma-enhanced chemical vapor deposition of methane. Photoelectron spectroscopy with x-ray and ultraviolet excitation has been employed for surface studies that comprise as-deposited sample spectra recordings, measurements at off-normal takeoff angle, in situ in-depth profiling by Ar+ ion etching, and thiophene adsorption at the sample surface. The results of these extended studies firmly support previously drawn conclusions [I. R. Videnovic, V. Thommen, P. Oelhafen, D. Mathys, M. Dueggelin, and R. Guggenheim, Appl. Phys. Lett 80, 2863 (2002)] that by deposition on electrically grounded substrates one obtains samples with topmost Au clusters covered with a thin layer of a-C:H. Introducing a dc substrate bias voltage results in bald Au clusters on the surface and increased sp2/sp3 coordinated carbon ratio in the a-C:H matrix

  18. 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.

  19. 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.

  20. Direct experimental observation of the low ionization potentials of guanine in free oligonucleotides by using photoelectron spectroscopy

    OpenAIRE

    Yang, Xin; Wang, Xue-Bin; Vorpagel, Erich R.; Wang, Lai-Sheng

    2004-01-01

    Photodetachment photoelectron spectroscopy is used to probe the electronic structure of mono-, di-, and trinucleotide anions in the gas phase. A weak and well defined threshold band was observed in the photoelectron spectrum of 2′-deoxyguanosine 5′-monophosphate at a much lower ionization energy than the other three mononucleotides. Density function theory calculations revealed that this unique spectral feature is caused by electron-detachment from a π orbital of the guanine base on 2′-deoxyg...

  1. Resonance-enhanced multiphoton ionization photoelectron spectroscopy of Rydberg states of N2O below the X ionization limit

    OpenAIRE

    Scheper, C.R.; Kuijt, J.; Buma, W.J.; Lange

    1998-01-01

    A three-photon resonance-enhanced multiphoton ionization spectroscopic study on N2O is carried out in the spectral range from 80 000 cm - 1 up to the lowest ionization limit at 103 963 cm - 1. High-resolution photoelectron spectroscopy is used to identify and characterize the observed excited states. Eighteen origins are reported which have either not been assigned before or are reassigned now. Moreover, the photoelectron spectra taken at higher-lying resonances often show extensive vibronic ...

  2. Very low energy photoelectron spectroscopy in multiphoton ionization of H2

    OpenAIRE

    Bordas, C.; Dyer, M.; Helm, H.

    1994-01-01

    We apply a novel photoelectron imaging spectrometer [1] to the energy and angular analysis of photoelectrons resulting from resonantly enhanced multiphoton ionization of H2. Photoelectron images with well resolved individual rotational structure of the resulting H2+ ion are obtained, demonstrating the capability of this technique for analyzing photoelectrons in the meV energy range.

  3. Ambient pressure photoelectron spectroscopy: a new tool for surface science and nanotechnology

    Energy Technology Data Exchange (ETDEWEB)

    Salmeron, Miquel; Salmeron, Miquel; Schlogl, Robert

    2008-03-12

    Progress in science often follows or parallels the development of new techniques. The optical microscope helped convert medicine and biology from a speculative activity in old times to today's sophisticated scientific disciplines. The telescope changed the study and interpretation of heavens from mythology to science. X-ray diffraction enabled the flourishing of solid state physics and materials science. The technique object of this review, Ambient Pressure Photoelectron Spectroscopy or APPES for short, has also the potential of producing dramatic changes in the study of liquid and solid surfaces, particularly in areas such as atmospheric, environment and catalysis sciences. APPES adds an important missing element to the host of techniques that give fundamental information, i.e., spectroscopy and microscopy, about surfaces in the presence of gases and vapors, as encountered in industrial catalysis and atmospheric environments. APPES brings electron spectroscopy into the realm of techniques that can be used in practical environments. Decades of surface science in ultra high vacuum (UHV) has shown the power of electron spectroscopy in its various manifestations. Their unique property is the extremely short elastic mean free path of electrons as they travel through condensed matter, of the order of a few atomic distances in the energy range from a few eV to a few thousand eV. As a consequence of this the information obtained by analyzing electrons emitted or scattered from a surface refers to the top first few atomic layers, which is what surface science is all about. Low energy electron diffraction (LEED), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), Ultraviolet photoelectron spectroscopy (UPS), and other such techniques have been used for decades and provided some of the most fundamental knowledge about surface crystallography, composition and electronic structure available today. Unfortunately the high interaction cross section of

  4. Electronic Structures of Uranium Compounds Studied by Soft X-ray Photoelectron Spectroscopy

    Science.gov (United States)

    Fujimori, Shin-ichi; Takeda, Yukiharu; Okane, Tetsuo; Saitoh, Yuji; Fujimori, Atsushi; Yamagami, Hiroshi; Haga, Yoshinori; Yamamoto, Etsuji; Ōnuki, Yoshichika

    2016-06-01

    The electronic structures of uranium-based compounds have been studied by photoelectron spectroscopy with soft X-ray synchrotron radiation. Angle-resolved photoelectron spectroscopy with soft X-rays has made it possible to directly observe their bulk band structures and Fermi surfaces. It has been shown that the band structures and Fermi surfaces of itinerant compounds such as UB2, UN, and UFeGa5 are quantitatively described by a band-structure calculation treating all U 5f electrons as itinerant. Furthermore, the overall electronic structures of heavy-fermion compounds such as UPd2Al3, UNi2Al3, and URu2Si2 are also explained by a band-structure calculation, although some disagreements exist, which might originate from the electron correlation effect. This suggests that the itinerant description of U 5f states is an appropriate starting point for the description of their electronic structures. The situation is similar for ferromagnetic superconductors such as UGe2, URhGe, UCoGe, and UIr, although the complications from their low-symmetry crystal structures make it more difficult to describe their detailed electronic structures. The local electronic structures of the uranium site have been probed by core-level photoelectron spectroscopy with soft X-rays. The comparisons of core-level spectra of heavy-fermion compounds with typical itinerant and localized compounds suggest that the local electronic structures of most itinerant and heavy-fermion compounds are close to the U 5f3 configuration except for UPd2Al3 and UPt3. The core-level spectrum of UPd2Al3 has similarities to those of both itinerant and localized compounds, suggesting that it is located at the boundary between the itinerant and localized states. Moreover, the spectrum of UPt3 is very close to that of the localized compound UPd3, suggesting that it is nearly localized, although there are narrow quasi-particle bands in the vicinity of EF.

  5. EDITORIAL: Focus on Attosecond Physics

    Science.gov (United States)

    Bandrauk, André D.; Krausz, Ferenc; Starace, Anthony F.

    2008-02-01

    Chelkowski and A D Bandrauk Broadband generation in a Raman crystal driven by a pair of time-delayed linearly chirped pulses Miaochan Zhi and Alexei V Sokolov Ultrafast nanoplasmonics under coherent control Mark I Stockman Attosecond pulse carrier-envelope phase effects on ionized electron momentum and energy distributions: roles of frequency, intensity and an additional IR pulse Liang-You Peng, Evgeny A Pronin and Anthony F Starace Angular encoding in attosecond recollision Markus Kitzler, Xinhua Xie, Stefan Roither, Armin Scrinzi and Andrius Baltuska Polarization-resolved pump-probe spectroscopy with high harmonics Y Mairesse, S Haessler, B Fabre, J Higuet, W Boutu, P Breger, E Constant, D Descamps, E Mével, S Petit and P Salières Macroscopic effects in attosecond pulse generation T Ruchon, C P Hauri, K Varjú, E Mansten, M Swoboda, R López-Martens and A L'Huillier Monitoring long-term evolution of molecular vibrational wave packet using high-order harmonic generation M Yu Emelin, M Yu Ryabikin and A M Sergeev Intense single attosecond pulses from surface harmonics using the polarization gating technique S G Rykovanov, M Geissler, J Meyer-ter-Vehn and G D Tsakiris Imaging of carrier-envelope phase effects in above-threshold ionization with intense few-cycle laser fields M F Kling, J Rauschenberger, A J Verhoef, E Hasović, T Uphues, D B Milošević, H G Muller and M J J Vrakking Self-compression of optical laser pulses by filamentation A Mysyrowicz, A Couairon and U Keller Towards efficient generation of attosecond pulses from overdense plasma targets N M Naumova, C P Hauri, J A Nees, I V Sokolov, R Lopez-Martens and G A Mourou Quantum-path control in high-order harmonic generation at high photon energies Xiaoshi Zhang, Amy L Lytle, Oren Cohen, Margaret M Murnane and Henry C Kapteyn Time-resolved mapping of correlated electron emission from helium atom in an intense laser pulse C Ruiz and A Becker Pump and probe ultrafast electron dynamics in LiH: a computational study

  6. 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.

  7. X-ray photoelectron spectroscopy investigations of zinc-magnesium alloy coated steel

    Energy Technology Data Exchange (ETDEWEB)

    Chen Sheng, E-mail: chen_sheng@baosteel.com [Research Institute of Baoshan Iron and Steel Co. Ltd., 655 Fujin Road, Baoshan District, Shanghai 201900 (China); Yan Fei; Xue Fei; Yang Lihong; Liu Junliang [Research Institute of Baoshan Iron and Steel Co. Ltd., 655 Fujin Road, Baoshan District, Shanghai 201900 (China)

    2010-11-01

    The coating layer composition depth profiles and element chemical states of zinc-magnesium alloy coated steel were investigated by X-ray photoelectron spectroscopy depth profiling. Through the analysis of photoelectron signals and Auger signals of different elements on different depth planes of the coating layer, it can be found that the surface of the coating layer contains MgCO{sub 3}, MgO, Mg(OH){sub 2}, metallic Mg, metallic Zn and some complex zinc compounds. Under the surface, there is a Zn{sub 2}Mg alloy layer with the thickness of about 300 nm accompanied with MgO and Mg(OH){sub 2} in the layer. There is a transitional layer with the thickness of about 200 nm between the Zn{sub 2}Mg alloy layer and the pure Zn layer, whose components consist of zinc-magnesium alloy without fixed stoichiometry, a little MgO and a little Mg(OH){sub 2}.

  8. 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.

  9. Ultrafast XUV Pulses at High Repetition Rate for Time Resolved Photoelectron Spectroscopy of Surface Dynamics

    Science.gov (United States)

    Corder, Christopher; Zhao, Peng; Li, Xinlong; Muraca, Amanda R.; Kershis, Matthew D.; White, Michael G.; Allison, Thomas K.

    2016-05-01

    Ultrafast photoelectron studies of surface dynamics are often limited by low repetition rates. At Stony Brook we have built a cavity-enhanced high-harmonic generation XUV source that delivers ultrafast pulses to a surface science apparatus for photoelectron spectroscopy. We begin with a Ytterbium fiber laser at a repetition rate of 78 MHz and up to 90 W of average power. After compression the pulses have μJ's of energy with high harmonic generation. The enhancement cavity is a six mirror double folded bow-tie geometry with a focus of 15 μm at a Krypton gas jet, followed by a Sapphire crystal at Brewster's angle for the fundamental to allow outcoupling of the harmonics. A single harmonic is selected using a time-preserving monochromator to maintain the short pulses, and is sent to an ultra high vacuum chamber with sample preparation and diagnostic tools as well as an electron energy spectrometer. This allows us to study the electronic dynamics of semiconductor surfaces and their interfaces with adsorbed molecules which enable various charge transfer effects. Supported by AFOSR.

  10. Nonadiabatic Dynamics May Be Probed through Electronic Coherence in Time-Resolved Photoelectron Spectroscopy.

    Science.gov (United States)

    Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul

    2016-02-01

    We present a hierarchy of Fermi golden rules (FGRs) that incorporate strongly coupled electronic/nuclear dynamics in time-resolved photoelectron spectroscopy (TRPES) signals at different levels of theory. Expansion in the joint electronic and nuclear eigenbasis yields the numerically most challenging exact FGR (eFGR). The quasistatic Fermi Golden Rule (qsFGR) neglects nuclear motion during the photoionization process but takes into account electronic coherences as well as populations initially present in the pumped matter as well as those generated internally by coupling between electronic surfaces. The standard semiclassical Fermi Golden Rule (scFGR) neglects the electronic coherences and the nuclear kinetic energy during the ionizing pulse altogether, yielding the classical Condon approximation. The coherence contributions depend on the phase-profile of the ionizing field, allowing coherent control of TRPES signals. The photoelectron spectrum from model systems is simulated using these three levels of theory. The eFGR and the qsFGR show temporal oscillations originating from the electronic or vibrational coherences generated as the nuclear wave packet traverses a conical intersection. These oscillations, which are missed by the scFGR, directly reveal the time-evolving splitting between electronic states of the neutral molecule in the curve-crossing regime. PMID:26691822

  11. 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.

  12. Relaxation of Cs atomic polarization at surface coatings characterized by X-ray photoelectron spectroscopy

    CERN Document Server

    Kushida, K; Moriya, T; Shimizu, T; Meguro, K; Nakazawa, H; Hatakeyama, A

    2014-01-01

    Paraffin coatings on glass slides were investigated through both X-ray photoelectron spectroscopy (XPS) and spin relaxation measurement for cesium (Cs) vapor. The components of the glass substrate, such as silicon (Si) and oxygen (O), existed in the XPS spectra of the coated slides, indicating the imperfection of the prepared paraffin coatings. The substrate was not observed after the annealing of the coatings in Cs vapor, which is known as a `ripening' process for spin relaxation measurement. We found a general trend that effective anti-spin relaxation performance requires high paraffin and low Cs coverage on the surface. We also examined a type of diamond-like carbon (DLC) film, anticipating the effect of anti-spin relaxation; our attempts have failed to date.

  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. Self-assembled heterogeneous argon/neon core-shell clusters studied by photoelectron spectroscopy.

    Science.gov (United States)

    Lundwall, M; Pokapanich, W; Bergersen, H; Lindblad, A; Rander, T; Ohrwall, G; Tchaplyguine, M; Barth, S; Hergenhahn, U; Svensson, S; Björneholm, O

    2007-06-01

    Clusters formed by a coexpansion process of argon and neon have been studied using synchrotron radiation. Electrons from interatomic Coulombic decay as well as ultraviolet and x-ray photoelectron spectroscopy were used to determine the heterogeneous nature of the clusters and the cluster structure. Binary clusters of argon and neon produced by coexpansion are shown to exhibit a core-shell structure placing argon in the core and neon in the outer shells. Furthermore, the authors show that 2 ML of neon on the argon core is sufficient for neon valence band formation resembling the neon solid. For 1 ML of neon the authors observe a bandwidth narrowing to about half of the bulk value.

  15. Ambient-Pressure X-ray Photoelectron Spectroscopy through Electron Transparent Graphene Membranes

    CERN Document Server

    Kraus, Jurgen; Gunther, Sebastian; Gregoratti, Luca; Amati, Matteo; Kiskinova, Maya; Yulaev, Alexander; Vlassiouk, Ivan; Kolmakov, Andrei

    2014-01-01

    Photoelectron spectroscopy (PES) and microscopy are highly demanded for exploring morphologically complex solid-gas and solid-liquid interfaces under realistic conditions, but the very small electron mean free path inside the dense media imposes serious experimental challenges. Currently, near ambient pressure PES is conducted using sophisticated and expensive electron energy analyzers coupled with differentially pumped electron lenses. An alternative economical approach proposed in this report uses ultrathin graphene membranes to isolate the ambient sample environment from the PES detection system. We demonstrate that the graphene membrane separating windows are both mechanically robust and sufficiently transparent for electrons in a wide energy range to allow PES of liquid and gaseous water. The reported proof-of-principle experiments also open a principal possibility to probe vacuum-incompatible toxic or reactive samples enclosed inside the hermetic environmental cells.

  16. Prediction of protein interaction behaviour with PEG-grafted matrices using X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Damodaran, Vinod Babu; Fee, Conan J. [Biomolecular Interaction Centre, Department of Chemical and Process Engineering, University of Canterbury, Christchurch 8140 (New Zealand); Popat, Ketul C., E-mail: Ketul.Popat@colostate.edu [Biomaterials and Surface Micro/Nano-Engineering Laboratory, Department of Mechanical Engineering, School of Biomedical Engineering, Colorado State University, 1374 Campus Delivery, Fort Collins, CO 80523 (United States)

    2010-06-01

    Due to the considerable scientific and commercial interest in poly(ethylene glycol) (PEG) grafted solid surfaces for biomedical applications, it is important to characterize the properties and behaviour of these modified surfaces. In this study, we applied a unique method to predict the magnitude of interactive forces exerted between a globular protein and PEG-grafted matrices. Carboxyl functionalized solid matrices were covalently grafted with PEG-amine derivatives at varying PEG surface concentrations and layer thicknesses by controlling the grafting reaction parameters. X-ray photoelectron spectroscopy was used to characterize these PEG-grafted matrices using the standard overlay model. A detailed and systematic correlation between PEG layer thickness and the distance between the grafted PEG chains resulted in valuable information regarding protein interactions with these PEG-grafted matrices. Finally, this predicted interaction behaviour was validated with fluorescent images obtained from fluorescein isothiocyanate-labelled Cytochrome c-conjugated solid matrices using confocal laser scanning microscopy.

  17. Prediction of protein interaction behaviour with PEG-grafted matrices using X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Due to the considerable scientific and commercial interest in poly(ethylene glycol) (PEG) grafted solid surfaces for biomedical applications, it is important to characterize the properties and behaviour of these modified surfaces. In this study, we applied a unique method to predict the magnitude of interactive forces exerted between a globular protein and PEG-grafted matrices. Carboxyl functionalized solid matrices were covalently grafted with PEG-amine derivatives at varying PEG surface concentrations and layer thicknesses by controlling the grafting reaction parameters. X-ray photoelectron spectroscopy was used to characterize these PEG-grafted matrices using the standard overlay model. A detailed and systematic correlation between PEG layer thickness and the distance between the grafted PEG chains resulted in valuable information regarding protein interactions with these PEG-grafted matrices. Finally, this predicted interaction behaviour was validated with fluorescent images obtained from fluorescein isothiocyanate-labelled Cytochrome c-conjugated solid matrices using confocal laser scanning microscopy.

  18. Materials characterization by photoelectron spectroscopy; Caracterizacao de materiais por espectroscopia de fotoeletrons

    Energy Technology Data Exchange (ETDEWEB)

    Nascente, P.A.P., E-mail: nascente@ufscar.b [Universidade Federal de Sao Carlos (DEMa/UFSCar), SP (Brazil). Dept. de Engenharia de Materiais

    2010-07-01

    Low energy electrons are suitable for investigating surfaces due to their low mean free path in solids, which correspond to a few atomic layers (0.5 to 3.0 nm), and could be used in one of the following ways: incident electrons cause the emission of backscattered and secondary electrons and the electrons are excited by irradiated photons. The first case includes the emission of Auger electrons, while photoemission corresponds to the second case. X-ray photoelectron spectroscopy (XPS) is one of the most used surface analysis techniques since it is able to identify not only the surface constituents but also their chemical states. XPS can be employed in several areas of science and engineering, but in this report it will be presented only few examples of its use in the characterization of metallic materials, with an emphasis on thin films of noble and transition metals. (author)

  19. Aqueous solution/metal interfaces investigated in operando by photoelectron spectroscopy.

    Science.gov (United States)

    Karslıoğlu, O; Nemšák, S; Zegkinoglou, I; Shavorskiy, A; Hartl, M; Salmassi, F; Gullikson, E M; Ng, M L; Rameshan, Ch; Rude, B; Bianculli, D; Cordones, A A; Axnanda, S; Crumlin, E J; Ross, P N; Schneider, C M; Hussain, Z; Liu, Z; Fadley, C S; Bluhm, H

    2015-01-01

    We describe a new in operando approach for the investigation of heterogeneous processes at solid/liquid interfaces with elemental and chemical specificity which combines the preparation of thin liquid films using the meniscus method with standing wave ambient pressure X-ray photoelectron spectroscopy [Nemšák et al., Nat. Commun., 5, 5441 (2014)]. This technique provides information about the chemical composition across liquid/solid interfaces with sub-nanometer depth resolution and under realistic conditions of solution composition and concentration, pH, as well as electrical bias. In this article, we discuss the basics of the technique and present the first results of measurements on KOH/Ni interfaces. PMID:25912462

  20. Coincidence and covariance data acquisition in photoelectron and -ion spectroscopy. II. Analysis and applications

    Science.gov (United States)

    Mikosch, Jochen; Patchkovskii, Serguei

    2013-10-01

    We use an analytical theory of noisy Poisson processes, developed in the preceding companion publication, to compare coincidence and covariance measurement approaches in photoelectron and -ion spectroscopy. For non-unit detection efficiencies, coincidence data acquisition (DAQ) suffers from false coincidences. The rate of false coincidences grows quadratically with the rate of elementary ionization events. To minimize false coincidences for rare event outcomes, very low event rates may hence be required. Coincidence measurements exhibit high tolerance to noise introduced by unstable experimental conditions. Covariance DAQ on the other hand is free of systematic errors as long as stable experimental conditions are maintained. In the presence of noise, all channels in a covariance measurement become correlated. Under favourable conditions, covariance DAQ may allow orders of magnitude reduction in measurement times. Finally, we use experimental data for strong-field ionization of 1,3-butadiene to illustrate how fluctuations in experimental conditions can contaminate a covariance measurement, and how such contamination can be detected.

  1. Photodissociation and charge transfer dynamics of negative ions studied with femtosecond photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zanni, Martin T.

    1999-12-17

    This dissertation presents studies aimed at understanding the potential energy surfaces and dynamics of isolated negative ions, and the effects of solvent on each. Although negative ions play important roles in atmospheric and solution phase chemistry, to a large extent the ground and excited state potential energy surfaces of gas phase negative ions are poorly characterized, and solvent effects even less well understood. In an effort to fill this gap, the author's coworkers and the author have developed a new technique, anion femtosecond photoelectron spectroscopy, and applied it to gas phase photodissociation and charge transfer processes. Studies are presented that (1) characterize the ground and excited states of isolated and clustered anions, (2) monitor the photodissociation dynamics of isolated and clustered anions, and (3) explore the charge-transfer-to-solvent states of atomic iodide clustered with polar and non-polar solvents.

  2. Photodissociation and charge transfer dynamics of negative ions studied with femtosecond photoelectron spectroscopy

    International Nuclear Information System (INIS)

    This dissertation presents studies aimed at understanding the potential energy surfaces and dynamics of isolated negative ions, and the effects of solvent on each. Although negative ions play important roles in atmospheric and solution phase chemistry, to a large extent the ground and excited state potential energy surfaces of gas phase negative ions are poorly characterized, and solvent effects even less well understood. In an effort to fill this gap, the author's coworkers and the author have developed a new technique, anion femtosecond photoelectron spectroscopy, and applied it to gas phase photodissociation and charge transfer processes. Studies are presented that (1) characterize the ground and excited states of isolated and clustered anions, (2) monitor the photodissociation dynamics of isolated and clustered anions, and (3) explore the charge-transfer-to-solvent states of atomic iodide clustered with polar and non-polar solvents

  3. [Surface and interface analysis of PTCDA/ITO using X-ray photoelectron spectroscopy (XPS)].

    Science.gov (United States)

    Ou, Gu-ping; Song, Zhen; Gui, Wen-ming; Zhang, Fu-jia

    2006-04-01

    X-ray photoelectron spectroscopy (XPS) of surface and interface of PTCDA/ITO in PTCDA/p-Si organic-on-inorganic photoelectric detector was investigated. From C1s fine spectrum we found that the binding energy of C atoms in perylene rings was 284.6 eV; and the binding energy of C atoms in acid radical was 288.7 eV; moreover, some C atoms were oxidized by O atoms from ITO. The binding energy of O atoms in C=O bonds and C-O-C bonds was 531.5 and 533.4 eV, respectively. At the interface, the peak of high binding energy in C1s spectrum disappeared, and the main peak shifted toward lower binding energy.

  4. Thermal oxidation of vanadium-free Ti alloys: An X-ray photoelectron spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, Maria Francisca, E-mail: mflopez@icmm.csic.es [Department of Surfaces and Coatings, ICMM-CSIC, Sor Juana Ines de la Cruz, 3, Cantoblanco, 28049 Madrid (Spain); Gutierrez, Alejandro [Departamento de Fisica Aplicada and Instituto Nicolas Cabrera, Universidad Autonoma de Madrid, Cantoblanco, E-28049 Madrid (Spain); Jimenez, Jose Antonio [Centro Nacional de Investigaciones Metalurgicas, CSIC, Avda. Gregorio del Amo 8, E-28040 Madrid (Spain); Martinesi, Maria; Stio, Maria; Treves, Cristina [Department of Biochemical Sciences of University of Florence, Viale Morgagni 50, 50134 Florence (Italy)

    2010-04-06

    In the present work, X-ray photoelectron spectroscopy (XPS) was used to study the surface chemical composition of three alloys for biomedical applications: Ti-7Nb-6Al, Ti-13Nb-13Zr and Ti-15Zr-4Nb. The surface of these alloys was modified by annealing in air at 750 deg. C for different times with the aim of developing an oxide thick layer on top. The evolution of surface composition with annealing time was studied by XPS, and compared with the composition of the native oxide layer present on the samples before annealing. Two different oxidation trends were observed depending on the alloying elements and their corresponding diffusion kinetics, which give rise to different chemical species at the topmost layers. These results were linked with an evaluation of the biological response of the alloys by bringing them in contact with human peripheral blood mononuclear cells (PBMC).

  5. Structural analysis of carbon materials by X-ray photoelectron spectroscopy using computational chemistry

    International Nuclear Information System (INIS)

    X-ray photoelectron spectroscopy (XPS) has been frequently utilized to analyze the structures of carbon materials. However, few types of defects such as functional groups have been identified and reported, and some of these assignments are controversial. For example, the structures of oxygen-containing functional groups of carbon materials such as graphite oxide and graphene oxide are still under debate. Reported assignments for the C1s spectra of nitrogen-containing functional groups in carbon materials are few and there has been little discussion of such spectra. One effective method to clarify the structures of carbon materials in detail is simulation of XPS spectra using computational chemistry. This work explains the current problems for the XPS analysis of the C1s spectra of carbon materials and suggests the peak positions of various oxygen- and nitrogen-containing functional groups in addition to their full width at half maximum. (author)

  6. Detection of ultrashort VUV radiation pulses using photoelectron spectroscopy at DELTA

    International Nuclear Information System (INIS)

    At the 1.5-GeV electron storage ring DELTA operated by the TU-Dortmund University, coherent VUV radiation is generated in a short-pulse facility based on the Coherent Harmonic Generation (CHG) scheme. In this scheme, a femtosecond laser pulse is used to induce a periodic modulation of the electron energy in an undulator. The energy modulation is converted to a density modulation in a dispersive section. The resulting electron microbunches radiate coherently at higher harmonics of the laser wavelength in a second undulator. The VUV beamline operated by the Forschungszentrum Juelich will be employed for pump-probe experiments. It comprises a plane-grating monochromator and a photoelectron spectrometer optimized for angle-resolved photoemission spectroscopy. While a dedicated setup was initially used during commissioning of the short-pulse facility, the CHG-generated pulses can now be characterized directly in the VUV beamline.

  7. Thermal oxidation of vanadium-free Ti alloys: An X-ray photoelectron spectroscopy study

    International Nuclear Information System (INIS)

    In the present work, X-ray photoelectron spectroscopy (XPS) was used to study the surface chemical composition of three alloys for biomedical applications: Ti-7Nb-6Al, Ti-13Nb-13Zr and Ti-15Zr-4Nb. The surface of these alloys was modified by annealing in air at 750 deg. C for different times with the aim of developing an oxide thick layer on top. The evolution of surface composition with annealing time was studied by XPS, and compared with the composition of the native oxide layer present on the samples before annealing. Two different oxidation trends were observed depending on the alloying elements and their corresponding diffusion kinetics, which give rise to different chemical species at the topmost layers. These results were linked with an evaluation of the biological response of the alloys by bringing them in contact with human peripheral blood mononuclear cells (PBMC).

  8. 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.

  9. Electronic Structure of EuAl4 Studied by Photoelectron Spectroscopy

    Science.gov (United States)

    Kobata, Masaaki; Fujimori, Shin-ichi; Takeda, Yukiharu; Okane, Tetsuo; Saitoh, Yuji; Kobayashi, Keisuke; Yamagami, Hiroshi; Nakamura, Ai; Hedo, Masato; Nakama, Takao; Ōnuki, Yoshichika

    2016-09-01

    The electronic structure of the divalent Eu compound EuAl4, which shows a charge density wave transition at TCDW = 140 K, was studied by hard X-ray angle-integrated photoelectron spectroscopy (HAXPES) and soft X-ray angle-resolved photoelectron spectroscopy (ARPES). The valence band and core-level spectra obtained by HAXPES are consistent with the divalent nature of Eu atoms in EuAl4. From the ARPES results, the Fermi surface as well as band structure in the vicinity of the Fermi energy (EF) of EuAl4 are very similar to those of its isostructural divalent Sr compound SrAl4, which has no 4f electrons. This suggests that the Eu atoms are divalent in EuAl4, and the 4f electrons are localized below 1.8 eV with the Eu 4f7 electronic configuration in the ground state. The ARPES spectra measured along the Γ-(Σ)-Z high-symmetry line did not show significant temperature dependences above and below TCDW within the energy resolution of 80-90 meV. Moreover, the Fermi surface mapping along the kz direction showed that both EuAl4 and SrAl4 have mostly three-dimensional electronic structures, suggesting that the nesting of the Fermi surface is not simple. The Fermi surface and the band structure of EuAl4 were well explained by the band-structure calculation of SrAl4 based on the local density approximation.

  10. Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

    International Nuclear Information System (INIS)

    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 ≤ 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

  11. 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.

  12. Probing attosecond pulse structures by XUV-induced hole dynamics

    CERN Document Server

    You, Jhih-An; Dahlström, Jan Marcus

    2015-01-01

    We investigate a two-photon ionization process in neon by an isolated attosecond pump pulse and two coherent extreme ultraviolet probe fields. The probe fields, tuned to the 2s-2p transition in the residual ion, allow for coherent control of the photoelectron via indirect interactions with the hole. We show that the photoelectron-ion coincidence signal contains an interference pattern that can be used to reconstruct the temporal structure of attosecond pump pulses. Our results are supported by simulations based on time-dependent configuration-interaction singles and lowest-order perturbation theory within second quantization.

  13. UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tewell, Craig R.

    2002-08-19

    X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl{sub 4} and a Al(Et){sub 3} co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl{sub 2} and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl{sub 4} in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl{sub 2} by TiCl{sub 4} resulting in a thin film of MgCl{sub 2}/TiCl{sub x}, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl{sub 2}/TiCl{sub x} on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to {approx}1 Torr of Al(Et){sub 3}.

  14. 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.

  15. Electronic structure of germanium selenide investigated using ultra-violet photo-electron spectroscopy

    International Nuclear Information System (INIS)

    The valence band electronic structure of GeSe single crystals has been investigated using angle resolved photoemission spectroscopy (ARPES) and x-ray photoelectron spectroscopy. The experimentally observed bands from ARPES, match qualitatively with our LDA-based band structure calculations along the Γ–Z, Γ–Y and Γ–T symmetry directions. The valence band maximum occurs nearly midway along the Γ–Z direction, at a binding energy of −0.5 eV, substantiating the indirect band gap of GeSe. Non-dispersive features associated with surface states and indirect transitions have been observed. The difference in hybridization of Se and Ge 4p orbitals leads to the variation of dispersion along the three symmetry directions. The predominance of the Se 4pz orbitals, evidenced from theoretical calculations, may be the cause for highly dispersive bands along the Γ–T direction. Detailed electronic structure analysis reveals the significance of the cation–anion 4p orbitals hybridization in the valence band dispersion of IV–VI semiconductors. This is the first comprehensive report of the electronic structure of a GeSe single crystal using ARPES in conjugation with theoretical band structure analysis. (paper)

  16. Challenges for lithium species identification in complementary Auger and X-ray photoelectron spectroscopy

    Science.gov (United States)

    Hoffmann, M.; Zier, M.; Oswald, S.; Eckert, J.

    2015-08-01

    The combination of high spatial resolution and near-surface chemical information makes Auger electron spectroscopy (AES) a powerful tool for comprehensive surface analysis. The recent interest in lithium metal as an active material in lithium sulphur or lithium air batteries increases the demand for a thorough knowledge of the reactions happening at the electrode interface. Applying AES to the complex surfaces of batteries, however, requires a detailed understanding of the interactions occurring with the highly reactive materials during investigation, especially when using metallic lithium with its passivation layers formed even under glove box atmosphere. The article is focused on the influence of electron beam damage and residual gas under ultra-high vacuum conditions on the observations made. Immediate irradiation effects are shown to highly depend on electron dose leading to misinterpretation the surface composition and a non-sufficient stability of the sample. The results are further supported by coupled X-ray photoelectron spectroscopy (XPS) measurements that help to understand the beam induced phenomena. An improved output of the spectroscopic measurement could be achieved employing AES mappings. This allows an improved insight into the local distribution of different lithium compounds in the material surface and can also be applied to other battery active materials.

  17. Investigations into the electronic structure of the high-Tc superconductors by means of photoelectron spectroscopy

    International Nuclear Information System (INIS)

    The electronic structure of various polycrystalline samples including the new YBaCuO- and BiCaSrCuO- high Tc superconductors (HTSC) and related systems is investigated by photoelectron spectroscopy. Additional characterization is performed by conductivity measurements. In particular, the binding energy of the Cu-2p3/2- and the O-1s-levels of various HTSC is determined. For the first time the controversial 531 eV oxygen line was shown to be an intrinsic electronic structure effect. Sintered CuO-samples are obtained for the first time. The electronic structure of the sintered CuO turns out to be drastically different with respect to pressed CuO powder. For the first time a crossover resonance from a O-1s- into a Cu-3d-level was observed with synchrotron radiation. This is additional evidence for the strong hybridization between the Cu-3d and the O-2p states. Photoemission spectroscopy shows that the holes in the HTSC's are located at the oxygen p-band. Fe and Al overlayers on the HTSC-samples induce a drastic change in the electronic properties of the interface: apparently oxygen is removed from the HTSC to the overlayer. (orig./BHO)

  18. Fessibility Study on Nitrogen in Explosives using X-ray Photoelectron Spectroscopy: Chemical Fertilizer

    International Nuclear Information System (INIS)

    It was known that an explosive is defined as a material which contains a large amount of energy stored in chemical bonds. The energetic stability of gaseous products, and hence, their generation come from the strong bond formation of carbon (mono/di)oxide and (di)nitrogen. Consequently, most commercial explosives are contained -NO2, -ONO2 and/or -NHNO2 groups which when detonated release gases like the aforementioned ones, e.g., nitroglycerin, TNT, HMX, PETN, nitrocellulose, etc. It was revealed that the elemental compositions, especially N was found in most of the explosive and fertilizer. Chemical fertilizers that used as explosive stimulants were analyzed using X-ray photoelectron spectroscopy (XPS) and scanning electron microscope coupled with energy-dispersive X-ray fluorescence spectroscopy (SEM-EDS). XPS spectra showed relatively high amount of nitrogen (N) in the various samples, especially sample #6 and #7. In addition, the elemental analysis revealed the presence of trace elements. Explosives and fertilizers have differences in specific compositions. It can be concluded that these methods seem to be used as a fingerprint examination to identify various kinds of explosives and fertilizers.

  19. [Characterization of biochar by X-ray photoelectron spectroscopy and 13C nuclear magnetic resonance].

    Science.gov (United States)

    Xu, Dong-yu; Jin, Jie; Yan, Yu; Han, Lan-fang; Kang, Ming-jie; Wang, Zi-ying; Zhao, Ye; Sun, Ke

    2014-12-01

    The wood (willow branch) and grass (rice straw) materials were pyrolyzed at different temperatures (300, 450 and 600 °C) to obtain the biochars used in the present study. The biochars were characterized using elementary analysis, X-ray photoelectron spectroscopy (XPS) and solid state 13C cross-polarization and magic angle spinning nuclear magnetic resonance spectroscopy (13C NMR) to illuminate the structure and composition of the biochars which were derived from the different thermal temperatures and biomass. The results showed that the H/C, O/C and (O+N)/C ratios of the biochars decreased with the increase in the pyrolysis temperatures. The surface polarity and ash content of the grass-derived biochars were higher than those of the wood-derived biochars. The minerals of the wood-derived biochars were mainly covered by the organic matter; in contrast, parts of the mineral surfaces of the grass-derived biochars were not covered by organic matter? The 13C NMR of the low temperature-derived biochars revealed a large contribution of aromatic carbon, aliphatic carbon, carboxyl and carbonyl carbon, while the high temperature-derived biochars contained a large amount of aromatic carbon. Moreover, the wood-derived biochars produced at low heat treatment temperatures contained more lignin residues than grass-derived ones, probably due to the existence of high lignin content in the feedstock soures of wood-derived biochars. The results of the study would be useful for environmental application of biochars.

  20. Investigating Surface and Interface Phenomena in LiFeBO3 Electrodes Using Photoelectron Spectroscopy Depth Profiling

    DEFF Research Database (Denmark)

    Maibach, Julia; Younesi, Reza; Schwarzburger, Nele;

    2014-01-01

    The formation of surface and interface layers at the electrodes is highly important for the performance and stability of lithium ion batteries. To unravel the surface composition of electrode materials, photoelectron spectroscopy (PES) is highly suitable as it probes chemical surface and interfac...

  1. Electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy study of the corrosion behaviour of galvanized steel and electroplating steel

    Energy Technology Data Exchange (ETDEWEB)

    Lebrini, M., E-mail: mlebrini@yahoo.fr [Laboratoire des Procedes d' Elaboration des Revetements Fonctionnels, PERF-LSPES UMR CNRS 8008, ENSCL, BP 90108, F-59652 Villeneuve d' Ascq Cedex (France); Traisnel, M. [Laboratoire des Procedes d' Elaboration des Revetements Fonctionnels, PERF-LSPES UMR CNRS 8008, ENSCL, BP 90108, F-59652 Villeneuve d' Ascq Cedex (France); Gengembre, L. [Unite de Catalyse et Chimie du solide UMR 8181 Bat C3, USTL, F-59655, Villeneuve d' Ascq Cedex (France); Fontaine, G. [Laboratoire des Procedes d' Elaboration des Revetements Fonctionnels, PERF-LSPES UMR CNRS 8008, ENSCL, BP 90108, F-59652 Villeneuve d' Ascq Cedex (France); Lerasle, O.; Genet, N. [TOTAL France, Centre de Recherche de Solaize, Chemin du canal, BP 22, F-69360 Solaize (France)

    2011-02-01

    The efficiency of a formula containing 2-{l_brace}(2-hydroxyethyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl] amino{r_brace}ethanol (tolyltriazole) and decanoic acid as corrosion inhibitor for galvanized steel and electroplating steel in aqueous solution have been determined by electrochemical impedance spectroscopy (EIS) techniques. The experimental data obtained from this method show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The corrosion behaviour in the presence of different concentration of decanoic acid (DA) in the formula was also investigated by EIS. Results obtained reveal that, the formula is a good inhibitor for galvanized steel and electroplating steel in aqueous solution, the better performance was obtained in the case of galvanized steel. The ability of the inhibitor to be adsorbed on the surface was dependent on the nature of metal. X-ray photoelectron spectroscopy surface analysis with inhibitor shows that it's chemisorbed at the galvanized and electroplating steel/aqueous solution interface.

  2. 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.

  3. Ambient pressure photoelectron spectroscopy: a new tool for surface science and nanotechnology

    Energy Technology Data Exchange (ETDEWEB)

    Salmeron, Miquel; Salmeron, Miquel; Schlogl, Robert

    2008-03-12

    Progress in science often follows or parallels the development of new techniques. The optical microscope helped convert medicine and biology from a speculative activity in old times to today's sophisticated scientific disciplines. The telescope changed the study and interpretation of heavens from mythology to science. X-ray diffraction enabled the flourishing of solid state physics and materials science. The technique object of this review, Ambient Pressure Photoelectron Spectroscopy or APPES for short, has also the potential of producing dramatic changes in the study of liquid and solid surfaces, particularly in areas such as atmospheric, environment and catalysis sciences. APPES adds an important missing element to the host of techniques that give fundamental information, i.e., spectroscopy and microscopy, about surfaces in the presence of gases and vapors, as encountered in industrial catalysis and atmospheric environments. APPES brings electron spectroscopy into the realm of techniques that can be used in practical environments. Decades of surface science in ultra high vacuum (UHV) has shown the power of electron spectroscopy in its various manifestations. Their unique property is the extremely short elastic mean free path of electrons as they travel through condensed matter, of the order of a few atomic distances in the energy range from a few eV to a few thousand eV. As a consequence of this the information obtained by analyzing electrons emitted or scattered from a surface refers to the top first few atomic layers, which is what surface science is all about. Low energy electron diffraction (LEED), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), Ultraviolet photoelectron spectroscopy (UPS), and other such techniques have been used for decades and provided some of the most fundamental knowledge about surface crystallography, composition and electronic structure available today. Unfortunately the high interaction cross section of

  4. Attosecond nanoscale near-field sampling

    CERN Document Server

    Förg, Benjamin; Suessmann, Frederik; Foerster, Michael; Krueger, Michael; Ahn, Byung-Nam; Wintersperger, Karen; Zherebtsov, Sergey; Guggenmos, Alexander; Pervak, Vladimir; Kessel, Alexander; Trushin, Sergei; Azzeer, Abdallah; Stockman, Mark; Kim, Dong-Eon; Krausz, Ferenc; Hommelhoff, Peter; Kling, Matthias

    2015-01-01

    The promise of ultrafast light field driven electronic nanocircuits has stimulated the development of the new research field of attosecond nanophysics. An essential prerequisite for advancing this new area is the ability to characterize optical nearfields from light interaction with nanostructures with sub cycle resolution. Here, we experimentally demonstrate attosecond nearfield retrieval with a gold nanotip using streaking spectroscopy. By comparison of the results from gold nanotips to those obtained for a noble gas, the spectral response of the nanotip near field arising from laser excitation can be extracted. Monte Carlo MC trajectory simulations in near fields obtained with the macroscopic Maxwells equations elucidate the streaking mechanism on the nanoscale.

  5. Attosecond Delays in Molecular Photoionization

    Science.gov (United States)

    Huppert, Martin; Jordan, Inga; Baykusheva, Denitsa; von Conta, Aaron; Wörner, Hans Jakob

    2016-08-01

    We report measurements of energy-dependent photoionization delays between the two outermost valence shells of N2O and H2O . The combination of single-shot signal referencing with the use of different metal foils to filter the attosecond pulse train enables us to extract delays from congested spectra. Remarkably large delays up to 160 as are observed in N2O , whereas the delays in H2O are all smaller than 50 as in the photon-energy range of 20-40 eV. These results are interpreted by developing a theory of molecular photoionization delays. The long delays measured in N2O are shown to reflect the population of molecular shape resonances that trap the photoelectron for a duration of up to ˜110 as. The unstructured continua of H2O result in much smaller delays at the same photon energies. Our experimental and theoretical methods make the study of molecular attosecond photoionization dynamics accessible.

  6. Analyse de l'interface cuivre/Teflon AF1600 par spectroscopie des photoelectrons rayons x

    Science.gov (United States)

    Popovici, Dan

    The speed of electrical signals through the microelectronic multilevel interconnects depends of the delay time R x C. In order to improve the transmission speed of future microdevices, the microelectronics industry requires the use of metals having lower resistivities and insulators having lower permittivities. Copper and fluoropolymers are interesting candidates for the replacement of the presently used Al/polyimide technology. This thesis presents an X-ray photoelectron spectroscopy (XPS) analysis of the Cu/Teflon AF1600 interface, in order to have a better understanding of those interfacial interactions leading to improved adhesion. Several deposition methods, such as evaporation, sputtering and laser-induced chemical deposition were analyzed and compared. X-ray photoelectron spectroscopy (XPS) was used as the primary characterization technique of the different surfaces and interfaces. In the case of evaporation and sputtering, the loss of fluorine and oxygen atoms leads to graphitization and the crosslinking of carbon chains. The extent of damage caused by copper deposition is higher for sputter deposition because of the higher energies of the incidents atoms. This energy (two orders of magnitude higher than the energy involved in the evaporation) is also responsible for the total reaction of Cu with F and C. For the physical depositions (sputtering and evaporation), an angle-resolved XPS diffusion study showed the copper distribution as a function of depth. (i) For sputter deposition, this distribution is uniform. (ii) In the case of evaporation, we computed the concentration profile using the inverse Laplace transform. Several samples, annealed at different temperatures, were used to calculate the diffusion coefficients for the Cu/Teflon AF1600 interface. The study of interactions at the interface between Teflon AF1600 and copper deposited by different metallization techniques permitted us to elucidate some aspects related to the chemistry and structure of

  7. Total photoelectron yield spectroscopy of diamond: teaching an old dog new tricks

    International Nuclear Information System (INIS)

    Full text: Total photoelectron yield spectroscopy (Yield) has been widely used in the past to determine the work function of metals, and the density of tail and gap states in amorphous semiconductors and at the Si/SiO2 interface, for example. In all cases advantage is taken of the unrivalled sensitivity of yield which covers more than eight orders of magnitude in the density of occupied states. However, like all photoelectron spectroscopies, Yield suffers from a short sampling depth that seldom exceeds a few nm and is determined by the inelastic mean free path of electrons with finite kinetic energies. The situation changes completely when a semiconductor with true negative electron affinity such as hydrogenated diamond is used where the vacuum level falls below the conduction band minimum. Now even electrons at the conduction band minimum contribute to the yield and the spectrum reflects the absorption process as well as the transport of thermalized electrons and excitons to the surface as has been discussed first by Bandis and Pate. Here, we have utilized yield spectra of hydrogenated homoepitaxial diamond layers with different thicknesses to determine the diffusion lengths of electrons and excitons in diamond which amount to 16 and 20 μm, respectively for the highest quality diamond. Furthermore, from changes in the relative contributions of exciton and electron excitations to the yield spectra we are able to extract the sign of subsurface band bending over the diffusion length in hydrogenated diamond. This is so because electrons are affected by the electric fields connected with band bending whereas excitons as neutral entities are not. By following the band bending as a function of surface treatment we are able to unravel the mechanism behind the p-type surface conductivity that is observed on hydrogenated diamond surfaces after exposure to air. The mechanism relies on a transfer of electrons from diamond to a redox couple in an aqueous surface layer that

  8. Attosecond photoionization dynamics with stimulated core-valence transitions

    Science.gov (United States)

    You, Jhih-An; Rohringer, Nina; Dahlström, Jan Marcus

    2016-03-01

    We investigate ionization of neon atoms by an isolated attosecond pump pulse in the presence of two coherent extreme ultraviolet or x-ray probe fields. The probe fields are tuned to a core-valence transition in the residual ion and induce spectral shearing of the photoelectron distributions. We show that the photoelectron-ion coincidence signal contains an interference pattern that depends on the temporal structure of the attosecond pump pulse and the stimulated core-valence transition. Many-body perturbation theory is used to compute "atomic response times" for the processes and we find strikingly different behavior for stimulation to the outer-core hole (2 p ↔2 s ) and stimulation to the inner-core hole (2 p ↔1 s ). The response time of the inner-core transition is found to be comparable to that of state-of-the-art laser-based characterization techniques for attosecond pulses.

  9. Electron Interference in Molecular Circular Polarization Attosecond XUV Photoionization

    Directory of Open Access Journals (Sweden)

    Kai-Jun Yuan

    2015-01-01

    Full Text Available Two-center electron interference in molecular attosecond photoionization processes is investigated from numerical solutions of time-dependent Schrödinger equations. Both symmetric H\\(_2^+\\ and nonsymmetric HHe\\(^{2+}\\ one electron diatomic systems are ionized by intense attosecond circularly polarized XUV laser pulses. Photoionization of these molecular ions shows signature of interference with double peaks (minima in molecular attosecond photoelectron energy spectra (MAPES at critical angles \\(\\vartheta_c\\ between the molecular \\(\\textbf{R}\\ axis and the photoelectron momentum \\(\\textbf{p}\\. The interferences are shown to be a function of the symmetry of electronic states and the interference patterns are sensitive to the molecular orientation and pulse polarization. Such sensitivity offers possibility for imaging of molecular structure and orbitals.

  10. Fundamentals of attosecond optics

    CERN Document Server

    Chang, Zenghu

    2011-01-01

    Attosecond optical pulse generation, along with the related process of high-order harmonic generation, is redefining ultrafast physics and chemistry. A practical understanding of attosecond optics requires significant background information and foundational theory to make full use of these cutting-edge lasers and advance the technology toward the next generation of ultrafast lasers. Fundamentals of Attosecond Optics provides the first focused introduction to the field. The author presents the underlying concepts and techniques required to enter the field, as well as recent research advances th

  11. Advances in attosecond science

    Science.gov (United States)

    Calegari, Francesca; Sansone, Giuseppe; Stagira, Salvatore; Vozzi, Caterina; Nisoli, Mauro

    2016-03-01

    Attosecond science offers formidable tools for the investigation of electronic processes at the heart of important physical processes in atomic, molecular and solid-state physics. In the last 15 years impressive advances have been obtained from both the experimental and theoretical points of view. Attosecond pulses, in the form of isolated pulses or of trains of pulses, are now routinely available in various laboratories. In this review recent advances in attosecond science are reported and important applications are discussed. After a brief presentation of various techniques that can be employed for the generation and diagnosis of sub-femtosecond pulses, various applications are reported in atomic, molecular and condensed-matter physics.

  12. Atmospheric pressure X-ray photoelectron spectroscopy apparatus: Bridging the pressure gap.

    Science.gov (United States)

    Velasco-Vélez, J J; Pfeifer, V; Hävecker, M; Wang, R; Centeno, A; Zurutuza, A; Algara-Siller, G; Stotz, E; Skorupska, K; Teschner, D; Kube, P; Braeuninger-Weimer, P; Hofmann, S; Schlögl, R; Knop-Gericke, A

    2016-05-01

    One of the main goals in catalysis is the characterization of solid/gas interfaces in a reaction environment. The electronic structure and chemical composition of surfaces become heavily influenced by the surrounding environment. However, the lack of surface sensitive techniques that are able to monitor these modifications under high pressure conditions hinders the understanding of such processes. This limitation is known throughout the community as the "pressure gap." We have developed a novel experimental setup that provides chemical information on a molecular level under atmospheric pressure and in presence of reactive gases and at elevated temperatures. This approach is based on separating the vacuum environment from the high-pressure environment by a silicon nitride grid-that contains an array of micrometer-sized holes-coated with a bilayer of graphene. Using this configuration, we have investigated the local electronic structure of catalysts by means of photoelectron spectroscopy and in presence of gases at 1 atm. The reaction products were monitored online by mass spectrometry and gas chromatography. The successful operation of this setup was demonstrated with three different examples: the oxidation/reduction reaction of iridium (noble metal) and copper (transition metal) nanoparticles and with the hydrogenation of propyne on Pd black catalyst (powder). PMID:27250406

  13. Near surface composition of some alloys by X-ray photoelectron spectroscopy

    Indian Academy of Sciences (India)

    M Sreemany; T B Ghosh

    2001-10-01

    Chemical compositions of the alloys of CuNi (Cu0.10Ni0.90, Cu0.30Ni0.70, Cu0.70Ni0.30) and BiSb (Bi0.80Sb0.20, Bi0.64Sb0.34, Bi0.55Sb0.45) are determined by X-ray photoelectron spectroscopy. The stoichiometries are determined and are compared with the bulk compositions. Possible sources of systematic errors contributing to the results are discussed. Errors arising out of preferential etching in these alloys have been investigated. It has been inferred from such studies that the preferential etching does not enrich the surface composition with a particular component for the two systems reported here. Quantitative results of CuNi system indicate that the surface regions of the Cu0.70Ni0.30 alloy is Cu-rich, although no such evidence is observed in case of BiSb system.

  14. Effect of Space Radiation Processing on Lunar Soil Surface Chemistry: X-Ray Photoelectron Spectroscopy Studies

    Science.gov (United States)

    Dukes, C.; Loeffler, M.J.; Baragiola, R.; Christoffersen, R.; Keller, J.

    2009-01-01

    Current understanding of the chemistry and microstructure of the surfaces of lunar soil grains is dominated by a reference frame derived mainly from electron microscopy observations [e.g. 1,2]. These studies have shown that the outermost 10-100 nm of grain surfaces in mature lunar soil finest fractions have been modified by the combined effects of solar wind exposure, surface deposition of vapors and accretion of impact melt products [1,2]. These processes produce surface-correlated nanophase Feo, host grain amorphization, formation of surface patinas and other complex changes [1,2]. What is less well understood is how these changes are reflected directly at the surface, defined as the outermost 1-5 atomic monolayers, a region not easily chemically characterized by TEM. We are currently employing X-ray Photoelectron Spectroscopy (XPS) to study the surface chemistry of lunar soil samples that have been previously studied by TEM. This work includes modification of the grain surfaces by in situ irradiation with ions at solar wind energies to better understand how irradiated surfaces in lunar grains change their chemistry once exposed to ambient conditions on earth.

  15. Magnetron Plasma Sputtered Nanocomposite Thin Films: Structural Surface Studies by In Vacuo Photoelectron Spectroscopy

    International Nuclear Information System (INIS)

    The experimental system that enables thin film deposition by chemical vapor deposition combined with magnetron sputtering and sample surface characterization by photoelectron spectroscopy (PES), without breaking the vacuum between the deposition and the characterization stage, is described. The particular goal of this work was study of the surface arrangement of embedded metallic nanoclusters of 1B group (Au, Ag, and Cu) in amorphous hydrogenated carbon (a-C:H). From the range of applied material characterization tools, we present here the results of several PES-based experiments used to reveal cluster properties at the surface: as-deposited sample PES measurements, off-normal take-off angle XPS, and in situ in-depth XPS profiling by Ar+ ion etching. Clear distinction in all PES results of the samples deposited on the grounded substrates from those deposited on -150 V dc biased ones is obtained, revealing that keeping the substrate grounded during deposition results in topmost metallic clusters covered with a very thin layer of a-C:H, while applying negative bias voltage to the substrate results in partially bald clusters on the surface

  16. Chemistry of carbon polymer composite electrode - An X-ray photoelectron spectroscopy study

    Science.gov (United States)

    Andersen, Shuang Ma; Dhiman, Rajnish; Skou, Eivind

    2015-01-01

    Surface chemistry of the electrodes in a proton exchange membrane fuel cell is of great importance for the cell performance. Many groups have reported that electrode preparation condition has a direct influence on the resulting electrode properties. In this work, the oxidation state of electrode components and the composites (catalyst ionomer mixtures) in various electrode structures were systematically studied with X-ray photoelectron spectroscopy (XPS). Based on the spectra, when catalyst is physically mixed with Nafion ionomer, the resulting electrode surface chemistry is a combination of the two components. When the electrode is prepared with a lamination procedure, the ratio between fluorocarbon and graphitic carbon is decreased. Moreover, ether type oxide content is decreased although carbon oxide is slightly increased. This indicates structure change of the catalyst layer due to an interaction between the ionomer and the catalyst and possible polymer structural change during electrode fabrication. The surface of micro porous layer was found to be much more influenced by the lamination, especially when it is in contact with catalysts in the interphase. Higher amount of platinum oxide was observed in the electrode structures (catalyst ionomer mixture) compared to the catalyst powder. This also indicates a certain interaction between the functional groups in the polymer and platinum surface.

  17. A fast and flexible multichannel electron detector with parallel readout for photoelectron spectroscopy

    Science.gov (United States)

    Manning, P. P.; Clague, N. J.; Kirkman, I. W.; Quinn, F. M.; Hicks, P. J.

    1997-02-01

    To satisfy end user requirements for higher throughput and reliability in photoelectron spectroscopy, a new multichannel electron detector with discrete electronics has been designed and commissioned at Daresbury Laboratory. Count rate performance has been enhanced by the use of low resistance microchannel plates which amplify the electron pulses incident on the anode array. The low resistance microchannel plates are linear to 2.5 × 10 4 s -1 mm -2 for a bias voltage of 900 V per plate, providing more than an order of magnitude improvement in count rate performance over high resistance microchannel plates, microchannel plate outgassing in the ultra-high vacuum environment limits the scale of this improvement. A novel anode design maximizes the collection efficiency, while minimising crosstalk between channels (rail and electrodes on the anode. Each data collection channel comprises a fast current amplifier and discriminator, capable of a throughput of 2.5 × 10 7 s -1, and a 24 bit scaler. The integral non-linearity for flat-field illumination is better than 10% with no correction. The fast multichannel detection system gives a throughput enhancement of 10-20 on single-channel detection systems. It has also proved to be significantly better than previous multichannel detection systems with discrete electronics due to its high throughput, modular design and flexible structure.

  18. CHARACTERIZING SURFACE LAYERS IN NITINOL USING X-RAY PHOTOELECTRON SPECTROSCOPY

    Energy Technology Data Exchange (ETDEWEB)

    Christopfel, R.; Mehta, A.

    2008-01-01

    Nitinol is a shape memory alloy whose properties allow for large reversible deformations and a return to its original geometry. This nickel-titanium (NiTi) alloy has become a material used widely in the biomedical fi eld as a stent to open up collapsed arteries. Both ambient and biological conditions cause surface oxidation in these devices which in turn change its biocompatibility. The thickness of oxidized layers can cause fractures in the material if too large and can allow for penetration if too thin. Depending on the type and abundance of the chemical species on or near the surface, highly toxic metal ions can leak into the body causing cell damage or even cell death. Thus, biocompatibility of such devices is crucial. By using highly surface sensitive x-ray photoelectron spectroscopy to probe the surface of these structures, it is possible to decipher both layer composition and layer thickness. Two samples, both of which were mechanically polished, were investigated. Of the two samples, one was then exposed to a phosphate buffered saline (PBS) solution to mimic the chemical properties of blood, while the other remained unexposed. Although both samples were found to have oxide layers of appropriate thickness (on the order of a few nm), it was found that the sample exposed to the saline solution had a slightly thicker oxide layer and more signifi cantly, a phosphate layer very near the surface suggesting toxic metal components are well contained within the sample. These are considerable indications of a biocompatible device.

  19. Lanthanum, cerium, praseodymium, and neodymium metals and their interaction with oxygen studied by photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Clean films of La, Ce, Pr, and Nd, prepared by in situ evaporation have been investigated by photoelectron spectroscopy. Different light sources He I (hv = 21.2 eV), He II (hv = 40.8 eV) and Mg Kα (hv = 1253.6 eV) have been used for the electron excitation in order to characterize the metals. Measurements have been performed after exposing the clean metals to various amounts of oxygen. From the vanishing of the emission from the sd conduction band upon exposure the conclusion is drawn that an oxide layer thicker than the probing depth (20 A) is formed on all four metals and that the oxide (at room temperature) has the form: Me2O3, Me=La, Ce, Pr, Nd. The tetravalent cerium oxide is obtained when the film is heated to about 6000C during oxygen exposure. The interaction with oxygen is also characterized by recording the oxygen 1s level and some metal core levels (Me 3d, 4d and 4p). The results from the pure metals and from the metal oxides give further experimental evidence for a 4f level binding energy of 1.9 eV in γ-cerium. (Auth.)

  20. X-ray photoelectron spectroscopy studies of MgB 2 for valence state of Mg

    Science.gov (United States)

    A. Talapatra; Bandyopadhyay, S. K.; Sen, Pintu; Barat, P.; Mukherjee, S.; Mukherjee, M.

    2005-03-01

    Core level X-ray photoelectron spectroscopy (XPS) studies have been carried out on polycrystalline MgB 2 pellets over the whole binding energy range with a view to having an idea of the charge state of magnesium (Mg). We observe three distinct peaks in Mg 2p spectra at 49.3 eV (trace), 51.3 eV (major) and 54.0 eV (trace), corresponding to metallic Mg, MgB 2 and MgCO 3 or, divalent Mg species, respectively. Similar trend has been noticed in Mg 2s spectra. The binding energy of Mg in MgB 2 is lower than that corresponding to Mg(2+), indicative of the fact that the charge state of Mg in MgB 2 is less than (2+). Lowering of the formal charge of Mg promotes the σ → π electron transfer in boron (B) giving rise to holes on the top of the σ-band which are involved in coupling with B E 2g phonons for superconductivity. Through this charge transfer, Mg plays a positive role in hole superconductivity. B 1s spectra consist of three peaks corresponding to MgB 2, boron and B 2O 3. There is also evidence of MgO due to surface oxidation as seen from O 1s spectra.

  1. Covalently Bound Tetracoordinated Organoborons are Superhalogens: A Combined Negative Ion Photoelectron Spectroscopy and Theoretical Study

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jian; Yang, Ping; Sun, Zhenrong; Wang, Xue B.

    2014-09-18

    Molecular species with electron affinities (EAs) larger than that of the chlorine atom (3.6131 eV) are superhalogens. The corresponding negative ions, namely, superhalogen anions, are intrinsically very stable with high electron binding energies (EBEs), and widely exist as building blocks of bulk materials and ionic liquids. The most common superhalogen anions proposed and confirmed to date are either ionic salts or compact inorganic species. Herein we report a new class of superhalogen species, a series of tetracoordinated organoboron anions [BL4]– (L = phenyl (1), 4-fluorophenyl (2), 1-imidazolyl (3), L4 = H(pyrazolyl)3 (4)) with bulky organic ligands covalently bound to the central B atom. Negative ion photoelectron spectroscopy (NIPES) reveals all of these anions possessing EBEs higher than that of Cl- with the adiabatic / vertical detachment energy (ADE / VDE) of 4.44/4.8 (1), 4.78/5.2 (2), 5.08/5.4 (3), and 4.59/4.9 eV (4), respectively. First-principles calculations confirmed high EBEs of [BL4]– and predicted that these anions are thermodynamically stable against fragmentation. The unraveled superhalogen nature of these species provides a molecular basis to explain the wide-range applications of tetraphenylborate (TPB) (1) and trispyrazolylborate (Tp) (4) in many areas spanning from industrial waste treatment to soft material synthesis and organometallic chemistry

  2. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    Science.gov (United States)

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2016-01-01

    In this work, a detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented for select MXenes-a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Herein we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, sbnd O, sbnd OH and sbnd F, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. From XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

  3. Light-induced atom desorption from glass surfaces characterized by X-ray photoelectron spectroscopy

    Science.gov (United States)

    Kumagai, Ryo; Hatakeyama, Atsushi

    2016-07-01

    We analyzed the surfaces of vitreous silica (quartz) and borosilicate glass (Pyrex) substrates exposed to rubidium (Rb) vapor by X-ray photoelectron spectroscopy (XPS) to understand the surface conditions of alkali metal vapor cells. XPS spectra indicated that Rb atoms adopted different bonding states in quartz and Pyrex. Furthermore, Rb atoms in quartz remained in the near-surface region, while they diffused into the bulk in Pyrex. For these characterized surfaces, we measured light-induced atom desorption (LIAD) of Rb atoms. Clear differences in time evolution, photon energy dependence, and substrate temperature dependence were found; the decay of LIAD by continuous ultraviolet irradiation for quartz was faster than that for Pyrex, a monotonic increase in LIAD with increasing photon energy from 1.8 to 4.3 eV was more prominent for quartz, and LIAD from quartz was more efficient at higher temperatures in the range from 300 to 580 K, while that from Pyrex was almost independent of temperature.

  4. Electronic structure dynamics in a low bandgap polymer studied by time-resolved photoelectron spectroscopy.

    Science.gov (United States)

    Cappel, Ute B; Plogmaker, Stefan; Terschlüsen, Joachim A; Leitner, Torsten; Johansson, Erik M J; Edvinsson, Tomas; Sandell, Anders; Karis, Olof; Siegbahn, Hans; Svensson, Svante; Mårtensson, Nils; Rensmo, Håkan; Söderström, Johan

    2016-08-01

    Means to measure the temporal evolution following a photo-excitation in conjugated polymers are a key for the understanding and optimization of their function in applications such as organic solar cells. In this paper we study the electronic structure dynamics by direct pump-probe measurements of the excited electrons in such materials. Specifically, we carried out a time-resolved photoelectron spectroscopy (TRPES) study of the polymer PCPDTBT by combining an extreme ultraviolet (XUV) high harmonic generation source with a time-of-flight spectrometer. After excitation to either the 1st excited state or to a higher excited state, we follow how the electronic structure develops and relaxes on the electron binding energy scale. Specifically, we follow a less than 50 fs relaxation of the higher exited state and a 10 times slower relaxation of the 1st excited state. We corroborate the results using DFT calculations. Our study demonstrates the power of TRPES for studying photo-excited electron energetics and dynamics of solar cell materials. PMID:27440450

  5. X-ray photoelectron spectroscopy studies of MgB2 for valence state of Mg

    International Nuclear Information System (INIS)

    Core level X-ray photoelectron spectroscopy (XPS) studies have been carried out on polycrystalline MgB2 pellets over the whole binding energy range with a view to having an idea of the charge state of magnesium (Mg). We observe three distinct peaks in Mg 2p spectra at 49.3 eV (trace), 51.3 eV (major) and 54.0 eV (trace), corresponding to metallic Mg, MgB2 and MgCO3 or, divalent Mg species, respectively. Similar trend has been noticed in Mg 2s spectra. The binding energy of Mg in MgB2 is lower than that corresponding to Mg(2+), indicative of the fact that the charge state of Mg in MgB2 is less than (2+). Lowering of the formal charge of Mg promotes the σ → π electron transfer in boron (B) giving rise to holes on the top of the σ-band which are involved in coupling with B E2g phonons for superconductivity. Through this charge transfer, Mg plays a positive role in hole superconductivity. B 1s spectra consist of three peaks corresponding to MgB2, boron and B2O3. There is also evidence of MgO due to surface oxidation as seen from O 1s spectra

  6. Investigation of buried metal-organic interface with photoelectron spectroscopy (PES)

    Energy Technology Data Exchange (ETDEWEB)

    Vrdoljak, Pavo; Schoell, Achim; Reinert, Friedrich [Universitaet Wuerzburg, Experimentelle Physik II, 97074 Wuerzburg (Germany); Umbach, Eberhard [Forschungszentrum Karlsruhe, 76021 Karlsruhe (Germany)

    2008-07-01

    Metal-organic interfaces are of crucial importance for electronic devices since they influence the layer morphology, the electronic structure at contacts, and the charge carrier transport. Various investigations have addressed this issue from the viewpoint of surface science, applying model systems with thin organic films on flat (single crystalline or amorphous) metal substrates. The contacts in electronic devices, however, can be very different. This is mainly due to the morphological roughness of the interface in case of a metal top contact deposited on an organic layer and the possible influence on the electronic structure. In case of real contacts also interdiffusion has to be taken into account. However, surface sensitive techniques such as photoelectron spectroscopy (PES) and atomic force microscopy (AFM) can not immediately access the buried interface. To tackle this problem we have applied and optimised a lift-off technique which allows the removal of the metal top-contact in the UHV and analyse the interface between the contact and the organic film. We present first PES and AFM results of Au contacts deposited on PTCDA layers.

  7. High resolution photoelectron spectroscopy at the SnPc/Ag(111) interface

    Energy Technology Data Exchange (ETDEWEB)

    Scheuermann, C.; Haeming, M.; Kroeger, I.; Stadler, C.; Kumpf, C.; Schoell, A.; Reinert, F.; Umbach, E. [Universitaet Wuerzburg, Experimentelle Physik II, 97074 Wuerzburg (Germany)

    2008-07-01

    Phthalocyanines are interesting for applications in organic devices due to the potential of tailoring their properties by introducing different metal ligands into the heterocycle. Some derivates offer the potential of tuning the work function of metal contacts due to an intrinsic dipole moment. We present a high resolution photoelectron spectroscopy study on SnPc submonolayers on Ag(111). Based on a structural analysis, which shows the existence of different adsorption phases with different orientation of the molecular dipoles depending on temperature and coverage, the PES data indicate a significant effect on the surface work function. The valence and core spectra allow identifying a covalent interaction at the interface with the appearance of a new state at EF. Moreover, the data provide evidence for a systematic weakening of the interfacial interaction with increasing coverage. This is accompanied by a constriction of the substrate-adsorbate charge transfer, which becomes evident from an analysis of the core level line shapes. As a consequence, a comprehensive description of the electronic structure in the contact regime, of the resulting interface dipole, and of work function effects needs to account not only for structural properties such as the intrinsic molecular geometry, but also for intermolecular- and interfacial interactions which may involve significant charge transfer.

  8. Photoelectron spectroscopy study on Li substituted NiO using PES beamline installed on Indus-1

    CERN Document Server

    Banerjee, A; Phase, D M; Dasannacharya, B A

    2003-01-01

    Photoelectron spectroscopy beamline based on a toroidal grating monochromator (TGM) is recently commissioned on Indus-1 storage ring. It has been used to carry out valence band photoemission study of Li substituted NiO. In this paper initially a brief description of the beamline components and the experimental station for angle integrated photoemission experiment is presented. The later part of this paper is devoted to studies carried out on Li sub x Ni sub 1 sub - sub x O with x=0.0, 0.35 and 0.5 samples. Thin pellets of polycrystalline samples were used for the measurements reported here. Valence band spectra recorded on polycrystalline Li sub x Ni sub 1 sub - sub x O samples show drastic changes in various features as compared to that of pure NiO. The prominent changes are: (i) change in the relative contributions of Ni-3d and O-2p emissions, (ii) change in the peak position of Ni-3d from the top of the valance band of NiO and (iii) no noticeable change in the Ni satellite peak. These results are evaluated...

  9. Study of the oxidation of gold-tin preforms using x-ray photoelectron spectroscopy

    Science.gov (United States)

    Taylor, J. Ashley; Merchant, Sailesh M.; Perry, D. L.

    1995-11-01

    This study uses x-ray photoelectron spectroscopy (XPS) to investigate the nature of the oxide formed on clean Au-Sn binary alloys (ζ and δ phases) and on preforms with the eutectic composition (29 at % Sn) at low O2 pressures (oxide layer. The oxidation of the Au-Sn alloys is basically similar to the oxidation of metallic Sn. The Auger parameter indicates that with low-pressure oxidation a layered oxide structure is formed consisting of SnO and a slightly tin-rich oxide at the interface. Probably a thin skin of Sn(IV) oxide exists on the outer surface of the low-pressure oxide. High-temperature and low-pressure promotes the growth of SnO. As the pressure is increased the Sn(IV) oxide grows more noticeably and with high-pressure oxidation the Sn(IV) oxide grows thicker than the Sn(II) oxide at the interface. The Sn(II) oxide at the interface appears similar to the Sn(II) oxide structure formed at low pressure. The Auger parameter indicates that the Sn(IV) oxide possesses a structure different than that of Cassiterite.

  10. The surface of 1-euro coins studied by X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Gou, F.; Gleeson, M.A.; Villette, J.; Kleyn, S.E.F.; Kleyn, A.W

    2004-03-30

    The two alloy surfaces (pill and ring) that are present on 1-euro coins have been studied by X-ray photoelectron spectroscopy (XPS). Comparison is made between coins from general circulation and coin surfaces that have been subjected to a variety of cleaning and oxidation treatments. The concentrations and possible oxidation states of the metals (nickel, copper and zinc) at the surface were derived from analysis of the 2p{sub 3/2} core levels. The surface atomic ratios measured for the pill and the ring parts of the euro coins were compared to the official bulk ratios. This study shows a clear nickel enrichment of both pill and ring surfaces. Nickel at surface seems to be present mainly in hydroxide form although the chloride form cannot be excluded. A small concentration of zinc was present on the surface of the pill, even though it is not present in the bulk alloy. Evidence of both nickel and zinc surface enrichment is observed for the ring. No surface enrichment is observed for the atomically clean or oxidized alloy surfaces over a 60-h time scale.

  11. High temperature and high resolution uv photoelectron spectroscopy using supersonic molecular beams

    International Nuclear Information System (INIS)

    A high temperature molecular beam source with electron bombardment heating has been built for high resolution photoelectron spectroscopic studies of high temperature species and clusters. This source has the advantages of: producing an intense, continuous, seeded molecular beam, eliminating the interference of the heating mechanism from the photoelectron measurement. Coupling the source with our hemispherical electron energy analyzer, we can obtain very high resolution HeIα (584 angstrom) photoelectron spectra of high temperature species. Vibrationally-resolved photoelectron spectra of PbSe, As2, As4, and ZnCl2 are shown to demonstrate the performance of the new source. 25 refs., 8 figs., 1 tab

  12. Ab-initio angle and energy resolved photoelectron spectroscopy with time-dependent density-functional theory

    CERN Document Server

    De Giovannini, U; Marques, M A L; Appel, H; Gross, E K U; Rubio, A

    2012-01-01

    We present a time-dependent density-functional method able to describe the photoelectron spectrum of atoms and molecules when excited by laser pulses. This computationally feasible scheme is based on a geometrical partitioning that efficiently gives access to photoelectron spectroscopy in time-dependent density-functional calculations. By using a geometrical approach, we provide a simple description of momentum-resolved photoe- mission including multi-photon effects. The approach is validated by comparison with results in the literature and exact calculations. Furthermore, we present numerical photoelectron angular distributions for randomly oriented nitrogen molecules in a short near infrared intense laser pulse and helium-(I) angular spectra for aligned carbon monoxide and benzene.

  13. Multiphoton Double Ionization of Ar in Intense Extreme Ultraviolet Laser Fields Studied by Shot-by-Shot Photoelectron Spectroscopy

    International Nuclear Information System (INIS)

    Photoelectron spectroscopy has been performed to study the multiphoton double ionization of Ar in an intense extreme ultraviolet laser field (hν∼21 eV, ∼5 TW/cm2), by using a free electron laser (FEL). Three distinct peaks identified in the observed photoelectron spectra clearly show that the double ionization proceeds sequentially via the formation of Ar+: Ar+hν→Ar++e- and Ar++2hν→Ar2++e-. Shot-by-shot recording of the photoelectron spectra allows simultaneous monitoring of FEL spectrum and the multiphoton process for each FEL pulse, revealing that the two-photon ionization from Ar+ is significantly enhanced by intermediate resonances in Ar+.

  14. 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.

  15. Photoelectron Spectroscopy and Theoretical Studies of Anion-pi Interactions: Binding Strength and Anion Specificity

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jian; Zhou, Bin; Sun, Zhenrong; Wang, Xue B.

    2015-01-01

    illustrates that size-selective photoelectron spectroscopy combined with theoretical calculations represent a powerful technique to probe intrinsic anion–π interactions and has potential to provide quantitative guest-host molecular binding strengths and unravel fundamental insights in specific anion recognitions.

  16. Photoelectron spectroscopy and theoretical studies of anion-π interactions: binding strength and anion specificity.

    Science.gov (United States)

    Zhang, Jian; Zhou, Bin; Sun, Zhen-Rong; Wang, Xue-Bin

    2015-02-01

    Proposed in theory and then their existence confirmed, anion-π interactions have been recognized as new and important non-covalent binding forces. Despite extensive theoretical studies, numerous crystal structural identifications, and a plethora of solution phase investigations, anion-π interaction strengths that are free from complications of condensed-phase environments have not been directly measured in the gas phase. Herein we present a joint photoelectron spectroscopic and theoretical study on this subject, in which tetraoxacalix[2]arene[2]triazine 1, an electron-deficient and cavity self-tunable macrocyclic, was used as a charge-neutral molecular host to probe its interactions with a series of anions with distinctly different shapes and charge states (spherical halides Cl(-), Br(-), I(-), linear thiocyanate SCN(-), trigonal planar nitrate NO3(-), pyramidic iodate IO3(-), and tetrahedral sulfate SO4(2-)). The binding energies of the resultant gaseous 1 : 1 complexes (1·Cl(-), 1·Br(-), 1·I(-), 1·SCN(-), 1·NO3(-), 1·IO3(-) and 1·SO4(2-)) were directly measured experimentally, exhibiting substantial non-covalent interactions with pronounced anion-specific effects. The binding strengths of Cl(-), NO3(-), IO3(-) with 1 are found to be strongest among all singly charged anions, amounting to ca. 30 kcal mol(-1), but only about 40% of that between 1 and SO4(2-). Quantum chemical calculations reveal that all the anions reside in the center of the cavity of 1 with an anion-π binding motif in the complexes' optimized structures, where 1 is seen to be able to self-regulate its cavity structure to accommodate anions of different geometries and three-dimensional shapes. Electron density surface and charge distribution analyses further support anion-π binding formation. The calculated binding energies of the anions and 1 nicely reproduce the experimentally estimated electron binding energy increase. This work illustrates that size-selective photoelectron

  17. Photoelectron Spectroscopy Study of [Ta2B6]-: a Hexagonal Bipyramdial Cluster

    Science.gov (United States)

    Jian, Tian; Li, Weili; Romanescu, Constantin; Wang, Lai-Sheng

    2014-06-01

    It has been a long-sought goal in cluster science to discover stable atomic clusters as building blocks for cluster-assembled nanomaterials, as exemplified by the fullerenes and their subsequent bulk syntheses.[1,2] Clusters have also been considered as models to understand bulk properties, providing a bridge between molecular and solid-state chemistry.[3] Herein we report a joint photoelectron spectroscopy and theoretical study on the [Ta2B6]- and [Ta2B6] clusters.[4] The photoelectron spectrum of [Ta2B6]- displays a simple spectral pattern and a large HOMO-LUMO gap, suggesting its high symmetry. Theoretical calculations show that both the neutral and anion are D6h pyramidal. The chemical bonding analyses for [Ta2B6] revealed the nature of the B6 and Ta interactions and uncovered strong covalent bonding between B6 and Ta. The D6h-[TaB6Ta] gaseous cluster is reminiscent of the structural pattern in the ReB6X6Re core in the [(Cp*Re)2B6H4Cl2] and the TiB6Ti motif in the newly synthesized Ti7Rh4Ir2B8 solid-state compound.[5,6] The current work provides an intrinsic link between a gaseous cluster and motifs for solid materials. Continued investigations of the transition-metal boron clusters may lead to the discovery of new structural motifs involving pure boron clusters for the design of novel boride materials. Reference [1] H.W. Kroto, J. R. Heath, S. C. OBrien, R. F. Curl, R. E. Smalley, Nature 1985, 318, 162 - 163. [2] W. Krtschmer, L. D. Lamb, K. Fostiropoulos, D. R. Huffman, Nature 1990, 347, 354 - 358. [3] T. P. Fehlner, J.-F. Halet, J.-Y. Saillard, Molecular Clusters: A Bridge to Solid-State Chemitry, Cambridge University Press, UK, 2007. [4] W. L. Li, L. Xie, T. Jian, C. Romanescu, X. Huang, L.-S. Wang, Angew. Chem. Int. Ed. 2014, 126, 1312 - 1316. [5] B. Le Guennic, H. Jiao, S. Kahlal, J.-Y. Saillard, J.-F. Halet, S. Ghosh, M. Shang, A. M. Beatty, A. L. Rheingold, T. P. Fehlner, J. Am. Chem. Soc. 2004, 126, 3203 - 3217. [6] B. P. T. Fokwa, M. Hermus, Angew

  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. Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy

    OpenAIRE

    Lichterman, Michael F.; Hu, Shu; Richter, Matthias H.; Crumlin, Ethan J.; Axnanda, Stephanus; Favaro, Marco; Drisdell, Walter; Hussain, Zahid; Mayer, Thomas; Brunschwig, Bruce S.; Lewis, Nathan S.; Liu, Zhi; Lewerenz, Hans-Joachim

    2015-01-01

    Photoelectrochemical (PEC) cells based on semiconductor/liquid interfaces provide a method of converting solar energy to electricity or fuels. Currently, the understanding of semiconductor/liquid interfaces is inferred from experiments and models. Operando ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) has been used herein to directly characterize the semiconductor/liquid junction at room temperature under real-time electrochemical control. X-ray synchrotron radiation in conjuncti...

  20. 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

  1. Improved performances of nanosilicon electrodes using the salt LiFSI: a photoelectron spectroscopy study.

    Science.gov (United States)

    Philippe, Bertrand; Dedryvère, Rémi; Gorgoi, Mihaela; Rensmo, Håkan; Gonbeau, Danielle; Edström, Kristina

    2013-07-01

    Silicon is a very good candidate for the next generation of negative electrodes for Li-ion batteries, due to its high rechargeable capacity. An important issue for the implementation of silicon is the control of the chemical reactivity at the electrode/electrolyte interface upon cycling, especially when using nanometric silicon particles. In this work we observed improved performances of Li//Si cells by using the new salt lithium bis(fluorosulfonyl)imide (LiFSI) with respect to LiPF6. The interfacial chemistry upon long-term cycling was investigated by photoelectron spectroscopy (XPS or PES). A nondestructive depth resolved analysis was carried out by using both soft X-rays (100-800 eV) and hard X-rays (2000-7000 eV) from two different synchrotron facilities and in-house XPS (1486.6 eV). We show that LiFSI allows avoiding the fluorination process of the silicon particles surface upon long-term cycling, which is observed with the common salt LiPF6. As a result the composition in surface silicon phases is modified, and the favorable interactions between the binder and the active material surface are preserved. Moreover a reduction mechanism of the salt LiFSI at the surface of the electrode could be evidenced, and the reactivity of the salt toward reduction was investigated using ab initio calculations. The reduction products deposited at the surface of the electrode act as a passivation layer which prevents further reduction of the salt and preserves the electrochemical performances of the battery. PMID:23763546

  2. Investigation of the surface composition of electrodeposited black chromium by X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Survilienė, S., E-mail: sveta@ktl.mii.lt; Češūnienė, A.; Jasulaitienė, V.; Jurevičiūtė, I.

    2015-01-01

    Highlights: • Black chromium electrodeposited from a Cr(III) bath is composed of oxide, hydroxide and metallic chromium. • Metallic phase is absent in black chromium electrodeposited from a Cr(III) + ZnO bath. • The near-surface layer is rich in hydroxides, whereas oxides of both metals predominate in the depth of the coatings. - Abstract: The paper reviews black chromium electrodeposited from a trivalent chromium bath containing ZnO as a second main component. The chemical compositions of the top layers of the black chromium coatings were studied by the X-ray photoelectron spectroscopy method. The surface of black chromium was found to be almost entirely covered with organic substances. To gain information on the state of each element in the deposit bulk, the layer-by-layer etching of the black chromium surface with argon gas was used. Analysis of XPS spectra has shown that the top layers of black chromium without zinc are composed of various Cr(III) components, organic substances and metallic Cr, whereas metallic Cr is almost absent in black chromium containing some amount of Zn(II) compounds. The ratios of metal/oxide phases were found to be 10/27 and 2/28 for black chromium without and with zinc, respectively. It has been determined that owing to the presence of ZnO in the Cr(III) bath, the percentage of metallic chromium is substantially reduced in black chromium which is quite important for good solar selective characteristics of the coating. The results confirm some of earlier observations and provide new information on the composition of the near-surface layers.

  3. Assessment of Quantum Mechanical Methods for Copper and Iron Complexes by Photoelectron Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Shuqiang; Huang, Dao-Ling; Dau, Phuong D.; Liu, Hong-Tao; Wang, Lai S.; Ichiye, Toshiko

    2014-03-11

    Broken-symmetry density functional theory (BS-DFT) calculations are assessed for redox energetics [Cu(SCH3)2]1–/0, [Cu(NCS)2]1–/0, [FeCl4]1–/0, and [Fe(SCH3)4]1–/0 against vertical detachment energies (VDE) from valence photoelectron spectroscopy (PES), as a prelude to studies of metalloprotein analogs. The M06 and B3LYP hybrid functionals give VDE that agree with the PES VDE for the Fe complexes, but both underestimate it by 400 meV for the Cu complexes; other hybrid functionals give VDEs that are an increasing function of the amount of Hartree–Fock (HF) exchange and so cannot show good agreement for both Cu and Fe complexes. Range-separated (RS) functionals appear to give a better distribution of HF exchange since the negative HOMO energy is approximately equal to the VDEs but also give VDEs dependent on the amount of HF exchange, sometimes leading to ground states with incorrect electron configurations; the LRC-ωPBEh functional reduced to 10% HF exchange at short-range give somewhat better values for both, although still 150 meV too low for the Cu complexes and 50 meV too high for the Fe complexes. Overall, the results indicate that while HF exchange compensates for self-interaction error in DFT calculations of both Cu and Fe complexes, too much may lead to more sensitivity to nondynamical correlation in the spin-polarized Fe complexes.

  4. Exploring the aqueous vertical ionization of organic molecules by molecular simulation and liquid microjet photoelectron spectroscopy.

    Science.gov (United States)

    Tentscher, Peter R; Seidel, Robert; Winter, Bernd; Guerard, Jennifer J; Arey, J Samuel

    2015-01-01

    To study the influence of aqueous solvent on the electronic energy levels of dissolved organic molecules, we conducted liquid microjet photoelectron spectroscopy (PES) measurements of the aqueous vertical ionization energies (VIEaq) of aniline (7.49 eV), veratrole alcohol (7.68 eV), and imidazole (8.51 eV). We also reanalyzed previously reported experimental PES data for phenol, phenolate, thymidine, and protonated imidazolium cation. We then simulated PE spectra by means of QM/MM molecular dynamics and EOM-IP-CCSD calculations with effective fragment potentials, used to describe the aqueous vertical ionization energies for six molecules, including aniline, phenol, veratrole alcohol, imidazole, methoxybenzene, and dimethylsulfide. Experimental and computational data enable us to decompose the VIEaq into elementary processes. For neutral compounds, the shift in VIE upon solvation, ΔVIEaq, was found to range from ≈-0.5 to -0.91 eV. The ΔVIEaq was further explained in terms of the influence of deforming the gas phase solute into its solution phase conformation, the influence of solute hydrogen-bond donor and acceptor interactions with proximate solvent molecules, and the polarization of about 3000 outerlying solvent molecules. Among the neutral compounds, variability in ΔVIEaq appeared largely controlled by differences in solute-solvent hydrogen-bonding interactions. Detailed computational analysis of the flexible molecule veratrole alcohol reveals that the VIE is strongly dependent on molecular conformation in both gas and aqueous phases. Finally, aqueous reorganization energies of the oxidation half-cell ionization reaction were determined from experimental data or estimated from simulation for the six compounds aniline, phenol, phenolate, veratrole alcohol, dimethylsulfide, and methoxybenzene, revealing a surprising constancy of 2.06 to 2.35 eV. PMID:25516011

  5. Investigation of the surface composition of electrodeposited black chromium by X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Highlights: • Black chromium electrodeposited from a Cr(III) bath is composed of oxide, hydroxide and metallic chromium. • Metallic phase is absent in black chromium electrodeposited from a Cr(III) + ZnO bath. • The near-surface layer is rich in hydroxides, whereas oxides of both metals predominate in the depth of the coatings. - Abstract: The paper reviews black chromium electrodeposited from a trivalent chromium bath containing ZnO as a second main component. The chemical compositions of the top layers of the black chromium coatings were studied by the X-ray photoelectron spectroscopy method. The surface of black chromium was found to be almost entirely covered with organic substances. To gain information on the state of each element in the deposit bulk, the layer-by-layer etching of the black chromium surface with argon gas was used. Analysis of XPS spectra has shown that the top layers of black chromium without zinc are composed of various Cr(III) components, organic substances and metallic Cr, whereas metallic Cr is almost absent in black chromium containing some amount of Zn(II) compounds. The ratios of metal/oxide phases were found to be 10/27 and 2/28 for black chromium without and with zinc, respectively. It has been determined that owing to the presence of ZnO in the Cr(III) bath, the percentage of metallic chromium is substantially reduced in black chromium which is quite important for good solar selective characteristics of the coating. The results confirm some of earlier observations and provide new information on the composition of the near-surface layers

  6. Introductory Lecture. Probing wavepacket dynamics with femtosecond energy- and angle-resolved photoelectron spectroscopy

    OpenAIRE

    Takatsuka, Kazuo; Arasaki, Yasuki; Wang, Kwanghsi; McKoy, Vincent

    2000-01-01

    Several recent studies have demonstrated how well-suited femtosecond time-resolved photoelectron spectra are for mapping wavepacket dynamics in molecular systems. Theoretical studies of femtosecond photoelectron spectra which incorporate a robust description of the underlying photoionization dynamics should enhance the utility of such spectra as a probe of wavepackets and of the evolution of electronic structure. This should be particularly true in regions of avoided crossings where the photo...

  7. Broadband multilayer soft X-ray mirrors for attosecond pulse formation at photon energies above 100 eV

    Energy Technology Data Exchange (ETDEWEB)

    Hofstetter, Michael; Schuster, Joerg; Kleineberg, Ulf [LMU, Physik (Germany); Aquila, Andrew [CXRO (United States); Schulze, Martin; Fiess, Markus; Gouliemakis, Eleftherios; Krausz, Ferenc [MPQ (Germany); Huth, Martin [LMU, Chemie (Germany)

    2009-07-01

    We report on the development, fabrication and application of multilayer mirrors as broadband soft-X-ray optical components for the formation of attosecond (1 asec=10{sup -18}s)pulses from high harmonic radiation. Until recently, attosecond physics was merely confined to the photon energy range below 100 eV due to the properties of Mo/Si multilayer and single isolated pulses of 80 asec pulse duration have been achieved. For many applications, e.g. in the characterization of the photoemission dynamics from solid surfaces or the characterization of ultrafast surface plasmon dynamics in metallic nanostructures by attosecond pump-probe spectroscopy, higher photon energies are desirable to address deeper bound electronic core states or to increase the kinetic energy of the emitted photoelectrons. Here, we introduce new aperiodic broad bandwidth multilayer systems based on lanthanum (e.g. LaMo, LaB{sub 4}CMo, LaB{sub 4}C, MoB{sub 4}C),for the 100-190 eV photon energy range. Multilayer properties like interface roughness, interlayer formation and reflectivity are discussed. Finally, first applications for spectral filtering of the HHG comb above 100 eV are presented.

  8. Practical chemical analysis of Pt and Pd based heterogeneous catalysts with hard X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Highlights: •Hard X-ray photoelectron spectroscopy (HAXPES) enables interface analysis of catalyst. •HAXPES enables overall analysis of porous film of Pt-doped CeO2 and related catalyst. •HAXPES enables analysis of trace elements for Pd and Pt3Ni nanoparticle catalysts. -- Abstract: Interfacial properties including configuration, porosity, chemical states, and atomic diffusion greatly affect the performance of supported heterogeneous catalysts. Hard X-ray photoelectron spectroscopy (HAXPES) can be used to analyze the interfaces of heterogeneous catalysts because of its large information depth of more than 20 nm. We use HAXPES to examine Pt-doped CeO2 and related thin film catalysts evaporated on Si, carbon, and carbon nanotube substrates, because Pt-doped CeO2 has great potential as a noble metal-based heterogeneous catalyst for fuel cells. The HAXPES measurements clarify that the dopant material, substrate material, and surface pretreatment of substrate are important parameters that affect the interfacial properties of Pt-doped CeO2 and related thin film catalysts. Another advantage of HAXPES measurement of heterogeneous catalysts is that it can be used for chemical analysis of trace elements by detecting photoelectrons from deep core levels, which have large photoionization cross-sections in the hard X-ray region. We use HAXPES for chemical analysis of trace elements in Pd nanoparticle catalysts immobilized on sulfur-terminated substrates and Pt3Ni nanoparticle catalysts enveloped by dendrimer molecules

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

    Science.gov (United States)

    Niedermaier, Inga; Kolbeck, Claudia; Steinrück, Hans-Peter; Maier, Florian

    2016-04-01

    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.

  10. Radiation effects and metalloproteins studied by x-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wurzbach, J.A.

    1975-07-01

    X-ray photoelectron spectroscopy (XPS) is used to study the bonding structure at the iron site of cytochrome c and the bonding of rare earth ions to the phosphate oxygens of ATP. Radiation effects are studied on several amino acid and simple peptide model systems. The emission spectrum of the x-ray source is calculated from literature references. The distributions of photon energy as a function of photon frequency and as a function of take-off angle are obtained. From these distributions, the radiation dose absorbed by an organic sample is found to be 10/sup 6/ rads/sec. The C 1s and N 1s spectra of amino acids and peptides are studied to characterize an internal reference standard for protein XPS spectra. Samples of native cytochrome c prepared from solutions of pH 1.5, 3, 7, and 11 are studied. Control samples include porphyrin cytochrome c (PCC), the metal free analogue of the native protein, and microperoxidase (MP), a mixture of heme peptides derived from the peptic digestion of cytochrome c. These samples show two S 2p peaks. The first peak has a binding energy (BE) of 163 eV, which corresponds to the S containing amino acids; the second peak is shifted to 167 eV. This large shift may be the result of Fe-S binding, or oxidation, or both. Low spin ferricytochrome c and ferri-MP were found to have Fe 3p BE's that are unusually low (51 eV) compared to other ferric compounds (54 to 58 eV) and even Fe metal (53 eV). X-ray crystal structures of these compounds show that low spin heme Fe lies in the porphyrin plane; while, high spin heme Fe is displaced above the plane. The N 1s and P 2p spectra of ATP show no change except slight broadening when Nd/sup 3 +/ is substituted for Na/sup +/. Thus, there is no inconsistency with proposals that rare earth ions might be useful as substitutes for alkali metal ions and alkaline earth ions in proteins.

  11. Femtosecond photoelectron spectroscopy: a new tool for the study of anion dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Greenblatt, B.J.

    1999-02-01

    A new experimental technique for the time-resolved study of anion reactions is presented. Using femtosecond laser pulses, which provide extremely fast ({approx} 100 fs) time resolution, in conjunction with photoelectron spectroscopy, which reveals differences between anion and neutral potential energy surfaces, a complex anion reaction can be followed from its inception through the formation of asymptotic products. Experimental data can be modeled quantitatively using established theoretical approaches, allowing for the refinement of potential energy surfaces as well as dynamical models. After a brief overview, a detailed account of the construction of the experimental apparatus is presented. Documentation of the data acquisition program is contained in the Appendix. The first experimental demonstration of the technique is then presented for I{sub 2}{sup -} photodissociation, modeled using a simulation program which is also detailed in the Appendix. The investigation of I{sub 2}{sup -} photodissociation in several size-selected I{sub 2}{sup -}(Ar){sub n} (n = 6-20) and I{sub 2}{sup -}(CO{sub 2}){sub n} (n = 4-16) clusters forms the heart of the dissertation. In a series of chapters, the numerous effects of solvation on this fundamental bond-breaking reaction are explored, the most notable of which is the recombination of I{sub 2}{sup -} on the ground {tilde X}({sup 2}{Sigma}{sub u}{sup +}) state in sufficiently large clusters. Recombination and trapping of I{sub 2}{sup -} on the excited {tilde A}({sup 2}{Pi}{sub 3/2,g}) state is also observed in both types of clusters. The studies have revealed electronic state transitions, the first step in recombination, on a {approx}500 fs to {approx}10 ps timescale. Accompanying the changes in electronic state is solvent reorganization, which occurs on a similar timescale. Over longer periods ({approx}1 ps to >200 ps), energy is transferred from vibrationally excite d I{sub 2}{sup -} to modes of the solvent, which in turn leads

  12. Radiation effects and metalloproteins studied by x-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    X-ray photoelectron spectroscopy (XPS) is used to study the bonding structure at the iron site of cytochrome c and the bonding of rare earth ions to the phosphate oxygens of ATP. Radiation effects are studied on several amino acid and simple peptide model systems. The emission spectrum of the x-ray source is calculated from literature references. The distributions of photon energy as a function of photon frequency and as a function of take-off angle are obtained. From these distributions, the radiation dose absorbed by an organic sample is found to be 106 rads/sec. The C 1s and N 1s spectra of amino acids and peptides are studied to characterize an internal reference standard for protein XPS spectra. Samples of native cytochrome c prepared from solutions of pH 1.5, 3, 7, and 11 are studied. Control samples include porphyrin cytochrome c (PCC), the metal free analogue of the native protein, and microperoxidase (MP), a mixture of heme peptides derived from the peptic digestion of cytochrome c. These samples show two S 2p peaks. The first peak has a binding energy (BE) of 163 eV, which corresponds to the S containing amino acids; the second peak is shifted to 167 eV. This large shift may be the result of Fe-S binding, or oxidation, or both. Low spin ferricytochrome c and ferri-MP were found to have Fe 3p BE's that are unusually low (51 eV) compared to other ferric compounds (54 to 58 eV) and even Fe metal (53 eV). X-ray crystal structures of these compounds show that low spin heme Fe lies in the porphyrin plane; while, high spin heme Fe is displaced above the plane. The N 1s and P 2p spectra of ATP show no change except slight broadening when Nd3+ is substituted for Na+. Thus, there is no inconsistency with proposals that rare earth ions might be useful as substitutes for alkali metal ions and alkaline earth ions in proteins

  13. 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

  14. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Yi-Chun; Crumlin, Ethan J.; Veith, Gabriel M.; Harding, Jonathon R.; Mutoro, Eva; Baggetto, Loïc; Dudney, Nancy J.; Liu, Zhi; Shao-Horn, Yang

    2012-10-08

    The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and near ambient-pressure of oxygen using X-ray photoelectron spectroscopy (APXPS). Oxygen reduction and evolution reactions take place on the surface of the mixed electronic and Li+ ionic conductor, LixV2O5, which eliminate parasitic reactions between oxygen reduction/evolution reaction intermediates and aprotic electrolytes used in Li-O2 batteries reported to date. Under UHV, reversible lithium intercalation and de-intercalation from LixV2O5 was noted, where the changes in the vanadium valence state revealed from XPS in this study were comparable to that reported previously from Li/LixV2O5 thin film batteries. In presence of oxygen near ambient pressure, the LixV2O5 surface was covered gradually by the reaction product of oxygen reduction, namely lithium peroxide (Li2O2) (approximately 1-2 unit cells) upon discharge. Interestingly, the LixV2O5 surface became re-exposed upon charging, and the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of Li-O2 cells (~1000 mV) with aprotic electrolytes, which can be attributed to subnanometer-thick Li2O2 with surfaces free of contaminants such as carbonate species. Our study provides first evidence of reversible lithium peroxide formation and decomposition in situ on an oxide surface using a solid-state cell, and new insights into the reaction mechanism of Li-O2 chemistry.

  15. X-Ray photoelectron spectroscopy (XPS) studies of copper-sodium tellurite glasses

    International Nuclear Information System (INIS)

    Sodium tellurite glasses containing CuO with the nominal composition [(Na2O)0.3(TeO2)0.7-x (CuO)x], where x=0.00, 0.05, 0.15, and 0.20, have been prepared and investigated by X-ray photoelectron spectroscopy (XPS). The binding energies of Te 3p, Te 3d, O 1s, and Cu 2p core levels in these glasses have been measured and compared to the corresponding binding energies in TeO2 and CuO powders. The Te 3p and Te 3d core levels for the glasses were essentially unchanged from those of TeO2 powder and have little dependence upon the CuO content. Although the O 1s peak showed a small asymmetry on the higher energy side of the peak in the glasses, it was primarily the result of hydroxide contamination on the glass surface rather than the appearance of non-bridging oxygen atoms arising from a structural change in the TeO4. For glasses with x=0.05 and 0.15, the Cu 2p peaks were shifted by more than 1 eV towards lower binding energies in comparison to their values in CuO powder, which suggests the presence of Cu+ ions in these glasses. The appearance of satellite peaks in the Cu 2p spectra, however, provided definitive evidence for the presence of Cu2+ ions in these glass samples as well. The broadened Cu 2p3/2 peaks were correspondingly decomposed into two distinct peaks separated by approximately 1.25 eV, with the lower energy peak being associated with Cu+ and the higher one with Cu2+. The relative Cu2+ content estimated from the spectral analysis was found to vary from 15% for the x=0.05 glass sample to over 70% for the x=0.20 sample

  16. 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.

  17. Effect of laser spectral bandwidth on coherent control of resonance-enhanced multiphoton-ionization photoelectron spectroscopy

    International Nuclear Information System (INIS)

    The high-resolution (2 + 1) resonance-enhanced multiphoton-ionization photoelectron spectroscopy (REMPI-PS) can be obtained by measuring the photoelectron intensity at a given kinetic energy and scanning the single π phase step position. In this paper, we further demonstrate that the high-resolution (2 + 1) REMPI-PS cannot be achieved at any measured position of the kinetic energy by this measurement method, which is affected by the laser spectral bandwidth. We propose a double π phase step modulation to eliminate the effect of the laser spectral bandwidth, and show the advantage of the double π phase step modulation on achieving the high-resolution (2 + 1) REMPI-PS by considering the contributions involving on- and near-resonant three-photon excitation pathways

  18. Direct Imaging of Transient Fano Resonances in N2 Using Time-, Energy-, and Angular-Resolved Photoelectron Spectroscopy

    Science.gov (United States)

    Eckstein, Martin; Yang, Chung-Hsin; Frassetto, Fabio; Poletto, Luca; Sansone, Giuseppe; Vrakking, Marc J. J.; Kornilov, Oleg

    2016-04-01

    Autoionizing Rydberg states of molecular N2 are studied using time-, energy-, and angular-resolved photoelectron spectroscopy. A femtosecond extreme ultraviolet pulse with a photon energy of 17.5 eV excites the resonance and a subsequent IR pulse ionizes the molecule before the autoionization takes place. The angular-resolved photoelectron spectra depend on pump-probe time delay and allow for the distinguishing of two electronic states contributing to the resonance. The lifetime of one of the contributions is determined to be 14 ±1 fs , while the lifetime of the other appears to be significantly shorter than the time resolution of the experiment. These observations suggest that the Rydberg states in this energy region are influenced by the effect of interference stabilization and merge into a complex resonance.

  19. Direct Imaging of Transient Fano Resonances in N_{2} Using Time-, Energy-, and Angular-Resolved Photoelectron Spectroscopy.

    Science.gov (United States)

    Eckstein, Martin; Yang, Chung-Hsin; Frassetto, Fabio; Poletto, Luca; Sansone, Giuseppe; Vrakking, Marc J J; Kornilov, Oleg

    2016-04-22

    Autoionizing Rydberg states of molecular N_{2} are studied using time-, energy-, and angular-resolved photoelectron spectroscopy. A femtosecond extreme ultraviolet pulse with a photon energy of 17.5 eV excites the resonance and a subsequent IR pulse ionizes the molecule before the autoionization takes place. The angular-resolved photoelectron spectra depend on pump-probe time delay and allow for the distinguishing of two electronic states contributing to the resonance. The lifetime of one of the contributions is determined to be 14±1  fs, while the lifetime of the other appears to be significantly shorter than the time resolution of the experiment. These observations suggest that the Rydberg states in this energy region are influenced by the effect of interference stabilization and merge into a complex resonance. PMID:27152799

  20. Introduction to attosecond delays in photoionization

    International Nuclear Information System (INIS)

    This tutorial presents an introduction to the interaction of light and matter on the attosecond timescale. Our aim is to detail the theoretical description of ultra-short time delays and to relate these to the phase of extreme ultraviolet (XUV) light pulses and to the asymptotic phaseshifts of photoelectron wave packets. Special emphasis is laid on time-delay experiments, where attosecond XUV pulses are used to photoionize target atoms at well-defined times, followed by a probing process in real time by a phase-locked, infrared laser field. In this way, the laser field serves as a ‘clock’ to monitor the ionization event, but the observable delays do not correspond directly to the delay associated with single-photon ionization. Instead, a significant part of the observed delay originates from a measurement induced process, which obscures the single-photon ionization dynamics. This artefact is traced back to a phaseshift of the above-threshold ionization transition matrix element, which we call the continuum-continuum phase. It arises due to the laser-stimulated transitions between Coulomb continuum states. As we shall show here, these measurement-induced effects can be separated from the single-photon ionization process, using analytical expressions of universal character, so that eventually the attosecond time delays in photoionization can be accessed.

  1. Metal-polymer interfaces studied with adsorption microcalorimetry and photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bebensee, Fabian

    2010-06-21

    The interface formation between calcium and two different semiconducting, ?-conjugated polymers, namely poly(3-hexylthiophene) (P3HT) and poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-(1-cyanovilylene)phenylene] (CN-MEH-PPV), was investigated using adsorption microcalorimetry, low energy ion scattering spectroscopy (LEIS), atomic beam scattering and X-ray photoelectron spectroscopy. In addition to the interface formation on pristine, i.e., untreated polymer surfaces, the influence of electron irradiation prior to calcium deposition and the effect of dosing calcium at a low substrate temperature was studied. The reactive site for the interaction of calcium atoms impinging on a pristine P3HT surface appears to be the sulfur in the thiophene ring, as is concluded from a combination of XPS, adsorption calorimetry and theory results. The interaction, in fact, is strong enough that the sulfur atoms abstracted from the thiophene ring under formation of calcium sulfide with an overall reaction energy of this process of 405 kJ per mol. Quantitative evaluation of XPS data reveal that the depth up to which Ca atoms react with sulfur in the polymer is 3 nm, irrespective of increasing the amount of Ca dosed onto the substrate. A closed layer of Ca is only formed at a Ca coverage exceeding 11 ML, as suggested by LEIS. Irradiation of P3HT with electrons with a kinetic energy of 100 eV results in dehydrogenation of the hexyl side chains and formation of new C=C double bonds. This in turn results in a higher initial sticking probability of 0.63 for Ca, while no other significant changes could be observed: XPS indicates that the thiophene rings remain intact and the measured heat of adsorption is the same as observed for the deposition of Ca on pristine P3HT. Dosing Ca onto P3HT held at low temperature (130 K) is found to result in a very low saturation thickness of the reacted layer of approximately 0.3 nm. Upon warming the sample up to room temperature, the thickness of the reacted layer

  2. 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.

  3. Phase Determination Method to Directly Measure Intensity and Frequency of Temporal Profiles of Attosecond EUV Pulses

    Institute of Scientific and Technical Information of China (English)

    GE Yu-Cheng

    2005-01-01

    @@ A new method of phase determination is presented to directly measure the intensity and frequency temporalprofiles of attosecond EUV pulses. The profiles can be reconstructed from the photoelectron energy spectra measured with two different laser intensities at 0° and 180° with respect to the linear laser polarization using a cross correlation between the femtosecond laser and the attosecond EUV. The method has a temporal measurement range from a quarter to about half of a laser oscillation period. The time resolution depends on the jitter and control precision of laser and EUV pulses. This method improves the time resolution in measuring attosecond EUV pulses.

  4. Adsorbate induced surface alloy formation investigated by near ambient pressure X-ray photoelectron spectroscopy

    DEFF Research Database (Denmark)

    Nierhoff, Anders Ulrik Fregerslev; Conradsen, Christian Nagstrup; McCarthy, David Norman;

    2014-01-01

    for engineering of more active or selective catalyst materials. Dynamical surface changes on alloy surfaces due to the adsorption of reactants in high gas pressures are challenging to investigate using standard characterization tools. Here we apply synchrotron illuminated near ambient pressure X-ray photoelectron...

  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. Surface analysis of BPA-polycarbonate/ poly(butylene terephthalate) blends by X-ray photoelectron spectroscopy

    Science.gov (United States)

    Burrell, Michael C.; Chera, John J.

    1988-10-01

    X-ray photoelectron spectroscopy is used to measure the surface composition of polycarbonate/ poly(butylene terephthalate) blends. The blend surface is enriched in PC compared to the bulk, with the surface PC/PBT ratio equal to about 1.6 times to bulk formation. For blends containing an impact modifier as a third component, the XPS spectra of the molded surface indicates that no impact modifier is present within the XPS sampling depth. A spectral simulation scheme improves the accuracy of the computed PC/PBT ratio over conventional data reduction schemes involving curve fitting.

  8. Resonance-enhanced multiphoton ionization photoelectron spectroscopy of even-parity autoionizing Rydberg states of atomic sulphur

    OpenAIRE

    Woutersen, S.; Milan,, M; Lange; Buma, W.J.

    1997-01-01

    Several previously unobserved Rydberg states of the sulphur atom above the lowest ionization threshold are identified and assigned using (2 + 1) resonance-enhanced multiphoton-ionization photoelectron spectroscopy. All states were accessed by two-photon transitions from either the 3P ground or the 1D excited state, prepared by in situ photodissociation of H2S. The observed states derive from the (2Do)5p and (2Po)4p configurations. For the (2Do)5p 3F and (2Po)4p 3D triplets, extensive photoele...

  9. Resonance enhanced multiphoton ionization photoelectron spectroscopy on nano- and picosecond timescales of Rydberg states of methyl iodide

    OpenAIRE

    Buma, W.J.; Dobber, M.R.; Lange

    1993-01-01

    Rydberg states of methyl iodide have been investigated using resonance enhanced multiphoton ionization in combination with photoelectron spectroscopy with nanosecond and picosecond laser pulses. The study of the ns (6n10) Rydberg states in two-, three-, and four-photon excitations has resulted in an unambiguous identification of state [1] in the 7s and 8s Rydberg states. As a consequence, it is concluded that the transition to 6s[1] in two- and three-photon excitations is anomalously weak. Th...

  10. Oxidation of nanostructured Ti films produced by low energy cluster beam deposition: An X-ray Photoelectron Spectroscopy characterization

    Energy Technology Data Exchange (ETDEWEB)

    Simone, Monica de, E-mail: desimone@tasc.infm.it [CNR-IOM Laboratorio TASC, Area Science Park Basovizza, 34149 Trieste (Italy); Snidero, Elena [CNR-IOM Laboratorio TASC, Area Science Park Basovizza, 34149 Trieste (Italy); Coreno, Marcello [CNR-IMIP, c/o Laboratorio TASC Area Science Park Basovizza, 34149 Trieste (Italy); Sincrotrone Trieste ScpA, Area Science Park Basovizza, 34149 Trieste (Italy); Bongiorno, Gero [Fondazione Filarete, v.le Ortles 22/4, 20139 Milano (Italy); Giorgetti, Luca [Istituto Europeo di Oncologia, Dip. di Oncologia Sperimentale, Via Adamello 16, 20139, Milano (Italy); Amati, Matteo [Sincrotrone Trieste ScpA, Area Science Park Basovizza, 34149 Trieste (Italy); Cepek, Cinzia [CNR-IOM Laboratorio TASC, Area Science Park Basovizza, 34149 Trieste (Italy)

    2012-05-01

    We used in-situ X-ray Photoelectron Spectroscopy (XPS) to study the oxidation process of a cluster-assembled metallic titanium film exposed to molecular oxygen at room temperature. The nanostructured film has been grown on a Si(111) substrate, in ultra high vacuum conditions, by coupling a supersonic cluster beam deposition system with an XPS experimental chamber. Our results show that upon in-situ oxygen exposure Ti{sup 3+} is the first oxidation state observed, followed by Ti{sup 4+}, whereas Ti{sup 2+} is practically absent during the whole process. Our results compare well with the existing literature on Ti films produced using other techniques.

  11. 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.

  12. Communication: Vibrationally resolved photoelectron spectroscopy of the tetracyanoquinodimethane (TCNQ) anion and accurate determination of the electron affinity of TCNQ

    Science.gov (United States)

    Zhu, Guo-Zhu; Wang, Lai-Sheng

    2015-12-01

    Tetracyanoquinodimethane (TCNQ) is widely used as an electron acceptor to form highly conducting organic charge-transfer solids. Surprisingly, the electron affinity (EA) of TCNQ is not well known and has never been directly measured. Here, we report vibrationally resolved photoelectron spectroscopy (PES) of the TCNQ- anion produced using electrospray and cooled in a cryogenic ion trap. Photoelectron spectrum taken at 354.7 nm represents the detachment transition from the ground state of TCNQ- to that of neutral TCNQ with a short vibrational progression. The EA of TCNQ is measured accurately to be 3.383 ± 0.001 eV (27 289 ± 8 cm-1), compared to the 2.8 ± 0.1 eV value known in the literature and measured previously using collisional ionization technique. In addition, six vibrational peaks are observed in the photoelectron spectrum, yielding vibrational frequencies for three totally symmetric modes of TCNQ. Two-photon PES via a bound electronic excited state of TCNQ- at 3.100 eV yields a broad low kinetic energy peak due to fast internal conversion to vibrationally excited levels of the anion ground electronic state. The high EA measured for TCNQ underlies its ability as a good electron acceptor.

  13. Communication: Vibrationally resolved photoelectron spectroscopy of the tetracyanoquinodimethane (TCNQ) anion and accurate determination of the electron affinity of TCNQ

    International Nuclear Information System (INIS)

    Tetracyanoquinodimethane (TCNQ) is widely used as an electron acceptor to form highly conducting organic charge-transfer solids. Surprisingly, the electron affinity (EA) of TCNQ is not well known and has never been directly measured. Here, we report vibrationally resolved photoelectron spectroscopy (PES) of the TCNQ− anion produced using electrospray and cooled in a cryogenic ion trap. Photoelectron spectrum taken at 354.7 nm represents the detachment transition from the ground state of TCNQ− to that of neutral TCNQ with a short vibrational progression. The EA of TCNQ is measured accurately to be 3.383 ± 0.001 eV (27 289 ± 8 cm−1), compared to the 2.8 ± 0.1 eV value known in the literature and measured previously using collisional ionization technique. In addition, six vibrational peaks are observed in the photoelectron spectrum, yielding vibrational frequencies for three totally symmetric modes of TCNQ. Two-photon PES via a bound electronic excited state of TCNQ− at 3.100 eV yields a broad low kinetic energy peak due to fast internal conversion to vibrationally excited levels of the anion ground electronic state. The high EA measured for TCNQ underlies its ability as a good electron acceptor

  14. 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.

  15. Oxidation half-reaction of aqueous nucleosides and nucleotides via photoelectron spectroscopy augmented by ab initio calculations.

    Science.gov (United States)

    Schroeder, Christi A; Pluhařová, Eva; Seidel, Robert; Schroeder, William P; Faubel, Manfred; Slavíček, Petr; Winter, Bernd; Jungwirth, Pavel; Bradforth, Stephen E

    2015-01-14

    Oxidative damage to DNA and hole transport between nucleobases in oxidized DNA are important processes in lesion formation for which surprisingly poor thermodynamic data exist, the relative ease of oxidizing the four nucleobases being one such example. Theoretical simulations of radiation damage and charge transport in DNA depend on accurate values for vertical ionization energies (VIEs), reorganization energies, and standard reduction potentials. Liquid-jet photoelectron spectroscopy can be used to directly study the oxidation half-reaction. The VIEs of nucleic acid building blocks are measured in their native buffered aqueous environment. The experimental investigation of purine and pyrimidine nucleotides, nucleosides, pentose sugars, and inorganic phosphate demonstrates that photoelectron spectra of nucleotides arise as a spectral sum over their individual chemical components; that is, the electronic interactions between each component are effectively screened from one another by water. Electronic structure theory affords the assignment of the lowest energy photoelectron band in all investigated nucleosides and nucleotides to a single ionizing transition centered solely on the nucleobase. Thus, combining the measured VIEs with theoretically determined reorganization energies allows for the spectroscopic determination of the one-electron redox potentials that have been difficult to establish via electrochemistry. PMID:25551179

  16. Applications of Elliptically Polarized, Few-Cycle Attosecond Pulses

    Science.gov (United States)

    Starace, Anthony F.

    2016-05-01

    Use of elliptically-polarized light opens the possibility of investigating effects that are not accessible with linearly-polarized pulses. This talk presents two new physical effects that are predicted for ionization of the helium atom by few-cycle, elliptically polarized attosecond pulses. For double ionization of He by an intense elliptically polarized attosecond pulse, we predict a nonlinear dichroic effect (i.e., the difference of the two-electron angular distributions in the polarization plane for opposite helicities of the ionizing pulse) that is sensitive to the carrier-envelope phase, ellipticity, peak intensity I, and temporal duration of the pulse. For single ionization of He by two oppositely circularly polarized, time-delayed attosecond pulses we predict that the photoelectron momentum distributions in the polarization plane have helical vortex structures that are exquisitely sensitive to the time-delay between the pulses, their relative phase, and their handedness. Both of these effects manifest the ability to control the angular distributions of the ionized electrons by means of the attosecond pulse parameters. Our predictions are obtained numerically by solving the six-dimensional two-electron time-dependent Schrödinger equation for the case of elliptically polarized attosecond pulses. They are interpreted analytically by means of perturbation theory analyses of the two ionization processes. This work is supported in part by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Award No. DE-FG03-96ER14646.

  17. Attosecond quantum stroboscope.

    Science.gov (United States)

    Paulus, Gerhard G; Stania, Gernot

    2009-04-14

    Electron disco: A "quantum stroboscope" for capturing the electron motion on a subfemtosecond timescale for a particular class of problems is highlighted. The picture shows a diffraction pattern caused by wave packets obtained by synchronizing attosecond UV pulses to a near-IR field and ionizing rare-gas atoms. PMID:19294685

  18. Photoelectron and UV absorption spectroscopy for determination of electronic configurations of negative molecular ions: Chlorophenols

    Energy Technology Data Exchange (ETDEWEB)

    Tseplin, E.E. [Institute of Molecular and Crystal Physics, Ufa Research Centre, Russian Academy of Sciences, October Prospect 151, Ufa 450075 (Russian Federation)], E-mail: tzeplin@mail.ru; Tseplina, S.N.; Tuimedov, G.M.; Khvostenko, O.G. [Institute of Molecular and Crystal Physics, Ufa Research Centre, Russian Academy of Sciences, October Prospect 151, Ufa 450075 (Russian Federation)

    2009-04-15

    The photoelectron and UV absorption spectra of p-, m-, and o-chlorophenols in the gas phase have been obtained. On the basis of DFT B3LYP/6-311++G(d, p) calculations, the photoelectron bands have been assigned to occupied molecular orbitals. From the TDDFT B3LYP/6-311++G(d, p) calculation results, the UV absorption bands have been assigned to excited singlet states of the molecules under investigation. For each excited state a dominant transition was found. It has been shown that the energies of these singlet transitions correlate with the energy differences between the ground-state molecular orbitals participating in them. Using the UV spectra interpretation, the electronic states of molecular anions detected earlier for the same compounds by means of the resonant electron capture mass-spectrometry have been determined.

  19. Coincidence and covariance data acquisition in photoelectron and -ion spectroscopy. I. Formal theory

    Science.gov (United States)

    Mikosch, Jochen; Patchkovskii, Serguei

    2013-10-01

    We derive a formal theory of noisy Poisson processes with multiple outcomes. We obtain simple, compact expressions for the probability distribution function of arbitrarily complex composite events and its moments. We illustrate the utility of the theory by analyzing properties of coincidence and covariance photoelectron-photoion detection involving single-ionization events. The results and techniques introduced in this work are directly applicable to more general coincidence and covariance experiments, including multiple ionization and multiple-ion fragmentation pathways.

  20. X-ray photoelectron spectroscopy characterization of copper-iron spinel as a catalyst for steam reforming of oxygenated hydrocarbon

    Energy Technology Data Exchange (ETDEWEB)

    Faungnawakij, Kajornsak [National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency, 111 Thailand Science Park, Paholyothin Rd., Klong Luang, Patumthani 12120 (Thailand); Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)], E-mail: kajornsak@nanotec.or.th; Kikuchi, Ryuji; Eguchi, Koichi [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)

    2009-04-15

    Well-crystallized spinel CuFe{sub 2}O{sub 4} in the tetragonal phase is obtained by calcination at 900 deg. C of the cubic CuFe{sub 2}O{sub 4} prepared via a citrate sol-gel method. X-ray photoelectron spectroscopy coupled with Auger electron spectroscopy analysis reveals a high Cu{sup 1+}/Cu{sup 0} ratio of {approx}3/2 with negligible Cu{sup 2+} over the calcined CuFe{sub 2}O{sub 4} subjected to in situ H{sub 2} reduction. The Cu{sup 1+}-rich surface is considered to play a key role on the excellent catalytic performance in steam reforming of dimethyl ether for hydrogen generation.

  1. 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.

  2. Irradiation-induced degradation of PTB7 investigated by valence band and S 2p photoelectron spectroscopy

    Science.gov (United States)

    Darlatt, Erik; Muhsin, Burhan; Roesch, Roland; Lupulescu, Cosmin; Roth, Friedrich; Kolbe, Michael; Gottwald, Alexander; Hoppe, Harald; Richter, Mathias

    2016-08-01

    Monochromatic radiation with known absolute radiant power from an undulator at the electron storage ring Metrology Light Source (MLS) was used to irradiate PTB7 (a thieno[3, 4-b]thiophene-alt-benzodithiophene polymer) thin films at wavelengths (photon energies) of 185 nm (6.70 eV), 220 nm (5.64 eV), 300 nm (4.13 eV), 320 nm (3.88 eV), 356 nm (3.48 eV) and 675 nm (1.84 eV) under ultra-high vacuum conditions for the investigation of radiation-induced degradation effects. The characterization of the thin films is focused at ultraviolet photoelectron spectroscopy (UPS) of valence bands and is complemented by S 2p x-ray photoelectron spectroscopy (S 2p XPS) before and after the irradiation procedure. The radiant exposure was determined for each irradiation by means of photodiodes traceably calibrated to the international system of units SI. The valence band spectra show the strongest changes for the shortest wavelengths and no degradation effect at 356 nm and 675 nm even with the highest radiant exposure applied. In the spectral range where the Sun appears bright on the Earth’s surface, no degradation effects are observed.

  3. X-ray photoelectron spectroscopy study of irradiation-induced amorphizaton of Gd2Ti2O7

    Science.gov (United States)

    Chen, J.; Lian, J.; Wang, L. M.; Ewing, R. C.; Boatner, L. A.

    2001-09-01

    The radiation-induced evolution of the microstructure of Gd2Ti2O7, an important pyrochlore phase in radioactive waste disposal ceramics and a potential solid electrolyte and oxygen gas sensor, has been characterized using transmission electron microscopy and x-ray photoelectron spectroscopy. Following the irradiation of a Gd2Ti2O7 single crystal with 1.5 MeV Xe+ ions at a fluence of 1.7×1014Xe+/cm2, cross-sectional transmission electron microscopy revealed a 300-nm-thick amorphous layer at the specimen surface. X-ray photoelectron spectroscopy analysis of the Ti 2p and O 1s electron binding energy shifts of Gd2Ti2O7 before and after amorphization showed that the main results of ion-irradiation-induced disorder are a decrease in the coordination number of titanium and a transformation of the Gd-O bond. These features resemble those occurring in titanate glass formation, and they have implications for the chemical stability and electronic properties of pyrochlores subjected to displacive radiation damage.

  4. Steering continuum electron dynamics by low-energy attosecond streaking

    Science.gov (United States)

    Geng, Ji-Wei; Xiong, Wei-Hao; Xiao, Xiang-Ru; Gong, Qihuang; Peng, Liang-You

    2016-08-01

    A semiclassical model is developed to understand the electronic dynamics in the low-energy attosecond streaking. Under a relatively strong infrared (IR) pulse, the low-energy part of photoelectrons initialized by a single attosecond pulse (SAP) can either rescatter with the ionic core and induce interferences structures in the momentum spectra of the ionized electrons or be recaptured into the Rydberg states. The Coulomb potential plays essential roles in both the electron rescattering and recapturing processes. We find that by changing the time delay between the SAP and the IR pulse, the photoelectrons yield or the population of the Rydberg states can be effectively controlled. The present study demonstrates a fascinating way to steer the electron motion in the continuum.

  5. 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.

  6. 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.

  7. 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...

  8. 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.

  9. 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.

  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. 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

    2016-02-28

    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 (3)H4 spectral term derived from a U 7sσ(2)5fφ(1)5fδ(1) electron configuration, whereas the ground state of neutral UFO has a (4)H(7/2) spectral term with a U 7sσ(1)5fφ(1)5fδ(1) 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. PMID:26931704

  12. 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

    2016-02-28

    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 (3)H4 spectral term derived from a U 7sσ(2)5fφ(1)5fδ(1) electron configuration, whereas the ground state of neutral UFO has a (4)H(7/2) spectral term with a U 7sσ(1)5fφ(1)5fδ(1) 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.

  13. Surface study of stainless steel electrode deposition from soil electrokinetic (EK) treatment using X-ray photoelectron spectroscopy (XPS)

    Energy Technology Data Exchange (ETDEWEB)

    Embong, Zaidi, E-mail: zaidi@uthm.edu.my [Faculty of Science, Technology and Human Development, Universiti Tun Hussien Onn Malaysia (UTHM) 86400, Parit Raja, Batu, Johor (Malaysia); Research Centre for Soft Soils (RECESS), Office for Research, Innovation, Commercialization and Consultancy Management (ORICC), Universiti Tun Hussien Onn Malaysia UTHM 86400, Parit Raja, Batu, Johor (Malaysia); Johar, Saffuwan [Faculty of Science, Technology and Human Development, Universiti Tun Hussien Onn Malaysia (UTHM) 86400, Parit Raja, Batu, Johor (Malaysia); Tajudin, Saiful Azhar Ahmad [Research Centre for Soft Soils (RECESS), Office for Research, Innovation, Commercialization and Consultancy Management (ORICC), Universiti Tun Hussien Onn Malaysia UTHM 86400, Parit Raja, Batu, Johor (Malaysia); Sahdan, Mohd Zainizan [Microelectronics and Nanotechnology Centre (MiNT-SRC), Office for Research, Innovation, Commercialization and Consultancy Management (ORICC), Universiti Tun Hussien Onn Malaysia UTHM 86400, Parit Raja, Batu, Johor (Malaysia)

    2015-04-29

    Electrokinetic (EK) remediation relies upon application of a low-intensity direct current through the soil between stainless steel electrodes that are divided into a cathode array and an anode array. This mobilizes charged species, causing ions and water to move toward the electrodes. Metal ions and positively charged organic compounds move toward the cathode. Anions such as chloride, fluoride, nitrate, and negatively charged organic compounds move toward the anode. Here, this remediation techniques lead to a formation of a deposition at the both cathode and anode surface that mainly contributed byanion and cation from the remediated soil. In this research, Renggam-Jerangau soil species (HaplicAcrisol + RhodicFerralsol) with a surveymeter reading of 38.0 ± 3.9 μR/hr has been investigation in order to study the mobility of the anion and cation under the influence electric field. Prior to the EK treatment, the elemental composition of the soil and the stainless steel electrode are measured using XRF analyses. Next, the soil sample is remediated at a constant electric potential of 30 V within an hour of treatment period. A surface study for the deposition layer of the cathode and anode using X-ray Photoelectron spectroscopy (XPS) revealed that a narrow photoelectron signal from oxygen O 1s, carbon, C 1s silica, Si 2p, aluminium, Al 2p and chromium, Cr 2p exhibited on the electrode surface and indicate that a different in photoelectron intensity for each element on both electrode surface. In this paper, the mechanism of Si{sup 2+} and Al{sup 2+} cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.

  14. Surface study of stainless steel electrode deposition from soil electrokinetic (EK) treatment using X-ray photoelectron spectroscopy (XPS)

    Science.gov (United States)

    Embong, Zaidi; Johar, Saffuwan; Tajudin, Saiful Azhar Ahmad; Sahdan, Mohd Zainizan

    2015-04-01

    Electrokinetic (EK) remediation relies upon application of a low-intensity direct current through the soil between stainless steel electrodes that are divided into a cathode array and an anode array. This mobilizes charged species, causing ions and water to move toward the electrodes. Metal ions and positively charged organic compounds move toward the cathode. Anions such as chloride, fluoride, nitrate, and negatively charged organic compounds move toward the anode. Here, this remediation techniques lead to a formation of a deposition at the both cathode and anode surface that mainly contributed byanion and cation from the remediated soil. In this research, Renggam-Jerangau soil species (HaplicAcrisol + RhodicFerralsol) with a surveymeter reading of 38.0 ± 3.9 μR/hr has been investigation in order to study the mobility of the anion and cation under the influence electric field. Prior to the EK treatment, the elemental composition of the soil and the stainless steel electrode are measured using XRF analyses. Next, the soil sample is remediated at a constant electric potential of 30 V within an hour of treatment period. A surface study for the deposition layer of the cathode and anode using X-ray Photoelectron spectroscopy (XPS) revealed that a narrow photoelectron signal from oxygen O 1s, carbon, C 1s silica, Si 2p, aluminium, Al 2p and chromium, Cr 2p exhibited on the electrode surface and indicate that a different in photoelectron intensity for each element on both electrode surface. In this paper, the mechanism of Si2+ and Al2+ cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.

  15. 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.

  16. HeI photoelectron spectroscopy of the isoproxy (CH 3) 2CHO radical

    Science.gov (United States)

    Zheng, Sun; Shijun, Zheng; Lingpeng, Meng; Dianxun, Wang

    2003-02-01

    A continuous (CH 3) 2CHO radical beam is generated by pyrolysis of (CH 3) 2CHONO at 145(±0.5) °C. The HeI photoelectron spectrum of (CH 3) 2CHO is recorded in situ. The IP of (CH 3) 2CHO is 9.70 eV and the spectrum of the X3A″ state of (CH 3) 2CHO + exhibits a vibrational progression of 1200±60 cm-1. The removal of an electron from the highest occupied molecular orbital 11a ', which corresponds to ionization process of ( CH3) 2CHO+( 1A')←( CH3) 2CHO( X2A') , leads to a very sharp peak at 10.21 eV. This study provides new experimental and theoretical ionization energies of several ionic states of (CH 3) 2CHO.

  17. X-ray photoelectron spectroscopy of the uranium/oxygen system: Part 13

    International Nuclear Information System (INIS)

    The reaction between commercial H2 and uranium metal leads to the formation of UO2 due to traces of water vapour or oxygen. When extremely pure H2 is used uranium hydride may be formed but, even with 99.9999% H2, uranium dioxide forms preferentially. The present work identifies the presence of UH3 in the X-ray photoelectron spectrum of a uranium sample which has been exposed to ∼ 5 mbar H2 at ∼ 2000C for 1 hour. This spectrum indicates that the hydride possesses a high degree of covalency, since the oxidation state of uranium in UH3 appears to be ∼ 1.4. (U.K.)

  18. First stages of surface steel nitriding: X-ray photoelectron spectroscopy and electrical measurements

    Science.gov (United States)

    Flori, M.; Gruzza, B.; Bideux, L.; Monier, G.; Robert-Goumet, C.; Benamara, Z.

    2009-08-01

    Quantitative and qualitative analysis techniques were employed to study the first stages of ultra-high vacuum plasma nitriding of the 42CrMo4 steel. At constant treatment temperature, maintained for all samples at about 360 °C, we have established the influence of treatment time on the chemical composition, thickness and electrical properties of the nitrided layer. In this purpose it was used a stacking atomic layer model describing the sample surface, which takes into account the attenuation depth of photoelectrons by the atomic monolayers. So, we have found that after 2 h of nitriding in laboratory conditions, 70% of the nitrided layer was composed of iron oxide. Also, I- V measurements indicate an influence of the nitride overlayer with increasing treatment time.

  19. First stages of surface steel nitriding: X-ray photoelectron spectroscopy and electrical measurements

    Energy Technology Data Exchange (ETDEWEB)

    Flori, M., E-mail: flori.mihaela@fih.upt.ro [' Politehnica' University of Timisoara, Faculty of Engineering of Hunedoara, 331128 Hunedoara (Romania); Gruzza, B.; Bideux, L.; Monier, G.; Robert-Goumet, C. [LASMEA, UMR CNRS 6602, Blaise Pascal University, 63177 Aubiere Cedex (France); Benamara, Z. [Laboratoire de Microelectronique Appliquee, Sidi Bel Abbes University, 22000 Sidi Bel Abbes (Algeria)

    2009-08-30

    Quantitative and qualitative analysis techniques were employed to study the first stages of ultra-high vacuum plasma nitriding of the 42CrMo4 steel. At constant treatment temperature, maintained for all samples at about 360 deg. C, we have established the influence of treatment time on the chemical composition, thickness and electrical properties of the nitrided layer. In this purpose it was used a stacking atomic layer model describing the sample surface, which takes into account the attenuation depth of photoelectrons by the atomic monolayers. So, we have found that after 2 h of nitriding in laboratory conditions, 70% of the nitrided layer was composed of iron oxide. Also, I-V measurements indicate an influence of the nitride overlayer with increasing treatment time.

  20. Lineshapes, shifts and broadenings in dynamical X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    We describe in detail a model that can be used to estimate the X-ray photoelectron spectroscopic data of surfaces when a time varying bias or a modulation of the electrical properties of the surface is applied by external stimulation, in the presence of a neutralizing electron beam. Using the model and spectra recorded under periodic sample bias modulation, certain electronic properties related to charging dynamics of the surface can be estimated. The resulting technique is a non-contact impedance measurement technique with chemical specificity. Typical behavior of spectra under a square wave bias is given. Alternative modulation schemes are investigated, including small-signal square wave modulation, sinusoidal modulation and modulation of sample resistivity under fixed bias.

  1. Anion Photoelectron Spectroscopy of Mo-V Binary Transition Metal Suboxide Clusters

    Science.gov (United States)

    Jarrold, Caroline Chick; Mann, Jennifer E.; Waller, Sarah E.; Rothgeb, David W.

    2010-06-01

    Vibrationally-resolved photoelectron spectra of molybdenum vanadium oxo cluster anions with 2 to 5 oxygen atoms and measured using 2.33 eV, 3.49 eV and 4.66 eV photon energies generally exhibit broad and overlapping electronic states. The adiabatic electron affinities for the series are 1.68(3) eV, 1.73(3) eV, 2.89(1) eV, and 3.4(1) eV for two through five oxygen atoms, respectively. Vibrational structure observed in the spectra can be reconciled with the lowest energy structural isomers of the anions determined in DFT calculations: The lowest energy isomers have low symmetry, with the Mo center in a higher oxidation state than the V center, and high spin states are favored.

  2. Forward scattering in hard X-ray photoelectron spectroscopy: Structural investigation of buried Mn–Ga films

    Energy Technology Data Exchange (ETDEWEB)

    ViolBarbosa, Carlos E., E-mail: carlos.barbosa@cpfs.mpg.de; Ouardi, Siham; Fecher, Gerhard H., E-mail: fecher@cpfs.mpg.de; Felser, Claudia [Max-Planck-Institut für Chemische Physik fester Stoffe, 01187 Dresden (Germany); Kubota, Takahide; Mizukami, Shigemi; Miyazaki, Terunobu [WPI Advanced Institute for Materials Research Tohoku University, Sendai 980-8577 (Japan); Ikenaga, Eiji [Japan Synchrotron Radiation Research Institute, SPring-8, Sayo, Hyogo 679-5198 (Japan)

    2015-02-02

    X-ray photoelectron diffraction (XPD) in combination with hard X-ray photoelectron spectroscopy (HAXPES) has been used to study the structure of buried layers in thin multilayer films. A detailed layer-by-layer investigation was performed using the element-specific, local-probe character of XPD. In the present work, angular-resolved HAXPES at a photon energy of 7.94 keV photon energy was used to investigate a Cr/Mn{sub 62}Ga{sub 38}/Mg/MgO multilayer system. Differences in the angular distributions of electrons emitted from Mn and Ga atoms revealed that the structure of Mn{sub 62}Ga{sub 38} changes from L1{sub 0} towards D0{sub 22} for increasing annealing temperatures. A c/a ratio of 1.81 ± 0.06 was determined for the buried Mn{sub 62}Ga{sub 38} layer in a D0{sub 22} structure from the XPD experiment. The improvement of the structural order of the Mn{sub 62}Ga{sub 38} layer is accompanied by an improvement of the structure of the overlying MgO layer.

  3. Electronic structure at the perylene-tetracarboxylic acid dianhydride/Ag(111) interface studied with two-photon photoelectron spectroscopy.

    Science.gov (United States)

    Sachs, Sönke; Schwalb, Christian H; Marks, Manuel; Schöll, Achim; Reinert, Friedrich; Umbach, Eberhard; Höfer, Ulrich

    2009-10-14

    The electronic structure of the prototype metal/organic contact 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) on a Ag(111)-surface has been investigated using time- and angle-resolved two-photon photoelectron spectroscopy (2PPE). Our analysis addresses particularly the nature of the interface state (IS) emerging at the interface due to the substrate-adsorbate interaction [C. H. Schwalb, S. Sachs, M. Marks et al., Phys. Rev. Lett. 101, 146801 (2008)]. Its free-electron-like dispersion and a possible backfolding at the surface Brillouin zone boundaries are discussed. Time-resolved pump-probe experiments reveal the inelastic electron lifetime along the dispersion parabola and show its decrease for increasing parallel momentum. The temperature dependence of the peak linewidth indicates a coupling of the IS to molecular vibrations. Moreover, additional aspects are addressed, such as the determination of the electron attenuation length of photoelectrons for low kinetic energy originating from the IS and the work function change of the sample upon PTCDA adsorption with very high energy resolution. PMID:19831458

  4. Forward scattering in hard X-ray photoelectron spectroscopy: Structural investigation of buried Mn–Ga films

    International Nuclear Information System (INIS)

    X-ray photoelectron diffraction (XPD) in combination with hard X-ray photoelectron spectroscopy (HAXPES) has been used to study the structure of buried layers in thin multilayer films. A detailed layer-by-layer investigation was performed using the element-specific, local-probe character of XPD. In the present work, angular-resolved HAXPES at a photon energy of 7.94 keV photon energy was used to investigate a Cr/Mn62Ga38/Mg/MgO multilayer system. Differences in the angular distributions of electrons emitted from Mn and Ga atoms revealed that the structure of Mn62Ga38 changes from L10 towards D022 for increasing annealing temperatures. A c/a ratio of 1.81 ± 0.06 was determined for the buried Mn62Ga38 layer in a D022 structure from the XPD experiment. The improvement of the structural order of the Mn62Ga38 layer is accompanied by an improvement of the structure of the overlying MgO layer

  5. Direct Experimental Observation of the Low Ionization Potentials of Guanine in Free Oligonucleotides by Using Photoelectron Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Xin; Wang, Xue B.; Vorpagel, Erich R.; Wang, Lai S.

    2004-12-21

    Photodetachment photoelectron spectroscopy is used to probe the electronic structure of mono-, di-, and trinucleotide anions in the gas phase. A weak and well defined threshold band was observed in the photoelectron spectrum of 2' -deoxyguanosine 5' -mono-phosphate at a much lower ionization energy than the other three mononucleotides. Density function theory calculations revealed that this unique spectral feature is caused by electron-detachment from a ? orbital of the guanine base on 2? ?deoxyguanosine 5? ?monophosphate, whereas the lowest ionization channel for the other three mononucleotides takes place from the phosphate group. This low-energy feature was shown to be a ?fingerprint? in all the spectra of dinucleotides and trinucleotides that contain the guanine base. The current experiment provides direct spectroscopic evidence that the guanine base is the site with the lowest ionization potential in oligonucleotides and DNA and is consistent with the fact that guanine is most susceptible to oxidation to give the guanine cation in DNA damage.

  6. Difluorocarbene studied with threshold photoelectron spectroscopy (TPES): measurement of the first adiabatic ionization energy (AIE) of CF(2).

    Science.gov (United States)

    Innocenti, Fabrizio; Eypper, Marie; Lee, Edmond P F; Stranges, Stefano; Mok, Daniel K W; Chau, Foo-tim; King, George C; Dyke, John M

    2008-01-01

    The first photoelectron band of difluorocarbene CF(2), has been studied by threshold photoelectron (TPE) spectroscopy. CF(2) was prepared by microwave discharge of a flowing mixture of hexafluoropropene, C(3)F(6), and argon. A vibrationally resolved band was observed in which at least twenty-two components were observed. In the first PE band of CF(2), the adiabatic ionization energy differs significantly from the vertical ionization energy because, for the ionization CF(2) (+) (X(2)A(1))+e(-) CF(2) (X(1)A(1)), there is an increase in the FCF bond angle (by approximately 20 degrees ) and a decrease in the C--F bond length (by approximately 0.7 A). The adiabatic component was not observed in the experimental TPE spectrum. However, on comparing this spectrum with an ab initio/Franck-Condon simulation of this band, using results from high-level ab initio calculations, the structure associated with the vibrational components could be assigned. This led to alignment of the experimental TPE spectrum and the computed Franck-Condon envelope, and a determination of the first adiabatic ionization energy of CF(2) as (11.362+/-0.005) eV. From the assignment of the vibrational structure, values were obtained for the harmonic and fundamental frequencies of the symmetric stretching mode (nu(1)') and symmetric bending mode (nu(2)') in CF(2) (+) (X(2)A(1)). PMID:19006171

  7. Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission

    International Nuclear Information System (INIS)

    We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine, and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ∼1.7 eV, values that are lower than the RCB of the uncomplexed PtCl62− dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl62− ⋅ thymine and PtCl62− ⋅ adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)42− ⋅ nucleobase complexes [A. Sen et al., J. Phys. Chem. B 119, 11626 (2015)]. The observation of delayed electron emission bands in the PtCl62− ⋅ nucleobase spectra obtained in this work, as for the previously studied Pt(CN)42− ⋅ nucleobase complexes, is attributed to one-photon excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase decays over a time scale long enough to allow autodetachment

  8. Photoelectron Spectroscopy of Hexachloroplatinate-Nucleobase Complexes: Nucleobase Excited State Decay Observed via Delayed Electron Emission

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Ananya; Matthews, Edward M.; Hou, Gao-Lei; Wang, Xue B.; Dessent, Caroline

    2015-11-14

    We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ~1.7 eV, values that are lower than the RCB of the uncomplexed PtCl6 2- dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl6 2-∙thymine and PtCl6 2-∙adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)4 2-∙nucleobase complexes [Sen et al, J. Phys. Chem. B, 119, 11626, 2015]. The observation of delayed electron emission bands in the PtCl6 2-∙nucleobase spectra obtained in this work, as for the previously studied Pt(CN)4 2-∙nucleobase complexes, is attributed to onephoton excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase decays over a timescale long enough to allow autodetachment.

  9. Elemental content of enamel and dentin after bleaching of teeth (a comparative study between laser-induced breakdown spectroscopy and x-ray photoelectron spectroscopy)

    International Nuclear Information System (INIS)

    The elemental content of the superficial and inner enamel as well as that of dentin was analyzed using laser-induced breakdown spectroscopy (LIBS) and x-ray photoelectron spectroscopy (XPS) of bleached and unbleached tooth specimens. It is thus clear from the spectral analysis using both the LIBS and XPS technique that elemental changes (though insignificant within the scopes of this study) of variable intensities do occur on the surface of the enamel and extend deeper to reach dentin. The results of the LIBS revealed a slight reduction in the calcium levels in the bleached compared to the control specimens in all the different bleaching groups and in both enamel and dentin. The good correlation found between the LIBS and XPS results demonstrates the possibility of LIBS technique for detection of minor loss in calcium and phosphorus in enamel and dentin.

  10. Elemental content of enamel and dentin after bleaching of teeth (a comparative study between laser-induced breakdown spectroscopy and x-ray photoelectron spectroscopy)

    Energy Technology Data Exchange (ETDEWEB)

    Imam, H. [National Institute of Laser Enhanced Sciences, NILES, Cairo University, Giza (Egypt); Ahmed, Doaa [Department of Restorative Sciences, Faculty of Dentistry, Alexandria University, Alexandria (Egypt); Eldakrouri, Ashraf [National Institute of Laser Enhanced Sciences, NILES, Cairo University, Giza (Egypt); Department of Optometry and Vision Science, College of Applied Medical Science, King Saud University, Riyadh (Saudi Arabia)

    2013-06-21

    The elemental content of the superficial and inner enamel as well as that of dentin was analyzed using laser-induced breakdown spectroscopy (LIBS) and x-ray photoelectron spectroscopy (XPS) of bleached and unbleached tooth specimens. It is thus clear from the spectral analysis using both the LIBS and XPS technique that elemental changes (though insignificant within the scopes of this study) of variable intensities do occur on the surface of the enamel and extend deeper to reach dentin. The results of the LIBS revealed a slight reduction in the calcium levels in the bleached compared to the control specimens in all the different bleaching groups and in both enamel and dentin. The good correlation found between the LIBS and XPS results demonstrates the possibility of LIBS technique for detection of minor loss in calcium and phosphorus in enamel and dentin.

  11. Electronic structure of MoSe2, MoS2, and WSe2. I. Band-structure calculations and photoelectron spectroscopy

    OpenAIRE

    Coehoorn, R.; Haas, C.; Dijkstra, J.; Flipse, C.J.F.; de Groot, R. A.; Wold, A.

    1987-01-01

    The band structures of the semiconducting layered compounds MoSe2, MoS2, and WSe2 have been calculated self-consistently with the augmented-spherical-wave method. Angle-resolved photoelectron spectroscopy of MoSe2 using He I, He II, and Ne I radiation, and photon-energy-dependent normal-emission photoelectron spectroscopy using synchrotron radiation, show that the calculational results give a good description of the valence-band structure. At about 1 eV below the top of the valence band a dis...

  12. X-ray photoelectron spectroscopy of pulsed laser deposited Pb(Zr,Ti)O{sub 3-{delta}}

    Energy Technology Data Exchange (ETDEWEB)

    Dragoi, Cristina; Gheorghe, Nicoleta G.; Lungu, George A.; Trupina, Lucian; Ibanescu, Andra G.; Teodorescu, Cristian M. [National Institute of Materials Physics, Magurele-Ilfov (Romania)

    2012-06-15

    High quality pulsed laser deposited lead zirconate titanate (PZT) films are obtained by pulsed laser deposition on SrRuO{sub 3}(111) single crystal layers and characterized by X-ray photoelectron spectroscopy (XPS), to determine the surface composition. It is found that a minor amount of Pb forms PbO{sub 2} at the surface and also some Pb is included into the contamination layer, in form of a Pb(CO{sub 3}){sub 2} layer of about 1 nm thickness, occupying about one quarter of the PZT surface. The stoichiometry of the outermost 4-5 nm layers yielded as PbZr{sub 0.25}Ti{sub 0.80}O{sub 2.5}, which suggest the formation of an oxygen depleted, Brownmillerite-like layer at the surface, of at least 5 nm thickness. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Adsorption of ethylene on Sn and In terminated Si(001) surface studied by photoelectron spectroscopy and scanning tunneling microscopy.

    Science.gov (United States)

    Zimmermann, Petr; Sobotík, Pavel; Kocán, Pavel; Ošt'ádal, Ivan; Vorokhta, Mykhailo; Acres, Robert George; Matolín, Vladimír

    2016-09-01

    Interaction of ethylene (C2H4) with Si(001)-Sn-2 × 2 and Si(001)-In-2 × 2 at room temperature has been studied using core level (C 1s) X-ray photoelectron spectroscopy with synchrotron radiation and scanning tunneling microscopy. Sn and In form similar dimer chains on Si(001)2 × 1, but exhibit different interaction with ethylene. While ethylene adsorbs on top of Sn dimers of the Si(001)-Sn-2 × 2 surface, the Si(001)-In-2 × 2 surface turned out to be inert. Furthermore, the reactivity of the Sn terminated surface is found to be considerably decreased in comparison with Si(001)2 × 1. According to the proposed adsorption model ethylene bonds to Sn dimers via [2 + 2] cycloaddition by interacting with their π dimer bonds. In contrast, indium dimers do not contain π bonds, which renders the In terminated Si(001) surface inert for ethylene adsorption.

  14. Structure of Se-rich As-Se glasses by high-resolution x-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    To establish the validity of various proposed structural models, we have investigated the structure of the binary AsxSe100-x chalcogenide glass family (x≤40) by high-resolution x-ray photoelectron spectroscopy. From the composition dependence of the valence band, the contributions to the density of states from the 4p lone pair electrons of Se and the 4p bonding states and 4s electrons of Se and As are identified in the top part of the band. The analysis of Se 3d and As 3d core-level spectra supports the so-called chain crossing model for the atomic structure of Se-rich AsxSe100-x bulk glasses. The results also indicate small deviations (∼3-8%) from this model, especially for glass compositions with short Se chains (2540Se60 and of Se-Se-Se fragments in a glass with composition x=30 is established

  15. Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

    International Nuclear Information System (INIS)

    The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found (p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength

  16. Analysis of X-Ray Photoelectron Spectroscopy of Polymethyl Methacrylate Etched by a KrF Excimer Laser

    Institute of Scientific and Technical Information of China (English)

    ZHU Xiao-Li; LIU Shi-Bing; CHEN Tao; JIANG Yi-Jian; ZUO Tie-Chuan

    2005-01-01

    @@ The C1s and O 1s electrons in polymethyl methacrylate etched by different incident laser intensities are analysed by x-ray photoelectron spectroscopy. The results show that when the incident laser fluence increases gradually,the percentage of carbon atoms in C-C bonds decreases while the one in carbonyl group (C=O) and alkoxy group (C-O) increases, and the percentage of oxygen atoms in C=O bonds increases while the one in C-O bonds decreases. Based on the analysis of the chemical structure, the energy level transition, energy diversion, and dissociation of bonds are theoretically examined, which is consistent with the experimental results.

  17. Employing X-ray Photoelectron Spectroscopy for Determining Layer Homogeneity in Mixed Polar Self-Assembled Monolayers

    Science.gov (United States)

    2016-01-01

    Self-assembled monolayers (SAMs) containing embedded dipolar groups offer the particular advantage of changing the electronic properties of a surface without affecting the SAM–ambient interface. Here we show that such systems can also be used for continuously tuning metal work functions by growing mixed monolayers consisting of molecules with different orientations of the embedded dipolar groups. To avoid injection hot-spots when using the SAM-modified electrodes in devices, a homogeneous mixing of the two components is crucial. We show that a combination of high-resolution X-ray photoelectron spectroscopy with state-of-the-art simulations is an ideal tool for probing the electrostatic homogeneity of the layers and thus for determining phase separation processes in polar adsorbate assemblies down to inhomogeneities at the molecular level. PMID:27429041

  18. Austenitic and duplex stainless steels in simulated physiological solution characterized by electrochemical and X-ray photoelectron spectroscopy studies.

    Science.gov (United States)

    Kocijan, Aleksandra; Conradi, Marjetka; Schön, Peter M

    2012-04-01

    A study of oxide layers grown on 2205 duplex stainless steel (DSS) and AISI 316L austenitic stainless steel in simulated physiological solution is presented here in order to establish the possibility of replacement of AISI 316 L with 2205 DSS in biomedical applications. The results of the potentiodynamic measurements show that the extent of the passive range significantly increased for DSS 2205 compared to AISI 316L stainless steel. Cyclic voltammetry was used to investigate electrochemical processes taking place on the steel surfaces. Oxide layers formed by electrochemical oxidation at different oxidation potentials were studied by X-ray photoelectron spectroscopy, and their compositions were analyzed as a function of depth. The main constituents on both the investigated materials were Cr- and Fe-oxides. Atomic force microscopy topography studies revealed the higher corrosion resistance of the DSS 2205 compared to the AISI 316L under the chosen experimental conditions. PMID:22331841

  19. Band alignment of TiO2/FTO interface determined by X-ray photoelectron spectroscopy: Effect of annealing

    International Nuclear Information System (INIS)

    The energy band alignment between pulsed-laser-deposited TiO2 and FTO was firstly characterized using high-resolution X-ray photoelectron spectroscopy. A valence band offset (VBO) of 0.61 eV and a conduction band offset (CBO) of 0.29 eV were obtained across the TiO2/FTO heterointerface. With annealing process, the VBO and CBO across the heterointerface were found to be -0.16 eV and 1.06 eV, respectively, with the alignment transforming from type-I to type-II. The difference in the band alignment is believed to be dominated by the core level down-shift of the FTO substrate, which is a result of the oxidation of Sn. Current-voltage test has verified that the band alignment has a significant effect on the current transport of the heterojunction

  20. Band alignment of HfO2/AlN heterojunction investigated by X-ray photoelectron spectroscopy

    Science.gov (United States)

    Ye, Gang; Wang, Hong; Ji, Rong

    2016-04-01

    The band alignment between AlN and Atomic-Layer-Deposited (ALD) HfO2 was determined by X-ray photoelectron spectroscopy (XPS). The shift of Al 2p core-levels to lower binding energies with the decrease of take-off angles θ indicated upward band bending occurred at the AlN surface. Based on the angle-resolved XPS measurements combined with numerical calculations, valence band discontinuity ΔEV of 0.4 ± 0.2 eV at HfO2/AlN interface was determined by taking AlN surface band bending into account. By taking the band gap of HfO2 and AlN as 5.8 eV and 6.2 eV, respectively, a type-II band line-up was found between HfO2 and AlN.

  1. Electronic structure of Al- and Ga-doped ZnO films studied by hard X-ray photoelectron spectroscopy

    Directory of Open Access Journals (Sweden)

    M. Gabás

    2014-01-01

    Full Text Available Al- and Ga-doped sputtered ZnO films (AZO, GZO are semiconducting and metallic, respectively, despite the same electronic valence structure of the dopants. Using hard X-ray photoelectron spectroscopy we observe that both dopants induce a band in the electronic structure near the Fermi level, accompanied by a narrowing of the Zn 3d/O 2p gap in the valence band and, in the case of GZO, a substantial shift in the Zn 3d. Ga occupies substitutional sites, whereas Al dopants are in both substitutional and interstitial sites. The latter could induce O and Zn defects, which act as acceptors explaining the semiconducting character of AZO and the lack of variation in the optical gap. By contrast, mainly substitutional doping is consistent with the metallic-like behavior of GZO.

  2. Electronic structure of Al- and Ga-doped ZnO films studied by hard X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Gabás, M.; Ramos Barrado, José R. [Lab. de Materiales and Superficies, Dpto. de Física Aplicada I, Universidad de Málaga, 29071 Málaga (Spain); Torelli, P. [Laboratorio TASC, IOM-CNR, S.S. 14 km 163.5, Basovizza, I-34149 Trieste (Italy); Barrett, N. T. [CEA, DSM/IRAMIS/SPCSI, F-91191 Gif-sur-Yvette Cedex (France); Sacchi, M. [Synchrotron SOLEIL, BP 48, 91192 Gif-sur-Yvette, France and Institut des NanoSciences de Paris, UPMC Paris 06, CNRS UMR 7588, 4 Place Jussieu, 75005 Paris (France)

    2014-01-01

    Al- and Ga-doped sputtered ZnO films (AZO, GZO) are semiconducting and metallic, respectively, despite the same electronic valence structure of the dopants. Using hard X-ray photoelectron spectroscopy we observe that both dopants induce a band in the electronic structure near the Fermi level, accompanied by a narrowing of the Zn 3d/O 2p gap in the valence band and, in the case of GZO, a substantial shift in the Zn 3d. Ga occupies substitutional sites, whereas Al dopants are in both substitutional and interstitial sites. The latter could induce O and Zn defects, which act as acceptors explaining the semiconducting character of AZO and the lack of variation in the optical gap. By contrast, mainly substitutional doping is consistent with the metallic-like behavior of GZO.

  3. Band alignment of TiO2/FTO interface determined by X-ray photoelectron spectroscopy: Effect of annealing

    Directory of Open Access Journals (Sweden)

    Haibo Fan

    2016-01-01

    Full Text Available The energy band alignment between pulsed-laser-deposited TiO2 and FTO was firstly characterized using high-resolution X-ray photoelectron spectroscopy. A valence band offset (VBO of 0.61 eV and a conduction band offset (CBO of 0.29 eV were obtained across the TiO2/FTO heterointerface. With annealing process, the VBO and CBO across the heterointerface were found to be -0.16 eV and 1.06 eV, respectively, with the alignment transforming from type-I to type-II. The difference in the band alignment is believed to be dominated by the core level down-shift of the FTO substrate, which is a result of the oxidation of Sn. Current-voltage test has verified that the band alignment has a significant effect on the current transport of the heterojunction.

  4. X-ray photoelectron spectroscopy as a probe of the interaction between rhodium acetate and ionic liquids

    Science.gov (United States)

    Men, Shuang; Jiang, Jing

    2016-02-01

    X-ray photoelectron spectroscopy (XPS) is used as a probe of the interaction between rhodium acetate ([Rh2(OAc)4]) and ionic liquids. Due to the impact of the anion of ionic liquids on the electronic environment of the rhodium centre, the measured Rh 3d binding energies of [Rh2(OAc)4] dissolved in a series of ionic liquids were found to decrease along with the increasing of the basicity of anions. The reduction of Rh(II) to Rh(0) in 1-octyl-3methylimidazolium acetate ([C8C1Im][OAc]) under UHV condition was monitored by XPS. The intensity of the new formed metallic Rh(0) peak was found increased along with time. The surface enrichment of the new formed Rh(0) species in the system was also concluded.

  5. Sidewall passivation layer thickness and composition profiles of etched silicon patterns from angle resolved x-ray photoelectron spectroscopy analysis

    Energy Technology Data Exchange (ETDEWEB)

    Haass, Moritz; Darnon, Maxime; Joubert, Olivier [CNRS/UJF-Grenoble1/CEA LTM, 17 avenue des Martyrs, 38054 Grenoble cedex 9 (France)

    2012-06-15

    In this study, we present a technique to analyze side wall passivation layers formed on silicon sidewalls after plasma processing. The thickness and chemical composition are derived from angle resolved x-ray photoelectron spectroscopy analyses. It is a non-destructive, quasi in situ method to determine profiles of the thickness and the chemical composition of passivation layers in trenches up to an aspect ratio of about 3. The performance of this technique to quantify the passivation layer thickness is compared to a standard technique using secondary electron microscopy images with respect to two different samples and is found to be at least equivalent. The possible uncertainties and limitations of this technique are discussed as well.

  6. Employing X-ray Photoelectron Spectroscopy for Determining Layer Homogeneity in Mixed Polar Self-Assembled Monolayers.

    Science.gov (United States)

    Hehn, Iris; Schuster, Swen; Wächter, Tobias; Abu-Husein, Tarek; Terfort, Andreas; Zharnikov, Michael; Zojer, Egbert

    2016-08-01

    Self-assembled monolayers (SAMs) containing embedded dipolar groups offer the particular advantage of changing the electronic properties of a surface without affecting the SAM-ambient interface. Here we show that such systems can also be used for continuously tuning metal work functions by growing mixed monolayers consisting of molecules with different orientations of the embedded dipolar groups. To avoid injection hot-spots when using the SAM-modified electrodes in devices, a homogeneous mixing of the two components is crucial. We show that a combination of high-resolution X-ray photoelectron spectroscopy with state-of-the-art simulations is an ideal tool for probing the electrostatic homogeneity of the layers and thus for determining phase separation processes in polar adsorbate assemblies down to inhomogeneities at the molecular level. PMID:27429041

  7. Surface Oxidative Characterization of LPE HgCdTe Epilayer Studied by X-ray Photoelectron Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    李毅; 易新建; 蔡丽萍

    2000-01-01

    The surface oxidative characterization of Liquid Phase Epitaxy (LPE) HgCdTe epilayer has been studied by X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). HgCdTe surface is exposed by various processing steps. After measurement and analysis, we draw a conclusion that the native oxide film can be reduced and removed by the solution of lactic acid in ethylene glycol after being etched by bromine in absolute ethyl alcohol. The result shows the main optical and electrical parameters have not been changed after the treatment and the processing method given here can successfully remove the native oxides of LPE HgCdTe epilayer to obtain a clean surface. It indicates that the pre-treatment before HgCdTe surface passivation can affect the passivant/HgCdTe interface properties.

  8. Band alignment of TiO{sub 2}/FTO interface determined by X-ray photoelectron spectroscopy: Effect of annealing

    Energy Technology Data Exchange (ETDEWEB)

    Fan, Haibo, E-mail: hbfan@nwu.edu.cn, E-mail: liusz@snnu.edu.cn [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); School of Physics, Northwest University, Xi’an 710069 (China); Yang, Zhou; Ren, Xianpei; Gao, Fei [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); Yin, Mingli [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); School of Science, Xi’an Technological University, Xi’an, Shaanxi 710062 (China); Liu, Shengzhong, E-mail: hbfan@nwu.edu.cn, E-mail: liusz@snnu.edu.cn [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); Dalian Institute of Chemical Physics, Dalian National Laboratory for Clean Energy, Chinese Academy of Sciences, Dalian, 116023 (China)

    2016-01-15

    The energy band alignment between pulsed-laser-deposited TiO{sub 2} and FTO was firstly characterized using high-resolution X-ray photoelectron spectroscopy. A valence band offset (VBO) of 0.61 eV and a conduction band offset (CBO) of 0.29 eV were obtained across the TiO{sub 2}/FTO heterointerface. With annealing process, the VBO and CBO across the heterointerface were found to be -0.16 eV and 1.06 eV, respectively, with the alignment transforming from type-I to type-II. The difference in the band alignment is believed to be dominated by the core level down-shift of the FTO substrate, which is a result of the oxidation of Sn. Current-voltage test has verified that the band alignment has a significant effect on the current transport of the heterojunction.

  9. X-ray Photoelectron Spectroscopy Study of Disordering in Gd2(Ti1-xZrx)2O7 Pyrochlores

    Science.gov (United States)

    Chen, J.; Lian, J.; Wang, L. M.; Ewing, R. C.; Wang, R. G.; Pan, W.

    2002-03-01

    The dramatic increases in ionic conductivity in Gd2(Ti1-xZrx)2O7 solid solution are related to disordering on the cation and anion lattices. Disordering in Gd2(Ti1-xZrx)2O7 was characterized using x-ray photoelectron spectroscopy (XPS). As Zr substitutes for Ti in Gd2Ti2O7 to form Gd2(Ti1-xZrx)2O7 (0.25

  10. Further insights into the photodegradation of poly(3-hexylthiophene) by means of X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Manceau, Matthieu [Clermont Universite, Universite Blaise Pascal, LPMM, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6505, LPMM, F-63177 Aubiere (France); CEA-Grenoble DRT/LITEN/DTS/LCS, INES-RDI, Laboratoire des Composants Solaires, 50 avenue du Lac Leman BP 332, 73377 Le Bourget Du Lac (France); Gaume, Julien; Rivaton, Agnes [Clermont Universite, Universite Blaise Pascal, LPMM, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6505, LPMM, F-63177 Aubiere (France); Gardette, Jean-Luc, E-mail: luc.gardette@univ-bpclermont.f [Clermont Universite, Universite Blaise Pascal, LPMM, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6505, LPMM, F-63177 Aubiere (France); Monier, Guillaume; Bideux, Luc [Clermont Universite, Universite Blaise Pascal, LASMEA, BP 10448, F-63000 Clermont-Ferrand (France); CNRS, UMR 6602, LASMEA, F-63177 Aubiere (France)

    2010-09-30

    X-ray photoelectron spectroscopy (XPS) was used to monitor the chemical changes resulting from irradiation (> 295 nm) in air of poly(3-hexylthiophene) (P3HT), polymer which is a good candidate for photovoltaic applications. The formation of carbonyl moieties and the stepwise oxidation of sulphur atoms were characterised. The oxidation and the cleavage of the hexyl side-chain was monitored. It is also shown that sulfur was first converted into sulfoxides, then into sulfones and finally into sulfinate esters. The formation of these ultimate degradation products provoked a disruption of {pi}-conjugation in P3HT, leading to diminished visible absorbance. Based on these results, a mechanism of P3HT photooxidation is proposed. Comparison of XPS data with previously reported infrared and UV-visible spectral analysis showed that the information provided by these techniques is completely consistent.

  11. X-ray photoelectron spectroscopy analysis of cleaning procedures for synchrotron radiation beamline materials at the Advanced Photon Source

    International Nuclear Information System (INIS)

    TZM (a high temperature molybdenum alloy), machinable tungsten, and 304 stainless steel were cleaned using environmentally safe, commercially available cleaning detergents. The surface cleanliness was evaluated by x-ray photoelectron spectroscopy (XPS). It was found that a simple alkaline detergent is very effective at removal of organic and inorganic surface contaminants or foreign particle residue from machining processes. The detergent can be used with ultrasonic agitation at 140 F to clean the TZM molybdenum, machinable tungsten, and 304 stainless steel. A citric-acid-based detergent was also found to be effective at cleaning metal oxides, such as iron oxide, molybdenum oxide, as well as tungsten oxides at mild temperatures with ultrasonic agitation, and it can be used to replace strong inorganic acids to improve cleaning safety and minimize waste disposal and other environmental problems. The efficiency of removing the metal oxides depends on both cleaning temperature and time

  12. Investigation of Ohmic mechanism for chlorine-treated p-type GaN using x-ray photoelectron spectroscopy

    Science.gov (United States)

    Chen, Po-Sung; Lee, Ching-Ting

    2006-08-01

    To investigate the function and mechanism of oxidation, the surface of the chlorine-treated p-type GaN semiconductor was analyzed using x-ray photoelectron spectroscopy. The chlorinated surface treatment was performed by electrolyzing HCl chemical solution to generate HClO, which in turn could be used to oxidize the p-type GaN. The chlorinated surface treatment enhances the formation of GaOx on the GaN surface and removing GaOx layer from the surface thereafter leads to the creation of additional Ga vacancies. Consequently, more holes are generated as a result of the generated Ga vacancies. Therefore, a relatively higher Ohmic performance with a specific contact resistance of 6.1×10-6Ωcm2 can be obtained for Ni /Au metal contact subsequently patterned on the chlorine-treated p-type GaN via the enhanced formation of GaOx.

  13. Adsorption of ethylene on Sn and In terminated Si(001) surface studied by photoelectron spectroscopy and scanning tunneling microscopy

    Science.gov (United States)

    Zimmermann, Petr; Sobotík, Pavel; Kocán, Pavel; Ošt'ádal, Ivan; Vorokhta, Mykhailo; Acres, Robert George; Matolín, Vladimír

    2016-09-01

    Interaction of ethylene (C2H4) with Si(001)-Sn-2 × 2 and Si(001)-In-2 × 2 at room temperature has been studied using core level (C 1s) X-ray photoelectron spectroscopy with synchrotron radiation and scanning tunneling microscopy. Sn and In form similar dimer chains on Si(001)2 × 1, but exhibit different interaction with ethylene. While ethylene adsorbs on top of Sn dimers of the Si(001)-Sn-2 × 2 surface, the Si(001)-In-2 × 2 surface turned out to be inert. Furthermore, the reactivity of the Sn terminated surface is found to be considerably decreased in comparison with Si(001)2 × 1. According to the proposed adsorption model ethylene bonds to Sn dimers via [2 + 2] cycloaddition by interacting with their π dimer bonds. In contrast, indium dimers do not contain π bonds, which renders the In terminated Si(001) surface inert for ethylene adsorption.

  14. Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Ananya; Matthews, Edward M.; Dessent, Caroline E. H., E-mail: caroline.dessent@york.ac.uk, E-mail: xuebin.wang@pnnl.gov [Department of Chemistry, University of York, Heslington, York YO10 5DD (United Kingdom); Hou, Gao-Lei; Wang, Xue-Bin, E-mail: caroline.dessent@york.ac.uk, E-mail: xuebin.wang@pnnl.gov [Physical Sciences Division, Pacific Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352 (United States)

    2015-11-14

    We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine, and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ∼1.7 eV, values that are lower than the RCB of the uncomplexed PtCl{sub 6}{sup 2−} dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl{sub 6}{sup 2−} ⋅ thymine and PtCl{sub 6}{sup 2−} ⋅ adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN){sub 4}{sup 2−} ⋅ nucleobase complexes [A. Sen et al., J. Phys. Chem. B 119, 11626 (2015)]. The observation of delayed electron emission bands in the PtCl{sub 6}{sup 2−} ⋅ nucleobase spectra obtained in this work, as for the previously studied Pt(CN){sub 4}{sup 2−} ⋅ nucleobase complexes, is attributed to one-photon excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase decays over a time scale long enough to

  15. Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

    Science.gov (United States)

    Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

    2016-07-01

    We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen‑ (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen‑ clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen‑/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters.

  16. Non-adiabatic and time-resolved photoelectron spectroscopy for molecular systems

    CERN Document Server

    Flick, Johannes; Rubio, Angel

    2014-01-01

    We quantify the non-adiabatic contributions to the vibronic sidebands of equilibrium and explicitly time-resolved non-equilibrium photoelectron spectra for a vibronic model system of Trans-Polyacetylene. Using exact diagonalization, we directly evaluate the sum-over-states expressions for the linear-response photocurrent. We show that spurious peaks appear in the Born-Oppenheimer approximation for the vibronic spectral function, which are not present in the exact spectral function of the system. The effect can be traced back to the factorized nature of the Born-Oppenheimer initial and final photoemission states and also persists when either only initial, or final states are replaced by correlated vibronic states. Only when correlated initial and final vibronic states are taken into account, the spurious spectral weights of the Born-Oppenheimer approximation are suppressed. In the non-equilibrium case, we illustrate for an initial Franck-Condon excitation and an explicit pump-pulse excitation how the vibronic ...

  17. Silica-supported silicotungstic acid: A study by X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Berry, Frank J.; Derrick, Glyn R. [Department of Chemistry and Analytical Sciences, Robert Hooke Building, Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom); Marco, Jose F. [Instituto de Quimica -Fisica ' Rocasolano' , Consejo Superior de Investigaciones Cientificas, Serrano 119, 28006 Madrid (Spain); Mortimer, Michael [Department of Chemistry and Analytical Sciences, Robert Hooke Building, Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom)], E-mail: m.mortimer@open.ac.uk

    2009-04-15

    W 4f and O 1s X-ray photoelectron spectra for silicotungstic acid, H{sub 4}SiW{sub 12}O{sub 40}, in pure and silica-supported form are reported. W 4f XP spectra for the supported acid are analysed in terms of contributions from two W(VI) spin-orbit doublets arising from tungsten atoms in terminal W=O bonds some of which directly interact with the silica surface. At low loading (3.2 wt.%) significant changes in the relative contributions and binding energies of the two spin-orbit doublets are taken as evidence of a strong interaction of individual [SiW{sub 12}O{sub 40}]{sup 4-} anions with highly active sites on the silica surface. It is suggested that selective ordering of silanol groups can occur on the silica surface in order to accommodate the adsorption of individual [SiW{sub 12}O{sub 40}]{sup 4-} anions.

  18. Pyrolysis of 3-Methoxypyridine. Detection and Characterization of the Pyrrolyl Radical by Threshold Photoelectron Spectroscopy.

    Science.gov (United States)

    Holzmeier, Fabian; Wagner, Isabella; Fischer, Ingo; Bodi, Andras; Hemberger, Patrick

    2016-07-14

    Pyrolysis of 3-methoxypyridine in a heated pyrolysis reactor was found to be an efficient way to generate the pyrrolyl radical, c-C4H4N, in the gas phase. The threshold photoelectron (TPE) spectrum of this radical was recorded using vacuum ultraviolet synchrotron radiation. The spectrum revealed a singlet ground state at 9.11 ± 0.02 eV (X̃(+ 1)A) and an excited triplet state (ã(+ 3)A) at 9.43 ± 0.05 eV. Vibrational structure was observed for both cationic states and could be assigned to ring deformation modes. Furthermore, (E)- and (Z)-1-cyanoallyl radicals were found to contribute to the TPE spectrum below 8.9 eV. In addition, we have identified two parallel decomposition channels of the pyrrolyl radical, yielding either hydrogen cyanide and propargyl radical or acetylene and cyanomethyl radical. The reaction energy profiles have also been calculated for these reactions. In addition, the dissociative photoionization of the precursor 3-methoxypyridine is reported. PMID:26698131

  19. Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

    Science.gov (United States)

    Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

    2016-01-01

    We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen− (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen− clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen−/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters. PMID:27439955

  20. Attosecond streaking measurement of extreme ultraviolet pulses using a long-wavelength electric field

    Science.gov (United States)

    Saito, Nariyuki; Ishii, Nobuhisa; Kanai, Teruto; Watanabe, Shuntaro; Itatani, Jiro

    2016-01-01

    Long-wavelength lasers have great potential to become a new-generation drive laser for tabletop coherent light sources in the soft X-ray region. Because of the significantly low conversion efficiency from a long-wavelength light field to high-order harmonics, their pulse characterization has been carried out by measuring the carrier-envelope phase and/or spatial dependences of high harmonic spectra. However, these photon detection schemes, in general, have difficulty in obtaining information on the spectral phases, which is crucial to determine the temporal structures of high-order harmonics. Here, we report the first attosecond streaking measurement of high harmonics generated by few-cycle optical pulses at 1.7 μm from a BiB3O6–based optical parametric chirped-pulse amplifier. This is also the first demonstration of time-resolved photoelectron spectroscopy using high harmonics from a long-wavelength drive laser other than Ti:sapphire lasers, which paves the way towards ultrafast soft X-ray photoelectron spectroscopy. PMID:27752115

  1. Manifestation of attosecond XUV fields temporal structures in attosecond streaking spectrogram

    Institute of Scientific and Technical Information of China (English)

    Guanglong Chen; Yunjiu Cao; Dong Eon Kim

    2011-01-01

    @@ The features of an attosecond extreme ultraviolet (XUV) field are encoded in the attosecond XUV spectrogram.We investigate the effect of the temporal structures of attosecond XUV fields on the attosecond streaking spectrogram.Factors such as the number of attosecond XUV pulses and the temporal chirp of attosecond XUV pulses are considered.Results indicate that unlike the attosecond streaking spectrogram for an attosecond XUV field with two pulses of a half-cycle separation of streaking field, the spectrogram for the attosecond XUV field with three pulses demonstrates fine spectral fringes in separated traces.%The features of an attosecond extreme ultraviolet (XUV) field are encoded in the attosecond XUV spectrogram. We investigate the effect of the temporal structures of attosecond XUV fields on the attosecond streaking spectrogram. Factors such as the number of attosecond XUV pulses and the temporal chirp of attosecond XUV pulses are considered. Results indicate that unlike the attosecond streaking spectrogram for an attosecond XUV field with two pulses of a half-cycle separation of streaking field, the spectrogram for the attosecond XUV field with three pulses demonstrates fine spectral fringes in separated traces.

  2. Theory of attosecond delays in laser-assisted photoionization

    Energy Technology Data Exchange (ETDEWEB)

    Dahlström, J.M., E-mail: marcus.dahlstrom@fysik.su.se [Department of Physics, Lund University, P.O. Box 118, 22100 Lund (Sweden); Atomic Physics, Fysikum, Stockholm University, AlbaNova University Center, SE-106 91 Stockholm (Sweden); Guénot, D.; Klünder, K.; Gisselbrecht, M.; Mauritsson, J. [Department of Physics, Lund University, P.O. Box 118, 22100 Lund (Sweden); L’Huillier, A., E-mail: anne.lhuillier@fysik.lth.se [Department of Physics, Lund University, P.O. Box 118, 22100 Lund (Sweden); Maquet, A. [UPMC Université Paris 6, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); CNRS, UMR 7614, LCPMR, Paris (France); Taïeb, R., E-mail: richard.taieb@upmc.fr [UPMC Université Paris 6, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); CNRS, UMR 7614, LCPMR, Paris (France)

    2013-03-12

    Highlights: ► We find the phase for laser-assisted XUV ionization transition matrix elements (M). ► The phase of M is simply: the sum of the scattering phase of the intermediate continuum state and an universal phase. ► The universal phase is independent of the initial state and it leads to a delay observed in attosecond time-delay experiments. - Abstract: We study the temporal aspects of laser-assisted extreme ultraviolet (XUV) photoionization using attosecond pulses of harmonic radiation. The aim of this paper is to establish the general form of the phase of the relevant transition amplitudes and to make the connection with the time-delays that have been recently measured in experiments. We find that the overall phase contains two distinct types of contributions: one is expressed in terms of the phase-shifts of the photoelectron continuum wavefunction while the other is linked to continuum–continuum transitions induced by the infrared (IR) laser probe. Our formalism applies to both kinds of measurements reported so far, namely the ones using attosecond pulse trains of XUV harmonics and the others based on the use of isolated attosecond pulses (streaking). The connection between the phases and the time-delays is established with the help of finite difference approximations to the energy derivatives of the phases. The observed time-delay is a sum of two components: a one-photon Wigner-like delay and a universal delay that originates from the probing process itself.

  3. Theory of attosecond delays in laser-assisted photoionization

    International Nuclear Information System (INIS)

    Highlights: ► We find the phase for laser-assisted XUV ionization transition matrix elements (M). ► The phase of M is simply: the sum of the scattering phase of the intermediate continuum state and an universal phase. ► The universal phase is independent of the initial state and it leads to a delay observed in attosecond time-delay experiments. - Abstract: We study the temporal aspects of laser-assisted extreme ultraviolet (XUV) photoionization using attosecond pulses of harmonic radiation. The aim of this paper is to establish the general form of the phase of the relevant transition amplitudes and to make the connection with the time-delays that have been recently measured in experiments. We find that the overall phase contains two distinct types of contributions: one is expressed in terms of the phase-shifts of the photoelectron continuum wavefunction while the other is linked to continuum–continuum transitions induced by the infrared (IR) laser probe. Our formalism applies to both kinds of measurements reported so far, namely the ones using attosecond pulse trains of XUV harmonics and the others based on the use of isolated attosecond pulses (streaking). The connection between the phases and the time-delays is established with the help of finite difference approximations to the energy derivatives of the phases. The observed time-delay is a sum of two components: a one-photon Wigner-like delay and a universal delay that originates from the probing process itself

  4. X-ray photoelectron spectroscopy (XPS) investigation of the surface film on magnesium powders.

    Science.gov (United States)

    Burke, Paul J; Bayindir, Zeynel; Kipouros, Georges J

    2012-05-01

    Magnesium (Mg) and its alloys are attractive for use in automotive and aerospace applications because of their low density and good mechanical properties. However, difficulty in forming magnesium and the limited number of available commercial alloys limit their use. Powder metallurgy may be a suitable solution for forming near-net-shape parts. However, sintering pure magnesium presents difficulties due to surface film that forms on the magnesium powder particles. The present work investigates the composition of the surface film that forms on the surface of pure magnesium powders exposed to atmospheric conditions and on pure magnesium powders after compaction under uniaxial pressing at a pressure of 500 MPa and sintering under argon at 600 °C for 40 minutes. Initially, focused ion beam microscopy was utilized to determine the thickness of the surface layer of the magnesium powder and found it to be ~10 nm. The X-ray photoelectron analysis of the green magnesium sample prior to sintering confirmed the presence of MgO, MgCO(3)·3H(2)O, and Mg(OH)(2) in the surface layer of the powder with a core of pure magnesium. The outer portion of the surface layer was found to contain MgCO(3)·3H(2)O and Mg(OH)(2), while the inner portion of the layer is primarily MgO. After sintering, the MgCO(3)·3H(2)O was found to be almost completely absent, and the amount of Mg(OH)(2) was also decreased significantly. This is postulated to occur by decomposition of the compounds to MgO and gases during the high temperature of sintering. An increase in the MgO content after sintering supports this theory. PMID:22524956

  5. Isolated attosecond soft X-rays and water window XAFS

    Science.gov (United States)

    Biegert, Jens

    2016-05-01

    We demonstrate generation of isolated attosecond soft X-ray pulses with duration less than 350 as at the carbon K-edge at 284 eV. This reproducible and CEP stable attosecond soft X-ray continuum covers the entire water window from 200 eV to 550 eV with a flux of 7.3x 107 photons/s and corresponds to a pulse energy of 2.9 pJ. We demonstrate the utility of our table-top source through soft X-ray near-edge fine-structure spectroscopy at K-shell absorption edges in condensed matter and retrieve the specific absorption features corresponding to the binding orbitals. We believe that these results herald attosecond material science by bridging the gap between ultrafast temporal resolution and element specific probing at the fundamental absorption edges of matter.

  6. Attosecond streaking in a nano-plasmonic field

    Science.gov (United States)

    Kelkensberg, F.; Koenderink, A. F.; Vrakking, M. J. J.

    2012-09-01

    A theoretical study of the application of attosecond streaking spectroscopy to time-resolved studies of the plasmonic fields surrounding isolated, resonantly excited spherical nanoparticles is presented. A classification of the different regimes in attosecond streaking is proposed and identified in our results that are derived from Mie calculations of plasmon fields, coupled to classical electron trajectory simulations. It is shown that in an attosecond streaking experiment, the electrons are almost exclusively sensitive to the component of the field parallel to the direction in which they are detected. This allows one to probe the different components of the field individually by resolving the angle of emission of the electrons. Finally, simulations based on fields calculated by finite-difference time-domain (FDTD) are compared with the results obtained using Mie fields. The two are found to be in good agreement with each other, supporting the notion that FDTD methods can be used to reliably investigate non-spherical structures.

  7. ANALYSIS OF PASSIVATED SURFACES FOR MASS SPECTROMETER INLET SYSTEMS BY AUGER ELECTRON AND X-RAY PHOTOELECTRON SPECTROSCOPY

    Energy Technology Data Exchange (ETDEWEB)

    Ajo, H.; Clark, E.

    2010-09-01

    Stainless steel coupons approximately 0.5' in diameter and 0.125' thick were passivated with five different surface treatments and an untreated coupon was left as a control. These surface treatments are being explored for use in tritium storage containers. These coupons were made to allow surface analysis of the surface treatments using well-know surface analysis techniques. Depth profiles using Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were performed on these coupons to characterize the surface and near surface regions. Scanning electron microscope (SEM) images were collected as well. All of the surface treatments studied here appear to change the surface morphology dramatically, as evidenced by lack of tool marks on the treated samples. In terms of the passivation treatment, Vendors A-D appeared to have oxide layers that were very similar in thickness to each other (0.7-0.9 nm thick) as well as the untreated samples (the untreated sample oxide layers appeared to be somewhat larger). Vendor E's silicon coating appears to be on the order of 200 nm thick.

  8. Depth profiling the solid electrolyte interphase on lithium titanate (Li4Ti5O12) using synchrotron-based photoelectron spectroscopy

    DEFF Research Database (Denmark)

    Nordh, Tim; Younesi, Reza; Brandell, Daniel;

    2015-01-01

    The presence of a surface layer on lithium titanate (Li4Ti5O12, LTO) anodes, which has been a topic of debate in scientific literature, is here investigated with tunable high surface sensitive synchrotron-based photoelectron spectroscopy (PES) to obtain a reliable depth profile of the interphase...

  9. X-Ray Photoelectron Spectroscopy Study of the Effect of Hydrocarbon Contamination on Poly(Tetrafluoroethylene) Exposed to a Nitrogen Plasma

    Science.gov (United States)

    Golub, Morton A.; Lopata, Eugene S.; Finney, Lorie S.

    1993-01-01

    It has been shown that unless the surface of poly(tetrafluoroethylene)(PTFE) is free of hydrocarbon contamination, anomalous changes in the oxygen and fluorine contents, as measured by X-ray photoelectron spectroscopy (XPS), and hence also the surface properties, may be improperly ascribed to a PTFE film exposed to a oxygen plasma.

  10. An X-ray photoelectron spectroscopy study of the acidity of SiO{sub 2}-ZrO{sub 2} mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bosman, H.J.M.; Pijpers, A.P.; Jaspers, A.W.M.A. [DSM Research B.V., MD Geleen (Netherlands)

    1996-07-01

    X-ray photoelectron spectroscopy (XPS) of SiO{sub 2}-ZrO{sub 2} mixed oxides was studied. Surface acidity was investigated in light of the relationship between acidity and catalytic effects. 28 refs., 12 figs., 3 tabs.

  11. Route to One Atomic Unit of Time: Development of a Broadband Attosecond Streak Camera

    Science.gov (United States)

    Zhao, Kun; Zhang, Qi; Chini, Michael; Chang, Zenghu

    A new attosecond streak camera based on a three-meter-long magnetic-bottle time-of-flight electron spectrometer (MBES) is developed. The temporal resolution of the photoelectron detection system is measured to be better than 250 ps, which is sufficient to achieve an energy resolution of 0.5 eV at 150 eV photoelectron energy. In preliminary experiments, a 94-as isolated XUV pulse was generated and characterized. With a new algorithm to retrieve the amplitude and phase of XUV pulses (PROOF—phase retrieval by omega oscillation filtering), the attosecond streak camera will be able to characterize isolated attosecond pulses as short as one atomic unit of time (25 as).

  12. 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.

  13. Probing the Vibrational Spectroscopy of the Deprotonated Thymine Radical by Photodetachment and State-Selective Autodetachment Photoelectron Spectroscopy via Dipole-Bound States

    Science.gov (United States)

    Huang, Dao-Ling; Zhu, Guo-Zhu; Wang, Lai-Sheng

    2016-06-01

    Deprotonated thymine can exist in two different forms, depending on which of its two N sites is deprotonated: N1[T-H]^- or N3[T-H]^-. Here we report a photodetachment study of the N1[T-H]^- isomer cooled in a cryogenic ion trap and the observation of an excited dipole-bound state. Eighteen vibrational levels of the dipole-bound state are observed, and its vibrational ground state is found to be 238 ± 5 wn below the detachment threshold of N1[T-H]^-. The electron affinity of the deprotonated thymine radical (N1[T-H]^.) is measured accruately to be 26 322 ± 5 wn (3.2635 ± 0.0006 eV). By tuning the detachment laser to the sixteen vibrational levels of the dipole-bound state that are above the detachment threshold, highly non-Franck-Condon resonant-enhanced photoelectron spectra are obtained due to state- and mode-selective vibrational autodetachment. Much richer vibrational information is obtained for the deprotonated thymine radical from the photodetachment and resonant-enhanced photoelectron spectroscopy. Eleven fundamental vibrational frequencies in the low-frequency regime are obtained for the N1[T-H]^. radical, including the two lowest-frequency internal rotational modes of the methyl group at 70 ± 8 wn and 92 ± 5 wn. D. L. Huang, H. T. Liu, C. G. Ning, G. Z. Zhu and L. S. Wang, Chem. Sci., 6, 3129-3138 (2015)

  14. Surface functional group characterization using chemical derivatization X-ray photoelectron spectroscopy (CD-XPS)

    Energy Technology Data Exchange (ETDEWEB)

    Jagst, Eda

    2011-03-18

    Chemical derivatization - X-ray photolectron spectroscopy (CD-XPS) was applied successfully in order to determine different functional groups on thin film surfaces. Different amino group carrying surfaces, prepared by spin coating, self-assembly and plasma polymerization, were successfully investigated by (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Amino groups were derivatized with the widely used primary amino group tags, pentafluorobenzaldehyde (PFB) and 4-(trifluoromethyl)-benzaldehyde (TFBA), prior to analysis. Primary amino group quantification was then carried out according to the spectroscopical data. Self-assembled monolayers (SAMs) of different terminal groups were prepared and investigated with XPS and spectra were compared with reference surfaces. An angle resolved NEXAFS measurement was applied to determine the orientation of SAMs. Plasma polymerized allylamine samples with different duty cycle, power and pressure values were prepared in order to study the effects of external plasma parameters on the primary amino group retention. CD-XPS was used to quantify the amino groups and experiments show, that the milder plasma conditions promote the retention of amino groups originating from the allylamine monomer. An interlaboratory comparison of OH group determination on plasma surfaces of polypropylene treated with oxygen plasma, was studied. The surfaces were investigated with XPS and the [OH] amount on the surfaces was calculated. (orig.)

  15. Electronic structure of ReO3Me by variable photon energy photoelectron spectroscopy, absorption spectroscopy and density functional calculations.

    Science.gov (United States)

    de Simone, Monica; Coreno, Marcello; Green, Jennifer C; McGrady, Sean; Pritchard, Helen

    2003-03-24

    Valence photoelectron (PE) spectra have been measured for ReO(3)Me using a synchrotron source for photon energies ranging between 20 and 110 eV. Derived branching ratios (BR) and relative partial photoionization cross sections (RPPICS) are interpreted in the context of a bonding model calculated using density functional theory (DFT). Agreement between calculated and observed ionization energies (IE) is excellent. The 5d character of the orbitals correlates with the 5p --> 5d resonances of the associated RPPICS; these resonances commence around 47 eV. Bands with 5d character also show a RPPICS maximum at 35 eV. The RPPICS associated with the totally symmetric 4a(1) orbital, which has s-like character, shows an additional shape resonance with an onset of 43 eV. The PE spectrum of the inner valence and core region measured with photon energies of 108 and 210 eV shows ionization associated with C 2s, O 2s, and Re 4f and 5p electrons. Absorption spectra measured in the region of the O1s edge showed structure assignable to excitation to the low lying empty "d" orbitals of this d(0) molecule. The separation of the absorption bands corresponded with the calculated orbital splitting and their intensity with the calculated O 2p character. Broad bands associated with Re 4d absorption were assigned to (2)D(5/2) and (2)D(3/2) hole states. Structure was observed associated with the C1s edge but instrumental factors prevented firm assignment. At the Re 5p edge, structure was observed on the (2)P(3/2) absorption band resulting from excitation to the empty "d" levels. The intensity ratios differed from that of the O 1s edge structure but were in good agreement with the calculated 5d character of these orbitals. An absorption was observed at 45 eV, which, in the light of the resonance in the 4a(1) RPPICS, is assigned to a 4a(1) --> ne, na(2) transition. The electronic structure established for ReO(3)Me differs substantially from that of TiCl(3)Me and accounts for the difference in

  16. X-ray photoelectron spectroscopy (XPS) and FTIR studies of vanadium barium phosphate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Majjane, Abdelilah [Laboratoire de Physico-Chimie des Matériaux Vitreux et Cristallisés, Université Ibn Tofail, Faculté des Sciences, Kénitra 14090 (Morocco); Chahine, Abdelkrim, E-mail: abdelkrimchahine@gmail.com [Laboratoire de Physico-Chimie des Matériaux Vitreux et Cristallisés, Université Ibn Tofail, Faculté des Sciences, Kénitra 14090 (Morocco); Et-tabirou, Mohamed [Laboratoire de Physico-Chimie des Matériaux Vitreux et Cristallisés, Université Ibn Tofail, Faculté des Sciences, Kénitra 14090 (Morocco); Echchahed, Bousselham [Laboratoire d' Electrochimie, Corrosion et Environnement, Université Ibn Tofail, Faculté des Sciences, Kénitra (Morocco); Do, Trong-On [Département de génie chimique, Université Laval, G1K 7P4 (Canada); Breen, Peter Mc [Département de chimie, Université Laval, G1K 7P4 (Canada)

    2014-01-15

    Barium vanadophosphate glasses, having composition 50BaO–xV{sub 2}O{sub 5}–(50 − x)P{sub 2}O{sub 5}, (x = 0–50 mol%), were prepared by conventional melt quench method. Density, molar volume and glass transition temperature (T{sub g}) were measured as a function of V{sub 2}O{sub 5} content. Structural investigation was done using XPS and FTIR spectroscopy. First, substitution of the P{sub 2}O{sub 5} by the V{sub 2}O{sub 5} in the metaphosphate 50BaO–50P{sub 2}O{sub 5} glass increases the density and T{sub g} and decreases the molar volume. When the amount of V{sub 2}O{sub 5} increases, all these properties show a reverse trend. XPS measurement found in the O1s, P2p, and V2p core level spectra indicate the presence of primarily P–O–P, P–O–V and V–O–V structural bonds, the asymmetry in the P 2p spectra indeed arises from the spin-orbit splitting of P 2p core level, and more than one valence state of V ions being present. IR spectroscopy reveals the depolymerization of the phosphate glass network by systematic conversion of metaphosphate chains into pyrophosphate groups and then orthophosphate groups. Even though metaphosphate to pyrophosphate conversion is taking place due to breaking of P–O–P linkages, formation of P–O–V and P–O–Ba linkages provide cross linking between short P-structural units, which make the glass network more rigid. Above 10–20 mol% V{sub 2}O{sub 5} content, network is highly depolymerized due to the formation of orthophosphate units and V–O–V bridge bonds, resulting in poor cross-linking, making the glass network less rigid. - Highlights: • Barium–vanadium–phosphate glasses. • Structure has been investigated by XPS and IR spectra. • Variation in structure and properties with substitution of V{sub 2}O{sub 5} for P{sub 2}O{sub 5}. • Conversion of metaphosphate to pyrophosphate and finally to orthophosphate. • Substitution of P–O–P linkages by P–O–V, P–O–Ba and V–O–V linkages.

  17. Quantitative Surface Analysis by Xps (X-Ray Photoelectron Spectroscopy: Application to Hydrotreating Catalysts

    Directory of Open Access Journals (Sweden)

    Beccat P.

    1999-07-01

    Full Text Available XPS is an ideal technique to provide the chemical composition of the extreme surface of solid materials, vastly applied to the study of catalysts. In this article, we will show that a quantitative approach, based upon fundamental expression of the XPS signal, has enabled us to obtain a consistent set of response factors for the elements of the periodic table. In-depth spadework has been necessary to know precisely the transmission function of the spectrometer used at IFP. The set of response factors obtained enables to perform, on a routine basis, a quantitative analysis with approximately 20% relative accuracy, which is quite acceptable for an analysis of such a nature. While using this quantitative approach, we have developed an analytical method specific to hydrotreating catalysts that allows obtaining the sulphiding degree of molybdenum quite reliably and reproducibly. The usage of this method is illustrated by two examples for which XPS spectroscopy has provided with information sufficiently accurate and quantitative to help understand the reactivity differences between certain MoS2/Al2O3 or NiMoS/Al2O3-type hydrotreating catalysts.

  18. Photoelectron spectra of actinide compounds

    International Nuclear Information System (INIS)

    A brief overview of the application of photoelectron spectroscopy is presented for the study of actinide materials. Phenomenology as well as specific materials are discussed with illustrative examples

  19. Modulation of attosecond beating in resonant two-photon ionization

    CERN Document Server

    Galán, Álvaro J; Martín, Fernando

    2014-01-01

    We present a theoretical study of the photoelectron attosecond beating at the basis of RABBIT (Reconstruction of Attosecond Beating By Interference of Two-photon transitions) in the presence of autoionizing states. We show that, as a harmonic traverses a resonance, its sidebands exhibit a peaked phase shift as well as a modulation of the beating frequency itself. Furthermore, the beating between two resonant paths persists even when the pump and the probe pulses do not overlap, thus providing a sensitive non-holographic interferometric means to reconstruct coherent metastable wave packets. We characterize these phenomena quantitatively with a general finite-pulse analytical model that accounts for the effect of both intermediate and final resonances on two-photon processes, at a negligible computational cost. The model predictions are in excellent agreement with those of accurate ab initio calculations for the helium atom in the region of the N=2 doubly excited states.

  20. Investigation of the grain-boundary chemistry in used CANDU fuel by x-ray photoelectron spectroscopy (XPS)

    International Nuclear Information System (INIS)

    The grain-boundary chemistry of used CANDU fuel is being systematically investigated by X-ray photoelectron spectroscopy (XPS) using a McPherson ESCA-36 instrument that has been adapted for routine studies of highly radioactive materials. Initial stages of fuel corrosion under various storage and disposal conditions can be identified from chemical-shift effects for uranium. For example, pervasive but highly selective grain-boundary oxidation has been revealed in CANDU fuels exposed to moist air at 150 deg. C for extended periods, suggesting aggressive radiolytic processes operating in a thin film of adsorbed water. Pronounced segregation of a number of fission products to cracks and grain boundaries in used CANDU fuels has been explicitly demonstrated by XPS as well. Model calculations and composition depth profiles are indicative of near monolayer films. Some correlations between fuel power history and fission-product distributions have been established and possible evidence of migration during moist-air exposure has been obtained. The key advantages and limitations of XPS in this context are discussed and illustrated with selected results. (author). 23 refs, 8 figs, 1 tab

  1. Bias induced Cu ion migration behavior in resistive change memory structure observed by hard X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    The Cu ion migration behavior of a Pt/Cu/HfO2/Pt structure, which is an oxide-based resistive random access memory (ReRAM) and exhibits resistance switching behavior at voltages of ±0.8 V, was investigated by hard X-ray photoelectron spectroscopy under a bias operation. A forward bias application, during switching from a high resistive state (HRS) to a low resistive state, reduced the Cu2O bonding state at the interface and the intensity ratio of Cu 2p3/2/Hf 3d5/2 (Cu/Hf) by 23 ± 5%, providing evidence of reductions in unintentionally formed Cu2O and Cu diffusion into the HfO2 layer. After switching to HRS again, Cu/Hf increased by 15 ± 5%, indicating that the Cu ion moved back to the top electrode side, though oxygen showed no bias voltage dependence. Consequently, the Cu ion has a key role in the switching. We directly observed the Cu migration behavior related to the resistive change at the Cu/HfO2 interface under bias operation. (author)

  2. Chemical analysis of semiconducting and metallic SmS thin films by X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    We studied the chemical state of semiconducting and metallic SmS thin films by X-ray photoelectron spectroscopy (XPS), which were fabricated using dual-target magnetron sputtering by controlling the power applied to both metal and chalcogenide targets. On the basis of the valence band spectra obtained, it was suggested that semiconducting SmS has the final state corresponding to the Sm2+(4f6) configuration below the Fermi level, and metallic SmS has mainly the Sm3+(4f5) final state and a virtual band state in the Sm 5d band, contributing to the delocalization of 4f electrons and the emergence of metallic conductivity (4f6d0-4f5d1). Thus, the spectra of our fabricated SmS thin films correspond to the band structure obtained from the dielectric property. This is the first work performed on the intrinsically prepared metallic SmS while the former works done for the sample transformed from semiconductor to metal phase by hard polishing

  3. Reactivity of Au nanoparticles supported over SiO2 and TiO2 studiedby ambient pressure photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Herranz, Tirma; Deng, Xingyi; Cabot, Andreu; Alivisatos, Paul; Liu, Zhi; Soler-Illia, Galo; Salmeron, Miquel

    2009-04-15

    The influence of the metal cluster size and the identity of the support on the reactivity of gold based catalysts have been studied in the CO oxidation reaction. To overcome the structural complexity of the supported catalysts, gold nanoparticles synthesized from colloidal chemistry with precisely controlled size have been used. Those particles were supported over SiO{sub 2} and TiO{sub 2} and their catalytic activity was measured in a flow reactor. The reaction rate was dependent on the particle size and the support, suggesting two reaction pathways in the CO oxidation reaction. In parallel, ambient pressure photoelectron spectroscopy (APPS) has been performed under reaction conditions using bidimensional model catalysts prepared upon supporting the Au nanoparticles over planar polycrystalline SiO{sub 2} and TiO{sub 2} thin films by means of the Langmuir-Blodgett (LB) technique to mimic the characteristic of the powder samples. In this way, the catalytically active surface was characterized under true reaction conditions, revealing that during CO oxidation gold remains in the metallic state.

  4. X-ray photoelectron spectroscopy analysis of boron defects in silicon crystal: A first-principles study

    Science.gov (United States)

    Yamauchi, Jun; Yoshimoto, Yoshihide; Suwa, Yuji

    2016-05-01

    We carried out a comprehensive study on the B 1s core-level X-ray photoelectron spectroscopy (XPS) binding energies and formation energies for boron defects in crystalline silicon by first-principles calculation with careful evaluation of the local potential boundary condition for the model system using the supercell corresponding to 1000 Si atoms. It is reconfirmed that the cubo-octahedral B12 cluster in silicon crystal is unstable and exists at the saddle point decaying to the icosahedral and S4 B12 clusters. The electrically active clusters without any postannealing of ion-implanted Si are identified as icosahedral B12 clusters. The experimentally proposed threefold coordinated B is also identified as a ⟨ 001 ⟩ B - Si defect. For an as-doped sample prepared by plasma doping, the calculated XPS spectra for complexes consisting of vacancies and substitutional B atoms are consistent with the experimental spectra. It is proposed that, assuming that the XPS peak at 187.1 eV is due to substitutional B (Bs), the experimental XPS peaks at 187.9 and 186.7 eV correspond to interstitial B at the H-site and ⟨ 001 ⟩ B - Si defects, respectively. In the annealed samples, the complex of Bs and interstitial Si near the T-site is proposed as a candidate for the experimental XPS peak at 188.3 eV.

  5. SmB6 electron-phonon coupling constant from time- and angle-resolved photoelectron spectroscopy

    Science.gov (United States)

    Sterzi, A.; Crepaldi, A.; Cilento, F.; Manzoni, G.; Frantzeskakis, E.; Zacchigna, M.; van Heumen, E.; Huang, Y. K.; Golden, M. S.; Parmigiani, F.

    2016-08-01

    SmB6 is a mixed valence Kondo system resulting from the hybridization between localized f electrons and delocalized d electrons. We have investigated its out-of-equilibrium electron dynamics by means of time- and angle-resolved photoelectron spectroscopy. The transient electronic population above the Fermi level can be described by a time-dependent Fermi-Dirac distribution. By solving a two-temperature model that well reproduces the relaxation dynamics of the effective electronic temperature, we estimate the electron-phonon coupling constant λ to range from 0.13 ±0.03 to 0.04 ±0.01 . These extremes are obtained assuming a coupling of the electrons with either a phonon mode at 10 or 19 meV. A realistic value of the average phonon energy will give an actual value of λ within this range. Our results provide an experimental report on the material electron-phonon coupling, contributing to both the electronic transport and the macroscopic thermodynamic properties of SmB6.

  6. Photoelectron spectroscopy study of AlN films grown on n-type 6H-SiC by MOCVD

    Science.gov (United States)

    Liang, F.; Chen, P.; Zhao, D. G.; Jiang, D. S.; Zhao, Z. J.; Liu, Z. S.; Zhu, J. J.; Yang, J.; Liu, W.; He, X. G.; Li, X. J.; Li, X.; Liu, S. T.; Yang, H.; Liu, J. P.; Zhang, L. Q.; Zhang, Y. T.; Du, G. T.

    2016-09-01

    Photoelectron spectroscopy has been employed to analyze the content and chemical states of the elements on the surface of AlN films with different thickness, which are synthesized by metalorganic chemical vapor deposition on the n-type SiC substrates under low pressure. It is found that, besides the carbon and gallium on the AlN surface, the atom percentage of surface oxygen increases from 4.9 to 8.4, and the electron affinity also increases from 0.36 to 0.97 eV, when the thickness of AlN films increase from 50 to 400 nm. Furthermore, accompanying with the high-resolution XPS spectra of the O 1s, it is speculated that surface oxygen may be the major influence on the electron affinity, where the surface oxygen changes the surface chemical states through replacing N to form Al-O bond and Ga-O bond, although there are also a few of Ga and C contaminations in the chemical sate of Ga-O and C-C, respectively.

  7. Time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analyses of Bixa orellana seeds.

    Science.gov (United States)

    Felicissimo, Marcella P; Bittencourt, Carla; Houssiau, Laurent; Pireaux, Jean-Jacques

    2004-04-01

    Three different experiments were performed in order to obtain the major carotenoid composition of the natural colorant annatto (E160b) through ToF-SIMS (time-of-flight secondary ion mass spectrometry) and XPS (X-ray photoelectron spectroscopy) analyses. In the first experiment, Bixa orellana seeds aril as well as its interior part were analyzed. The analysis of the seeds aril by ToF-SIMS gives the colorant fingerprint without any sample treatment, showing the presence of bixin and its characteristic fragments. The analysis performed in the interior part of the seeds indicates the presence of Fe. The second set of measurements was conducted on the seeds organic extract right after extraction revealing the same components observed by in situ measurement. A third set of measurements was performed aiming to determine the reason for the organic extract color shift observed after 3 months of exposure to ambient light at room temperature. In this case, it was possible to evidence the degradation of bixin by the loss of xylene molecules through ToF-SIMS and the probable carotenoid oxidation based on the C1s XPS spectrum of the degraded extract. PMID:15053514

  8. Probing Co/Si interface behaviour by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM)

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    In this work, we investigate the Co-Si reaction, the Co growth mode at room temperature, diffusion behaviour as well as morphology evolution during annealing on both H-terminated and clean Si(001) and Si(111) surfaces. From in-situ X-ray photoelectron spectroscopy (XPS) investigation, "Co-Si" reaction appears to occur on both H-terminated and clean surfaces at room temperature (RT) and the silicide crystallinity is improved upon annealing.Co growth mode on H-terminated Si surfaces occurs in a pseudo layer-by-layer manner while small close-packed island growth mode is observed on the clean Si surface. Upon annealing at different temperatures, Co atom concentration decreases versus annealing time, which in part is attributed to Co atoms inward diffusion. The diffusion behaviour on both types of surfaces demonstrates a similar trend. Morphology study using ex-situ atomic force microscopy (AFM) shows that the islands formed on Si(001) surface after annealing at 700 ℃ are elongated with growth directions alternate between the two perpendicular [(-1)10] and [110] directions. Triangular islands are observed on Si(111) surface.

  9. Photoelectron spectroscopy study of thin Ag films deposited on to amorphous In–Ga–Zn–O surface

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Se Jun [Department of Physics, Pohang University of Science and Technology, Pohang 790-784 (Korea, Republic of); Baik, Jaeyoon; Ha, Taekyun; Park, Chong Do [Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang 790-784 (Korea, Republic of); Shin, Hyun-Joon, E-mail: shj001@postech.ac.kr [Department of Physics, Pohang University of Science and Technology, Pohang 790-784 (Korea, Republic of); Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang 790-784 (Korea, Republic of); Chung, JaeGwan; Lee, Jaecheol [A E Group, Samsung Advanced Institute of Technology, Giheung-Gu, Yongin-Si, GyeingGi-Do 449-712 (Korea, Republic of)

    2014-11-03

    Ag was thermally evaporated onto amorphous In–Ga–Zn–O (a-IGZO) thin film, and the Ag-thickness (< 0.3 nm)-dependent chemical states of the Ag-deposited a-IGZO thin-film surfaces were investigated by high-resolution X-ray photoelectron spectroscopy. As Ag layer thickness increased, Ag 3d shifted towards the lower binding energy (BE) side and In 3d developed a lower-BE component; however, O 1s, Ga 3d, and Zn 3d showed much smaller spectral feature changes than Ag 3d or In 3d. The analysis suggests that Ag atoms preferentially interact and share electrons with In atoms. The Ag 4d split feature at the valence band and the metallic states near the Fermi edge were noticeably visible when the Ag thickness was greater than 0.1 nm. - Highlights: • Ag was deposited on a-IGZO thin film using thermal evaporation method. • Chemical state changes of Ag-deposited a-IGZO were investigated by XPS. • As Ag layer thickness increased, In 3d developed a lower-BE component. • As Ag layer thickness increased, Ag 3d shifted towards the lower BE side. • Ag atoms preferentially interact and share electrons with In atoms.

  10. Photoelectric characteristics of silicon P—N junction with nanopillar texture: Analysis of X-ray photoelectron spectroscopy

    Science.gov (United States)

    Liu, Jing; Wang, Jia-Ou; Yi, Fu-Ting; Wu, Rui; Zhang, Nian; Ibrahim, Kurash

    2014-09-01

    Silicon nanopillars are fabricated by inductively coupled plasma (ICP) dry etching with the cesium chloride (CsCl) islands as masks originally from self-assembly. Wafers with nanopillar texture or planar surface are subjected to phosphorus (P) diffusion by liquid dopant source (POCl3) at 870 °C to form P—N junctions with a depth of 300 nm. The X-ray photoelectron spectroscopy (XPS) is used to measure the Si 2p core levels of P—N junction wafer with nanopillar texture and planar surface. With a visible light excitation, the P—N junction produces a new electric potential for photoelectric characteristic, which causes the Si 2p core level to have a energy shift compared with the spectrum without the visible light. The energy shift of the Si 2p core level is -0.27 eV for the planar P—N junction and -0.18 eV for the nanopillar one. The difference in Si 2p energy shift is due to more space lattice defects and chemical bond breaks for nanopillar compared with the planar one.

  11. X-ray photoelectron spectroscopy studies of MgB{sub 2} for valence state of Mg

    Energy Technology Data Exchange (ETDEWEB)

    Talapatra, A. [Department of Physics, Variable Energy Cyclotron Centre, 1/AF, Bidhan Nagar, Kolkata 700 064 (India); Bandyopadhyay, S.K. [Department of Physics, Variable Energy Cyclotron Centre, 1/AF, Bidhan Nagar, Kolkata 700 064 (India)]. E-mail: skband@veccal.ernet.in; Sen, Pintu [Department of Physics, Variable Energy Cyclotron Centre, 1/AF, Bidhan Nagar, Kolkata 700 064 (India); Barat, P. [Department of Physics, Variable Energy Cyclotron Centre, 1/AF, Bidhan Nagar, Kolkata 700 064 (India); Mukherjee, S. [Saha Institute of Nuclear Physics, 1/AF, Bidhan Nagar, Kolkata 700 064 (India); Mukherjee, M. [Saha Institute of Nuclear Physics, 1/AF, Bidhan Nagar, Kolkata 700 064 (India)

    2005-03-01

    Core level X-ray photoelectron spectroscopy (XPS) studies have been carried out on polycrystalline MgB{sub 2} pellets over the whole binding energy range with a view to having an idea of the charge state of magnesium (Mg). We observe three distinct peaks in Mg 2p spectra at 49.3 eV (trace), 51.3 eV (major) and 54.0 eV (trace), corresponding to metallic Mg, MgB{sub 2} and MgCO{sub 3} or, divalent Mg species, respectively. Similar trend has been noticed in Mg 2s spectra. The binding energy of Mg in MgB{sub 2} is lower than that corresponding to Mg(2+), indicative of the fact that the charge state of Mg in MgB{sub 2} is less than (2+). Lowering of the formal charge of Mg promotes the {sigma} {yields} {pi} electron transfer in boron (B) giving rise to holes on the top of the {sigma}-band which are involved in coupling with B E{sub 2g} phonons for superconductivity. Through this charge transfer, Mg plays a positive role in hole superconductivity. B 1s spectra consist of three peaks corresponding to MgB{sub 2}, boron and B{sub 2}O{sub 3}. There is also evidence of MgO due to surface oxidation as seen from O 1s spectra.

  12. In situ x-ray photoelectron spectroscopy studies of gas/solidinterfaces at near-ambient conditions

    Energy Technology Data Exchange (ETDEWEB)

    Bluhm, Hendrik; Havecker, Michael; Knop-Gericke, Axel; Kiskinova,Maya; Schlogl, Robert; Salmeron, Miquel

    2007-12-03

    X-ray photoelectron spectroscopy (XPS) is a quantitative, chemically specific technique with a probing depth of a few angstroms to a few nanometers. It is therefore ideally suited to investigate the chemical nature of the surfaces of catalysts. Because of the scattering of electrons by gas molecules, XPS is generally performed under vacuum conditions. However, for thermodynamic and/or kinetic reasons, the catalyst's chemical state observed under vacuum reaction conditions is not necessarily the same as that of a catalyst under realistic operating pressures. Therefore, investigations of catalysts should ideally be performed under reaction conditions, i.e., in the presence of a gas or gas mixtures. Using differentially pumped chambers separated by small apertures, XPS can operate at pressures of up to 1 Torr, and with a recently developed differentially pumped lens system, the pressure limit has been raised to about 10 Torr. Here, we describe the technical aspects of high-pressure XPS and discuss recent applications of this technique to oxidation and heterogeneous catalytic reactions on metal surfaces.

  13. Adsorption of Saliva Related Protein on Denture Materials: An X-Ray Photoelectron Spectroscopy and Quartz Crystal Microbalance Study

    Directory of Open Access Journals (Sweden)

    Akiko Miyake

    2016-01-01

    Full Text Available The aim of this study was to evaluate the difference in the adsorption behavior of different types of bovine salivary proteins on the PMMA and Ti QCM sensors are fabricated by spin-coating and sputtering onto bare QCM sensors by using QCM and X-ray photoelectron spectroscopy (XPS. SPM, XPS, and contact angle investigations were carried out to determine the chemical composition and surface wettability of the QCM surface. We discuss the quality of each sensor and evaluate the potential of the high-frequency QCM sensors by investigating the binding between the QCM sensor and the proteins albumin and mucin (a salivary-related protein. The SPM image showed a relatively homogeneous surface with nano-order roughness. The XPS survey spectra of the thin films coated on the sensors were similar to the binding energy of the characteristic spectra of PMMA and Ti. Additionally, the amount of salivary-related protein on the PMMA QCM sensor was higher than those on the Ti and Au QCM sensors. The difference of protein adsorption is proposed to be related to the wettability of each material. The PMMA and Ti QCM sensors are useful tools to study the adsorption and desorption of albumin and mucin on denture surfaces.

  14. X-ray photoelectron spectroscopy and micro-Raman analysis of conductive RuO2 thin films

    Science.gov (United States)

    Bhaskar, S.; Dobal, P. S.; Majumder, S. B.; Katiyar, R. S.

    2001-03-01

    Ruthenium oxide (RuO2) was synthesized in thin film and powder forms using the solution chemistry technique. The oxide electrodes on Si substrates were characterized in terms of their structure, composition, stoichiometry, and conductivity. X-ray lattice parameter calculations and micro-Raman analysis revealed the rutile structure in the material. Both films and powders exhibited an unassigned Raman band at about 477 cm-1 in their Raman spectra. Performing peak frequency calculations for B2g and A1g modes of RuO2 using the rigid-ion model, which ruled out the possibility that this band originated from disorder induced symmetry, allowed silent mode. Based on the x-ray photoelectron spectroscopy (XPS) and temperature dependent Raman studies, this band was assigned to hydrated RuO2. XPS characterizations of our samples revealed minute surface contamination of oxygen and chlorine, probably due to the film preparation and high temperature deposition processes. Films with uniform microstructure, low surface roughness, and good electrical properties meet the requirements for serving as the bottom electrode for the ferroelectric capacitor.

  15. Hard X-ray photoelectron and X-ray absorption spectroscopy characterization of oxidized surfaces of iron sulfides

    Science.gov (United States)

    Mikhlin, Yuri; Tomashevich, Yevgeny; Vorobyev, Sergey; Saikova, Svetlana; Romanchenko, Alexander; Félix, Roberto

    2016-11-01

    Hard X-ray photoelectron spectroscopy (HAXPES) using an excitation energy range of 2 keV to 6 keV in combination with Fe K- and S K-edge XANES, measured simultaneously in total electron (TEY) and partial fluorescence yield (PFY) modes, have been applied to study near-surface regions of natural polycrystalline pyrite FeS2 and pyrrhotite Fe1-xS before and after etching treatments in an acidic ferric chloride solution. It was found that the following near-surface regions are formed owing to the preferential release of iron from oxidized metal sulfide lattices: (i) a thin, no more than 1-4 nm in depth, outer layer containing polysulfide species, (ii) a layer exhibiting less pronounced stoichiometry deviations and low, if any, concentrations of polysulfide, the composition and dimensions of which vary for pyrite and pyrrhotite and depend on the chemical treatment, and (iii) an extended almost stoichiometric underlayer yielding modified TEY XANES spectra, probably, due to a higher content of defects. We suggest that the extended layered structure should heavily affect the near-surface electronic properties, and processes involving the surface and interfacial charge transfer.

  16. Uniqueness plots: A simple graphical tool for identifying poor peak fits in X-ray photoelectron spectroscopy

    Science.gov (United States)

    Singh, Bhupinder; Diwan, Anubhav; Jain, Varun; Herrera-Gomez, Alberto; Terry, Jeff; Linford, Matthew R.

    2016-11-01

    Peak fitting is an essential part of X-ray photoelectron spectroscopy (XPS) narrow scan analysis, and the Literature contains both good and bad examples of peak fitting. A common cause of poor peak fitting is the inclusion of too many fit parameters, often without a sound chemical and/or physical basis for them, and/or the failure to reasonably constrain them. Under these conditions, fit parameters are often correlated, and therefore lacking in statistical meaning. Here we introduce the uniqueness plot as a simple graphical tool for identifying bad peak fits in XPS, i.e., fit parameter correlation. These plots are widely used in spectroscopic ellipsometry. We illustrate uniqueness plots with two data sets: a C 1s narrow scan from ozone-treated carbon nanotube forests and an Si 2p narrow scan from an air-oxidized silicon wafer. For each fit, we consider different numbers of parameters and constraints on them. As expected, the uniqueness plots are parabolic when fewer fit parameters and/or more constraints are applied. However, they fan out and eventually become horizontal lines as more unconstrained parameters are included in the fits. Uniqueness plots are generated by plotting the chi squared (χ2) value for a fit vs. a systematically varied value of a parameter in the fit. The Abbe criterion is also considered as a figure of merit for uniqueness plots in the Supporting Information. We recommend that uniqueness plots be used by XPS practitioners for identifying inappropriate peak fits.

  17. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy of Cobalt Perovskite Surfaces under Cathodic Polarization at High Temperatures

    KAUST Repository

    Crumlin, Ethan J.

    2013-08-08

    Heterostructured oxide interfaces have demonstrated enhanced oxygen reduction reaction rates at elevated temperatures (∼500-800 C); however, the physical origin underlying this enhancement is not well understood. By using synchrotron-based in situ ambient pressure X-ray photoelectron spectroscopy (APXPS), we focus on understanding the surface electronic structure, elemental composition, and chemical nature of epitaxial La0.8Sr 0.2CoO3-δ (LSC113), (La 0.5Sr0.5)2CoO4±δ (LSC214), and LSC214-decorated LSC113 (LSC 113/214) thin films as a function of applied electrical potentials (0 to -800 mV) at 520 C and p(O2) of 1 × 10-3 atm. Shifts in the top of the valence band binding energy and changes in the Sr 3d and O 1s spectral components under applied bias reveal key differences among the film chemistries, most notably in the degree of Sr segregation to the surface and quantity of active oxygen sites in the perovskite termination layer. These differences help to identify important factors governing the enhanced activity of oxygen electrocatalysis observed for the LSC113/214 heterostructured surface. © 2013 American Chemical Society.

  18. Reduction of Vanadium Oxide (VOx) under High Vacuum Conditions as Investigated by X-Ray Photoelectron Spectroscopy

    Science.gov (United States)

    Chourasia, A.

    2015-03-01

    Vanadium oxide thin films were formed by depositing thin films of vanadium on quartz substrates and oxidizing them in an atmosphere of oxygen. The deposition was done by the e-beam technique. The oxide films were annealed at different temperatures for different times under high vacuum conditions. The technique of x-ray photoelectron spectroscopy has been employed to study the changes in the oxidation states of vanadium and oxygen in such films. The spectral features in the vanadium 2p, oxygen 1s, and the x-ray excited Auger regions were investigated. The Auger parameter has been utilized to study the changes. The complete oxidation of elemental vanadium to V2O5 was observed to occur at 700°C. At any other temperature, a mixture of oxides consisting of V2O5 and VO2 was observed in the films. Annealing of the films resulted in the gradual loss of oxygen followed by reduction in the oxidation state from +5 to 0. The reduction was observed to depend upon the annealing temperature and the annealing time. Organized Research, TAMU-Commerce.

  19. X-ray photoelectron spectroscopy of CeO2-Na2O-SiO2 glasses

    International Nuclear Information System (INIS)

    A series of (CeO2)x-(Na2O)0.3-(SiO2)(0.7-x) glasses, where 0.025 ≤ x ≤ 0.075, have been synthesized and investigated by mean of X-ray photoelectron spectroscopy (XPS). The Ce 3d spin-orbit doublet was curve fitted in order to quantify the proportions of each cerium oxidation state in these glasses. It was found that Ce ions are predominantly in the Ce(III) state in glasses with compositions x ≤ 0.075, while mixed Ce valences were found in the glass with composition x = 0.10. The O 1s spectra have also been curve fitted with two components, one from bridging oxygen (BO) and the other from non-bridging oxygen atoms (NBO). The measured number of NBO, based on the fact that only oxygen atoms in the site Si-O-Na+ contribute to the NBO peak, was found to be constant at ∼35% for all samples, in good agreement with the value calculated from the glass composition and inductively coupled plasma (ICP) suggesting that Ce ions enter the network as a glass intermediate. The thermal measurements done on these glasses agree well with the XPS findings

  20. 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.

  1. A Method for Distinguishing Attosecond Single Pulse from Attosecond Pulse Train

    Institute of Scientific and Technical Information of China (English)

    HUO Yi-Ping; ZENG Zhi-Nan; LI Ru-Xin; XU Zhi-Zhan

    2004-01-01

    @@ The driving laser field assisted attosecond soft-extreme-ultraviolet (XUV) photo-ionization was used successfully to measure the duration of the attosecond pulse based on the cross-correlation method. However, this method in principle cannot distinguish a single attosecond pulse from the attosecond pulse train. We propose a technique for directly distinguishing attosecond single pulse from attosecond pulse train based on the photo-ionization of atoms by attosecond XUV pulse in the presence of a two-colour strong laser pulse.

  2. Far-Infrared Spectroscopy of Cationic Polycyclic Aromatic Hydrocarbons: Zero Kinetic Energy Photoelectron Spectroscopy of Pentacene Vaporized from Laser Desorption

    CERN Document Server

    Zhang, J; Pei, L; Kong, W; Li, Aigen

    2012-01-01

    The distinctive set of infrared (IR) emission bands at 3.3, 6.2, 7.7, 8.6, and 11.3{\\mu}m are ubiquitously seen in a wide variety of astrophysical environments. They are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. However, not a single PAH species has yet been identified in space, as the mid-IR vibrational bands are mostly representative of functional groups and thus do not allow one to fingerprint individual PAH molecules. In contrast, the far-IR (FIR) bands are sensitive to the skeletal characteristics of a molecule, hence they are important for chemical identification of unknown species. With an aim to offer laboratory astrophysical data for the Herschel Space Observatory, Stratospheric Observatory for Infrared Astronomy, and similar future space missions, in this work we report neutral and cation FIR spectroscopy of pentacene (C_22H_14), a five-ring PAH molecule. We report three IR active modes of cationic pentacene at 53.3, 84.8, and 266{\\mu}m that may be detectable by space ...

  3. Characterizing reactions to fabricate thin films of charge transfer complexes by synchrotron photoelectron spectroscopy: A case study of DCNQI-Cu

    Science.gov (United States)

    Shimada, Toshihiro; Mochida, Michihiro; Koma, Atsushi

    1997-04-01

    Ultraviolet photoelectron spectroscopy with various photon energies using synchrotron radiation was used to characterize chemical reactions associated with thin film growth of organic charge transfer complex (DMe-DCNQI) 2Cu. Other molecular systems H 2Pc, CuPc and C 60 were also studied to clarify the origin of the systematic relation between the spectra and the incident photon energy. Characteristic photon energy dependence of the photo-ionization cross section of molecular orbitals is useful to analyze the intermolecular reactions.

  4. X-ray photoelectron spectroscopy analysis of whole cells and isolated cell walls of gram-positive bacteria: comparison with biochemical analysis.

    OpenAIRE

    Dufrêne, Yves; van der Wal, A.; Norde, W; Rouxhet, Paul

    1997-01-01

    The surface chemical composition of whole cells and isolated cell walls of four coryneform bacteria and of a Bacillus brevis strain has been determined by X-ray photoelectron spectroscopy (XPS). The XPS data were converted into concentrations of model compounds: peptides, polysaccharides, and hydrocarbonlike compounds. The composition of the surface of B. brevis differed markedly from that of coryneforms: the peptide concentration was about twice higher in the former case, which is attributed...

  5. Effects of Varied Cleaning Methods on Ni-5% W Substrate for Dip-Coating of Water-based Buffer Layers: An X-ray Photoelectron Spectroscopy Study

    OpenAIRE

    Isabel Van Driessche; Ruben Hühne; Els Bruneel; Vyshnavi Narayanan

    2012-01-01

    This work describes various combinations of cleaning methods involved in the preparation of Ni-5% W substrates for the deposition of buffer layers using water-based solvents. The substrate has been studied for its surface properties using X-ray photoelectron spectroscopy (XPS). The contaminants in the substrates have been quantified and the appropriate cleaning method was chosen in terms of contaminants level and showing good surface crystallinity to further consider them for depositing chemi...

  6. Application of the Auger and X-ray photoelectron electronic spectroscopies to the study of superficial segregation in the system Pt-Rh

    International Nuclear Information System (INIS)

    The Auger and X-ray photoelectron spectroscopies are applied to the study of the superficial segregation in the system of the binary alloy Pt-Rh. The methodology for the cleaning of the samples, which is essential for the obtainment of reproducible results, has been established. The spectra qualitative analysis allows to identify the element segregated. The application of the Gallon model permits to develop a quantitative study of the phenomenon. (S.M.)

  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. Organic heterojunctions of layered perylene and phthalocyanine dyes: characterization with UV-photoelectron spectroscopy and luminescence quenching

    Energy Technology Data Exchange (ETDEWEB)

    Alloway, Dana M.; Armstrong, Neal R. [University of Arizona, Department of Chemistry, Tucson, AZ (United States)

    2009-04-15

    We present here the characterization of organic/organic' heterojunctions created from either of two perylene dyes, perylenetetracarboxylicdianhydride (PTCDA) or the bisimide derivative perylenetetracarboxylicdianhydride-N,N'-bis (butyl)imide (C4-PTCDI), and two chloro-metallated donor phthalocyanines (ClAlPc or ClInPc). The perylene dyes were selected to create thin films with the core of the perylene dye parallel to the substrate plane (PTCDA) or nearly vertical to the substrate plane, with layer planes defined by the butyl substituents (C4-PTCDI). We compare the frontier orbital offsets revealed by UV-photoelectron spectroscopy, and quenching of luminescence of the perylene dyes, as a function of Pc coverage. The ionization potentials (IPs) of the Pc layers, the degree to which interface dipoles are formed at the Pc/perylene dye interface, and the degree of quenching of the perylene luminescence are affected by the structure of the Pc/perylene interface. Pc/PTCDA heterojunctions show significant interface dipoles and higher IPs for the first-deposited Pc layers compared to Pc/C4-PTCDI heterojunctions, which show negligible interface dipoles and lower overall IP values for initial Pc layers. Luminescence of the selectively excited perylene layers is quenched by the addition of even submonolayer coverages of Pc. This quenching process occurs as a result of both energy transfer (perylene to Pc) and charge transfer (Pc to perylene). Luminescence from monomeric and aggregated ClAlPc and ClInPc monolayers is seen on C4-PTCDI films, whereas only luminescence from the aggregated forms of these Pcs is seen on PTCDA films. These studies reveal aspects of organic heterojunction energetics which may have important implications for organic solar cell design. (orig.)

  9. X-ray photoelectron spectroscopy study of the passivation of NiAl(100) by water vapor.

    Science.gov (United States)

    Cai, Na; Liu, Qianqian; Tong, Xiao; Zhou, Guangwen

    2014-01-28

    The oxidation of NiAl(100) surfaces by water vapor is studied using X-ray photoelectron spectroscopy (XPS) to elucidate the effect of temperature and vapor pressure on the surface passivation mechanism of the NiAl alloy. The water-vapor oxidation at ambient temperature (25 °C) results in self-limiting Al(OH)3/Al2O3 bilayer film growth to a less extent of the limiting thickness regimes, in which the growth of the inner Al2O3 layer occurs via dehydration of the outer Al(OH)3 layer. The growth of the passivating overlayer at the ambient temperature depletes Al and forms a Ni-rich layer at the oxide/alloy interface that impedes supply of Al atoms to the outer surface for Al(OH)3 formation via the hydration reaction, whereby resulting in a more Al-deficient structure of the outer Al(OH)3 layer upon increasing the vapor pressure. In contrast, the water-vapor oxidation at 300 °C results in Al2O3 single-layer film growth to a larger limiting thickness without involving the transient hydroxide phase of Al(OH)3. It is shown that increasing the oxidation temperatures results in the formation of a more compact Al2O3 film owning to the enhanced bulk diffusion rate that maintains an adequate supply of Al atoms to the oxide/alloy interface to sustain the oxide film growth to the full extent of the limiting thickness. PMID:24417205

  10. X-ray photoelectron spectroscopy study of the growth kinetics of biomimetically grown hydroxyapatite thin-film coatings

    Science.gov (United States)

    McLeod, K.; Kumar, S.; Dutta, N. K.; Smart, R. St. C.; Voelcker, N. H.; Anderson, G. I.

    2010-09-01

    Hydroxyapatite (HA) thin-film coatings grown biomimetically using simulated body fluid (SBF) are desirable for a range of applications such as improved fixation of fine- and complex-shaped orthopedic and dental implants, tissue engineering scaffolds and localized and sustained drug delivery. There is a dearth of knowledge on two key aspects of SBF-grown HA coatings: (i) the growth kinetics over short deposition periods, hours rather than weeks; and (ii) possible difference between the coatings deposited with and without periodic SBF replenishment. A study centred on these aspects is reported. X-ray photoelectron spectroscopy (XPS) has been used to study the growth kinetics of SBF-grown HA coatings for deposition periods ranging from 0.5 h to 21 days. The coatings were deposited with and without periodic replenishment of SBF. The XPS studies revealed that: (i) a continuous, stable HA coating fully covered the titanium substrate after a growth period of 13 h without SBF replenishment; (ii) thicker HA coatings about 1 μm in thickness resulted after a growth period of 21 days, both with and without SBF replenishment; and (iii) the Ca/P ratio at the surface of the HA coating was significantly lower than that in its bulk. No significant difference between HA grown with and without periodic replenishment of SBF was found. The coatings were determined to be carbonated, a characteristic desirable for improved implant fixation. The atomic force and scanning electron microscopies results suggested that heterogeneous nucleation and growth are the primary deposition mode for these coatings. Primary osteoblast cell studies demonstrated the biocompatibility of these coatings, i.e., osteoblast colony coverage of approximately 80%, similar to the control substrate (tissue culture polystyrene).

  11. X-ray photoelectron spectroscopy study of the growth kinetics of biomimetically grown hydroxyapatite thin-film coatings

    International Nuclear Information System (INIS)

    Hydroxyapatite (HA) thin-film coatings grown biomimetically using simulated body fluid (SBF) are desirable for a range of applications such as improved fixation of fine- and complex-shaped orthopedic and dental implants, tissue engineering scaffolds and localized and sustained drug delivery. There is a dearth of knowledge on two key aspects of SBF-grown HA coatings: (i) the growth kinetics over short deposition periods, hours rather than weeks; and (ii) possible difference between the coatings deposited with and without periodic SBF replenishment. A study centred on these aspects is reported. X-ray photoelectron spectroscopy (XPS) has been used to study the growth kinetics of SBF-grown HA coatings for deposition periods ranging from 0.5 h to 21 days. The coatings were deposited with and without periodic replenishment of SBF. The XPS studies revealed that: (i) a continuous, stable HA coating fully covered the titanium substrate after a growth period of 13 h without SBF replenishment; (ii) thicker HA coatings about 1 μm in thickness resulted after a growth period of 21 days, both with and without SBF replenishment; and (iii) the Ca/P ratio at the surface of the HA coating was significantly lower than that in its bulk. No significant difference between HA grown with and without periodic replenishment of SBF was found. The coatings were determined to be carbonated, a characteristic desirable for improved implant fixation. The atomic force and scanning electron microscopies results suggested that heterogeneous nucleation and growth are the primary deposition mode for these coatings. Primary osteoblast cell studies demonstrated the biocompatibility of these coatings, i.e., osteoblast colony coverage of approximately 80%, similar to the control substrate (tissue culture polystyrene).

  12. X-ray photoelectron spectroscopy analysis of aluminum and copper cleaning procedures for the Advanced Photon Source

    International Nuclear Information System (INIS)

    The Advanced Photon Source (APS), presently under construction, will produce x rays of unprecedented brightness. The storage ring where the x rays will be produced will be constructed from an extruded 6063 aluminum alloy, while transition pieces (flanges, etc.) will be made from a 2219 aluminum alloy. In addition, cooled photon absorbers will be placed in strategic locations throughout the ring to intercept the majority of the unused high power-density radiation. These will be made of either CDA-101 (OFHC) copper or glidcop (a dispersion strengthened copper alloy). Before any of these components can be assembled they must be cleaned to remove surface contaminants so that the ultrahigh vacuum (<0.1 nTorr) necessary for successful operation can be achieved. Many recipes for cleaning aluminum and copper exist; however, most of them involve the use of chemicals that present safety and/or environmental concerns. We have undertaken an x-ray photoelectron spectroscopy study of the effects of a variety of commercially available cleaners on the surface cleanliness of aluminum and copper. Several important results have been identified in this study. A simple alkaline detergent in an ultrasonic bath cleans aluminum alloys as effectively as the more aggressive cleaning solutions. The detergent can be used at 65 degree C to clean the 6063 alloy and at 50 degree C to clean the 2219 alloy. A citric acid based cleaner was found to be effective at cleaning copper, although the surface oxidizes rapidly. To date, we have been unable to find a universal cleaning procedure, i.e., one that is optimal for cleaning both Al and Cu

  13. X-ray photoelectron spectroscopy study of the growth kinetics of biomimetically grown hydroxyapatite thin-film coatings

    Energy Technology Data Exchange (ETDEWEB)

    McLeod, K. [Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095 (Australia); Kumar, S., E-mail: sunil.kumar@unisa.edu.au [Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095 (Australia); Dutta, N.K. [Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095 (Australia); Smart, R.St.C. [Applied Centre for Structural and Synchrotron Studies, University of South Australia, Mawson Lakes, SA 5095 (Australia); Voelcker, N.H. [School of Chemistry, Physics and Earth Sciences, Flinders University of South Australia, GPO Box 2100, Adelaide 5001 (Australia); Anderson, G.I. [School of Veterinary Science, University of Adelaide, Adelaide, SA 5005 (Australia)

    2010-09-15

    Hydroxyapatite (HA) thin-film coatings grown biomimetically using simulated body fluid (SBF) are desirable for a range of applications such as improved fixation of fine- and complex-shaped orthopedic and dental implants, tissue engineering scaffolds and localized and sustained drug delivery. There is a dearth of knowledge on two key aspects of SBF-grown HA coatings: (i) the growth kinetics over short deposition periods, hours rather than weeks; and (ii) possible difference between the coatings deposited with and without periodic SBF replenishment. A study centred on these aspects is reported. X-ray photoelectron spectroscopy (XPS) has been used to study the growth kinetics of SBF-grown HA coatings for deposition periods ranging from 0.5 h to 21 days. The coatings were deposited with and without periodic replenishment of SBF. The XPS studies revealed that: (i) a continuous, stable HA coating fully covered the titanium substrate after a growth period of 13 h without SBF replenishment; (ii) thicker HA coatings about 1 {mu}m in thickness resulted after a growth period of 21 days, both with and without SBF replenishment; and (iii) the Ca/P ratio at the surface of the HA coating was significantly lower than that in its bulk. No significant difference between HA grown with and without periodic replenishment of SBF was found. The coatings were determined to be carbonated, a characteristic desirable for improved implant fixation. The atomic force and scanning electron microscopies results suggested that heterogeneous nucleation and growth are the primary deposition mode for these coatings. Primary osteoblast cell studies demonstrated the biocompatibility of these coatings, i.e., osteoblast colony coverage of approximately 80%, similar to the control substrate (tissue culture polystyrene).

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

    Science.gov (United States)

    Hassan, S.; Yusof, M. S.; Embong, Z.; Maksud, M. I.

    2016-01-01

    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 (La2O3) 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 La2O3 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 La2O3 and La(OH)3. The information of oxygen species, O2- component from O 1s narrow scan indicated that there are four types of species which are contributed from the bulk (O2-), two chemisorb component (La2O3) and La(OH)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.

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

    International Nuclear Information System (INIS)

    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 (La2O3) 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 La2O3 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 La2O3 and La(OH)3. The information of oxygen species, O2- component from O 1s narrow scan indicated that there are four types of species which are contributed from the bulk (O2−), two chemisorb component (La2O3) and La(OH)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

  16. (3+1) Resonance enhanced multiphoton ionization-photoelectron spectroscopy on the E, F, and G Rydberg states of ClO

    OpenAIRE

    Buma, W.J.; Wales, N. P. L.; Lange

    1996-01-01

    (3 + 1) resonance enhanced multiphoton ionization-photoelectron spectroscopy is employed to investigate the spectroscopy and ionization dynamics of the E, F, and G Rydberg states of ClO. The results establish that the E and F Rydberg states converge upon the X3- ground ionic state, while the G state belongs to a Rydberg series with an excited a 1D ioni core. Improved ionization thresholds of these two ionic states are determined as 10.887 ± 0.005 and 11.750 ± 0.005 eV.

  17. Direct observation of electron dynamics in the attosecond domain.

    Science.gov (United States)

    Föhlisch, A; Feulner, P; Hennies, F; Fink, A; Menzel, D; Sanchez-Portal, D; Echenique, P M; Wurth, W

    2005-07-21

    Dynamical processes are commonly investigated using laser pump-probe experiments, with a pump pulse exciting the system of interest and a second probe pulse tracking its temporal evolution as a function of the delay between the pulses. Because the time resolution attainable in such experiments depends on the temporal definition of the laser pulses, pulse compression to 200 attoseconds (1 as = 10(-18) s) is a promising recent development. These ultrafast pulses have been fully characterized, and used to directly measure light waves and electronic relaxation in free atoms. But attosecond pulses can only be realized in the extreme ultraviolet and X-ray regime; in contrast, the optical laser pulses typically used for experiments on complex systems last several femtoseconds (1 fs = 10(-15) s). Here we monitor the dynamics of ultrafast electron transfer--a process important in photo- and electrochemistry and used in solid-state solar cells, molecular electronics and single-electron devices--on attosecond timescales using core-hole spectroscopy. We push the method, which uses the lifetime of a core electron hole as an internal reference clock for following dynamic processes, into the attosecond regime by focusing on short-lived holes with initial and final states in the same electronic shell. This allows us to show that electron transfer from an adsorbed sulphur atom to a ruthenium surface proceeds in about 320 as. PMID:16034414

  18. Thermal decomposition of methyl 2-azidopropionate studied by UV photoelectron spectroscopy and matrix isolation IR spectroscopy: heterocyclic intermediate vs imine formation.

    Science.gov (United States)

    Pinto, R M; Dias, A A; Costa, M L; Rodrigues, P; Barros, M T; Ogden, J S; Dyke, J M

    2011-08-01

    Methyl 2-azidopropionate (N(3)CH(3)CHCOOCH(3), M2AP) has been synthesized and characterized by different spectroscopic methods, and the thermal decomposition of this molecule has been investigated by matrix isolation infrared (IR) spectroscopy and ultraviolet photoelectron spectroscopy (UVPES). Computational methods have been employed in the spectral simulation of both UVPES and matrix IR spectra and in the rationalization of the thermal decomposition results. M2AP presents a HOMO vertical ionization energy (VIE) of 9.60 ± 0.03 eV and contributions from all four lowest-energy conformations of this molecule are detected in the gas phase. Its thermal decomposition starts at ca. 400 °C and is complete at ca. 650 °C, yielding N(2), CO, CO(2), CH(3)CN, and CH(3)OH as the final decomposition products. Methyl formate (MF) and CH(4) are also found during the pyrolysis process. Analysis of the potential energy surface of the decomposition of M2AP indicates that M2AP decomposes preferentially into the corresponding imine (M2IP), through a 1,2-H shift synchronous with the N(2) elimination (Type 1 mechanism), requiring an activation energy of 160.8 kJ/mol. The imine further decomposes via two competitive routes: one accounting for CO, CH(3)OH, and CH(3)CN (ΔE(G3) = 260.2 kJ/mol) and another leading to CO(2), CH(4), and CH(3)CN (ΔE(G3) = 268.6 kJ/mol). A heterocyclic intermediate (Type 2 mechanism)-4-Me-5-oxazolidone-can also be formed from M2AP via H transfer from the remote O-CH(3) group, together with the N(2) elimination (ΔE(G3) = 260.2 kJ/mol). Finally, a third pathway which accounts for the formation of MF through an M2AP isomer is envisioned.

  19. Attosecond physics at the nanoscale

    CERN Document Server

    Ciappina, M F; Landsman, A S; Okell, W; Zherebtsov, S; Förg, B; Schötz, J; Seiffert, J L; Fennel, T; Shaaran, T; Zimmermann, T; Chacón, A; Guichard, R; Zaïr, A; Tisch, J W G; Marangos, J P; Witting, T; Braun, A; Maier, S A; Roso, L; Krüger, M; Hommelhoff, P; Kling, M F; Krausz, F; Lewenstein, M

    2016-01-01

    Recently two emerging areas of research, attosecond and nanoscale physics, have started to come together. Attosecond physics deals with phenomena occurring when ultrashort laser pulses, with duration on the femto- and sub-femtosecond time scales, interact with atoms, molecules or solids. The laser-induced electron dynamics occurs natively on a timescale down to a few hundred or even tens of attoseconds, which is comparable with the optical field. On the other hand, the second branch involves the manipulation and engineering of mesoscopic systems, such as solids, metals and dielectrics, with nanometric precision. Although nano-engineering is a vast and well-established research field on its own, the merger with intense laser physics is relatively recent. In this article we present a comprehensive experimental and theoretical overview of physics that takes place when short and intense laser pulses interact with nanosystems, such as metallic and dielectric nanostructures. In particular we elucidate how the spati...

  20. Theory of attosecond delays in laser-assisted photoionization

    CERN Document Server

    Dahlström, J M; Klünder, K; Gisselbrecht, M; Mauritsson, J; L'Huillier, A; Maquet, A; Taïeb, R

    2011-01-01

    We study the temporal aspects of laser-assisted extreme ultraviolet (XUV) photoionization using attosecond pulses of harmonic radiation. The aim of this paper is to establish the general form of the phase of the relevant transition amplitudes and to make the connection with the time-delays that have been recently measured in experiments. We find that the overall phase contains two distinct types of contributions: one is expressed in terms of the phase-shifts of the photoelectron continuum wavefunction while the other is linked to continuum--continuum transitions induced by the infrared (IR) laser probe. Our formalism applies to both kinds of measurements reported so far, namely the ones using attosecond pulse trains of XUV harmonics and the others based on the use of isolated attosecond pulses (streaking). The connection between the phases and the time-delays is established with the help of finite difference approximations to the energy derivatives of the phases. This makes clear that the observed time-delays...

  1. Attosecond double-slit experiment.

    Science.gov (United States)

    Lindner, F; Schätzel, M G; Walther, H; Baltuska, A; Goulielmakis, E; Krausz, F; Milosević, D B; Bauer, D; Becker, W; Paulus, G G

    2005-07-22

    A new scheme for a double-slit experiment in the time domain is presented. Phase-stabilized few-cycle laser pulses open one to two windows (slits) of attosecond duration for photoionization. Fringes in the angle-resolved energy spectrum of varying visibility depending on the degree of which-way information are measured. A situation in which one and the same electron encounters a single and a double slit at the same time is observed. The investigation of the fringes makes possible interferometry on the attosecond time scale. From the number of visible fringes, for example, one derives that the slits are extended over about 500 as.

  2. Attosecond lighthouses from plasma mirrors

    OpenAIRE

    A. Wheeler, Jonathan; Borot, Antonin; Monchocé, Sylvain; Vincenti, Henri; Ricci, Aurélien; Malvache, Arnaud; Lopez-Martens, Rodrigo B.; Quéré, Fabien

    2012-01-01

    International audience The nonlinear interaction of an intense femtosecond laser pulse with matter can lead to the emission of a train of sub-laser-cycle--attosecond--bursts of short-wavelength radiation1, 2. Much effort has been devoted to producing isolated attosecond pulses, as these are better suited to real-time imaging of fundamental electronic processes3, 4, 5, 6. Successful methods developed so far rely on confining the nonlinear interaction to a single sub-cycle event7, 8, 9. Here...

  3. Study of attosecond delays using perturbation diagrams and exterior complex scaling

    CERN Document Server

    Dahlström, J M

    2014-01-01

    We describe in detail how attosecond delays in laser-assisted photoionization can be computed using perturbation theory based on two-photon matrix elements. Special emphasis is laid on above-threshold ionization, where the electron interacts with an infrared field after photoionization by an extreme ultraviolet field. Correlation effects are introduced using diagrammatic many-body theory to the level of the random-phase approximation with exchange (RPAE). Our aim is to provide an ab initio route to correlated multi-photon processes that are required for an accurate description of experiments on the attosecond time scale. Here, our results are focused on photoionization of the M -shell of argon atoms, where experiments have been carried out using the so-called RABITT technique. An influence of autoionizing resonances in attosecond delay measurements is observed. Further, it is shown that the delay depends on both detection angle of the photoelectron and energy of the probe photon.

  4. 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.

  5. Al capping layers for nondestructive x-ray photoelectron spectroscopy analyses of transition-metal nitride thin films

    Energy Technology Data Exchange (ETDEWEB)

    Greczynski, Grzegorz, E-mail: grzgr@ifm.liu.se; Hultman, Lars [Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping (Sweden); Petrov, Ivan [Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping, Sweden and Materials Science Department and Frederick Seitz Materials Research Laboratory, University of Illinois, Urbana, Illinois 61801 (United States); Greene, J. E. [Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping (Sweden); Materials Science Department and Frederick Seitz Materials Research Laboratory, University of Illinois, Urbana, Illinois 61801(United States); Department of Physics, University of Illinois, Urbana, Illinois 61801 (United States)

    2015-09-15

    X-ray photoelectron spectroscopy (XPS) compositional analyses of materials that have been air exposed typically require ion etching in order to remove contaminated surface layers. However, the etching step can lead to changes in sample surface and near-surface compositions due to preferential elemental sputter ejection and forward recoil implantation; this is a particular problem for metal/gas compounds and alloys such as nitrides and oxides. Here, the authors use TiN as a model system and compare XPS analysis results from three sets of polycrystalline TiN/Si(001) films deposited by reactive magnetron sputtering in a separate vacuum chamber. The films are either (1) air-exposed for ≤10 min prior to insertion into the ultrahigh-vacuum (UHV) XPS system; (2) air-exposed and subject to ion etching, using different ion energies and beam incidence angles, in the XPS chamber prior to analysis; or (3) Al-capped in-situ in the deposition system prior to air-exposure and loading into the XPS instrument. The authors show that thin, 1.5–6.0 nm, Al capping layers provide effective barriers to oxidation and contamination of TiN surfaces, thus allowing nondestructive acquisition of high-resolution core-level spectra representative of clean samples, and, hence, correct bonding assignments. The Ti 2p and N 1s satellite features, which are sensitive to ion bombardment, exhibit high intensities comparable to those obtained from single-crystal TiN/MgO(001) films grown and analyzed in-situ in a UHV XPS system and there is no indication of Al/TiN interfacial reactions. XPS-determined N/Ti concentrations acquired from Al/TiN samples agree very well with Rutherford backscattering and elastic recoil analysis results while ion-etched air-exposed samples exhibit strong N loss due to preferential resputtering. The intensities and shapes of the Ti 2p and N 1s core level signals from Al/TiN/Si(001) samples do not change following long-term (up to 70 days) exposure to ambient conditions

  6. Flexible Acyclic Polyol-Chloride Anion Complexes and Their Characterization by Photoelectron Spectroscopy and Variable Temperature Binding Constant Determinations.

    Science.gov (United States)

    Shokri, Alireza; Wang, Xue-Bin; Wang, Yanping; O'Doherty, George A; Kass, Steven R

    2016-03-17

    Flexible acyclic alcohols with one to five hydroxyl groups were bound to a chloride anion and these complexes were interrogated by negative ion photoelectron spectroscopy and companion density functional theory computations. The resulting vertical detachment energies are reproduced on average to 0.10 eV by M06-2X/aug-cc-pVTZ predictions and range from 4.45-5.96 eV. These values are 0.84-2.35 eV larger than the adiabatic detachment energy of Cl(-) as a result of the larger hydrogen bond networks in the bigger polyols. Adiabatic detachment energies of the alcohol-Cl(-) clusters are more difficult to determine both experimentally and computationally. This is due to the large geometry changes that occur upon photodetachment and the large bond dissociation energy of H-Cl which enables the resulting chlorine atom to abstract a hydrogen from any of the methylene (CH2) or methine (CH) positions. Both ionic and nonionic hydrogen bonds (i.e., OH···Cl(-) and OH···OH···Cl(-)) form in the larger polyols complexes and are found to be energetically comparable. Subtle structural differences, consequently can lead to the formation of different types of hydrogen bonds, and maximizing the ionic ones is not always preferred. Solution equilibrium binding constants between the alcohols and tetrabutylammonium chloride (TBACl) in acetonitrile at -24.2, +22.0, and +53.6 °C were also determined. The free energies of association are nearly identical for all of the substrates (i.e., ΔG° = -2.8 ± 0.7 kcal mol(-1)). Compensating enthalpy and entropy values reveal, contrary to expectation and the intrinsic gas-phase preferences, that the bigger systems with more hydroxyl groups are entropically favored and enthalpically disfavored relative to the smaller species. This suggests that more solvent molecules are released upon binding TBACl to alcohols with more hydroxyl groups and is consistent with the measured negative heat capacities. These quantities increase with molecular

  7. Flexible Acyclic Polyol-Chloride Anion Complexes and Their Characterization by Photoelectron Spectroscopy and Variable Temperature Binding Constant Determinations

    Energy Technology Data Exchange (ETDEWEB)

    Shokri, Alireza; Wang, Xue B.; Wang, Yangping; O' Doherty, George A.; Kass, Steven R.

    2016-03-17

    Flexible acyclic alcohols with 1–5 hydroxyl groups were bound to chloride anion and these complexes were interrogated by negative ion photoelectron spectroscopy and companion density functional theory computations. The resulting vertical detachment energies are reproduced on average to 0.10 eV by M06-2X/aug-cc-pVTZ predictions and range from 4.45 – 5.96 eV. These values are 0.84 – 2.35 eV larger than the adiabatic detachment energy of Cl– as a result of the larger hydrogen bond networks in the bigger polyols. Adiabatic detachment energies of the alcohol–Cl– clusters are more difficult to determine both experimentally and computationally. This is due to the large geometry changes that occur upon photodetachment and the large bond dissociation energy of H–Cl which enables the resulting chlorine atom to abstract a hydrogen from any of the methylene (CH2) or methine (CH) positions. Both ionic and non-ionic hydrogen bonds (i.e., OH•••Cl– and OH•••OH•••Cl–) form in the larger polyols complexes, and are found to be energetically comparable. Subtle structural differences, consequently can lead to the formation of different types of hydrogen bonds and maximizing the ionic ones is not always preferred. Solution equilibrium binding constants between the alcohols and tetrrabuylammonium chloride (TBACl) in acetonitrile at -24.2, 22.0, and 53.6 °C were also determined. The free energies of association are nearly identical for all of the substrates (i.e., ΔG° = -2.8 ± 0.7 kcal mol–1). Compensating enthalpy and entropy values reveal, contrary to expectation and the intrinsic gas-phase preferences, that the bigger systems with more hydroxyl groups are entropically favored and enthalpically disfavored relative to the smaller species. This suggests that more solvent molecules are released upon binding TBACl to alcohols with more hydroxyl groups and is consistent with the measured negative heat capacities. These quantities increase with

  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

    2012-07-28

    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. PMID:22852618

  9. Photoelectron spectroscopy of aqueous solutions: Streaming potentials of NaX (X = Cl, Br, and I) solutions and electron binding energies of liquid water and X−

    International Nuclear Information System (INIS)

    The streaming potentials of liquid beams of aqueous NaCl, NaBr, and NaI solutions are measured using soft X-ray, He(I), and laser multiphoton ionization photoelectron spectroscopy. Gaseous molecules are ionized in the vicinity of liquid beams and the photoelectron energy shifts are measured as a function of the distance between the ionization point and the liquid beam. The streaming potentials change their polarity with concentration of electrolytes, from which the singular points of concentration eliminating the streaming potentials are determined. The streaming currents measured in air also vanish at these concentrations. The electron binding energies of liquid water and I−, Br−, and Cl− anions are revisited and determined more accurately than in previous studies

  10. Ptychographic reconstruction of attosecond pulses

    CERN Document Server

    Lucchini, M; Ludwig, A; Gallmann, L; Keller, U; Feurer, T

    2015-01-01

    We demonstrate a new attosecond pulse reconstruction modality which uses an algorithm that is derived from ptychography. In contrast to other methods, energy and delay sampling are not correlated, and as a result, the number of electron spectra to record is considerably smaller. Together with the robust algorithm, this leads to a more precise and fast convergence of the reconstruction.

  11. Photoelectron spectroscopy of sequential three-photon double ionization of Ar irradiated by EUV free-electron laser pulses

    International Nuclear Information System (INIS)

    We have investigated the ionization of the Ar atom by 51 nm extreme-ultraviolet light pulses at the free-electron laser facility, SPring-8 Compact SASE Source test accelerator, in Japan. The angle-resolved photoelectron spectra contain lines due to sequential three-photon double ionization with the second ionization step proceeding via the resonantly enhanced two-photon absorption. The relative intensities of the corresponding photoelectron peaks and their angular dependence are explained in the framework of a three-step model of the process. (fast track communication)

  12. Photoelectron spectroscopy of sequential three-photon double ionization of Ar irradiated by EUV free-electron laser pulses

    Energy Technology Data Exchange (ETDEWEB)

    Fukuzawa, H; Gryzlova, E V; Motomura, K; Yamada, A; Ueda, K; Piseri, P; Mazza, T; Devetta, M [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan); Grum-Grzhimailo, A N; Strakhova, S I [Institute of Nuclear Physics, Moscow State University, Moscow 119991 (Russian Federation); Nagaya, K; Sugishima, A; Mizoguchi, Y; Iwayama, H; Yao, M; Saito, N; Coreno, M; Nagasono, M; Tono, K; Yabashi, M, E-mail: fukuzawa@tagen.tohoku.ac.j [RIKEN, XFEL Project Head Office, Sayo, Hyogo 679-5148 (Japan)

    2010-06-14

    We have investigated the ionization of the Ar atom by 51 nm extreme-ultraviolet light pulses at the free-electron laser facility, SPring-8 Compact SASE Source test accelerator, in Japan. The angle-resolved photoelectron spectra contain lines due to sequential three-photon double ionization with the second ionization step proceeding via the resonantly enhanced two-photon absorption. The relative intensities of the corresponding photoelectron peaks and their angular dependence are explained in the framework of a three-step model of the process. (fast track communication)

  13. Two-Dimensional Attosecond Electron Wave Packet Interferometry

    CERN Document Server

    Xie, Xinhua

    2014-01-01

    We propose a two-dimensional interferometry based on electron wave packet interference with a cycle-shaped orthogonally polarized two-color laser field. With such method, sub-cycle and inter-cycle interferences can be disentangled into different direction in the measured photoelectron momentum spectra. With the cycle-shaped laser field, the Coulomb influence can be minimized and the overlapping of interference fringes with the complicate low-energy structures can be avoided as well. The contributions of excitation effect and long-range Coulomb potential can be traced in the Fourier domain of the photoelectron distributions. With these advantages, it allows to get precise information on valence electron dynamics of atoms or molecules with attosecond resolution and additional spatial information with angstrom resolution.

  14. Attosecond Coherent Control of the Photo-Dissociation of Oxygen Molecules

    Science.gov (United States)

    Sturm, Felix; Ray, Dipanwita; Wright, Travis; Shivaram, Niranjan; Bocharova, Irina; Slaughter, Daniel; Ranitovic, Predrag; Belkacem, Ali; Weber, Thorsten

    2016-05-01

    Attosecond Coherent Control has emerged in recent years as a technique to manipulate the absorption and ionization in atoms as well as the dissociation of molecules on an attosecond time scale. Single attosecond pulses and attosecond pulse trains (APTs) can coherently excite multiple electronic states. The electronic and nuclear wave packets can then be coupled with a second pulse forming multiple interfering quantum pathways. We have built a high flux extreme ultraviolet (XUV) light source delivering APTs based on HHG that allows to selectively excite neutral and ion states in molecules. Our beamline provides spectral selectivity and attosecond interferometric control of the pulses. In the study presented here, we use APTs, generated by High Harmonic Generation in a high flux extreme ultraviolet light source, to ionize highly excited states of oxygen molecules. We identify the ionization/dissociation pathways revealing vibrational structure with ultra-high resolution ion 3D-momentum imaging spectroscopy. Furthermore, we introduce a delay between IR pulses and XUV/IR pulses to constructively or destructively interfere the ionization and dissociation pathways, thus, enabling the manipulation of both the O2+and the O+ ion yields with attosecond precision. Supported by DOE under Contract No. DE-AC02-05CH11231.

  15. Ionization and transient absorption control with a resonant attosecond clock

    International Nuclear Information System (INIS)

    Metastable states are important actors in the ionisation of atoms and molecules. Sub-femtosecond extreme ultraviolet pulses can coherently populate several transiently bound states at once, thus starting the attosecond clocks which are required to monitor and control ultrafast electronic evolution above the ionisation threshold. Here we illustrate, from a theoretical point of view, the effects coherent superpositions of 1Po doubly excited states in the helium atom have on channel-resolved photoelectron spectra as well as on the transient absorption spectrum of the atom in the extreme ultraviolet region, when they are created by a single-attosecond pulse in the presence of a strong few-cycle near-infrared/visible pulse which acts as a probe. Interference fringes varying rapidly with the pump-probe time delay are visible in both photoelectron and transient absorption spectra. From such fringes, the wave packet itself can conceivably be reconstructed. Conversely, all observables are modulated by the characteristic beating periods of the wave packet, so that control of partial ionisation yields, branching ratios, and light absorption or amplification can be achieved

  16. Efficient generation of isolated attosecond pulses with high beam-quality by two-color Bessel-Gauss beams

    CERN Document Server

    Wang, Zhe; Zhang, Qingbin; Wang, Shaoyi; Lu, Peixiang

    2011-01-01

    The generation of isolated attosecond pulses with high efficiency and high beam quality is essential for attosec- ond spectroscopy. We numerically investigate the supercontinuum generation in a neutral rare-gas medium driven by a two-color Bessel-Gauss beam. The results show that an efficient smooth supercontinuum in the plateau is obtained after propagation, and the spatial profile of the generated attosecond pulse is Gaussian-like with the divergence angle of 0.1 degree in the far field. This bright source with high beam quality is beneficial for detecting and controlling the microscopic processes on attosecond time scale.

  17. Attosecond VUV Coherent Control of Molecular Dynamics

    CERN Document Server

    Ranitovic, P; Riviere, P; Palacios, A; Tong, X M; Toshima, N; Gonzalez-Castrillo, A; Martin, L; Martin, F; Murnane, M M; Kapteyn, H C

    2014-01-01

    High harmonic light sources make it possible to access attosecond time-scales, thus opening up the prospect of manipulating electronic wave packets for steering molecular dynamics. However, two decades after the birth of attosecond physics, the concept of attosecond chemistry has not yet been realized. This is because excitation and manipulation of molecular orbitals requires precisely controlled attosecond waveforms in the deep ultraviolet, which have not yet been synthesized. Here, we present a novel approach using attosecond vacuum ultraviolet pulse-trains to coherently excite and control the outcome of a simple chemical reaction in a deuterium molecule in a non-Born Oppenheimer regime. By controlling the interfering pathways of electron wave packets in the excited neutral and singly-ionized molecule, we unambiguously show that we can switch the excited electronic state on attosecond timescales, coherently guide the nuclear wave packets to dictate the way a neutral molecule vibrates, and steer and manipula...

  18. Investigation of Oxygen Vacancy and Interstitial Oxygen Defects in ZnO Films by Photoluminescence and X-Ray Photoelectron Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    FAN Hai-Bo; YANG Shao-Yan; ZHANG Pan-Feng; WEI Hong-Yuan; LIU Xiang-Lin; JIAO Chun-Mei; ZHU Qin-Sheng; CHEN Yong-Hai; WANG Zhan-Guo

    2007-01-01

    ZnO films prepared at different temperatures and annealed at 900 C in oxygen are studied by photoluminescence (PL) and x-ray photoelectron spectroscopy (XPS). It is observed that in the PL of the as-grown films the green luminescence (GL) and the yellow luminescence (YL) are related, and after annealing the GL is restrained and the YL is enhanced. The O 1s XPS results also show the coexistence of oxygen vacancy (Vo) and interstitial oxygen (Oi) before annealing and the quenching of the Vo after annealing. By combining the two results it is deduced that the GL and YL are related to the Vo and Oi defects, respectively.

  19. 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.

  20. Study by X-ray photoelectron spectroscopy (XPS) and radiochemistry (Cl36) of the interaction of chloride ions with a passive film formed on nickel

    International Nuclear Information System (INIS)

    This research thesis reports the study of the influence of chlorides on nickel passivation by using a radiochemical method based on the use of the Cl36 isotope and the X-ray photoelectron spectroscopy (XPS). The first one allows the in-situ determination of the adsorption of chlorides on the surface, or their inclusion in surface films during the electrochemical treatment. The XPS analysis allows the characterization of modifications induced by chlorides in passive films. The obtained results allow a better understanding in the interpretation of the mechanisms of corrosion induced by chloride ions

  1. X-ray photoelectron spectroscopy investigation of the Schottky barrier at low-k a-SiO(C):H/Cu interfaces

    International Nuclear Information System (INIS)

    In order to understand the fundamental mechanisms involved in electrical leakage in low-k/Cu interconnects, we have utilized x-ray photoelectron spectroscopy to determine the Schottky barrier present at interfaces formed by plasma enhanced chemical vapor deposition of low-k a-SiOxCy:H thin films on polished Cu substrates. We find the Schottky Barrier at this interface to range widely from 1 to >4 eV and to be dependent on the amount of network carbon incorporated into the a-SiOC:H thin films.

  2. Complementary low energy ion scattering and X-ray photoelectron spectroscopy characterization of polystyrene submitted to N{sub 2}/H{sub 2} glow discharge

    Energy Technology Data Exchange (ETDEWEB)

    Bonatto, F., E-mail: bonatto02@yahoo.com.br [Instituto de Fisica, Universidade Federal do Rio Grande do Sul, Porto Alegre, Rio Grande do Sul 91509-900 (Brazil); Rovani, S. [Universidade de Caxias do Sul, Caxias do Sul, Rio Grande do Sul 95070-560 (Brazil); Kaufmann, I.R.; Soares, G.V. [Instituto de Fisica, Universidade Federal do Rio Grande do Sul, Porto Alegre, Rio Grande do Sul 91509-900 (Brazil); Baumvol, I.J.R. [Instituto de Fisica, Universidade Federal do Rio Grande do Sul, Porto Alegre, Rio Grande do Sul 91509-900 (Brazil); Universidade de Caxias do Sul, Caxias do Sul, Rio Grande do Sul 95070-560 (Brazil); Krug, C. [Instituto de Fisica, Universidade Federal do Rio Grande do Sul, Porto Alegre, Rio Grande do Sul 91509-900 (Brazil)

    2012-02-15

    Low energy ion scattering (LEIS) and X-ray photoelectron spectroscopy (XPS) were used to access the elemental composition and chemical bonding characteristics of polystyrene (PS) surfaces sequentially treated by corona and glow discharge (plasma) processing in N{sub 2}/H{sub 2} ambient. The latter has shown activity as suppressor of pathogenic Staphylococcus epidermidis biofilms. LEIS indicated that oxygen from the corona discharge process is progressively replaced by nitrogen at the PS surface. XPS shows C=N and N-C=O chemical groups as significant inhibitors of bacterial adhesion, suggesting application in medical devices.

  3. Zero kinetic energy-pulsed field ionization and resonance enhanced multiphoton ionization photoelectron spectroscopy: ionization dynamics of Rydberg states in HBr.

    OpenAIRE

    Wales, N.P.L.; Buma, W.J.; Lange; Lefebvre-Brion, H.; Wang, K.; McKoy, V.

    1996-01-01

    The results of rotationally resolved resonance enhanced multiphoton ionization photoelectron spectroscopy and zero kinetic energy‐pulsed field ionization studies on HBr via various rotational levels of the F^ 1Δ_2 and f^ 3Δ_2 Rydberg states are reported. These studies lead to an accurate determination of the lowest ionization threshold as 94 098.9±1 cm^(−1). Observed rotational and spin–orbit branching ratios are compared to the results of ab initio calculations. The differences between theor...

  4. X-ray photoelectron spectroscopy studies of Ag-doped thin amorphous Ge{sub x}Sb{sub 40-x}S{sub 60} films

    Energy Technology Data Exchange (ETDEWEB)

    Debnath, R.K.; Fitzgerald, A.G.; Christova, K

    2002-12-30

    X-ray photoelectron spectroscopy has been used to determine the binding energies of the core electrons in Ag-doped amorphous thin Ge{sub x}Sb{sub 40-x}S{sub 60} films (x=15, 20, 25 and 27). Chemical shifts of the constituent elements have revealed that electrons are transferred from chalcogenide to metal and compounds such as Ag{sub 2}S and Ag{sub 2}O are likely to foue to photo-induced chemical modification and oxidation, respectively. Charge defects are induced in the amorphous system.

  5. X-ray photoelectron spectroscopy analysis for undegraded and degraded Gd2O2S:Tb3+ phosphor thin films

    International Nuclear Information System (INIS)

    This paper presents the X-ray Photoelectron Spectroscopy (XPS) analysis for the undegraded and degraded Gd2O2S:Tb3+ thin film phosphor. The thin films were grown with the pulsed laser deposition (PLD) technique. XPS measurements were done on Gd2O2S:Tb3+ phosphor thin films before and after electron degradation. The XPS technique has proven the presence of Gd2O3 on the degraded and undegraded thin film spots. The presence of the SO2 bonding was also detected after degradation. This clearly indicates that surface reactions did occur during prolonged electron bombardment in an oxygen atmosphere.

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

    OpenAIRE

    Strocov, V. N.; Schmitt, T; U. Flechsig; Schmidt, T.; Imhof, A; Q. Chen; J. Raabe; Betemps, R.; Zimoch, D.; Krempasky, J.; A. Piazzalunga; X Wang; Grioni, M.; Patthey, L.

    2009-01-01

    We describe the concepts and technical realization 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). 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 deg rotatable linear polarizations) but als...

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

    OpenAIRE

    Strocov, V. N.; Schmitt, T; U. Flechsig; Schmidt, T.; Imhof, A; Q. Chen; J. Raabe; Betemps, R.; Zimoch, D.; Krempasky, J.; X Wang; Grioni, M.; A. Piazzalunga; Patthey, L.

    2010-01-01

    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...

  8. 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.

  9. A photoelectron spectroscopy study of the electronic structure evolution in CuInSe2-related compounds at changing copper content

    International Nuclear Information System (INIS)

    Evolution of the valence-band structure at gradually increasing copper content has been analysed by x-ray photoelectron spectroscopy (XPS) in In2Se3, CuIn5Se8, CuIn3Se5, and CuInSe2 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.

  10. Photoelectron Spectroscopy and Electronic Structure Calculations of d1 Vanadocene Compounds with Chelated Dithiolate Ligands: Implications for Pyranopterin Mo/W Enzymes

    OpenAIRE

    Cranswick, Matthew A.; Dawson, Alice; Cooney, J. Jon A.; Gruhn, Nadine E.; Lichtenberger, Dennis L.; Enemark, John H.

    2007-01-01

    Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the electronic structures of open-shell bent vanadocene compounds with chelating dithiolate ligands, which are minimum molecular models of the active sites of pyranopterin Mo/W enzymes. The compounds Cp2V(dithiolate) [where dithiolate is 1,2-ethenedithiolate (S2C2H2) or 1,2-benzenedithiolate (bdt), and Cp is cyclopentadienyl] provide access to a 17-electron, d1 electron configuration at the metal ...

  11. Dynamic secondary ion mass spectrometry and X-ray photoelectron spectroscopy on artistic bronze and copper artificial patinas

    International Nuclear Information System (INIS)

    To prevent the natural processes of decay and to develop and improve the treatments of conservation and restoration of artistic bronzes meaning statues and sculptures, it is important understanding the patination processes and the knowledge of artificially corroded surfaces. Chemical and physical characterization of artificial patinas obtained on artistic bronzes and coppers by using the 19th century Western traditional patination techniques and recipes by means of SEM-EDS, light microscopy and ATR/FT-IR has been done in previous studies [I.Z. Balta, L. Robbiola, Characterization of artificial black patinas on artistic cast bronze and pure copper by using SEM-EDS and light microscopy, in: Proceedings of the 13th European Microscopy Congress, 22-27 August 2004, Antwerp, Belgium, EMC 2004 CD-Rom Conference Preprints; I.Z. Balta, L. Robbiola, Traditional artificial artistic bronze and copper patinas-an investigation by SEM-EDS and ATR/FT-IR, in: Proceedings of the 8th International Conference on Non Destructive Investigations and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage, 15-19 May 2005, Lecce, Italy, ART'05 CD-Rom Conference Preprints]. Differences in morphology (structure, thickness, porosity, adherence, compactity, uniformity, homogeneity) and also in composition, on both artistic cast bronze and pure copper patinas, were clearly evidenced. Further in-depth investigation is required to be carried out in order to better understand the patinas mechanisms of formation and the layers kinetics of growth. The elemental and chemical analysis, either on a surface monolayer or in a depth profile, by using the Secondary Ion Mass Spectrometry (SIMS) and X-ray Photoelectron Spectroscopy (XPS) techniques, can provide this kind of information, unique at trace-level sensitivity. SIMS has proved to be a suitable analytical technique for analyzing small amounts of material with high atomic sensitivity (ppm or even ppb) and high

  12. Dynamic secondary ion mass spectrometry and X-ray photoelectron spectroscopy on artistic bronze and copper artificial patinas

    Science.gov (United States)

    Balta, I. Z.; Pederzoli, S.; Iacob, E.; Bersani, M.

    2009-04-01

    To prevent the natural processes of decay and to develop and improve the treatments of conservation and restoration of artistic bronzes meaning statues and sculptures, it is important understanding the patination processes and the knowledge of artificially corroded surfaces. Chemical and physical characterization of artificial patinas obtained on artistic bronzes and coppers by using the 19th century Western traditional patination techniques and recipes by means of SEM-EDS, light microscopy and ATR/FT-IR has been done in previous studies [I.Z. Balta, L. Robbiola, Characterization of artificial black patinas on artistic cast bronze and pure copper by using SEM-EDS and light microscopy, in: Proceedings of the 13th European Microscopy Congress, 22-27 August 2004, Antwerp, Belgium, EMC 2004 CD-Rom Conference Preprints; I.Z. Balta, L. Robbiola, Traditional artificial artistic bronze and copper patinas—an investigation by SEM-EDS and ATR/FT-IR, in: Proceedings of the 8th International Conference on Non Destructive Investigations and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage, 15-19 May 2005, Lecce, Italy, ART'05 CD-Rom Conference Preprints]. Differences in morphology (structure, thickness, porosity, adherence, compactity, uniformity, homogeneity) and also in composition, on both artistic cast bronze and pure copper patinas, were clearly evidenced. Further in-depth investigation is required to be carried out in order to better understand the patinas mechanisms of formation and the layers kinetics of growth. The elemental and chemical analysis, either on a surface monolayer or in a depth profile, by using the Secondary Ion Mass Spectrometry (SIMS) and X-ray Photoelectron Spectroscopy (XPS) techniques, can provide this kind of information, unique at trace-level sensitivity. SIMS has proved to be a suitable analytical technique for analyzing small amounts of material with high atomic sensitivity (ppm or even ppb) and high

  13. Spectroscopy

    CERN Document Server

    Walker, S

    1976-01-01

    The three volumes of Spectroscopy constitute the one comprehensive text available on the principles, practice and applications of spectroscopy. By giving full accounts of those spectroscopic techniques only recently introduced into student courses - such as Mössbauer spectroscopy and photoelectron spectroscopy - in addition to those techniques long recognised as being essential in chemistry teaching - sucha as e.s.r. and infrared spectroscopy - the book caters for the complete requirements of undergraduate students and at the same time provides a sound introduction to special topics for graduate students.

  14. Attosecond Interference Induced by Coulomb-Field-Driven Transverse Backward-Scattering Electron Wave-Packets

    CERN Document Server

    Song, Xiaohong; Lin, Cheng; Sheng, Zhihao; Yu, Xianhuan; Yang, Weifeng; Hu, Shilin; Chen, Jing; Xu, SongPo; Chen, YongJu; Quan, Wei; Liu, XiaoJun

    2016-01-01

    A novel and universal interference structure is found in the photoelectron momentum distribution of atoms in intense infrared laser field. Theoretical analysis shows that this structure can be attributed to a new form of Coulomb-field-driven backward-scattering of photoelectrons in the direction perpendicular to the laser field, in contrast to the conventional rescattering along the laser polarization direction. This transverse backward-scattering process is closely related to a family of photoelectrons initially ionized within a time interval of less than 200 attosecond around the crest of the laser electric field. Those electrons, acquiring near-zero return energy in the laser field, will be pulled back solely by the ionic Coulomb field and backscattered in the transverse direction. Moreover, this rescattering process mainly occurs at the first or the second return times, giving rise to different phases of the photoelectrons. The interference between these photoelectrons leads to unique curved interference ...

  15. Confirmation of intrinsic electron gap states at nonpolar GaN(1-100) surfaces combining photoelectron and surface optical spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Himmerlich, M., E-mail: marcel.himmerlich@tu-ilmenau.de; Eisenhardt, A.; Shokhovets, S.; Krischok, S. [Institut für Physik and Institut für Mikro- und Nanotechnologien, TU Ilmenau, PF 100565, 98684 Ilmenau (Germany); Räthel, J.; Speiser, E.; Neumann, M. D.; Navarro-Quezada, A.; Esser, N. [Leibniz-Institut für Analytische Wissenschaften - ISAS - e.V., Albert-Einstein-Strasse 9, 12489 Berlin (Germany)

    2014-04-28

    The electronic structure of GaN(1–100) surfaces is investigated in-situ by photoelectron spectroscopy (PES) and reflection anisotropy spectroscopy (RAS). Occupied surface states 3.1 eV below the Fermi energy are observed by PES, accompanied by surface optical transitions found in RAS around 3.3 eV, i.e., below the bulk band gap. These results indicate that the GaN(1–100) surface band gap is smaller than the bulk one due to the existence of intra-gap states, in agreement with density functional theory calculations. Furthermore, the experiments demonstrate that RAS can be applied for optical surface studies of anisotropic crystals.

  16. X-ray photoelectron spectroscopy of Er{sup 3+}-activated SiO{sub 2}-HfO{sub 2} glass-ceramic waveguides

    Energy Technology Data Exchange (ETDEWEB)

    Minati, L; Speranza, G; Micheli, V [FBK via Sommarive 18, Povo, 38100 Trento (Italy); Ferrari, M; Jestin, Y [CNR-IFN, Istituto di Fotonica e Nanotecnologie, CSMFO Lab., Via alla Cascata, 56/C, Povo, 38100 Trento (Italy)], E-mail: luminati@fbk.eu

    2009-01-07

    xHfO{sub 2}-(100 - x) SiO{sub 2} (x = 10, 20, 30 mol%) glass-ceramic planar waveguides doped with 0.3 mol% Er{sup 3+} ions, prepared by the sol-gel route and heat treated at 1000 deg. C to nucleate HfO{sub 2} crystals, were analysed by x-ray photoelectron spectroscopy, x-ray diffraction, high resolution transmission electron microscopy and photoluminescence spectroscopy. Formation of tetragonal HfO{sub 2} nanocrystals has been evidenced in all the samples. Spectroscopic parameters concerning the {sup 4}I{sub 13/2} metastable state of Er{sup 3+}ion are revisited as a function of XPS analysis.

  17. Hard X-ray photoelectron spectroscopy (HAXPES) (15 keV) at SpLine, the Spanish CRG beamline at the ESRF

    International Nuclear Information System (INIS)

    In this contribution we present the actual status of the SpLine project devoted to the implementation of hard (15 keV) X-ray photoelectron spectroscopy (HAXPES) in combination with surface X-ray diffraction (SXRD) at the Spanish CRG beamline (SpLine) at the European Synchrotron Radiation Facility (ESRF). The beamline is located at the bending magnet D25 at the ESRF and can be operated in the X-ray energy range 5-45 keV. The main project goals are the detection of very high kinetic energy photoelectrons up to 15 keV, in particular the simultaneous detection of the diffracted photons and photo-emitted electrons. Therefore, special effort has been devoted to develop a novel electron analyzer, capable of working at very high as well as low energies. The analyzer is a sector of a Cylindrical Mirror Analyzer (CSA300HV) with a five-elements retarding-lens system and a very compact size compared to standard hemispherical analyzers. Additionally, an ultra-high-vacuum system has been constructed which will simultaneously fulfill the requirements for HAXPES and SXRD. The vacuum chamber has two Be windows so that the in-coming and out-going X-ray beam will hit the sample and the X-ray detector, respectively. The complete system will be installed on a massive 2S+3D diffractometer. Photoelectron spectroscopy and SXRD can be operated either simultaneously or independently from each other. Test experiments with a UV discharge lamp and a RHEED electron gun have been conducted demonstrating that the analyzer performs satisfactorily. The whole set-up is in the commissioning phase and full operation is expected in the course of 2005

  18. Adsorption and deposition of anthraquinone-2-carboxylic acid on alumina studied by inelastic electron tunneling spectroscopy, infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Higo, Morihide [Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima 890-0065 (Japan)], E-mail: higo@apc.kagoshima-u.ac.jp; Miake, Takeshi; Mitsushio, Masaru; Yoshidome, Toshifumi [Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima 890-0065 (Japan); Ozono, Yoshihisa [Center for Instrumental analysis, Kagoshima University, 1-21-40 Korimoto, Kagoshima 890-0065 (Japan)

    2008-04-30

    The adsorption state of anthraquinone-2-carboxylic acid (AQ-2-COOH) deposited from acetone solutions (0.01-1.00 mg/ml) on native oxide surfaces of Al films was characterized by inelastic electron tunneling spectroscopy, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy. The oxide was prepared on evaporated Al films at room temperature in an oxygen-dc glow discharge. The morphology of the deposited AQ-2-COOH on the oxide surfaces was observed and analyzed by atomic force microscopy. These surface analyses showed that AQ-2-COOH is adsorbed predominantly as a uniform nanometer-scale film of carboxylate anions on the oxide surfaces deposited from solutions with concentrations lower than or equal to 0.02 mg/ml. It was found that AQ-2-COOH is adsorbed as both a uniform film of anions and as micron-sized particles of neutral molecules with heights of a few tens of nanometers when AQ-2-COOH is deposited from solutions with concentrations higher than 0.02 mg/ml. A comparison of the results obtained by these surface analytical techniques clearly shows the features and advantages of these analytical techniques.

  19. Adsorption and deposition of anthraquinone-2-carboxylic acid on alumina studied by inelastic electron tunneling spectroscopy, infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy

    International Nuclear Information System (INIS)

    The adsorption state of anthraquinone-2-carboxylic acid (AQ-2-COOH) deposited from acetone solutions (0.01-1.00 mg/ml) on native oxide surfaces of Al films was characterized by inelastic electron tunneling spectroscopy, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy. The oxide was prepared on evaporated Al films at room temperature in an oxygen-dc glow discharge. The morphology of the deposited AQ-2-COOH on the oxide surfaces was observed and analyzed by atomic force microscopy. These surface analyses showed that AQ-2-COOH is adsorbed predominantly as a uniform nanometer-scale film of carboxylate anions on the oxide surfaces deposited from solutions with concentrations lower than or equal to 0.02 mg/ml. It was found that AQ-2-COOH is adsorbed as both a uniform film of anions and as micron-sized particles of neutral molecules with heights of a few tens of nanometers when AQ-2-COOH is deposited from solutions with concentrations higher than 0.02 mg/ml. A comparison of the results obtained by these surface analytical techniques clearly shows the features and advantages of these analytical techniques

  20. In situ study of an oxidation reaction on a Pt/C electrode by ambient pressure hard X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Takagi, Yasumasa, E-mail: ytakagi@ims.ac.jp; Uemura, Yohei; Yokoyama, Toshihiko [Department of Molecular Structure, Institute for Molecular Science, Myodaiji-cho, Okazaki, Aichi 444-8585 (Japan); The Graduate University for Advanced Studies (SOKENDAI), Myodaiji-cho, Okazaki, Aichi 444-8585 (Japan); Wang, Heng [Department of Molecular Structure, Institute for Molecular Science, Myodaiji-cho, Okazaki, Aichi 444-8585 (Japan); Ikenaga, Eiji; Ohashi, Haruhiko; Senba, Yasunori; Yumoto, Hirokatsu; Yamazaki, Hiroshi; Goto, Shunji [Japan Synchrotron Radiation Research Institute, SPring-8, Koto, Sayo, Hyogo 679-5198 (Japan); Sekizawa, Oki; Iwasawa, Yasuhiro [Innovation Research Center for Fuel Cells, The University of Electro-Communications, Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Uruga, Tomoya [Japan Synchrotron Radiation Research Institute, SPring-8, Koto, Sayo, Hyogo 679-5198 (Japan); Innovation Research Center for Fuel Cells, The University of Electro-Communications, Chofugaoka, Chofu, Tokyo 182-8585 (Japan); Tada, Mizuki [Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8602 (Japan)

    2014-09-29

    We have constructed an ambient pressure X-ray photoelectron spectroscopy instrument that uses hard X-ray radiation at the high-performance undulator beamline BL36XU of SPring-8. The dependence of the Au 4f peak intensity from Au foil on the ambient N{sub 2} pressure was measured. At a photon energy of 7.94 keV, the Au 4f peak intensity maintained 40% at 3000 Pa compared with that at high vacuum. We designed a polymer electrolyte fuel cell that allows us to perform X-ray photoelectron spectroscopy measurements of an electrode under working conditions. The oxidized Pt peaks were observed in the Pt 3d{sub 5/2} level of Pt nanoparticles in the cathode, and the peaks clearly depended on the applied voltage between the anode and cathode. Our apparatus can be applied as a valuable in situ tool for the investigation of the electronic states and adsorbed species of polymer electrolyte fuel cell electrode catalysts under the reaction conditions.

  1. Attosecond beamline with actively stabilized and spatially separated beam paths

    Science.gov (United States)

    Huppert, M.; Jordan, I.; Wörner, H. J.

    2015-12-01

    We describe a versatile and compact beamline for attosecond spectroscopy. The setup consists of a high-order harmonic source followed by a delay line that spatially separates and then recombines the extreme-ultraviolet (XUV) and residual infrared (IR) pulses. The beamline introduces a controlled and actively stabilized delay between the XUV and IR pulses on the attosecond time scale. A new active-stabilization scheme combining a helium-neon-laser and a white-light interferometer minimizes fluctuations and allows to control delays accurately (26 as rms during 1.5 h) over long time scales. The high-order-harmonic-generation region is imaged via optical systems, independently for XUV and IR, into an interaction volume to perform pump-probe experiments. As a consequence of the spatial separation, the pulses can be independently manipulated in intensity, polarization, and frequency content. The beamline can be combined with a variety of detectors for measuring attosecond dynamics in gases, liquids, and solids.

  2. Electronic state spectroscopy by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy and ab initio calculations of ethyl acetate

    Science.gov (United States)

    Śmialek, Malgorzata A.; Łabuda, Marta; Guthmuller, Julien; Hubin-Franskin, Marie-Jeanne; Delwiche, Jacques; Hoffmann, Søren Vrønning; Jones, Nykola C.; Mason, Nigel J.; Limão-Vieira, Paulo

    2016-06-01

    The high-resolution vacuum ultraviolet photoabsorption spectrum of ethyl acetate, C4H8O2, is presented over the energy range 4.5-10.7 eV (275.5-116.0 nm). Valence and Rydberg transitions and their associated vibronic series observed in the photoabsorption spectrum, have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Also, the photoabsorption cross sections have been used to calculate the photolysis lifetime of this ester in the upper stratosphere (20-50 km). Calculations have also been carried out to determine the ionisation energies and fine structure of the lowest ionic state of ethyl acetate and are compared with a newly recorded photoelectron spectrum (from 9.5 to 16.7 eV). Vibrational structure is observed in the first photoelectron band of this molecule for the first time.

  3. An investigation of the electronic structure of some 3-monosubstituted-2-methylpropenes through computational chemistry and photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Schuquel, Ivania T.A.; Ducati, Lucas C.; Custodio, Rogerio [Chemistry Institute, State University of Campinas, Caixa Postal 6154, 13084-971 Campinas, SP (Brazil); Rittner, Roberto [Chemistry Institute, State University of Campinas, Caixa Postal 6154, 13084-971 Campinas, SP (Brazil)], E-mail: rittner@iqm.unicamp.br; Klapstein, Dieter [Department of Chemistry, St. Francis Xavier University, Antigonish, Nova Scotia, B2G 1C0 (Canada)

    2008-06-16

    The photoelectron (PE) spectra of some 3-monosubstituted 2-methylpropenes H{sub 2}C=C(CH{sub 3})CH{sub 2}X [X = Cl, Br, I, OH, OMe, OEt, SH, SMe, SEt, N(Me){sub 2} and N(Et){sub 2}] have been recorded. A preliminary analysis is presented indicating some trends in the ionization potentials associated with application of OVGF method and NBO analysis from MP2/6-31G(d,p) and cc-pVDZ level of theory indicating that the more effective hyperconjugation effect leads to the most stable conformers. The sensitivity of the outermost ionization energies of selected molecules with respect to the level of theory was analyzed. Application of the CASPT2 method with ANO basis set and geometries from MP2 calculations provided results in excellent agreement with the experimental data.

  4. Structural and X-Ray Photoelectron Spectroscopy Study of Al-Doped Zinc-Oxide Thin Films

    Directory of Open Access Journals (Sweden)

    Bong Ju Lee

    2015-01-01

    Full Text Available Al-doped zinc-oxide (AZO thin films were prepared by RF magnetron sputtering at different oxygen partial pressures and substrate temperatures. The charge-carrier concentrations in the films decreased from 1.69 × 1021 to 6.16 × 1017 cm−3 with increased gas flow rate from 7 to 21 sccm. The X-ray diffraction (XRD patterns show that the (002/(103 peak-intensity ratio decreased as the gas flow rate increased, which was related to the increase of AZO thin film disorder. X-ray photoelectron spectra (XPS of the O1s were decomposed into metal oxide component (peak A and the adsorbed molecular oxygen on thin films (peak B. The area ratio of XPS peaks (A/B was clearly related to the stoichiometry of AZO films; that is, the higher value of A/B showed the higher stoichiometric properties.

  5. Photoelectron spectroscopy of boron-gold alloy clusters and boron boronyl clusters: B3Au(n)(-) and B3(BO)n(-) (n = 1, 2).

    Science.gov (United States)

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

    2013-07-28

    Photoelectron spectroscopy and density-functional theory are combined to study the structures and chemical bonding in boron-gold alloy clusters and boron boronyl clusters: B3Au(n)(-) and B3(BO)n(-) (n = 1, 2). Vibrationally resolved photoelectron spectra are obtained for all four species and the B-Au and B-BO clusters exhibit similar spectral patterns, with the latter species having higher electron binding energies. The electron affinities of B3Au, B3Au2, B3(BO), and B3(BO)2 are determined to be 2.29 ± 0.02, 3.17 ± 0.03, 2.71 ± 0.02, and 4.44 ± 0.02 eV, respectively. The anion and neutral clusters turn out to be isostructural and isovalent to the B3H(n)(-)∕B3H(n) (n = 1, 2) species, which are similar in bonding owing to the fact that Au, BO, and H are monovalent σ ligands. All B3Au(n)(-) and B3(BO)n(-) (n = 1, 2) clusters are aromatic with 2π electrons. The current results provide new examples for the Au∕H and BO∕H isolobal analogy and enrich the chemistry of boronyl and gold. PMID:23901981

  6. The design and construction of a high-resolution velocity-map imaging apparatus for photoelectron spectroscopy studies of size-selected clusters

    Science.gov (United States)

    León, Iker; Yang, Zheng; Liu, Hong-Tao; Wang, Lai-Sheng

    2014-08-01

    A new velocity-map imaging apparatus equipped with a laser-vaporization supersonic cluster source and a time-of-flight mass spectrometer is described for high-resolution photoelectron spectroscopy studies of size-selected cluster anions. Vibrationally cold anion clusters are produced using a laser-vaporization supersonic cluster source, size-selected by a time-of-flight mass spectrometer, and then focused co-linearly into the interaction zone of the high-resolution velocity-map imaging (VMI) system. The multilens VMI system is optimized via systematic simulations and can reach a resolution of 1.2 cm-1 (FWHM) for near threshold electrons while maintaining photoelectron kinetic energy resolutions (ΔKE/KE) of ˜0.53% for higher energy electrons. The new VMI lens has superior focusing power over a large energy range, yielding highly circular images with distortions no larger than 1.0025 between the long and short radii. The detailed design, simulation, construction, testing, and performance of the high-resolution VMI apparatus are presented.

  7. The design and construction of a high-resolution velocity-map imaging apparatus for photoelectron spectroscopy studies of size-selected clusters

    Energy Technology Data Exchange (ETDEWEB)

    León, Iker; Yang, Zheng; Liu, Hong-Tao; Wang, Lai-Sheng, E-mail: Lai-Sheng-Wang@brown.edu [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States)

    2014-08-15

    A new velocity-map imaging apparatus equipped with a laser-vaporization supersonic cluster source and a time-of-flight mass spectrometer is described for high-resolution photoelectron spectroscopy studies of size-selected cluster anions. Vibrationally cold anion clusters are produced using a laser-vaporization supersonic cluster source, size-selected by a time-of-flight mass spectrometer, and then focused co-linearly into the interaction zone of the high-resolution velocity-map imaging (VMI) system. The multilens VMI system is optimized via systematic simulations and can reach a resolution of 1.2 cm{sup −1} (FWHM) for near threshold electrons while maintaining photoelectron kinetic energy resolutions (ΔKE/KE) of ∼0.53% for higher energy electrons. The new VMI lens has superior focusing power over a large energy range, yielding highly circular images with distortions no larger than 1.0025 between the long and short radii. The detailed design, simulation, construction, testing, and performance of the high-resolution VMI apparatus are presented.

  8. Evaluation of valence band top and electron affinity of SiO2 and Si-based semiconductors using X-ray photoelectron spectroscopy

    Science.gov (United States)

    Fujimura, Nobuyuki; Ohta, Akio; Makihara, Katsunori; Miyazaki, Seiichi

    2016-08-01

    An evaluation method for the energy level of the valence band (VB) top from the vacuum level (VL) for metals, dielectrics, and semiconductors from the results of X-ray photoelectron spectroscopy (XPS) is presented for the accurate determination of the energy band diagram for materials of interest. In this method, the VB top can be determined by the energy difference between the onset of VB signals and the cut-off energy for secondary photoelectrons by considering the X-ray excitation energy (hν). The energy level of the VB top for three kinds of Si-based materials (H-terminated Si, wet-cleaned 4H-SiC, and thermally grown SiO2) has been investigated by XPS under monochromatized Al Kα radiation (hν = 1486.6 eV). We have also demonstrated the determination of the electron affinity for the samples by this measurement technique in combination with the measured and reported energy bandgaps (E g).

  9. 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.

  10. ZnO/ZnAl2O4 Nanocomposite Films Studied by X-Ray Diffraction, FTIR, and X-Ray Photoelectron Spectroscopy

    Directory of Open Access Journals (Sweden)

    S. Iaiche

    2015-01-01

    Full Text Available ZnO/ZnAl2O4 nanocomposite films were synthesised by ultrasonic spray pyrolysis (USP by extracting Al2O(SO42 oxide with zinc chloride hydrate in deionised water. The sample was then subjected to heat treatment at 650°C and 700°C for 1 h, which led to the formation of the spinel oxide (ZnAl2O4 and wurtzite (ZnO phases. Al2(SO43·18H2O salt was transformed into aluminum oxide sulfate Al2O(SO42, which is an intermediary decomposition product, by calcination at 795°C for 3 h. The structures of the synthesised ZnO/ZnAl2O4 films were confirmed by XRD, FTIR, and X-ray photoelectron spectroscopy (XPS. XPS spectra of the major Zn, Al, and O photoelectron lines and the major X-ray induced Zn LMM Auger lines for ZnO/ZnAl2O4 are presented.

  11. Characterisation of PEGylated PLGA nanoparticles comparing the nanoparticle bulk to the particle surface using UV/vis spectroscopy, SEC, {sup 1}H NMR spectroscopy, and X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Spek, S.; Haeuser, M. [Institute of Pharmaceutical Technology and Biopharmacy, University of Muenster, Corrensstrasse 48, 48149 Muenster (Germany); Schaefer, M.M. [nanoAnalytics, Heisenbergstrasse 11, 48149 Muenster (Germany); Langer, K., E-mail: k.langer@wwu.de [Institute of Pharmaceutical Technology and Biopharmacy, University of Muenster, Corrensstrasse 48, 48149 Muenster (Germany)

    2015-08-30

    Graphical abstract: - Highlights: • We compared nanoparticles prepared on the basis of PLGA and PEG–PLGA for their polymeric composition in the particle bulk and on the surface. • We validated three analytical methods (UV/vis, SEC, {sup 1}H NMR) for quantification of the polymeric stabiliser PVA and {sup 1}H NMR for the quantification of PEG. • In the case of PEG–PLGA as starting material we observed significant PEG contents not only on the surface but even in the particle bulk. • We observed an unexpected accumulation of the polymeric stabiliser PVA on PEGylated particle surfaces. - Abstract: Hypothesis: The bulk and the surface structure of nanoparticles based on poly(lactic-co-glycolic acid) (PLGA) and PLGA–PEG copolymer is expected to consist of different polymer compositions. An enrichment of hydrophilic PEG on the surface in combination with an accumulation of PLGA in the bulk is anticipated. Hence, the imbalance between bulk and surface composition should be detectable by suitable analytical methods. Experiments: Nanoparticles were assembled using an emulsion-evaporation method with polyvinyl alcohol (PVA) as stabiliser. Mixtures of PLGA and PLGA–PEG copolymer were applied to achieve variably PEGylated nanoparticles. The nanoparticle composition was analysed with respect to PLGA, PVA and PEG, comparing the polymer content of the nanoparticle bulk to the surface. For the bulk, PVA was quantified by a UV/vis spectroscopic method as well as size exclusion chromatography (SEC), and {sup 1}H nuclear magnetic resonance (NMR) spectroscopy. PEG determination of the bulk was carried out using quantitative {sup 1}H NMR spectroscopy. Surface composition was investigated by X-ray photoelectron spectroscopy (XPS). Findings: For the characterisation of the polymer composition {sup 1}H NMR, SEC, and XPS-methods were successfully established and validated. Unexpectedly, a significant PEG content was detected within the particle bulk. The comparison of

  12. Attosecond time delays in the nuclear dynamics of strong-field molecular dissociation

    Science.gov (United States)

    Armstrong, Greg; Ultrafast Molecular Physics Group Collaboration

    2016-05-01

    The relative time delay in the photoemission from neighboring atomic valence sub-shells has become an area of considerable recent interest, with delays of tens of attoseconds reported in pump-probe experiments for a number of atomic targets. Such delays may be extracted, for example, from phase differences in the photoelectron energy spectra for the different sub-shells as a function of delay between pump and probe pulses. The focus of such experiments has, to date, been atomic targets, on the assumption that only electronic motion can lead to delays on the attosecond scale.We investigate the molecular analogue of such studies by calculating the kinetic-energy release (KER) spectrum for neighboring vibrational states as a function of pump-probe delay time. In particular, we focus on molecular targets where electronic excitation is negligible, and show that attosecond time delays are also possible for purely nuclear motion. We will present evidence of these attosecond delays derived from both numerical solutions of the time-dependent Schrödinger equation and experiment. We analyze and understand the observed shifts using the photon-phase formalism. G.S.J. Armstrong, J. McKenna, B. Gaire, M. Zohrabi, B. Berry, B. Jochim, Kanaka Raju, P., P. Feizollah, K.D. Carnes, Ben-Itzhak, B.D. Esry.

  13. Study of attosecond delays using perturbation diagrams and exterior complex scaling

    International Nuclear Information System (INIS)

    We describe in detail how attosecond delays in laser-assisted photoionization can be computed using perturbation theory based on two-photon matrix elements. Special emphasis is laid on above-threshold ionization, where the electron interacts with an infrared field after photoionization by an extreme ultraviolet field. Correlation effects are introduced using diagrammatic many-body theory to the level of the random-phase approximation with exchange. Our aim is to provide an ab initio route to correlated multi-photon processes that are required for an accurate description of experiments on the attosecond time scale. Here, our results are focused on photoionization of the M-shell of argon atoms, where experiments have been carried out using the so-called reconstruction of attosecond beating by the two-photon interference transitions technique. An influence of autoionizing resonances in attosecond delay measurements is observed. Further, it is shown that the delay depends on both detection angle of the photoelectron and energy of the probe photon. (paper)

  14. Thermodynamic Equilibrium Studies of Nanocrystallite CeO2 Grain Boundaries by High Temperature X-Ray Photoelectron Spectroscopy and Thermal Gravimetric Analysis

    Institute of Scientific and Technical Information of China (English)

    LIU Zhen-Xiang; XIE Kan

    2000-01-01

    Nanostructured CeO2 thin films and powders are studied by high temperature x-ray photoelectron spectroscopy and thermal gravimetric analysis. The results indicate that the surface composition strongly depends on temperature, the surface O/Ce ratio initially increases with increasing temperature, then decreases with the further increase of temperature, the maximum surface O/Ce ratio is at about 300℃ C. The variation of the surface composition with temperature arises from the ion migration, redistribution and transformation between lattice oxygen and gas phase oxygen near the grain boundaries during the thermodynamic equilibrium process. The results also show that CeO2 has a weakly bond oxygen, high oxygen mobility in the bulk and a high molecular dissociation rate at the surface, especially for the sol-gel prepared nanocrystallite CeO2.

  15. High-resolution electron-energy-loss spectroscopy and photoelectron-diffraction studies of the geometric structure of adsorbates on single-crystal metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Rosenblatt, D.H.

    1982-11-01

    Two techniques which have made important contributions to the understanding of surface phenomena are high resolution electron energy loss spectroscopy (EELS) and photoelectron diffraction (PD). EELS is capable of directly measuring the vibrational modes of clean and adsorbate covered metal surfaces. In this work, the design, construction, and performance of a new EELS spectrometer are described. These results are discussed in terms of possible structures of the O-Cu(001) system. Recommendations for improvements in this EELS spectrometer and guidelines for future spectrometers are given. PD experiments provide accurate quantitative information about the geometry of atoms and molecules adsorbed on metal surfaces. The technique has advantages when used to study disordered overlayers, molecular overlayers, multiple site systems, and adsorbates which are weak electron scatterers. Four experiments were carried out which exploit these advantages.

  16. Ammonia plasma treated polyethylene films for adsorption or covalent immobilization of trypsin: quantitative correlation between X-ray photoelectron spectroscopy data and enzyme activity.

    Science.gov (United States)

    Ghasemi, Mahsa; Minier, Michel J G; Tatoulian, Michaël; Chehimi, Mohamed M; Arefi-Khonsari, Farzaneh

    2011-09-01

    The ammonia plasma process was used for generating reactive groups, particularly primary amine functions on the surface of polyethylene (PE) films, to immobilize the enzyme trypsin. The attachment of the enzyme was achieved by directly applying an aqueous solution of trypsin to the plasma-activated surface or by using glutaraldehyde as a chemical linker. In both cases, the utilization of sodium cyanoborohydride efficiently stabilized the immobilization. The surfaces were analyzed by X-ray photoelectron spectroscopy (XPS) and enzymatic activity measurements. Active trypsin was successfully immobilized on the surface with a mean activity of 0.09 ± 0.02 U/cm(2). The study of the stability of the immobilized enzyme during repetitive assays showed that some activity could be maintained during several months. An original quantitative correlation between the immobilized enzyme activity and the XPS signal intensity of the S 2p electrons present in the sulfur-containing amino acid residues was evidenced. PMID:21770448

  17. Electronic structure of the polymer-cathode interface of an organic electroluminescent device investigated using operando hard x-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ikeuchi, J.; Hamamatsu, H.; Miyamoto, T. [Sumitomo Chemical Co., Ltd., Advanced Materials Research Laboratory, 6 Kitahara, Tsukuba, Ibaraki 300-3294 (Japan); Tanaka, S. [Sumitomo Chemical Co., Ltd., Tsukuba Material Development Laboratory, 6 Kitahara, Tsukuba, Ibaraki 300-3294 (Japan); Yamashita, Y.; Yoshikawa, H.; Ueda, S. [National Institute for Materials Science, Synchrotron X-ray Station at SPring-8, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan)

    2015-08-28

    The electronic structure of a polymer-cathode interface of an operating organic light-emitting diode (OLED) was directly investigated using hard X-ray photoelectron spectroscopy (HAXPES). The potential distribution profile of the light-emitting copolymer layer as a function of the depth under the Al/Ba cathode layer in the OLED depended on the bias voltage. We found that band bending occurred in the copolymer of 9,9-dioctylfluorene (50%) and N-(4-(2-butyl)-phenyl)diphenylamine (F8-PFB) layer near the cathode at 0 V bias, while a linear potential distribution formed in the F8-PFB when a bias voltage was applied to the OLED. Direct observation of the built-in potential and that band bending formed in the F8-PFB layer in the operating OLED suggested that charges moved in the F8-PFB layer before electron injection from the cathode.

  18. Electronic structure of the polymer-cathode interface of an organic electroluminescent device investigated using operando hard x-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    The electronic structure of a polymer-cathode interface of an operating organic light-emitting diode (OLED) was directly investigated using hard X-ray photoelectron spectroscopy (HAXPES). The potential distribution profile of the light-emitting copolymer layer as a function of the depth under the Al/Ba cathode layer in the OLED depended on the bias voltage. We found that band bending occurred in the copolymer of 9,9-dioctylfluorene (50%) and N-(4-(2-butyl)-phenyl)diphenylamine (F8-PFB) layer near the cathode at 0 V bias, while a linear potential distribution formed in the F8-PFB when a bias voltage was applied to the OLED. Direct observation of the built-in potential and that band bending formed in the F8-PFB layer in the operating OLED suggested that charges moved in the F8-PFB layer before electron injection from the cathode

  19. Electronic structure of the polymer-cathode interface of an organic electroluminescent device investigated using operando hard x-ray photoelectron spectroscopy

    Science.gov (United States)

    Ikeuchi, J.; Hamamatsu, H.; Miyamoto, T.; Tanaka, S.; Yamashita, Y.; Yoshikawa, H.; Ueda, S.

    2015-08-01

    The electronic structure of a polymer-cathode interface of an operating organic light-emitting diode (OLED) was directly investigated using hard X-ray photoelectron spectroscopy (HAXPES). The potential distribution profile of the light-emitting copolymer layer as a function of the depth under the Al/Ba cathode layer in the OLED depended on the bias voltage. We found that band bending occurred in the copolymer of 9,9-dioctylfluorene (50%) and N-(4-(2-butyl)-phenyl)diphenylamine (F8-PFB) layer near the cathode at 0 V bias, while a linear potential distribution formed in the F8-PFB when a bias voltage was applied to the OLED. Direct observation of the built-in potential and that band bending formed in the F8-PFB layer in the operating OLED suggested that charges moved in the F8-PFB layer before electron injection from the cathode.

  20. Structure, Mobility, and Composition of Transition Metal Catalyst Surfaces. High-Pressure Scanning Tunneling Microscopy and Ambient-Pressure X-ray Photoelectron Spectroscopy Studies

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Zhongwei [Univ. of California, Berkeley, CA (United States)

    2013-12-06

    Surface structure, mobility, and composition of transition metal catalysts were studied by high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at high gas pressures. HP-STM makes it possible to determine the atomic or molecular rearrangement at catalyst surfaces, particularly at the low-coordinated active surface sites. AP-XPS monitors changes in elemental composition and chemical states of catalysts in response to variations in gas environments. Stepped Pt and Cu single crystals, the hexagonally reconstructed Pt(100) single crystal, and Pt-based bimetallic nanoparticles with controlled size, shape and composition, were employed as the model catalysts for experiments in this thesis.

  1. Harmonium: A pulse preserving source of monochromatic extreme ultraviolet (30–110 eV radiation for ultrafast photoelectron spectroscopy of liquids

    Directory of Open Access Journals (Sweden)

    J. Ojeda

    2016-03-01

    Full Text Available A tuneable repetition rate extreme ultraviolet source (Harmonium for time resolved photoelectron spectroscopy of liquids is presented. High harmonic generation produces 30–110 eV photons, with fluxes ranging from ∼2 × 1011 photons/s at 36 eV to ∼2 × 108 photons/s at 100 eV. Four different gratings in a time-preserving grating monochromator provide either high energy resolution (0.2 eV or high temporal resolution (40 fs between 30 and 110 eV. Laser assisted photoemission was used to measure the temporal response of the system. Vibrational progressions in gas phase water were measured demonstrating the ∼0.2 eV energy resolution.

  2. Band offsets of Er{sub 2}O{sub 3} films grown on Ge substrates by X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Ting; Peng, Lining; Cui, Yanxia; Hao, Yuying [Taiyuan University of Technology, Key Laboratory of Advanced Transducers and Intelligent Control System (Ministry of Education), College of Physics and Optoelectronics, Taiyuan (China); Fang, Zebo [Shaoxing University, Department of Physics, Shaoxing (China)

    2014-06-15

    The band alignments of high-k Er{sub 2}O{sub 3} films grown on Ge substrates by molecular beam epitaxy are determined by X-ray photoelectron spectroscopy. The valenceband and the conduction-band offsets of Er{sub 2}O{sub 3} to Ge are found to be 3.16 ± 0.02 and 2.13 ± 0.02 eV, respectively. The energy gap of Er{sub 2}O{sub 3} is 5.96 ± 0.02 eV as determined by the optical spectrophotometry. From the band offset viewpoint, the above results indicate that Er{sub 2}O{sub 3} could be a promising candidate for high-k gate dielectrics on Ge substrate. (orig.)

  3. Zero kinetic energy-pulsed field ionization and resonance enhanced multiphoton ionization photoelectron spectroscopy: Ionization dynamics of Rydberg states in HBr

    International Nuclear Information System (INIS)

    The results of rotationally resolved resonance enhanced multiphoton ionization photoelectron spectroscopy and zero kinetic energy-pulsed field ionization studies on HBr via various rotational levels of the F1Δ2 and f3Δ2 Rydberg states are reported. These studies lead to an accurate determination of the lowest ionization threshold as 94098.9±1 cm-1. Observed rotational and spin endash orbit branching ratios are compared to the results of ab initio calculations. The differences between theory and experiment highlight the dominant role of rotational and spin endash orbit interactions for the dynamic properties of the high-n Rydberg states involved in the pulsed field ionization process. copyright 1996 American Institute of Physics

  4. Elucidating the electronic structure of supported gold nanoparticles and its relevance to catalysis by means of hard X-ray photoelectron spectroscopy

    Science.gov (United States)

    Reinecke, Benjamin N.; Kuhl, Kendra P.; Ogasawara, Hirohito; Li, Lin; Voss, Johannes; Abild-Pedersen, Frank; Nilsson, Anders; Jaramillo, Thomas F.

    2016-08-01

    We report on the electronic structure of Au (gold) nanoparticles supported onto TiO2 with a goal of elucidating the most important effects that contribute to their high catalytic activity. We synthesize and characterize with high resolution transmission electron microscopy (HRTEM) 3.4, 5.3, and 9.5 nm diameter TiO2-supported Au nanoparticles with nearly spherical shape and measure their valence band using Au 5d subshell sensitive hard X-ray photoelectron spectroscopy (HAXPES) conducted at Spring-8. Based on density functional theory (DFT) calculations of various Au surface structures, we interpret the observed changes in the Au 5d valence band structure as a function of size in terms of an increasing percentage of Au atoms at corners/edges for decreasing particle size. This work elucidates how Au coordination number impacts the electronic structure of Au nanoparticles, ultimately giving rise to their well-known catalytic activity.

  5. Structural and bonding properties of ScSi-n(n=2~6)clusters:photoelectron spectroscopy and density functional calculations

    Institute of Scientific and Technical Information of China (English)

    Xu Hong-Guang; Wu Miao-Miao; Zhang Zeng-Guang; Sun Qiang; Zheng Wei-Jun

    2011-01-01

    Anion ion photoelectron spectroscopy and density functional theory(DFT)are used to investigate the electronicand structural properties of ScSi-n(n=2~6)clusters and their neutrals. We find that the structures of ScSin are similar to those of Si-n+1. The most stable isomers of ScSin cluster anions and their neutrals are similar for n=2, 3and 5 but different for n=4 and 6, indicating that the charge effect on geometry is size dependent for small scandiumsilicon clusters. The low electron binding energy(EBE)tails observed in the spectra of ScSi-4,6 can be explained by the existence of less stable isomers. A comparison between ScSi-n and VSi-n clusters shows the effects of metal size and electron configuration on cluster geometries.

  6. Light-matter interaction on the attosecond timescale

    CERN Document Server

    Dahlström, J M; Maquet, A

    2012-01-01

    This tutorial presents an introduction to the interaction of light and matter on the attosecond timescale. Our aim is to detail the theoretical description of ultra-short time-delays, and to relate these to the phase of extreme ultraviolet (XUV) light pulses and to the asymptotic phase-shifts of photoelectron wave packets. Special emphasis is laid on time-delay experiments, where attosecond XUV pulses are used to photoionize target atoms at well-defined times, followed by a probing process in real time by a phase-locked, infrared laser field. In this way, the laser field serves as a "clock" to monitor the ionization event, but the observable delays do not correspond directly to the delay associated with single-photon ionization. Instead, a significant part of the observed delay originates from a measurement induced process, which obscures the single-photon ionization dynamics. This artifact is traced back to a phase-shift of the above-threshold ionization transition matrix element, which we call the continuum...

  7. Strong-field ionization inducing multi-electron-hole coherence probed by attosecond pulses

    Science.gov (United States)

    Zhao, Jing; Yuan, Jianmin; Zhao, Zengxiu

    2016-05-01

    Recent advances in attosecond spectroscopy has enabled resolving electron-hole dynamics in real time. The correlated electron-hole dynamics and the resulted coherence are directly related to how fast the ionization is completed. How the laser-induced electron-hole coherence evolves and whether it can be utilized to probe the core dynamics are among the key questions in attosecond physics or even attosecond chemistry. In this work, we propose a new scenario to apply IR-pump-XUV-probe schemes to resolving strong field ionization induced and attosecond pulse driven electron-hole dynamics and coherence in real time. The coherent driving of both the infrared laser and the attosecond pulse correlates the dynamics of the core-hole and the valence-hole which leads to the otherwise forbidden absorption and emission of XUV photon. An analytical model is developed based on the strong-field approximation by taking into account of the essential multielectron configurations. The emission spectra from the core-valence transition and the core-hole recombination are found modulating strongly as functions of the time delay between the two pulses, which provides a unique insight into the instantaneous ionization and the interplay of the multi-electron-hole coherence.

  8. Toward new techniques to measure heterogeneous oxidation of aerosol: Electrodynamic Balance-Mass Spectrometry (EDB-MS) and Aerosol X-ray Photoelectron Spectroscopy

    Science.gov (United States)

    Jacobs, M. I.; Heine, N.; Xu, B.; Davies, J. F.; Kirk, B. B.; Kostko, O.; Alayoglu, S.; Wilson, K. R.; Ahmed, M.

    2015-12-01

    The chemical composition and physical properties of aerosol can be changed via heterogeneous oxidation with the OH radical. However, the physical state of the aerosol influences the kinetics of this reaction; liquid particles with a high diffusion coefficient are expected to be well mixed and homogenously oxidized, while oxidation of solid, diffusion-limited aerosol is expected to occur primarily on the surface, creating steep chemical gradients within the particle. We are working to develop several new techniques to study the heterogeneous oxidation of different types of aerosol. We are developing a "modular" electrodynamic balance (EDB) that will enable us to study heterogeneous oxidation at aqueous interfaces using a mass-spectrometer (and potentially other detection techniques). Using a direct analysis in real time (DART) interface, preliminary droplet train measurements have demonstrated single-droplet mass spectrometry to be possible. With long reaction times in our EDB, we will be able to study heterogeneous oxidation of a wide variety of organic species in aqueous droplets. Additionally, we are working to use aerosol photoemission and velocity map imaging (VMI) to study the surface of aerosol particles as they undergo heterogeneous oxidation. With VMI, we're able to collect electrons with a 4π collection efficiency over conventional electron energy analyzers. Preliminary results looking at the ozonolysis of squalene using ultraviolet photoelectron spectroscopy (UPS) show that heterogeneous oxidation kinetic data can be extracted from photoelectron spectra. By moving to X-ray photoemission spectroscopy (XPS), we will determine elemental and chemical composition of the aerosol surface. Thus, aerosol XPS will provide information on the steep chemical gradients that form as diffusion-limited aerosol undergo heterogeneous oxidation.

  9. Photoelectron spectroscopy investigation of the temperature-induced deprotonation and substrate-mediated hydrogen transfer in a hydroxyphenyl-substituted porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Smykalla, Lars, E-mail: lars.smykalla@physik.tu-chemnitz.de [Technische Universität Chemnitz, Institute of Physics, Solid Surfaces Analysis Group, D-09107 Chemnitz (Germany); Shukrynau, Pavel [Technische Universität Chemnitz, Institute of Physics, Solid Surfaces Analysis Group, D-09107 Chemnitz (Germany); Mende, Carola; Lang, Heinrich [Technische Universität Chemnitz, Institute of Chemistry, Inorganic Chemistry, D-09107 Chemnitz (Germany); Knupfer, Martin [Electronic and Optical Properties Department, IFW Dresden, D-01171 Dresden (Germany); Hietschold, Michael [Technische Universität Chemnitz, Institute of Physics, Solid Surfaces Analysis Group, D-09107 Chemnitz (Germany)

    2015-04-01

    Highlights: • Photoelectron spectroscopy of tetra(p-hydroxyphenyl)porphyrin on Au(1 1 1) and Ag(1 1 0). • Ratio of amount of −NH− to −N= in the molecule on Au(1 1 1) decreases after annealing. • Dissociation of −OH groups and transfer of hydrogen atoms to −N= on Ag(1 1 0). • Cleavage of C−H bonds of porphyrin macro-cycle at high temperature. • Changes of the valence band of the molecule in dependance of annealing temperature. - Abstract: The temperature dependent stepwise deprotonation of 5,10,15,20-tetra(p-hydroxyphenyl)-porphyrin is investigated using photoelectron spectroscopy. An abundance of pyrrolic relative to iminic nitrogen and a decrease in the ratio of the amount of −NH− to −N= with increasing annealing temperature is found. In contrast to the molecules adsorbed on Au(1 1 1), on the more reactive Ag(1 1 0) surface, partial dissociation of the hydroxyl groups and subsequent diffusion and rebonding of hydrogen to the central nitrogen atoms resulting in a zwitterionic molecule was clearly observed. Moreover, partial C−H bond cleavage and the formation of new covalent bonds with adjacent molecules or the surface starts at a relatively high annealing temperature of 300 °C. This reaction is identified to occur at the carbon atoms of the pyrrole rings, which leads also to a shift in the N 1s signal and changes in the valence band of the molecules. Our results show that annealing can significantly alter the molecules which were deposited depending on the maximum temperature and the catalytic properties of the specific substrate. The thermal stability should be considered if a molecular monolayer is prepared from a multilayer by desorption, or if annealing is applied to enhance the self-assembly of molecular structures.

  10. The influence of biosurfactant adsorption on the physicochemical behaviour of carbon steel surfaces using contact angle measurements and X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Shubina, V., E-mail: varvara.shubina2014@gmail.com [LUNAM Université, IFSTTAR, MAST, SMC, F-44340 Bouguenais (France); Gaillet, L. [LUNAM Université, IFSTTAR, MAST, SMC, F-44340 Bouguenais (France); Ababou-Girard, S. [Institut de Physique de Rennes, Département Matériaux et Nanosciences, UMR 6251 CNRS, Université Rennes 1, 35000 Rennes-Cedex (France); Gaudefroy, V. [LUNAM Université, IFSTTAR, MAST, SMC, F-44340 Bouguenais (France); Chaussadent, T.; Farças, F. [Université Paris-Est, IFSTTAR, MAST, CPDM, F-77447 Marne-la-Vallée (France); Meylheuc, T. [INRA, UMR1319 Micalis, F-78352 Jouy-en-Josas (France); AgroParisTech, UMR Micalis, F-78352 Jouy-en-Josas (France); Dagbert, C. [2 Chemin de la Grand’côte, 36270 Éguzon-Chantôme (France); Creus, J. [LaSIE, UMR7356, Université de La Rochelle, Pôle Sciences et Technologie, Bâtiment Marie Curie, Avenue Michel Crépeau, 17000 La Rochelle (France)

    2015-10-01

    Highlights: • Surface modifications to carbon steel surfaces due to the adsorption of a biosurfactant derived from Pseudomonas fluorescens bacteria cells were investigated using contact angle measurements (CAM) and X-ray photoelectron spectroscopy (XPS). • CAM allowed to establish an increase of electron-donating properties of steel surface due to the biosurfactant adsorption. • XPS demonstrated that biosurfactant molecules change the stoichiometry of mixted-oxide layer and the new outer layer mostly composed of magnetite. • Thickness and density of adsorbed biosurfactants layers were highlighted using a semiquantitative approach for 3 different concentrations of biomolecules. - Abstract: We investigated modifications to carbon steel surfaces due to the adsorption of a biosurfactant derived from Pseudomonas fluorescens bacteria cells using contact angle measurements (CAM) and X-ray photoelectron spectroscopy (XPS). After conditioning carbon steel in solutions with three different concentrations of biosurfactant molecules: 0.05, 0.3 and 1 g L{sup −1}, the average thickness of the biosurfactant layer on the carbon steel specimens was 7.9 ± 0.3, 12.1 ± 0.5 and 16.4 ± 0.7 Å, respectively. The biosurfactants changed the composition of both the Fe{sup 2+} and Fe{sup 3+} mixed-oxide layer and the outer layer, mostly composed of Fe{sup 3+} associated with magnetite. Contact angle measurements indicate decreased hydrophobic properties after the carbon steel was modified by biosurfactant. It was shown that the carbon steel surface free energy depends on the biosurfactant concentration, due to an acquisition of strong electron-donating properties.

  11. Attosecond X-ray free electron laser

    Directory of Open Access Journals (Sweden)

    Kim D. E.

    2013-03-01

    Full Text Available For a real, meaningful pump-probe experiment with attosecond temporal resolution, an isolated attosecond pulse is in demand. In this vein we report the generation of an isolated ~ 148 attosecond pulse duration radiation pulse at 0.1 angstrom wavelength using current enhanced self-amplified spontaneous emission free electron laser. We consider the 10-GeV PAL-XFEL e-beam for enhanced self-amplified spontaneous emission (ESASE scheme. In ESASE, X-ray SASE FEL is combined with a femtosecond laser system. An 800 nm wavelength, 5 fs FWHM carrier envelope phase stabilized laser was employed in ESASE scheme.

  12. The optical spectra of matrix-isolated palladium-nitrogen complexes: An investigation by absorption, emission, and photoelectron spectroscopy

    Science.gov (United States)

    Schrittenlacher, W.; Schroeder, W.; Rotermund, H. H.; Wiggenhauser, H.; Grinter, R.; Kolb, D. M.

    1986-08-01

    The optical spectra of palladium in neon and argon matrices containing up to 100% dinitrogen have been studied. Beside the known bands of isolated Pd atoms new strong bands assigned to weakly bonded Pd(N2)m (m=1, 2) complexes appear. The bands are attributed to three different types of transition. The dominant lines are essentially due to transitions localized at the Pd atom but strongly perturbed by a ``crystal field'' due to the weakly bonded N2 molecules. Secondly, a vibrational progression at lower energies is assigned to a Pd to N2 charge transfer transition and thirdly, at high energies, a vibrational progression assigned to a locally excited state of an N2 molecule perturbed by weak bonding to Pd is observed. No evidence has been found for the presence of Pd(N2)3. Photoelectron spectra of the Pd(N2)m complexes in neon have been observed. The Pd 4d photoemission peak is shifted with respect to the Pd atom in Ne by ˜1.1 eV to higher binding energies.

  13. Probing microhydration effect on the electronic structure of the GFP chromophore anion: Photoelectron spectroscopy and theoretical investigations

    Energy Technology Data Exchange (ETDEWEB)

    Bhaskaran-Nair, Kiran; Shelton, William A. [Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Center for Computation and Technology, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Valiev, Marat; Kowalski, Karol, E-mail: karol.kowalski@pnnl.gov [William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, K8-91, P.O. Box 999, Richland, Washington 99352 (United States); Deng, S. H. M.; Wang, Xue-Bin, E-mail: xuebin.wang@pnnl.gov [Physical Sciences Division, Pacific Northwest National Laboratory, K8-88, P.O. Box 999, Richland, Washington 99352 (United States)

    2015-12-14

    The photophysics of the Green Fluorescent Protein (GFP) chromophore is critically dependent on its local structure and on its environment. Despite extensive experimental and computational studies, there remain many open questions regarding the key fundamental variables that govern this process. One outstanding problem is the role of autoionization as a possible relaxation pathway of the excited state under different environmental conditions. This issue is considered in our work through combined experimental and theoretical studies of microsolvated clusters of the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI{sup −}), an analog of the GFP chromophore. Through selective generation of microsolvated structures of predetermined size and subsequent analysis of experimental photoelectron spectra by high level ab initio methods, we are able to precisely identify the structure of the system, establish the accuracy of theoretical data, and provide reliable description of auto-ionization process as a function of hydrogen-bonding environment. Our study clearly illustrates the first few water molecules progressively stabilize the excited state of the chromophore anion against the autodetached neutral state, which should be an important trait for crystallographic water molecules in GFPs that has not been fully explored to date.

  14. Probing microhydration effect on the electronic structure of the GFP chromophore anion. Photoelectron spectroscopy and theoretical investigations

    Energy Technology Data Exchange (ETDEWEB)

    Bhaskaran-Nair, Kiran [Louisiana State Univ., Baton Rouge, LA (United States); Valiev, Marat [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Deng, Shihu [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shelton, William A. [Louisiana State Univ., Baton Rouge, LA (United States); Kowalski, Karol [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Wang, Xue B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-12-14

    The photophysics of Green Fluorescent Protein (GFP) chromophore is critically dependent on its local structure and on its environment. Despite extensive experimental and computational studies, there remain many open questions regarding the key fundamental variables that govern this process. One outstanding problem is the role of autoionization as a possible relaxation pathway of the excited state under different environmental conditions. This issue is considered in our work through combined experimental and theoretical studies of microsolvated clusters of the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI⁻), an analog of GFP chromophore. Through selective generation of microsolvated structures of predetermined size and subsequent analysis of experimental photoelectron spectra by high level ab-initio methods we are able to precisely identify the structure of the system, establish the accuracy of theoretical data, and provide reliable description of auto-ionization process as a function of hydrogen-bonding environment. Our study clearly illustrates the first few water molecules progressively stabilize the excited state of the chromophore anion against the autodetached neutral state, which should be an important trait for crystallographic water molecules in GFPs that has not been fully explored to date.

  15. Surface characterization by X-ray photoelectron spectroscopy and cyclic voltammetry of products formed during the potentiostatic reduction of chalcopyrite

    Energy Technology Data Exchange (ETDEWEB)

    Nava, Dora [Universidad Autonoma Metropolitana - Iztapalapa, Departamento de Quimica, Area de Electroquimica, A.P. 55-534, C.P. 09340, Mexico, D.F. (Mexico); Gonzalez, Ignacio [Universidad Autonoma Metropolitana - Iztapalapa, Departamento de Quimica, Area de Electroquimica, A.P. 55-534, C.P. 09340, Mexico, D.F. (Mexico)], E-mail: igm@xanum.uam.mx; Leinen, Dietmar; Ramos-Barrado, Jose R. [Departamento de Fisica Aplicada, Laboratorio de Materiales y Superficie, Unidad asociada al CSIC, Universidad de Malaga, Campus Teatinos, Malaga, C.P. 29071 (Spain)

    2008-05-30

    Surface characterization of the transient products that precede chalcocite formation during chalcopyrite reduction was carried out. The experimental strategy employed in the present work consisted of the application of different potential pulses (fixed energetic conditions) on the surface of chalcopyrite electrodes in 1.7 M H{sub 2}SO{sub 4}. The chemical products formed at different potential pulses were characterized by cyclic voltammetry (CV) and XPS. Each electrogenerated species presented a specific voltammetric behavior and an XPS spectrum, in which the values of principal photoelectronic peak bond energies for Cu 2p{sub 3/2}, Fe 2p{sub 3/2} and S 2p{sub 3/2} and the atomic concentrations were considered. Several potential intervals could be identified: in 0.115 {>=} E{sub cat} {>=} -0.085 V vs. SHE, an intermediate copper sulfide is formed whose composition is between those of chalcopyrite and bornite, such as talnakhite. The reduction of this product occurs slowly, giving bornite at potentials less than -0.085 V. In the applied potential region -0.085 {>=} E{sub cat} > -0.185 V, the bornite gradually decomposes causing the incomplete conversion to chalcocite. In the potential interval -0.185 > E{sub cat} {>=} -0.285 V, energetic conditions are large enough to allow the immediate decomposition of bornite, forming chalcocite in a more quantitative manner.

  16. Probing microhydration effect on the electronic structure of the GFP chromophore anion: Photoelectron spectroscopy and theoretical investigations

    Science.gov (United States)

    Bhaskaran-Nair, Kiran; Valiev, Marat; Deng, S. H. M.; Shelton, William A.; Kowalski, Karol; Wang, Xue-Bin

    2015-12-01

    The photophysics of the Green Fluorescent Protein (GFP) chromophore is critically dependent on its local structure and on its environment. Despite extensive experimental and computational studies, there remain many open questions regarding the key fundamental variables that govern this process. One outstanding problem is the role of autoionization as a possible relaxation pathway of the excited state under different environmental conditions. This issue is considered in our work through combined experimental and theoretical studies of microsolvated clusters of the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI-), an analog of the GFP chromophore. Through selective generation of microsolvated structures of predetermined size and subsequent analysis of experimental photoelectron spectra by high level ab initio methods, we are able to precisely identify the structure of the system, establish the accuracy of theoretical data, and provide reliable description of auto-ionization process as a function of hydrogen-bonding environment. Our study clearly illustrates the first few water molecules progressively stabilize the excited state of the chromophore anion against the autodetached neutral state, which should be an important trait for crystallographic water molecules in GFPs that has not been fully explored to date.

  17. Negative Ion Photoelectron Spectroscopy Reveals Thermodynamic Advantage of Organic Acids in Facilitating Formation of Bisulfate Ion Clusters: Atmospheric Implications

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Gao-Lei; Lin, Wei; Deng, Shihu; Zhang, Jian; Zheng, Weijun; Paesani, Francesco; Wang, Xue B.

    2013-03-07

    Recent lab and field measurements have indicated critical roles of organic acids in enhancing new atmospheric aerosol formation. Such findings have stimulated theoretical studies with the aim of understanding interaction of organic acids with common aerosol nucleation precursors like bisulfate (HSO4-). In this Letter, we report a combined negative ion photoelectron spectroscopic and theoretical investigation of molecular clusters formed by HSO4- with succinic acid (SUA, HO2C(CH2)2CO2H), HSO4-(SUA)n (n = 0-2), along with HSO4-(H2O)n and HSO4-(H2SO4)n. It is found that one SUA molecule can stabilize HSO4- by ca. 39 kcal/mol, triple the corresponding value that one water molecule is capable of (ca. 13 kcal/mol). Molecular dynamics simulations and quantum chemical calculations reveal the most plausible structures of these clusters and attribute the stability of these clusters due to formation of strong hydrogen bonds. This work provides direct experimental evidence showing significant thermodynamic advantage by involving organic acid molecules to promote formation and growth in bisulfate clusters and aerosols.

  18. Surface spin-polarized currents generated in topological insulators by circularly polarized synchrotron radiation and their photoelectron spectroscopy indication

    Science.gov (United States)

    Shikin, A. M.; Klimovskikh, I. I.; Filyanina, M. V.; Rybkina, A. A.; Pudikov, D. A.; Kokh, K. A.; Tereshchenko, O. E.

    2016-08-01

    A new method for generating spin-polarized currents in topological insulators has been proposed and investigated. The method is associated with the spin-dependent asymmetry of the generation of holes at the Fermi level for branches of topological surface states with the opposite spin orientation under the circularly polarized synchrotron radiation. The result of the generation of holes is the formation of compensating spin-polarized currents, the value of which is determined by the concentration of the generated holes and depends on the specific features of the electronic and spin structures of the system. The indicator of the formed spin-polarized current can be a shift of the Fermi edge in the photoelectron spectra upon photoexcitation by synchrotron radiation with the opposite circular polarization. The topological insulators with different stoichiometric compositions (Bi1.5Sb0.5Te1.8Se1.2 and PbBi2Se2Te2) have been investigated. It has been found that there is a correlation in the shifts and generated spin-polarized currents with the specific features of the electronic spin structure. Investigations of the graphene/Pt(111) system have demonstrated the possibility of using this method for other systems with a spin-polarized electronic structure.

  19. New method for attosecond-terawatt pulse generation in X-ray free electron laser

    International Nuclear Information System (INIS)

    We propose a novel scheme for generating a terawatt-attosecond pulse from X-ray free-electron laser (XFEL), which is perfectly synchronized to the few cycle IR pulse. Our approach utilizes baseline configuration similar to PAL-XFEL, but adds a current enhanced self-amplified emission (ESASE) module inserted between the linac and the undulater that introduces only a few cycle energy and current modulation in the electron beam. Our scheme is compact and easy to implement and does not require a slotted foil, thereby leading to improved longitudinal coherence of the beam. We demonstrate the viability of our scheme with simulations using PAL-XFEL beam parameters. Attosecond science has emerged as an important research area of ultrafast phenomena during the past decade as it provides a direct access to capturing, measuring and controlling the electronic dynamics in atoms, molecules and condensed matters. However, high-energy isolated attosecond pulses required for the most intriguing nonlinear attosecond experiments spectroscopy are still lacking. Therefore, techniques are to be further developed to make a powerful isolated attosecond pulse in the x-ray range (1 keV and higher). Several techniques have been proposed to achieve attosecond pulses in a free electron laser (FEL). In this vein, we demonstrate in simulation a TW-attosecond pulse in FEL. In our scheme, it utilizes a laser-induced energy modulation to generate a few-cycle current modulation and small optical-delays between undulator modules for radiation alignment. In this work, we are able to show that an isolated 280 attosecond FWHM, 1 TW pulse at 1 keV (1.25 nm) photon energy and an 100 attosecond FWHM, 1 TW pulse at 12.4 keV (0.1 mn) can be generated. This scheme is simple and easy to implement and can be adapted to the existing FEL facilities. It is worthwhile to mention that in this scheme there is still a room for higher power even for shorter undulator lengths via tapering of the undulator or high

  20. 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.

  1. Thiolsulfinates/Thiolsulfonates  formation:  X-ray photoelectron spectroscopy (XPS) of oxidized thiols on flat surfaces

    OpenAIRE

    Lebrun, Delphine

    2010-01-01

    In order  to  find  another way to fix peptides      on      surfaces      we      study      the      chemical      and      electro      oxidation       of      a      Silicon      flat      surface      after      silanization.      Traditional      experimental      setup      is      used      to      make      the       oxidations      and      Xray      photoelectron      spectroscope      (XPS)      is      used      to      analyze      the      surfaces.      We      find      that ...

  2. Electronic structure of Pc2Lu and (PcAlF)n oriented thin films using angle resolved photoelectron spectroscopy

    Science.gov (United States)

    Fahy, M. R.; Fujimoto, H.; Dann, A. J.; Hoshi, H.; Inokuchi, H.; Maruyama, Y.; Willis, M. R.

    1990-04-01

    Ultraviolet photoelectron spectra have been measured for the radical phthalocyanine dimer, Pc2Lu, and the fluorine bridge stacked phthalocyanine polymer (PcAlF)n. Previous workers have shown that both materials can, under appropriate conditions, be prepared in a well characterised, highly oriented thin film form. Thus, samples for this work were prepared by in situ sublimation at very slow evaporation rates onto crystalline substrates to try to maximise the degree of sample orientation. The angle dependence of the spectra were measured and the sample structure subsequently examined using high resolution TEM. The TEM results show that the (PcAlF)n films have a much higher level of orientation than the Pc2Lu films and this is reflected by the angle dependences of the UPS measurements. The spectra for (PcAlF)n are very similar to measurements on most other simple phthalocyanine compounds and have a small angular dependence. The spectra for Pc2Lu show almost no angular dependence. Again the spectra are broadly similar to that of other Pc's with two significant differences, the lowest energy peak is split and the whole spectra is shifted to lower energy. This result will be discussed in terms of simple molecular orbital ideas. The effect of air on the spectra of both materials was examined and the spectra of (PcAlF)n was found to be particularly sensitive. Attempts to determine the position of the lutetium orbitals by varying the light frequency around the lutetium resonance energies was attempted but no significant variation in the spectra was observed.

  3. Ultrahigh vacuum sample mount for x-ray photoelectron spectroscopy up to very high temperature (150-1400 K)

    International Nuclear Information System (INIS)

    Spectroscopic studies are rarely performed at very high temperature, especially when combined with light from a synchrotron source. Demanding conditions of maintaining ultrahigh vacuum (UHV) during heating, together with the typically brief access to beam time at multiuser synchrotron end stations, may contribute to some of the reasons for the difficulty of such experiments. Consequently, a large number of materials with interesting properties and industrial applications at high temperature remain unexplored. The authors describe here a simple portable sample mount assembly that can be easily utilized at a beamline, with potential utility for a variety of spectroscopic measurements requiring elevated temperatures and an UHV environment. In the specific application described here, the authors use a resistive cartridge heater interfaced with a standard manipulator previously designed for cooling by liquid nitrogen with an UHV chamber and a cylindrical mirror analyzer for x-ray photoemission spectroscopy (XPS) [also known as electron spectroscopy for chemical analysis (ESCA)] at the Synchrotron Radiation Center in Stoughton, WI. The heater cartridge required only modest power to reach target temperatures using an open-loop temperature control. Finally, the authors describe the measurements of XPS (ESCA) and total-electron yield x-ray absorption spectroscopy on nanopowders and on single crystals grown by them. They emphasize the simplicity of the setup, which they believe would be of interest to groups performing measurements at large facilities, where access and time are both limited.

  4. Investigations on surface chemical analysis using X-ray photoelectron spectroscopy and optical properties of Dy3+-doped LiNa3P2O7 phosphor

    Science.gov (United States)

    Munirathnam, K.; Dillip, G. R.; Chaurasia, Shivanand; Joo, S. W.; Deva Prasad Raju, B.; John Sushma, N.

    2016-08-01

    Near white-light emitting LiNa3P2O7:Dy3+ phosphors were prepared by a conventional solid-state reaction method. The orthorhombic crystal structure of the phosphors was confirmed using X-ray diffraction (XRD), and the valence states of the surface elements were determined from the binding energies of Li 1s, O 1s, Na 1s, P 2p, and Dy 3d by X-ray photoelectron spectroscopy (XPS). Attenuated total reflectance (ATR) - Fourier transform infrared (FT-IR) spectroscopy was employed to identify the pyrophosphate groups in the phosphors. Diffuse reflectance spectra (DRS) show the absorption bands of the Dy3+ ions in the host material. Intense blue (481 nm) and yellow (575 nm) emissions were obtained at an excitation wavelength of 351 nm and are attributed to the 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transitions of Dy3+ ions, respectively. The combination of these two intense bands generates light emission in the near-white region of the chromaticity diagram.

  5. Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure study on oxidative etching of diamond-like carbon films by hyperthermal atomic oxygen

    International Nuclear Information System (INIS)

    Surface structural changes of a hydrogenated diamond-like carbon (DLC) film exposed to a hyperthermal atomic oxygen beam were investigated by Rutherford backscattering spectroscopy (RBS), synchrotron radiation photoelectron spectroscopy (SR-PES), and near-edge X-ray absorption fine structure (NEXAFS). It was confirmed that the DLC surface was oxidized and etched by high-energy collisions of atomic oxygen. RBS and real-time mass-loss data showed a linear relationship between etching and atomic oxygen fluence. SR-PES data suggested that the oxide layer was restricted to the topmost surface of the DLC film. NEXAFS data were interpreted to mean that the sp2 structure at the DLC surface was selectively etched by collisions with hyperthermal atomic oxygen, and an sp3-rich region remained at the topmost DLC surface. The formation of an sp3-rich layer at the DLC surface led to surface roughening and a reduced erosion yield relative to the pristine DLC surface.

  6. Temperature-dependent Raman and ultraviolet photoelectron spectroscopy studies on phase transition behavior of VO{sub 2} films with M1 and M2 phases

    Energy Technology Data Exchange (ETDEWEB)

    Okimura, Kunio, E-mail: okifn@keyaki.cc.u-tokai.ac.jp; Hanis Azhan, Nurul [Graduate School of Engineering, Tokai University, Hiratsuka 259-1292 (Japan); Hajiri, Tetsuya [UVSOR Facility, Institute for Molecular Science, Okazaki 444-8585 (Japan); Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan); Kimura, Shin-ichi [UVSOR Facility, Institute for Molecular Science, Okazaki 444-8585 (Japan); Graduate School of Frontier Biosciences, Osaka University, Suita 565-0871 (Japan); Zaghrioui, Mustapha; Sakai, Joe [GREMAN, UMR 7347 CNRS, Université François Rabelais de Tours, Parc de Grandmont, 37200 Tours (France)

    2014-04-21

    Structural and electronic phase transitions behavior of two polycrystalline VO{sub 2} films, one with pure M1 phase and the other with pure M2 phase at room temperature, were investigated by temperature-controlled Raman spectroscopy and ultraviolet photoelectron spectroscopy (UPS). We observed characteristic transient dynamics in which the Raman modes at 195 cm{sup −1} (V-V vibration) and 616 cm{sup −1} (V-O vibration) showed remarkable hardening along the temperature in M1 phase film, indicating the rearrangements of V-V pairs and VO{sub 6} octahedra. It was also shown that the M1 Raman mode frequency approached those of invariant M2 peaks before entering rutile phase. In UPS spectra with high energy resolution of 0.03 eV for the M2 phase film, narrower V{sub 3d} band was observed together with smaller gap compared to those of M1 phase film, supporting the nature of Mott insulator of M2 phase even in the polycrystalline film. Cooperative behavior of lattice rearrangements and electronic phase transition was suggested for M1 phase film.

  7. Aging of Zerovalent Iron in Synthetic Groundwater: X-ray Photoelectron Spectroscopy Depth Profiling Characterization and Depassivation with Uniform Magnetic Field.

    Science.gov (United States)

    Xu, Hanyang; Sun, Yuankui; Li, Jinxiang; Li, Fengmin; Guan, Xiaohong

    2016-08-01

    Scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) depth profiling were employed to characterize the aged zerovalent iron (AZVI) samples incubated in synthetic groundwater. The AZVI samples prepared under different conditions exhibited the passive layers of different morphologies, amounts, and constituents. Owing to the accumulation of iron oxides on their surface, all the prepared AZVI samples were much less reactive than the pristine ZVI for Se(IV) removal. However, the reactivity of all AZVI samples toward Se(IV) sequestration could be significantly enhanced by applying a uniform magnetic field (UMF). Moreover, the flux intensity of UMF necessary to depassivate an AZVI sample was strongly dependent on the properties of its passive layer. The UMF of 1 mT was strong enough to restore the reactivity of the AZVI samples with Fe3O4 as the major constituent of the passive film or with a thin layer of α-Fe2O3 and γ-FeOOH in the external passive film. The flux intensity of UMF necessary to depassivate the AZVI samples would increase to 2 mT or even 5 mT if the AZVI samples were covered with passive films being thicker, denser, and contained more γ-FeOOH and α-Fe2O3. Furthermore, increasing the flux intensity of UMF facilitated the reduction of Se(IV) to Se(0) by AZVI samples. PMID:27384928

  8. X-ray Photoelectron Spectroscopy ofGaP_{1-x}N_x Photocorroded as a Result of Hydrogen Productionthrough Water Electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Mayer, Marie A.; /Illinois U., Urbana /SLAC

    2006-09-27

    Photoelectrochemical (PEC) cells produce hydrogen gas through the sunlight driven electrolysis of water. By extracting hydrogen and oxygen from water and storing solar energy in the H-H bond, they offer a promising renewable energy technology. Addition of dilute amounts of nitrogen to III-V semiconductors has been shown to dramatically increase the stability of these materials for hydrogen production. In an effort to learn more about the origin of semiconductor photocorrosion in PEC cells, three samples of p-type GaP with varying levels of nitrogen content (0%, 0.2%, 2%) were photocorroded and examined by X-ray Photoelectron Spectroscopy (XPS). GaPN samples were observed to be more efficient during the hydrogen production process than the pure GaP samples. Sample surfaces contained gallium oxides in the form of Ga{sub 2}O{sub 3} and Ga(OH){sub 3} and phosphorus oxide (P{sub 2}O{sub 5}), as well as surface oxides from exposure to air. A significant shift in intensity from bulk to surface peaks dramatic nitrogen segregation to the surface during photoelectrochemical hydrogen production. Further investigations, including using a scanning electron microscope to investigate sample topography and inductively coupled plasma mass spectroscopy (ICP-MS) analysis for solution analyses, are under way to determine the mechanism for these changes.

  9. Degradation of all-vanadium redox flow batteries (VRFB) investigated by electrochemical impedance and X-ray photoelectron spectroscopy: Part 2 electrochemical degradation

    Science.gov (United States)

    Derr, Igor; Bruns, Michael; Langner, Joachim; Fetyan, Abdulmonem; Melke, Julia; Roth, Christina

    2016-09-01

    Electrochemical degradation (ED) of carbon felt electrodes was investigated by cycling of a flow through all-vanadium redox flow battery (VRFB) and conducting half-cell measurements with two reference electrodes inside the test bench. ED was detected using half-cell and full-cell electrochemical impedance spectroscopy (EIS) at different states of charge (SOC). Reversing the polarity of the battery to recover cell performance was performed with little success. Renewing the electrolyte after a certain amount of cycles restored the capacity of the battery. X-ray photoelectron spectroscopy (XPS) reveals that the amount of surface functional increases by more than a factor of 3 for the negative side as well as for the positive side. Scanning electron microscope (SEM) images show a peeling of the fiber surface after cycling the felts, which leads to a loss of electrochemically active surface area (ECSA). Long term cycling shows that ED has a stronger impact on the negative half-cell [V(II)/V(III)] than the positive half-cell [V(IV)/V(V)] and that the negative half-cell is the rate-determining half-cell for the VRFB.

  10. X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry characterization of aging effects on the mineral fibers treated with aminopropylsilane and quaternary ammonium compounds

    DEFF Research Database (Denmark)

    Zafar, Ashar; Schjødt-Thomsen, Jan; Sodhi, R.;

    2012-01-01

    X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry were used to investigate the aging effects on the aminopropylsilane (APS) and quaternary ammonium surfactant-treated mineral fibers. APS-coated mineral fiber samples were treated with cationic surfactant and...

  11. Time-resolved photoemission using attosecond streaking

    CERN Document Server

    Nagele, Stefan; Wais, Michael; Wachter, Georg; Burgdörfer, Joachim

    2014-01-01

    We theoretically study time-resolved photoemission in atoms as probed by attosecond streaking. We review recent advances in the study of the photoelectric effect in the time domain and show that the experimentally accessible time shifts can be decomposed into distinct contributions that stem from the field-free photoionization process itself and from probe-field induced corrections. We perform accurate quantum-mechanical as well as classical simulations of attosecond streaking for effective one-electron systems and determine all relevant contributions to the time delay with attosecond precision. In particular, we investigate the properties and limitations of attosecond streaking for the transition from short-ranged potentials (photodetachment) to long-ranged Coulomb potentials (photoionization). As an example for a more complex system, we study time-resolved photoionization for endohedral fullerenes $A$@$\\text{C}_{60}$ and discuss how streaking time shifts are modified due to the interaction of the $\\text{C}_...

  12. Ionization of atoms by chirped attosecond pulses

    Institute of Scientific and Technical Information of China (English)

    Tan Fang; Peng Liang-You; Gong Qi-Huang

    2009-01-01

    We investigate the ionization dynamics of atoms by chirped attosecond pulses using the strong field approximation method. The pulse parameters are carefully chosen in the regime where the strong field approximation method is valid. We analyse the effects of the chirp of attosecond pulses on the energy distributions and the corresponding left-right asymmetry of the ionized electrons. For a single chirped attosecond pulse, the ionized electrons can be redistributed and the left-right asymmetry shows oscillations because of the introduction of the chirp. For time-delayed double attosecond pulses at different intensities with the weaker one chirped, exchanging the order of the two pulses shows a relative shift of the energy spectra, which can be explained by the different effective time delays of different frequency components because of the chirp.

  13. 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.

  14. Measurement of valence-band offset at native oxide/BaSi{sub 2} interfaces by hard x-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Takabe, Ryota; Du, Weijie; Takeuchi, Hiroki; Toko, Kaoru [Institute of Applied Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan); Ito, Keita [Institute of Applied Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan); Japan Society for the Promotion of Science (JSPS), Chiyoda, Tokyo 102-0083 (Japan); Department of Electronic Engineering, Graduate School of Engineering, Tohoku University, Sendai 980-8579 (Japan); Ueda, Shigenori [Synchrotron X-ray Station at SPring-8, National Institute for Materials Science (NIMS), Hyogo 679-5148 (Japan); Quantum Beam Unit, NIMS, Tsukuba, Ibaraki 305-0047 (Japan); Kimura, Akio [Graduate School of Science, Hiroshima University, Higashi-hiroshima 739-8526 (Japan); Suemasu, Takashi [Institute of Applied Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan); Japan Science and Technology Agency, CREST, Tokyo 102-0075 (Japan)

    2016-01-14

    Undoped n-type BaSi{sub 2} films were grown on Si(111) by molecular beam epitaxy, and the valence band (VB) offset at the interface between the BaSi{sub 2} and its native oxide was measured by hard x-ray photoelectron spectroscopy (HAXPES) at room temperature. HAXPES enabled us to investigate the electronic states of the buried BaSi{sub 2} layer non-destructively thanks to its large analysis depth. We performed the depth-analysis by varying the take-off angle (TOA) of photoelectrons as 15°, 30°, and 90° with respect to the sample surface and succeeded to obtain the VB spectra of the BaSi{sub 2} and the native oxide separately. The VB maximum was located at −1.0 eV from the Fermi energy for the BaSi{sub 2} and −4.9 eV for the native oxide. We found that the band bending did not occur near the native oxide/BaSi{sub 2} interface. This result was clarified by the fact that the core-level emission peaks did not shift regardless of TOA (i.e., analysis depth). Thus, the barrier height of the native oxide for the minority-carriers in the undoped n-BaSi{sub 2} (holes) was determined to be 3.9 eV. No band bending in the BaSi{sub 2} close to the interface also suggests that the large minority-carrier lifetime in undoped n-BaSi{sub 2} films capped with native oxide is attributed not to the band bending in the BaSi{sub 2}, which pushes away photogenerated minority carriers from the defective surface region, but to the decrease of defective states by the native oxide.

  15. 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.

  16. Attosecond pulse shaping using partial phase matching

    OpenAIRE

    Austin, Dane R.; Biegert, Jens

    2014-01-01

    We propose a method for programmable shaping of the amplitude and phase of the XUV and x-ray attosecond pulses produced by high-order harmonic generation. It overcomes the bandwidth limitations of existing spectral filters and enables removal of the intrinsic attosecond chirp as well as the synthesis of pulse sequences. It is based on partial phase matching, such as quasi-phase matching, using a longitudinally addressable modulation.

  17. Optical vortices discern attosecond time delay in electron emission from magnetic sublevels

    CERN Document Server

    Wätzel, Jonas

    2016-01-01

    Photoionization from energetically distinct electronic states may have a relative time delay of tens of attoseconds. Here we demonstrate that pulses of optical vortices allow measuring such attoseconds delays from magnetic sublevels, even from a spherically symmetric target. The di?erence in the time delay is substantial and exhibits a strong angular dependence. Furthermore, we find an atomic scale variation in the time delays depending on the target orbital position in the laser spot. The findings o?er thus a qualitatively new way for a spatio-temporal sensing of the magnetic states from which the photoelectrons originate, with a spatial resolution way below the di?raction limit of the vortex beam. Our conclusions follow from analytical considerations based on symmetry, complemented and confirmed with full numerical simulations of the quantum dynamics.

  18. 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.

  19. Optical attosecond pulses and tracking the nonlinear response of bound electrons.

    Science.gov (United States)

    Hassan, M Th; Luu, T T; Moulet, A; Raskazovskaya, O; Zhokhov, P; Garg, M; Karpowicz, N; Zheltikov, A M; Pervak, V; Krausz, F; Goulielmakis, E

    2016-02-01

    The time it takes a bound electron to respond to the electromagnetic force of light sets a fundamental speed limit on the dynamic control of matter and electromagnetic signal processing. Time-integrated measurements of the nonlinear refractive index of matter indicate that the nonlinear response of bound electrons to optical fields is not instantaneous; however, a complete spectral characterization of the nonlinear susceptibility tensors--which is essential to deduce the temporal response of a medium to arbitrary driving forces using spectral measurements--has not yet been achieved. With the establishment of attosecond chronoscopy, the impulsive response of positive-energy electrons to electromagnetic fields has been explored through ionization of atoms and solids by an extreme-ultraviolet attosecond pulse or by strong near-infrared fields. However, none of the attosecond studies carried out so far have provided direct access to the nonlinear response of bound electrons. Here we demonstrate that intense optical attosecond pulses synthesized in the visible and nearby spectral ranges allow sub-femtosecond control and metrology of bound-electron dynamics. Vacuum ultraviolet spectra emanating from krypton atoms, exposed to intense waveform-controlled optical attosecond pulses, reveal a finite nonlinear response time of bound electrons of up to 115 attoseconds, which is sensitive to and controllable by the super-octave optical field. Our study could enable new spectroscopies of bound electrons in atomic, molecular or lattice potentials of solids, as well as light-based electronics operating on sub-femtosecond timescales and at petahertz rates. PMID:26842055

  20. Photoelectron spectroscopy of self-assembled monolayers of molecular switches on noble metal surfaces; Photoelektronenspektroskopie selbstorganisierter Adsorbatschichten aus molekularen Schaltern auf Edelmetalloberflaechen

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, Nils

    2012-09-12

    Self-assembled monolayers (SAMs) of butanethiolate (C4) on single crystalline Au(111) surfaces were prepared by adsorption from solution. The thermally activated desorption behaviour of the C4 molecules from the gold substrate was examined by qualitative thermal desorption measurements (TDM), through this a desorption temperature T{sub Des}=473 K could be determined. With this knowledge, it was possible to produce samples of very good surface quality, by thermal treatment T{sub Sample}spectroscopy of C4/Au was on the samples of the p x {radical}(3) phase using two-photon photoemission spectroscopy (2PPE). The spectra revealed clear signatures of two unoccupied resonance states at energies E-E{sub F}=3.7 eV and 3.9 eV. The low-energy state was assigned to the characteristic {sigma}*-resonance associated with the Au-S bond of the thiolate. The energy of the other resonance state agreed well with an interface state reported before for SAMs of an other alkanethiol on Au(111) in a densely packed phase. Furthermore the 2PPE data indicated that the high quality of the ex situ prepared SAMs supported the formation of image potential states. The reversible photo- and thermally activated isomerization of the molecular switch 3-(4-(4-Hexyl-phenylazo)-phenoxy)-propane-1-thiol (ABT), deposited by self-assembly from solution on Au(111), was examined using laser-based photoelectron spectroscopy. Differences in the molecular dipole moment characteristic for the trans and the cis isomer of ABT were observed via changes in the sample work function, accessible by detection of the threshold energy for photoemission. A quantitative

  1. Mechanism of anodic oxidation of molybdenum in nearly-neutral electrolytes studied by electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Petrova, Manuela [University of Chemical Technology and Metallurgy, 8 Kl. Ohridski Blvd., 1756 Sofia (Bulgaria); Bojinov, Martin, E-mail: martin@uctm.edu [University of Chemical Technology and Metallurgy, 8 Kl. Ohridski Blvd., 1756 Sofia (Bulgaria); Zanna, Sandrine; Marcus, Philippe [Laboratoire de Physico-Chimie des Surfaces, CNRS-ENSCP (UMR7045), 11 Rue Pierre et Marie Curie, 75005 Paris (France)

    2011-09-30

    Anodic oxidation of molybdenum in weakly acidic, nearly neutral and weakly alkaline electrolytes was studied by voltammetric and electrochemical impedance spectroscopic measurements in a wide potential and pH range. Current vs. potential curves were found to exhibit two pseudo-Tafel regions suggesting two parallel pathways of the dissolution process. Electrochemical impedance spectra indicated the presence of at least two reaction intermediates. X-ray photoelectron spectroscopic (XPS) results pointed to the formation of an oxide containing Mo(IV), Mo(V) and Mo(VI), the exact ratio between different valence states depending on potential and pH of the solution. A physico-chemical model of the processes is proposed and a set of kinetic equations for the steady-state current vs. potential curve and the impedance response are derived. The model is found to reproduce quantitatively the current vs. potential curves and impedance spectra at a range of potentials and pH and to agree qualitatively with the XPS results. Subject to further improvement, the model could serve as a starting point for the optimization of the electrochemical fabrication of functional molybdenum oxide coatings.

  2. Attosecond dynamics of electrons in molecules and liquids

    Science.gov (United States)

    Woerner, Hans Jakob

    2016-05-01

    The ultrafast motion of electrons and holes following light-matter interaction is fundamental to a broad range of chemical and biophysical processes. In this lecture, I will discuss two recent experiments carried out in our group that measure the atomic-scale motion of charge with attosecond temporal resolution (1 as = 10-18 s). The first experiment is carried out on isolated, spatially oriented molecules in the gas phase. We advance high-harmonic spectroscopy to resolve spatially and temporally the migration of an electron hole immediately following ionization of iodoacetylene, while simultaneously demonstrating extensive control over the process. A multidimensional approach, based on the measurement of both even and odd harmonic orders, enables us to reconstruct both quantum amplitudes and phases of the electronic states with a resolution of ~ 100 as. We separately reconstruct quasi-field-free and laser-controlled charge migration as a function of the spatial orientation of the molecule and determine the shape of the hole created by ionization. The second experiment is carried out on a free-flowing microjet of liquid water. We use an attosecond pulse train synchronized with a near-infrared laser pulse to temporally resolve the process of photoemission from liquid water using the RABBIT technique. We measure a delay on the order of 50 as between electrons emitted from the HOMO of liquid water compared to that of gas-phase water and a substantially reduced modulation contrast of the corresponding sidebands. Since our measurements on solvated water molecules are referenced to isolated ones, the measured delays reflect (i) the photoionization delays caused by electron transport through the aqueous environment and (ii) the effect of solvation on the parent molecule. The relative modulation contrast, in turn, contains information on (iii) the modification of transition amplitudes and (iv) dephasing processes. These experiments make the liquid phase and its fascinating

  3. Spin-orbit-induced photoelectron spin polarization in angle-resolved photoemission from both atomic and condensed matter targets

    International Nuclear Information System (INIS)

    The existence of highly spin polarized photoelectrons emitted from non-magnetic solids as well as from unpolarized atoms and molecules has been found to be very common in many studies over the past 40 years. This so-called Fano effect is based upon the influence of the spin-orbit interaction in the photoionization or the photoemission process. In a non-angle-resolved photoemission experiment, circularly polarized radiation has to be used to create spin polarized photoelectrons, while in angle-resolved photoemission even unpolarized or linearly polarized radiation is sufficient to get a high spin polarization. In past years the Rashba effect has become very important in the angle-resolved photoemission of solid surfaces, also with an observed high photoelectron spin polarization. It is the purpose of the present topical review to cross-compare the spin polarization experimentally found in angle-resolved photoelectron emission spectroscopy of condensed matter with that of free atoms, to compare it with the Rashba effect and topological insulators to describe the influence and the importance of the spin-orbit interaction and to show and disentangle the matrix element and phase shift effects therein. The relationship between the energy dispersion of these phase shifts and the emission delay of photoelectron emission in attosecond-resolved photoemission is also discussed. Furthermore the influence of chiral structures of the photo-effect target on the spin polarization, the interferences of different spin components in coherent superpositions in photoemission and a cross-comparison of spin polarization in photoemission from non-magnetic solids with XMCD on magnetic materials are presented; these are all based upon the influence of the spin-orbit interaction in angle-resolved photoemission. (topical review)

  4. Photoelectron spectroscopy investigation of the temperature-induced deprotonation and substrate-mediated hydrogen transfer in a hydroxyphenyl-substituted porphyrin

    CERN Document Server

    Smykalla, Lars; Mende, Carola; Lang, Heinrich; Knupfer, Martin; Hietschold, Michael

    2015-01-01

    The temperature dependent stepwise deprotonation of 5,10,15,20-tetra(p-hydroxyphenyl)porphyrin is investigated using photoelectron spectroscopy. An abundance of pyrrolic relative to iminic nitrogen and a decrease in the ratio of the amount of -NH- to -N= with increasing annealing temperature is found. In contrast to the molecules adsorbed on Au(111), on the more reactive Ag(110) surface, partial dissociation of the hydroxyl groups and subsequent diffusion and rebonding of hydrogen to the central nitrogen atoms resulting in a zwitterionic molecule was clearly observed. Moreover, partial C-H bond cleavage and the formation of new covalent bonds with adjacent molecules or the surface starts at a relatively high annealing temperature of 300{\\deg}C. This reaction is identified to occur at the carbon atoms of the pyrrole rings, which leads also to a shift in the N 1s signal and changes in the valence band of the molecules. Our results show that annealing can significantly alter the molecules which were deposited de...

  5. Electronic structure of (Ge2Sb2Te5)1-x(In3SbTe2)x investigated by x-ray photoelectron spectroscopy

    Science.gov (United States)

    Benayad, Anass; Kang, YounSeon; Shin, Hyun-Joon; Kim, Kihong; Suh, Dong-Seok; Kim, KiJoon; Kim, CheolKyu; Lee, Tae-Yon; Noh, Jin-Seo; Lee, JaeCheol; Khang, YoonHo

    2009-08-01

    We have investigated the core levels and the valence band of (Ge2Sb2Te5)1-x(In3Sb1Te2)x quaternary phase system (IGST) by means of x-ray photoelectron spectroscopy. A systematic shift of Sb 3d and Ge 2p core-level peaks toward lower binding energies side was observed with increasing indium amount, whereas the In 3d and Te 3d core peaks showed less change. The Sb 3d and Ge 2p core-level shift is attributed to an increase in the electronic charge of p-electrons dependent of indium amount. The valence band spectra show a distinct change in the sp configuration with indium concentration change. The change in the local bonding as the indium amount increase has a profound impact on both local atomic arrangement and amorphous-to-crystalline transformation temperature. The difference in the photoemission spectra have been discussed according to a simple structural model suggesting that the Na site in IGST can be occupied by Te, Sb, In, and vacancy, whereas in GST it is occupied only by Te.

  6. Evaluating the solid electrolyte interphase formed on silicon electrodes: a comparison of ex situ X-ray photoelectron spectroscopy and in situ neutron reflectometry.

    Science.gov (United States)

    Fears, T M; Doucet, M; Browning, J F; Baldwin, J K S; Winiarz, J G; Kaiser, H; Taub, H; Sacci, R L; Veith, G M

    2016-05-18

    This work details the in situ characterization of the interface between a silicon electrode and an electrolyte using a linear fluorinated solvent molecule, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in deuterated dimethyl perfluoroglutarate (d6-PF5M2) (1.87 × 10(-2) mS cm(-1)). The solid electrolyte interphase (SEI) composition and thickness determined via in situ neutron reflectometry (NR) and ex situ X-ray photoelectron spectroscopy (XPS) were compared. The data show that SEI expansion and contraction (breathing) during electrochemical cycling were observed via both techniques; however, ex situ XPS suggests that the SEI thickness increases during Si lithiation and decreases during delithiation, while in situ NR suggests the opposite. The most likely cause of this discrepancy is the selective removal of SEI components (top 20 nm of the SEI) during the electrode rinse process, which is required to remove the electrolyte residue prior to ex situ analysis, demonstrating the necessity of performing SEI characterization in situ. PMID:27149427

  7. In situ SERS and X-ray photoelectron spectroscopy studies on the pH-dependant adsorption of anthraquinone-2-carboxylic acid on silver electrode

    Science.gov (United States)

    Li, Dan; Jia, Shaojie; Fodjo, Essy Kouadio; Xu, Hu; Wang, Yuhong; Deng, Wei

    2016-03-01

    In this study, in situ surface-enhanced Raman scattering (SERS) spectroelectrochemistry and angle-resolved X-ray photoelectron spectroscopy (AR-XPS) are used to investigate the redox reaction and adsorption behavior of anthraquinone-2-carboxylic acid (AQ-2-COOH) on an Ag electrode at different pH values. The obtained results indicate that AQ-2-COOH is adsorbed tilted on the Ag electrode through O-atom of ring carbonyl in a potential range from -0.3 to -0.5 V vs. SCE, but the orientation turns to more tilted orientation with both O-atom of the ring carbonyl and carboxylate group in positive potential region for pH 6.0 and 7.4. However, at pH 10.0, the orientation adopts tilted conformation constantly on the Ag electrode with both O-atom of the anthraquinone ring and carboxylate group in the potential range from -0.3 to -0.5 V vs. SCE or at positive potentials. Moreover, the adsorption behavior of AQ-2-COOH has been further confirmed by AR-XPS on the Ag surface. Proposed reasons for the observed changes in orientation are presented.

  8. Hard X-ray photoelectron spectroscopy of Li{sub x}Ni{sub 1−x}O epitaxial thin films with a high lithium content

    Energy Technology Data Exchange (ETDEWEB)

    Kumara, L. S. R., E-mail: KUMARA.Rosantha@nims.go.jp; Yang, Anli [Synchrotron X-ray Station at SPring-8, National Institute for Materials Science (NIMS), 1-1-1 Kouto, Sayo, Hyogo 679-5148 (Japan); Sakata, Osami, E-mail: SAKATA.Osami@nims.go.jp [Synchrotron X-ray Station at SPring-8, National Institute for Materials Science (NIMS), 1-1-1 Kouto, Sayo, Hyogo 679-5148 (Japan); Synchrotron X-ray Group, Quantum Beam Unit, NIMS, 1-1-1 Kouto, Sayo, Hyogo 679-5148 (Japan); Department of Innovative and Engineered Materials, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-J3-16, Nagatsuta, Midori, Yokohama 226-8502 (Japan); Yamauchi, Ryosuke; Matsuda, Akifumi; Yoshimoto, Mamoru [Department of Innovative and Engineered Materials, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-J3-16, Nagatsuta, Midori, Yokohama 226-8502 (Japan); Taguchi, Munetaka [Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192 (Japan)

    2014-07-28

    The core-level and valence-band electronic structures of Li{sub x}Ni{sub 1−x}O epitaxial thin films with x = 0, 0.27, and 0.48 were studied by hard X-ray photoelectron spectroscopy. A double peak structure, consisting of a main peak and a shoulder peak, and a satellite structure were observed in the Ni 2p{sub 3/2} core-level spectra. The intensity ratio of the shoulder to main peak in this double peak structure increased with increasing lithium content in Li{sub x}Ni{sub 1−x}O. This lithium doping dependence of the Ni 2p{sub 3/2} core-level spectra was investigated using an extended cluster model, which included the Zhang–Rice (ZR) doublet bound states arising from a competition between O 2p – Ni 3d hybridization and the Ni on-site Coulomb interaction. The results indicated that the change in the intensity ratio in the main peak is because of a reduction in the ZR doublet bound states from lithium substitutions. This strongly suggests that holes compensating Li doping in Li{sub x}Ni{sub 1−x}O are of primarily ZR character.

  9. Band alignments at interface of Cu2ZnSnS4/ZnO heterojunction: An X-ray photoelectron spectroscopy and first-principles study

    International Nuclear Information System (INIS)

    Highlights: • XPS measurement indicates a type-I band alignment of Cu2ZnSnS4/ZnO heterojunction. • First-principles calculations support the type-I band alignment at Cu2ZnSnS4/ZnO interface. • ZnO can be a potential Cd-free buffer candidate for CZTS-based solar cells. - Abstract: The band alignments at the interface of Cu2ZnSnS4 (CZTS)/ZnO heterojunction were determined by X-ray photoelectron spectroscopy. Core levels of S2p and O1s were used to align the valence-band offset (VBO). The VBO was determined to be 1.78 ± 0.10 eV, and the conduction-band offset (CBO) was deduced to be 0.09 ± 0.10 eV, implying that the CZTS/ZnO heterojunction has a type-I band alignment. Furthermore, first-principles calculations based on hybrid functional method also indicate that the CZTS/ZnO interface has a type-I band alignment, well supporting our experimental results

  10. In situ investigations of laser and thermally modified As{sub 2}S{sub 3} nanolayers: Synchrotron radiation photoelectron spectroscopy and density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kondrat, O., E-mail: o.b.kondrat@gmail.com; Holomb, R.; Popovich, N.; Mitsa, V. [Institute of Solid State Physics and Chemistry, Uzhhorod National University, Pidhirna Str., 46, 88000 Uzhhorod (Ukraine); Veres, M. [Wigner Research Centre for Physics, Hungarian Academy of Sciences, 1121 Budapest (Hungary); Csik, A. [Institute for Nuclear Research, Hungarian Academy of Sciences, H-4001 Debrecen (Hungary); Feher, A. [Pavol Jozef Šafárik University in Košice, Park Angelinum 9, Košice (Slovakia); Tsud, N.; Matolín, V. [Department of Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University, V Holešovičkách 2, 18000 Prague 8 (Czech Republic); Vondráček, M. [Institute of Physics, Academy of Science of the Czech Republic, Na Slovance 2, CZ-182 21 Prague 8 (Czech Republic); Prince, K. C. [Elettra-Sincrotrone Trieste S.C.p.A., Strada Statale 14, km 163.5, in Area Science Park, 34149 Basovizza, Trieste (Italy); Istituto Officina dei Materiali, Consiglio Nazionale delle Ricerche, 34149 Basovizza, Trieste (Italy)

    2015-12-14

    As-deposited, annealed, and in situ As{sub 2}S{sub 3} nanolayers, illuminated by blue (405 nm) and red (650 nm) laser light, were studied using synchrotron radiation photoelectron spectroscopy and DFT electronic structure calculations. Changes in composition and local atomic coordination occurring in the irradiated region of As{sub 2}S{sub 3} films were monitored by analysis of As 3d and S 2p core levels. These studies show that both the thermal treatment and the red laser illumination of As{sub 2}S{sub 3} nanolayers decrease the concentration of homopolar (As-As and S-S) bonds. From the other hand, an increasing concentration of As-rich structural units (s.u.) with a homopolar As-As bond was observed under in situ blue laser illumination of As{sub 2}S{sub 3} nanolayers. Molecular orbital energies were calculated for different As- and S-centered s.u. and used for the interpretation of the core levels and valence band spectra. The surface local structure of the As{sub 2}S{sub 3} nanolayers and its photoinduced transformation are discussed in detail.

  11. Chemical interaction at the buried silicon/zinc oxide thin-film solar cell interface as revealed by hard X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wimmer, M., E-mail: mark.wimmer@helmholtz-berlin.de [Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Gerlach, D.; Wilks, R.G.; Scherf, S.; Félix, R. [Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Lupulescu, C. [Institute for Optics and Atomic Physics, Technische Universität Berlin, Hardenbergstr. 36, 10623 Berlin (Germany); Ruske, F.; Schondelmaier, G.; Lips, K. [Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Hüpkes, J. [Institute for Energy Research, Forschungszentrum Jülich GmbH, Leo-Brandt-Straße, 52425 Jülich (Germany); Gorgoi, M. [Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Eberhardt, W. [Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Institute for Optics and Atomic Physics, Technische Universität Berlin, Hardenbergstr. 36, 10623 Berlin (Germany); Rech, B. [Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Bär, M., E-mail: marcus.baer@helmholtz-berlin.de [Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Institut für Physik und Chemie, Brandenburgische Technische Universität Cottbus, Konrad-Wachsmann-Allee 1, 03046 Cottbus (Germany)

    2013-10-15

    Highlights: •We used HAXPES to identify chemical interactions at the buried silicon/aluminum-doped zinc oxide thin-film solar cell interface. •The results indicate a diffusion of zinc and aluminum into the silicon upon annealing procedures which are part of the solar cell processing. •The contamination of the silicon may be detrimental for the solar cell performance. -- Abstract: Hard X-ray photoelectron spectroscopy (HAXPES) is used to identify chemical interactions (such as elemental redistribution) at the buried silicon/aluminum-doped zinc oxide thin-film solar cell interface. Expanding our study of the interfacial oxidation of silicon upon its solid-phase crystallization (SPC), in which we found zinc oxide to be the source of oxygen, in this investigation we address chemical interaction processes involving zinc and aluminum. In particular, we observe an increase of zinc- and aluminum-related HAXPES signals after SPC of the deposited amorphous silicon thin films. Quantitative analysis suggests an elemental redistribution in the proximity of the silicon/aluminum-doped zinc oxide interface – more pronounced for aluminum than for zinc – as explanation. Based on these insights the complex chemical interface structure is discussed.

  12. Temperature effects on Li4Ti5O12 electrode/electrolyte interfaces at the first cycle: A X-ray Photoelectron Spectroscopy and Scanning Auger Microscopy study

    Science.gov (United States)

    Gieu, J.-B.; Courrèges, C.; El Ouatani, L.; Tessier, C.; Martinez, H.

    2016-06-01

    Li4Ti5O12-based negative electrodes for Lithium-ion batteries are of interest because of the high reversibility of Li+ insertion/extraction. In this study, the surface of cycled electrodes is analysed by X-ray Photoelectron Spectroscopy (XPS) and Scanning Auger Microscopy (SAM) to investigate the effects of cycling temperature (room temperature, 60 °C and 85 °C) upon the solid electrolyte interphase (SEI) formation, which plays a major role in batteries electrochemical performances. Half-cells, with a vinylene carbonate containing electrolyte, are galvanostatically cycled at different steps of the first cycle: the mid-plateau during the first discharge, the end of the first discharge at 1.2 V and the end of the first charge at 2.0 V. XPS analysis evidences that higher temperatures promote the formation of a thicker SEI, which can explain the increase of the irreversible capacity with temperature. SAM mappings (allowing high spatial resolution ∼10-100 nm) evidence that this SEI homogeneously covers the electrode surface, regardless of the cycling temperature. During charge, the SEI is partially dissolved at room temperature, more slightly at 60 °C whereas at 85 °C, no clear evidence of layer thinning is observed. The SEI chemical composition is also investigated and reveals a majority of organic species and an increasing proportion of LiF with the temperature.

  13. Understanding the Adsorption of CuPc and ZnPc on Noble Metal Surfaces by Combining Quantum-Mechanical Modelling and Photoelectron Spectroscopy

    Directory of Open Access Journals (Sweden)

    Yu Li Huang

    2014-03-01

    Full Text Available Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc and Zn-phthalocyanine (ZnPc on Au(111 and Ag(111 surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111 are exclusively due to Pauli pushback. On Ag(111, we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states.

  14. Photoelectron spectroscopy of aromatic compound clusters of the B12 all-boron benzene: B12Au- and B12(BO)-.

    Science.gov (United States)

    Bai, Hui; Zhai, Hua-Jin; Li, Si-Dian; Wang, Lai-Sheng

    2013-06-28

    We report a photoelectron spectroscopy and density-functional theory study of the B12Au(-) and B13O(-) clusters and their neutrals, which are shown to be six π electron aromatic compounds between the quasi-planar all-boron B12 benzene-analogue and a monovalent Au or BO ligand. Electron affinities of B12Au and B13O are measured to be 3.48 ± 0.04 and 3.90 ± 0.04 eV, respectively. Structural searches are performed for B12Au(-) and B13O(-), which are compared with the isovalent B12H(-) cluster. The global minima of B12Au(-) and B13O(-) both feature an almost intact B12 cluster with the Au and BO ligands bonded to its periphery, respectively. For B12Au(-), a low-lying isomer is also identified, which is only 0.4 kcal mol(-1) above the global minimum, in agreement with the experimental observation of a weakly populated isomer in the cluster beam of B12Au(-). These aromatic compound clusters provide new examples for the Au/H isolobal analogy and the boronyl (BO) chemistry. PMID:23666408

  15. Surface properties of Streptococcus salivarius HB and nonfibrillar mutants: measurement of zeta potential and elemental composition with X-ray photoelectron spectroscopy.

    Science.gov (United States)

    van der Mei, H C; Léonard, A J; Weerkamp, A H; Rouxhet, P G; Busscher, H J

    1988-01-01

    To characterize the functional cell surface, the zeta potentials and elemental surface composition of Streptococcus salivarius HB and a range of mutants with known molecular surface structures were determined. Zeta potentials of fully hydrated cells were measured as a function of pH in dilute potassium phosphate solutions, yielding isoelectric points of the strains. Elemental composition (O, C, N, and P) of the outer 2 to 5 nm of the freeze-dried cell surfaces were measured by X-ray photoelectron spectroscopy. An increasing loss of proteinaceous fibrillar surface antigens of the mutants was found to be accompanied by a progressive decrease in the N/C ratio from 0.104 in the parent strain HB to 0.053 in mutant HBC12. Simultaneously, the value of the isoelectric point shifted from 3.0 to 1.3. In a previous study (A.H. Weerkamp, H.C. van der Mei, and J. W. Slot, Infect. Immun. 55:438-455, 1987) on the cell surfaces of the same strains, it was shown that removal of fibrils led to increased exposure of (lipo)teichoic acid at the surface, which explains the low isoelectric point caused by the low pKa of the phosphate groups. PMID:3372474

  16. Evolution of the SrTiO3/MoO3 interface electronic structure: An in situ photoelectron spectroscopy study

    KAUST Repository

    Du, Yuanmin

    2015-05-12

    Modifying the surface energetics, particularly the work function, of advanced materials is of critical importance for a wide range of surface- and interface-based devices. In this work, using in situ photoelectron spectroscopy, we investigated the evolution of electronic structure at the SrTiO3 surface during the growth of ultrathin MoO3 layers. Thanks to the large work function difference between SrTiO3 and MoO3, the energy band alignment on the SrTiO3 surface is significantly modified. The charge transfer and dipole formation at the SrTiO3/MoO3 interface leads to a large modulation of work function and an apparent doping in SrTiO3. The measured evolution of electronic structure and upward band bending suggest that the growth of ultrathin MoO3 layers is a powerful tool to modulate the surface energetics of SrTiO3, and this surface-engineering approach could be generalized to other functional oxides.

  17. Water adsorption, solvation and deliquescence of alkali halide thin films on SiO2 studied by ambient pressure X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Arima, Kenta; Jiang, Peng; Deng, Xingyi; Bluhm, Henrik; Salmeron, Miquel

    2010-03-31

    The adsorption of water on KBr thin films evaporated onto SiO2 was investigated as a function of relative humidity (RH) by ambient pressure X-ray photoelectron spectroscopy. At 30percent RH adsorbed water reaches a coverage of approximately one monolayer. As the humidity continues to increase, the coverage of water remains constant or increases very slowly until 60percent RH, followed by a rapid increase up to 100percent RH. At low RH a significant number of the Br atoms are lost due to irradiation damage. With increasing humidity solvation increases ion mobility and gives rise to a partial recovery of the Br/K ratio. Above 60percent RH the increase of the Br/K ratio accelerates. Above the deliquescence point (85percent RH), the thickness of the water layer continues to increase and reaches more than three layers near saturation. The enhancement of the Br/K ratio at this stage is roughly a factor 2.3 on a 0.5 nm KBr film, indicating a strong preferential segregation of Br ions to the surface of the thin saline solution on SiO2.

  18. Electronic and geometric properties of Au nanoparticles on Highly Ordered Pyrolytic Graphite (HOPG) studied using X-ray Photoelectron Spectroscopy (XPS) and Scanning Tunneling Microscopy (STM).

    Science.gov (United States)

    Lopez-Salido, Ignacio; Lim, Dong Chan; Dietsche, Rainer; Bertram, Nils; Kim, Young Dok

    2006-01-26

    Au nanoparticles grown on mildly sputtered Highly Ordered Pyrolytic Graphite (HOPG) surfaces were studied using Scanning Tunneling Microscopy (STM) and X-ray Photoelectron Spectroscopy (XPS). The results were compared with those of Ag nanoparticles on the same substrate. By varying the defect densities of HOPG and the Au coverages, one can create Au nanoparticles in various sizes. At high Au coverages, the structures of the Au films significantly deviate from the ideal truncated octahedral form: the existence of many steps between different Au atomic layers can be observed, most likely due to a high activation barrier of the diffusion of Au atoms across the step edges. This implies that the particle growth at room temperature is strongly limited by kinetic factors. Hexagonal shapes of Au structures could be identified, indicating preferential growth of Au nanostructures along the (111) direction normal to the surface. In the case of Au, XPS studies reveal a weaker core level shift with decreasing particle size compared to the 3d level in similarly sized Ag particles. Also taking into account the Auger analysis of the Ag particles, the core level shifts of the metal nanoparticles on HOPG can be understood in terms of the metal/substrate charge transfer. Ag is (partially) positively charged, whereas Au negatively charged on HOPG. It is demonstrated that XPS can be a useful tool to study metal-support interactions, which plays an important role for heterogeneous catalysis, for example.

  19. Chemical state analysis of trace-level alkali metals sorbed in micaceous oxide by total reflection X-ray photoelectron spectroscopy

    Science.gov (United States)

    Baba, Y.; Shimoyama, I.; Hirao, N.

    2016-10-01

    In order to determine the chemical states of radioactive cesium (137Cs or 134Cs) sorbed in clay minerals, chemical states of cesium as well as the other alkali metals (sodium and rubidium) sorbed in micaceous oxides have been investigated by X-ray photoelectron spectroscopy (XPS). Since the number of atoms in radioactive cesium is extremely small, we specially focused on chemical states of trace-level alkali metals. For this purpose, we have measured XPS under X-ray total reflection (TR) condition. For cesium, it was shown that ultra-trace amount of cesium down to about 100 pg cm-2 can be detected by TR-XPS. This amount corresponds to about 200 Bq of 137Cs (t1/2 = 30.2 y). It was demonstrated that ultra-trace amount of cesium corresponding to radioactive cesium level can be measured by TR-XPS. As to the chemical states, it was found that core-level binding energy in TR-XPS for trace-level cesium shifted to lower-energy side compared with that for thicker layer. A reverse tendency is observed in sodium. Based on charge transfer within a simple point-charge model, it is concluded that chemical bond between alkali metal and micaceous oxide for ultra-thin layer is more polarized that for thick layer.

  20. Optical and X-ray photoelectron spectroscopy of PbGeO3 and Pb5Ge3O11 single crystals

    Indian Academy of Sciences (India)

    S C Sabharwal; S N Jha; Sangeeta

    2010-08-01

    Pb5Ge3O11 crystals are found to exhibit pale yellow colouration while PbGeO3 are colourless. X-ray photoelectron spectroscopy (XPS) measurements show lead deficiency in both the crystals. The results also reveal a stronger ionic character for PbGeO3 as compared to Pb5Ge3O11 crystal. The binding energy of Ge3 core level in the case of Pb5Ge3O11 crystal is found to be smaller than the binding energy of germanium oxide, thereby indicating the incomplete oxidation of Ge ions in the crystal lattice. On gamma ray irradiation, the transmission of both the crystals is observed to deteriorate uniformly over the entire wavelength range, which has been attributed to the oxidation of some of the lattice Pb ions. On gamma irradiation the changes observed in O1 core level energies for both the crystals are seen to be consistent with the changes noted in the Pb47/2 and Ge3 spectra. Interestingly, the results reveal oxidation of surface Ge atoms with atmospheric oxygen under gamma irradiation.

  1. Voltage contrast X-ray photoelectron spectroscopy reveals graphene-substrate interaction in graphene devices fabricated on the C- and Si- faces of SiC

    International Nuclear Information System (INIS)

    We report on an X-ray photoelectron spectroscopy (XPS) study of two graphene based devices that were analyzed by imposing a significant current under +3 V bias. The devices were fabricated as graphene layers(s) on hexagonal SiC substrates, either on the C- or Si-terminated faces. Position dependent potential distributions (IR-drop), as measured by variations in the binding energy of a C1s peak are observed to be sporadic for the C-face graphene sample, but very smooth for the Si-face one, although the latter is less conductive. We attribute these sporadic variations in the C-face device to the incomplete electrical decoupling between the graphene layer(s) with the underlying buffer and/or substrate layers. Variations in the Si2p and O1s peaks of the underlayer(s) shed further light into the electrical interaction between graphene and other layers. Since the potential variations are amplified only under applied bias (voltage-contrast), our methodology gives unique, chemically specific electrical information that is difficult to obtain by other techniques

  2. Voltage contrast X-ray photoelectron spectroscopy reveals graphene-substrate interaction in graphene devices fabricated on the C- and Si- faces of SiC

    Energy Technology Data Exchange (ETDEWEB)

    Aydogan, Pinar; Suzer, Sefik, E-mail: suzer@fen.bilkent.edu.tr [Department of Chemistry, Bilkent University, 06800 Ankara (Turkey); Arslan, Engin; Cakmakyapan, Semih; Ozbay, Ekmel [Department of Physics, Bilkent University, 06800 Ankara (Turkey); Strupinski, Wlodek [Institute of Electronic Materials Technology, Wolczynska 133, 01-919 Warsaw (Poland)

    2015-09-21

    We report on an X-ray photoelectron spectroscopy (XPS) study of two graphene based devices that were analyzed by imposing a significant current under +3 V bias. The devices were fabricated as graphene layers(s) on hexagonal SiC substrates, either on the C- or Si-terminated faces. Position dependent potential distributions (IR-drop), as measured by variations in the binding energy of a C1s peak are observed to be sporadic for the C-face graphene sample, but very smooth for the Si-face one, although the latter is less conductive. We attribute these sporadic variations in the C-face device to the incomplete electrical decoupling between the graphene layer(s) with the underlying buffer and/or substrate layers. Variations in the Si2p and O1s peaks of the underlayer(s) shed further light into the electrical interaction between graphene and other layers. Since the potential variations are amplified only under applied bias (voltage-contrast), our methodology gives unique, chemically specific electrical information that is difficult to obtain by other techniques.

  3. Analysis of bi-layer oxide on austenitic stainless steel, 316L, exposed to Lead–Bismuth Eutectic (LBE) by X-ray Photoelectron Spectroscopy (XPS)

    Energy Technology Data Exchange (ETDEWEB)

    Koury, D., E-mail: dan@physics.unlv.edu [Dept. of Physics and Astronomy, MS 4002, University of Nevada, Las Vegas, 4505 S. Maryland Pkwy, Las Vegas, NV 89154 (United States); Johnson, A.L. [Harry Reid Center, MS 4009, University of Nevada, Las Vegas, 4505 S. Maryland Pkwy, Las Vegas, NV 89154 (United States); Ho, T. [Dept. of Chemistry, MS 4002, University of Nevada, Las Vegas, 4505 S. Maryland Pkwy, Las Vegas, NV 89154 (United States); Farley, J.W. [Dept. of Physics and Astronomy, MS 4002, University of Nevada, Las Vegas, 4505 S. Maryland Pkwy, Las Vegas, NV 89154 (United States)

    2013-09-15

    Corrosion of the austenitic stainless steel alloy 316L by Lead–Bismuth Eutectic (LBE) was studied using X-ray Photoelectron Spectroscopy (XPS) with Sputter-Depth Profiling (SDP), and compared to data taken by Scanning Electron Microscopy (SEM) and Energy Dispersive X-rays (EDXs). Exposed and unexposed samples were compared. Annealed 316L samples, exposed to LBE for durations of 1000, 2000 and 3000 h, developed bi-layer oxides up to 30 μm thick. Analysis of the charge-states of the 2p{sub 3/2} peaks of iron, chromium, and nickel in the oxide layers reveal an inner layer consisting of iron and chromium oxides (likely spinel-structured) and an outer layer consisting of iron oxides (Fe{sub 3}O{sub 4}). Cold-rolled 316L samples, exposed for the same durations, form a chromium-rich, thin (⩽1 μm) oxide with some oxidized iron in the outermost ∼200 nm of the oxide layer. This is the first experiment to investigate what components of the 316L are oxidized by LBE exposure. It is shown here that nickel is metallic in the inner layer.

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

    CERN Document Server

    Strocov, V N; Flechsig, U; Schmidt, T; Imhof, A; Chen, Q; Raabe, J; Betemps, R; Zimoch, D; Krempasky, J; Piazzalunga, A; Wang, X; Grioni, M; Patthey, L

    2009-01-01

    We describe the concepts and technical realization 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). 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 deg 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 (PGM) operating in collimated light. The ultimate resolving power E/dE is above 33000 at 1 keV photon energy. The choice of blazed vs lamellar gratings and optimization of their profile parameters is described. Due to glancing angles on the mirrors as well as optimized groove densities and profiles of the gratings, high photon flux is achieved up to 1.0e13 photons/s/0.01%BW at 1 keV. Ellipsoida...

  5. An X-ray photoelectron spectroscopy study of the products of the interaction of gaseous IrF6 with fine UO2F2

    Directory of Open Access Journals (Sweden)

    Prusakov Vladimir N.

    2007-01-01

    Full Text Available Nuclear fuel reprocessing by fluorination, a dry method of regeneration of spent nuclear fuel, uses UO2F2 for the separation of plutonium from gaseous mixtures. Since plutonium requires special treatment, IrF6 was used as a thermodynamic model of PuF6. The model reaction of the interaction of gaseous IrF6 with fine UO2F2 in the sorption column revealed a change of color of the sorption column contents from pale-yellow to gray and black, indicating the formation of products of such an interaction. The X-ray photoelectron spectroscopy study showed that the interaction of gaseous IrF6 with fine UO2F2 at 125 °C results in the formation of stable iridium compounds where the iridium oxidation state is close to Ir3+. The dependence of the elemental compositions of the layers in the sorption column on the penetration depth of IrF6 was established.

  6. A study of the O/Ag(111) system with scanning tunneling microscopy and x-ray photoelectron spectroscopy at ambient pressures

    Science.gov (United States)

    Heine, Christian; Eren, Baran; Lechner, Barbara A. J.; Salmeron, Miquel

    2016-10-01

    The interaction of O2 with the Ag(111) surface was studied with scanning tunneling microscopy (STM) in the pressure range from 10- 9 Torr to 1 atm at room temperature and with X-ray photoelectron spectroscopy (XPS) up to 0.3 Torr O2 in the temperature range from RT to 413 K. STM images show that the Ag(111) surface topography is little affected in regions with large flat terraces, except for the appearance of mobile features due to oxygen atoms at pressures above 0.01 Torr. In regions where the step density is high, the surface became rough under 0.01 Torr of O2, due to the local oxidation of Ag. Various chemical states of oxygen due to chemisorbed, oxide and subsurface species were identified by XPS as a function of pressure and temperature. The findings from the STM images and XPS measurements indicate that formation of an oxide phase, the thermodynamically stable form at room temperature under ambient O2 pressure, is kinetically hindered in the flat terrace areas but proceeds readily in regions with high-step density.

  7. NH3 adsorption and decomposition on Ir(110): A combined temperature programmed desorption and high resolution fast x-ray photoelectron spectroscopy study

    International Nuclear Information System (INIS)

    The adsorption and decomposition of NH3 on Ir(110) has been studied in the temperature range from 80 K to 700 K. By using high-energy resolution x-ray photoelectron spectroscopy it is possible to distinguish chemically different surface species. At low temperature a NH3 multilayer, which desorbs at ∼110 K, was observed. The second layer of NH3 molecules desorbs around 140 K, in a separate desorption peak. Chemisorbed NH3 desorbs in steps from the surface and several desorption peaks are observed between 200 and 400 K. A part of the NH3ad decomposes into NHad between 225 and 300 K. NHad decomposes into Nad between 400 K and 500 K and the hydrogen released in this process immediately desorbs. N2 desorption takes place between 500 and 700 K via Nad combination. The steady state decomposition reaction of NH3 starts at 500 K. The maximum reaction rate is observed between 540 K and 610 K. A model is presented to explain the occurrence of a maximum in the reaction rate. Hydrogenation of Nad below 400 K results in NHad. No NH2ad or NH3ad/NH3 were observed. The hydrogenation of NHad only takes place above 400 K. On the basis of the experimental findings an energy scheme is presented to account for the observations

  8. The method of the photoelectron spectroscopy for the observation of ultrafst processes in metals; Die Methode der Photoelektronenspektroskopie zur Beobachtung ultraschneller Prozesse in Metallen

    Energy Technology Data Exchange (ETDEWEB)

    Heinz, Oliver

    2007-12-15

    An essential thematic main topic of this experimental-physical thesis is the observation of the thermalization of hot electrons of a metal film, which were excited and heated by an ultrashort laser pulse. Applied for this was a modification of the method of the photoelectron spectroscopy, at which it is by an optical-pump examination technique possible, to study the dynamics of the electron energy distribution in the metal with high time resolution. The laser pulses required for the surpassing of the metal escape work in the ultraviolet spectral range are by that produced, that pulses of a Ti:sapphire laser system in the infrared spectral region and a pulse duration of 40 femtoseconds are frequency-multiplied. For the success of this measurement method with high time resolution high requirements both on the quality of the exciting laser pulses and the ultrahigh-vacuum apparature of the photoelectron spectrometer are indispensable. The essential details of these special requirements are extensively discussed in this thesis. The excitation of the metal sample by intense and ultrashort laser pulses of different wavelength led after evaluation of the photoemission spectra and after analysis of the structural character of the metal surface to an extension of already existing knowledge concerning the photoemission at simultaneous absorption of two or several photons. [German] Ein wesentlicher thematischer Schwerpunkt dieser experimentalphysikalischen Arbeit ist die Beobachtung der Thermalisierung heisser Elektronen eines Metallfilms, welche mit einem ultrakurzen Laserimpuls angeregt und aufgeheizt wurden. Verwendet wurde dazu eine Abwandlung der Methode der Photoelektronenspektroskopie, bei der es durch eine optische Pump-Abfrage-Technik moeglich ist, die Dynamik der Elektronenenergieverteilung im Metall mit hoher Zeitaufloesung zu untersuchen. Die zur Ueberwindung der metallischen Austrittsarbeit erforderlichen Laserimpulse im ultravioletten Spektralbereich werden

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

    Energy Technology Data Exchange (ETDEWEB)

    Shavorskiy, Andrey; Slaughter, Daniel S.; Zegkinoglou, Ioannis; Rude, Bruce S.; Bluhm, Hendrik [Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Neppl, Stefan; Cryan, James P.; Siefermann, Katrin R.; Weise, Fabian; Lin, Ming-Fu; Bacellar, Camila; Ziemkiewicz, Michael P.; Fraund, Matthew W.; Khurmi, Champak; Wright, Travis W.; Schoenlein, Robert W.; Gessner, Oliver, E-mail: ogessner@lbl.gov [Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Hertlein, Marcus P.; Tyliszczak, Tolek [Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Huse, Nils [Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Physics Department, University of Hamburg and Max-Planck Institute for Structure and Dynamics of Matter, 22761 Hamburg (Germany); and others

    2014-09-15

    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{sub 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

  10. 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

  11. 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

  12. Temporal Characterization of individual Harmonics of an attosecond pulse train by THz Streaking

    CERN Document Server

    Ardana-Lamas, F; Stepanov, A; Gorgisyan, I; Juranic, P; Abela, R; Hauri, C P

    2015-01-01

    We report on the global temporal pulse characteristics of individual harmonics in an attosecond pulse train by means of photo-electron streaking in a strong low-frequency transient. The scheme allows direct retrieval of pulse durations and first order chirp of individual harmonics without the need of temporal scanning. The measurements were performed using an intense THz field generated by tilted phase front technique in LiNbO_3 . Pulse properties for harmonics of order 23, 25 and 27 show that the individual pulse durations and linear chirp are decreasing by the harmonic order.

  13. Attosecond pulse shaping using partial phase matching

    International Nuclear Information System (INIS)

    We propose a method for programmable shaping of the amplitude and phase of the extreme ultraviolet and x-ray attosecond pulses produced by high-order harmonic generation. It overcomes the bandwidth limitations of existing spectral filters and enables removal of the intrinsic attosecond chirp as well as the synthesis of pulse sequences. It is based on partial phase matching using a longitudinally addressable modulation. Although the method is in principle applicable to any form of partial phase matching, we focus on quasi-phase matching using a counterpropagating pulse train. We present simulations of the production of isolated attosecond pulses at 250 eV, including a 31 as transform-limited pulse, tunably chirped pulses and double pulses. (paper)

  14. Two-photon finite-pulse model for resonant transitions in attosecond experiments

    CERN Document Server

    Galán, Álvaro Jiménez; Argenti, Luca

    2015-01-01

    We present an analytical model capable of describing two-photon ionization of atoms with attosecond pulses in the presence of intermediate and final isolated autoionizing states. The model is based on the finite-pulse formulation of second-order time-dependent perturbation theory. It approximates the intermediate and final states with Fano's theory for resonant continua, and it depends on a small set of atomic parameters that can either be obtained from separate \\emph{ab initio} calculations, or be extracted from few selected experiments. We use the model to compute the two-photon resonant photoelectron spectrum of helium below the N=2 threshold for the RABITT (Reconstruction of Attosecond Beating by Interference of Two-photon Transitions) pump-probe scheme, in which an XUV attosecond pulse train is used in association to a weak IR probe, obtaining results in quantitative agreement with those from accurate \\emph{ab initio} simulations. In particular, we show that: i) Use of finite pulses results in a homogene...

  15. Two-photon finite-pulse model for resonant transitions in attosecond experiments

    Science.gov (United States)

    Jiménez-Galán, Álvaro; Martín, Fernando; Argenti, Luca

    2016-02-01

    We present an analytical model capable of describing two-photon ionization of atoms with attosecond pulses in the presence of intermediate and final isolated autoionizing states. The model is based on the finite-pulse formulation of second-order time-dependent perturbation theory. It approximates the intermediate and final states with Fano's theory for resonant continua, and it depends on a small set of atomic parameters that can either be obtained from separate ab initio calculations or be extracted from a few selected experiments. We use the model to compute the two-photon resonant photoelectron spectrum of helium below the N =2 threshold for the RABITT (reconstruction of attosecond beating by interference of two-photon transitions) pump-probe scheme, in which an XUV attosecond pulse train is used in association with a weak IR probe, obtaining results in quantitative agreement with those from accurate ab initio simulations. In particular, we show that (i) the use of finite pulses results in a homogeneous redshift of the RABITT beating frequency, as well as a resonant modulation of the beating frequency in proximity to intermediate autoionizing states; (ii) the phase of resonant two-photon amplitudes generally experiences a continuous excursion as a function of the intermediate detuning, with either zero or 2 π overall variation.

  16. 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.

  17. Resonance enhanced multiphoton ionization photoelectron spectroscopy and pulsed field ionization via the F 1D2(v'=0) and f 3D2(v'=0) Rydberg states of HCl

    OpenAIRE

    Buma, W.J.; Beer, de, VHJ Vincent; Lange

    1993-01-01

    In this paper, we report the first rotationally resolved one- and two-color resonance enhanced multiphoton ionization photoelectron spectroscopy (REMPI-PES) study of the HCl molecule. The agreement between our experimental branching ratios and theoretical investigations is excellent. We also report the first zero kinetic energy pulsed field ionization (ZEKE-PFI) experiments carried out in a "magnetic bottle'' electron spectrometer. A direct comparison is made between ZEKE-PFI and REMPI-PES sp...

  18. X-ray photoelectron spectroscopy and luminescent properties of Y{sub 2}O{sub 3}:Bi{sup 3+} phosphor

    Energy Technology Data Exchange (ETDEWEB)

    Jafer, R.M. [Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein, ZA 9300 South Africa (South Africa); Department of Physics, Faculty of Education, University of Khartoum, P.O. Box 321, Postal Code 11115 Omdurman (Sudan); Coetsee, E., E-mail: CoetseeE@ufs.ac.za [Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein, ZA 9300 South Africa (South Africa); Yousif, A. [Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein, ZA 9300 South Africa (South Africa); Department of Physics, Faculty of Education, University of Khartoum, P.O. Box 321, Postal Code 11115 Omdurman (Sudan); Kroon, R.E.; Ntwaeaborwa, O.M.; Swart, H.C. [Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein, ZA 9300 South Africa (South Africa)

    2015-03-30

    Highlights: • XPS results for high Bi concentration indicated the Bi 4f peaks inside the Y 3d energy range. • XPS also indicated the C{sub 2} and S{sub 6} sites in both Y{sub 2}O{sub 3} and Bi{sub 2}O{sub 3} that results in blue and green luminescence centers. • The false-color CL overlay results also proved the emission of the Bi{sup 3+} ion in the two different sites. - Abstract: X-ray photoelectron spectroscopy (XPS) results provided proof for the blue and green emission of Bi{sup 3+} in the Y{sub 2}O{sub 3}:Bi{sup 3+} phosphor. The Y{sub 2}O{sub 3}:Bi{sup 3+} phosphor was successfully prepared by the combustion process during the investigation of down-conversion materials for Si solar cell application. The X-ray diffraction (XRD) patterns indicated that a single-phase cubic crystal structure with the Ia3 space group was formed. X-ray photoelectron spectroscopy (XPS) showed that the Bi{sup 3+} ion replaces the Y{sup 3+} ion in two different coordination sites in the Y{sub 2}O{sub 3} crystal structure. The O 1s peak shows five peaks, two which correlate with the O{sup 2−} ion in Y{sub 2}O{sub 3} in the two different sites, two which correlate with O{sup 2−} in Bi{sub 2}O{sub 3} in the two different sites and the remaining peak relates to hydroxide. The Y 3d spectrum shows two peaks for the Y{sup 3+} ion in the Y{sub 2}O{sub 3} structure in two different sites and the Bi 4f spectrum shows the Bi{sup 3+} ion in the two different sites in Bi{sub 2}O{sub 3}. The photoluminescence (PL) results showed three broad emission bands in the blue and green regions under ultraviolet excitation, which were also present for panchromatic cathodoluminescence (CL) results. These three peaks have maxima at ∼3.4, 3.0 and 2.5 eV. The PL emission ∼3.0 eV (blue emission) showed two excitation bands centered at ∼3.7 and 3.4 eV while the PL emission at ∼2.5 eV (green emission) showed a broad excitation band from ∼4 to 3.4 eV. The panchromatic CL images were obtained

  19. Attosecond nanoscale near-field sampling

    Science.gov (United States)

    Förg, B.; Schötz, J.; Süßmann, F.; Förster, M.; Krüger, M.; Ahn, B.; Okell, W. A.; Wintersperger, K.; Zherebtsov, S.; Guggenmos, A.; Pervak, V.; Kessel, A.; Trushin, S. A.; Azzeer, A. M.; Stockman, M. I.; Kim, D.; Krausz, F.; Hommelhoff, P.; Kling, M. F.

    2016-01-01

    The promise of ultrafast light-field-driven electronic nanocircuits has stimulated the development of the new research field of attosecond nanophysics. An essential prerequisite for advancing this new area is the ability to characterize optical near fields from light interaction with nanostructures, with sub-cycle resolution. Here we experimentally demonstrate attosecond near-field retrieval for a tapered gold nanowire. By comparison of the results to those obtained from noble gas experiments and trajectory simulations, the spectral response of the nanotaper near field arising from laser excitation can be extracted. PMID:27241851

  20. Depth profiling of the elemental surface composition of the oral microorganism S. salivarius HB and fibrillar mutants by X-ray photoelectron spectroscopy.

    Science.gov (United States)

    van der Mei, H C; Handley, P S; Busscher, H J

    1992-02-01

    X-ray photoelectron spectroscopy (XPS) on microbial cell surfaces requires freeze-drying of cells, and as a result, the cell surface appendages flatten out on the cell surface and form a collapsed fibrillar mass. At present, it is unclear how the density, length and composition of these fibrils influence the elemental surface composition as probed by XPS. The sampling depth of XPS can be varied by changing the electron take-off angle. In this article, we made a depth profiling of the collapsed fibrillar mass of Streptococcus salivarius HB and fibril-deficient mutants by angle-dependent XPS. Methylamine tungstate negative staining and ruthenium red staining followed by sectioning revealed distinct classes of fibrils with various lengths on each of the strains. Interpretation of the angle dependence of the oxygen/carbon (O/C) and phosphorus/carbon (P/C) surface concentration ratios of these strains was difficult. However, the angle dependence of the nitrogen/carbon (N/C) surface concentration ratio could be fully interpreted: N/C did not vary with sampling depth on a bald strain, S. salivarius HBC12 and on S. salivarius HB7, a strain with a dense array of fibrils of uniform length. N/C decreased with sampling depth in case of a sparsely fibrillated strain, S. salivarius HBV51 and eventually reached the value observed for the bald strain, HBC12. A high N/C at small sampling depth was observed for S. salivarius HB with protruding, protein rich fibrils. We conclude that elemental depth profiling of microbial cell surfaces by XPS can be interpreted to coincide with structural and biochemical information on the cell surface as obtained by electron microscopy and can therefore be considered as a useful technique to study structural features of cell surfaces in combination with electron microscopy. PMID:1284785