WorldWideScience

Sample records for excited state dissociation

  1. Excited-State N2 Dissociation Pathway on Fe-Functionalized Au.

    Science.gov (United States)

    Martirez, John Mark P; Carter, Emily A

    2017-03-29

    Localized surface plasmon resonances (LSPRs) offer the possibility of light-activated chemical catalysis on surfaces of strongly plasmonic metal nanoparticles. This technology relies on lower-barrier bond formation and/or dissociation routes made available through energy transfer following the eventual decay of LSPRs. The coupling between these decay processes and a chemical trajectory (nuclear motion, charge-transfer, intersystem crossing, etc.) dictates the availability of these alternative (possibly lower barrier) excited-state channels. The Haber-Bosch method of NH 3 synthesis from N 2 and H 2 is notoriously energy intensive. This is due to the difficulty of N 2 dissociation despite the overall reaction being thermodynamically favorable at ambient temperatures and pressures. LSPRs may provide means to improve the kinetics of N 2 dissociation via induced resonance electronic excitation. In this work, we calculate, via embedded n-electron valence second-order perturbation theory within the density functional embedding theory, the excited-state potential energy surfaces for dissociation of N 2 on an Fe-doped Au(111) surface. This metal alloy may take advantage simultaneously of the strong LSPR of Au and the catalytic activity of Fe toward N 2 dissociation. We find the ground-state dissociation activation energy to be 4.74 eV/N 2 , with Fe as the active site on the surface. Consecutive resonance energy transfers (RETs) may be accessed due to the availability of many electronically excited states with intermediate energies arising from the metal surface that may couple to states induced by the Fe-dopant and the adsorbate molecule, and crossing between excited states may effectively lower the dissociation barrier to 1.33 eV. Our work illustrates that large energetic barriers, prohibitive toward chemical reaction, may be overcome through multiple RETs facilitating an otherwise difficult chemical process.

  2. Site selective dissociation of ozone upon core excitation

    International Nuclear Information System (INIS)

    Mocellin, A.; Mundim, M.S.P.; Coutinho, L.H.; Homem, M.G.P.; Naves de Brito, A.

    2007-01-01

    We present new measurements applied to core excitation of ozone molecule using to analyze the dissociation channels the photo-electron-photo-ion coincidence (PEPICO) and the photo-electron-photo-ion-photo-ion coincidence (PEPIPICO) technique. The new experimental set-up allows measuring O + /O + ion pair coincidences without discrimination. The dissociation channels of several core-excited states have been investigated. The relative yields of dissociation channels were determined from coincidence data. The core excitation from O terminal (O T ) or O central (O C ) induce different fragmentation; preferentially one bond is broken at the O terminal excitation and two bonds when O central is excited, showing site selectivity fragmentation of ozone upon core excitation. The ultra-fast dissociation of the O T 1s -1 7a 1 1 core-excited state is confirmed by the relative yield of dissociation

  3. Site selective dissociation of ozone upon core excitation

    Energy Technology Data Exchange (ETDEWEB)

    Mocellin, A. [Instituto de Fisica, Universidade de Brasilia-UnB, Box 04455, CEP 70919-970, Brasilia-DF (Brazil)], E-mail: mocellin@fis.unb.br; Mundim, M.S.P. [Instituto de Fisica, Universidade de Brasilia-UnB, Box 04455, CEP 70919-970, Brasilia-DF (Brazil); Coutinho, L.H. [Instituto de Quimica, Universidade Federal do Rio de Janeiro-UFRJ, Box 68563, CEP 21945-970, Rio de Janeiro-RJ (Brazil); Homem, M.G.P. [Laboratorio Nacional de Luz Sincrotron-LNLS, Box 6192, CEP 13084-971, Campinas-SP (Brazil); Naves de Brito, A. [Laboratorio Nacional de Luz Sincrotron-LNLS, Box 6192, CEP 13084-971, Campinas-SP (Brazil); Instituto de Fisica, Universidade de Brasilia-UnB, Box 04455, CEP 70919-970, Brasilia-DF (Brazil)

    2007-05-15

    We present new measurements applied to core excitation of ozone molecule using to analyze the dissociation channels the photo-electron-photo-ion coincidence (PEPICO) and the photo-electron-photo-ion-photo-ion coincidence (PEPIPICO) technique. The new experimental set-up allows measuring O{sup +}/O{sup +} ion pair coincidences without discrimination. The dissociation channels of several core-excited states have been investigated. The relative yields of dissociation channels were determined from coincidence data. The core excitation from O terminal (O{sub T}) or O central (O{sub C}) induce different fragmentation; preferentially one bond is broken at the O terminal excitation and two bonds when O central is excited, showing site selectivity fragmentation of ozone upon core excitation. The ultra-fast dissociation of the O{sub T} 1s{sup -1}7a{sub 1}{sup 1} core-excited state is confirmed by the relative yield of dissociation.

  4. A storage ring study of dissociative excitation and recombination of D3+

    International Nuclear Information System (INIS)

    Le Padellec, A.; Larson, Aa.; Semaniak, J.; Stroemholm, C.; Larsson, M.; Rosen, S.; Danared, H.; Peterson, J.R.

    1998-01-01

    Dissociative recombination and excitation of D 3 + have been studied in CRYRING, a heavy-ion storage ring at the Manne Siegbahn laboratory at Stockholm University. The measured cross section for dissociative recombination was used to deduce a 300 K rate constant of 2.7 x 10 -8 cm 3 s -1 . This is a factor of four smaller than the corresponding value for H 3 + measured earlier in CRYRING. Dissociative excitation into both the D and 2D channels (D + D or D 2 ) were studied. The 2D channel occurs at energies below threshold for the ion's dissociative states, which indicates that resonant enhanced dissociative excitation via autoionizing resonances takes place. No measurable effect could be observed for the dissociative recombination cross sections when an electric field of 30 V/cm was applied to the electron-ion interaction region. (orig.)

  5. Distinct site- and state-selective dissociation of methyl-trifluoroacetate observed in core-electron excitation at the oxygen K-edge region

    Science.gov (United States)

    Yamanaka, T.; Tabayashi, K.; Maruyama, T.; Harada, C.; Yoshida, H.

    2009-11-01

    Distinct site- and state-selective dissociation following the O1s core-excitation has been found in the gaseous molecules of methyl trifluoroacetate (MTFA). The site- and state-selective dissociation was examined by measuring the branching ratios of dominant CH3+ and CHO+ fragments. The branching ratios from MTFA showed that site-selective dissociation takes place via the excitation from the different atomic sites to the same π*CO resonance state, (O1sCO-1π*CO) and (O1sOMe-1π*CO). A pronounced O1sOMe site-selectivity was identified by a significant increment of CHO+ formation at the (O1sOMe→π*CO) band. The site-selectivity was also justified by an equivalent core approximation using the density functional theory calculation. State-selective dissociation was identified among the (O1sOMe-1π*CO), (O1sOMe-1σ*O-Me) and (O1sOMe-1σ*C-OMe) transitions originated from the same OMe core. State-selective production of CH3+ could be found at the (O1sOMe→σ*O-Me) band, whereas state-selective formation of CHO+ was observed at the (O1sOMe→π*CO) and (O1sOMe→σ*C-OMe) bands.

  6. Dissociative Excitation of Acetylene Induced by Electron Impact: Excitation-emission Cross-sections

    Energy Technology Data Exchange (ETDEWEB)

    Országh, Juraj; Danko, Marián; Čechvala, Peter; Matejčík, Štefan, E-mail: matejcik@fmph.uniba.sk [Department of Experimental Physics, Faculty of Mathematics, Physics and Informatics, Comenius University in Bratislava, Mlynská dolina F-2, 842 48 Bratislava (Slovakia)

    2017-05-20

    The optical emission spectrum of acetylene excited by monoenergetic electrons was studied in the range of 190–660 nm. The dissociative excitation and dissociative ionization associated with excitation of the ions initiated by electron impact were dominant processes contributing to the spectrum. The spectrum was dominated by the atomic lines (hydrogen Balmer series, carbon) and molecular bands (CH(A–X), CH(B–X), CH{sup +}(B–A), and C{sub 2}). Besides the discrete transitions, we have detected the continuum emission radiation of ethynyl radical C{sub 2}H(A–X). For most important lines and bands of the spectrum we have measured absolute excitation-emission cross sections and determined the energy thresholds of the particular dissociative channels.

  7. Emission spectroscopic studies on dynamics of molecular excitation and dissociation by controlled electron impact

    International Nuclear Information System (INIS)

    Ogawa, Teiichiro

    1986-01-01

    Emission spectrum by controlled electron impact has been a successful technique for the investigation of molecular dynamics. (1) Molecular excitation. Aromatic molecules give an optical emission similar to fluorescence. However, as is shown by the vibrational structure and the electron energy dependence of benzene emission, its excitation process is not necessarily optical. Some aliphatic molecules also exhibit an emission band at the ultraviolet region. (2) Molecular dissociation. Analysis of the Doppler profile, the threshold energy, the excitation function and the isotope effect of the atomic emission produced in electron-molecule collisions has clarified the dynamics of the molecular dissociation. Especially the Doppler profile has given the translational energy distribution of the fragment atom, which is very useful to disclose the potential energy curve. Its angular dependence has recently found to allow determination of the symmetry of the intermediate excited state and the magnetic sublevel distribution of the fragment atom. These finding has revealed detailed state-to-state dynamics of the molecular dissociation. (author)

  8. The role of dissociation channels of excited electronic states in quantum optimal control of ozone isomerization: A three-state dynamical model

    Energy Technology Data Exchange (ETDEWEB)

    Kurosaki, Yuzuru, E-mail: kurosaki.yuzuru@jaea.go.jp [Quantum Beam Science Directorate, Tokai Research and Development Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Ho, Tak-San, E-mail: tsho@Princeton.EDU [Department of Chemistry, Princeton University, Princeton, NJ 08544 (United States); Rabitz, Herschel, E-mail: hrabitz@Princeton.EDU [Department of Chemistry, Princeton University, Princeton, NJ 08544 (United States)

    2016-05-01

    The prospect of performing the open → cyclic ozone isomerization has attracted much research attention. Here we explore this consideration theoretically by performing quantum optimal control calculations to demonstrate the important role that excited-state dissociation channels could play in the isomerization transformation. In the calculations we use a three-state, one-dimensional dynamical model constructed from the lowest five {sup 1}A′ potential energy curves obtained with high-level ab initio calculations. Besides the laser field-dipole couplings between all three states, this model also includes the diabatic coupling between the two excited states at an avoided crossing leading to competing dissociation channels that can further hinder the isomerization process. The present three-state optimal control simulations examine two possible control pathways previously considered in a two-state model, and reveal that only one of the pathways is viable, achieving a robust ∼95% yield to the cyclic target in the three-state model. This work represents a step towards an ultimate model for the open → cyclic ozone transformation capable of giving adequate guidance about the necessary experimental control field resources as well as an estimate of the ro-vibronic spectral character of cyclic ozone as a basis for an appropriate probe of its formation.

  9. Dissociative electron attachment to vibrationally excited H2 molecules involving the 2Σg+ resonant Rydberg electronic state

    International Nuclear Information System (INIS)

    Celiberto, R.; Janev, R.K.; Wadehra, J.M.; Tennyson, J.

    2012-01-01

    Graphical abstract: Dissociative electron attachment cross sections as a function of the incident electron energy and for the initial vibration levels v i = 0–5, 10 of the H 2 molecule. Highlights: ► We calculated electron–hydrogen dissociative attachment cross sections and rates coefficients. ► Collision processes occurring through a resonant Rydberg state are considered. ► Cross sections and rates were obtained for vibrationally excited hydrogen molecules. ► The cross sections exhibit pronounced oscillatory structures. ► A comparison with the process involving the electron–hydrogen resonant ground state is discussed. - Abstract: Dissociative electron attachment cross sections (DEA) on vibrationally excited H 2 molecule taking place via the 2 Σ g + Rydberg-excited resonant state are studied using the local complex potential (LCP) model for resonant collisions. The cross sections are calculated for all initial vibrational levels (v i = 0–14) of the neutral molecule. In contrast to the previously noted dramatic increase in the DEA cross sections with increasing v i , when the process proceeds via the X 2 Σ u + shape resonance of H 2 , for the 2 Σ g + Rydberg resonance the cross sections increase only gradually up to v i = 3 and then decrease. Moreover, the cross sections for v i ⩾ 6 exhibit pronounced oscillatory structures. A discussion of the origin of the observed behavior of calculated cross sections is given. The DEA rate coefficients for all v i levels are also calculated in the 0.5–1000 eV temperature range.

  10. Dissociation dynamics of anionic and excited neutral fragments of gaseous SiCl4 following Cl 2p and Si 2p core-level excitations

    International Nuclear Information System (INIS)

    Chen, J M; Lu, K T; Lee, J M; Chou, T L; Chen, H C; Chen, S A; Haw, S C; Chen, T H

    2008-01-01

    The state-selective dissociation dynamics for anionic and excited neutral fragments of gaseous SiCl 4 following Cl 2p and Si 2p core-level excitations were characterized by combining measurements of the photon-induced anionic dissociation, x-ray absorption and UV/visible dispersed fluorescence. The transitions of core electrons to high Rydberg states/doubly excited states in the vicinity of both Si 2p and Cl 2p ionization thresholds of gaseous SiCl 4 lead to a remarkably enhanced production of anionic, Si - and Cl - , fragments and excited neutral atomic, Si*, fragments. This enhancement via core-level excitation near the ionization threshold of gaseous SiCl 4 is explained in terms of the contributions from the Auger decay of doubly excited states, shake-modified resonant Auger decay, or/and post-collision interaction. These complementary results provide insight into the state-selective anionic and excited neutral fragmentation of gaseous molecules via core-level excitation.

  11. Transient photoelectron spectroscopy of the dissociative Br2(1Piu) state.

    Science.gov (United States)

    Strasser, Daniel; Goulay, Fabien; Leone, Stephen R

    2007-11-14

    Photodissociation of bromine on the Br2(1Piu) state is probed with ultrafast extreme ultraviolet (53.7 nm) single-photon ionization. Time-resolved photoelectron spectra show simultaneously the depletion of ground state bromine molecules as well as the rise of Br(2P3/2) products due to 402.5 nm photolysis. A partial photoionization cross-section ratio of atomic versus molecular bromine is obtained. Transient photoelectron spectra of a dissociative wave packet on the excited state are presented in the limit of low-power-density, single-photon excitation to the dissociative state. Transient binding energy shifts of "atomic-like" photoelectron peaks are observed and interpreted as photoionization of nearly separated Br atom pairs on the Br2(1Piu) state to repulsive dissociative ionization states.

  12. Theoretical resonant electron-impact vibrational excitation, dissociative recombination and dissociative excitation cross sections of ro-vibrationally excited BeH"+ ion

    International Nuclear Information System (INIS)

    Laporta, V.; Chakrabarti, K.; Celiberto, R.; Janev, R. K.; Mezei, J. Zs.; Niyonzima, S.; Tennyson, J.; Schneider, I.F.

    2017-01-01

    A theoretical study of resonant vibrational excitation, dissociative recombination and dissociative excitation processes of the beryllium monohydride cation, BeH"+ , induced by electron impact, is reported. Full sets of ro-vibrationally-resolved cross sections and of the corresponding Maxwellian rate coefficients are presented for the three processes. Particular emphasis is given to the high-energy behaviour. Potential curves of "2σ"+, "2σ and "2δ symmetries and the corresponding resonance widths, obtained from R-matrix calculations, provide the input for calculations which use a local complex-potential model for resonant collisions in each of the three symmetries. Rotational motion of nuclei and isotopic effects are also discussed. The relevant results are compared with those obtained using a multichannel quantum defect theory method. Full results are available from the Phys4Entry database.

  13. Dissociative Excitation of Thymine by Electron Impact

    Science.gov (United States)

    McConkey, William; Tiessen, Collin; Hein, Jeffrey; Trocchi, Joshuah; Kedzierski, Wladek

    2014-05-01

    A crossed electron-gas beam system coupled to a VUV spectrometer has been used to investigate the dissociation of thymine (C5H6N2O2) into excited atomic fragments in the electron-impact energy range from threshold to 375 eV. A special stainless steel oven is used to vaporize the thymine and form it into a beam where it is intersected by a magnetically collimated electron beam, typical current 50 μA. The main features in the spectrum are the H Lyman series lines. The probability of extracting excited C or N atoms from the ring is shown to be very small. In addition to spectral data, excitation probability curves as a function of electron energy will be presented for the main emission features. Possible dissociation channels and excitation mechanisms in the parent molecule will be discussed. The authors thank NSERC (Canada) for financial support.

  14. Excited neutral atomic fragments in the strong-field dissociation of N2 molecules

    International Nuclear Information System (INIS)

    Nubbemeyer, T; Eichmann, U; Sandner, W

    2009-01-01

    Excited neutral N* fragments with energies between 3 eV and 15 eV have been observed from the dissociation of N 2 molecules in strong laser fields. The kinetic energy spectrum of the excited neutral atoms corresponds to Coulomb explosion processes involving N + ions. This supports the assumption that the production of excited neutral fragments stems from a process in which one of the participating ions in the Coulomb explosion captures an electron into a Rydberg state.

  15. Electronically excited negative ion resonant states in chloroethylenes

    Energy Technology Data Exchange (ETDEWEB)

    Khvostenko, O.G., E-mail: khv@mail.ru; Lukin, V.G.; Tuimedov, G.M.; Khatymova, L.Z.; Kinzyabulatov, R.R.; Tseplin, E.E.

    2015-02-15

    Highlights: • Several novel dissociative negative ion channels were revealed in chloroethylenes. • The electronically excited resonant states were recorded in all chloroethylenes under study. • The states were assigned to the inter-shell types, but not to the core-excited Feshbach one. - Abstract: The negative ion mass spectra of the resonant electron capture by molecules of 1,1-dichloroethylene, 1,2-dichloroethylene-cis, 1,2-dichloroethylene-trans, trichloroethylene and tetrachloroethylene have been recorded in the 0–12 eV range of the captured electron energy using static magnetic sector mass spectrometer modified for operation in the resonant electron capture regime. As a result, several novel low-intensive dissociation channels were revealed in the compounds under study. Additionally, the negative ion resonant states were recorded at approximately 3–12 eV, mostly for the first time. These resonant states were assigned to the electronically excited resonances of the inter-shell type by comparing their energies with those of the parent neutral molecules triplet and singlet electronically excited states known from the energy-loss spectra obtained by previous studies.

  16. VUV Study of Electron-Pyrimidine Dissociative Excitation

    Science.gov (United States)

    Hein, Jeff; Al-Khazraji, Hajar; Tiessen, Collin; Lukic, Dragan; Trocchi, Joshuah; McConkey, William

    2013-05-01

    A crossed electron-gas beam system coupled to a VUV spectrometer has been used to investigate the dissociation of pyrimidine (C4H4N2) into excited atomic fragments in the electron-impact energy range from threshold to 375 eV. Data have been made absolute using Lyman- α from H2 as a secondary standard. The main features in the spectrum are the H Lyman series lines. The emission cross section of Lyman- α is measured to be (2.44 +/- 0.25) 10-18 cm2 at 100 eV impact energy. The probability of extracting C or N atoms from the ring is shown to be very small. Possible dissociation channels and excitation mechanisms in the parent molecule will be discussed. The authors thank NSERC (Canada) for financial support.

  17. Dissociative excitation of lithium atom in electron collisions with LiBr molecules

    International Nuclear Information System (INIS)

    Smirnov, Yu.M.

    1998-01-01

    Effective cross sections of the lithium atom dissociative excitation in electron collisions with the LiBr molecules are measured. The measurement error equals 5-12%. The optical functions of the lithium atom dissociative excitation are calculated on the basis of the data obtained

  18. Rate coefficients for dissociative attachment and resonant electron-impact dissociation involving vibrationally excited O{sub 2} molecules

    Energy Technology Data Exchange (ETDEWEB)

    Laporta, V. [Istituto di Metodologie Inorganiche e dei Plasmi, CNR, Bari, Italy and Department of Physics and Astronomy, University College London, London WC1E 6BT (United Kingdom); Celiberto, R. [Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica, Politecnico di Bari, Italy and Istituto di Metodologie Inorganiche e dei Plasmi, CNR, Bari (Italy); Tennyson, J. [Department of Physics and Astronomy, University College London, London WC1E 6BT (United Kingdom)

    2014-12-09

    Rate coefficients for dissociative electron attachment and electron-impact dissociation processes, involving vibrationally excited molecular oxygen, are presented. Analytical fits of the calculated numerical data, useful in the applications, are also provided.

  19. Dissociation pathways of a single dimethyl disulfide on Cu(111): Reaction induced by simultaneous excitation of two vibrational modes

    Energy Technology Data Exchange (ETDEWEB)

    Motobayashi, Kenta, E-mail: kmotobayashi@cat.hokudai.ac.jp [Catalysis Research Center, Hokkaido University, Sapporo 001-0021 (Japan); Department of Advanced Materials Science, The University of Tokyo, Kashiwa 277-8561 (Japan); Surface and Interface Science Laboratory, RIKEN, Wako 351-0198 (Japan); Kim, Yousoo [Surface and Interface Science Laboratory, RIKEN, Wako 351-0198 (Japan); Arafune, Ryuichi [International Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba 305-0044 (Japan); Ohara, Michiaki; Ueba, Hiromu; Kawai, Maki, E-mail: maki@k.u-tokyo.ac.jp [Department of Advanced Materials Science, The University of Tokyo, Kashiwa 277-8561 (Japan)

    2014-05-21

    We present a novel reaction mechanism for a single adsorbed molecule that proceeds via simultaneous excitation of two different vibrational modes excited by inelastic tunneling electrons from a scanning tunneling microscope. Specifically, we analyze the dissociation of a single dimethyl disulfide (DMDS, (CH{sub 3}S){sub 2}) molecule on Cu(111) by using a versatile theoretical method, which permits us to simulate reaction rates as a function of sample bias voltage. The reaction is induced by the excitation of C-H stretch and S-S stretch modes by a two-electron process at low positive bias voltages. However, at increased voltages, the dissociation becomes a single-electron process that excites a combination mode of these stretches, where excitation of the C-H stretch is the energy source and excitation of the S-S stretch mode enhances the anharmonic coupling rate. A much smaller dissociation yield (few orders of magnitude) at negative bias voltages is understood in terms of the projected density of states of a single DMDS on Cu(111), which reflects resonant excitation through the molecular orbitals.

  20. Dissociation of deep-core-excited CH{sub 3}Cl

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, D.L.; Martin, R.; Vanderford, B. [Univ. of Nevada, Las Vegas, NV (United States)] [and others

    1997-04-01

    Using x-rays from B.L. 9.3.1, a space-focused time-of-flight (TOF) was used to study photofragmentation of CH{sub 3}Cl following excitation in the neighborhood of the Cl K-shell threshold ({approximately} 2.8 keV). Multi-ion coincidence measurements were used to search for selective dissociation of specific bonds in the molecule. Such selectivity has been observed for excitation near outer-core-level thresholds (e.g., Cl 2p), but this is the first study in deep core levels, where very-short core-hole lifetimes and Auger cascade effects may influence fragmentation. Both high-resolution time-of-flight spectroscopy and multi-coincidence photoelectron-photoion-photoion (PE-PIPICO), as well as photoelectron-photoion-photoion-photoion (PE3PICO) measurements were performed. Dramatic changes in the line shapes for different fragment ions are observed as a function of the excitation energy, and are attributed to selective dissociation of the CH{sub 3}Cl molecule along the C-Cl bond. In addition, pronounced angular distributions of the ejected ions are observed on resonance.

  1. Dissociative Excitation of Adenine by Electron Impact

    Science.gov (United States)

    McConkey, J. William; Trocchi, Joshuah; Dech, Jeffery; Kedzierski, Wladek

    2017-04-01

    Dissociative excitation of adenine (C6H5NH2) into excited atomic fragments has been studied in the electron impact energy range from threshold to 300 eV. A crossed beam system coupled to a vacuum ultraviolet (VUV) monochromator is used to study emissions in the wavelength range from 110 to 200 nm. The beam of adenine vapor from a stainless steel oven is crossed at right angles by the electron beam and the resultant UV radiation is detected in a mutually orthogonal direction. The strongest feature in the spectrum is H Lyman- α. Financial support from NSERC and CFI, Canada, is gratefully acknowledged.

  2. Data on ionization, excitation, dissociation and dissociative ionization of targets by helium ion bombardments, (1)

    International Nuclear Information System (INIS)

    Oda, Nobuo; Urakawa, Junji

    1984-03-01

    This report presents a compilation of the experimental data on cross sections for the ionization, excitation, dissociation and dissociative ionization processes of targets in helium ion impacts on atoms and molecules under a single collision condition. These measurements were carried out in the energy range from several keV to 3.5 MeV. A systematic survey has been made on the literatures from 1975 to the end of 1982. A list of references is also given, including relevant papers published before 1975. (author)

  3. Antibonding intermediate state in the theory of vibrational excitation of diatomic molecules by slow electrons

    International Nuclear Information System (INIS)

    Kazanskii, A.K.

    1982-01-01

    An exactly solvable model is constructed for the description of the processes that take place when a slow electron collides with a diatomic molecule (vibrational excitation, associative detachment, and dissociative attachment). As a particular model of the variant, the case of an antibonding (virtual) state of an intermediate state is considered, and a term of this state is parametrized in a very simple manner. The vibrational excitation and dissociative attachment are calculated for a system corresponding to the HCl molecule. The results are in good qualitative agreement with experiment

  4. Isotope separation by photoselective dissociative electron

    International Nuclear Information System (INIS)

    Stevens, C.G.

    1978-01-01

    A method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule is described. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, 235 UF 6 is separated from a UF 6 mixture by selective excitation followed by dissociative electron capture into 235 UF 5 - and F

  5. Ab initio calculations of dissociative excitation of water and methane molecules upon electron impact at low energies

    International Nuclear Information System (INIS)

    Gil, T.J.; McCurdy, C.W.; Rescigno, T.N.; Lengsfield, B.H. III

    1994-01-01

    The authors are reporting results of ab-initio calculations of electron-impact excitation of water and methane occurring at scattering energies up to 60 eV. The authors consider dissociative excited states of both systems since the understanding of their chemistry has considerable importance in plasma technology and atmospheric research. In the case of methane the authors are dealing with the promotion of a valence electron into Rydberg orbitals, while in water the excited states have one electron in an antibonding unoccupied valence orbital and support Feshbach resonances. The authors discuss issues related to convergence of the close-coupling expansion in the case of Rydberg excitation, where the authors have coupled up to 16 channels. The practical realization of the calculation within the framework of the complex Kohn variational principle represents merging of quantum chemistry and quantum scattering theory and is also discussed

  6. Laser ionization and dissociation of hydrogen

    International Nuclear Information System (INIS)

    Buck, J.D.

    1987-01-01

    Experiments undertaken to further characterize the spectroscopic and photophysical properties of some important excited singlet states of molecular hydrogen and its deuterium isotopes are described. Attention was centered on high vibrational levels of the B, C, and B' states within about 1000 cm -1 of the second dissociation limit. A double-resonance excitation scheme was needed to access levels with a large average bond distance from the ground state. Two-photon absorption of tunable uv-laser radiation-pumped ground-state hydrogen molecules into selected rovibronic levels of the metastable EF double-minimum electronic state. A second tunable near-IR probe laser was scanned to generate ions by resonant multiphoton ionization, where the resonant levels were provided by B, C, B', and other levels near the dissociation limit. New information was obtained regarding line shapes and intensities. Time-of-flight ion mass selection permitted observation of additional excitation channels with dissociation superimposed on the ionization process to produce protons

  7. Study of inner shell excitation effect on C-H dissociation in aromatic hydrocarbon solids

    International Nuclear Information System (INIS)

    Shimoyama, I.; Nakagawa, K.; Matsui, F.; Yoem, H.W.; Ohta, T.; Tanaka, S.; Mase, K.

    2000-01-01

    Since Carson et al. have reported the 'Coulomb Explosion' model, an inner shell excitation effect on dissociation is intensively attractive because multiply ionized states induced by Auger decay enhance dissociation. This effect on chemical reaction has been investigated especially for surface reaction processes such as desorption induced electron transition (DIET). Recently, some studies on DIET using monochromatic soft X-rays have reported that desorption yield depends on not only the repulsion energy but also the character of excited molecular orbital (MO). This means that inner shell resonant excitations to different MO result in different desorption. This Inner Shell Resonant Excitation Effect' is very interesting because it enables us to control photochemical reactions with synchrotron radiation. Two important problems lie ahead of us for application of this effect. One problem is secondary effect. When one irradiates soft X-rays to materials, following reaction includes two kinds of mixed effects; fundamental effect (FE) and secondary effect (SE). FE originates from interactions between photons and materials, while SE originates from interactions between secondary electrons and materials. Since the inner shell resonant excitation effect essentially originates from FE, it is important to know the ratio of FE to SE in a photochemical reaction in order to estimate true magnitude of the inner shell resonant excitation effect. The other problem is the difference between surface reaction and bulk reaction. Weather the bulk reaction shows inner shell excitation effect as well as the surface reaction does? Some studies of the inner shell excitation effect on damage in bulk have been reported. To our knowledge, however, there is no study which reports the difference between bulk and surface reaction. In this paper, we present two kinds of works with aromatic hydrocarbon compounds. First, we present photon stimulated ion desorption (PSID) on condensed benzene to study

  8. Atomic excitation and molecular dissociation by low energy electron collisions

    International Nuclear Information System (INIS)

    Weyland, Marvin

    2016-01-01

    In this work, momentum imaging experiments have been conducted for the electron impact excitation of metastable states in noble gases and for dissociative electron attachment (DEA) in polyatomic molecules. For the electron impact excitation study a new experimental technique has been developed which is able to measure the scattering angle distribution of the electrons by detection of the momentum transfer to the atoms. Momentum transfer images have been recorded for helium and neon at fixed electron impact energy close to the excitation threshold and good agreement with current R-matrix theory calculations was found. A new momentum imaging apparatus for negative ions has been built for the purpose of studying DEA in biologically relevant molecules. During this work, DEA was investigated in the molecules ammonia, water, formic acid, furan, pyridine and in two chlorofluorocarbons. Furthermore, the change of DEA resonance energies when molecules form clusters compared to monomers was investigated in ammonia and formic acid. The experimental results of most studied molecules could be compared to recent theoretical calculations and they support further development in the theoretical description of DEA. The new apparatus built in this work also delivered a superior momentum resolution compared to existing setups. This allows the momentum imaging of heavier fragments and fragments with lower kinetic energy.

  9. Atomic excitation and molecular dissociation by low energy electron collisions

    Energy Technology Data Exchange (ETDEWEB)

    Weyland, Marvin

    2016-11-16

    In this work, momentum imaging experiments have been conducted for the electron impact excitation of metastable states in noble gases and for dissociative electron attachment (DEA) in polyatomic molecules. For the electron impact excitation study a new experimental technique has been developed which is able to measure the scattering angle distribution of the electrons by detection of the momentum transfer to the atoms. Momentum transfer images have been recorded for helium and neon at fixed electron impact energy close to the excitation threshold and good agreement with current R-matrix theory calculations was found. A new momentum imaging apparatus for negative ions has been built for the purpose of studying DEA in biologically relevant molecules. During this work, DEA was investigated in the molecules ammonia, water, formic acid, furan, pyridine and in two chlorofluorocarbons. Furthermore, the change of DEA resonance energies when molecules form clusters compared to monomers was investigated in ammonia and formic acid. The experimental results of most studied molecules could be compared to recent theoretical calculations and they support further development in the theoretical description of DEA. The new apparatus built in this work also delivered a superior momentum resolution compared to existing setups. This allows the momentum imaging of heavier fragments and fragments with lower kinetic energy.

  10. Cross-sections for dissociative excitation of lead atom in collisions of slow electrons with PbI2 molecules

    International Nuclear Information System (INIS)

    Smirnov, Yu.M.

    2006-01-01

    The dissociative excitation of the lead atom in e-PbI 2 collisions has been studied experimentally. 27 excitation cross-sections are measured at an exciting-electron energy of 100 eV. Nine optical excitation functions are recorded at the electron energy varying in the 0-100 eV range. The most possible reaction channels at low electron energies along with the relation of the dissociative-excitation cross-sections of the lead atom both in e-PbI 2 and e-PbCl 2 collisions are discussed. (authors)

  11. From state dissociation to status dissociatus.

    Science.gov (United States)

    Antelmi, Elena; Ferri, Raffaele; Iranzo, Alex; Arnulf, Isabelle; Dauvilliers, Yves; Bhatia, Kailash P; Liguori, Rocco; Schenck, Carlos H; Plazzi, Giuseppe

    2016-08-01

    The states of being are conventionally defined by the simultaneous occurrence of behavioral, neurophysiological and autonomic descriptors. State dissociation disorders are due to the intrusion of features typical of a different state into an ongoing state. Disorders related to these conditions are classified according to the ongoing main state and comprise: 1) Dissociation from prevailing wakefulness as seen in hypnagogic or hypnopompic hallucinations, automatic behaviors, sleep drunkenness, cataplexy and sleep paralysis 2) Dissociation from rapid eye movement (REM) sleep as seen in REM sleep behavior disorder and lucid dreaming and 3) Dissociation from NREM sleep as seen in the disorders of arousal. The extreme expression of states dissociation is characterized by the asynchronous occurrence of the various components of the different states that prevents the recognition of any state of being. This condition has been named status dissociatus. According to the underlying disorders/diseases and to their severity, among status dissociatus we may recognize disorders in which such an extreme dissociation occurs only at night time or intermittently (i.e., autoimmune encephalopathies, narcolepsy type 1 and IgLON5 parasomnia), and others in which it occurs nearly continuously with complete loss of any conventionally defined state of being, and of the circadian pattern (agrypnia excitata). Here, we render a comprehensive review of all diseases/disorders associated with state dissociation and status dissociatus and propose a critical classification of this complex scenario. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Dissociative Recombination of HD+ - State-to-State Experimental Investigation Using Fragment Imaging and Storage Ring Techniques

    International Nuclear Information System (INIS)

    Amitay, Z.; Baer, A.; Dahan, M.; Levin, J.; Vager, Z.; Zajfman, D.

    1998-01-01

    When a molecular ion collides with a free electron it can capture the electron and dissociate. The resulting process of Dissociative Recombination (DR) is a process of great significance in a wide variety of plasma environments. In this process, the capture of a free electron leads to the formation of an highly excited state of the neutral molecule, which then dissociates into neutral fragments with kinetic energy and, possibly, internal excitation depending on the energy balance of the reaction. Despite its importance, the DR process is still not yet completely understood theoretically. This is mainly due to the complexity of the nature and dynamics of highly excited molecular states, especially when several channels are involved, as is usually the situation in DR. from experimental point of view, for direct comparison between experiment and theory, this complexity requires detailed experimental data, including the knowledge of both the initial state of the molecular ion, to which DR is very sensitive, and of the final quantum states of the DR products. Inherent un- certainties in the initial vibrational excitation of the laboratory molecular ions was the main drawback of the experiments conducted over the years to, study DR. A substantial progress in the understanding of the DR process was achieved with the introduction (about five years ago) of a new experimental approach, which uses heavy-ion storage ring technique. In a storage ring, one can store many molecular ions for a time which is long enough to allow complete radiative deexcitation of tile initial electronic and vibrational excitation coming from the ion source. Those vibrationally cold ions are then merged with an intense electron beam to measure their DR cross section. Further experimental progress was the inclusion of two and three-dimensional molecular imaging techniques [1] for the measurement of the branching ratio to different final quantum states of the neutral DR fragments. This talk will

  13. Resonantly enhanced production of excited fragments of gaseous molecules following core-level excitation

    International Nuclear Information System (INIS)

    Chen, J.M.; Lu, K.T.; Lee, J.M.; Ho, S.C.; Chang, H.W.; Lee, Y.Y.

    2005-01-01

    State-selective dissociation dynamics for the excited fragments of gaseous Si(CH 3 ) 2 Cl 2 following Cl 2p and Si 2p core-level excitations have been investigated by resonant photoemission spectroscopy and dispersed UV/optical fluorescence spectroscopy. The main features in the gaseous Si(CH 3 ) 2 Cl 2 fluorescence spectrum are identified as the emission from excited Si*, Si + *, CH* and H*. The core-to-Rydberg excitations at both Si 2p and Cl 2p edges lead to a noteworthy production of not only the excited atomic fragments, neutral and ionic (Si*, Si + *) but also the excited diatomic fragments (CH*). In particular, the excited neutral atomic fragments Si* are significantly reinforced. The experimental results provide deeper insight into the state-selective dissociation dynamics for the excited fragments of molecules via core-level excitation

  14. Resonances in dissociative recombination: Trends and patterns

    Energy Technology Data Exchange (ETDEWEB)

    Orel, A E; Ngassam, V; Royal, J [Department of Applied Science, University of California, Davis (United States); Roos, J B; Larson, A, E-mail: aeorel@ucdavis.ed [Department of Theoretical Chemistry, Royal Institute of Technology, Stockholm (Sweden)

    2009-11-15

    In dissociative recombination, the kinetic energy of the incident electron is transferred into excitation of the electrons of the target ion and then into kinetic energy of the fragments. In general, this proceeds via a resonance where the electron is temporarily trapped by the ion, leading to efficient energy transfer. The study of dissociative recombination is the study of these resonances, Rydberg states converging to the ground and excited states of the ion. For a number of systems, we have studied the electronic states involved in dissociative recombination, including the ground and excited states of the ion, the resonant states and the bound Rydberg states of the system, by combining electron scattering calculations with multi-reference configuration interaction quantum chemistry calculations. We will report on trends and patterns in these resonance states. We will discuss studies of dissociative recombination of the rare-gas ions, moving down the periodic table from He{sup +}{sub 2} to Ne{sup +}{sub 2} to Ar{sup +}{sub 2}, where the ground electronic state of the ion is constant, but its polarizability increases. We will also present results on isoelectronic polyatomic systems, such as HCO{sup +} and HCNH{sup +}, as well as the effects of changing the electronic structure slightly such as HCN{sup +}/HNC{sup +} and H{sub 2}CO{sup +}.

  15. Electron-impact dissociation of molecular hydrogen into neutral fragments

    Science.gov (United States)

    Scarlett, Liam H.; Tapley, Jonathan K.; Fursa, Dmitry V.; Zammit, Mark C.; Savage, Jeremy S.; Bray, Igor

    2018-02-01

    We present convergent close-coupling calculations of electron-impact dissociation of the ground state of molecular hydrogen into neutral fragments over the range of impact energies from 6 to 300 eV. The calculations account for dissociative excitation, excitation radiative decay dissociation, and predissociation through all bound electronic triplet states, and singlet states up to the D' 1 Π u state. An estimate is given for the contribution from the remaining bound electronic singlet states. Our results are in agreement with the recommended data of Yoon et al. [J. Phys. Chem. Ref. Data 37, 913 (2008)] in the low (6-12 eV) and high (60-70 eV) energy regions, but somewhat lower at the intermediate energies.

  16. Vibrational excitation and dissociative recombination of the LiH+ ion

    Czech Academy of Sciences Publication Activity Database

    Čurík, Roman; Greene, C. H.

    2007-01-01

    Roč. 105, 11-12 (2007), s. 1565-1574 ISSN 0026-8976 R&D Projects: GA AV ČR IAA100400501; GA AV ČR 1ET400400413 Institutional research plan: CEZ:AV0Z40400503 Keywords : dissociative recombination * vibrational excitation * lithium hydride * quantum defect the ory Subject RIV: CF - Physical ; The oretical Chemistry Impact factor: 1.568, year: 2007

  17. Dissociative Recombination and Excitation of CH+5 : Absolute Cross Sections and Branching Fractions

    International Nuclear Information System (INIS)

    Semaniak, J.; Larson, A.; Le Padellec, A.; Stroemholm, C.; Larsson, M.; Rosen, S.; Peverall, R.; Danared, H.; Djuric, N.; Dunn, G.H.; Datz, S.

    1998-01-01

    The heavy-ion storage ring CRYRING was used to measure the absolute dissociative recombination and dissociative excitation cross sections for collision energies below 50 eV. Deduced thermal rates coefficients are consistent with previous beams data but are lower by a factor of 3 than the rates measured by means of the flowing afterglow Langmuir probe technique. A resonant structure in dissociative recombination cross section was found at 9 eV. We have determined the branching fractions in DR of CH + 5 below 0.2 eV. The branching is dominated by three-body CH 3 + H + H and CH 2 + H 2 + H dissociation channels, which occur with branching ratios of ∼0.7 and ∼0.2, respectively; thus methane is a minor species among dissociation products. Both the measured absolute cross sections and branching in dissociative recombination of CH + 5 can have important implications for the models of dense interstellar clouds and abundance of CH 2 , CH 3 and CH 4 in these media. copyright copyright 1998. The American Astronomical Society

  18. The dissociation of vibrationally excited CH3OSO radicals and their photolytic precursor, methoxysulfinyl chloride.

    Science.gov (United States)

    Alligood, Bridget W; Womack, Caroline C; Straus, Daniel B; Blase, Frances R; Butler, Laurie J

    2011-05-21

    The dissociation dynamics of methoxysulfinyl radicals generated from the photodissociation of CH(3)OS(O)Cl at 248 nm is investigated using both a crossed laser-molecular beam scattering apparatus and a velocity map imaging apparatus. There is evidence of only a single photodissociation channel of the precursor: S-Cl fission to produce Cl atoms and CH(3)OSO radicals. Some of the vibrationally excited CH(3)OSO radicals undergo subsequent dissociation to CH(3) + SO(2). The velocities of the detected CH(3) and SO(2) products show that the dissociation occurs via a transition state having a substantial barrier beyond the endoergicity; appropriately, the distribution of velocities imparted to these momentum-matched products is fit by a broad recoil kinetic energy distribution extending out to 24 kcal/mol in translational energy. Using 200 eV electron bombardment detection, we also detect the CH(3)OSO radicals that have too little internal energy to dissociate. These radicals are observed both at the parent CH(3)OSO(+) ion as well as at the CH(3)(+) and SO(2)(+) daughter ions; they are distinguished by virtue of the velocity imparted in the original photolytic step. The detected velocities of the stable radicals are roughly consistent with the calculated barriers (both at the CCSD(T) and G3B3 levels of theory) for the dissociation of CH(3)OSO to CH(3) + SO(2) when we account for the partitioning of internal energy between rotation and vibration as the CH(3)OSOCl precursor dissociates. © 2011 American Institute of Physics.

  19. Energy redistribution in the dissociation of low Rydberg states of HeH and 02

    International Nuclear Information System (INIS)

    Zande, W.J.A. van der.

    1988-01-01

    In this thesis the dissocation process is studied of the diatomic molecules, heliumhydride and molecular oxygen. In ch.'s 2-4 results on the spectroscopy and dissociative decay of the excited states of heliumhydride (HeH) are explained. The positions and dissociation pathways of the A 2 Σ + and B 2 Π states are determined and a theoretical description of the decay of these states are given. An isotope dependent dissociation behaviour of the C 2 /σ + Rydberg state is reported which explained with this theory. In ch.'s 5-7 observations are presented regarding the first Rydberg states of molecular oxygen. The spectroscopy of the (3sσ)d 1 Π g and C 3 Π g states is treated, and the stability and decay of these Rydberg states is discussed qualitatively. An experimental study is described of the (3sσ)d 1 Π g , v=4-8 states. By isotope studies and resolving rotational lines and the measurements of natural linewidths quantitative estimates have been acquired on coupling strengths, positions of repulsive valence states and perturbations reported in literature from REMPI experiments. The electronic coupling strengths between the C 3 Π g state and the 3 Π g valence state has been established. Observed spin-orbit interactions have been quantified and the dissociation of the multiplet states (C 3 Π g , ω=0-2 has been correlated with the multiplet states of the fragment O 3 P J=0-2 . The spectroscopy of the (3sσ3) Rydberg states which con- verge to and are formed in collisions with the O + 2 , a 4 Π μ ion state, is treated. The (3sσ) 5 /π μ state competition between auto-ionizations and (pre-)dissociation has been observed. 207 refs.; 36 figs.; 18 tabs

  20. A nonlocal, ab initio model of dissociative electron attachment and vibrational excitation of NO

    International Nuclear Information System (INIS)

    Trevisan, Cynthia S.; Houfek, Karel; Zhang, Zhiyong; Orel, Ann E.; McCurdy, C. William; Rescigno, Thomas N.

    2005-01-01

    We present the results of an ab initio study of elastic scattering and vibrational excitation of NO by electron impact in the loW--energy (0-2 eV) region where the cross sections are dominated by resonance contributions. The 3Sigma-, 1Delta and 1Sigma+ NO- resonance lifetimes are taken from our earlier study [Phys. Rev. A 69, 062711 (2004)], but the resonance energies used here are obtained from new configuration-interaction studies. Here we employ a more elaborate nonlocal treatment of the nuclear dynamics, which is found to remedy the principal deficiencies of the local complex potential model we employed in our earlier study, and gives cross sections in better agreement with the most recent experiments. We also present cross sections for dissociative electron attachment to NO leading to groundstate products. The calculations show that, while the peak cross sections starting from NO in its ground vibrational state are very small, the cross sections are extremely sensitive to vibrational excitation of the target and should be readily observable for target NO molecules excited to v = 10 and above

  1. Fluorescence excitation involving multiple electron transition states of N{sub 2} and CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Wu, C.Y.R.; Chen, F.Z.; Hung, T.; Judge, D.L. [Univ. of Southern California, Los Angeles, CA (United States)

    1997-04-01

    The electronic states and electronic structures of N{sub 2} and CO{sub 2} in the 8-50 eV energy region have been studied extensively both experimentally and theoretically. In the energy region higher than 25 eV there exists many electronic states including multiple electron transition (MET) states which are responsible for producing most of the dissociative photoionization products. The electronic states at energies higher than 50 eV have been mainly determined by Auger spectroscopy, double charge transfer, photofragment spectroscopy and ion-ion coincidence spectroscopy. The absorption and ionization spectra of these molecules at energies higher than 50 eV mainly show a monotonic decrease in cross section values and exhibit structureless features. The decay channels of MET and Rydberg (or superexcited) states include autoionization, ionization, dissociative ionization, predissociation, and dissociation while those of single ion and multiple ion states may involve predissociation. and dissociation processes. The study of fluorescence specifically probes electronically excited species resulting from the above-mentioned decay channels and provides information for understanding the competition among these channels.

  2. Experimental investigation of dissociation pathways of cooled HeH+ following valence electron excitation at 32 nm by intense free-electron-laser radiation

    International Nuclear Information System (INIS)

    Pedersen, H. B.; Lammich, L.; Domesle, C.; Jordon-Thaden, B.; Ullrich, J.; Wolf, A.; Heber, O.; Treusch, R.; Guerassimova, N.

    2010-01-01

    The dissociation pathways of HeH + have been investigated below the first ionization continuum by photoabsorption at 32 nm, using fragment momentum imaging in a crossed-beams experiment at the free-electron laser in Hamburg (FLASH). Investigations were done both for ions with several vibrational levels excited in the ion source and for ions vibrationally cooled in an electrostatic ion trap prior to the irradiation. The product channels He + (1s)+H(nl) and He(1snl)+H + were separated and the He(1snl)+H + channel was particularly studied by coincidence detection of the He and H + fragments on two separate fragment detectors. At 32 nm excitation, the branching ratio between the product channels was found to be σ He + +H /σ He+H + =0.96±0.11 for vibrationally hot and 1.70±0.48 for vibrationally cold ions. The spectra of kinetic energy releases for both channels revealed that photodissociation at 32 nm leads to high Rydberg states (n > or approx. 3-4) of the emerging atomic fragments irrespective of the initial vibrational excitation of HeH + . The fragment angular distributions showed that dissociation into the He+H + channel mostly (∼70%) proceeds through 1 Π states, while for the He + +H channel 1 Σ and 1 Π states are of about equal importance.

  3. Simulations of the dissociation of small helium clusters with ab initio molecular dynamics in electronically excited states

    International Nuclear Information System (INIS)

    Closser, Kristina D.; Head-Gordon, Martin; Gessner, Oliver

    2014-01-01

    The dynamics resulting from electronic excitations of helium clusters were explored using ab initio molecular dynamics. The simulations were performed with configuration interaction singles and adiabatic classical dynamics coupled to a state-following algorithm. 100 different configurations of He 7 were excited into the 2s and 2p manifold for a total of 2800 trajectories. While the most common outcome (90%) was complete fragmentation to 6 ground state atoms and 1 excited state atom, 3% of trajectories yielded bound, He 2 * , and <0.5% yielded an excited helium trimer. The nature of the dynamics, kinetic energy release, and connections to experiments are discussed

  4. Symmetry Breakdown in Ground State Dissociation of HD+

    International Nuclear Information System (INIS)

    Ben-Itzhak, I.; Wells, E.; Carnes, K. D.; Krishnamurthi, Vidhya; Weaver, O. L.; Esry, B. D.

    2000-01-01

    Experimental studies of the dissociation of the electronic ground state of HD + following ionization of HD by fast proton impact indicate that the H + +D 1s dissociation channel is more likely than the H1s+D + dissociation channel by about 7% . This isotopic symmetry breakdown is due to the finite nuclear mass correction to the Born-Oppenheimer approximation which makes the 1sσ state 3.7 meV lower than the 2pσ state at the dissociation limit. The measured fractions of the two dissociation channels are in agreement with coupled-channels calculations of 1sσ to 2pσ transitions. (c) 2000 The American Physical Society

  5. Atom and molecule projectile and fast aggregate excitation, ionization and dissociation in thin targets in the out-of-charge equilibrium field

    International Nuclear Information System (INIS)

    Clouvas, A.

    1985-12-01

    The aim of this experimental study is to confirm the possible existence of bound states for light atomic and molecular projectiles inside solid targets, in the MeV energy range. For this purpose we have used, various experimental methods such as charge state distribution measurements, energy loss measurements, beam foil spectroscopy and electron spectroscopy. It was confirmed that bound states of light atomic and molecular projectiles can exist in a solid medium. The various cross sections (charge exchange, excitation, ionisation, dissociation) relative to these bound states have been measured [fr

  6. Charge-Transfer Dynamics in the Lowest Excited State of a Pentacene–Fullerene Complex: Implications for Organic Solar Cells

    KAUST Repository

    Joseph, Saju

    2017-10-02

    We characterize the dynamic nature of the lowest excited state in a pentacene/C60 complex on the femtosecond time scale, via a combination of ab initio molecular dynamics and time-dependent density functional theory. We analyze the correlations between the molecular vibrations of the complex and the oscillations in the electron-transfer character of its lowest excited state, which point to vibration-induced coherences between the (pentacene-based) local-excitation (LE) state and the complex charge-transfer (CT) state. We discuss the implications of our results on this model system for the exciton-dissociation process in organic solar cells.

  7. Control of concerted two bond versus single bond dissociation in CH3Co(CO)4 via an intermediate state using pump-dump laser pulses

    Science.gov (United States)

    Ambrosek, David; González, Leticia

    2007-10-01

    Wavepacket propagations on ab initio multiconfigurational two-dimensional potential energy surfaces for CH3Co(CO)4 indicate that after irradiation to the lowest first and second electronic excited states, concerted dissociation of CH3 and the axial CO ligand takes place. We employ a pump-dump sequence of pulses with appropriate frequencies and time delays to achieve the selective breakage of a single bond by controlling the dissociation angle. The pump and dump pulse sequence exploits the unbound surface where dissociation occurs in a counterintuitive fashion; stretching of one bond in an intermediate state enhances the single dissociation of the other bond.

  8. Control of concerted two bond versus single bond dissociation in CH(3)Co(CO)(4) via an intermediate state using pump-dump laser pulses.

    Science.gov (United States)

    Ambrosek, David; González, Leticia

    2007-10-07

    Wavepacket propagations on ab initio multiconfigurational two-dimensional potential energy surfaces for CH(3)Co(CO)(4) indicate that after irradiation to the lowest first and second electronic excited states, concerted dissociation of CH(3) and the axial CO ligand takes place. We employ a pump-dump sequence of pulses with appropriate frequencies and time delays to achieve the selective breakage of a single bond by controlling the dissociation angle. The pump and dump pulse sequence exploits the unbound surface where dissociation occurs in a counterintuitive fashion; stretching of one bond in an intermediate state enhances the single dissociation of the other bond.

  9. Multiphoton dissociation of polyatomic molecules

    International Nuclear Information System (INIS)

    Schulz, P.A.

    1979-10-01

    The dynamics of infrared multiphoton excitation and dissociation of SF 6 was investigated under collision free conditions by a crossed laser-molecular beam method. In order to understand the excitation mechanism and to elucidate the requirements of laser intensity and energy fluence, a series of experiments were carried out to measure the dissociation yield dependences on energy fluence, vibrational temperature of SF 6 , the pulse duration of the CO 2 laser and the frequency in both one and two laser experiments. Translational energy distributions of the SF 5 dissociation product measured by time of flight and angular distributions and the dissociation lifetime of excited SF 6 as inferred from the observation of secondary dissociation of SF 5 into SF 4 and F during the laser pulse suggest that the dynamics of dissociation of excited molecules is dominated by complete energy randomization and rapid intramolecular energy transfer on a nanosecond timescale, and can be adequately described by RRKM theory. An improved phenomenological model including the initial intensity dependent excitation, a rate equation describing the absorption and stimulated emission of single photons, and the unimolecular dissociation of excited molecules is constructed based on available experimental results. The model shows that the energy fluence of the laser determines the excitation of molecules in the quasi-continuum and the excess energy with which molecules dissociate after the laser pulse. The role played by the laser intensity in multiphoton dissociation is more significant than just that of overcoming the intensity dependent absorption in the lowest levels. 63 references

  10. Impulsive IR-multiphoton dissociation of acrolein: observation of non-statistical product vibrational excitation in CO ( v=1-12) by time resolved IR fluorescence spectroscopy

    Science.gov (United States)

    Chowdhury, P. K.

    2000-10-01

    On IR-multiphoton excitation, vibrationally highly excited acrolein molecules undergo concerted dissociation generating CO and ethylene. The vibrationally excited products, CO and ethylene, are detected immediately following the CO 2 laser pulse by observing IR fluorescence at 4.7 and 3.2 μm, respectively. The nascent CO is formed with significant vibrational excitation, with a Boltzmann population distribution for v=1-12 levels corresponding to T v=12 950±50 K. The average vibrational energy in the product CO is found to be 26 kcal mol -1, in contrast to its statistical share of 5 kcal mol -1, available from the product energy distribution. The nascent vibrationally excited ethylene either dissociates by absorbing further infrared laser photons from the tail of the CO 2 laser pulse or relaxes by collisional deactivation. Ethylene IR-fluorescence excitation spectrum showed a structure in the quasi-continuum, with a facile resonance at 10.53 μm corresponding to the 10P(14) CO 2 laser line, which explains the higher acetylene yield observed at a higher pressure. A hydrogen atom transfer mechanism followed by C-C impulsive break in the acrolein transition state may be responsible for such non-statistical product energy distribution.

  11. Dissociation energy of the ground state of NaH

    International Nuclear Information System (INIS)

    Huang, Hsien-Yu; Lu, Tsai-Lien; Whang, Thou-Jen; Chang, Yung-Yung; Tsai, Chin-Chun

    2010-01-01

    The dissociation energy of the ground state of NaH was determined by analyzing the observed near dissociation rovibrational levels. These levels were reached by stimulated emission pumping and fluorescence depletion spectroscopy. A total of 114 rovibrational levels in the ranges 9≤v '' ≤21 and 1≤J '' ≤14 were assigned to the X 1 Σ + state of NaH. The highest vibrational level observed was only about 40 cm -1 from the dissociation limit in the ground state. One quasibound state, above the dissociation limit and confined by the centrifugal barrier, was observed. Determining the vibrational quantum number at dissociation v D from the highest four vibrational levels yielded the dissociation energy D e =15 815±5 cm -1 . Based on new observations and available data, a set of Dunham coefficients and the rotationless Rydberg-Klein-Rees curve were constructed. The effective potential curve and the quasibound states were discussed.

  12. Excitation and dissociation of molecules by low-energy (0-15 eV) electrons

    International Nuclear Information System (INIS)

    Verhaart, G.J.

    1980-01-01

    The author deals with excitation and dissociation processes which result from the interaction between low-energy (0.15 eV) electrons and molecules. Low-energy electron-impact spectroscopy is used to gain a better knowledge of the electronic structure of halomethanes, ethylene and some of its halogen substituted derivatives, and some more complex organic molecules. (Auth.)

  13. Excited states 2

    CERN Document Server

    Lim, Edward C

    2013-01-01

    Excited States, Volume 2 is a collection of papers that deals with molecules in the excited states. The book describes the geometries of molecules in the excited electronic states. One paper describes the geometries of a diatomic molecule and of polyatomic molecules; it also discusses the determination of the many excited state geometries of molecules with two, three, or four atoms by techniques similar to diatomic spectroscopy. Another paper introduces an ordered theory related to excitons in pure and mixed molecular crystals. This paper also presents some experimental data such as those invo

  14. Dissociation of ethane by electron impact

    International Nuclear Information System (INIS)

    Winters, H.F.

    1979-01-01

    The absolute total dissociation cross section for ethane is reported for electron energies between 10 and 600 eV. A maximum value of 7.6 X 10 -16 cm 2 occurs at 80 eV while the apparent threshold is approximately 10 eV. Dissociative ionization is more probable than dissociation into neutral fragments at all energies except in the threshold region. The data indicates that fragmentation involving methane elimination (e - +C 2 H 6 → CH 4 + CH 2 ) occurs in less than 2% of the dissociative events for 50 < E < 600 eV. Arguments are presented which suggest that some of the lower excited states of ethane are stable against dissociation. (Auth.)

  15. Cathodoluminescence imaging and spectroscopy of excited states in InAs self-assembled quantum dots

    International Nuclear Information System (INIS)

    Khatsevich, S.; Rich, D.H.; Kim, Eui-Tae; Madhukar, A.

    2005-01-01

    We have examined state filling and thermal activation of carriers in buried InAs self-assembled quantum dots (SAQDs) with excitation-dependent cathodoluminescence (CL) imaging and spectroscopy. The InAs SAQDs were formed during molecular-beam epitaxial growth of InAs on undoped planar GaAs (001). The intensities of the ground- and excited-state transitions were analyzed as a function of temperature and excitation density to study the thermal activation and reemission of carriers. The thermal activation energies associated with the thermal quenching of the luminescence were measured for ground- and excited-state transitions of the SAQDs, as a function of excitation density. By comparing these activation energies with the ground- and excited-state transition energies, we have considered various processes that describe the reemission of carriers. Thermal quenching of the intensity of the QD ground- and first excited-state transitions at low excitations in the ∼230-300-K temperature range is attributed to dissociation of excitons from the QD states into the InAs wetting layer. At high excitations, much lower activation energies of the ground and excited states are obtained, suggesting that thermal reemission of single holes from QD states into the GaAs matrix is responsible for the observed temperature dependence of the QD luminescence in the ∼230-300-K temperature range. The dependence of the CL intensity of the ground-and first excited-state transition on excitation density was shown to be linear at all temperatures at low-excitation density. This result can be understood by considering that carriers escape and are recaptured as excitons or correlated electron-hole pairs. At sufficiently high excitations, state-filling and spatial smearing effects are observed together with a sublinear dependence of the CL intensity on excitation. Successive filling of the ground and excited states in adjacent groups of QDs that possess different size distributions is assumed to

  16. An ion cooling and state characterization apparatus for studies of molecular ion dissociative interactions

    International Nuclear Information System (INIS)

    Deng, Shihu; Vane, C R; Bannister, M E; Havener, C C; Meyer, F W; Krause, H F; Hettich, R L; Goeringer, D E; Van Berkel, G J

    2009-01-01

    An experimental capability is being developed at the Oak Ridge National Laboratory Multi-Charged Ion Research Facility (ORNL MIRF) to enable stored cooling and state characterization of molecular ions of essentially any mass. Ions selected from a variety of available sources are injected from the side into a 1.5 meter long electrostatic mirror trap, where excited internal states are cooled by radiative cooling. An electron beam target located near the middle of the ion-trap region, coupled with neutral fragment imaging detector systems at each end of the trap, permits state-specific studies of electron-molecular ion dissociation.

  17. Realisation and crossed molecular beams study of H2/O chemical reactions at several excited states

    International Nuclear Information System (INIS)

    Marx, Jacqueline

    1986-01-01

    This work is devoted to the study of the reactive collision O + H 2 OH + H in a crossed beam experiment. This process including several channels taken a part in the chemistry of the upper atmosphere as well as in the combustion of hydrogen. According to the electronic or vibrational state of the reactants, the OH radical is produced in its ground electronic state OH (X 2 π) or in its first excited state OH (A 2 Σ + ). When the reactants are in their ground state, the reaction is endothermic in the conditions of the experiment (center of mass kinetic energy ≅ 0.12 eV). The following reactions have been obtained: O( 1 D) +H 2 (v=O) → OH (X 2 π) +H( 2 S) and O( 1 D) +H 2 (v≥5) → OH (A 2 Σ + ) +H( 2 S). The atomic oxygen is produced in its excited state O( 1 D) in a radio-frequency discharge which dissociates the molecular oxygen seeded in a carrier gas (He or Ar) and the hydrogen molecules are excited vibrationally by electron bombardment. The first reaction is studied by time-of-flight measurements. In this way, it has been possible to observe the different vibrational levels on which the OH radical is produced. The analysis of this vibrational distribution shows the competition between the abstraction and insertion-dissociation mechanisms. In the second reaction, the analysis of the spontaneous fluorescence of OH (A 2 Σ + ) reveals a very hot and non-Boltzmann rotational excitation. (author) [fr

  18. Synthesis, Acidity Constants and Tautomeric Structure of the Diazonium Coupling Products of 2-(Benzylsulfanyl-7H-purin-6-one in Its Ground and Excited States

    Directory of Open Access Journals (Sweden)

    Hosam A. Saad

    2011-10-01

    Full Text Available A series of new 8-arylhydrazono-2-(benzylsulfanyl-7H-purin-6-ones 6 were synthesized, their electronic absorption spectra in different organic solvents of varying polarities were investigated and their acid dissociation constants in both the ground and excited states were determined spectrophotometrically. The tautomeric structures of such products were elucidated by spectral analyses and correlation of their acid dissociation constants with the Hammett equation. The results indicated that the studied compounds 6 exist predominantly in the hydrazone tautomeric form 6A in both the ground and excited states.

  19. Production of the Q2 doubly excited states of the hydrogen molecule by electron impact in a single step

    Science.gov (United States)

    Santos, Leonardo O.; Rocha, Alexandre B.; Faria, Nelson Velho de Castro; Jalbert, Ginette

    2017-03-01

    We calculate the single step cross sections for excitation of Q 2 states of H2 and its subsequent dissociation. The cross section calculations were performed within the first Born approximation and the electronic wave functions were obtained via State-Averaged Multiconfigurational Self-Consistent Field followed by Configuration Interaction. We have assumed autoionization is the only important process competing with dissociation into neutral atoms. We have estimated its probability through a semi classical approach and compared with results of literature. Special attention was given to the Q 2 1Σg +(1) state which, as has been shown in a previous work, may dissociate into H(2 sσ) + H(2 sσ) fragments (some figures in this article are in colour only in the electronic version).

  20. Diffraction dissociation at the LHC

    Energy Technology Data Exchange (ETDEWEB)

    Jenkovszky, Laszlo [Bogolyubov Institute for Theoretical Physics (BITP), Ukrainian National Academy of Sciences 14-b, Metrolohichna str., Kiev, 03680, Ukraine and Wigner Research Centre for Physics, Hungarian Academy of Sciences 1525 Budapest, POB 49 (Hungary); Orava, Risto [Institute of Physics, Division of Elementary Particle Physics, P.O. Box 64 (Gustaf Haellstroeminkatu 2a), FI-00014 University of Helsinki, Finland and CERN, CH-1211 Geneva 23 (Switzerland); Salii, Andrii [Bogolyubov Institute for Theoretical Physics (BITP), Ukrainian National Academy of Sciences 14-b, Metrolohichna str., Kiev, 03680 (Ukraine)

    2013-04-15

    We report on recent calculations of low missing mass single (SD) and double (DD) diffractive dissociation at LHC energies. The calculations are based on a dual-Regge model, dominated by a single Pomeron exchange. The diffractively excited states lie on the nucleon trajectory N*, appended by the isolated Roper resonance. Detailed predictions for the squared momentum transfer and missing mass dependence of the differential and integrated single-and double diffraction dissociation in the kinematical range of present and future LHC measurements are given.

  1. Diffraction dissociation at the LHC

    International Nuclear Information System (INIS)

    Jenkovszky, László; Orava, Risto; Salii, Andrii

    2013-01-01

    We report on recent calculations of low missing mass single (SD) and double (DD) diffractive dissociation at LHC energies. The calculations are based on a dual-Regge model, dominated by a single Pomeron exchange. The diffractively excited states lie on the nucleon trajectory N*, appended by the isolated Roper resonance. Detailed predictions for the squared momentum transfer and missing mass dependence of the differential and integrated single-and double diffraction dissociation in the kinematical range of present and future LHC measurements are given.

  2. Excited states v.6

    CERN Document Server

    Lim, Edward C

    1982-01-01

    Excited States, Volume 6 is a collection of papers that discusses the excited states of molecules. The first paper discusses the linear polyene electronic structure and potential surfaces, considering both the theoretical and experimental approaches in such electronic states. This paper also reviews the theory of electronic structure and cites some experimental techniques on polyene excitations, polyene spectroscopic phenomenology, and those involving higher states of polyenes and their triplet states. Examples of these experimental studies of excited states involve the high-resolution one-pho

  3. Excited states

    CERN Document Server

    Lim, Edward C

    1974-01-01

    Excited States, Volume I reviews radiationless transitions, phosphorescence microwave double resonance through optical spectra in molecular solids, dipole moments in excited states, luminescence of polar molecules, and the problem of interstate interaction in aromatic carbonyl compounds. The book discusses the molecular electronic radiationless transitions; the double resonance techniques and the relaxation mechanisms involving the lowest triplet state of aromatic compounds; as well as the optical spectra and relaxation in molecular solids. The text also describes dipole moments and polarizab

  4. Dissociative State and Competence

    Directory of Open Access Journals (Sweden)

    Yu-Ju Lin

    2007-10-01

    Full Text Available This report presents the results of forensic evaluation of the civil competence of a case of alleged dissociative identity disorder (DID and discusses whether such dissociative states substantially jeopardize civil competence. A 40-year-old woman claimed that she had had many personalities since her college days. From the age of 37 to 40, she shopped excessively, which left her with millions of dollars of debt. She ascribed her shopping to a certain identity state, over which she had no control. (In this article, we use the term identity state to replace personality as an objective description of a mental state. She thus raised the petition of civil incompetence. During the forensic evaluation, it was found that the identity states were relatively stable and mutually aware of each other. The switch into another identity state was sometimes under voluntary control. The subject showed consistency and continuity in behavioral patterns across the different identity states, and no matter which identity state she was in, there was no evidence of impairment in her factual knowledge of social situations and her capacity for managing personal affairs. We hence concluded that she was civilly competent despite the claimed DID. Considering that the existence and diagnosis of DID are still under dispute and a diagnosis of DID alone is not sufficient to interdict a person's civil right, important clinical and forensic issues remain to be answered.

  5. Optical observations of molecular dissociation in thin foils

    International Nuclear Information System (INIS)

    Berry, H.G.; Gay, T.J.; Brooks, R.L.

    1981-01-01

    We have measured the intensity and polarizations of light emitted from atomic excited states of dissociated molecular ions. Using HeH + projectiles, we have observed factors of 1-5 enhancements of the light from n=3, sup(1,3)P,D states of He I and some He II and H I emissions. Observations of Lyman alpha emission after dissociation of H 2 + and H 3 + show rapid variations in light yield for small internuclear separations at the foil surface. (author)

  6. Boltzmann rovibrational collisional coarse-grained model for internal energy excitation and dissociation in hypersonic flows.

    Science.gov (United States)

    Munafò, A; Panesi, M; Magin, T E

    2014-02-01

    A Boltzmann rovibrational collisional coarse-grained model is proposed to reduce a detailed kinetic mechanism database developed at NASA Ames Research Center for internal energy transfer and dissociation in N(2)-N interactions. The coarse-grained model is constructed by lumping the rovibrational energy levels of the N(2) molecule into energy bins. The population of the levels within each bin is assumed to follow a Boltzmann distribution at the local translational temperature. Excitation and dissociation rate coefficients for the energy bins are obtained by averaging the elementary rate coefficients. The energy bins are treated as separate species, thus allowing for non-Boltzmann distributions of their populations. The proposed coarse-grained model is applied to the study of nonequilibrium flows behind normal shock waves and within converging-diverging nozzles. In both cases, the flow is assumed inviscid and steady. Computational results are compared with those obtained by direct solution of the master equation for the rovibrational collisional model and a more conventional multitemperature model. It is found that the proposed coarse-grained model is able to accurately resolve the nonequilibrium dynamics of internal energy excitation and dissociation-recombination processes with only 20 energy bins. Furthermore, the proposed coarse-grained model provides a superior description of the nonequilibrium phenomena occurring in shock heated and nozzle flows when compared with the conventional multitemperature models.

  7. Dissociative recombination of rare gas hydride ions: II. ArH+

    International Nuclear Information System (INIS)

    Mitchell, J B A; Novotny, O; LeGarrec, J L; Florescu-Mitchell, A; Rebrion-Rowe, C; Stolyarov, A V; Child, M S; Svendsen, A; Ghazaly, M A El; Andersen, L H

    2005-01-01

    A storage ring measurement of the rate coefficient for the production of neutral Ar in e + ArH + collisions is described. It is found that the recombination rate is too small to measure at low centre-of-mass energies but the combined rate coefficient for dissociative recombination and dissociative excitation increases above 2.5 eV displaying peaks centred at 7.5 eV, 16 and 26 eV. Calculated potential energy curves for the ground and excited states of ArH + are presented and these aid in the elucidation of the recombination and excitation processes observed at higher energies. The implications for plasma modelling are discussed. (letter to the editor)

  8. Bound energy levels at the n=2 dissociation threshold in HD

    NARCIS (Netherlands)

    Pielage, T.G.P.; de Lange, A.; Brandi, F.; Ubachs, W.M.G.

    2002-01-01

    Level energies of g symmetry states lying just below the n = 2 dissociation threshold have been determined in a XUV + IR multi-step laser excitation experiment in HD, with an absolute accuracy of the excitation energy of 0.015 cm

  9. Giant resonances on excited states

    International Nuclear Information System (INIS)

    Besold, W.; Reinhard, P.G.; Toepffer, C.

    1984-01-01

    We derive modified RPA equations for small vibrations about excited states. The temperature dependence of collective excitations is examined. The formalism is applied to the ground state and the first excited state of 90 Zr in order to confirm a hypothesis which states that not only the ground state but every excited state of a nucleus has a giant resonance built upon it. (orig.)

  10. 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.

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

    International Nuclear Information System (INIS)

    Wu, Guorong; Neville, Simon P.; Schalk, Oliver; Sekikawa, Taro; Ashfold, Michael N. R.; Worth, Graham A.; Stolow, Albert

    2016-01-01

    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 2 (πσ ∗ ) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B 1 (π3p y ) Rydberg state, followed by prompt internal conversion to the A 2 (πσ ∗ ) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A 2 (πσ ∗ ) 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 2 (πσ ∗ ) state, facilitating wavepacket motion around the potential barrier in the N–CH 3 dissociation coordinate

  12. Dynamic modification of the fragmentation of COq+ excited states generated with high-order harmonics

    International Nuclear Information System (INIS)

    Cao, W.; De, S.; Singh, K. P.; Chen, S.; Laurent, G.; Ray, D.; Ben-Itzhak, I.; Cocke, C. L.; Schoeffler, M. S.; Belkacem, A.; Osipov, T.; Rescigno, T.; Alnaser, A. S.; Bocharova, I. A.; Zherebtsov, S.; Kling, M. F.; Litvinyuk, I. V.

    2010-01-01

    The dynamic process of fragmentation of CO q+ excited states is investigated using a pump-probe approach. EUV radiation (32-48 eV) generated by high-order harmonics was used to ionize and excite CO molecules and a time-delayed infrared (IR) pulse (800 nm) was used to influence the evolution of the dissociating multichannel wave packet. Two groups of states, separable experimentally by their kinetic-energy release (KER), are populated by the EUV and lead to C + -O + fragmentation: direct double ionization of the neutral molecule and fragmentation of the cation leading to C + -O*, followed by autoionization of O*. The IR pulse was found to modify the KER of the latter group in a delay-dependent way which is explained with a model calculation.

  13. Heterolytic dissociative adsorption state of dihydrogen favored by interfacial defects

    Science.gov (United States)

    Song, Zhenjun; Hu, Hanshi; Xu, Hu; Li, Yong; Cheng, Peng; Zhao, Bin

    2018-03-01

    The atomic-scale insight into dihydrogen on MgO(001) surface deposited on molybdenum substrate with interfacial defects was investigated in detail by employing density functional methods Here we report novel dissociative adsorption behaviors of single hydrogen molecule on the usually inert oxide surfaces, with consideration of two types of dissociation schemes. The heterolytic dissociation state -Mg(H)-O(H)- of dihydrogen is impossible to obtain on neighboring O-Mg sites of perfect bulk MgO(001) terraces. Unusually, the hydrogen molecule can form heterolytic fragmentation states on metal supported MgO(001) films with very low activation barrier (0.398 eV), and the heterolytic dissociation state is much more favorable than homolytic dissociation state both energetically and kinetically in all cases. Electronic properties and bonding attribution of adsorbates and the oxide-metal hybrid structure are revealed by analyzing density of states, differential charge densities, orbital interaction and electron localization function. The characteristic changes to the property and activity of magnesia (001) can have potential application in catalytic reactions.

  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. Integral cross sections for electron impact excitation of vibrational and electronic states in phenol

    Energy Technology Data Exchange (ETDEWEB)

    Neves, R. F. C. [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide SA 5001 (Australia); Instituto Federal do Sul de Minas Gerais, Campus Poços de Caldas, Minas Gerais (Brazil); Departamento de Física, Universidade Federal de Juiz de Fora, 36036-330 Juiz de Fora, Minas Gerais (Brazil); Jones, D. B. [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide SA 5001 (Australia); Lopes, M. C. A. [Departamento de Física, Universidade Federal de Juiz de Fora, 36036-330 Juiz de Fora, Minas Gerais (Brazil); Blanco, F. [Departamento de Física Atómica, Molecular y Nuclear, Universidad Complutense de Madrid, 28040 Madrid (Spain); García, G. [Instituto de Física Fundamental, CSIC, Serrano 113-bis, 28006 Madrid (Spain); Ratnavelu, K. [Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia); Brunger, M. J., E-mail: Michael.Brunger@flinders.edu.au [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide SA 5001 (Australia); Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia)

    2015-05-21

    We report on measurements of integral cross sections (ICSs) for electron impact excitation of a series of composite vibrational modes and electronic-states in phenol, where the energy range of those experiments was 15–250 eV. There are currently no other results against which we can directly compare those measured data. We also report results from our independent atom model with screened additivity rule correction computations, namely, for the inelastic ICS (all discrete electronic states and neutral dissociation) and the total ionisation ICS. In addition, for the relevant dipole-allowed excited electronic states, we also report f-scaled Born-level and energy-corrected and f-scaled Born-level (BEf-scaled) ICS. Where possible, our measured and calculated ICSs are compared against one another with the general level of accord between them being satisfactory to within the measurement uncertainties.

  16. Dipole-bound states as doorways in (dissociative) electron attachment

    International Nuclear Information System (INIS)

    Sommerfeld, Thomas

    2005-01-01

    This communication starts with a comparison of dissociative recombination and dissociative attachment placing emphasis on the role of resonances as reactive intermediates. The main focus is then the mechanism of electron attachment to polar molecules at very low energies (100 meV). The scheme considered consists of two steps: First, an electron is captured in a diffuse dipole-bound state depositing its energy in the vibrational degrees of freedom, in other words, a vibrational Feshbach resonance is formed. Then, owing to the coupling with a valence state, the electron is transferred into a compact valence orbital, and depending on the electron affinities of the valence state and possible dissociation products, as well as on the details of the intramolecular redistribution of vibrational energy, long-lived anions can be generated or dissociation reactions can be initiated. The key property in this context is the electronic coupling strength between the diffuse dipole-bound and the compact valence states. We describe how the coupling strength can be extracted from ab initio data, and present results for Nitromethane, Uracil and Cyanoacetylene

  17. Monte Carlo wave-packet approach to trace nuclear dynamics in molecular excited states by XUV-pump-IR-probe spectroscopy

    Science.gov (United States)

    Jing, Qingli; Bello, Roger Y.; Martín, Fernando; Palacios, Alicia; Madsen, Lars Bojer

    2018-04-01

    Recent research interests have been raised in uncovering and controlling ultrafast dynamics in excited neutral molecules. In this work we generalize the Monte Carlo wave packet (MCWP) approach to XUV-pump-IR-probe schemes to simulate the process of dissociative double ionization of H2 where singly excited states in H2 are involved. The XUV pulse is chosen to resonantly excite the initial ground state of H2 to the lowest excited electronic state of 1Σu + symmetry in H2 within the Franck-Condon region. The delayed intense IR pulse couples the excited states of 1Σu + symmetry with the nearby excited states of 1Σg + symmetry. It also induces the first ionization from H2 to H2 + and the second ionization from H2 + to H++H+. To reduce the computational costs in the MCWP approach, a sampling method is proposed to determine in time the dominant ionization events from H2 to H2+. By conducting a trajectory analysis, which is a unique possibility within the MCWP approach, the origins of the characteristic features in the nuclear kinetic energy release spectra are identified for delays ranging from 0 to 140 fs and the nuclear dynamics in the singly excited states in H2 is mapped out.

  18. Excited-state density functional theory

    International Nuclear Information System (INIS)

    Harbola, Manoj K; Hemanadhan, M; Shamim, Md; Samal, P

    2012-01-01

    Starting with a brief introduction to excited-state density functional theory, we present our method of constructing modified local density approximated (MLDA) energy functionals for the excited states. We show that these functionals give accurate results for kinetic energy and exchange energy compared to the ground state LDA functionals. Further, with the inclusion of GGA correction, highly accurate total energies for excited states are obtained. We conclude with a brief discussion on the further direction of research that include the construction of correlation energy functional and exchange potential for excited states.

  19. The role of high Rydberg states in the generation of negative ions in negative-ion discharges

    International Nuclear Information System (INIS)

    Hiskes, J.R.

    1995-01-01

    The generation of substantial yields of H - ions in a laser excited H 2 gas has been reported by Pinnaduwage and Christoforu. These H - yields have been attributed to (2 + 1) REMP photoexcitation processes leading to dissociative attachment of doubly-excited or superexcited states (SES), or dissociative attachment of high Rydberg product states. The new feature of these experiments is the implied large dissociative attachment rates, of order 10 -6 cm 3 sec -1 , values that are orders-of-magnitude larger than the dissociative attachment of the vibrationally excited levels of the ground electronic state. While these laser excitations are not directly applicable to a hydrogen negative-ion discharge, the implication of large dissociative attachment rates to the high Rydberg states may affect both the total negative-ion density and the interpretation of discharge performance. Within the discharge energetic electrons will collisionally excite the higher Rydberg states, and the relative contribution of the dissociative attachment of these states when compared with the dissociative attachment to the ground state vibrational levels, is the topic of this paper

  20. Electron beam induced fluorescence measurements of the degree of hydrogen dissociation in hydrogen plasmas

    NARCIS (Netherlands)

    Smit, C.; Brussaard, G.J.H.; de Beer, E.C.M.; Schram, D.C.; Sanden, van de M.C.M.

    2004-01-01

    The degree of dissociation of hydrogen in a hydrogen plasma has been measured using electron beam induced fluorescence. A 20 kV, 1 mA electron beam excites both the ground state H atom and H2 molecule into atomic hydrogen in an excited state. From the resulting fluorescence the degree of

  1. Dissociative states in dreams and brain chaos: Implications for creative awareness

    Directory of Open Access Journals (Sweden)

    Petr eBob

    2015-09-01

    Full Text Available This article reviews recent findings indicating some common brain processes during dissociative states and dreaming with the aim to outline a perspective that neural chaotic states during dreaming can be closely related to dissociative states that may manifest in dreams scenery. These data are in agreement with various clinical findings that dissociated states can be projected into the dream scenery in REM sleep periods and dreams may represent their specific interactions that may uncover unusual psychological potential of creativity in psychotherapy, art and scientific discoveries.

  2. Dissociative photoionization of IBr following I(4d) and Br(3d) inner-shell excitations in the range of 60 ∼ 133 eV: remarkable biased charge spread relevant to the core-hole states

    International Nuclear Information System (INIS)

    Boo, Bong Hyun; Koyano, Inosuke

    2002-01-01

    Dissociative photoionization of an interhalogen molecule, iodine monobromide (IBr), spanning the I(4d) and the Br(3d) inner-shell excitation/ionization regions has been studied by using time-of-flight (TOF) mass spectrometry coupled to synchrotron radiation in the range of 60 ∼ 133 eV. The total and the individual photoion yields have been recorded as functions of the photon energy. Here, a giant shape resonance has been observed owing to the I(4d 10 ) →I(4d 9 εf) transition, the transition probability for which outweighs that for the Br(3d 10 ) →Br(3d 9 εf) excitation. In addition to the huge resonance, discrete resonances owing to the Br(3d) -1 IBr(4pσ + ) and the Br(3d -1 )Br(5p) transitions, with very weak intensities, are observed at 70.5 and 73.6 eV and have spin-orbit splittings of = 1.0 and = 0.9 eV, respectively. The dissociation processes of singly and doubly charged parent ions have also been evaluated from the variations of the individual ion and photoion-photoion coincidence (PIPICO) yields with the photon energy. Below the Br(3d) threshold, including the Br(3d) discrete excitation region, 60 + and I 2+ ions are exclusively formed with a trace number of Br + ions. Slightly above the Br(3d) threshold, more specifically at 77.5 eV, however, photoionization events leading to the formations of Br + and Br 2- prevail. At higher energies beyond the Br(3d) threshold, 78 + and I 2+ turn out to exceed again those for Br + and Br 2+ , respectively. Over the entire energy range examined, a remarkable biased charge spread in dissociative photoionization events is observed, presumably reflecting the fact that charge localized mostly in the excited atoms relevant to the specific inner-shell excitation, which can be accounted for mainly by a two-step decay process via a fast dissociation followed by autoionization upon vuv absorption

  3. Electron impact excitation of xenon from the metastable state to the excited states

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Jun; Dong Chenzhong; Xie Luyou; Zhou Xiaoxin [College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou 730070 (China); Wang Jianguo [Institute of Applied Physics and Computational Mathematic, Beijing 100088 (China)], E-mail: dongcz@nwnu.edu.cn

    2008-12-28

    The electron impact excitation cross sections from the lowest metastable state 5p{sup 5}6sJ = 2 to the six lowest excited states of the 5p{sup 5}6p configuration of xenon are calculated systematically by using the fully relativistic distorted wave method. In order to discuss the effects of target state descriptions on the electron impact excitation cross sections, two correlation models are used to describe the target states based on the multiconfiguration Dirac-Fock (MCDF) method. It is found that the correlation effects play a very important role in low energy impact. For high energy impact, however, the cross sections are not sensitive to the description of the target states, but many more partial waves must be included.

  4. Ab initio calculation on the low-lying excited states of Si2+ cation including spin–orbit coupling

    International Nuclear Information System (INIS)

    Liu, Yanlei; Zhai, Hongsheng; Zhang, Xiaomei; Liu, Yufang

    2013-01-01

    Highlights: • 24 Λ–S states are correlated to the dissociation limit of Si( 3 P g ) + Si + ( 2 P u ) are first reported. • The dissociation energies of the calculated electronic states are predicted in our work. • It is first time that the entire 54 Ω states generated from the 24 Λ–S states have been studied. • PECs of Λ–S and Ω states are depicted with the aid of avoided crossing rule between the same symmetry. - Abstract: Ab initio all-electron relativistic calculations of the low-lying excited states of Si 2 + have been performed at MRCI+Q/AVQZ level. The calculated electronic states, including 12 doublet and 12 quartet Λ–S states, are correlated to the dissociation limit of Si( 3 P g ) + Si + ( 2 P u ). Spin–orbit interaction is taken into account via the state interaction approach with the full Breit-Pauli Hamiltonian, which causes the entire 24 Λ–S states to split into 54 Ω states. This is the first time that spin–orbit coupling (SOC) calculation has been performed on Si 2 + . The obtained potential energy curves (PECs) of Λ–S and Ω states are respectively depicted with the aid of the avoided crossing rule between the same symmetry. The spectroscopic constants of the bound Λ–S and Ω states are determined, and excellent agreements with the latest theoretical results are achieved

  5. Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO) 2I 2 complex

    Science.gov (United States)

    Lehtovuori, Viivi; Kallioinen, Jani; Myllyperkiö, Pasi; Haukka, Matti; Korppi-Tommola, Jouko

    2003-11-01

    Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [ trans-I-Ru(dcbpy)(CO) 2I 2] (dcbpy= 4,4 '-dicarboxy-2,2 '-bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [ cis-I-Ru(dcbpy)(CO)(Sol)I 2] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K indicate interligand charge transfer from mixed Ru-I states to empty dcbpy orbitals. For the photoproduct, no such transfer was observed. In both complexes recovery from the lowest energy excited triplet state to the ground state occurs via two channels: radiative relaxation and a parallel barrier controlled non-radiative relaxation. The barrier is much higher in the reactant (about 850 cm -1) than in the product. A combination of DFT and ZINDO/CI calculations was used to estimate excited singlet and triplet spectra of the reactant and the product molecules. Calculated singlet-triplet difference spectra qualitatively match the observed transient spectra 500 fs after excitation supporting the idea that observed excited state relaxation occurs from the triplet states in both complexes.

  6. Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO)2I2 complex

    International Nuclear Information System (INIS)

    Lehtovuori, Viivi; Kallioinen, Jani; Myllyperkioe, Pasi; Haukka, Matti; Korppi-Tommola, Jouko

    2003-01-01

    Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [trans-I-Ru(dcbpy)(CO) 2 I 2 ] (dcbpy4,4 ' -dicarboxy-2,2 ' -bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [cis-I-Ru(dcbpy)(CO)(Sol)I 2 ] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K indicate interligand charge transfer from mixed Ru-I states to empty dcbpy orbitals. For the photoproduct, no such transfer was observed. In both complexes recovery from the lowest energy excited triplet state to the ground state occurs via two channels: radiative relaxation and a parallel barrier controlled non-radiative relaxation. The barrier is much higher in the reactant (about 850 cm -1 ) than in the product. A combination of DFT and ZINDO/CI calculations was used to estimate excited singlet and triplet spectra of the reactant and the product molecules. Calculated singlet-triplet difference spectra qualitatively match the observed transient spectra 500 fs after excitation supporting the idea that observed excited state relaxation occurs from the triplet states in both complexes

  7. Dissociation mechanisms and dynamics of doubly charged CD3CN observed by PEPIPICO spectroscopy

    International Nuclear Information System (INIS)

    Harada, C.; Tada, S.; Yamamoto, K.; Senba, Y.; Yoshida, H.; Hiraya, A.; Wada, S.; Tanaka, K.; Tabayashi, K.

    2006-01-01

    Dissociation of free acetonitrile-d 3 molecule, CD 3 CN induced by core level excitation was studied near the nitrogen K-edge by time-of-flight fragment mass spectroscopy. A variety of atomic and molecular fragment cations such as D + , CD n + , C 2 D n + , and CD n CN + were detected using the effusive CD 3 CN beam. Photoelectron-photoion-photoion coincidence technique was applied to analyse the dissociation mechanisms and dynamics of doubly charged CD 3 CN 2+ following the N(1s-π * ) excitation. The charge separation mechanisms of core-excited CD 3 CN were discussed in connection with Auger final state distributions

  8. Formation of excited hydrogen atoms by charge transfer and dissociation. Progress report No. 12, December 1, 1975--November 1, 1976. [Summaries of research activities at Georgia Institute of Technology

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, E.W.; Rausch, E.O.; Harriss, J.E.; Bell, J.T.

    1976-11-01

    The scattering of energetic hydrogenic ions from surfaces was investigated. Protons at energies 1 to 30 keV are incident on metal surfaces and studies made of the charge state and excited state fractions of the scattered particles; measurements are also made of angular distributions and velocity spectra. The excited state distribution of back-scattered atoms is found to be governed by Auger de-excitation at the surface. Molecular hydrogen ions (H/sup +//sub 2/ and H/sup +//sub 3/) incident on metal surfaces dissociate on impact and the subsequent behavior of the fragments is uncorrelated. Contamination of metal surfaces with oxygen causes an increase in the backscattered flux of excited particles related to changes in the Auger de-excitation rate. A study of charge state distributions and angular distribution of the backscattered flux has disclosed irregularities related to methods of surface preparation. Measured backscattering coefficients have been compared with theoretical calculations of McCracken and Freeman. A limited study was made of the Mossbauer spectra of Fe after H/sup +/ bombardment. Substantial (1 percent) changes to the hyperfine field occur and anneal out after a period of some days at room temperature. It is suggested that the changes to hyperfine field are related to vacancy formation. A list of publications is included.

  9. Synthesis, Acidity Constants and Tautomeric Structure of the Diazonium Coupling Products of 2-(Benzylsulfanyl)-7H-purin-6-one in Its Ground and Excited States

    OpenAIRE

    Darwish, Elham S.; Mosselhi, Mosselhi A.; Altalbawy, Farag M.; Saad, Hosam A.

    2011-01-01

    A series of new 8-arylhydrazono-2-(benzylsulfanyl)-7H-purin-6-ones 6 were synthesized, their electronic absorption spectra in different organic solvents of varying polarities were investigated and their acid dissociation constants in both the ground and excited states were determined spectrophotometrically. The tautomeric structures of such products were elucidated by spectral analyses and correlation of their acid dissociation constants with the Hammett equation. The results indicated that t...

  10. Excited-state molecular photoionization dynamics

    International Nuclear Information System (INIS)

    Pratt, S.T.

    1995-01-01

    This review presents a survey of work using resonance-enhanced multiphoton ionization and double-resonance techniques to study excited-state photoionization dynamics in molecules. These techniques routinely provide detail and precision that are difficult to achieve in single-photon ionization from the ground state. The review not only emphasizes new aspects of photoionization revealed in the excited-state experiments but also shows how the excited-state techniques can provide textbook illustrations of some fundamental mechanisms in molecular photoionization dynamics. Most of the examples are confined to diatomic molecules. (author)

  11. Excited states in biological systems

    International Nuclear Information System (INIS)

    Cilento, G.; Zinner, K.; Bechara, E.J.H.; Duran, N.; Baptista, R.C. de; Shimizu, Y.; Augusto, O.; Faljoni-Alario, A.; Vidigal, C.C.C.; Oliveira, O.M.M.F.; Haun, M.

    1979-01-01

    Some aspects of bioluminescence related to bioenergetics are discussed: 1. chemical generation of excited species, by means of two general processes: electron transference and cyclic - and linear peroxide cleavage; 2. biological systems capable of generating excited states and 3. biological functions of these states, specially the non-emissive ones (tripletes). The production and the role of non-emissive excited states in biological systems are analysed, the main purpose of the study being the search for non-emissive states. Experiences carried out in biological systems are described; results and conclusions are given. (M.A.) [pt

  12. Process and device for the excitation and selective dissociation by absorption of a laser light and application to isotopic enrichment

    International Nuclear Information System (INIS)

    Rigny, Paul.

    1975-01-01

    The description is given of a process for the excitation and selective dissociation by absorption of the monochromatic light emitted by a high power laser. The laser light at frequency ν 1 is beamed on to an isotopic mixture of gaseous molecules, some of these molecules presenting transitions, between two vibration levels corresponding to a given isotope, separated by an energy interval ΔE 1 =2h ν 1 , and the molecules of a given isotopic species are thus preferentially dissociated into several component parts [fr

  13. Dissociative photoionization of molecular hydrogen. A joint experimental and theoretical study of the electron-electron correlations induced by XUV photoionization and nuclear dynamics on IR-laser dressed transition states

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, Andreas

    2015-01-13

    In this thesis, the dissociative single-ionization of molecular hydrogen is investigated in a kinematically complete experiment by employing extreme ultraviolet attosecond pulse trains and infrared femtosecond laser pulses. Induced by the absorption of a single XUV photon, a pronounced energy-dependent asymmetry of the relative emission direction of the photoelectron and the ion is observed. The asymmetry pattern is explained in terms of an interference of two ionization pathways involving a doubly-excited state. This interpretation is validated by a semi-classical model which only takes the nuclear motion into account. Using this model and the observed asymmetry, it is furthermore possible to disentangle the two dissociation pathways which allows for the determination of the autoionization lifetime of the contributing doubly-excited state as a function of the internuclear distance. Moreover, using a pump-probe experiment the dissociation dynamics of molecular hydrogen is investigated. A time-delay dependent momentum distribution of the fragments is observed. With a combined quantum mechanical and semi-classical approach the mechanism giving rise to the observed time-dependence is identified in terms of an intuitive elevator mechanism.

  14. Chemical reactions of water molecules on Ru(0001) induced by selective excitation of vibrational modes

    Energy Technology Data Exchange (ETDEWEB)

    Mugarza, Aitor; Shimizu, Tomoko K.; Ogletree, D. Frank; Salmeron, Miquel

    2009-05-07

    Tunneling electrons in a scanning tunneling microscope were used to excite specific vibrational quantum states of adsorbed water and hydroxyl molecules on a Ru(0 0 0 1) surface. The excited molecules relaxed by transfer of energy to lower energy modes, resulting in diffusion, dissociation, desorption, and surface-tip transfer processes. Diffusion of H{sub 2}O molecules could be induced by excitation of the O-H stretch vibration mode at 445 meV. Isolated molecules required excitation of one single quantum while molecules bonded to a C atom required at least two quanta. Dissociation of single H{sub 2}O molecules into H and OH required electron energies of 1 eV or higher while dissociation of OH required at least 2 eV electrons. In contrast, water molecules forming part of a cluster could be dissociated with electron energies of 0.5 eV.

  15. Effect of interchain coupling on the excited polaron in conjugated polymers

    International Nuclear Information System (INIS)

    Li, Xiao-xue; Chen, Gang

    2017-01-01

    Based on the one-dimensional extended Su–Schrieffer–Heeger model, we theoretically investigate the effect of interchain coupling on the formation and polarization of the single-excited state of polaron in conjugated polymers. It is found that there exists a turnover value of the coupling strength, over which the excited polaron could not be formed in either of the two coupled chains. Instead, a polaron-like particle is localized at the center of each chain. In addition, we also find that the reverse polarization of the excited polaron could be enhanced for some cases in polymer when the interchain coupling becomes strong until it exceeds the critical value. - Highlights: • Effect of interchain coupling on the single-excited state of polaron is studied. • When coupling strength exceeds critical value, the excited polaron is dissociated. • Soliton pair could be dissociated into polaron-like particle with strong coupling. • Reverse polarization of excited polaron is enhanced by weak interchain coupling. • Reverse polarization is obtained more easily in solid film of polymer molecules.

  16. Effect of interchain coupling on the excited polaron in conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiao-xue, E-mail: sps_lixx@ujn.edu.cn; Chen, Gang, E-mail: ss_cheng@ujn.edu.cn

    2017-02-05

    Based on the one-dimensional extended Su–Schrieffer–Heeger model, we theoretically investigate the effect of interchain coupling on the formation and polarization of the single-excited state of polaron in conjugated polymers. It is found that there exists a turnover value of the coupling strength, over which the excited polaron could not be formed in either of the two coupled chains. Instead, a polaron-like particle is localized at the center of each chain. In addition, we also find that the reverse polarization of the excited polaron could be enhanced for some cases in polymer when the interchain coupling becomes strong until it exceeds the critical value. - Highlights: • Effect of interchain coupling on the single-excited state of polaron is studied. • When coupling strength exceeds critical value, the excited polaron is dissociated. • Soliton pair could be dissociated into polaron-like particle with strong coupling. • Reverse polarization of excited polaron is enhanced by weak interchain coupling. • Reverse polarization is obtained more easily in solid film of polymer molecules.

  17. Electron-hole pair effects in methane dissociative chemisorption on Ni(111)

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Xuan; Jiang, Bin, E-mail: bjiangch@ustc.edu.cn [Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Juaristi, J. Iñaki [Centro de Física de Materiales CFM/MPC(CSIC-UPV/EHU), P. Manuel de Lardizabal 5, 20018 San Sebastián (Spain); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastián (Spain); Departamento de Física de Materiales, Facultad de Químicas, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080 San Sebastián (Spain); Alducin, Maite [Centro de Física de Materiales CFM/MPC(CSIC-UPV/EHU), P. Manuel de Lardizabal 5, 20018 San Sebastián (Spain); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastián (Spain); Guo, Hua [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

    2016-07-28

    The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitations on the dissociative chemisorption of CH{sub 4}/CH{sub 3}D/CHD{sub 3} on Ni(111). The energy dissipation induced by surface electron-hole pair excitations is modeled as a friction force introduced in the generalized Langevin equation, in which the independent atomic friction coefficients are determined within the local-density friction approximation. Quasi-classical trajectory calculations for CH{sub 4}/CH{sub 3}D/CHD{sub 3} have been carried out on a recently developed twelve-dimensional potential energy surface. Comparing the dissociation probabilities obtained with and without friction, our results clearly indicate that the electron-hole pair effects are generally small, both on absolute reactivity of each vibrational state and on the mode specificity and bond selectivity. Given similar observations in both water and methane dissociation processes, we conclude that electron-hole pair excitations would not play an important role as long as the reaction is direct and the interaction time between the molecule and metal electrons is relatively short.

  18. Characterization of Isomeric Glycans by Reversed Phase Liquid Chromatography-Electronic Excitation Dissociation Tandem Mass Spectrometry

    Science.gov (United States)

    Tang, Yang; Wei, Juan; Costello, Catherine E.; Lin, Cheng

    2018-04-01

    The occurrence of numerous structural isomers in glycans from biological sources presents a severe challenge for structural glycomics. The subtle differences among isomeric structures demand analytical methods that can provide structural details while working efficiently with on-line glycan separation methods. Although liquid chromatography-tandem mass spectrometry (LC-MS/MS) is a powerful tool for mixture analysis, the commonly utilized collision-induced dissociation (CID) method often does not generate a sufficient number of fragments at the MS2 level for comprehensive structural characterization. Here, we studied the electronic excitation dissociation (EED) behaviors of metal-adducted, permethylated glycans, and identified key spectral features that could facilitate both topology and linkage determinations. We developed an EED-based, nanoscale, reversed phase (RP)LC-MS/MS platform, and demonstrated its ability to achieve complete structural elucidation of up to five structural isomers in a single LC-MS/MS analysis. [Figure not available: see fulltext.

  19. MDMA-Induced Dissociative State not Mediated by the 5-HT2A Receptor

    Directory of Open Access Journals (Sweden)

    Drew J. Puxty

    2017-07-01

    Full Text Available Previous research has shown that a single dose of MDMA induce a dissociative state, by elevating feelings of depersonalization and derealization. Typically, it is assumed that action on the 5-HT2A receptor is the mechanism underlying these psychedelic experiences. In addition, other studies have shown associations between dissociative states and biological parameters (heart rate, cortisol, which are elevated by MDMA. In order to investigate the role of the 5-HT2 receptor in the MDMA-induced dissociative state and the association with biological parameters, a placebo-controlled within-subject study was conducted including a single oral dose of MDMA (75 mg, combined with placebo or a single oral dose of the 5-HT2 receptor blocker ketanserin (40 mg. Twenty healthy recreational MDMA users filled out a dissociative states scale (CADSS 90 min after treatments, which was preceded and followed by assessment of a number of biological parameters (cortisol levels, heart rate, MDMA blood concentrations. Findings showed that MDMA induced a dissociative state but this effect was not counteracted by pre-treatment with ketanserin. Heart rate was the only biological parameter that correlated with the MDMA-induced dissociative state, but an absence of correlation between these measures when participants were pretreated with ketanserin suggests an absence of directional effects of heart rate on dissociative state. It is suggested that the 5-HT2 receptor does not mediate the dissociative effects caused by a single dose of MDMA. Further research is needed to determine the exact neurobiology underlying this effect and whether these effects contribute to the therapeutic potential of MDMA.

  20. On the determination of double diffraction dissociation cross section at HERA

    International Nuclear Information System (INIS)

    Holtmann, H.; Nikolaev, N.N.; Speth, J.; Zakharov, B.G.

    1996-01-01

    The excitation of the proton into undetected multiparticle states (double diffraction dissociation) is an important background to single diffractive deep-inelastic processes ep→e'p'ρ 0 , e'p'J/Ψ, e'p'X at HERA. We present estimates of the admixture of the double diffraction dissociation events in all diffractive events. We find that in the J/Ψ photoproduction, electroproduction of the ρ 0 at large Q 2 and diffraction dissociation of real and virtual photons into high mass states X the contamination of the double diffraction dissociation can be as large as ∼30%, thus affecting substantially the experimental tests of the pomeron exchange in deep inelastic scattering at HERA. We discuss a possibility of tagging the double diffraction dissociation by neutrons observed in the forward neutron calorimeter. We present evaluations of the spectra of neutrons and efficiency of neutron tagging based on the experimental data for diffractive processes in the proton-proton collisions. (orig.)

  1. Dissociation of NH3 and NH2D by high power CO2 laser radiation

    International Nuclear Information System (INIS)

    Jacobs, R.R.

    1976-08-01

    Multiquantum dissociation of polyatomics using intense CO 2 lasers resulting in isotopic enrichment has been demonstrated for several molecules. In this presentation, the possibility of selective dissociation of NH 3 and NH 2 D by high power laser radiation at 10 μm will be considered. Relevant work performed at the Lawrence Livermore Laboratory and elsewhere will be summarized. In this review, attention will be given to four distinct mechanisms that can play varying degrees of importance in such investigations. Discussion will deal with the usefulness of two-resonant-frequency molecular excitation, the role of buffer gases, and the need to monitor the yields into the ground and excited electronic states of the dissociated fragments

  2. Accurate adiabatic energy surfaces for the ground and first excited states of He2+

    International Nuclear Information System (INIS)

    Lee, E.P.F.

    1993-01-01

    Different factors affecting the accuracy of the computed energy surfaces of the ground and first excited state of He 2 + have been examined, including the choice of the one-and many-particle bases, the configurational space in the MRCI (multi-reference configuration interaction) calculations and other corrections such as the Davidson and the full counterpoise (CP) correction. From basis-variation studies, it was concluded that multi-reference direct-CI calculations (MRDCI) using CASSCF MOs and/or natural orbitals (NOs) from a smaller CISD calculation, gave results close to full CI. The computed dissociation energies, D e , for the ground and first excited state of He 2 + were 2.4670 (2.4659) eV and 17.2 (17.1) cm -1 , respectively, at the highest level [without and with CP correction for basis-set superposition errors (BSSE)] of calculation with an [11s8p3d1f] GTO contraction, in reasonably good agreement with previous calculations, and estimated correct values, where available. It is believed that the computed D e , and the energy surface for the first excited state should be reasonably accurate. However, for the ground state, the effects of multiple f functions and/or functions of higher angular momentum have not been investigated owing to limitation of the available computing resources. This is probably the only weakness is the present study. (Author)

  3. Quantum optimal control pathways of ozone isomerization dynamics subject to competing dissociation: A two-state one-dimensional model

    International Nuclear Information System (INIS)

    Kurosaki, Yuzuru; Ho, Tak-San; Rabitz, Herschel

    2014-01-01

    We construct a two-state one-dimensional reaction-path model for ozone open → cyclic isomerization dynamics. The model is based on the intrinsic reaction coordinate connecting the cyclic and open isomers with the O 2 + O asymptote on the ground-state 1 A ′ potential energy surface obtained with the high-level ab initio method. Using this two-state model time-dependent wave packet optimal control simulations are carried out. Two possible pathways are identified along with their respective band-limited optimal control fields; for pathway 1 the wave packet initially associated with the open isomer is first pumped into a shallow well on the excited electronic state potential curve and then driven back to the ground electronic state to form the cyclic isomer, whereas for pathway 2 the corresponding wave packet is excited directly to the primary well of the excited state potential curve. The simulations reveal that the optimal field for pathway 1 produces a final yield of nearly 100% with substantially smaller intensity than that obtained in a previous study [Y. Kurosaki, M. Artamonov, T.-S. Ho, and H. Rabitz, J. Chem. Phys. 131, 044306 (2009)] using a single-state one-dimensional model. Pathway 2, due to its strong coupling to the dissociation channel, is less effective than pathway 1. The simulations also show that nonlinear field effects due to molecular polarizability and hyperpolarizability are small for pathway 1 but could become significant for pathway 2 because much higher field intensity is involved in the latter. The results suggest that a practical control may be feasible with the aid of a few lowly excited electronic states for ozone isomerization

  4. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu; Aly, Shawkat Mohammede; Usman, Anwar; Parida, Manas R.; Del Gobbo, Silvano; Alarousu, Erkki; Mohammed, Omar F.

    2015-01-01

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  5. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu

    2015-09-02

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  6. Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

    Science.gov (United States)

    Bao, Junwei Lucas; Zhang, Xin

    2016-01-01

    Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements. PMID:27834727

  7. Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO){sub 2}I{sub 2} complex

    Energy Technology Data Exchange (ETDEWEB)

    Lehtovuori, Viivi; Kallioinen, Jani; Myllyperkioe, Pasi; Haukka, Matti; Korppi-Tommola, Jouko

    2003-11-15

    Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [trans-I-Ru(dcbpy)(CO){sub 2}I{sub 2}] (dcbpy4,4{sup '}-dicarboxy-2,2{sup '}-bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [cis-I-Ru(dcbpy)(CO)(Sol)I{sub 2}] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K indicate interligand charge transfer from mixed Ru-I states to empty dcbpy orbitals. For the photoproduct, no such transfer was observed. In both complexes recovery from the lowest energy excited triplet state to the ground state occurs via two channels: radiative relaxation and a parallel barrier controlled non-radiative relaxation. The barrier is much higher in the reactant (about 850 cm{sup -1}) than in the product. A combination of DFT and ZINDO/CI calculations was used to estimate excited singlet and triplet spectra of the reactant and the product molecules. Calculated singlet-triplet difference spectra qualitatively match the observed transient spectra 500 fs after excitation supporting the idea that observed excited state relaxation occurs from the triplet states in both complexes.

  8. Spectroscopic probes of vibrationally excited molecules at chemically significant energies

    Energy Technology Data Exchange (ETDEWEB)

    Rizzo, T.R. [Univ. of Rochester, NY (United States)

    1993-12-01

    This project involves the application of multiple-resonance spectroscopic techniques for investigating energy transfer and dissociation dynamics of highly vibrationally excited molecules. Two major goals of this work are: (1) to provide information on potential energy surfaces of combustion related molecules at chemically significant energies, and (2) to test theoretical modes of unimolecular dissociation rates critically via quantum-state resolved measurements.

  9. Molecular structures and excited states of CpM(CO)(2) (Cp = eta(5)-C(5)H(5); M = Rh, Ir) and [Cl(2)Rh(CO)(2)](-). Theoretical evidence for a competitive charge transfer mechanism.

    Science.gov (United States)

    Hu, Zhenming; Boyd, Russell J; Nakatsuji, Hiroshi

    2002-03-20

    Molecular structures and excited states of CpM(CO)(2) (Cp = eta(5)-C(5)H(5); M = Rh, Ir) and [Cl(2)Rh(CO)(2)](-) complexes have been investigated using the B3LYP and the symmetry-adapted cluster (SAC)/SAC-configuration interaction (SAC-CI) theoretical methods. All the dicarbonyl complexes have singlet ground electronic states with large singlet-triplet separations. Thermal dissociations of CO from the parent dicarbonyls are energetically unfavorable. CO thermal dissociation is an activation process for [Cl(2)Rh(CO)(2)](-) while it is a repulsive potential for CpM(CO)(2). The natures of the main excited states of CpM(CO)(2) and [Cl(2)Rh(CO)(2)](-) are found to be quite different. For [Cl(2)Rh(CO)(2)](-), all the strong transitions are identified to be metal to ligand CO charge transfer (MLCT) excitations. A significant feature of the excited states of CpM(CO)(2) is that both MLCT excitation and a ligand Cp to metal and CO charge transfer excitation are strongly mixed in the higher energy states with the latter having the largest oscillator strength. A competitive charge transfer excited state has therefore been identified theoretically for CpRh(CO)(2) and CpIr(CO)(2). The wavelength dependence of the quantum efficiencies for the photoreactions of CpM(CO)(2) reported by Lees et al. can be explained by the existence of two different types of excited states. The origin of the low quantum efficiencies for the C-H/S-H bond activations of CpM(CO)(2) can be attributed to the smaller proportion of the MLCT excitation in the higher energy states.

  10. Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules

    International Nuclear Information System (INIS)

    Kimmel, Anna V.; Sushko, Peter V.; Shluger, Alexander L.; Kuklja, Maija M.

    2007-01-01

    The authors have calculated the electronic structure of individual 1,1-diamino-2,2-dinitroethylene molecules (FOX-7) in the gas phase by means of density functional theory with the hybrid B3LYP functional and 6-31+G(d,p) basis set and considered their dissociation pathways. Positively and negatively charged states as well as the lowest excited states of the molecule were simulated. They found that charging and excitation can not only reduce the activation barriers for decomposition reactions but also change the dominating chemistry from endo- to exothermic type. In particular, they found that there are two competing primary initiation mechanisms of FOX-7 decomposition: C-NO 2 bond fission and C-NO 2 to CONO isomerization. Electronic excitation or charging of FOX-7 disfavors CONO formation and, thus, terminates this channel of decomposition. However, if CONO is formed from the neutral FOX-7 molecule, charge trapping and/or excitation results in spontaneous splitting of an NO group accompanied by the energy release. Intramolecular hydrogen transfer is found to be a rare event in FOX-7 unless free electrons are available in the vicinity of the molecule, in which case HONO formation is a feasible exothermic reaction with a relatively low energy barrier. The effect of charged and excited states on other possible reactions is also studied. Implications of the obtained results to FOX-7 decomposition in condensed state are discussed

  11. Multiphoton dissociation and thermal unimolecular reactions induced by infrared lasers

    International Nuclear Information System (INIS)

    Dai, H.L.

    1981-04-01

    Multiphoton dissociation (MPD) of ethyl chloride was studied using a tunable 3.3 μm laser to excite CH stretches. The absorbed energy increases almost linearly with fluence, while for 10 μm excitation there is substantial saturation. Much higher dissociation yields were observed for 3.3 μm excitation than for 10 μm excitation, reflecting bottlenecking in the discrete region of 10 μm excitation. The resonant nature of the excitation allows the rate equations description for transitions in the quasicontinuum and continuum to be extended to the discrete levels. Absorption cross sections are estimated from ordinary ir spectra. A set of cross sections which is constant or slowly decreasing with increasing vibrational excitation gives good fits to both absorption and dissociation yield data. The rate equations model was also used to quantitatively calculate the pressure dependence of the MPD yield of SF 6 caused by vibrational self-quenching. Between 1000-3000 cm -1 of energy is removed from SF 6 excited to approx. > 60 kcal/mole by collision with a cold SF 6 molecule at gas kinetic rate. Calculation showed the fluence dependence of dissociation varies strongly with the gas pressure. Infrared multiphoton excitation was applied to study thermal unimolecular reactions. With SiF 4 as absorbing gas for the CO 2 laser pulse, transient high temperature pulses were generated in a gas mixture. IR fluorescence from the medium reflected the decay of the temperature. The activation energy and the preexponential factor of the reactant dissociation were obtained from a phenomenological model calculation. Results are presented in detail

  12. Dissociative recombination of the CH+ molecular ion at low energy

    Science.gov (United States)

    Chakrabarti, K.; Mezei, J. Zs; Motapon, O.; Faure, A.; Dulieu, O.; Hassouni, K.; Schneider, I. F.

    2018-05-01

    The reactive collision of the CH+ molecular ion with an electron is studied in the framework of the multichannel quantum defect theory, taking into account the contribution of the core-excited Rydberg states. In addition to the X 1Σ+ ground state of the ion, we also consider the contribution to the dynamics of the a 3Π and A 1Π excited states of CH+. Our results—in the case of the dissociative recombination in good agreement with the storage ring measurements—rely on decisive improvements—complete account of the ionisation channels and accurate evaluation of the reaction matrix—of a previously used model.

  13. Extended Lagrangian Excited State Molecular Dynamics.

    Science.gov (United States)

    Bjorgaard, J A; Sheppard, D; Tretiak, S; Niklasson, A M N

    2018-02-13

    An extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born-Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both for the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. The XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree-Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).

  14. Photoionization dynamics of excited molecular states

    International Nuclear Information System (INIS)

    Dehmer, J.L.; O'Halloran, M.A.; Tomkins, F.S.; Dehmer, P.M.; Pratt, S.T.

    1987-01-01

    Resonance Enhanced Multiphoton Ionization (REMPI) utilizes tunable dye lasers to ionize an atom or molecule by first preparing an excited state by multiphoton absorption and then ionizing that state before it can decay. This process is highly selective with respect to both the initial and resonant intermediate states of the target, and it can be extremely sensitive. In addition, the products of the REMPI process can be detected as needed by analyzing the resulting electrons, ions, fluorescence, or by additional REMPI. This points to a number of opportunities for exploring excited state physics and chemistry at the quantum-state-specific level. Here we will first give a brief overview of the large variety of experimental approaches to excited state phenomena made possible by REMPI. Then we will examine in more detail, recent studies of the three photon resonant, four photon (3 + 1) ionization of H 2 via the C 'PI/sup u/ state. Strong non-Franck-Condon behavior in the photoelectron spectra of this nominally simple Rydberg state has led to the examination of a variety of dynamical mechanisms. Of these, the role of doubly excited autoionizing states now seems decisive. Progress on photoelectron studies of autoionizing states in H 2 , excited in a (2 + 1) REMPI process via the E, F 1 Σ/sub g/ + will also be briefly discussed. 26 refs., 7 figs

  15. Kinetics studies following state-selective laser excitation

    International Nuclear Information System (INIS)

    Keto, J.W.

    1994-04-01

    The objective of this contract was the study of state-to-state, electronic energy transfer reactions relevant to the excited state chemistry observed in discharges. We studied deactivation reactions and excitation transfer in collisions of excited states of xenon and krypton atoms with Ar, Kr, Xe and chlorine. The reactant states were excited selectively in two-photon transitions using tunable u.v. and v.u.v. lasers. Excited states produced by the collision were observed by their fluorescence. Reaction rates were measured by observing the time dependent decay of signals from reactant and product channels. In addition we measured interaction potentials of the reactants by laser spectroscopy where the laser induced fluorescence or ionization is measured as a function of laser wavelength (excitation spectra) or by measuring fluorescence spectra at fixed laser frequencies with monochromators. The spectra were obtained in the form of either lineshapes or individual lines from rovibrational transitions of bound states. Our research then required several categories of experiments in order to fully understand a reaction process: 1. High resolution laser spectroscopy of bound molecules or lineshapes of colliding pairs is used to determine potential curves for reactants. 2. Direct measurements of state-to-state reaction rates were measured by studying the time dependent loss of excited reactants and the time dependent formation of products. 3. The energy selectivity of a laser can be used to excite reactants on an excited surface with controlled internuclear configurations. For free states of reactants (as exist in a gas cell) this has been termed laser assisted reactions, while for initially bound states (as chemically bound reactants or dimers formed in supersonic beams) the experiments have been termed photo-fragmentation spectroscopy

  16. CT-state dissociation and charge recombination in OPVs

    Energy Technology Data Exchange (ETDEWEB)

    Haeusermann, Roger; Reinke, Nils; Huber, Evelyne; Ruhstaller, Beat [ZHAW, Inst. of Computational Physics, Winterthur (Switzerland); Flatz, Thomas; Moos, Michael [Fluxim AG (Germany)

    2009-07-01

    The dissociation of the charge-transfer-state (CT) into free charge carriers is a very important process in the modeling of OPVs. A theoretical description of this mechanism has been developed by Onsager and Braun. The implications of this theory in real OPVs is not completely clear. Recently there was the proposition to reduce the whole device physics to the mechanisms at the donor-acceptor interface. This has been verified for a wide range of OPV materials, but it also raises questions about the universality of this simplification. In this study we developed a comprehensive device simulator. Our simulations have shown that a good agreement with measured J-V curves can be found by omitting any dissociation mechanism but at the same time increasing the influence of the Langevin recombination. This shows that distinct features of J-V curves are multi-causal and therefore a simplification by leaving out some of the mechanisms leads to an overestimation of the influence of other processes. We present the influence of the input parameters (CT-state dissociation, recombination and mobility) on the J-V curves and discuss in detail where and if each parameter can be seen separately in the shape of the J-V curve. The contributions of the different loss mechanisms, namely decay of excitons and CT-states as well as charge recombination will be addressed as function of material properties.

  17. The mechanisms of Excited states in enzymes

    DEFF Research Database (Denmark)

    Petersen, Frederic Nicolas Rønne; Bohr, Henrik

    2010-01-01

    Enzyme catalysis is studied on the basis of excited state processes, which are of electronic, vibrational and thermal nature. The ways of achieving the excited state, such as photo-absorption and ligand binding, are discussed and exemplified by various cases of enzymes.......Enzyme catalysis is studied on the basis of excited state processes, which are of electronic, vibrational and thermal nature. The ways of achieving the excited state, such as photo-absorption and ligand binding, are discussed and exemplified by various cases of enzymes....

  18. Excited state Intramolecular Proton Transfer in Anthralin

    DEFF Research Database (Denmark)

    Møller, Søren; Andersen, Kristine B.; Spanget-Larsen, Jens

    1998-01-01

    Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results in an unus......Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results......, associated with an excited-state intramolecular proton transfer process....

  19. Wave Packet Simulation of Nonadiabatic Dynamics in Highly Excited 1,3-Dibromopropane

    DEFF Research Database (Denmark)

    Brogaard, Rasmus Y.; Møller, Klaus Braagaard; Sølling, Theis Ivan

    2008-01-01

    ]. In the experiment. DBP is excited to a Rydberg state 8 eV above the ground state. The interpretation of the results is that a torsional motion of the bromomethylene groups with a vibrational period of 680 is is activated upon excitation. The Rydberg state decays to a valence state, causing a dissociation of one...... of the carbon bromine bonds oil a time scale of 2.5 ps. Building the theoretical framework for the wave packet propagation around this model of the reaction dynamics, the Simulations reproduce, to a good extent, the time scales observed in the experiment. Furthermore. the Simulations provide insight into how...... the torsion motion influences the bond breakage, and C we can conclude that the mechanism that delays the dissociation is solely the electronic transition from the Rydberg state to the valence state and does not involve, for example, intramolecular vibrational energy redistribution (IVR)....

  20. Excited-state imaging of cold atoms

    NARCIS (Netherlands)

    Sheludko, D.V.; Bell, S.C.; Vredenbregt, E.J.D.; Scholten, R.E.; Deshmukh, P.C.; Chakraborty, P.; Williams, J.F.

    2007-01-01

    We have investigated state-selective diffraction contrast imaging (DCI) of cold 85Rb atoms in the first excited (52P3/2) state. Excited-state DCI requires knowledge of the complex refractive index of the atom cloud, which was calculated numerically using a semi-classical model. The Autler-Townes

  1. Molecular dissociation and nascent product state distributions detected with atomic wavepacket interferometry and parametric four-wave mixing: Rb2 predissociation observed by quantum beating in Rb at 18.2 THz

    International Nuclear Information System (INIS)

    Xiao, Y; Senin, A A; Ricconi, B J; Kogler, R; Zhu, C J; Eden, J G

    2008-01-01

    Dissociation of a diatomic molecule and the excited-state distribution of the nascent atomic fragments can be detected and characterized by atomic wavepacket interferometry and a coherent nonlinear optical process, such as parametric four-wave mixing (PFWM), in ultrafast pump-probe experiments. Underlying these experiments is a reliance on atom-atom interaction to alter the properties of an atomic wavepacket which, in turn, impacts the phase and amplitude of a coherent optical signal. Specifically, quantum beating in the atomic species provides a sensitive, in situ probe of molecular dissociation by detecting approaching dissociation fragments through long-range dipole-dipole interaction. The resulting influence of this interaction on the amplitude and phase of the quantum beating is observed in temporal or Fourier domains by probing the wavepacket by interferometry and PFWM with 100-150 fs laser pulses. The wavepacket thus serves as a detector of molecular dissociation fragments and the dynamics of atom-atom interactions are converted into the macroscopic domain by the PFWM signal and idler waves. Femtosecond pump-probe experiments are described in which the predissociation of electronically excited Rb 2 states in the ∼24 000-28 000 cm -1 interval, and the distribution of nascent atomic fragments into Rb excited states (7s, 5d, 6s, 4d and 5p) spanning an energy range >1.25 eV, have been observed in Rb vapour with atomic number densities of ∼6 x 10 13 -3 x 10 17 cm -3 . Quantum beating at 18.2 THz (corresponding to the Rb 7s-5d J (J = 5/2) energy defect of ∼608 cm -1 ) is superimposed onto the axially phase matched PFWM signal wave generated at λ S ∼ 420 nm (Rb 6 2 P J → 5 2 S 1/2 transitions) and recovered by Fourier analysis of the signal wave intensity as the pump-probe time delay (Δt) is scanned. The dominant exit channels for Rb 2 predissociation are found to be sensitive to the interval of internuclear separation R in which the molecular

  2. Optical studies of multiply excited states

    International Nuclear Information System (INIS)

    Mannervik, S.

    1989-01-01

    Optical studies of multiply-excited states are reviewed with emphasis on emission spectroscopy. From optical measurements, properties such as excitation energies, lifetimes and autoionization widths can be determined with high accuracy, which constitutes a challenge for modern computational methods. This article mainly covers work on two-, three- and four-electron systems, but also sodium-like quartet systems. Furthermore, some comments are given on bound multiply-excited states in negative ions. Fine structure effects on transition wavelengths and lifetimes (autoionization) are discussed. In particular, the most recent experimental and theoretical studies of multiply-excited states are covered. Some remaining problems, which require further attention, are discussed in more detail. (orig.) With 228 refs

  3. Entanglement entropy of excited states

    International Nuclear Information System (INIS)

    Alba, Vincenzo; Fagotti, Maurizio; Calabrese, Pasquale

    2009-01-01

    We study the entanglement entropy of a block of contiguous spins in excited states of spin chains. We consider the XY model in a transverse field and the XXZ Heisenberg spin chain. For the latter, we developed a numerical application of the algebraic Bethe ansatz. We find two main classes of states with logarithmic and extensive behavior in the dimension of the block, characterized by the properties of excitations of the state. This behavior can be related to the locality properties of the Hamiltonian having a given state as the ground state. We also provide several details of the finite size scaling

  4. Search for mode-selective chemistry: The unimolecular dissociation of t-butyl hydroperoxide induced by vibrational overtone excitation

    International Nuclear Information System (INIS)

    Chandler, D.W.; Farneth, W.E.; Zare, R.N.

    1982-01-01

    The use of optoacoustic spectroscopy permits both the monitoring of the overtone excitation of t-butylhydroperoxide (t-BuOOH) and the in situ detection of the resulting reaction product t-butanol (t-BuOH). The sample is contained in a reaction cell, equipped with a microphone, in which all surfaces have been specially passivated. The cell is placed inside the cavity of a dye laser tuned to excite the 5--0 O--H stretch of the t-BuOOH at 619.0 nm. The dissociation process yields directly xOH and t-BuOx, and the latter readily abstracts a hydrogen atom from a parent molecule to form t-butanol (t-BuOH). The appearance rate of t-BuOH is obtained by ratioing the area under the 5--0 O--H stretch of t-BuOH to that of a combination band of t-BuOOH. At low pressures, below 40 Torr, a plot of the reciprocal of the t-BuOH appearance rate versus total pressure shows near linear behavior. This linearlity can be well described by a statistical model (RRKM) when careful averaging of the dissociation rate over the thermal energy distribution of the photoactivated molecules is included. At pressures above 40 Torr, a marked deviation from linearity appears. This deviation is fit to a kinetic model in which the dissociation rate of an energy nonrandomized molecule competes with the rate of intramolecular energy relaxation. This places a lower bound of > or =5.0 x 10 11 s -1 on the rate of energy randomization. A discussion of this model in the context of other possible kinetic schemes as well as other photoactivated and chemically activated systems is presented

  5. Cross-section and rate coefficient calculation for electron impact excitation, ionisation and dissociation of H2 and OH molecules

    International Nuclear Information System (INIS)

    Riahi, R.; Ben Lakhdar, Z.; Teulet, Ph.; Gleizes, A.

    2006-01-01

    The weighted total cross-sections (WTCS) theory is used to calculate electron impact excitation, ionization and dissociation cross-sections and rate coefficients of OH, H 2 , OH + , H 2 + , OH - and H 2 - diatomic molecules in the temperature range 1500-15000 K. Calculations are performed for H 2 (X, B, C), OH(X, A, B), H 2 + (X), OH + (X, a, A, b, c), H 2 - (X) and OH - (X) electronic states for which Dunham coefficients are available. Rate coefficients are calculated from WTCS assuming Maxwellian energy distribution functions for electrons and heavy particles. One and 2 temperatures (θ e and θ g respectively for electron and heavy particles kinetic temperatures) results are presented and fitting parameters (a, b and c) are given for each reaction rate coefficient: k(θ) a(θ b )exp(-c/θ). (authors)

  6. Characterization of weakly excited final states by shakedown spectroscopy of laser-excited potassium

    International Nuclear Information System (INIS)

    Schulz, J.; Heinaesmaeki, S.; Aksela, S.; Aksela, H.; Sankari, R.; Rander, T.; Lindblad, A.; Bergersen, H.; Oehrwall, G.; Svensson, S.; Kukk, E.

    2006-01-01

    3p shakedown spectra of laser excited potassium atoms as well as direct 3p photoemission of ground state potassium have been studied. These two excitation schemes lead to the same final states and thereby provide a good basis for a detailed study of the 3p 5 (4s3d) 1 configurations of singly ionized potassium and the photoemission processes leading to these configurations. The comparison of direct photoemission from the ground state and conjugate shakedown spectra from 4p 1/2 laser excited potassium made it possible to experimentally determine the character of final states that are only weakly excited in the direct photoemission but have a much higher relative intensity in the shakedown spectrum. Based on considerations of angular momentum and parity conservation the excitation scheme of the final states can be understood

  7. Excited states configurations of the quantum Toda lattice

    International Nuclear Information System (INIS)

    Matsuyama, A.

    2001-01-01

    Excited states configurations of the quantum Toda lattice are studied by the direct diagonalization of the Hamiltonian. The most probable configurations of one-hole and one-particle excitations are shown to be similar to the profiles of classical phonon and soliton excitations, respectively. One-hole excitation states, which are always ground states of definite E m -symmetry of the dihedral group D N , change those structures abruptly with the potential range varied. One-particle excitations, which are buried in complicated excitation spectra, have well-defined configurations similar to the conoidal profile of the classical periodic Toda lattice. The relationship that the hole (particle) excitations in quantum mechanics correspond to the phonon (soliton) excitations in classical mechanics, which has been suggested based on the similarity of dispersion relations, is confirmed in a geometrically understandable way. Based on the study of one-soliton and two-soliton states, the structure of multi-soliton states in quantum mechanics can be conjectured

  8. New Theoretical Developments in Exploring Electronically Excited States: Including Localized Configuration Interaction Singles and Application to Large Helium Clusters

    Science.gov (United States)

    Closser, Kristina Danielle

    superpositions of atomic states with surface states appearing close to the atomic excitation energies and interior states being blue shifted by up to ≈2 eV. The dynamics resulting from excitation of He_7 were subsequently explored using ab initio molecular dynamics (AIMD). These simulations were performed with classical adiabatic dynamics coupled to a new state-following algorithm on CIS potential energy surfaces. Most clusters were found to completely dissociate and resulted in a single excited atomic state (90%), however, some trajectories formed bound, He*2 (3%), and a few yielded excited trimers (<0.5%). Comparisons were made with available experimental information on much larger clusters. Various applications of this state following algorithm are also presented. In addition to AIMD, these include excited-state geometry optimization and minimal energy path finding via the growing string method. When using state following we demonstrate that more physical results can be obtained with AIMD calculations. Also, the optimized geometries of three excited states of cytosine, two of which were not found without state following, and the minimal energy path between the lowest two singlet excited states of protonated formaldimine are offered as example applications. Finally, to address large clusters, a local variation of CIS was developed. This method exploits the properties of absolutely localized molecular orbitals (ALMOs) to limit the total number of excitations to scaling only linearly with cluster size, which results in formal scaling with the third power of the system size. The derivation of the equations and design of the algorithm are discussed in detail, and computational timings as well as a pilot application to the size dependence of the helium cluster spectrum are presented.

  9. Ionization and dissociation dynamics of vinyl bromide probed by femtosecond extreme ultraviolet transient absorption spectroscopy

    International Nuclear Information System (INIS)

    Lin, Ming-Fu; Neumark, Daniel M.; Gessner, Oliver; Leone, Stephen R.

    2014-01-01

    Strong-field induced ionization and dissociation dynamics of vinyl bromide, CH 2 =CHBr, are probed using femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy. Strong-field ionization is initiated with an intense femtosecond, near infrared (NIR, 775 nm) laser field. Femtosecond XUV pulses covering the photon energy range of 50-72 eV probe the subsequent dynamics by measuring the time-dependent spectroscopic features associated with transitions of the Br (3d) inner-shell electrons to vacancies in molecular and atomic valence orbitals. Spectral signatures are observed for the depletion of neutral C 2 H 3 Br, the formation of C 2 H 3 Br + ions in their ground (X ~ ) and first excited (A ~ ) states, the production of C 2 H 3 Br ++ ions, and the appearance of neutral Br ( 2 P 3/2 ) atoms by dissociative ionization. The formation of free Br ( 2 P 3/2 ) atoms occurs on a timescale of 330 ± 150 fs. The ionic A ~ state exhibits a time-dependent XUV absorption energy shift of ∼0.4 eV within the time window of the atomic Br formation. The yield of Br atoms correlates with the yield of parent ions in the A ~ state as a function of NIR peak intensity. The observations suggest that a fraction of vibrationally excited C 2 H 3 Br + (A ~ ) ions undergoes intramolecular vibrational energy redistribution followed by the C–Br bond dissociation. The C 2 H 3 Br + (X ~ ) products and the majority of the C 2 H 3 Br ++ ions are relatively stable due to a deeper potential well and a high dissociation barrier, respectively. The results offer powerful new insights about orbital-specific electronic processes in high field ionization, coupled vibrational relaxation and dissociation dynamics, and the correlation of valence hole-state location and dissociation in polyatomic molecules, all probed simultaneously by ultrafast table-top XUV spectroscopy

  10. Excited states rotational effects on the behavior of excited molecules

    CERN Document Server

    Lim, Edward C

    2013-01-01

    Excited States, Volume 7 is a collection of papers that discusses the excited states of molecules. The first paper reviews the rotational involvement in intra-molecular in vibrational redistribution. This paper analyzes the vibrational Hamiltonian as to its efficacy in detecting the manifestations of intra-molecular state-mixing in time-resolved and time-averaged spectroscopic measurements. The next paper examines the temporal behavior of intra-molecular vibration-rotation energy transfer (IVRET) and the effects of IVRET on collision, reaction, and the decomposition processes. This paper also

  11. Angular-momentum-assisted dissociation of CO in strong optical fields

    Science.gov (United States)

    Mullin, Amy; Ogden, Hannah; Murray, Matthew; Liu, Qingnan; Toro, Carlos

    2017-04-01

    Filaments are produced in CO gas by intense, chirped laser pulses. Visible emission from C2 is observed as a result of chemical reactions of highly excited CO. At laser intensities greater than 1014 W cm-2, the C2 emission shows a strong dependence on laser polarization. Oppositely chirped pulses of light with ω0 = 800 nm are recombined spatially and temporally to generate angularly accelerating electric fields (up to 30 THz) that either have an instantaneous linear polarization or act as a dynamic polarization grating that oscillates among linear and circular polarizations. The angularly accelerating linear polarization corresponds to an optical centrifuge that concurrently drives molecules into high rotational states (with J 50) and induces strong-field dissociation. Higher order excitation is observed for the time-varying laser polarization configuration that does not induce rotational excitation. The results indicate that the presence of rotational angular momentum lowers the threshold for CO dissociation in strong optical fields by coupling nuclear and electronic degrees of freedom. Support from NSF CHE-1058721 and the University of Maryland.

  12. Electric quadrupole excitation of the first excited state of 11B

    International Nuclear Information System (INIS)

    Fewell, M.P.; Spear, R.H.; Zabel, T.H.; Baxter, A.M.

    1980-02-01

    The Coulomb excitation of backscattered 11 B projectiles has been used to measure the reduced E2 transition probability B(E2; 3/2 - →1/2 - ) between the 3/2 - ground state and the 1/2 - first excited state of 11 B. It is found that B(E2; 3/2 - →1/2 - ) = 2.1 +- 0.4 e 2 fm 4 , which agrees with shell-model predictions but is a factor of 10 larger than the prediction of the core-excitation model

  13. Dissociative charge exchange of H2+

    International Nuclear Information System (INIS)

    Bruijn, D. de.

    1983-01-01

    This thesis is devoted to molecular dissociation, in particular the dissociation of the hydrogen molecule H 2 arising from electron capture of its ion H 2 + in a collision. Thereby the important practical question how a chemical bond can be broken is implicitly addressed. This thesis opens (chapter I) with an overview of the available experimental approaches in molecular physics. Further the simple Demkov model for NRCE is described. In chapter II a novel experimental technique for measurements on dissociative processes is introduced which combines a high efficiency with a high energy resolution. A detailed description of the techniques applied in the detector, which has a high spatial and timing resolution with 30 μm and 350 psec FWHM respectively for the detection of one particle, is given in chapter III. A semi-classical theory for NRCE in the medium energy range between a diatomic molecular ion and an atom is developed in chapter IV. The experiments on dissociative charge exchange of H 2 + with Ar, Mg, Na and Cs targets at keV energies are described in Chapter V. The predissociation of the c 3 PIsub(u)-state of H 2 populated after charge exchange of H 2 with several targets at keV energies; is the subject of chapter VI. In chapter VII, orientational oscillations in the cross section for charge exchange of H 2 + with alkali targets are discussed. The last chapter deals with predissociation of highly excited states in H 2 . (Auth.)

  14. Spectroscopic constants and the potential energy curve of the iodine weakly bound 0+g state correlating with the I(2P1/2) + I(2P1/2) dissociation limit

    International Nuclear Information System (INIS)

    Akopyan, M E; Baturo, V V; Lukashov, S S; Poretsky, S A; Pravilov, A M

    2013-01-01

    The stepwise three-step three-colour aser excitation scheme and rotational as well as rovibrational energy transfer processes in the 0 + g state induced by collisions with He and Ar atoms are used for determination of rovibronic level energies of the weakly bound 0 + g state correlating with the I( 2 P 1/2 ) + I( 2 P 1/2 ) dissociation limit. Dunham coefficients of the state, Y i0 (i = 0–3), Y i1 (i = 0–3) and Y 02 for the v 0 g + = 0–16 and J 0 g + ≈ 14–135 ranges as well as the dissociation energy of the state, D e , and equilibrium I–I distance of the state, R e , are determined. The potential energy curve of the state constructed using these constants is also reported. (paper)

  15. Superior colliculus resting state networks in post-traumatic stress disorder and its dissociative subtype.

    Science.gov (United States)

    Olivé, Isadora; Densmore, Maria; Harricharan, Sherain; Théberge, Jean; McKinnon, Margaret C; Lanius, Ruth

    2018-01-01

    The innate alarm system (IAS) models the neurocircuitry involved in threat processing in posttraumatic stress disorder (PTSD). Here, we investigate a primary subcortical structure of the IAS model, the superior colliculus (SC), where the SC is thought to contribute to the mechanisms underlying threat-detection in PTSD. Critically, the functional connectivity between the SC and other nodes of the IAS remains unexplored. We conducted a resting-state fMRI study to investigate the functional architecture of the IAS, focusing on connectivity of the SC in PTSD (n = 67), its dissociative subtype (n = 41), and healthy controls (n = 50) using region-of-interest seed-based analysis. We observed group-specific resting state functional connectivity between the SC for both PTSD and its dissociative subtype, indicative of dedicated IAS collicular pathways in each group of patients. When comparing PTSD to its dissociative subtype, we observed increased resting state functional connectivity between the left SC and the right dorsolateral prefrontal cortex (DLPFC) in PTSD. The DLPFC is involved in modulation of emotional processes associated with active defensive responses characterising PTSD. Moreover, when comparing PTSD to its dissociative subtype, increased resting state functional connectivity was observed between the right SC and the right temporoparietal junction in the dissociative subtype. The temporoparietal junction is involved in depersonalization responses associated with passive defensive responses typical of the dissociative subtype. Our findings suggest that unique resting state functional connectivity of the SC parallels the unique symptom profile and defensive responses observed in PTSD and its dissociative subtype. Hum Brain Mapp 39:563-574, 2018. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  16. A note on calm excited states of inflation

    International Nuclear Information System (INIS)

    Ashoorioon, Amjad; Shiu, Gary

    2011-01-01

    We identify a two-parameter family of excited states within slow-roll inflation for which either the corrections to the two-point function or the characteristic signatures of excited states in the three-point function — i.e. the enhancement for the flattened momenta configurations– are absent. These excited states may nonetheless violate the adiabaticity condition maximally. We dub these initial states of inflation calm excited states. We show that these two sets do not intersect, i.e., those that leave the power-spectrum invariant can be distinguished from their bispectra, and vice versa. The same set of calm excited states that leave the two-point function invariant for slow-roll inflation, do the same task for DBI inflation. However, at the level of three-point function, the calm excited states whose flattened configuration signature is absent for slow-roll inflation, will lead to an enhancement for DBI inflation generally, although the signature is smaller than what suggested by earlier analysis. This example also illustrates that imposing the Wronskian condition is important for obtaining a correct estimate of the non-Gaussian signatures

  17. Double resonance spectroscopy of the D1Πu+ and B′′ B-bar 1Σu+ states near the third dissociation threshold of H2

    International Nuclear Information System (INIS)

    Ekey, R C; Cordova, A E; Duan, W; Chartrand, A M; McCormack, E F

    2013-01-01

    Double-resonance laser spectroscopy via the E,F 1 Σ g + ,v ′ =6,J ′ state was used to probe the energy region below the third dissociation limit of molecular hydrogen. Resonantly enhanced multi-photon ionization spectra were recorded by detecting ion production as a function of energy using a time-of-flight mass spectrometer. Energies and line widths for the v = 14–17 levels of the D 1 Π u + state of H 2 are reported and compared to experimental data obtained by using VUV synchrotron light excitation (Dickenson et al 2010 J. Chem. Phys. 133 144317) and fully ab initio non-adiabatic calculations of D 1 Π u + state energies and line widths (Glass-Maujean et al 2012 Phys. Rev. A 86 052507). Several high vibrational levels of the B ′′ B-bar 1 Σ u + state were also observed in this region. Term energies and rotational constants for the v = 67–69 vibrational levels are reported and compared to highly accurate ro-vibrational energy level predictions from fully ab initio non-adiabatic calculations of the first six 1 Σ u + levels of H 2 (Wolniewicz et al 2006 J. Mol. Spectrosc. 238 118). While additional observed transitions can be assigned to other states, several unassigned features in the spectra highlight the need for a fully integrated theoretical treatment of dissociation and ionization to understand the complex pattern of highly vibrationally excited states expected in this region. (paper)

  18. Excitation and multiple dissociation of 12C, 14N, and 16O projectiles in peripheral collisions at 32.5 MeV/nucleon

    International Nuclear Information System (INIS)

    Pouliot, J.; Chan, Y.; DiGregorio, D.E.; Harmon, B.A.; Knop, R.; Moisan, C.; Roy, R.; Stokstad, R.G.; Laboratoire de physique nucleaire, Universite Laval, Quebec, P.Q., Canada G1K7P4)

    1991-01-01

    Cross sections for the multiple breakup of 16 O, 14 N, and 12 C projectiles scattered by an Au target were measured with an array of 34 phoswich detectors. The dissociation of the projectiles into as many as five charged particles has been observed. The yields of different exit channels correlate approximately with the threshold energy for separation of the projectile into the observed fragments. The excitation spectrum of the primary projectile-like nucleus was reconstructed from the measured positions and kinetic energies of the individual fragments. The energy sharing between projectile and target is consistent with a fast excitation mechanism in which differential increases in projectile excitation energy appear to be accompanied by comparable increases in target excitation. Calculations of the yields based on a sequence of binary decays are presented

  19. Dissociative part-dependent resting-state activity in dissociative identity disorder: a controlled FMRI perfusion study.

    Science.gov (United States)

    Schlumpf, Yolanda R; Reinders, Antje A T S; Nijenhuis, Ellert R S; Luechinger, Roger; van Osch, Matthias J P; Jäncke, Lutz

    2014-01-01

    In accordance with the Theory of Structural Dissociation of the Personality (TSDP), studies of dissociative identity disorder (DID) have documented that two prototypical dissociative subsystems of the personality, the "Emotional Part" (EP) and the "Apparently Normal Part" (ANP), have different biopsychosocial reactions to supraliminal and subliminal trauma-related cues and that these reactions cannot be mimicked by fantasy prone healthy controls nor by actors. Arterial spin labeling perfusion MRI was used to test the hypotheses that ANP and EP in DID have different perfusion patterns in response to rest instructions, and that perfusion is different in actors who were instructed to simulate ANP and EP. In a follow-up study, regional cerebral blood flow of DID patients was compared with the activation pattern of healthy non-simulating controls. Compared to EP, ANP showed elevated perfusion in bilateral thalamus. Compared to ANP, EP had increased perfusion in the dorsomedial prefrontal cortex, primary somatosensory cortex, and motor-related areas. Perfusion patterns for simulated ANP and EP were different. Fitting their reported role-play strategies, the actors activated brain structures involved in visual mental imagery and empathizing feelings. The follow-up study demonstrated elevated perfusion in the left temporal lobe in DID patients, whereas non-simulating healthy controls had increased activity in areas which mediate the mental construction of past and future episodic events. DID involves dissociative part-dependent resting-state differences. Compared to ANP, EP activated brain structures involved in self-referencing and sensorimotor actions more. Actors had different perfusion patterns compared to genuine ANP and EP. Comparisons of neural activity for individuals with DID and non-DID simulating controls suggest that the resting-state features of ANP and EP in DID are not due to imagination. The findings are consistent with TSDP and inconsistent with the idea

  20. Dissociative part-dependent resting-state activity in dissociative identity disorder: a controlled FMRI perfusion study.

    Directory of Open Access Journals (Sweden)

    Yolanda R Schlumpf

    Full Text Available In accordance with the Theory of Structural Dissociation of the Personality (TSDP, studies of dissociative identity disorder (DID have documented that two prototypical dissociative subsystems of the personality, the "Emotional Part" (EP and the "Apparently Normal Part" (ANP, have different biopsychosocial reactions to supraliminal and subliminal trauma-related cues and that these reactions cannot be mimicked by fantasy prone healthy controls nor by actors.Arterial spin labeling perfusion MRI was used to test the hypotheses that ANP and EP in DID have different perfusion patterns in response to rest instructions, and that perfusion is different in actors who were instructed to simulate ANP and EP. In a follow-up study, regional cerebral blood flow of DID patients was compared with the activation pattern of healthy non-simulating controls.Compared to EP, ANP showed elevated perfusion in bilateral thalamus. Compared to ANP, EP had increased perfusion in the dorsomedial prefrontal cortex, primary somatosensory cortex, and motor-related areas. Perfusion patterns for simulated ANP and EP were different. Fitting their reported role-play strategies, the actors activated brain structures involved in visual mental imagery and empathizing feelings. The follow-up study demonstrated elevated perfusion in the left temporal lobe in DID patients, whereas non-simulating healthy controls had increased activity in areas which mediate the mental construction of past and future episodic events.DID involves dissociative part-dependent resting-state differences. Compared to ANP, EP activated brain structures involved in self-referencing and sensorimotor actions more. Actors had different perfusion patterns compared to genuine ANP and EP. Comparisons of neural activity for individuals with DID and non-DID simulating controls suggest that the resting-state features of ANP and EP in DID are not due to imagination. The findings are consistent with TSDP and inconsistent

  1. Metastablity of the undissociated state of dissociated dislocations

    International Nuclear Information System (INIS)

    Takeuchi, Shin

    2005-01-01

    Undissociated, metastable dislocations have been observed in various crystals in addition to stable dissociated dislocations by high-resolution transmission electron microscopy. The origin of the metastablity of the undissociated state has been discussed specifically for the dissociation into Shockley partial dislocations in fcc or hcp lattice. It is shown that the metastability is due either to a high Peierls-Nabarro stress larger than a few percent of the shear modulus of the partial dislocations and/or to the increase of the total core energy by an increase of the dangling bonds. The metastablity of undissociated dislocations in zincblende III-V compounds is concluded to be due to a contribution of the latter effect

  2. Process to produce excited states of atomic nuclei

    International Nuclear Information System (INIS)

    Morita, M.; Morita, R.

    The claims of a patented process which relates to the production of excited states of atomic nuclei are outlined. Among these are (1) production of nuclear excited states by bombarding the atoms with x rays or electrons under given conditions, (2) production of radioactive substances by nuclear excitation with x rays or electrons, (3) separation of specific isotopes from a mixture of isotopes of the same element by means of nuclear excitation followed by chemical treatment. The invention allows production of excited states of atomic nuclei in a relatively simple manner without the need of large apparatus and equipment

  3. Behavior of Excited Argon Atoms in Inductively Driven Plasmas

    International Nuclear Information System (INIS)

    HEBNER, GREGORY A.; MILLER, PAUL A.

    1999-01-01

    Laser induced fluorescence has been used to measure the spatial distribution of the two lowest energy argon excited states, 1s 5 and 1s 4 , in inductively driven plasmas containing argon, chlorine and boron trichloride. The behavior of the two energy levels with plasma conditions was significantly different, probably because the 1s 5 level is metastable and the 1s 4 level is radiatively coupled to the ground state but is radiation trapped. The argon data is compared with a global model to identify the relative importance of processes such as electron collisional mixing and radiation trapping. The trends in the data suggest that both processes play a major role in determining the excited state density. At lower rfpower and pressure, excited state spatial distributions in pure argon were peaked in the center of the discharge, with an approximately Gaussian profile. However, for the highest rfpowers and pressures investigated, the spatial distributions tended to flatten in the center of the discharge while the density at the edge of the discharge was unaffected. The spatially resolved excited state density measurements were combined with previous line integrated measurements in the same discharge geometry to derive spatially resolved, absolute densities of the 1s 5 and 1s 4 argon excited states and gas temperature spatial distributions. Fluorescence lifetime was a strong fi.mction of the rf power, pressure, argon fraction and spatial location. Increasing the power or pressure resulted in a factor of two decrease in the fluorescence lifetime while adding Cl 2 or BCl 3 increased the fluorescence lifetime. Excited state quenching rates are derived from the data. When Cl 2 or BCl 3 was added to the plasma, the maximum argon metastable density depended on the gas and ratio. When chlorine was added to the argon plasma, the spatial density profiles were independent of chlorine fraction. While it is energetically possible for argon excited states to dissociate some of the

  4. Electromagnetic dissociation of relativistic [sup 28]Si by nucleon emission

    Energy Technology Data Exchange (ETDEWEB)

    Sonnadara, U.J.

    1992-12-01

    A detailed study of the electromagnetic dissociation of [sup 28]Si by nucleon emission at E[sub lab]/A = 14.6 (GeV/nucleon was carried out with [sup 28]Si beams interacting on [sup 208]Pb). [sup 120]Sn. [sup 64]C targets. The measurements apparatus consists of detectors in the target area which measure the energy and charged multiplicity, and a forward spectrometer which measures the position, momentum and energy of the reaction fragments. The exclusive electromagnetic dissociation cross sections for decay channels having multiple nucleons in the final state have been measured which enables the selection of events produced in pure electromagnetic interactions. The measured cross sections agree well with previous measurements obtained for the removal of a few nucleons as well as with measurements on total charge removal cross sections from other experiments. The dependence of the integrated cross sections on the target charge Z[sub T] and the target mass AT confirms that for higher Z targets the excitation is largely electromagnetic. Direct measurements of the excitation energy for the electromagnetic dissociation of [sup 28]Si [yields] p+[sup 27]Al and [sup 28]Si [yields] n+[sup 27]Si have been obtained through a calculation of the invariant mass in kinematically, reconstructed events. The excitation energy spectrum for all targets peak near the isovector giant dipole resonance in [sup 28]Si. These distributions are well reproduced by combining the photon spectrum calculated using the Weizsaecker-Williams approximation with the experimental data on the photonuclear [sup 28]Si([sub [gamma],p])[sup 27]Al and [sup 28]Si([sub [gamma],n])[sup 27]Si. The possibilities of observing double giant dipole resonance excitations in [sup 28]Si have been investigated with cross section measurements as well as with excitation energy reconstruction.

  5. Photoionization of excited molecular states using multiphoton excitation techniques

    International Nuclear Information System (INIS)

    Dehmer, P.M.; Pratt, S.T.; Dehmer, J.L.

    1984-01-01

    Photoelectron spectra are reported for three photon resonant, four photon ionization of H 2 via the B 1 Σ + /sub u/, v = 7 (J = 2,4) and C 1 Pi/sub u/, v = 0-4 (J = 1) levels and of N 2 via the o 3 1 Pi/sub u/, v = 1,2, b 1 Pi/sub u/, v = 3-5, and c 1 Pi/sub u/, v = 0 levels. The results reflect both the spectroscopy and the dynamics of photoionization of excited molecular states and are discussed in terms of the selection rules for photoionization and the relative probabilities of photoionization from Rydberg and valence states. In some cases, in accordance with the Franck-Condon principle, the results demonstrate that resonant multiphoton ionization through Rydberg states may be a powerful technique for the production of electronic, vibrational, and rotational state selected ions. However, in other cases, systematic departures from Franck-Condon factors are observed, which reflect the more subtle dynamics of excited state photoionization

  6. Ultrafast excited state relaxation in long-chain polyenes

    International Nuclear Information System (INIS)

    Antognazza, Maria Rosa; Lueer, Larry; Polli, Dario; Christensen, Ronald L.; Schrock, Richard R.; Lanzani, Guglielmo; Cerullo, Giulio

    2010-01-01

    Graphical abstract: Excited state dynamics of a long-chain polyene studied by femtosecond pump-probe spectroscopy. - Abstract: We present a comprehensive study, by femtosecond pump-probe spectroscopy, of excited state dynamics in a polyene that approaches the infinite chain limit. By excitation with sub-10-fs pulses resonant with the 0-0 S 0 → S 2 transition, we observe rapid loss of stimulated emission from the bright excited state S 2 , followed by population of the hot S 1 state within 150 fs. Vibrational cooling of S 1 takes place within 500 fs and is followed by decay back to S 0 with 1 ps time constant. By excitation with excess vibrational energy we also observe the ultrafast formation of a long-living absorption, that is assigned to the triplet state generated by singlet fission.

  7. Excited state kinetics of anthracene-bridge-aniline intramolecular exciplexes

    DEFF Research Database (Denmark)

    Thyrhaug, Erling; Hammershøj, Peter; Kjær, Kasper Skov

    2014-01-01

    excited anthracene state (LE) and an excited state complex (exciplex, EP) in non-polar solvents. The kinetics of the excited state processes were established in decalin from the time-resolved emission, and was shown to be strongly influenced by an electron-transfer state (ET). For quantitative studies...

  8. Charge transfer excitations from excited state Hartree-Fock subsequent minimization scheme

    International Nuclear Information System (INIS)

    Theophilou, Iris; Tassi, M.; Thanos, S.

    2014-01-01

    Photoinduced charge-transfer processes play a key role for novel photovoltaic phenomena and devices. Thus, the development of ab initio methods that allow for an accurate and computationally inexpensive treatment of charge-transfer excitations is a topic that nowadays attracts a lot of scientific attention. In this paper we extend an approach recently introduced for the description of single and double excitations [M. Tassi, I. Theophilou, and S. Thanos, Int. J. Quantum Chem. 113, 690 (2013); M. Tassi, I. Theophilou, and S. Thanos, J. Chem. Phys. 138, 124107 (2013)] to allow for the description of intermolecular charge-transfer excitations. We describe an excitation where an electron is transferred from a donor system to an acceptor one, keeping the excited state orthogonal to the ground state and avoiding variational collapse. These conditions are achieved by decomposing the space spanned by the Hartree-Fock (HF) ground state orbitals into four subspaces: The subspace spanned by the occupied orbitals that are localized in the region of the donor molecule, the corresponding for the acceptor ones and two more subspaces containing the virtual orbitals that are localized in the neighborhood of the donor and the acceptor, respectively. Next, we create a Slater determinant with a hole in the subspace of occupied orbitals of the donor and a particle in the virtual subspace of the acceptor. Subsequently we optimize both the hole and the particle by minimizing the HF energy functional in the corresponding subspaces. Finally, we test our approach by calculating the lowest charge-transfer excitation energies for a set of tetracyanoethylene-hydrocarbon complexes that have been used earlier as a test set for such kind of excitations

  9. Excited State Spectra and Dynamics of Phenyl-Substituted Butadienes

    DEFF Research Database (Denmark)

    Wallace-Williams, Stacie E.; Schwartz, Benjamin J.; Møller, Søren

    1994-01-01

    indicate that phenyl torsional motion is not important to the excited-state dynamics and reveal alternative excited-state reaction pathways. The results demonstrate how molecular systems that are structually similar can exhibit different electronic properties and excited-state dynamics....

  10. Tracking Potentiating States of Dissociation: An Intensive Clinical Case Study of Sleep, Daydreaming, Mood, and Depersonalization/Derealization

    Science.gov (United States)

    Poerio, Giulia L.; Kellett, Stephen; Totterdell, Peter

    2016-01-01

    This study examined in real time the role of sleep and daydreaming as potentiating states for subsequent dissociation in depersonalization/derealization disorder (DDD). Research and theory suggests that dissociation may be exacerbated and maintained by a labile sleep-wake cycle in which “dream-like” mentation intrudes into waking life and fuels dissociative symptoms. We explore and extend this idea by examining the state of daydreaming in dissociation. Daydreaming is a state of consciousness between dreaming and waking cognition that involves stimulus-independent and task-unrelated mentation. We report the results of a unique intensive N = 1 study with an individual meeting diagnostic criteria for DDD. Using experience-sampling methodology, the participant rated (six times daily for 40 days) current daydreaming, mood, and dissociative symptoms. At the start of each day sleep quality and duration was also rated. Daydreaming was reported on 45% of occasions and significantly predicted greater dissociation, in particular when daydreams were repetitive and negative (but not fanciful) in content. These relationships were mediated by feelings of depression and anxiety. Sleep quality but not duration was a negative predictor of daily dissociation and also negatively predicted depression but not anxiety. Findings offer initial evidence that the occurrence and content of daydreams may act as potentiating states for heightened, in the moment, dissociation. The treatment implications of targeting sleep and daydreaming for dissociative disorders are discussed. PMID:27582722

  11. Tracking potentiating states of dissociation: An intensive clinical case study of sleep, daydreaming, mood, and depersonalization/derealization

    Directory of Open Access Journals (Sweden)

    Giulia Lara Poerio

    2016-08-01

    Full Text Available This study examined in real time the role of sleep and daydreaming as potentiating states for subsequent dissociation in depersonalization/derealization disorder (DDD. Research and theory suggests that dissociation may be exacerbated and maintained by a labile sleep-wake cycle in which ‘dream-like’ mentation intrudes into waking life and fuels dissociative symptoms. We explore and extend this idea by examining the state of daydreaming in dissociation. Daydreaming is a state of consciousness between dreaming and waking cognition that involves stimulus-independent and task-unrelated mentation. We report the results of a unique intensive N=1 study with an individual meeting diagnostic criteria for DDD. Using experience-sampling methodology, the participant rated (six times daily for 40 days current daydreaming, mood, and dissociative symptoms. At the start of each day sleep quality and duration was also rated. Daydreaming was reported on 45% of occasions and significantly predicted greater dissociation, in particular when daydreams were repetitive and negative (but not fanciful in content. These relationships were mediated by feelings of depression and anxiety. Sleep quality but not duration was a negative predictor of daily dissociation and also negatively predicted depression but not anxiety. Findings offer initial evidence that the occurrence and content of daydreams may act as potentiating states for heightened, in the moment, dissociation. The treatment implications of targeting sleep and daydreaming for dissociative disorders are discussed.

  12. Multimode optical fibers: steady state mode exciter.

    Science.gov (United States)

    Ikeda, M; Sugimura, A; Ikegami, T

    1976-09-01

    The steady state mode power distribution of the multimode graded index fiber was measured. A simple and effective steady state mode exciter was fabricated by an etching technique. Its insertion loss was 0.5 dB for an injection laser. Deviation in transmission characteristics of multimode graded index fibers can be avoided by using the steady state mode exciter.

  13. Effects of surface motion and electron-hole pair excitations in CO2 dissociation and scattering on Ni(100)

    Science.gov (United States)

    Luo, Xuan; Zhou, Xueyao; Jiang, Bin

    2018-05-01

    The energy transfer between different channels is an important aspect in chemical reactions at surfaces. We investigate here in detail the energy transfer dynamics in a prototypical system, i.e., reactive and nonreactive scattering of CO2 on Ni(100), which is related to heterogeneous catalytic processes with Ni-based catalysts for CO2 reduction. On the basis of our earlier nine-dimensional potential energy surface for CO2/Ni(100), dynamical calculations have been done using the generalized Langevin oscillator (GLO) model combined with local density friction approximation (LDFA), in which the former accounts for the surface motion and the latter accounts for the low-energy electron-hole pair (EHP) excitation. In spite of its simplicity, it is found that the GLO model yields quite satisfactory results, including the significant energy loss and product energy disposal, trapping, and steering dynamics, all of which agree well with the ab initio molecular dynamics ones where many surface atoms are explicitly involved with high computational cost. However, the GLO model fails to describe the reactivity enhancement due to the lattice motion because it intrinsically does not incorporate the variance of barrier height on the surface atom displacement. On the other hand, in LDFA, the energy transferred to EHPs is found to play a minor role and barely alter the dynamics, except for slightly reducing the dissociation probabilities. In addition, vibrational state-selected dissociative sticking probabilities are calculated and previously observed strong mode specificity is confirmed. Our work suggests that further improvement of the GLO model is needed to consider the lattice-induced barrier lowering.

  14. Atomic collisions research with excited atomic species

    International Nuclear Information System (INIS)

    Hoogerland, M.D.; Gulley, R.J.; Colla, M.; Lu, W.; Milic, D.; Baldwin, K.G.H.; Buckman, S.J.

    1999-01-01

    Measurements and calculations of fundamental atomic collision and spectroscopic properties such as collision cross sections, reaction rates, transition probabilities etc. underpin the understanding and operation of many plasma and gas-discharge-based devices and phenomena, for example plasma processing and deposition. In almost all cases the complex series of reactions which sustains the discharge or plasma, or produces the reactive species of interest, has a precursor electron impact excitation, attachment, dissociation or ionisation event. These processes have been extensively studied in a wide range of atomic and molecular species and an impressive data base of collision cross sections and reaction rates now exists. However, most of these measurements are for collisions with stable atomic or molecular species which are initially in their ground electronic state. Relatively little information is available for scattering from excited states or for scattering from unstable molecular radicals. Examples of such species would be metastable excited rare gases, which are often used as buffer gases, or CF 2 radicals formed by electron impact dissociation in a CF 4 plasma processing discharge. We are interested in developing experimental techniques which will enable the quantitative study of such exotic atomic and molecular species. In this talk I would like to outline one such facility which is being used for studies of collisions with metastable He(2 3 S) atoms

  15. Photoionization of excited molecular states using multiphoton excitation techniques

    International Nuclear Information System (INIS)

    Dehmer, P.M.; Pratt, S.T.; Dehmer, J.L.

    1984-01-01

    Photoelectron spectra are reported for three photon resonant, four photon ionization of H 2 via the B 1 Σ/sub u/ + , v = 7 (J = 2,4) and C 1 π/sub u'/, v = 0-4 (J = 1) levels and of N 2 via the o 3 1 π/sub u'/, v = 1,2, b 1 π/sub u'/, v = 3-5, and c 1 π/sub u'/, v = 0 levels. The results reflect both the spectroscopy and the dynamics of photoionization of excited molecular states and are discussed in terms of the selection rules for photoionization and the relative probabilities of photoionization from Rydberg and valence states. In some cases, in accordance with the Franck-Condon principle, the results demonstrate that resonant multiphoton ionization through Rydberg states may be a powerful technique for the production of electronic, vibrational, and rotational state selected ions. However, in other cases, systematic departures from Franck-Condon factors are observed, which reflect the more subtle dynamics of excited state photoionization. 23 references, 6 figures, 2 tables

  16. Low-lying excited states by constrained DFT

    Science.gov (United States)

    Ramos, Pablo; Pavanello, Michele

    2018-04-01

    Exploiting the machinery of Constrained Density Functional Theory (CDFT), we propose a variational method for calculating low-lying excited states of molecular systems. We dub this method eXcited CDFT (XCDFT). Excited states are obtained by self-consistently constraining a user-defined population of electrons, Nc, in the virtual space of a reference set of occupied orbitals. By imposing this population to be Nc = 1.0, we computed the first excited state of 15 molecules from a test set. Our results show that XCDFT achieves an accuracy in the predicted excitation energy only slightly worse than linear-response time-dependent DFT (TDDFT), but without incurring into problems of variational collapse typical of the more commonly adopted ΔSCF method. In addition, we selected a few challenging processes to test the limits of applicability of XCDFT. We find that in contrast to TDDFT, XCDFT is capable of reproducing energy surfaces featuring conical intersections (azobenzene and H3) with correct topology and correct overall energetics also away from the intersection. Venturing to condensed-phase systems, XCDFT reproduces the TDDFT solvatochromic shift of benzaldehyde when it is embedded by a cluster of water molecules. Thus, we find XCDFT to be a competitive method among single-reference methods for computations of excited states in terms of time to solution, rate of convergence, and accuracy of the result.

  17. Dissociation of 1P states in hot QCD Medium Using Quasi-Particle Model

    Science.gov (United States)

    Nilima, Indrani; Agotiya, Vineet Kumar

    2018-03-01

    We extend the analysis of a very recent work [1] to study the dissociation phenomenon of 1P states of the charmonium and bottomonium spectra (χc and χb) in a hot QCD medium using Quasi-Particle Model. This study employed a medium modified heavy quark potential which has quite different form in the sense that it has a lomg range Coulombic tail in addition to the Yukawa term even above the deconfinement temperature. Then we study the flavor dependence of their binding energies and explore the nature of dissociation temperatures by employing the Quasi-Particle debye mass for pure gluonic and full QCD case. Interestingly, the dissociation temperatures obtained by employing EoS1 and EoS2 with the Γ criterion, is closer to the upper bound of the dissociation temperatures which are obtained by the dissolution of a given quarkonia state by the mean thermal energy of the quasi-partons in the hot QCD/QGP medium.

  18. State dissociation moderates response to dialectical behavior therapy for posttraumatic stress disorder in women with and without borderline personality disorder

    Directory of Open Access Journals (Sweden)

    Nikolaus Kleindienst

    2016-07-01

    Full Text Available Background: Patients with posttraumatic stress disorder (PTSD are prone to dissociation, which in theory should interfere with successful treatment. However, most empirical studies do not substantiate this assumption. Objective: The primary objective was to test whether state dissociation predicts the success of an adaptation of dialectical behavior therapy designed for the treatment of patients with PTSD after childhood sexual abuse (CSA (DBT-PTSD. We further explored whether the operationalization of dissociation as state versus trait dissociation made a difference with respect to prediction of improvement. Methods: We present a hypothesis-driven post hoc analysis of a randomized controlled trial on the efficacy in patients with PTSD after CSA. Regression analyses relating pre–post improvements in the Clinician-Administered PTSD Scale (CAPS and the Posttraumatic Diagnostic Scale (PDS to dissociation were applied to the women who participated in the active treatment arm (DBT-PTSD. Multivariate models accounting for major confounders were used to relate improvements in both the CAPS and the PDS to (1 state dissociation as assessed after each treatment session and (2 trait dissociation as assessed at baseline. Results: State dissociation during psychotherapy sessions predicted improvement after DBT-PTSD: patients with low state dissociation during treatment had a higher chance to show substantial improvement. This relation consistently emerged across subgroups of PTSD patients with and without borderline personality disorder. The operationalization of dissociation as state versus trait dissociation made a difference as improvement was not significantly predicted from trait dissociation. Conclusions: Dissociation during treatment sessions may reduce success with trauma-focused therapies such as DBT-PTSD. Accordingly, clinical studies aimed at improving ways to address dissociation are needed.

  19. State dissociation moderates response to dialectical behavior therapy for posttraumatic stress disorder in women with and without borderline personality disorder.

    Science.gov (United States)

    Kleindienst, Nikolaus; Priebe, Kathlen; Görg, Nora; Dyer, Anne; Steil, Regina; Lyssenko, Lisa; Winter, Dorina; Schmahl, Christian; Bohus, Martin

    2016-01-01

    Patients with posttraumatic stress disorder (PTSD) are prone to dissociation, which in theory should interfere with successful treatment. However, most empirical studies do not substantiate this assumption. The primary objective was to test whether state dissociation predicts the success of an adaptation of dialectical behavior therapy designed for the treatment of patients with PTSD after childhood sexual abuse (CSA) (DBT-PTSD). We further explored whether the operationalization of dissociation as state versus trait dissociation made a difference with respect to prediction of improvement. We present a hypothesis-driven post hoc analysis of a randomized controlled trial on the efficacy in patients with PTSD after CSA. Regression analyses relating pre-post improvements in the Clinician-Administered PTSD Scale (CAPS) and the Posttraumatic Diagnostic Scale (PDS) to dissociation were applied to the women who participated in the active treatment arm (DBT-PTSD). Multivariate models accounting for major confounders were used to relate improvements in both the CAPS and the PDS to (1) state dissociation as assessed after each treatment session and (2) trait dissociation as assessed at baseline. State dissociation during psychotherapy sessions predicted improvement after DBT-PTSD: patients with low state dissociation during treatment had a higher chance to show substantial improvement. This relation consistently emerged across subgroups of PTSD patients with and without borderline personality disorder. The operationalization of dissociation as state versus trait dissociation made a difference as improvement was not significantly predicted from trait dissociation. Dissociation during treatment sessions may reduce success with trauma-focused therapies such as DBT-PTSD. Accordingly, clinical studies aimed at improving ways to address dissociation are needed.

  20. Localized excitations and the geometry of the 1nπ* excited states of pyrazine

    International Nuclear Information System (INIS)

    Kleier, D.A.; Martin, R.L.; Wadt, W.R.; Moomaw, W.R.

    1982-01-01

    Previous theoretical work has shown that the lowest excited singlet state of pyrazine, the π* 1 B 3 u state, is best described in terms of interacting excitations localized on each nitrogen. The present work refines the localized excitation model and considers its implications for the geometry of the 1 B 3 u state. Hartree-Fock calculations show that the best single configuration description of the nπ* state has broken ( 1 B 1 ) symmetry with the excitation strongly localized at one end of the molcule. If the symmetry-restricted hf result is used for reference, this localization describes an important correlation effect. The excited-state geometry was probed using configuration interaction wave functions based on the symmetry-restricted orbitals, as well as properly symmetrized ''valance-bond'' wave functions based on the broken symmetry solutions. Both descriptions lead to a very flat potential for a b/sub 1u/ vibrational mode. This mode reduces the molecular geometry from D/sub 2h/ to C/sub 2v/. We present spectroscopic evidence of our own and of other workers which is consistent with such a flat potential

  1. Rydberg energies using excited state density functional theory

    International Nuclear Information System (INIS)

    Cheng, C.-L.; Wu Qin; Van Voorhis, Troy

    2008-01-01

    We utilize excited state density functional theory (eDFT) to study Rydberg states in atoms. We show both analytically and numerically that semilocal functionals can give quite reasonable Rydberg energies from eDFT, even in cases where time dependent density functional theory (TDDFT) fails catastrophically. We trace these findings to the fact that in eDFT the Kohn-Sham potential for each state is computed using the appropriate excited state density. Unlike the ground state potential, which typically falls off exponentially, the sequence of excited state potentials has a component that falls off polynomially with distance, leading to a Rydberg-type series. We also address the rigorous basis of eDFT for these systems. Perdew and Levy have shown using the constrained search formalism that every stationary density corresponds, in principle, to an exact stationary state of the full many-body Hamiltonian. In the present context, this means that the excited state DFT solutions are rigorous as long as they deliver the minimum noninteracting kinetic energy for the given density. We use optimized effective potential techniques to show that, in some cases, the eDFT Rydberg solutions appear to deliver the minimum kinetic energy because the associated density is not pure state v-representable. We thus find that eDFT plays a complementary role to constrained DFT: The former works only if the excited state density is not the ground state of some potential while the latter applies only when the density is a ground state density.

  2. Cartesian coupled coherent states simulations: Ne(n)Br2 dissociation as a test case.

    Science.gov (United States)

    Reed, Stewart K; González-Martínez, Maykel L; Rubayo-Soneira, Jesús; Shalashilin, Dmitrii V

    2011-02-07

    In this article, we describe coupled coherent states (CCS) simulations of vibrational predissociation of weakly bounded complexes. The CCS method is implemented in the Cartesian frame in a manner that is similar to classical molecular dynamics. The calculated lifetimes of the vibrationally excited Ne-Br(2)(ν) complexes agree with experiment and previous calculations. Although the CCS method is, in principle, a fully quantum approach, in practice it typically becomes a semiclassical technique at long times. This is especially true following dissociation events. Consequently, it is very difficult to converge the quantum calculations of the final Br(2) vibrational distributions after predissociation and of the autocorrelation functions. However, the main advantage of the method is that it can be applied with relative ease to determine the lifetimes of larger complexes and, in order to demonstrate this, preliminary results for tetra- and penta-atomic clusters are reported.

  3. Kinetics of highly vibrationally excited O2(X) molecules in inductively-coupled oxygen plasmas

    Science.gov (United States)

    Annušová, Adriana; Marinov, Daniil; Booth, Jean-Paul; Sirse, Nishant; Lino da Silva, Mário; Lopez, Bruno; Guerra, Vasco

    2018-04-01

    The high degree of vibrational excitation of O2 ground state molecules recently observed in inductively coupled plasma discharges is investigated experimentally in more detail and interpreted using a detailed self-consistent 0D global kinetic model for oxygen plasmas. Additional experimental results are presented and used to validate the model. The vibrational kinetics considers vibrational levels up to v = 41 and accounts for electron impact excitation and de-excitation (e-V), vibration-to-translation relaxation (V-T) in collisions with O2 molecules and O atoms, vibration-to-vibration energy exchanges (V-V), excitation of electronically excited states, dissociative electron attachment, and electron impact dissociation. Measurements were performed at pressures of 10–80 mTorr (1.33 and 10.67 Pa) and radio frequency (13.56 MHz) powers up to 500 W. The simulation results are compared with the absolute densities in each O2 vibrational level obtained by high sensitivity absorption spectroscopy measurements of the Schumann–Runge bands for O2(X, v = 4–18), O(3 P) atom density measurements by two-photon absorption laser induced fluorescence (TALIF) calibrated against Xe, and laser photodetachment measurements of the O‑ negative ions. The highly excited O2(X, v) distribution exhibits a shape similar to a Treanor-Gordiets distribution, but its origin lies in electron impact e-V collisions and not in V-V up-pumping, in contrast to what happens in all other molecular gases known to date. The relaxation of vibrational quanta is mainly due to V-T energy-transfer collisions with O atoms and to electron impact dissociation of vibrationally excited molecules, e+O2(X, v)→O(3P)+O(3P).

  4. The triplet excited state of Bodipy: formation, modulation and application.

    Science.gov (United States)

    Zhao, Jianzhang; Xu, Kejing; Yang, Wenbo; Wang, Zhijia; Zhong, Fangfang

    2015-12-21

    Boron dipyrromethene (Bodipy) is one of the most extensively investigated organic chromophores. Most of the investigations are focused on the singlet excited state of Bodipy, such as fluorescence. In stark contrast, the study of the triplet excited state of Bodipy is limited, but it is an emerging area, since the triplet state of Bodipy is tremendously important for several areas, such as the fundamental photochemistry study, photodynamic therapy (PDT), photocatalysis and triplet-triplet annihilation (TTA) upconversion. The recent developments in the study of the production, modulation and application of the triplet excited state of Bodipy are discussed in this review article. The formation of the triplet state of Bodipy upon photoexcitation, via the well known approach such as the heavy atom effect (including I, Br, Ru, Ir, etc.), and the new methods, such as using a spin converter (e.g. C60), charge recombination, exciton coupling and the doubly substituted excited state, are summarized. All the Bodipy-based triplet photosensitizers show strong absorption of visible or near IR light and the long-lived triplet excited state, which are important for the application of the triplet excited state in PDT or photocatalysis. Moreover, the methods for switching (or modulation) of the triplet excited state of Bodipy were discussed, such as those based on the photo-induced electron transfer (PET), by controlling the competing Förster-resonance-energy-transfer (FRET), or the intermolecular charge transfer (ICT). Controlling the triplet excited state will give functional molecules such as activatable PDT reagents or molecular devices. It is worth noting that switching of the singlet excited state and the triplet state of Bodipy may follow different principles. Application of the triplet excited state of Bodipy in PDT, hydrogen (H2) production, photoredox catalytic organic reactions and TTA upconversion were discussed. The challenges and the opportunities in these areas were

  5. Vibronic coupling in the excited-states of carotenoids

    Energy Technology Data Exchange (ETDEWEB)

    Miki, Takeshi [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg; Germany; Buckup, Tiago [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg; Germany; Krause, Marie S. [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg; Germany; Southall, June [College of Medical; Veterinary, and Life Science; University of Glasgow; G12 8QQ Glasgow; UK; Cogdell, Richard J. [College of Medical; Veterinary, and Life Science; University of Glasgow; G12 8QQ Glasgow; UK; Motzkus, Marcus [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg; Germany

    2016-01-01

    The ultrafast femtochemistry of carotenoids is governed by the interaction between electronic excited states, which has been explained by the relaxation dynamics within a few hundred femtoseconds from the lowest optically allowed excited state S2to the optically dark state S1.

  6. Sequential nonadiabatic excitation of large molecules and ions driven by strong laser fields

    International Nuclear Information System (INIS)

    Markevitch, Alexei N.; Levis, Robert J.; Romanov, Dmitri A.; Smith, Stanley M.; Schlegel, H. Bernhard; Ivanov, Misha Yu.

    2004-01-01

    Electronic processes leading to dissociative ionization of polyatomic molecules in strong laser fields are investigated experimentally, theoretically, and numerically. Using time-of-flight ion mass spectroscopy, we study the dependence of fragmentation on laser intensity for a series of related molecules and report regular trends in this dependence on the size, symmetry, and electronic structure of a molecule. Based on these data, we develop a model of dissociative ionization of polyatomic molecules in intense laser fields. The model is built on three elements: (i) nonadiabatic population transfer from the ground electronic state to the excited-state manifold via a doorway (charge-transfer) transition; (ii) exponential enhancement of this transition by collective dynamic polarization of all electrons, and (iii) sequential energy deposition in both neutral molecules and resulting molecular ions. The sequential nonadiabatic excitation is accelerated by a counterintuitive increase of a large molecule's polarizability following its ionization. The generic theory of sequential nonadiabatic excitation forms a basis for quantitative description of various nonlinear processes in polyatomic molecules and ions in strong laser fields

  7. Rearrangements in ground and excited states

    CERN Document Server

    de Mayo, Paul

    1980-01-01

    Rearrangements in Ground and Excited States, Volume 3 presents essays on the chemical generation of excited states; the cis-trans isomerization of olefins; and the photochemical rearrangements in trienes. The book also includes essays on the zimmerman rearrangements; the photochemical rearrangements of enones; the photochemical rearrangements of conjugated cyclic dienones; and the rearrangements of the benzene ring. Essays on the photo rearrangements via biradicals of simple carbonyl compounds; the photochemical rearrangements involving three-membered rings or five-membered ring heterocycles;

  8. Excitation of lowest electronic states of thymine by slow electrons

    Science.gov (United States)

    Chernyshova, I. V.; Kontros, E. J.; Markush, P. P.; Shpenik, O. B.

    2013-11-01

    Excitation of lowest electronic states of the thymine molecules in the gas phase is studied by elec- tron energy loss spectroscopy. In addition to dipole-allowed transitions to singlet states, transitions to the lowest triplet states were observed. The low-energy features of the spectrum at 3.66 and 4.61 eV are identified with the excitation of the first triplet states 13 A' (π → π*) and 13 A″ ( n → π*). The higher-lying features at 4.96, 5.75, 6.17, and 7.35 eV are assigned mainly to the excitation of the π → π* transitions to the singlet states of the molecule. The excitation dynamics of the lowest states is studied. It is found that the first triplet state 13 A'(π → π*) is most efficiently excited at a residual energy close to zero, while the singlet 21 A'(π → π*) state is excited with almost identical efficiency at different residual energies.

  9. Electron-impact excitation and ionization cross sections for ground state and excited helium atoms

    International Nuclear Information System (INIS)

    Ralchenko, Yu.; Janev, R.K.; Kato, T.; Fursa, D.V.; Bray, I.; Heer, F.J. de

    2008-01-01

    Comprehensive and critically assessed cross sections for the electron-impact excitation and ionization of ground state and excited helium atoms are presented. All states (atomic terms) with n≤4 are treated individually, while the states with n≥5 are considered degenerate. For the processes involving transitions to and from n≥5 levels, suitable cross section scaling relations are presented. For a large number of transitions, from both ground and excited states, convergent close coupling calculations were performed to achieve a high accuracy of the data. The evaluated/recommended cross section data are presented by analytic fit functions, which preserve the correct asymptotic behavior of the cross sections. The cross sections are also displayed in graphical form

  10. A Theoretical Study of the Photodissociation Mechanism of Cyanoacetylene in Its Lowest Singlet and Triplet Excited States

    Science.gov (United States)

    Luo, Cheng; Du, Wei-Na; Duan, Xue-Mei; Li, Ze-Sheng

    2008-11-01

    Cyanoacetylene (H5-C4 ≡ C3-C2 ≡ N1) is a minor constituent of the atmosphere of Titan, and its photochemistry plays an important role in the formation of the haze surrounding the satellite. In this paper, the complete active space self-consistent field (CASSCF) and multiconfigurational second-order perturbation (CASPT2) approaches are employed to investigate the photochemical processes for cyanoacetylene in its first singlet and triplet excited states with the cc-pVTZ basis set. Fissions of the C4-H5 and C2-C3 bonds in S1 yield H(2S) + CCCN(A2Π) and HCC(A2Π) + CN(X2Σ+), respectively. In T1, the corresponding dissociation products are H(2S) + CCCN(X2Σ+) and HCC(X2Σ) + CN(X2Σ+). At the CASPT2(14,13)//CASSCF(14,13) + ZPE level, the barriers for the adiabatic dissociation of the C4-H5 and C2-C3 bonds are 6.11 and 6.94 eV in S1 and 5.71 and 6.39 eV in T1, respectively, taking the energy of S0 minimum as reference. Based on the calculated potential energy surfaces, the existence of a metastable excited molecule is anticipated upon 260-230 nm photoexcitation, which provides a probable approach for cyanoacetylene to polymerize. The internal conversion (IC) process through vibronic interaction followed by C4-H5 fission in the ground state is found to account for the observed diffuse character in the UV absorption spectrum below 240 nm.

  11. Dissociative ionization of liquid water induced by vibrational overtone excitation

    International Nuclear Information System (INIS)

    Natzle, W.C.

    1983-03-01

    Photochemistry of vibrationally activated ground electronic state liquid water to produce H + and OH - ions has been initiated by pulsed, single-photon excitation of overtone and combination transitions. Transient conductivity measurements were used to determine quantum yields as a function of photon energy, isotopic composition, and temperature. The equilibrium relaxation rate following perturbation by the vibrationally activated reaction was also measured as a function of temperature reaction and isotopic composition. In H 2 O, the quantum yield at 283 +- 1 K varies from 2 x 10 -9 to 4 x 10 -5 for wave numbers between 7605 and 18140 cm -1 . In D 2 O, the dependence of quantum yield on wavelength has the same qualitative shape as for H 2 O, but is shifted to lower quantum yields. The position of a minimum in the quantum yield versus hydrogen mole fraction curve is consistent with a lower quantum yield for excitation of HOD in D 2 O than for excitation of D 2 O. The ionic recombination distance of 5.8 +- 0.5 A is constant within experimental error with temperature in H 2 O and with isotopic composition at 25 +- 1 0 C

  12. Models for calculation of dissociation energies of homonuclear diatomic molecules

    International Nuclear Information System (INIS)

    Brewer, L.; Winn, J.S.

    1979-08-01

    The variation of known dissociation energies of the transition metal diatomics across the Periodic Table is rather irregular like the bulk sublimation enthalpy, suggesting that the valence-bond model for bulk metallic systems might be applicable to the gaseous diatomic molecules and the various intermediate clusters. Available dissociation energies were converted to valence-state bonding energies considering various degrees of promotion to optimize the bonding. The degree of promotion of electrons to increase the number of bonding electrons is smaller than for the bulk, but the trends in bonding energy parallel the behavior found for the bulk metals. Thus using the established trends in bonding energies for the bulk elements, it was possible to calculate all unknown dissociation energies to provide a complete table of dissociation energies for all M 2 molecules from H 2 to Lr 2 . For solids such as Mg, Al, Si and most of the transition metals, large promotion energies are offset by strong bonding between the valence state atoms. The main question is whether bonding in the diatomics is adequate to sustain extensive promotion. The most extreme example for which a considerable difference would be expected between the bulk and the diatomics would be that of the Group IIA and IIB metals. The first section of this paper which deals with the alkaline earths Mg and Ca demonstrates a significant influence of the excited valence state even for these elements. The next section then expands the treatment to transition metals

  13. Charge transfer excitations from exact and approximate ensemble Kohn-Sham theory

    Science.gov (United States)

    Gould, Tim; Kronik, Leeor; Pittalis, Stefano

    2018-05-01

    By studying the lowest excitations of an exactly solvable one-dimensional soft-Coulomb molecular model, we show that components of Kohn-Sham ensembles can be used to describe charge transfer processes. Furthermore, we compute the approximate excitation energies obtained by using the exact ensemble densities in the recently formulated ensemble Hartree-exchange theory [T. Gould and S. Pittalis, Phys. Rev. Lett. 119, 243001 (2017)]. Remarkably, our results show that triplet excitations are accurately reproduced across a dissociation curve in all cases tested, even in systems where ground state energies are poor due to strong static correlations. Singlet excitations exhibit larger deviations from exact results but are still reproduced semi-quantitatively.

  14. Dissociative photoionization of the NO molecule studied by photoelectron-photon coincidence technique

    International Nuclear Information System (INIS)

    Kivimaeki, A.; Alvarez-Ruiz, J.; Coreno, M.; Simone, M. de; Moise, A.; Partanen, L.; Richter, R.; Stankiewicz, M.

    2010-01-01

    Low-energy photoelectron-vacuum ultraviolet (VUV) photon coincidences have been measured using synchrotron radiation excitation in the inner-valence region of the nitric oxide molecule. The capabilities of the coincidence set-up were demonstrated by detecting the 2s -1 → 2p -1 radiative transitions in coincidence with the 2s photoelectron emission in Ne. In NO, the observed coincidence events are attributed to dissociative photoionization with excitation, whereby photoelectron emission is followed by fragmentation of excited NO + ions into O + + N* or N + + O* and VUV emission from an excited neutral fragment. The highest coincidence rate occurs with the opening of ionization channels which are due to correlation satellites of the 3σ photoionization. The decay time of VUV photon emission was also measured, implying that specific excited states of N atoms contribute significantly to observed VUV emission.

  15. Study of a Quantum Dot in an Excited State

    Science.gov (United States)

    Slamet, Marlina; Sahni, Viraht

    We have studied the first excited singlet state of a quantum dot via quantal density functional theory (QDFT). The quantum dot is represented by a 2D Hooke's atom in an external magnetostatic field. The QDFT mapping is from an excited singlet state of this interacting system to one of noninteracting fermions in a singlet ground state. The results of the study will be compared to (a) the corresponding mapping from a ground state of the quantum dot and (b) to the similar mapping from an excited singlet state of the 3D Hooke's atom.

  16. Ultrafast excited-state dynamics of 2,5-dimethylpyrrole.

    Science.gov (United States)

    Yang, Dongyuan; Min, Yanjun; Chen, Zhichao; He, Zhigang; Yuan, Kaijun; Dai, Dongxu; Yang, Xueming; Wu, Guorong

    2018-04-17

    The ultrafast excited-state dynamics of 2,5-dimethylpyrrole following excitation at wavelengths in the range of 265.7-216.7 nm is studied using the time-resolved photoelectron imaging method. It is found that excitation at longer wavelengths (265.7-250.2 nm) results in the population of the S1(1πσ*) state, which decays out of the photoionization window in about 90 fs. At shorter pump wavelengths (242.1-216.7 nm), the assignments are less clear-cut. We tentatively assign the initially photoexcited state(s) to the 1π3p Rydberg state(s) which has lifetimes of 159 ± 20, 125 ± 15, 102 ± 10 and 88 ± 10 fs for the pump wavelengths of 242.1, 238.1, 232.6 and 216.7 nm, respectively. Internal conversion to the S1(1πσ*) state represents at most a minor decay channel. The methyl substitution effects on the decay dynamics of the excited states of pyrrole are also discussed. Methyl substitution on the pyrrole ring seems to enhance the direct internal conversion from the 1π3p Rydberg state to the ground state, while methyl substitution on the N atom has less influence and the internal conversion to the S1(πσ*) state represents a main channel.

  17. Dissociative ionization of O2 and N2 by electron impact

    International Nuclear Information System (INIS)

    Deleanu, L.; Stockdale, J.A.

    1975-05-01

    A crossed molecular-pulsed electron beam apparatus used for the study of dissociative ionization of molecules by electron impact is described. The kinetic energy spectra of O + , N + and N ++ ions formed from dissociation of O 2 and N 2 by impact of threshold to 300 eV electrons measured by a time-of-flight method are presented. The ion energy spectra were obtained as a function of incident electron energy at a fixed electron beam-ion detector angle and at a fixed electron energy for electron beam-ion detector angles between 30 and 110 0 . Four main groups of O + ions were observed peaking at 0.8, 2.0, 3.0, and 5.0 eV kinetic energy. Angular distributions of all four of these groups are essentially isotropic. Four distinct groups of N + ions were observed in the N + kinetic energy spectra peaking at 1.9 eV, 2.2 to 2.5 eV, 3 to 4 eV and 6 to 7.6 eV. The angular distributions for N + ions of various kinetic energies were substantially isotropic. An attempt was made to measure the excitation function of N + from N 2 but the results were not very satisfactory. Nevertheless the excitation function data were analyzed by plotting the N + kinetic energy versus the value of the electron energy at which the abrupt changes in the slope of the excitation functions (''breaks'') occurred. The data on kinetic energy, angular distribution and excitation function of the ionic fragments were used in an attempt to identify the molecular ion states involved in the dissociation process. The kinetic energy spectra of N ++ /N 2 showed at least four major peaks and the total N ++ angular distributions was isotropic. (U.S.)

  18. Photo-dissociation of hydrogen passivated dopants in gallium arsenide

    International Nuclear Information System (INIS)

    Tong, L.; Larsson, J.A.; Nolan, M.; Murtagh, M.; Greer, J.C.; Barbe, M.; Bailly, F.; Chevallier, J.; Silvestre, F.S.; Loridant-Bernard, D.; Constant, E.; Constant, F.M.

    2002-01-01

    A theoretical and experimental study of the photo-dissociation mechanisms of hydrogen passivated n- and p-type dopants in gallium arsenide is presented. The photo-induced dissociation of the Si Ga -H complex has been observed for relatively low photon energies (3.48 eV), whereas the photo-dissociation of C As -H is not observed for photon energies up to 5.58 eV. This fundamental difference in the photo-dissociation behavior between the two dopants is explained in terms of the localized excitation energies about the Si-H and C-H bonds

  19. Multiorbital effects in strong-field ionization and dissociation of aligned polar molecules CH3I and CH3Br

    Science.gov (United States)

    Luo, Sizuo; Zhou, Shushan; Hu, Wenhui; Li, Xiaokai; Ma, Pan; Yu, Jiaqi; Zhu, Ruihan; Wang, Chuncheng; Liu, Fuchun; Yan, Bing; Liu, Aihua; Yang, Yujun; Guo, Fuming; Ding, Dajun

    2017-12-01

    Controlling the molecular axis offers additional ways to study molecular ionization and dissociation in strong laser fields. We measure the ionization and dissociation yields of aligned polar CH3X (X =I , Br) molecules in a linearly polarized femtosecond laser field. The current data show that maximum ionization occurs when the laser polarization is perpendicular to the molecular C -X axis, and dissociation prefers to occur at the laser polarization parallel to the C -X axis. The observed angular distributions suggest that the parent ions are generated by ionization from the HOMO. The angular distribution of fragment ions indicates that dissociation occurs mainly from an ionic excited state produced by ionization from the HOMO-1.

  20. Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH{sub 4} on Pt(111)

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Han; Jackson, Bret, E-mail: jackson@chem.umass.edu [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States)

    2016-05-14

    A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH{sub 4} dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v{sub 3} and 2v{sub 3}, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v{sub 1} symmetric stretch of CH{sub 4} is more effective at promoting the dissociative chemisorption of CH{sub 4} than exciting the 1v{sub 3} antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v{sub 3} state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. Our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.

  1. Dissociative ionization of liquid water induced by vibrational overtone excitation

    Energy Technology Data Exchange (ETDEWEB)

    Natzle, W.C.

    1983-03-01

    Photochemistry of vibrationally activated ground electronic state liquid water to produce H/sup +/ and OH/sup -/ ions has been initiated by pulsed, single-photon excitation of overtone and combination transitions. Transient conductivity measurements were used to determine quantum yields as a function of photon energy, isotopic composition, and temperature. The equilibrium relaxation rate following perturbation by the vibrationally activated reaction was also measured as a function of temperature reaction and isotopic composition. In H/sub 2/O, the quantum yield at 283 +- 1 K varies from 2 x 10/sup -9/ to 4 x 10/sup -5/ for wave numbers between 7605 and 18140 cm/sup -1/. In D/sub 2/O, the dependence of quantum yield on wavelength has the same qualitative shape as for H/sub 2/O, but is shifted to lower quantum yields. The position of a minimum in the quantum yield versus hydrogen mole fraction curve is consistent with a lower quantum yield for excitation of HOD in D/sub 2/O than for excitation of D/sub 2/O. The ionic recombination distance of 5.8 +- 0.5 A is constant within experimental error with temperature in H/sub 2/O and with isotopic composition at 25 +- 1/sup 0/C.

  2. IR and visible luminescence studies in the infrared multiphoton dissociation of 1,2-dibromo-1,1-difluoroethane

    Science.gov (United States)

    Pushpa, K. K.; Kumar, Awadhesh; Vatsa, R. K.; Naik, P. D.; Annaji Rao, K.; Mittal, J. P.; Parthasarathy, V.; Sarkar, S. K.

    1995-07-01

    The infrared multiphoton dissociation of 1,2-dibromo-1,1-difluoroethane gives rise to IR and visible luminescence. Vibrationally excited parent molecules dissociate via two primary channels yielding bromine and vibrationally excited HBr. The strong visible emission observed between 350 to 750 nm has been assigned to electronically excited carbene CF 2Br CH.

  3. Steering dissociation of Br2 molecules with two femtosecond pulses via wave packet interference.

    Science.gov (United States)

    Han, Yong-Chang; Yuan, Kai-Jun; Hu, Wen-Hui; Yan, Tian-Min; Cong, Shu-Lin

    2008-04-07

    The dissociation dynamics of Br2 molecules induced by two femtosecond pump pulses are studied based on the calculation of time-dependent quantum wave packet. Perpendicular transition from X 1Sigma g+ to A 3Pi 1u+ and 1Pi 1u+ and parallel transition from X 1Sigma g+ to B 3Pi 0u+, involving two product channels Br (2P3/2)+Br (2P3/2) and Br (2P3/2)+Br* (2P1/2), respectively, are taken into account. Two pump pulses create dissociating wave packets interfering with each other. By varying laser parameters, the interference of dissociating wave packets can be controlled, and the dissociation probabilities of Br2 molecules on the three excited states can be changed to different degrees. The branching ratio of Br*/(Br+Br*) is calculated as a function of pulse delay time and phase difference.

  4. Negative-ion states

    International Nuclear Information System (INIS)

    Compton, R.N.

    1982-01-01

    In this brief review, we discuss some of the properties of atomic and molecular negative ions and their excited states. Experiments involving photon reactions with negative ions and polar dissociation are summarized. 116 references, 14 figures

  5. Electromagnetic dissociation of relativistic 28Si by nucleon emission

    Energy Technology Data Exchange (ETDEWEB)

    Sonnadara, Upal Jayasiri [Univ. of Pittsburgh, PA (United States)

    1992-12-01

    A detailed study of the electromagnetic dissociation of 28Si by nucleon emission at Elab/A = 14.6 (GeV/nucleon was carried out with 28Si beams interacting on 208Pb). 120Sn. 64C targets. The measurements apparatus consists of detectors in the target area which measure the energy and charged multiplicity, and a forward spectrometer which measures the position, momentum and energy of the reaction fragments. The exclusive electromagnetic dissociation cross sections for decay channels having multiple nucleons in the final state have been measured which enables the selection of events produced in pure electromagnetic interactions. The measured cross sections agree well with previous measurements obtained for the removal of a few nucleons as well as with measurements on total charge removal cross sections from other experiments. The dependence of the integrated cross sections on the target charge ZT and the target mass AT confirms that for higher Z targets the excitation is largely electromagnetic. Direct measurements of the excitation energy for the electromagnetic dissociation of 28Si → p+27Al and 28Si → n+27Si have been obtained through a calculation of the invariant mass in kinematically, reconstructed events. The excitation energy spectrum for all targets peak near the isovector giant dipole resonance in 28Si. These distributions are well reproduced by combining the photon spectrum calculated using the Weizsaecker-Williams approximation with the experimental data on the photonuclear 28Si(γ,p)27Al and 28Si(γ,n)27Si. The possibilities of observing double giant dipole resonance excitations in 28Si have been investigated with cross section measurements as well as with excitation energy reconstruction.

  6. Lifetime measurements of excited states in 196Pt

    International Nuclear Information System (INIS)

    Bolotin, H.H.; Katayama, Ichiro; Sakai, Hideyuki; Fujita, Yoshitaka; Fujiwara, Mamoru

    1979-01-01

    The lifetimes of six excited states in 196 Pt up to an excitation energy of 1525 keV were measured by the recoil-distance method (RDM). These levels were populated by Coulomb excitation using both 90 MeV 20 Ne and 220 MeV 58 Ni ion beams. The measured lifetimes of the 2 1 + , 4 1 + , 6 1 + , 2 2 + , 4 2 + and 0 2 + states and the B(E2) values inferred for the depopulating transitions from these levels are presented. With the exception of the 2 1 + state, the meanlives of all other levels are the first such direct experimental determinations to be reported. (author)

  7. Computing correct truncated excited state wavefunctions

    Science.gov (United States)

    Bacalis, N. C.; Xiong, Z.; Zang, J.; Karaoulanis, D.

    2016-12-01

    We demonstrate that, if a wave function's truncated expansion is small, then the standard excited states computational method, of optimizing one "root" of a secular equation, may lead to an incorrect wave function - despite the correct energy according to the theorem of Hylleraas, Undheim and McDonald - whereas our proposed method [J. Comput. Meth. Sci. Eng. 8, 277 (2008)] (independent of orthogonality to lower lying approximants) leads to correct reliable small truncated wave functions. The demonstration is done in He excited states, using truncated series expansions in Hylleraas coordinates, as well as standard configuration-interaction truncated expansions.

  8. Probability of collective excited state decay

    International Nuclear Information System (INIS)

    Manykin, Eh.A.; Ozhovan, M.I.; Poluehktov, P.P.

    1987-01-01

    Decay mechanisms of condensed excited state formed of highly excited (Rydberg) atoms are considered, i.e. stability of so-called Rydberg substance is analyzed. It is shown that Auger recombination and radiation transitions are the basic processes. The corresponding probabilities are calculated and compared. It is ascertained that the ''Rydberg substance'' possesses macroscopic lifetime (several seconds) and in a sense it is metastable

  9. Exciplex formation accompanied with excitation quenching.

    Science.gov (United States)

    Fedorenko, Stanislav G; Burshtein, Anatoly I

    2010-04-08

    The competence of the reversible exciplex formation and parallel quenching of excitation (by electron or energy transfer) was considered using a non-Markovian pi-forms approach, identical to integral encounter theory (IET). General equations accounting for the reversible quenching and exciplex formation are derived in the contact approximation. Their general solution was obtained and adopted to the most common case when the ground state particles are in great excess. Particular cases of only photoionization or just exciplex formation separately studied earlier by means of IET are reproduced. In the case of the irreversible excitation quenching, the theory allows specifying the yields of the fluorescence and exciplex luminescence, as well as the long time kinetics of excitation and exciplex decays, in the absence of quenching. The theory distinguishes between the alternative regimes of (a) fast equilibration between excitations and exciplexes followed by their decay with a common average rate and (b) the fastest and deep excitation decay followed by the weaker and slower delayed fluorescence, backed by exciplex dissociation.

  10. Excited-state dynamics of pentacene derivatives with stable radical substituents.

    Science.gov (United States)

    Ito, Akitaka; Shimizu, Akihiro; Kishida, Noriaki; Kawanaka, Yusuke; Kosumi, Daisuke; Hashimoto, Hideki; Teki, Yoshio

    2014-06-23

    The excited-state dynamics of pentacene derivatives with stable radical substituents were evaluated in detail through transient absorption measurements. The derivatives showed ultrafast formation of triplet excited state(s) in the pentacene moiety from a photoexcited singlet state through the contributions of enhanced intersystem crossing and singlet fission. Detailed kinetic analyses for the transient absorption data were conducted to quantify the excited-state characteristics of the derivatives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Calculations on the vibrational level density in highly excited formaldehyde

    International Nuclear Information System (INIS)

    Rashev, Svetoslav; Moule, David C.

    2003-01-01

    The object of the present work is to develop a model that provides realistic estimates of the vibrational level density in polyatomic molecules in a given electronic state, at very high (chemically relevant) vibrational excitation energies. For S 0 formaldehyde (D 2 CO), acetylene, and a number of triatomics, the estimates using conventional spectroscopic formulas have yielded densities at the dissociation threshold, very much lower than the experimentally measured values. In the present work we have derived a general formula for the vibrational energy levels of a polyatomic molecule, which is a generalization of the conventional Dunham spectroscopic expansion. Calculations were performed on the vibrational level density in S 0 D 2 CO, H 2 C 2 , and NO 2 at excitation energies in the vicinity of the dissociation limit, using the newly derived formula. The results from the calculations are in reasonable agreement with the experimentally measured data

  12. Excitation of nuclear states by synchrotron radiation

    International Nuclear Information System (INIS)

    Olariu, Albert

    2003-01-01

    We study the excitation of nuclear states by gamma ray beams of energy up to 200 keV produced as synchrotron radiation. We consider the possibility to populate an excited state |i> in two steps, from the ground state |g> to an intermediary state |n> which decays by gamma emission or internal conversion to a lower state |i>. The aim of this study is to establish that the probability P 2 of the two-step transition |g> → |n> → |i> should be greater than the probability P 1 of the direct transition |g> → |i>. The probabilities P 1 and P 2 correspond to a radiation pulse of duration equal to the half-time of the state |i>. We have written a computer program in C++ which computes the probability P 2 , the ratio P 2 /P 1 and the rate C 2 of the two-step transitions for any nuclei and different configurations of states. The program uses a database which contains information on the energy levels, half-lives, spins and parities of nuclear states and on the relative intensities of the nuclear transitions. If the half-lives or the relative intensities are not known the program uses the Weisskopf estimates for the transition half-lives. An interpolation program of internal conversion coefficients has also been used. We listed the values obtained for P 2 , P 2 /P 1 and C 2 in a number of cases in which P 2 is significant from the 2900 considered cases. The states |i> and |n> have the energies E i and E n , the corresponding half-lives being t i and t n . The spectral density of the synchrotron radiation has been considered to be 10 12 photons cm -2 s -1 eV -1 . We listed only the cases for which the relative intensities of the transitions from levels |n> and |i> to lower states are known. The calculations carried out in this study allowed us to identify nuclei for which P 2 has relatively great values. In the listed cases P 2 /P 1 >>1, so that the two-step excitation by synchrotron radiation is more efficient than the direct excitation |g> → |i>. For a sample having 10

  13. Directed forgetting between, but not within, dissociative personality states.

    Science.gov (United States)

    Elzinga, Bernet M; Phaf, R Hans; Ardon, Angelique M; van Dyck, Richard

    2003-05-01

    To investigate amnesia between identities in dissociative identity disorder (DID), the authors assessed explicit and implicit memory performance on a directed-forgetting task in 12 DID patients who switched from one state to an "amnesic" state between presentation and memory testing. DID patients were instructed either to remember or to forget neutral and emotional words. Besides an overall decrease in explicit memory, patients demonstrated selective forgetting of to-be-forgotten, but not of to-be-remembered words in the amnesic state. Patients did not exhibit any directed forgetting within the same state. Implicit memory was fully preserved across states. Independent of state, patients recalled more emotional than neutral information. These results may extend the conceptualization of memory processes in DID, suggesting an important role for retrieval inhibition.

  14. The formation and decay of triply excited He- states in e-He scattering

    International Nuclear Information System (INIS)

    Heideman, H.G.M.

    1988-01-01

    A description is given of doubly and triply excited negative-ion states and their effects on the electron impact excitation of atomic states. Mechanisms for indirect excitation of singly excited states are discussed with respect to:- negative-ion resonance, autoionisation and post-collision interaction, and excitation of an autoionising state via a negative ion resonance. A classification of doubly excited states is considered. Experimental results on the excitation of the n'S states of helium as a function of the incident electron energy are presented, along with theoretical PCI (post collision interaction) profiles in excitation functions, and an interpretation of the results. (UK)

  15. Observation of double-well potential of NaH C 1Σ+ state: Deriving the dissociation energy of its ground state.

    Science.gov (United States)

    Chu, Chia-Ching; Huang, Hsien-Yu; Whang, Thou-Jen; Tsai, Chin-Chun

    2018-03-21

    Vibrational levels (v = 6-42) of the NaH C 1 Σ + state including the inner and outer wells and the near-dissociation region were observed by pulsed optical-optical double resonance fluorescence depletion spectroscopy. The absolute vibrational quantum number is identified by comparing the vibrational energy difference of this experiment with the ab initio calculations. The outer well with v up to 34 is analyzed using the Dunham expansion and a Rydberg-Klein-Rees (RKR) potential energy curve is constructed. A hybrid double-well potential combined with the RKR potential, the ab initio calculation, and a long-range potential is able to describe the whole NaH C 1 Σ + state including the higher vibrational levels (v = 35-42). The dissociation energy of the NaH C 1 Σ + state is determined to be D e (C) = 6595.10 ± 5 cm -1 and then the dissociation energy of the NaH ground state D e (X) = 15 807.87 ± 5 cm -1 can be derived.

  16. Excitation and decay of correlated atomic states

    International Nuclear Information System (INIS)

    Rau, A.R.P.

    1992-01-01

    Doubly excited states of atoms and ions in which two electrons are excited from the ground configuration display strong radial and angular electron correlations. They are prototypical examples of quantum-mechanical systems with strong coupling. Two distinguishing characteristics of these states are: (1) their organization into successive families, with only weak coupling between families, and (2) a hierarchical nature of this coupling, with states from one family decaying primarily to those in the next lower family. A view of the pair of electrons as a single entity, with the electron-electron repulsion between them divided into a adiabatic and nonadiabatic piece, accounts for many of the dominant features. The stronger, adiabatic part determines the family structure and the weaker, nonadiabatic part the excitation and decay between successive families. Similar considerations extend to three-electron atomic states, which group into five different classes. They are suggestive of composite models for quarks in elementary particle physics, which exhibit analogous groupings into families with a hierarchical arrangement of masses and electroweak decays. 49 refs., 6 figs., 2 tabs

  17. Proton and electron impact on molecular and atomic oxygen: I. High resolution fluorescence spectra in the visible and VUV spectral range and emission cross-sections for dissociative ionisation and excitation of O2

    International Nuclear Information System (INIS)

    Wilhelmi, O.; Schartner, K.H.

    2000-01-01

    For pt.II see ibid., vol.11, p.45-58, 2000. Molecular oxygen O 2 was dissociated in collisions with protons and electrons in the intermediate velocity range (p + -energies: 17-800 keV, e - -energies: 0.2-2 keV). Fluorescence from excited atomic and singly ionised fragments and from singly ionised molecules was detected in the VUV and in the visible and near UV spectral range. Highly resolved spectra are presented for the VUV (46-131 nm) and the near UV/visible (340-605 nm) spectral range. Absolute emission cross-sections have been determined for dissociative ionisation and excitation leading to fluorescence in the VUV. Results are compared with published data. (orig.)

  18. Sub-50 fs excited state dynamics of 6-chloroguanine upon deep ultraviolet excitation.

    Science.gov (United States)

    Mondal, Sayan; Puranik, Mrinalini

    2016-05-18

    The photophysical properties of natural nucleobases and their respective nucleotides are ascribed to the sub-picosecond lifetime of their first singlet states in the UV-B region (260-350 nm). Electronic transitions of the ππ* type, which are stronger than those in the UV-B region, lie at the red edge of the UV-C range (100-260 nm) in all isolated nucleobases. The lowest energetic excited states in the UV-B region of nucleobases have been investigated using a plethora of experimental and theoretical methods in gas and solution phases. The sub-picosecond lifetime of these molecules is not a general attribute of all nucleobases but specific to the five primary nucleobases and a few xanthine and methylated derivatives. To determine the overall UV photostability, we aim to understand the effect of more energetic photons lying in the UV-C region on nucleobases. To determine the UV-C initiated photophysics of a nucleobase system, we chose a halogen substituted purine, 6-chloroguanine (6-ClG), that we had investigated previously using resonance Raman spectroscopy. We have performed quantitative measurements of the resonance Raman cross-section across the Bb absorption band (210-230 nm) and constructed the Raman excitation profiles. We modeled the excitation profiles using Lee and Heller's time-dependent theory of resonance Raman intensities to extract the initial excited state dynamics of 6-ClG within 30-50 fs after photoexcitation. We found that imidazole and pyrimidine rings of 6-ClG undergo expansion and contraction, respectively, following photoexcitation to the Bb state. The amount of distortions of the excited state structure from that of the ground state structure is reflected by the total internal reorganization energy that is determined at 112 cm(-1). The contribution of the inertial component of the solvent response towards the total reorganization energy was obtained at 1220 cm(-1). In addition, our simulation also yields an instantaneous response of the first

  19. Excitation of autoionizing states of helium by 100 keV proton impact: II. Excitation cross sections and mechanisms of excitation

    Energy Technology Data Exchange (ETDEWEB)

    Godunov, A.L. [Department of Physics, Tulane University, New Orleans, LA 70118-5698 (United States); Ivanov, P.B.; Schipakov, V.A. [Troitsk Institute of Innovation and Fusion Research Troitsk, Moscow region, 142092 (Russian Federation); Moretto-Capelle, P.; Bordenave-Montesquieu, D.; Bordenave-Montesquieu, A. [Laboratoire Collisions, Agregats, Reactivite, IRSAMC, UMR 5589, CNRS-Universite Paul Sabatier, 31062 Toulouse Cedex (France)

    2000-03-14

    Mechanisms of two-electron excitation of the (2s{sup 2}){sup 1} S, (2p{sup 2} ){sup 1} D and (2s2p){sup 1} P autoionizing states of helium are studied both experimentally and theoretically. It is shown that an explicit introduction of a kinematic factor, with a process-specific phase leads to a productive parametrization of experimental cross sections of ionization, allowing one to extract cross sections of excitation of autoionizing states. Using a new fitting procedure together with the proposed parametrization made it possible to obtain the excitation cross sections and magnetic sublevel population from electron spectra as well as, for the first time, to resolve the contribution of resonance and interference components to resonance profiles. Interference with direct ionization is shown to contribute significantly into resonance formation even for backward ejection angles. We demonstrate theoretically that the excitation cross sections thus extracted from experimental electron spectra hold information about the interaction of autoionizing states with an adjacent continuum. (author)

  20. Bound state and localization of excitation in many-body open systems

    Science.gov (United States)

    Cui, H. T.; Shen, H. Z.; Hou, S. C.; Yi, X. X.

    2018-04-01

    We study the exact bound state and time evolution for single excitations in one-dimensional X X Z spin chains within a non-Markovian reservoir. For the bound state, a common feature is the localization of single excitations, which means the spontaneous emission of excitations into the reservoir is prohibited. Exceptionally, the pseudo-bound state can be found, for which the single excitation has a finite probability of emission into the reservoir. In addition, a critical energy scale for bound states is also identified, below which only one bound state exists, and it is also the pseudo-bound state. The effect of quasirandom disorder in the spin chain is also discussed; such disorder induces the single excitation to locate at some spin sites. Furthermore, to display the effect of bound state and disorder on the preservation of quantum information, the time evolution of single excitations in spin chains is studied exactly. An interesting observation is that the excitation can stay at its initial location with high probability only when the bound state and disorder coexist. In contrast, when either one of them is absent, the information of the initial state can be erased completely or becomes mixed. This finding shows that the combination of bound state and disorder can provide an ideal mechanism for quantum memory.

  1. Vibrational spectroscopy of the electronically excited state. 4. Nanosecond and picosecond time-resolved resonance Raman spectroscopy of carotenoid excited states

    International Nuclear Information System (INIS)

    Dallinger, R.F.; Farquharson, S.; Woodruff, W.H.; Rodgers, M.A.J.

    1981-01-01

    Resonance Raman and electronic absorption spectra are reported for the S 0 and T 1 states of the carotenoids β-carotene, zeaxanthin, echinenone, canthaxanthin, dihydroxylycopene, astaxanthin, decapreno(C 50 )-β-carotene, β-apo-8'-carotenal, and ethyl β-apo-8'-carotenoate. The results reveal qualitatively similar ground-state spectra and similar frequency shifts in all observed resonance Raman modes between S 0 and T 1 , regardless of carotenoid structure. Examinations of the relationship of the putative C--C and C==C frequencies in S 0 and T 1 reveals anomalous shifts to lower frequency in the ''single-bond'' mode upon electronic excitation. These shifts may be due to molecular distortions in the excited state which force changes in molecular motions comprising the observed modes. However, another possibility requiring no distortion is that the interaction (off-diagonal) force constants connecting the C--C and C==C modes change sign upon electronic excitation. This latter phenomenon may provide a unitary explanation for the ''anomalous'' frequency shifts in the C--C and C==C modes, both in the T 1 states of carotenoids and in the S 1 states of simpler polyenes, without postulating large, unpredicted structural changes upon excitation or general errors in existing vibrational or theoretical analyses. Resonance Raman and absorbance studies with 35-ps time resolution suggest that S 1 lifetime (of the 1 B/sub u/ and/or the 1 A/sub g/* states) of β-carotene in benzene is less than 1 ps

  2. Inelastic scattering of 9Li and excitation mechanism of its first excited state

    International Nuclear Information System (INIS)

    Al Falou, H.; Kanungo, R.; Andreoiu, C.; Cross, D.S.; Davids, B.; Djongolov, M.; Gallant, A.T.; Galinski, N.; Howell, D.; Kshetri, R.; Niamir, D.; Orce, J.N.; Shotter, A.C.; Sjue, S.; Tanihata, I.; Thompson, I.J.; Triambak, S.; Uchida, M.; Walden, P.; Wiringa, R.B.

    2013-01-01

    The first measurement of inelastic scattering of 9 Li from deuterons at the ISAC facility is reported. The measured angular distribution for the first excited state confirms the nature of excitation to be an E2 transition. The quadrupole deformation parameter is extracted from an analysis of the angular distribution

  3. Direct conversion of graphite into diamond through electronic excited states

    CERN Document Server

    Nakayama, H

    2003-01-01

    An ab initio total energy calculation has been performed for electronic excited states in diamond and rhombohedral graphite by the full-potential linearized augmented plane wave method within the framework of the local density approximation (LDA). First, calculations for the core-excited state in diamond have been performed to show that the ab initio calculations based on the LDA describe the wavefunctions in the electronic excited states as well as in the ground state quite well. Fairly good coincidence with both experimental data and theoretical prediction has been obtained for the lattice relaxation of the core exciton state. The results of the core exciton state are compared with nitrogen-doped diamond. Next, the structural stability of rhombohedral graphite has been investigated to examine the possibility of the transition into the diamond structure through electronic excited states. While maintaining the rhombohedral symmetry, rhombohedral graphite can be spontaneously transformed to cubic diamond. Tota...

  4. Dissociative Part-Dependent Resting-State Activity in Dissociative Identity Disorder : A Controlled fMRI Perfusion Study

    NARCIS (Netherlands)

    Schlumpf, Yolanda R.; Reinders, Antje A. T. S.; Nijenhuis, Ellert R. S.; Luechinger, Roger; van Osch, Matthias J. P.; Jaencke, Lutz

    2014-01-01

    Background: In accordance with the Theory of Structural Dissociation of the Personality (TSDP), studies of dissociative identity disorder (DID) have documented that two prototypical dissociative subsystems of the personality, the "Emotional Part'' (EP) and the "Apparently Normal Part'' (ANP), have

  5. Excitation energies with linear response density matrix functional theory along the dissociation coordinate of an electron-pair bond in N-electron systems

    International Nuclear Information System (INIS)

    Meer, R. van; Gritsenko, O. V.; Baerends, E. J.

    2014-01-01

    Time dependent density matrix functional theory in its adiabatic linear response formulation delivers exact excitation energies ω α and oscillator strengths f α for two-electron systems if extended to the so-called phase including natural orbital (PINO) theory. The Löwdin-Shull expression for the energy of two-electron systems in terms of the natural orbitals and their phases affords in this case an exact phase-including natural orbital functional (PILS), which is non-primitive (contains other than just J and K integrals). In this paper, the extension of the PILS functional to N-electron systems is investigated. With the example of an elementary primitive NO functional (BBC1) it is shown that current density matrix functional theory ground state functionals, which were designed to produce decent approximations to the total energy, fail to deliver a qualitatively correct structure of the (inverse) response function, due to essential deficiencies in the reconstruction of the two-body reduced density matrix (2RDM). We now deduce essential features of an N-electron functional from a wavefunction Ansatz: The extension of the two-electron Löwdin-Shull wavefunction to the N-electron case informs about the phase information. In this paper, applications of this extended Löwdin-Shull (ELS) functional are considered for the simplest case, ELS(1): one (dissociating) two-electron bond in the field of occupied (including core) orbitals. ELS(1) produces high quality ω α (R) curves along the bond dissociation coordinate R for the molecules LiH, Li 2 , and BH with the two outer valence electrons correlated. All of these results indicate that response properties are much more sensitive to deficiencies in the reconstruction of the 2RDM than the ground state energy, since derivatives of the functional with respect to both the NOs and the occupation numbers need to be accurate

  6. Self-Consistent Optimization of Excited States within Density-Functional Tight-Binding.

    Science.gov (United States)

    Kowalczyk, Tim; Le, Khoa; Irle, Stephan

    2016-01-12

    We present an implementation of energies and gradients for the ΔDFTB method, an analogue of Δ-self-consistent-field density functional theory (ΔSCF) within density-functional tight-binding, for the lowest singlet excited state of closed-shell molecules. Benchmarks of ΔDFTB excitation energies, optimized geometries, Stokes shifts, and vibrational frequencies reveal that ΔDFTB provides a qualitatively correct description of changes in molecular geometries and vibrational frequencies due to excited-state relaxation. The accuracy of ΔDFTB Stokes shifts is comparable to that of ΔSCF-DFT, and ΔDFTB performs similarly to ΔSCF with the PBE functional for vertical excitation energies of larger chromophores where the need for efficient excited-state methods is most urgent. We provide some justification for the use of an excited-state reference density in the DFTB expansion of the electronic energy and demonstrate that ΔDFTB preserves many of the properties of its parent ΔSCF approach. This implementation fills an important gap in the extended framework of DFTB, where access to excited states has been limited to the time-dependent linear-response approach, and affords access to rapid exploration of a valuable class of excited-state potential energy surfaces.

  7. Systematics in Rydberg state excitations for ion-atom collisions

    International Nuclear Information System (INIS)

    Andresen, B.; Jensen, K.; Petersen, N.B.; Veje, E.

    1976-01-01

    Rydberg state excitations in the Ne + , Mg + -He collisions have been studied in the projectile energy range 10-75 keV by means of optical spectrometry in a search for systematic trends. The relative excitation cross sections for levels of a Rydberg term series are found to follow a general (nsup(x))sup(P) behaviour with P < approximately -3 varying with collision energy and particles, regardless of whether the excited state population results from direct excitation, single electron transfer, or double electron transfer. At higher collision energies P is approximately -3 as predicted by theory. Polarization of the emitted line radiation indicates that there is no general rule for the relative excitation of the different magnetic substates of the same level. A statistical distribution of excitation is found for levels within the same term when the fine structure splitting is small. (Auth.)

  8. Electron Capture Dissociation of Weakly Bound Polypeptide Polycationic Complexes

    DEFF Research Database (Denmark)

    Haselmann, Kim F; Jørgensen, Thomas J D; Budnik, Bogdan A

    2002-01-01

    as well as specific complexes of modified glycopeptide antibiotics with their target peptide. The weak nature of bonding is substantiated by blackbody infrared dissociation, low-energy collisional excitation and force-field simulations. The results are consistent with a non-ergodic ECD cleavage mechanism.......We have previously reported that, in electron capture dissociation (ECD), rupture of strong intramolecular bonds in weakly bound supramolecular aggregates can proceed without dissociation of weak intermolecular bonds. This is now illustrated on a series of non-specific peptide-peptide dimers...

  9. σ-SCF: A direct energy-targeting method to mean-field excited states.

    Science.gov (United States)

    Ye, Hong-Zhou; Welborn, Matthew; Ricke, Nathan D; Van Voorhis, Troy

    2017-12-07

    The mean-field solutions of electronic excited states are much less accessible than ground state (e.g., Hartree-Fock) solutions. Energy-based optimization methods for excited states, like Δ-SCF (self-consistent field), tend to fall into the lowest solution consistent with a given symmetry-a problem known as "variational collapse." In this work, we combine the ideas of direct energy-targeting and variance-based optimization in order to describe excited states at the mean-field level. The resulting method, σ-SCF, has several advantages. First, it allows one to target any desired excited state by specifying a single parameter: a guess of the energy of that state. It can therefore, in principle, find all excited states. Second, it avoids variational collapse by using a variance-based, unconstrained local minimization. As a consequence, all states-ground or excited-are treated on an equal footing. Third, it provides an alternate approach to locate Δ-SCF solutions that are otherwise hardly accessible by the usual non-aufbau configuration initial guess. We present results for this new method for small atoms (He, Be) and molecules (H 2 , HF). We find that σ-SCF is very effective at locating excited states, including individual, high energy excitations within a dense manifold of excited states. Like all single determinant methods, σ-SCF shows prominent spin-symmetry breaking for open shell states and our results suggest that this method could be further improved with spin projection.

  10. Electron streaking and dissociation in laser-assisted photoionization of molecular hydrogen

    International Nuclear Information System (INIS)

    Palacios, Alicia; González-Castrillo, Alberto; Martín, Fernando

    2014-01-01

    We report ab initio calculations on laser-assisted photoionization of the hydrogen molecule in the energy region where autoionization from doubly excited states is expected to occur. We use a UV-pump/IR-probe scheme in which an isolated attosecond UV pulse and a 750 nm IR pulse are combined. The IR pulse has a relatively low intensity (10 12 W cm −2 ), which allows us to perform a perturbative analysis of the calculated ionization probabilities differential in either electron or nuclear energy or both. We show that, for dissociative ionization, the electron energy distributions as a function of time delay exhibit unusual streaking patterns that are due to the presence of autoionizing states. These patterns significantly differ from the standard ones observed in direct single ionization of atoms and molecules. We also show that, by using such a pump–probe scheme, one can suppress autoionization from doubly excited states for time delays between 0 and 4 fs. (paper)

  11. Excited state conformational dynamics in carotenoids: dark intermediates and excitation energy transfer.

    Science.gov (United States)

    Beck, Warren F; Bishop, Michael M; Roscioli, Jerome D; Ghosh, Soumen; Frank, Harry A

    2015-04-15

    A consideration of the excited state potential energy surfaces of carotenoids develops a new hypothesis for the nature of the conformational motions that follow optical preparation of the S2 (1(1)Bu(+)) state. After an initial displacement from the Franck-Condon geometry along bond length alternation coordinates, it is suggested that carotenoids pass over a transition-state barrier leading to twisted conformations. This hypothesis leads to assignments for several dark intermediate states encountered in femtosecond spectroscopic studies. The Sx state is assigned to the structure reached upon the onset of torsional motions near the transition state barrier that divides planar and twisted structures on the S2 state potential energy surface. The X state, detected recently in two-dimensional electronic spectra, corresponds to a twisted structure well past the barrier and approaching the S2 state torsional minimum. Lastly, the S(∗) state is assigned to a low lying S1 state structure with intramolecular charge transfer character (ICT) and a pyramidal conformation. It follows that the bent and twisted structures of carotenoids that are found in photosynthetic light-harvesting proteins yield excited-state structures that favor the development of an ICT character and optimized energy transfer yields to (bacterio)chlorophyll acceptors. Copyright © 2015 Elsevier Inc. All rights reserved.

  12. On excited states in real-time AdS/CFT

    Energy Technology Data Exchange (ETDEWEB)

    Botta-Cantcheff, Marcelo; Martínez, Pedro J.; Silva, Guillermo A. [Instituto de Física de La Plata - CONICET & Departamento de Física - UNLP,C.C. 67, 1900 La Plata (Argentina)

    2016-02-25

    The Skenderis-van Rees prescription, which allows the calculation of time-ordered correlation functions of local operators in CFT’s using holographic methods is studied and applied for excited states. Calculation of correlators and matrix elements of local CFT operators between generic in/out states are carried out in global Lorentzian AdS. We find the precise form of such states, obtain an holographic formula to compute the inner product between them, and using the consistency with other known prescriptions, we argue that the in/out excited states built according to the Skenderis-Van Rees prescription correspond to coherent states in the (large-N) AdS-Hilbert space. This is confirmed by explicit holographic computations. The outcome of this study has remarkable implications on generalizing the Hartle-Hawking construction for wave functionals of excited states in AdS quantum gravity.

  13. From fusion hierarchy to excited state TBA

    International Nuclear Information System (INIS)

    Juettner, G.; Kluemper, A.

    1998-01-01

    Functional relations among the fusion hierarchy of quantum transfer matrices give a novel derivation of the TBA equations, namely without string hypothesis. This is demonstrated for two important models of 1D highly correlated electron systems, the supersymmetric t-J model and the supersymmetric extended Hubbard model. As a consequence, ''the excited state TBA'' equations, which characterize correlation lengths, are explicitly derived for the t-J model. To the authors' knowledge, this is the first explicit derivation of excited state TBA equations for 1D lattice electron systems. (orig.)

  14. Coulomb dissociation of N 20,21

    OpenAIRE

    Röder, Marko; Adachi, Tatsuya; Aksyutina, Yulia; Alcantara, Juan; Altstadt, Sebastian; Alvarez-Pol, Hector; Ashwood, Nicholas; Atar, Leyla; Aumann, Thomas; Avdeichikov, Vladimir; Barr, M.; Beceiro, Saul; Bemmerer, Daniel; Benlliure, Jose; Bertulani, Carlos

    2016-01-01

    Neutron-rich light nuclei and their reactions play an important role in the creation of chemical elements. Here, data from a Coulomb dissociation experiment on N20,21 are reported. Relativistic N20,21 ions impinged on a lead target and the Coulomb dissociation cross section was determined in a kinematically complete experiment. Using the detailed balance theorem, the N19(n,γ)N20 and N20(n,γ)N21 excitation functions and thermonuclear reaction rates have been determined. The N19(n,γ)N20 rate is...

  15. Fact or factitious? A psychobiological study of authentic and simulated dissociative identity states.

    Science.gov (United States)

    Reinders, A A T S; Reinders, A A T Simone; Willemsen, Antoon T M; Vos, Herry P J; den Boer, Johan A; Nijenhuis, Ellert R S

    2012-01-01

    Dissociative identity disorder (DID) is a disputed psychiatric disorder. Research findings and clinical observations suggest that DID involves an authentic mental disorder related to factors such as traumatization and disrupted attachment. A competing view indicates that DID is due to fantasy proneness, suggestibility, suggestion, and role-playing. Here we examine whether dissociative identity state-dependent psychobiological features in DID can be induced in high or low fantasy prone individuals by instructed and motivated role-playing, and suggestion. DID patients, high fantasy prone and low fantasy prone controls were studied in two different types of identity states (neutral and trauma-related) in an autobiographical memory script-driven (neutral or trauma-related) imagery paradigm. The controls were instructed to enact the two DID identity states. Twenty-nine subjects participated in the study: 11 patients with DID, 10 high fantasy prone DID simulating controls, and 8 low fantasy prone DID simulating controls. Autonomic and subjective reactions were obtained. Differences in psychophysiological and neural activation patterns were found between the DID patients and both high and low fantasy prone controls. That is, the identity states in DID were not convincingly enacted by DID simulating controls. Thus, important differences regarding regional cerebral bloodflow and psychophysiological responses for different types of identity states in patients with DID were upheld after controlling for DID simulation. The findings are at odds with the idea that differences among different types of dissociative identity states in DID can be explained by high fantasy proneness, motivated role-enactment, and suggestion. They indicate that DID does not have a sociocultural (e.g., iatrogenic) origin.

  16. Method of producing excited states of atomic nuclei

    International Nuclear Information System (INIS)

    Morita, M.; Morita, R.

    1976-01-01

    A method is claimed of producing excited states of atomic nuclei which comprises bombarding atoms with x rays or electrons, characterized in that (1) in the atoms selected to be produced in the excited state of their nuclei, (a) the difference between the nuclear excitation energy and the difference between the binding energies of adequately selected two electron orbits is small enough to introduce the nuclear excitation by electron transition, and (b) the system of the nucleus and the electrons in the case of ionizing an orbital electron in said atoms should satisfy the spin and parity conservation laws; and (2) the energy of the bombarding x rays or electrons should be larger than the binding energy of one of the said two electron orbits which is located at shorter distance from the atomic nucleus. According to the present invention, atomic nuclei can be excited in a relatively simple manner without requiring the use of large scale apparatus, equipment and production facilities, e.g., factories. It is also possible to produce radioactive substances or separate a particular isotope with an extremely high purity from a mixture of isotopes by utilizing nuclear excitation

  17. Electron impact excitation of the lowest doublet and quartet core-excited autoionizing states in Rb atoms

    International Nuclear Information System (INIS)

    Borovik, A; Roman, V; Zatsarinny, O; Bartschat, K

    2013-01-01

    Electron impact excitation of the (4p 5 5s 2 ) 2 P 3/2,1/2 and (4p 5 4d5s) 4 P 1/2,3/2,5/2 autoionizing states in rubidium atoms was studied experimentally by measuring the ejected-electron excitation functions and theoretically by employing a fully relativistic Dirac B-spline R-matrix (close-coupling) model. The experimental data were collected in an impact energy range from the respective excitation thresholds up to 50 eV with an incident electron energy resolution of 0.2 eV and an observation angle of 54.7°. Absolute values of the excitation cross sections were obtained by normalizing to the theoretical predictions. The observed near-threshold resonance structures were also analysed by comparison with theory. For the 2 P 3/2,1/2 doublet states, a detailed analysis of the R-matrix results reveals that the most intense resonances are related to odd-parity negative-ion states with dominant configurations 4p 5 5s5p 2 and 4p 5 4d5s6s. The measured excitation functions for the 2 P 1/2 and 4 P J states indicate a noticeable cascade population due to the radiative decay from high-lying autoionizing states. A comparative analysis with similar data for other alkali atoms is also presented.

  18. Systematics of 2-body diffractive dissociations and search of double diffractive dissociation in K-p interactions at 14.3 GeV/c

    International Nuclear Information System (INIS)

    Pons, Yvette.

    1977-12-01

    The diffractive dissociation mechanism is shown to be general when looking at 22 mesonic or baryonic threshold enhancements. The dissociation systems are all produced peripherally and present the property of slope-mass correlation. The production slopes and cross-sections mainly depend on the diffractive excitation mass. The comparison of the results with those from the I.S.R. shows that dissociation systems are very similar in their effective mass shape, momentum transfer structure and angular distributions at center-of-mass energies differing by a factor of ten. Evidence for double diffractive dissociation mechanism is found in 2 exclusive reactions at a cross section level of 5-10+-2 μb. The factorisation hypothesis seems well verified [fr

  19. Avoided crossings, conical intersections, and low-lying excited states with a single reference method: the restricted active space spin-flip configuration interaction approach.

    Science.gov (United States)

    Casanova, David

    2012-08-28

    The restricted active space spin-flip CI (RASCI-SF) performance is tested in the electronic structure computation of the ground and the lowest electronically excited states in the presence of near-degeneracies. The feasibility of the method is demonstrated by analyzing the avoided crossing between the ionic and neutral singlet states of LiF along the molecular dissociation. The two potential energy surfaces (PESs) are explored by means of the energies of computed adiabatic and approximated diabatic states, dipole moments, and natural orbital electronic occupancies of both states. The RASCI-SF methodology is also used to study the ground and first excited singlet surface crossing involved in the double bond isomerization of ethylene, as a model case. The two-dimensional PESs of the ground (S(0)) and excited (S(1)) states are calculated for the complete configuration space of torsion and pyramidalization molecular distortions. The parameters that define the state energetics in the vicinity of the S(0)/S(1) conical intersection region are compared to complete active space self-consistent field (CASSCF) results. These examples show that it is possible to describe strongly correlated electronic states using a single reference methodology without the need to expand the wavefunction to high levels of collective excitations. Finally, RASCI is also examined in the electronic structure characterization of the ground and 2(1)A(g)(-), 1(1)B(u)(+), 1(1)B(u)(-), and 1(3)B(u)(-) states of all-trans polyenes with two to seven double bonds and beyond. Transition energies are compared to configuration interaction singles, time-dependent density functional theory (TDDFT), CASSCF, and its second-order perturbation correction calculations, and to experimental data. The capability of RASCI-SF to describe the nature and properties of each electronic state is discussed in detail. This example is also used to expose the properties of different truncations of the RASCI wavefunction and to

  20. Controlling excited-state contamination in nucleon matrix elements

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Boram; Gupta, Rajan; Bhattacharya, Tanmoy; Engelhardt, Michael; Green, Jeremy; Joó, Bálint; Lin, Huey-Wen; Negele, John; Orginos, Kostas; Pochinsky, Andrew; Richards, David; Syritsyn, Sergey; Winter, Frank

    2016-06-01

    We present a detailed analysis of methods to reduce statistical errors and excited-state contamination in the calculation of matrix elements of quark bilinear operators in nucleon states. All the calculations were done on a 2+1 flavor ensemble with lattices of size $32^3 \\times 64$ generated using the rational hybrid Monte Carlo algorithm at $a=0.081$~fm and with $M_\\pi=312$~MeV. The statistical precision of the data is improved using the all-mode-averaging method. We compare two methods for reducing excited-state contamination: a variational analysis and a two-state fit to data at multiple values of the source-sink separation $t_{\\rm sep}$. We show that both methods can be tuned to significantly reduce excited-state contamination and discuss their relative advantages and cost-effectiveness. A detailed analysis of the size of source smearing used in the calculation of quark propagators and the range of values of $t_{\\rm sep}$ needed to demonstrate convergence of the isovector charges of the nucleon to the $t_{\\rm sep} \\to \\infty $ estimates is presented.

  1. Ultrafast dissociation: An unexpected tool for probing molecular dynamics

    International Nuclear Information System (INIS)

    Morin, Paul; Miron, Catalin

    2012-01-01

    Highlights: ► Ultrafast dissociation has been investigated by means of XPS and mass spectrometry. ► The interplay between electron relaxation and molecular dynamics is evidenced. ► Extension toward polyatomics, clusters, adsorbed molecules is considered. ► Quantum effects (spectral hole, angular effects) evidence the molecular field anisotropy. -- Abstract: Ultrafast dissociation following core–shell excitation into an antibonding orbital led to the early observation in HBr of atomic Auger lines associated to the decay of dissociated excited atoms. The purpose of this article is to review the very large variety of systems where such a situation has been encountered, extending from simple diatomic molecules toward more complex systems like polyatomics, clusters, or adsorbed molecules. Interestingly, this phenomenon has revealed an extremely rich and powerful tool for probing nuclear dynamics and its subtle interplay with electron relaxation occurring on a comparable time scale. Consequently this review covers a surprisingly large period, starting in 1986 and still ongoing.

  2. Nonadiabatic excited-state molecular dynamics: On-the-fly limiting of essential excited states

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Tammie [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Naumov, Artem [Skolkovo Institute of Science and Technology, Moscow 143026 (Russian Federation); Fernandez-Alberti, Sebastian [Universidad Nacional de Quilmes, Roque Saenz Pea 352, B1876BXD Bernal (Argentina); Tretiak, Sergei, E-mail: serg@lanl.gov [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2016-12-20

    The simulation of nonadiabatic dynamics in extended molecular systems involving hundreds of atoms and large densities of states is particularly challenging. Nonadiabatic coupling terms (NACTs) represent a significant numerical bottleneck in surface hopping approaches. Rather than using unreliable NACT cutting schemes, here we develop “on-the-fly” state limiting methods to eliminate states that are no longer essential for the non-radiative relaxation dynamics as a trajectory proceeds. We propose a state number criteria and an energy-based state limit. The latter is more physically relevant by requiring a user-imposed energy threshold. For this purpose, we introduce a local kinetic energy gauge by summing contributions from atoms within the spatial localization of the electronic wavefunction to define the energy available for upward hops. The proposed state limiting schemes are implemented within the nonadiabatic excited-state molecular dynamics framework to simulate photoinduced relaxation in poly-phenylene vinylene (PPV) and branched poly-phenylene ethynylene (PPE) oligomers for benchmark evaluation.

  3. Excited state populations and charge-exchange of fast ions in solids

    International Nuclear Information System (INIS)

    Miller, P.D.; Sofield, C.J.; Woods, C.J.

    1984-01-01

    Excited state populations and charge state fractions of 445 MeV Cl ions have been measured for a range of thicknesses of solid C targets. Cross sections for electron capture, loss, excitation and excited state quenching have been determined and these data are found to predict a quantitative difference between equilibrium charge state distributions from gases and solids for a special case of the Bohr-Lindhard density effect model. 8 references, 1 figure, 1 table

  4. Dynamics of infrared multiphonon dissociation of SF6 by molecular beam method

    International Nuclear Information System (INIS)

    Grant, E.R.; Coggiola, M.J.; Lee, Y.T.; Schulz, P.A.; Shen, Y.R.

    1977-01-01

    A crossed molecular beam apparatus has been adapted to study the dynamics of excitation and dissociation of polyatomic molecules in intense IR laser fields. Initial experiments have involved the study of the dissociation of SF 6 by CO 2 laser radiation at 10.6 μm. A molecular beam of SF 6 was formed by supersonic expansion using three stages of differential pumping. A grating tuned pulsed CO 2 TEA laser was used as the excitation source. The laser beam was focused by a 25 cm focal length ZnSe lens, and crossed the molecular beam near its focal point. The fragments produced by multiphonon dissociation of SF 6 within the small interaction region were detected as a function of recoil angle and velocity. (Auth.)

  5. Excited states of open strings from N=4 SYM

    International Nuclear Information System (INIS)

    Dzienkowski, Eric

    2015-01-01

    We continue the analysis of building open strings stretched between giant gravitons from N=4 SYM by going to second order in perturbation theory using the three-loop dilatation generator from the field theory. In the process we build a Fock-like space of states using Cuntz oscillators which can be used to access the excited open string states. We find a remarkable cancellation among the excited states that shows the ground state energy is consistent with a fully relativistic dispersion relation.

  6. [Factitious disorders in dermatology: Value of the dissociative state concept].

    Science.gov (United States)

    Fekih-Romdhane, F; Homri, W; Labbane, R

    2016-03-01

    Factitious disorders in dermatology consist of intentionally self-inflicted skin lesions that vary in morphology and distribution and occur on surfaces readily accessible to the patient's hands. They tend to be a chronic condition that waxes and wanes according to the circumstances of the patient's life. Patient management poses a particular challenge to the clinician and the prognosis is considered poor. The aetiopathogenesis of factitious disorders in dermatology is not completely understood. We present a case in which we suggested the occurrence of factitious behaviour during a dissociative state, and we briefly describe our diagnostic and therapeutic approach. A 48-year-old unemployed woman was referred to our department of psychiatry by her dermatologist for suspected factitious disorder. The patient was diagnosed with diabetes mellitus type 1 and had been hospitalized repeatedly for confirmed diabetic ketoacidosis. The onset of the disease was related to marital discord with her spouse. Numerous skin lesions had appeared on her face, arms, legs, neck and back. These lesions resulted in multiple hospital admissions and in amputation of her left leg. The condition had worsened considerably after her separation from her husband. During the initial conversation, the patient was unable to provide a clear history of the disease. She denied any knowledge of the circumstances in which these skin lesions appeared, and she did not admit self-infliction. Her mood was depressed and her speech was slow. We suspected that our patient was herself causing her skin lesions while in a dissociative state. Several arguments militate in favour of our hypothesis, particularly her history of childhood maltreatment and the association of traumatic life events with simultaneous deterioration of the skin. The explanation of the dissociative mechanism helped us to strengthen the therapeutic relationship. Within a few days, we noted a slow regression of the lesions, but the patient was

  7. σ-SCF: A direct energy-targeting method to mean-field excited states

    Science.gov (United States)

    Ye, Hong-Zhou; Welborn, Matthew; Ricke, Nathan D.; Van Voorhis, Troy

    2017-12-01

    The mean-field solutions of electronic excited states are much less accessible than ground state (e.g., Hartree-Fock) solutions. Energy-based optimization methods for excited states, like Δ-SCF (self-consistent field), tend to fall into the lowest solution consistent with a given symmetry—a problem known as "variational collapse." In this work, we combine the ideas of direct energy-targeting and variance-based optimization in order to describe excited states at the mean-field level. The resulting method, σ-SCF, has several advantages. First, it allows one to target any desired excited state by specifying a single parameter: a guess of the energy of that state. It can therefore, in principle, find all excited states. Second, it avoids variational collapse by using a variance-based, unconstrained local minimization. As a consequence, all states—ground or excited—are treated on an equal footing. Third, it provides an alternate approach to locate Δ-SCF solutions that are otherwise hardly accessible by the usual non-aufbau configuration initial guess. We present results for this new method for small atoms (He, Be) and molecules (H2, HF). We find that σ-SCF is very effective at locating excited states, including individual, high energy excitations within a dense manifold of excited states. Like all single determinant methods, σ-SCF shows prominent spin-symmetry breaking for open shell states and our results suggest that this method could be further improved with spin projection.

  8. Does phasic trauma treatment make patients with dissociative identity disorder treatment more dissociative?

    Science.gov (United States)

    Brand, Bethany; Loewenstein, Richard J

    2014-01-01

    Proponents of the iatrogenic model of the etiology of dissociative identity disorder (DID) have expressed concern that treatment focused on direct engagement and interaction with dissociated self-states harms DID patients. However, empirical data have shown that this type of DID treatment is beneficial. Analyzing data from the prospective Treatment of Patients With Dissociative Disorders (TOP DD) Study, we test empirically whether DID treatment is associated with clinically adverse manifestations of dissociated self-states: acting so differently that one feels like different people, hearing voices, and dissociative amnesia. We show that, over the course of the study, there were significant decreases in feeling like different people and hearing voices. These results indicate that this form of DID treatment does not lead to symptomatic worsening in these dimensions, as predicted by the iatrogenic model. Indeed, treatment provided by TOP DD therapists reduced, rather than increased, the extent to which patients experienced manifestations of pathological dissociation. Because severe symptomatology and impairment are associated with DID, iatrogenic harm may come from depriving DID patients of treatment that targets DID symptomatology.

  9. Fragmentation of HCl following excitation at the chlorine K edge

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, D.L.; Arrasate, M.E. [Univ. of Nevada, Las Vegas, NV (United States); Cotter, J.P. [Univ. of Nevada, Reno, NV (United States)] [and others

    1997-04-01

    A space-focused time-of-flight (TOF) mass spectrometer was used to study the relaxation dynamics of HCl following excitation in the vicinity of the Cl-K edge ({approximately}2.8 keV) using x-rays from B.L. 9.3.1. At the lowest resonant excitation to a {sigma}{sup *} antibonding orbital (1{sigma} {r_arrow} 6{sigma}), a significant fraction of the excited molecules decay by emission of a neutral H atom. While neutral-H emission has been observed for shallow core levels (e.g., Cl 2p in HCl), the authors believe this to be the first observation of neutral-atom emission as a significant decay channel following resonant excitation of a deep core hole. The dissociation of neutral hydrogen atoms raises the issue of how effectively dissociation competes with Auger decay in the relaxation of these deep core levels (i.e., Cl 1s). Graphical evidence is presented to support the dissociation agrument. In addition, trends in fractional ion yields from Photo-Ion Photo-Ion COincidence (PIPICO) spectra suggest the presence of post-collision interaction (PCI). While, electron spectroscopy studies are required to confirm the observation of this effect, the authors believe this to be the first evidence of PCI moderated dissociation in molecules.

  10. PREFACE: Sixth International Conference on Dissociative Recombination: Theory, Experiments and Applications

    Science.gov (United States)

    Wolf, Andreas; Lammich, Lutz; Schmelcher, Peter

    2005-01-01

    Dissociative recombination between electrons and molecular ions is an elementary reaction in electron-induced chemistry attracting strong attention across discipline boundaries, from fundamental questions of intramolecular dynamics to astrophysics, plasma science, as well as atmospheric and planetary physics. The process is explored on the level of atomic quantum dynamics both experimentally and theoretically, employing cold collisions at temperatures down to 10 Kelvin involving small molecules or also very large systems ranging up to biomolecules. Dissociative recombination (DR) and related processes, such as dissociative excitation, collisional cooling of vibrations and rotations, photodissociation via high-lying electronic states, resonant electron attachment, and electron-induced processes in large molecules and clusters, are studied by a variety of experimental methods, including stored and trapped molecular ions, plasma techniques such as stationary and flowing afterglow, and laser spectroscopic diagnostic of molecular excitations. The Sixth International Conference on Dissociative Recombination: Theory, Experiments and Applications (DR2004) was organized by the Research Group on Atomic and Molecular Physics with Stored Ions at the Max-Planck Institute for Nuclear Physics in Heidelberg, Germany, and held near Heidelberg in the town of Mosbach in July 2004. It was attended by about 90 scientists working in atomic and molecular physics, astrophysics, plasma- and biophysics. International Conferences on Dissociative Recombination and related processes were held before at Lake Louise, Alberta, Canada (1988), Saint Jacut, Brittany, France (1992), Ein Gedi, Israel (1995), Nässlingen, Stockholm Archipelago, Sweden (1999), and last within a symposium at the American Chemical Society meeting in Chicago, USA (2001). The presentations of this conference document a strong development of theoretical ideas towards the understanding of DR in particular in polyatomic

  11. Inelastic scattering of {sup 9}Li and excitation mechanism of its first excited state

    Energy Technology Data Exchange (ETDEWEB)

    Al Falou, H. [Astronomy and Physics Department, Saint Mary' s University, Halifax, Nova Scotia B3H 3C3 (Canada); TRIUMF, Vancouver, British Columbia V6T 2A3 (Canada); Kanungo, R., E-mail: ritu@triumf.ca [Astronomy and Physics Department, Saint Mary' s University, Halifax, Nova Scotia B3H 3C3 (Canada); Andreoiu, C.; Cross, D.S. [Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); Davids, B.; Djongolov, M. [TRIUMF, Vancouver, British Columbia V6T 2A3 (Canada); Gallant, A.T. [TRIUMF, Vancouver, British Columbia V6T 2A3 (Canada); Department of Physics, University of British Columbia, British Columbia V6T 1Z4 (Canada); Galinski, N.; Howell, D. [TRIUMF, Vancouver, British Columbia V6T 2A3 (Canada); Department of Physics, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); Kshetri, R.; Niamir, D. [TRIUMF, Vancouver, British Columbia V6T 2A3 (Canada); Orce, J.N. [TRIUMF, Vancouver, British Columbia V6T 2A3 (Canada); Department of Physics, University of the Western Cape, P/B X17, Bellville, ZA-7535 (South Africa); Shotter, A.C. [Department of Physics and Astronomy, University of Edinburgh, Edinburgh (United Kingdom); Sjue, S. [TRIUMF, Vancouver, British Columbia V6T 2A3 (Canada); Tanihata, I. [Research Center for Nuclear Physics, Osaka University, Mihogaoka, Ibaraki, Osaka 567 0047 (Japan); Thompson, I.J. [Lawrence Livermore National Laboratory, Livermore, CA 94551 (United States); Triambak, S. [TRIUMF, Vancouver, British Columbia V6T 2A3 (Canada); Uchida, M. [Astronomy and Physics Department, Saint Mary' s University, Halifax, Nova Scotia B3H 3C3 (Canada); Walden, P. [TRIUMF, Vancouver, British Columbia V6T 2A3 (Canada); Wiringa, R.B. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2013-04-25

    The first measurement of inelastic scattering of {sup 9}Li from deuterons at the ISAC facility is reported. The measured angular distribution for the first excited state confirms the nature of excitation to be an E2 transition. The quadrupole deformation parameter is extracted from an analysis of the angular distribution.

  12. Fact or factitious? A psychobiological study of authentic and simulated dissociative identity states.

    Directory of Open Access Journals (Sweden)

    A A T S Reinders

    Full Text Available BACKGROUND: Dissociative identity disorder (DID is a disputed psychiatric disorder. Research findings and clinical observations suggest that DID involves an authentic mental disorder related to factors such as traumatization and disrupted attachment. A competing view indicates that DID is due to fantasy proneness, suggestibility, suggestion, and role-playing. Here we examine whether dissociative identity state-dependent psychobiological features in DID can be induced in high or low fantasy prone individuals by instructed and motivated role-playing, and suggestion. METHODOLOGY/PRINCIPAL FINDINGS: DID patients, high fantasy prone and low fantasy prone controls were studied in two different types of identity states (neutral and trauma-related in an autobiographical memory script-driven (neutral or trauma-related imagery paradigm. The controls were instructed to enact the two DID identity states. Twenty-nine subjects participated in the study: 11 patients with DID, 10 high fantasy prone DID simulating controls, and 8 low fantasy prone DID simulating controls. Autonomic and subjective reactions were obtained. Differences in psychophysiological and neural activation patterns were found between the DID patients and both high and low fantasy prone controls. That is, the identity states in DID were not convincingly enacted by DID simulating controls. Thus, important differences regarding regional cerebral bloodflow and psychophysiological responses for different types of identity states in patients with DID were upheld after controlling for DID simulation. CONCLUSIONS/SIGNIFICANCE: The findings are at odds with the idea that differences among different types of dissociative identity states in DID can be explained by high fantasy proneness, motivated role-enactment, and suggestion. They indicate that DID does not have a sociocultural (e.g., iatrogenic origin.

  13. Fact or Factitious? A Psychobiological Study of Authentic and Simulated Dissociative Identity States

    Science.gov (United States)

    Simone Reinders, A. A. T.; Willemsen, Antoon T. M.; Vos, Herry P. J.; den Boer, Johan A.; Nijenhuis, Ellert R. S.

    2012-01-01

    Background Dissociative identity disorder (DID) is a disputed psychiatric disorder. Research findings and clinical observations suggest that DID involves an authentic mental disorder related to factors such as traumatization and disrupted attachment. A competing view indicates that DID is due to fantasy proneness, suggestibility, suggestion, and role-playing. Here we examine whether dissociative identity state-dependent psychobiological features in DID can be induced in high or low fantasy prone individuals by instructed and motivated role-playing, and suggestion. Methodology/Principal Findings DID patients, high fantasy prone and low fantasy prone controls were studied in two different types of identity states (neutral and trauma-related) in an autobiographical memory script-driven (neutral or trauma-related) imagery paradigm. The controls were instructed to enact the two DID identity states. Twenty-nine subjects participated in the study: 11 patients with DID, 10 high fantasy prone DID simulating controls, and 8 low fantasy prone DID simulating controls. Autonomic and subjective reactions were obtained. Differences in psychophysiological and neural activation patterns were found between the DID patients and both high and low fantasy prone controls. That is, the identity states in DID were not convincingly enacted by DID simulating controls. Thus, important differences regarding regional cerebral bloodflow and psychophysiological responses for different types of identity states in patients with DID were upheld after controlling for DID simulation. Conclusions/Significance The findings are at odds with the idea that differences among different types of dissociative identity states in DID can be explained by high fantasy proneness, motivated role-enactment, and suggestion. They indicate that DID does not have a sociocultural (e.g., iatrogenic) origin. PMID:22768068

  14. Lifetime and g-factor measurements of excited states using Coulomb excitation and alpha transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Guevara, Z. E., E-mail: zjguevaram@unal.edu.co; Torres, D. A., E-mail: datorresg@unal.edu.co [Physics Department, Universidad Nacional de Colombia, Bogotá D.C. (Colombia)

    2016-07-07

    In this contribution the challenges in the use of a setup to simultaneously measure lifetimes and g-factor values will be presented. The simultaneous use of the transient field technique and the Doppler Shift Attenuation Method, to measure magnetic moments and lifetimes respectively, allows to obtain a complete characterization of the currents of nucleons and the deformation in excited states close to the ground state. The technique is at the moment limited to Coulomb excitation and alpha-transfer reactions, what opens an interesting perspective to consider this type of experiments with radioactive beams. The use of deep-inelastic and fusion-evaporation reactions will be discussed. An example of a setup that makes use of a beam of {sup 106}Cd to study excited states of {sup 110}Sn and the beam nuclei itself will be presented.

  15. The Sommerfeld enhancement for dark matter with an excited state

    International Nuclear Information System (INIS)

    Slatyer, Tracy R.

    2010-01-01

    We present an analysis of the Sommerfeld enhancement to dark matter annihilation in the presence of an excited state, where the interaction inducing the enhancement is purely off-diagonal, such as in models of exciting or inelastic dark matter. We derive a simple and accurate semi-analytic approximation for the s-wave enhancement, which is valid provided the mass splitting between the ground and excited states is not too large, and discuss the cutoff of the enhancement for large mass splittings. We reproduce previously derived results in the appropriate limits, and demonstrate excellent agreement with numerical calculations of the enhancement. We show that the presence of an excited state leads to generically larger values of the Sommerfeld enhancement, larger resonances, and shifting of the resonances to lower mediator masses. Furthermore, in the presence of a mass splitting the enhancement is no longer a monotonic function of velocity: the enhancement where the kinetic energy is close to that required to excite the higher state can be up to twice as large as the enhancement at zero velocity

  16. The excited states of 79Kr

    International Nuclear Information System (INIS)

    Liptak, J.; Kristiak, J.; Kristiakova, K.

    1977-01-01

    The β + -decay of 79 Rb has been studied with Ge(Li) detectors in single and coincidence modes. The half-life of the 147.06 keV level in 79 Kr has been determined to be (78+-6) ns. The relative electron intensities of seventeen transitions have been measured with a magnetic Si(Li) spectrometer. The internal conversion coefficients have been determined. The transition multipolarities have been deduced. The spin-parity assignments have been made for excited states of 79 Kr and a β-decaying sta 79 Rb(5/2 + ). The structure of excited states in 79 Kr is discussed in the framework of the Alaga and Coriolis coupling models. It is shown that the properties of some levels in 79 Kr can be explained by the existence of relatively pure rotational bands

  17. Excited state electron affinity calculations for aluminum

    Science.gov (United States)

    Hussein, Adnan Yousif

    2017-08-01

    Excited states of negative aluminum ion are reviewed, and calculations of electron affinities of the states (3s^23p^2)^1D and (3s3p^3){^5}{S}° relative to the (3s^23p)^2P° and (3s3p^2)^4P respectively of the neutral aluminum atom are reported in the framework of nonrelativistic configuration interaction (CI) method. A priori selected CI (SCI) with truncation energy error (Bunge in J Chem Phys 125:014107, 2006) and CI by parts (Bunge and Carbó-Dorca in J Chem Phys 125:014108, 2006) are used to approximate the valence nonrelativistic energy. Systematic studies of convergence of electron affinity with respect to the CI excitation level are reported. The calculated value of the electron affinity for ^1D state is 78.675(3) meV. Detailed Calculations on the ^5S°c state reveals that is 1216.8166(3) meV below the ^4P state.

  18. Experimentally-induced dissociation impairs visual memory.

    Science.gov (United States)

    Brewin, Chris R; Mersaditabari, Niloufar

    2013-12-01

    Dissociation is a phenomenon common in a number of psychological disorders and has been frequently suggested to impair memory for traumatic events. In this study we explored the effects of dissociation on visual memory. A dissociative state was induced experimentally using a mirror-gazing task and its short-term effects on memory performance were investigated. Sixty healthy individuals took part in the experiment. Induced dissociation impaired visual memory performance relative to a control condition; however, the degree of dissociation was not associated with lower memory scores in the experimental group. The results have theoretical and practical implications for individuals who experience frequent dissociative states such as patients with posttraumatic stress disorder (PTSD). Copyright © 2013 Elsevier Inc. All rights reserved.

  19. Nested variant of the method of moments of coupled cluster equations for vertical excitation energies and excited-state potential energy surfaces.

    Science.gov (United States)

    Kowalski, Karol

    2009-05-21

    In this article we discuss the problem of proper balancing of the noniterative corrections to the ground- and excited-state energies obtained with approximate coupled cluster (CC) and equation-of-motion CC (EOMCC) approaches. It is demonstrated that for a class of excited states dominated by single excitations and for states with medium doubly excited component, the newly introduced nested variant of the method of moments of CC equations provides mathematically rigorous way of balancing the ground- and excited-state correlation effects. The resulting noniterative methodology accounting for the effect of triples is tested using its parallel implementation on the systems, for which iterative CC/EOMCC calculations with full inclusion of triply excited configurations or their most important subset are numerically feasible.

  20. Dissociative Part-Dependent Resting-State Activity in Dissociative Identity Disorder: A Controlled fMRI Perfusion Study

    OpenAIRE

    Schlumpf, Yolanda R.; Reinders, Antje A. T. S.; Nijenhuis, Ellert R. S.; Luechinger, Roger; van Osch, Matthias J. P.; Jäncke, Lutz

    2014-01-01

    Background: In accordance with the Theory of Structural Dissociation of the Personality (TSDP), studies of dissociative identity disorder (DID) have documented that two prototypical dissociative subsystems of the personality, the "Emotional Part'' (EP) and the "Apparently Normal Part'' (ANP), have different biopsychosocial reactions to supraliminal and subliminal trauma-related cues and that these reactions cannot be mimicked by fantasy prone healthy controls nor by actors. Methods: Arterial ...

  1. Dissociation Energies of Diatomic Molecules

    International Nuclear Information System (INIS)

    Qun-Chao, Fan; Wei-Guo, Sun

    2008-01-01

    Molecular dissociation energies of 10 electronic states of alkali molecules of KH, 7 LiD, 7 LiH, 6 LiH, NaK, NaLi and NaRb are studied using the highest three accurate vibrational energies of each electronic state, and an improved parameter-free analytical formula which is obtained starting from the LeRoy–Bernstein vibrational energy expression near the dissociation limit. The results show that as long as the highest three vibrational energies are accurate, the current analytical formula will give accurate theoretical dissociation energies D e theory , which are in excellent agreement with the experimental dissociation energies D e expt . (atomic and molecular physics)

  2. Doubly and triply excited states for different plasma sources

    International Nuclear Information System (INIS)

    More, R.M.; Safronova, U.I.

    2000-01-01

    Autoionizing rates of doubly excited states as nln'l' configurations with n=2-9 and n'=2-9 are calculated. Analytical expressions of decay amplitude for two-electron system are derived. Expressions for autoionizing rates with averaging over LS are obtained for many-electron systems. The n and l dependence of doubly excited states as nln'l' configurations are investigated. (author)

  3. Low missing mass, single- and double diffraction dissociation at the LHC

    CERN Document Server

    Jenkovszky, Laszlo; Orava, Risto; Salii, Andrii

    2014-01-01

    Low missing mass, single- and double diffraction dissociation is calculated for the LHC energies from a dual-Regge model, dominated by a Pomeron Regge pole exchange. The model reproduces the rich resonance structure in the low missing mass Mx region. The diffractionly excited states lie on the nucleon trajectory, appended by the isolated Roper resonance. Detailed predictions for the squared momentum transfer and missing mass dependence of the differential and integrated single- and double diffraction dissociation in the kinematical range of present and future LHC measurements are given. The model predicts a possible turn-down of the cross section towards, t -> 0 in a region probably accessible in future experiments in the nearly forward direction. The present work is a continuation and extension (e.g. with double diffraction) of a previous work using the dual Regge approach.

  4. Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States.

    Science.gov (United States)

    Chen, Zehua; Zhang, Du; Jin, Ye; Yang, Yang; Su, Neil Qiang; Yang, Weitao

    2017-09-21

    To describe static correlation, we develop a new approach to density functional theory (DFT), which uses a generalized auxiliary system that is of a different symmetry, such as particle number or spin, from that of the physical system. The total energy of the physical system consists of two parts: the energy of the auxiliary system, which is determined with a chosen density functional approximation (DFA), and the excitation energy from an approximate linear response theory that restores the symmetry to that of the physical system, thus rigorously leading to a multideterminant description of the physical system. The electron density of the physical system is different from that of the auxiliary system and is uniquely determined from the functional derivative of the total energy with respect to the external potential. Our energy functional is thus an implicit functional of the physical system density, but an explicit functional of the auxiliary system density. We show that the total energy minimum and stationary states, describing the ground and excited states of the physical system, can be obtained by a self-consistent optimization with respect to the explicit variable, the generalized Kohn-Sham noninteracting density matrix. We have developed the generalized optimized effective potential method for the self-consistent optimization. Among options of the auxiliary system and the associated linear response theory, reformulated versions of the particle-particle random phase approximation (pp-RPA) and the spin-flip time-dependent density functional theory (SF-TDDFT) are selected for illustration of principle. Numerical results show that our multireference DFT successfully describes static correlation in bond dissociation and double bond rotation.

  5. Double diffractive dissociation in the reaction K-p→K-π+π-nπ+ at 14.3 GeV/c and pomeron factorisation

    International Nuclear Information System (INIS)

    Denegri, D.; Pons, Y.; Borg, A.; Spiro, M.; Paler, K.; Tovey, S.; Comber, C.; Shah, T.P.

    1975-01-01

    Evidence is presented for the double dissociation process K - p→QN*sub(1/2)→(anti K* 0 π - ) (nπ + ) at 14.3GeV/c. The cross section for the process is of the order of 10 μb. The production differential cross section is steep (for near-threshold excitation masses), as typical of diffractive processes, and exhibits a strong correlation between the production slope and the masses of the dissociated systems. The spin-parity composition and states of the two dissociation systems closely resemble those found in single dissociation, indicating that a common diffraction-like mechanism is responsible for both processes. The mass variations of the differential cross-section slope, the decay angular correlations and the total cross section of the double dissociation component are consistent with the predictions of a factorisable pomeron exchange model. (Auth.)

  6. Examination of excited state populations in sputtering using Multiphoton Resonance Ionization

    International Nuclear Information System (INIS)

    Kimock, F.M.; Baxter, J.P.; Pappas, D.L.; Kobrin, P.H.; Winograd, N.

    1984-01-01

    Multiphoton Resonance Ionization has been employed to study the populations of excited state atoms ejected from ion bombarded metal surfaces. Preliminary investigations have focused on three model systems: aluminum, indium and cobalt. In this paper the authors examine the effect of primary ion energy (2 to 12 keV Ar + ) on excited state yields for these three systems. The influence of the sample matrix on excited state populations of sputtered atoms is also discussed

  7. Analytical study of doubly excited ridge states

    International Nuclear Information System (INIS)

    Wong, H.Y.

    1988-01-01

    Two different non-separable problems are explored and analyzed. Non-perturbative methods need to be used to handle them, as the competing forces involved in these problems are equally strong and do not yield to a perturbative analysis. The first one is the study of doubly excited ridge states of atoms, in which two electrons are comparably excited. An analytical wavefunction for such states is introduced and is used to solve the two-electron Hamiltonian in the pair coordinates called hyperspherical coordinates variationally. The correlation between the electrons is built in analytically into the structure of the wavefunction. Sequences of ridge states out to very high excitation are computed and are organized as Rydberg series converging to the double ionization limit. Numerical results of such states in He and H - are compared with other theoretical calculations where available. The second problem is the analysis of the photodetachment of negative ions in an electric field via the frame transformation theory. The presence of the electron field requires a transformation from spherical to cylindrical symmetry for the outgoing photoelectron. This gives an oscillatory modulating factor as the effect of the electric field on cross-sections. All of this work is derived analytically in a general form applicable to the photodetachment of any negative ion. The expressions are applied to H - and S - for illustration

  8. Dinamical polarizability of highly excited hydrogen-like states

    International Nuclear Information System (INIS)

    Delone, N.B.; Krajnov, V.P.

    1982-01-01

    Analytic expressions are derived for the dynamic polarizability of highly excited hydrogen-like atomic states. It is shown that in the composite matrix element which determines the dynamic polarizability there is a strong compensation of the terms as a result of which the resulting magnitude of the dynamic polarizability is quasiclasically small compared to the individual terms of the composite matrix. It is concluded that the resonance behaviour of the dynamic polarizability of highly excited states differs significantly from the resonance behaviour of the polarizability for the ground and low-lying atomic states. The static limit and high-frequency limit of on electromagnetic field are considered

  9. Excitation of non-normal parity states by inelastic proton scattering

    Energy Technology Data Exchange (ETDEWEB)

    Emery, G. T. [Indiana Univ. (USA). Cyclotron Facility; Ikegami, Hidetsugu; Muraoka, Mitsuo [eds.; Osaka Univ., Suita (Japan). Research Center for Nuclear Physics

    1980-01-01

    This is a review of the works done at the Indiana University Cyclotron Facility. The purposes of works are to find excitations that should have especially simple particle-hole structure in proton inelastic scattering, to use the data on these excitations to try to understand the mechanism and the effective interaction for the (p, p') reaction in this energy range, and to go on to study the nuclear structure involved in less simple excitation. As an example, the single-nucleon level diagram for the region of Si-28 is presented. A high spin state was made, and its spin-parity was 6/sup -/. It was tried to interpret the data in terms of a on-step distorted-wave impulse approximation. The optical model parameters derived from the extensive and precise elastic scattering results were used. The cross sections for the excitation of the 6/sup -/ states found in various reactions were not large. The T = 1 state is mainly excited by the direct tensor interaction, while the T = 0 state gets its strength mainly from the knock-on exchange contribution of both the tensor and spin-orbit interactions. Experiments on Pb-208 and Fe-54 are being performed.

  10. Examination of excited state populations in sputtering using multiphoton resonance ionization

    International Nuclear Information System (INIS)

    Kimock, F.M.; Baxter, J.P.; Pappas, D.L.; Kobrin, P.H.; Winograd, N.

    1984-01-01

    Multiphoton Resonance Ionization has been employed to study the populations of excited state atoms ejected from ion bombarded metal surfaces. Preliminary investigations have focused on three model systems: aluminum, indium and cobalt. In this paper we examine the effect of primary ion energy (2 to 12 keV Ar + ) on excited state yields for these three systems. The influence of the sample matrix on excited state populations of sputtered atoms is also discussed. 8 refs., 4 figs

  11. Visible luminescence studies in the infrared multiphoton dissociation of 1,2-dichloro-1,1-difluoroethane

    Science.gov (United States)

    Pushpa, K. K.; Kumar, Awadesh; Naik, P. D.; Annaji Rao, K.; Parthasarathy, V.; Sarkar, S. K.; Mittal, J. P.

    1997-11-01

    A strong visible luminescence was observed in the CO 2 laser induced infrared multiphoton dissociation of 1,2-dichloro-1,1-difluoroethane. The emission observed between 350-750 nm is attributed to electronically excited carbene CF 2ClCH. The temporal profile of this luminescence was studied as a function of laser pulse duration, pulse energy, excitation frequency and substrate pressure. A suitable dissociation mechanism is presented considering various channels of IRMPD of this molecule.

  12. Excited-State Dynamics of Carotenoids Studied by Femtosecond Transient Absorption Spectroscopy

    International Nuclear Information System (INIS)

    Lee, Ingu; Pang, Yoonsoo; Lee, Sebok

    2014-01-01

    Carotenoids, natural antenna pigments in photosynthesis share a symmetric backbone of conjugated polyenes. Contrary to the symmetric and almost planar geometries of carotenoids, excited state structure and dynamics of carotenoids are exceedingly complex. In this paper, recent infrared and visible transient absorption measurements and excitation dependent dynamics of 8'-apo-β-caroten-8'-al and 7',7'-dicyano-7'-apo-β-carotene will be reviewed. The recent visible transient absorption measurements of 8'-apo-β-caroten-8'-al in polar and nonpolar solvents will also be introduced to emphasize the complex excited-state dynamics and unsolved problems in the S 2 and S 1 excited states

  13. Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state

    DEFF Research Database (Denmark)

    Reynisson, J.; Wilbrandt, R.; Brinck, V.

    2002-01-01

    . The physical and chemical properties of the excited singlet state of the trioxatriangulenium (TOTA(+)) carbenium ion are investigated by experimental and Computational means. The degeneracy of the lowest excited states is counteracted by Jahn-Teller-type distortion, which leads to vibronic broadening...... of the long wavelength absorption band. A strong fluorescence is observed at 520 nm (tau(n) = 14.6 ns, phi(n) = 0.12 in deaerated acetonitrile). The fluorescence is quenched by 10 aromatic electron donors predominantly via a dynamic charge transfer mechanism, but ground state complexation is shown...... triphenylenes is studied separately. Phosphorescence spectra, triplet lifetimes, and triplet-triplet absorption spectra are provided. In the discussion, TOTA(+) is compared to the unsubstituted xanthenium ion and its 9-phenyl derivative with respect to the excited state properties....

  14. Photoionization of furan from the ground and excited electronic states.

    Science.gov (United States)

    Ponzi, Aurora; Sapunar, Marin; Angeli, Celestino; Cimiraglia, Renzo; Došlić, Nađa; Decleva, Piero

    2016-02-28

    Here we present a comparative computational study of the photoionization of furan from the ground and the two lowest-lying excited electronic states. The study aims to assess the quality of the computational methods currently employed for treating bound and continuum states in photoionization. For the ionization from the ground electronic state, we show that the Dyson orbital approach combined with an accurate solution of the continuum one particle wave functions in a multicenter B-spline basis, at the density functional theory (DFT) level, provides cross sections and asymmetry parameters in excellent agreement with experimental data. On the contrary, when the Dyson orbitals approach is combined with the Coulomb and orthogonalized Coulomb treatments of the continuum, the results are qualitatively different. In excited electronic states, three electronic structure methods, TDDFT, ADC(2), and CASSCF, have been used for the computation of the Dyson orbitals, while the continuum was treated at the B-spline/DFT level. We show that photoionization observables are sensitive probes of the nature of the excited states as well as of the quality of excited state wave functions. This paves the way for applications in more complex situations such as time resolved photoionization spectroscopy.

  15. Pain sensitivity and neural processing during dissociative states in patients with borderline personality disorder with and without comorbid posttraumatic stress disorder: a pilot study.

    Science.gov (United States)

    Ludäscher, Petra; Valerius, Gabriele; Stiglmayr, Christian; Mauchnik, Jana; Lanius, Ruth A; Bohus, Martin; Schmahl, Christian

    2010-05-01

    Stress-induced dissociative states involving analgesia are a common feature of borderline personality disorder (BPD) and posttraumatic stress disorder (PTSD). Our aim was to investigate the psychologic, somatosensory (pain sensitivity) and neural correlates of dissociative states in patients with these disorders. We included 15 women with BPD who were not taking medication; 10 of these women had comorbid PTSD. While undergoing functional magnetic resonance imaging at 1.5 Tesla, participants were exposed to a script describing a personalized dissociation-inducing situation and a personalized script describing a neutral situation. We assessed dissociative psychopathology and pain sensitivity. Dissociative psychopathology scores were significantly higher and pain sensitivity was lower after the dissociation-inducing script was read compared with the neutral script. The blood oxygen level-dependent (BOLD) signal was significantly increased in the left inferior frontal gyrus (Brodmann area [BA] 9) during the presentation of the dissociation-inducing script. Regression analyses revealed positive correlations between BOLD signal and dissociative psychopathology in the left superior frontal gyrus (BA 6) and negative correlations in the right middle (BA 21) and inferior temporal gyrus (BA 20). In the subgroup of participants with comorbid PTSD, we also found increased activity in the left cingulate gyrus (BA 32) during script-driven imagery-induced dissociation, a positive correlation between dissociation scores and activity in the right and left insula (BA 13) and a negative correlation in the right parahippocampal gyrus (BA 35). The main limitation of this pilot study is the absence of a control group. Therefore, the results may also reflect the neural correlates of non-BPD/PTSD specific dissociative states or the neural correlates of emotionally stressful or "loaded" memories. Another limitation is the uncorrected statistical level of the functional magnetic resonance

  16. DILEPTON YIELD FROM THE DECAY OF EXCITED SI-28 STATES

    NARCIS (Netherlands)

    BACELAR, JC; BUDA, A; BALANDA, A; KRASZNAHORKAY, A; VANDERPLOEG, H; SUJKOWSKI, Z; VANDERWOUDE, A

    1994-01-01

    The first dilepton yield measurements from excited nuclear states obtained with a new Positron-Electron Pair Spectroscopic Instrument (PEPSI) are reported. Nuclear states in Si-28, with an initial excitation energy E* = 50 MeV, were populated via the isospin T = 0 reaction He-4 + Mg-24 and the

  17. Opposite brain emotion-regulation patterns in identity states of dissociative identity disorder : A PET study and neurobiological model

    NARCIS (Netherlands)

    Reinders, Antje A. T. S.; Willemsen, Antoon T. M.; den Boer, Johan A.; Vos, Herry P. J.; Veltman, Dick J.; Loewenstein, Richard J.

    2014-01-01

    Imaging studies in posttraumatic stress disorder (PTSD) have shown differing neural network patterns between hypo-aroused/dissociative and hyper-aroused subtypes. Since dissociative identity disorder (DID) involves different emotional states, this study tests whether DID fits aspects of the

  18. Thermality and excited state Rényi entropy in two-dimensional CFT

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Feng-Li [Department of Physics, National Taiwan Normal University,Taipei 11677, Taiwan (China); Wang, Huajia [Department of Physics, University of Illinois,Urbana-Champaign, IL 61801 (United States); Zhang, Jia-ju [Dipartimento di Fisica, Università degli Studi di Milano-Bicocca,Piazza della Scienza 3, I-20126 Milano (Italy); Theoretical Physics Division, Institute of High Energy Physics, Chinese Academy of Sciences,19B Yuquan Rd, Beijing 100049 (China); Theoretical Physics Center for Science Facilities, Chinese Academy of Sciences,19B Yuquan Rd, Beijing 100049 (China)

    2016-11-21

    We evaluate one-interval Rényi entropy and entanglement entropy for the excited states of two-dimensional conformal field theory (CFT) on a cylinder, and examine their differences from the ones for the thermal state. We assume the interval to be short so that we can use operator product expansion (OPE) of twist operators to calculate Rényi entropy in terms of sum of one-point functions of OPE blocks. We find that the entanglement entropy for highly excited state and thermal state behave the same way after appropriate identification of the conformal weight of the state with the temperature. However, there exists no such universal identification for the Rényi entropy in the short-interval expansion. Therefore, the highly excited state does not look thermal when comparing its Rényi entropy to the thermal state one. As the Rényi entropy captures the higher moments of the reduced density matrix but the entanglement entropy only the average, our results imply that the emergence of thermality depends on how refined we look into the entanglement structure of the underlying pure excited state.

  19. Electronic excited states and relaxation dynamics in polymer heterojunction systems

    Science.gov (United States)

    Ramon, John Glenn Santos

    The potential for using conducting polymers as the active material in optoelectronic devices has come to fruition in the past few years. Understanding the fundamental photophysics behind their operations points to the significant role played by the polymer interface in their performance. Current device architectures involve the use of bulk heterojunctions which intimately blend the donor and acceptor polymers to significantly increase not only their interfacial surface area but also the probability of exciton formation within the vicinity of the interface. In this dissertation, we detail the role played by the interface on the behavior and performance of bulk heterojunction systems. First, we explore the relation between the exciton binding energy to the band offset in determining device characteristics. As a general rule, when the exciton binding energy is greater than the band offset, the exciton remains the lowest energy excited state leading to efficient light-emitting properties. On the other hand, if the offset is greater than the binding energy, charge separation becomes favorable leading to better photovoltaic behavior. Here, we use a Wannier function, configuration interaction based approach to examine the essential excited states and predict the vibronic absorption and emission spectra of the PPV/BBL, TFB/F8BT and PFB/F8BT heterojunctions. Our results underscore the role of vibrational relaxation in the formation of charge-transfer states following photoexcitation. In addition, we look at the relaxation dynamics that occur upon photoexcitation. For this, we adopt the Marcus-Hush semiclassical method to account for lattice reorganization in the calculation of the interconversion rates in TFB/F8BT and PFB/F8BT. We find that, while a tightly bound charge-transfer state (exciplex) remains the lowest excited state, a regeneration pathway to the optically active lowest excitonic state in TFB/F8BT is possible via thermal repopulation from the exciplex. Finally

  20. Interference between radiative emission and autoionization in the decay of excited states of atoms

    International Nuclear Information System (INIS)

    Armstrong, L. Jr.; Theodosiou, C.E.; Wall, M.J.

    1978-01-01

    An excited state of an atom which can autoionize can also undergo radiative decay. We consider the interaction between the final states resulting from these two modes of decay, and its effects on such quantities as the fluorescence yield of the excited state, excitation profile of the excited state, and the spectra of the emitted photons and electrons. It is shown that the fraction of decays of the excited state resulting in a photon (fluorescence yield) is particularly sensitive to the details of the final-state interaction. In lowest order in the final-state interaction, the fluorescence yield is increased by a factor (1 + 1/q 2 ) from the traditional value, where q is the Fano q parameter relating to the excited state and the final atomic state

  1. Mirror Writing and a Dissociative Identity Disorder

    Directory of Open Access Journals (Sweden)

    Catherine Le

    2009-01-01

    Full Text Available Individuals with dissociative identity disorder (DID have been known to show varied skills and talents as they change from one dissociative state to another. For example, case reports have described people who have changed their handedness or have spoken foreign languages during their dissociative states. During an interview with a patient with DID, a surprising talent emerged when she wrote a sentence for the Folstein Mini-Mental State Exam—mirror writing. It is not known whether her mirror writing had a deeper level of meaning; however, it does emphasize the idiosyncratic nature of dissociative identity disorder.

  2. Mirror writing and a dissociative identity disorder.

    Science.gov (United States)

    Le, Catherine; Smith, Joyce; Cohen, Lewis

    2009-01-01

    Individuals with dissociative identity disorder (DID) have been known to show varied skills and talents as they change from one dissociative state to another. For example, case reports have described people who have changed their handedness or have spoken foreign languages during their dissociative states. During an interview with a patient with DID, a surprising talent emerged when she wrote a sentence for the Folstein Mini-Mental State Exam-mirror writing. It is not known whether her mirror writing had a deeper level of meaning; however, it does emphasize the idiosyncratic nature of dissociative identity disorder.

  3. Laser separation of nitrogen isotopes by the IR+UV dissociation of ammonia molecules

    International Nuclear Information System (INIS)

    Apatin, V M; Klimin, S A; Laptev, V B; Lokhman, V N; Ogurok, D D; Pigul'skii, S V; Ryabov, E A

    2008-01-01

    The separation of nitrogen isotopes is studied upon successive single-photon IR excitation and UV dissociation of ammonia molecules. The excitation selectivity was provided by tuning a CO 2 laser to resonance with 14 NH 3 molecules [the 9R(30) laser line] or with 15 NH 3 molecules [the 9R(10) laser line]. Isotopic mixtures containing 4.8% and 0.37% (natural content) of the 15 NH isotope were investigated. The dependences of the selectivity and the dissociation yield for each isotopic component on the buffer gas pressure (N 2 , O 2 , Ar) and the ammonia pressure were obtained. In the limit of low NH 3 pressures (0.5-2 Torr), the dissociation selectivity α(15/14) for 15 N was 17. The selectivity mechanism of the IR+UV dissociation is discussed and the outlook is considered for the development of the nitrogen isotope separation process based on this approach. (laser isotope separation)

  4. The influence of autoionizing states on the excitation of helium by electrons

    International Nuclear Information System (INIS)

    Ittersum, T. van

    1976-01-01

    The work described in this thesis deals with resonance effects in the scattering of electrons by helium at energies near the threshold of the autoionizing states (50-70 eV). The investigation is performed by studying light emission following the excitation of singly excited states. In some cases, the polarization of the radiation was also investigated. The purpose of the research was (i) to enlarge our knowledge of triply excited negative ion states, i.e. resonance states which are formed by temporary binding of the incident electron to a doubly excited (autoionizing) state of neutral helium, and (ii) to clear up the nature of some resonance structures which could not be explained in terms of negative ion resonances

  5. Theoretical study on the cooperative exciton dissociation process based on dimensional and hot charge-transfer state effects in an organic photocell

    International Nuclear Information System (INIS)

    Shimazaki, Tomomi; Nakajima, Takahito

    2016-01-01

    This paper discusses the exciton dissociation process at the donor–acceptor interface in organic photocells. In our previous study, we introduced a local temperature to handle the hot charge-transfer (CT) state and calculated the exciton dissociation probability based on the 1D organic semiconductor model [T. Shimazaki and T. Nakajima, Phys. Chem. Chem. Phys. 17, 12538 (2015)]. Although the hot CT state plays an essential role in exciton dissociations, the probabilities calculated are not high enough to efficiently separate bound electron–hole pairs. This paper focuses on the dimensional (entropy) effect together with the hot CT state effect and shows that cooperative behavior between both effects can improve the exciton dissociation process. In addition, we discuss cooperative effects with site-disorders and external-electric-fields.

  6. Three-body dissociations: The photodissociation of dimethyl sulfoxide at 193 nm

    International Nuclear Information System (INIS)

    Blank, D.A.; North, S.W.; Stranges, D.

    1997-01-01

    When a molecule with two equivalent chemical bonds is excited above the threshold for dissociation of both bonds, how the rupture of the two bonds is temporally coupled becomes a salient question. Following absorption at 193 nm dimethyl sulfoxide (CH 3 SOCH 3 ) contains enough energy to rupture both C-S bonds. This can happen in a stepwise (reaction 1) or concerted (reaction 2) fashion where the authors use rotation of the SOCH 3 intermediate prior to dissociation to define a stepwise dissociation: (1) CH 3 SOCH 3 → 2CH 3 + SO; (2a) CH 3 SOCH 3 → CH 3 + SOCH 3 ; and (2b) SOCH 3 → SO + CH 3 . Recently, the dissociation of dimethyl sulfoxide following absorption at 193 nm was suggested to involve simultaneous cleavage of both C-S bonds on an excited electronic surface. This conclusion was inferred from laser induced fluorescence (LIF) and resonant multiphoton ionization (2+1 REMPI) measurements of the internal energy content in the CH 3 and SO photoproducts and a near unity quantum yield measured for SO. Since this type of concerted three body dissociation is very interesting and a rather rare event in photodissociation dynamics, the authors chose to investigate this system using the technique of photofragment translational spectroscopy at beamline 9.0.2.1. The soft photoionization provided by the VUV undulator radiation allowed the authors to probe the SOCH 3 intermediate which had not been previously observed and provided good evidence that the dissociation of dimethyl sulfoxide primarily proceeds via a two step dissociation, reaction 2

  7. The dissociative chemisorption of methane on Ni(100) and Ni(111): Classical and quantum studies based on the reaction path Hamiltonian

    International Nuclear Information System (INIS)

    Mastromatteo, Michael; Jackson, Bret

    2013-01-01

    Electronic structure methods based on density functional theory are used to construct a reaction path Hamiltonian for CH 4 dissociation on the Ni(100) and Ni(111) surfaces. Both quantum and quasi-classical trajectory approaches are used to compute dissociative sticking probabilities, including all molecular degrees of freedom and the effects of lattice motion. Both approaches show a large enhancement in sticking when the incident molecule is vibrationally excited, and both can reproduce the mode specificity observed in experiments. However, the quasi-classical calculations significantly overestimate the ground state dissociative sticking at all energies, and the magnitude of the enhancement in sticking with vibrational excitation is much smaller than that computed using the quantum approach or observed in the experiments. The origin of this behavior is an unphysical flow of zero point energy from the nine normal vibrational modes into the reaction coordinate, giving large values for reaction at energies below the activation energy. Perturbative assumptions made in the quantum studies are shown to be accurate at all energies studied

  8. Excited-state relaxation of some aminoquinolines

    Directory of Open Access Journals (Sweden)

    2006-01-01

    Full Text Available The absorption and fluorescence spectra, fluorescence quantum yields and lifetimes, and fluorescence rate constants ( k f of 2-amino-3-( 2 ′ -benzoxazolylquinoline (I, 2-amino-3-( 2 ′ -benzothiazolylquinoline (II, 2-amino-3-( 2 ′ -methoxybenzothiazolyl-quinoline (III, 2-amino-3-( 2 ′ -benzothiazolylbenzoquinoline (IV at different temperatures have been measured. The shortwavelength shift of fluorescence spectra of compounds studied (23–49 nm in ethanol as the temperature decreases (the solvent viscosity increases points out that the excited-state relaxation process takes place. The rate of this process depends essentially on the solvent viscosity, but not the solvent polarity. The essential increasing of fluorescence rate constant k f (up to about 7 times as the solvent viscosity increases proves the existence of excited-state structural relaxation consisting in the mutual internal rotation of molecular fragments of aminoquinolines studied, followed by the solvent orientational relaxation.

  9. Excited-State Dynamics of Carotenoids Studied by Femtosecond Transient Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ingu; Pang, Yoonsoo [Department of Physics and Photon Science, Gwangju (Korea, Republic of); Lee, Sebok [Gwangju Institute of Science and Technology, Gwangju (Korea, Republic of)

    2014-03-15

    Carotenoids, natural antenna pigments in photosynthesis share a symmetric backbone of conjugated polyenes. Contrary to the symmetric and almost planar geometries of carotenoids, excited state structure and dynamics of carotenoids are exceedingly complex. In this paper, recent infrared and visible transient absorption measurements and excitation dependent dynamics of 8'-apo-β-caroten-8'-al and 7',7'-dicyano-7'-apo-β-carotene will be reviewed. The recent visible transient absorption measurements of 8'-apo-β-caroten-8'-al in polar and nonpolar solvents will also be introduced to emphasize the complex excited-state dynamics and unsolved problems in the S{sub 2} and S{sub 1} excited states.

  10. Study of the Dissociative Processes in O{sub 2} Discharges. Development of an Atomic Oxygen Beam Source; Etude de la dissociation de O{sub 2} dans les decharges d'oxygene. Application a la realisation de sources d'atomes

    Energy Technology Data Exchange (ETDEWEB)

    Pagnon, Daniel

    1992-09-24

    The first part of this work is devoted to the study of dissociative processes in an oxygen glow discharge at low pressure (0,1-5 Torr, 1-80 mA). The kinetics of oxygen atoms has been determined supported by the measurements of atomic concentrations by VUV absorption spectroscopy and actinometry. The reaction coefficients for dissociative excitation and direct excitation of oxygen atoms have been calculated using the cross sections of the literature and a previously calculated EEDF. It has been demonstrated that dissociative excitation is negligible in respect with direct excitation for dissociation rates smaller than 2,5 %. An upper limit of 20 % for dissociative rates is observed. This limit has been explained by the increase of the atomic recombination at the discharge wall with increasing wall temperature. Using all these results, we have designed and optimized a source of oxygen atoms which has then been adapted on a MBE device. The spatial distribution of the atomic density has been measured in molecular jet by laser induced fluorescence (LIF) and Resonant Multi-Photon Ionization (RMPI). A stimulated emission has been evidenced and the coefficient for this process evaluated. A model for the effusion of atoms has been developed from which the flow of atoms on the sample can be predicted. This source has already been used in industrial MBE devices for in-situ oxidation of copper films, superconductors, and substrates for VLSI high speed applications. The methodology of this work and the diagnostics developed can be applied to other kinds of discharges, of other molecular gases, to design sources of atoms for the treatment of large area samples. (author) [French] Ce travail debute par l'etude de la dissociation dans une decharge luminescente d'oxygene a basse pression (0,1-5 torr, 1-80 ma). La cinetique des atomes d'oxygene a ete etablie a partir de la mesure des concentrations atomiques par spectroscopie d'absorption vuv et par actinometrie. Les coefficients de

  11. Excited state dynamics of beta-carotene explored with dispersed multi-pulse transient absorption

    NARCIS (Netherlands)

    Larsen, D.S.; Papagiannakis, E.; van Stokkum, I.H.M.; Vengris, M.; Kennis, J.T.M.; van Grondelle, R.

    2003-01-01

    The excited-state dynamics of β-carotene in hexane was studied with dispersed ultrafast transient absorption techniques. A new excited state is produced after blue-edge excitation. Pump-repump-probe and pump-dump-probe measurements identified and characterized this state, termed S‡, which exhibits a

  12. Quantum entanglement of localized excited states at finite temperature

    Energy Technology Data Exchange (ETDEWEB)

    Caputa, Paweł [Yukawa Institute for Theoretical Physics (YITP), Kyoto University,Kyoto 606-8502 (Japan); Nordita, KTH Royal Institute of Technology and Stockholm University,Roslagstullsbacken 23, SE-106 91 Stockholm (Sweden); Simón, Joan; Štikonas, Andrius [School of Mathematics and Maxwell Institute for Mathematical Sciences,University of Edinburgh,King’s Buildings, Edinburgh EH9 3FD (United Kingdom); Takayanagi, Tadashi [Yukawa Institute for Theoretical Physics (YITP), Kyoto University,Kyoto 606-8502 (Japan); Kavli Institute for the Physics and Mathematics of the Universe (Kavli IPMU),University of Tokyo,Kashiwa, Chiba 277-8582 (Japan)

    2015-01-20

    In this work we study the time evolutions of (Renyi) entanglement entropy of locally excited states in two dimensional conformal field theories (CFTs) at finite temperature. We consider excited states created by acting with local operators on thermal states and give both field theoretic and holographic calculations. In free field CFTs, we find that the growth of Renyi entanglement entropy at finite temperature is reduced compared to the zero temperature result by a small quantity proportional to the width of the localized excitations. On the other hand, in finite temperature CFTs with classical gravity duals, we find that the entanglement entropy approaches a characteristic value at late time. This behaviour does not occur at zero temperature. We also study the mutual information between the two CFTs in the thermofield double (TFD) formulation and give physical interpretations of our results.

  13. Dielectronic recombination rate coefficients to the excited states of CI from CII

    International Nuclear Information System (INIS)

    Dubau, J.; Kato, T.; Safronova, U.I.

    1998-01-01

    The dielectronic recombination rate coefficients to the excited states for n=2-6 are calculated including 1s 2 2l 1 2l 2 2l 3 nl (n=2-6, l≤(n-1)) states. The values for the excited states higher than n=6 are extrapolated and the total dielectronic recombination rate coefficients are derived. The rate coefficients to the excited states are fitted to an analytical formula and the fit parameters are given. (author)

  14. Excited-state dynamics of acetylene excited to individual rotational level of the V04K01 subband

    Science.gov (United States)

    Makarov, Vladimir I.; Kochubei, Sergei A.; Khmelinskii, Igor V.

    2006-01-01

    Dynamics of the IR emission induced by excitation of the acetylene molecule using the (32Ka0,1,2,ÃAu1←41la1,X˜Σg+1) transition was investigated. The observed IR emission was assigned to transitions between the ground-state vibrational levels. Acetylene fluorescence quenching induced by external electric and magnetic fields acting upon the system prepared using the (34Ka1,ÃAu1←00la0,X˜Σg+1) excitation was also studied. External electric field creates an additional radiationless pathway to the ground-state levels, coupling levels of the ÃAu1 excited state to the quasiresonant levels of the X˜Σg+1 ground state. The level density of the ground state in the vicinity of the excited state is very high, thus the electric-field-induced transition is irreversible, with the rate constant described by the Fermi rule. Magnetic field alters the decay profile without changing the fluorescence quantum yield in collisionless conditions. IR emission from the CCH transient was detected, and was also affected by the external electric and magnetic fields. Acetylene predissociation was demonstrated to proceed by the direct S1→S0 mechanism. The results were explained using the previously developed theoretical approach, yielding values of the relevant model parameters.

  15. Excited state properties of aryl carotenoids

    Czech Academy of Sciences Publication Activity Database

    Fuciman, M.; Chábera, P.; Župčanová, Anita; Hříbek, P.; Arellano, J.B.; Vácha, František; Pšenčík, J.; Polívka, Tomáš

    2010-01-01

    Roč. 12, č. 13 (2010), s. 3112-3120 ISSN 1463-9076 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * excited-states * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 3.454, year: 2010

  16. Spectroscopic properties of the S1 state of linear carotenoids after excess energy excitation

    Science.gov (United States)

    Kuznetsova, Valentyna; Southall, June; Cogdell, Richard J.; Fuciman, Marcel; Polívka, Tomáš

    2017-09-01

    Properties of the S1 state of neurosporene, spheroidene and lycopene were studied after excess energy excitation in the S2 state. Excitation of carotenoids into higher vibronic levels of the S2 state generates excess vibrational energy in the S1 state. The vibrationally hot S1 state relaxes faster when carotenoid is excited into the S2 state with excess energy, but the S1 lifetime remains constant regardless of which vibronic level of the S2 state is excited. The S∗ signal depends on excitation energy only for spheroidene, which is likely due to asymmetry of the molecule, facilitating conformations responsible for the S∗ signal.

  17. Formation and role of excited states in radiolysis - a foreword

    International Nuclear Information System (INIS)

    Singh, A.

    1976-01-01

    It is stated that the choice of contributions to the special issue of this Journal has been limited to those which bear on the details of the mechanisms of excited state formation and are likely to be useful to radiation chemists. Since more than half the energy deposited in radiolysis goes into excitation, studies on the fate of the excited species formed are very important. A brief reference is made to the subject matter of each of the fifteen contributions, and its significance to the development of the technique of radiolysis is outlined. (U.K.)

  18. Local density approximation for exchange in excited-state density functional theory

    OpenAIRE

    Harbola, Manoj K.; Samal, Prasanjit

    2004-01-01

    Local density approximation for the exchange energy is made for treatment of excited-states in density-functional theory. It is shown that taking care of the state-dependence of the LDA exchange energy functional leads to accurate excitation energies.

  19. The study of excited oxygen molecule gas species production and quenching on thermal protection system materials

    Science.gov (United States)

    Nordine, Paul C.; Fujimoto, Gordon T.; Greene, Frank T.

    1987-01-01

    The detection of excited oxygen and ozone molecules formed by surface catalyzed oxygen atom recombination and reaction was investigated by laser induced fluorescence (LIF), molecular beam mass spectrometric (MBMS), and field ionization (FI) techniques. The experiment used partially dissociated oxygen flows from a microwave discharge at pressures in the range from 60 to 400 Pa or from an inductively coupled RF discharge at atmospheric pressure. The catalyst materials investigated were nickel and the reaction cured glass coating used for Space Shuttle reusable surface insulation tiles. Nonradiative loss processes for the laser excited states makes LIF detection of O2 difficult such that formation of excited oxygen molecules could not be detected in the flow from the microwave discharge or in the gaseous products of atom loss on nickel. MBMS experiments showed that ozone was a product of heterogeneous O atom loss on nickel and tile surfaces at low temperatures and that ozone is lost on these materials at elevated temperatures. FI was separately investigated as a method by which excited oxygen molecules may be conveniently detected. Partial O2 dissociation decreases the current produced by FI of the gas.

  20. Dielectronic recombination rate coefficients to the excited states of CI from CII

    Energy Technology Data Exchange (ETDEWEB)

    Dubau, J. [Observatoire of Paris, 92 MEUDON (France); Kato, T.; Safronova, U.I.

    1998-01-01

    The dielectronic recombination rate coefficients to the excited states for n=2-6 are calculated including 1s{sup 2}2l{sub 1}2l{sub 2}2l{sub 3}nl (n=2-6, l{<=}(n-1)) states. The values for the excited states higher than n=6 are extrapolated and the total dielectronic recombination rate coefficients are derived. The rate coefficients to the excited states are fitted to an analytical formula and the fit parameters are given. (author)

  1. Mirror Writing and a Dissociative Identity Disorder

    OpenAIRE

    Le, Catherine; Smith, Joyce; Cohen, Lewis

    2009-01-01

    Individuals with dissociative identity disorder (DID) have been known to show varied skills and talents as they change from one dissociative state to another. For example, case reports have described people who have changed their handedness or have spoken foreign languages during their dissociative states. During an interview with a patient with DID, a surprising talent emerged when she wrote a sentence for the Folstein Mini-Mental State Exam—mirror writing. It is not known whether her mirror...

  2. Excited-state Raman spectroscopy with and without actinic excitation: S1 Raman spectra of trans-azobenzene

    International Nuclear Information System (INIS)

    Dobryakov, A. L.; Quick, M.; Ioffe, I. N.; Granovsky, A. A.; Ernsting, N. P.; Kovalenko, S. A.

    2014-01-01

    We show that femtosecond stimulated Raman spectroscopy can record excited-state spectra in the absence of actinic excitation, if the Raman pump is in resonance with an electronic transition. The approach is illustrated by recording S 1 and S 0 spectra of trans-azobenzene in n-hexane. The S 1 spectra were also measured conventionally, upon nπ* (S 0 → S 1 ) actinic excitation. The results are discussed and compared to earlier reports

  3. A Comparative Study of H2 Excitation and Physical Conditions in Interstellar and Circumstellar Photo-dissociation Regions

    Science.gov (United States)

    Kaplan, Kyle; Dinerstein, Harriet L.; Jaffe, Daniel Thomas

    2017-06-01

    “Photo-dissociation” or “Photon-dominated” Regions (PDRs) exist in the ISM at the interfaces between photo-ionized and molecular gas, where UV radiation sets the ionization state, chemistry, and excitation at the edge of the molecular zone. In these regions, excited rotational-vibrational (“rovibrational”) states of the ground electronic state of H2 are fluorescently populated when the absorption of far-UV photons conveys the molecules into excited electronic states from which they rapidly decay. Downward transitions from the excited rovibrational states produce a rich spectrum of near-infrared emission lines. Since these quadrupole lines are generally optically thin, their fluxes scale with the populations of the upper levels of the respective transitions, providing excellent probes of the excitation and physical conditions in the emitting regions. We present and compare high resolution (R~45,000) near-infrared (1.45-2.45 μm) spectra, obtained on the 2.7 m Harlan J. Smith Telescope at McDonald Observatory with the Immersion Grating INfrared Spectrometer (IGRINS) (Park et al. 2014, SPIE, 9147, 1), for a variety of Galactic PDRs including regions of high mass star formation, reflection nebulae, and planetary nebulae. Typically a large number of transitions, up to about 100 individual lines, are seen in each source. We fit grids of Cloudy models (Ferland et al. 2013, RMxAA, 49, 137) to the observed H2 emission to constrain physical parameters such as the temperature, density, and UV field of each PDR and explore the similarities and differences between the various environments where PDRs arise.This work used the Immersion Grating INfrared Spectrometer (IGRINS), developed under a collaboration between the University of Texas at Austin and the Korea Astronomy and Space Science Institute (KASI) with the financial support of the US National Science Foundation (NSF grant AST-1229522) to the University of Texas at Austin, and the Korean GMT Project of KASI. We

  4. Electron collisions and internal excitation in stored molecular ion beams

    International Nuclear Information System (INIS)

    Buhr, H.

    2006-01-01

    In storage ring experiments the role, which the initial internal excitation of a molecular ion can play in electron collisions, and the effect of these collisions on the internal excitation are investigated. Dissociative recombination (DR) and inelastic and super-elastic collisions are studied in the system of He + 2 . The DR rate coefficient at low energies depends strongly on the initial vibrational excitation in this system. Therefore changes in the DR rate coefficient are a very sensitive probe for changes in the vibrational excitation in He + 2 , which is used to investigate the effects of collisions with electrons and residual gas species. The low-energy DR of HD + is rich with resonances from the indirect DR process, when certain initial rotational levels in the molecular ion are coupled to levels in neutral Rydberg states lying below the ion state. Using new procedures for high-resolution electron-ion collision spectroscopy developed here, these resonances in the DR cross section can be measured with high energy sensitivity. This allows a detailed comparison with results of a MQDT calculation in an effort to assign some or all of the resonances to certain intermediate Rydberg levels. (orig.)

  5. Electron collisions and internal excitation in stored molecular ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Buhr, H.

    2006-07-26

    In storage ring experiments the role, which the initial internal excitation of a molecular ion can play in electron collisions, and the effect of these collisions on the internal excitation are investigated. Dissociative recombination (DR) and inelastic and super-elastic collisions are studied in the system of He{sup +}{sub 2}. The DR rate coefficient at low energies depends strongly on the initial vibrational excitation in this system. Therefore changes in the DR rate coefficient are a very sensitive probe for changes in the vibrational excitation in He{sup +}{sub 2}, which is used to investigate the effects of collisions with electrons and residual gas species. The low-energy DR of HD{sup +} is rich with resonances from the indirect DR process, when certain initial rotational levels in the molecular ion are coupled to levels in neutral Rydberg states lying below the ion state. Using new procedures for high-resolution electron-ion collision spectroscopy developed here, these resonances in the DR cross section can be measured with high energy sensitivity. This allows a detailed comparison with results of a MQDT calculation in an effort to assign some or all of the resonances to certain intermediate Rydberg levels. (orig.)

  6. A theoretical study of CH4 dissociation on pure and gold-alloyed Ni(111) surfaces

    DEFF Research Database (Denmark)

    Kratzer, P.; Hammer, Bjørk; Nørskov, Jens Kehlet

    1996-01-01

    We present a density functional theory study of the first step of CH4 adsorption on the Ni(111) surface, dissociation into adsorbed CH3 and H. The rupture of the C-H bond occurs preferentially on top of a Ni atom, with a dissociation barrier of about 100 kJ/mol (including zero point corrections......). The transition state involves considerable internal excitation of the molecule. The active C-H bond is both stretched to 1.6 Angstrom and tilted relative to the methyl group. A normal mode analysis shows that the reaction coordinate is mainly a C-H stretch, while the orientation of the C-H bond relative...... to the surface is responsible for the highest real mode. Alloying the surface with gold also affects the reactivity of the Ni atoms on adjacent surface sites. The dissociation barrier is increased by 16 and 38 kJ/mol for a Ni atom with one or two gold neighbors, respectively. We attribute these changes...

  7. Atomic excitation and acceleration in strong laser fields

    International Nuclear Information System (INIS)

    Zimmermann, H; Eichmann, U

    2016-01-01

    Atomic excitation in the tunneling regime of a strong-field laser–matter interaction has been recently observed. It is conveniently explained by the concept of frustrated tunneling ionization (FTI), which naturally evolves from the well-established tunneling picture followed by classical dynamics of the electron in the combined laser field and Coulomb field of the ionic core. Important predictions of the FTI model such as the n distribution of Rydberg states after strong-field excitation and the dependence on the laser polarization have been confirmed in experiments. The model also establishes a sound basis to understand strong-field acceleration of neutral atoms in strong laser fields. The experimental observation has become possible recently and initiated a variety of experiments such as atomic acceleration in an intense standing wave and the survival of Rydberg states in strong laser fields. Furthermore, the experimental investigations on strong-field dissociation of molecules, where neutral excited fragments after the Coulomb explosion of simple molecules have been observed, can be explained. In this review, we introduce the subject and give an overview over relevant experiments supplemented by new results. (paper)

  8. Strong-field dissociation dynamics

    International Nuclear Information System (INIS)

    DiMauro, L.F.; Yang, Baorui.

    1993-01-01

    The strong-field dissociation behavior of diatomic molecules is examined under two distinctive physical scenarios. In the first scenario, the dissociation of the isolated hydrogen and deuterium molecular ions is discussed. The dynamics of above-threshold dissociation (ATD) are investigated over a wide range of green and infrared intensities and compared to a dressed-state model. The second situation arises when strong-field neutral dissociation is followed by ionization of the atomic fragments. The study results in a direct measure of the atomic fragment's ac-Stark shift by observing the intensity-dependent shifts in the electron or nuclear fragment kinetic energy. 8 figs., 14 refs

  9. Microscopic description and excitation of unitary analog states

    Energy Technology Data Exchange (ETDEWEB)

    Kisslinger, L S [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA); Van Giai, N [Paris-11 Univ., 91 - Orsay (France). Inst. de Physique Nucleaire

    1977-12-05

    A microscopic investigation in a self-consistent particle-hole model reveals approximate unitary analog states in spite of large symmetry breaking. The K-nucleus elastic scattering and (K/sup -/, ..pi../sup -/) excitation of these states are studied, showing strong surface effects.

  10. Ultrafast electronic relaxation of excited state vitamin B12 in the gas phase

    International Nuclear Information System (INIS)

    Shafizadeh, Niloufar; Poisson, Lionel; Soep, Benoit

    2008-01-01

    The time evolution of electronically excited vitamin B 12 (cyanocobalamin) has been observed for the first time in the gas phase. It reveals an ultrafast decay to a state corresponding to metal excitation. This decay is interpreted as resulting from a ring to metal electron transfer. This opens the observation of the excited state of other complex biomimetic systems in the gas phase, the key to the characterisation of their complex evolution through excited electronic states

  11. Three-body dissociations: The photodissociation of dimethyl sulfoxide at 193 nm

    Energy Technology Data Exchange (ETDEWEB)

    Blank, D.A.; North, S.W.; Stranges, D. [Lawrence Berkeley National Lab., CA (United States)] [and others

    1997-04-01

    When a molecule with two equivalent chemical bonds is excited above the threshold for dissociation of both bonds, how the rupture of the two bonds is temporally coupled becomes a salient question. Following absorption at 193 nm dimethyl sulfoxide (CH{sub 3}SOCH{sub 3}) contains enough energy to rupture both C-S bonds. This can happen in a stepwise (reaction 1) or concerted (reaction 2) fashion where the authors use rotation of the SOCH{sub 3} intermediate prior to dissociation to define a stepwise dissociation: (1) CH{sub 3}SOCH{sub 3} {r_arrow} 2CH{sub 3} + SO; (2a) CH{sub 3}SOCH{sub 3} {r_arrow} CH{sub 3} + SOCH{sub 3}; and (2b) SOCH{sub 3} {r_arrow} SO + CH{sub 3}. Recently, the dissociation of dimethyl sulfoxide following absorption at 193 nm was suggested to involve simultaneous cleavage of both C-S bonds on an excited electronic surface. This conclusion was inferred from laser induced fluorescence (LIF) and resonant multiphoton ionization (2+1 REMPI) measurements of the internal energy content in the CH{sub 3} and SO photoproducts and a near unity quantum yield measured for SO. Since this type of concerted three body dissociation is very interesting and a rather rare event in photodissociation dynamics, the authors chose to investigate this system using the technique of photofragment translational spectroscopy at beamline 9.0.2.1. The soft photoionization provided by the VUV undulator radiation allowed the authors to probe the SOCH{sub 3} intermediate which had not been previously observed and provided good evidence that the dissociation of dimethyl sulfoxide primarily proceeds via a two step dissociation, reaction 2.

  12. Two-dimensional H2O-Cl2 and H2O-Br2 potential surfaces: an ab initio study of ground and valence excited electronic states.

    Science.gov (United States)

    Hernandez-Lamoneda, Ramón; Rosas, Victor Hugo Uc; Uruchurtu, Margarita I Bernal; Halberstadt, Nadine; Janda, Kenneth C

    2008-01-10

    All electron ab initio calculations for the interaction of H2O with Cl2 and Br2 are reported for the ground state and the lowest triplet and singlet Pi excited states as a function of both the X-X and O-X bond lengths (X = Cl or Br). For the ground state and lowest triplet state, the calculations are performed with the coupled cluster singles, doubles, and perturbative triple excitation level of correlation using an augmented triple-zeta basis set. For the 1Pi state the multireference average quadratic coupled cluster technique was employed. For several points on the potential, the calculations were repeated with the augmented quadruple-zeta basis set. The ground-state well depths were found to be 917 and 1,183 cm-1 for Cl2 and Br2, respectively, with the triple-zeta basis set, and they increased to 982 and 1,273 cm-1 for the quadruple-zeta basis set. At the geometry of the ground-state minimum, the lowest energy state corresponding to the unperturbed 1Pi states of the halogens increases in energy by 637 and 733 cm-1, respectively, relative to the ground-state dissociation limit of the H2O-X2 complex. Adding the attractive ground-state interaction energy to that of the repulsive excited state predicts a blue-shift, relative to that of the free halogen molecules, of approximately 1,600 cm-1 for H2O-Cl2 and approximately 2,000 cm-1 for H2O-Br2. These vertical blue-shifts for the dimers are greater than the shift of the band maximum upon solvation of either halogen in liquid water.

  13. First 3- excited state of 56Fe

    International Nuclear Information System (INIS)

    Fotiades, N.; Nelson, R. O.; Devlin, M.

    2010-01-01

    There is no reliable evidence for the existence of the 3.076 MeV (3 - ) level adopted in the ENSDF evaluation for 56 Fe although it has been reported in a few experiments. Previous reports of the observation of this level appear to be based on an incorrect assignment in early (e,e ' ) work. Recent neutron inelastic scattering measurements by Demidov et al. [Phys. At. Nucl. 67, 1884, (2004)] show that the assigned γ-ray decay of this state does not occur at a level consistent with known properties of inelastic scattering. In the present work the 56 Fe(n,n ' γ) reaction was used to populate excited states in 56 Fe. Neutrons in the energy range from 1 to 250 MeV were provided by the pulsed neutron source of the Los Alamos Neutron Science Center's WNR facility. Deexciting γ rays were detected with the GEANIE spectrometer, a Compton suppressed array of 26 Ge detectors. The γ-γ data obtained with GEANIE were used to establish coincidence relations between transitions. All previously reported levels up to E x =3.6 MeV excitation energy were observed except for the 3.076 MeV (3 - ) level. The 991- and 2229-keV transitions, previously reported to deexcite this level, were not observed in the γ-γ coincidence data obtained in the present experiment. The present work supports the assignment of the 4509.6 keV level as the first 3 - excited state in 56 Fe by observation of two previously known transitions deexciting this state.

  14. Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

    Energy Technology Data Exchange (ETDEWEB)

    Van Tassle, Aaron Justin [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    This dissertation describes the development andimplementation of a visible/near infrared pump/mid-infrared probeapparatus. Chapter 1 describes the background and motivation ofinvestigating optically induced structural dynamics, paying specificattention to solvation and the excitation selection rules of highlysymmetric molecules such as carotenoids. Chapter 2 describes thedevelopment and construction of the experimental apparatus usedthroughout the remainder of this dissertation. Chapter 3 will discuss theinvestigation of DCM, a laser dye with a fluorescence signal resultingfrom a charge transfer state. By studying the dynamics of DCM and of itsmethyl deuterated isotopomer (an otherwise identical molecule), we areable to investigate the origins of the charge transfer state and provideevidence that it is of the controversial twisted intramolecular (TICT)type. Chapter 4 introduces the use of two-photon excitation to the S1state, combined with one-photon excitation to the S2 state of thecarotenoid beta-apo-8'-carotenal. These 2 investigations show evidencefor the formation of solitons, previously unobserved in molecular systemsand found only in conducting polymers Chapter 5 presents an investigationof the excited state dynamics of peridinin, the carotenoid responsiblefor the light harvesting of dinoflagellates. This investigation allowsfor a more detailed understanding of the importance of structuraldynamics of carotenoids in light harvesting.

  15. Stability of quantum-dot excited-state laser emission under simultaneous ground-state perturbation

    Energy Technology Data Exchange (ETDEWEB)

    Kaptan, Y., E-mail: yuecel.kaptan@physik.tu-berlin.de; Herzog, B.; Schöps, O.; Kolarczik, M.; Woggon, U.; Owschimikow, N. [Institut für Optik und Atomare Physik, Technische Universität Berlin, Berlin (Germany); Röhm, A.; Lingnau, B.; Lüdge, K. [Institut für Theoretische Physik, Technische Universität Berlin, Berlin (Germany); Schmeckebier, H.; Arsenijević, D.; Bimberg, D. [Institut für Festkörperphysik, Technische Universität Berlin, Berlin (Germany); Mikhelashvili, V.; Eisenstein, G. [Technion Institute of Technology, Faculty of Electrical Engineering, Haifa (Israel)

    2014-11-10

    The impact of ground state amplification on the laser emission of In(Ga)As quantum dot excited state lasers is studied in time-resolved experiments. We find that a depopulation of the quantum dot ground state is followed by a drop in excited state lasing intensity. The magnitude of the drop is strongly dependent on the wavelength of the depletion pulse and the applied injection current. Numerical simulations based on laser rate equations reproduce the experimental results and explain the wavelength dependence by the different dynamics in lasing and non-lasing sub-ensembles within the inhomogeneously broadened quantum dots. At high injection levels, the observed response even upon perturbation of the lasing sub-ensemble is small and followed by a fast recovery, thus supporting the capacity of fast modulation in dual-state devices.

  16. Embedding potentials for excited states of embedded species

    International Nuclear Information System (INIS)

    Wesolowski, Tomasz A.

    2014-01-01

    Frozen-Density-Embedding Theory (FDET) is a formalism to obtain the upper bound of the ground-state energy of the total system and the corresponding embedded wavefunction by means of Euler-Lagrange equations [T. A. Wesolowski, Phys. Rev. A 77(1), 012504 (2008)]. FDET provides the expression for the embedding potential as a functional of the electron density of the embedded species, electron density of the environment, and the field generated by other charges in the environment. Under certain conditions, FDET leads to the exact ground-state energy and density of the whole system. Following Perdew-Levy theorem on stationary states of the ground-state energy functional, the other-than-ground-state stationary states of the FDET energy functional correspond to excited states. In the present work, we analyze such use of other-than-ground-state embedded wavefunctions obtained in practical calculations, i.e., when the FDET embedding potential is approximated. Three computational approaches based on FDET, that assure self-consistent excitation energy and embedded wavefunction dealing with the issue of orthogonality of embedded wavefunctions for different states in a different manner, are proposed and discussed

  17. Selective excitation of atoms or molecules to high-lying states

    International Nuclear Information System (INIS)

    Ducas, T.W.

    1978-01-01

    This specification relates to the selective excitation of atoms or molecules to high lying states and a method of separating different isotopes of the same element by selective excitation of the isotopes. (U.K.)

  18. Interaction of VUV-photons with molecules. Spectroscopy and dynamics of molecular superexcited states

    International Nuclear Information System (INIS)

    Hatano, Y.

    2002-01-01

    Complete text of publication follows. A survey is given of recent progress in experimental studies of the interaction of VUV-photons with molecules, i.e., those of photoabsorption, photoionization, and photodissociation of molecules in the excitation photon energy range of 10-50 eV, with a particular emphasis placed on current understanding of the spectroscopy and dynamics of formed molecular superexcited states. These studies are of great importance in understanding the interaction of ionizing radiation with matter. Molecules studied are ranged from simple diatomic and triatomic molecules to polyatomic molecules such as hydrocarbons. Most of the observed molecular superexcited states are assigned to high Rydber states which are vibrationally, doubly, or inner-core excited and converge to each of ion states. Non-Rydberg superexcited states are also observed. Dissociation into neutral fragments in comparison with ionization is of unexpectedly great importance in the observed decay of each of these state-assigned superexcited molecules. Dissociation dynamics as well as its products of superexcited states are remarkably different from those of lower excited states below about ionization thresholds. Some remarks are also presented of molecules in the condensed phase

  19. Quantum chemical molecular dynamical investigation of alkyl nitrite photo-dissociated on copper surfaces

    International Nuclear Information System (INIS)

    Wang Xiaojing; Wang Wei; Han Peilin; Kubo, Momoji; Miyamoto, Akira

    2008-01-01

    An accelerated quantum chemical molecular dynamical code 'Colors-Excite' was used to investigate the photolysis of alkyl nitrites series, RONO (R=CH 3 and C(CH 3 ) 3 ) on copper surfaces. Our calculations showed that the photo-dissociated processes are associated with the alkyl substituents of RONO when adsorbed on copper surfaces. For R=CH 3 , a two-step photolysis reaction occurred, yielding diverse intermediate products including RO radical, NO, and HNO, consistent with those reported in gas phase. While for R=C(CH 3 ) 3 , only one-step photolysis reaction occurred and gave intermediate products of RO radical and NO. Consequently, pure RO species were achieved to adsorb on metal surfaces by removing the NO species in photolysis reaction. The detailed photo-dissociated behaviors of RONO on copper surfaces with different alkyl substituents which are uncovered by the present simulation can be extended to explain the diverse dissociative mechanism experimentally observed. The quantum chemical molecular dynamical code 'Colors-Excite' is proved to be highly applicable to the photo-dissociations on metal surfaces

  20. Correlation diagram approach to the dissociative ionization mechanisms of methanol

    International Nuclear Information System (INIS)

    Momigny, J.; Wankenne, H.; Krier, C.

    1980-01-01

    A systematic survey is made of the dissociation processes from the ground state and from the electronically excited states of CH 3 OH + . Most metastable processes occurring in the mass spectrum of CD 3 OH are studied also, including measurement of the kinetic energy release and appearance potentials. It is shown that if ionic species such as CH 2 OH + , CH 2 O + and HCO + are present in the mass spectrum of CH 3 OH, the isomers CH 3 O + , HCOH + and COH + are also present. The precursors of these ions having been identified by the metastable processes, correlation diagrams are used to show that, from the first ionization potential of CH 3 OH to 14 eV, the only exception being CH 3 O + which results from an electronically spin-forbidden predissociation, the fragment ions can be considered to result from adiabatic decay of the ground state of CH 3 OH + . The potential barriers involved in these adiabatic processes result either from conical intersection or from avoided-crossing between the ground state of CH 3 OH + and the electronically excited states occurring up to 14 eV. At higher energies, many non-adiabatic processes occur; for example, the appearance of CD 2 O + and the electronically excited states of HCO + and COH + ions. It is shown additionally that kinetic energy releases observed in the collision-induced processes CH 3 OH + → CH 2 OH + + H and CH 2 OH + → HCO + + H 2 are in good agreement with the mechanistic approach via the correlation diagram for the appearance of the non-collision-induced ion processes. (orig.)

  1. Does the excited state of the 3He nucleus exist?

    International Nuclear Information System (INIS)

    Barabanov, A.L.

    1994-01-01

    The suggestion is made that the excited state of the 3 He nucleus found out recently in the reaction has spin and parity 1/2 + and the same configuration that the ground open of 6 He. It is shown that in an elastic nd-scattering a resonance associated with the excited state may be absent due to destructive interference of potential and resonant scattering phases

  2. A benchmark study of electronic excitation energies, transition moments, and excited-state energy gradients on the nicotine molecule

    Energy Technology Data Exchange (ETDEWEB)

    Egidi, Franco, E-mail: franco.egidi@sns.it; Segado, Mireia; Barone, Vincenzo, E-mail: vincenzo.barone@sns.it [Scuola Normale Superiore, Piazza dei Cavalieri, 7 I-56126 Pisa (Italy); Koch, Henrik [Department of Chemistry, Norwegian University of Science and Technology, 7491 Trondheim (Norway); Cappelli, Chiara [Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via G. Moruzzi, 3 I-56124 Pisa (Italy)

    2014-12-14

    In this work, we report a comparative study of computed excitation energies, oscillator strengths, and excited-state energy gradients of (S)-nicotine, chosen as a test case, using multireference methods, coupled cluster singles and doubles, and methods based on time-dependent density functional theory. This system was chosen because its apparent simplicity hides a complex electronic structure, as several different types of valence excitations are possible, including n-π{sup *}, π-π{sup *}, and charge-transfer states, and in order to simulate its spectrum it is necessary to describe all of them consistently well by the chosen method.

  3. Supersymmetric quantum mechanics and higher excited states of a non-polynomial potential

    International Nuclear Information System (INIS)

    Drigo Filho, E.; Ricotta, R.M.

    1989-03-01

    Supersymmetric quantum mechanics is used to evaluate new excited states of a non-polynomial potential. This illustrates a method of evaluating higher excited states of quantum mechanical potentials. (A.C.A.S.) [pt

  4. Competition between excited core states and 1homega single-particle excitations at comparable energies in {sup 207}Pb from photon scattering

    Energy Technology Data Exchange (ETDEWEB)

    Pietralla, N., E-mail: pietralla@ikp.tu-darmstadt.d [Institut fuer Kernphysik, Technische Universitaet Darmstadt, 64289 Darmstadt (Germany); Nuclear Structure Laboratory, SUNY at Stony Brook, Stony Brook, NY 11794-3800 (United States); Institut fuer Kernphysik, Universitaet zu Koeln, 50937 Koeln (Germany); Li, T.C. [Nuclear Structure Laboratory, SUNY at Stony Brook, Stony Brook, NY 11794-3800 (United States); Fritzsche, M. [Institut fuer Kernphysik, Technische Universitaet Darmstadt, 64289 Darmstadt (Germany); Ahmed, M.W. [Triangle Universities Nuclear Laboratory (TUNL), Duke University, Durham, NC 27708 (United States); Ahn, T.; Costin, A. [Institut fuer Kernphysik, Technische Universitaet Darmstadt, 64289 Darmstadt (Germany); Nuclear Structure Laboratory, SUNY at Stony Brook, Stony Brook, NY 11794-3800 (United States); Institut fuer Kernphysik, Universitaet zu Koeln, 50937 Koeln (Germany); Enders, J. [Institut fuer Kernphysik, Technische Universitaet Darmstadt, 64289 Darmstadt (Germany); Li, J. [Duke Free Electron Laser Laboratory (DFELL), Duke University, Durham, NC 27708 (United States); Mueller, S.; Neumann-Cosel, P. von [Institut fuer Kernphysik, Technische Universitaet Darmstadt, 64289 Darmstadt (Germany); Pinayev, I.V. [Duke Free Electron Laser Laboratory (DFELL), Duke University, Durham, NC 27708 (United States); Ponomarev, V.Yu.; Savran, D. [Institut fuer Kernphysik, Technische Universitaet Darmstadt, 64289 Darmstadt (Germany); Tonchev, A.P.; Tornow, W.; Weller, H.R. [Triangle Universities Nuclear Laboratory (TUNL), Duke University, Durham, NC 27708 (United States); Werner, V. [A.W. Wright Nuclear Structure Laboratory (WNSL), Yale University, New Haven, CT (United States); Wu, Y.K. [Duke Free Electron Laser Laboratory (DFELL), Duke University, Durham, NC 27708 (United States); Zilges, A. [Institut fuer Kernphysik, Universitaet zu Koeln, 50937 Koeln (Germany)

    2009-10-26

    The Pb(gamma{sup -}>,gamma{sup '}) photon scattering reaction has been studied with the nearly monochromatic, linearly polarized photon beams at the High Intensity gamma-ray Source (HIgammaS) at the DFELL. Azimuthal scattering intensity asymmetries measured with respect to the polarization plane of the beam have been used for the first time to assign both the spin and parity quantum numbers of dipole excited states of {sup 206,207,208}Pb at excitation energies in the vicinity of 5.5 MeV. Evidence for dominant particle-core coupling is deduced from these results along with information on excitation energies and electromagnetic transition matrix elements. Implications of the existence of weakly coupled states built on highly excited core states in competition with 1homega single particle (hole) excitations at comparable energies are discussed.

  5. Fast kinetics of calcium dissociation from calsequestrin

    Directory of Open Access Journals (Sweden)

    MARIANELA BELTRÁN

    2006-01-01

    Full Text Available We measured the kinetics of calcium dissociation from calsequestrin in solution or forming part of isolated junctional sarcoplasmic reticulum membranes by mixing calsequestrin equilibrated with calcium with calcium-free solutions in a stopped-flow system. In parallel, we measured the kinetics of the intrinsic fluorescence changes that take place following calcium dissociation from calsequestrin. We found that at 25ºC calcium dissociation was 10-fold faster for calsequestrin attached to junctional membranes (k = 109 s-1 than in solution. These results imply that calcium dissociation from calsequestrin in vivo is not rate limiting during excitation-contraction coupling. In addition, we found that the intrinsic fluorescence decrease for calsequestrin in solution or forming part of junctional membranes was significantly slower than the rates of calcium dissociation. The kinetics of intrinsic fluorescence changes had two components for calsequestrin associated to junctional membranes and only one for calsequestrin in solution; the faster component was 8-fold faster (k = 54.1 s-1 than the slower component (k = 6.9 s-1, which had the same k value as for calsequestrin in solution. These combined results suggest that the presence of calsequestrin at high concentrations in a restricted space, such as when bound to the junctional membrane, accelerates calcium dissociation and the resulting structural changes, presumably as a result of cooperative molecular interactions.

  6. The properties of 4'-N,N-dimethylaminoflavonol in the ground and excited states

    Science.gov (United States)

    Moroz, V. V.; Chalyi, A. G.; Roshal, A. D.

    2008-09-01

    The mechanism of protonation of 4-N,N-dimethylaminoflavonol and the structure of its protolytic forms in the ground and excited states were studied by electron absorption and fluorescence (steady-state and time-resolved) spectroscopy and with the use of the RM1 quantum-chemical method. A comparison of equilibrium constants and the theoretical enthalpies of formation showed that excitation should be accompanied by the inversion of the basicity of the electron acceptor groups of this compound and, as a consequence, changes in the structure of its monocationic form. An analysis of the spectral parameters of the protolytic 4-N,N-dimethylaminoflavonol forms, however, showed that their structure and the sequence of protonation in the excited state were the same as in the ground state. Changes in the structure of the monocation in the excited state were not observed because of the fast radiationless deactivation of this form and the occurrence of excited state intramolecular proton transfer in aprotic solvents.

  7. Predictors of trait dissociation and peritraumatic dissociation induced via cold pressor.

    Science.gov (United States)

    Gómez-Pérez, Lydia; López-Martínez, Alicia Eva; Asmundson, Gordon John Glenn

    2013-11-30

    Understanding which factors predict individual dissociative response during stressful situations is important to clarify the nature of dissociation and the mechanisms associated to its use as a coping strategy. The present study examined (1) whether experiential avoidance (EA), anxiety sensitivity (AS), depressive symptoms, and state anxiety concurrently predicted trait dissociation (TD)-absorption, amnesia, depersonalization, and total TD scores-and laboratory induced dissociation (LID); and (2) whether TD and catastrophizing predicted LID. We also examined whether catastrophizing mediated the relationships between both AS and depressive symptoms and LID. A total of 101 female undergraduate students participated in a cold pressor task, which significantly induced dissociation. Results of hierarchical regression analyses showed that AS at Time 1 (9 months before the experimental session), as well as depressive symptoms and catastrophizing at the time of the experiment (Time 2), predicted LID at Time 2. Depressive symptoms at Time 2 predicted total TD, absorption, and amnesia scores. AS at Time 1 and depressive symptoms at Time 2 predicted depersonalization. AS, depressive symptoms, and catastrophizing seem to facilitate the use of dissociative strategies by healthy individuals, even in response to non-traumatic but discomforting stress. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  8. Optimal control of peridinin excited-state dynamics

    Czech Academy of Sciences Publication Activity Database

    Dietzek, B.; Chábera, P.; Hanf, R.; Tschierlei, S.; Popp, J.; Pascher, T.; Yartsev, A.; Polívka, Tomáš

    2010-01-01

    Roč. 373, 1-2 (2010), s. 129-136 ISSN 0301-0104 Institutional research plan: CEZ:AV0Z50510513 Keywords : peridin * excited-state dynamics * coherent control Subject RIV: BO - Biophysics Impact factor: 2.017, year: 2010

  9. Anisotropy of electronic states excited in ion-atom collisions

    International Nuclear Information System (INIS)

    Boskamp, E.B.

    1983-01-01

    The author reports coincidence measurements made on the He + + Ne and He + + He systems. The complex population amplitudes for the magnetic sublevels of the investigated excited states, Ne(2p 4 3s 2 ) 1 D and He(2p 2 ) 1 D, were completely determined and possible excitation mechanisms are described. (Auth.)

  10. Can $\\beta$-decay probe excited state halos?

    CERN Multimedia

    2002-01-01

    In the first experiment at the newly constructed ISOLDE Facility the first-forbidden $\\beta$-decay of $^{17}$Ne into the first excited state of $^{17}$F has been measured. It is a factor two faster than the corresponding mirror decay and thus gives one of the largest recorded asymmetries for $\\beta$-decays feeding bound final states. Shell-model calculations can only reproduce the asymmetry if the halo structure of the $^{17}$F state is taken into account.

  11. Dissociation: a developmental psychoneurobiological perspective

    African Journals Online (AJOL)

    Adele

    ... the stream of con- sciousness and memory.1 It is a frequent symptom of a range ... infant for long time spans in an extremely disturbed psycho- biological state that ... Advantage: Dissociation is adaptive in the short-term. Dissociation can be ...

  12. Spectroscopic Diagnosis of Excited-State Aromaticity: Capturing Electronic Structures and Conformations upon Aromaticity Reversal.

    Science.gov (United States)

    Oh, Juwon; Sung, Young Mo; Hong, Yongseok; Kim, Dongho

    2018-03-06

    Aromaticity, the special energetic stability derived from cyclic [4 n + 2]π-conjugated electronic structures, has been the topic of intense interest in chemistry because it plays a critical role in rationalizing molecular stability, reactivity, and physical/chemical properties. Recently, the pioneering work by Colin Baird on aromaticity reversal, postulating that aromatic (antiaromatic) character in the ground state reverses to antiaromatic (aromatic) character in the lowest excited triplet state, has attracted much scientific attention. The completely reversed aromaticity in the excited state provides direct insight into understanding the photophysical/chemical properties of photoactive materials. In turn, the application of aromatic molecules to photoactive materials has led to numerous studies revealing this aromaticity reversal. However, most studies of excited-state aromaticity have been based on the theoretical point of view. The experimental evaluation of aromaticity in the excited state is still challenging and strenuous because the assessment of (anti)aromaticity with conventional magnetic, energetic, and geometric indices is difficult in the excited state, which practically restricts the extension and application of the concept of excited-state aromaticity. Time-resolved optical spectroscopies can provide a new and alternative avenue to evaluate excited-state aromaticity experimentally while observing changes in the molecular features in the excited states. Time-resolved optical spectroscopies take advantage of ultrafast laser pulses to achieve high time resolution, making them suitable for monitoring ultrafast changes in the excited states of molecular systems. This can provide valuable information for understanding the aromaticity reversal. This Account presents recent breakthroughs in the experimental assessment of excited-state aromaticity and the verification of aromaticity reversal with time-resolved optical spectroscopic measurements. To

  13. Production of autoionizing di-excited states of barium with high angular momentum

    International Nuclear Information System (INIS)

    Roussel, F.; Breger, P.; Gounand, F.; Spiess, G.

    1988-01-01

    Autoionizing di-excited states Ba(6p 1/2 27l) with 7 ≤l≤26, have been experimentally detected. They have been produced by a method combining excitation by two lasers and l-mixing collisions between barium and xenon. Results show that a long delay between the two laser excitation steps is favourable to the production of these states. The method has proved to be very efficient (measured cross-section: σ = 3.1 . 10 -13 cm 2 ) for populating high-angular-momentum autoionizing states of barium

  14. Excited State Structural Dynamics of Carotenoids and Charge Transfer Systems

    International Nuclear Information System (INIS)

    Van Tassle, Aaron Justin

    2006-01-01

    This dissertation describes the development and implementation of a visible/near infrared pump/mid-infrared probe apparatus. Chapter 1 describes the background and motivation of investigating optically induced structural dynamics, paying specific attention to solvation and the excitation selection rules of highly symmetric molecules such as carotenoids. Chapter 2 describes the development and construction of the experimental apparatus used throughout the remainder of this dissertation. Chapter 3 will discuss the investigation of DCM, a laser dye with a fluorescence signal resulting from a charge transfer state. By studying the dynamics of DCM and of its methyl deuterated isotopomer (an otherwise identical molecule), we are able to investigate the origins of the charge transfer state and provide evidence that it is of the controversial twisted intramolecular (TICT) type. Chapter 4 introduces the use of two-photon excitation to the S1 state, combined with one-photon excitation to the S2 state of the carotenoid beta-apo-8'-carotenal. These 2 investigations show evidence for the formation of solitons, previously unobserved in molecular systems and found only in conducting polymers Chapter 5 presents an investigation of the excited state dynamics of peridinin, the carotenoid responsible for the light harvesting of dinoflagellates. This investigation allows for a more detailed understanding of the importance of structural dynamics of carotenoids in light harvesting

  15. Giant dipole resonances built on excited states

    International Nuclear Information System (INIS)

    Snover, K.A.

    1983-01-01

    The properties of giant dipole resonances built on excited nuclear states are reviewed, with emphasis on recent results. Nonstatistical (p,γ) reactions in light nuclei, and statistical complex-particle reactions in light and heavy nuclei are discussed. 27 references

  16. Coulomb and nuclear excitations of narrow resonances in 17Ne

    Directory of Open Access Journals (Sweden)

    J. Marganiec

    2016-08-01

    Full Text Available New experimental data for dissociation of relativistic 17Ne projectiles incident on targets of lead, carbon, and polyethylene targets at GSI are presented. Special attention is paid to the excitation and decay of narrow resonant states in 17Ne. Distributions of internal energy in the O15+p+p three-body system have been determined together with angular and partial-energy correlations between the decay products in different energy regions. The analysis was done using existing experimental data on 17Ne and its mirror nucleus 17N. The isobaric multiplet mass equation is used for assignment of observed resonances and their spins and parities. A combination of data from the heavy and light targets yielded cross sections and transition probabilities for the Coulomb excitations of the narrow resonant states. The resulting transition probabilities provide information relevant for a better understanding of the 17Ne structure.

  17. Lifetime broadening of atomic lines produced upon ultrafast dissociation of HCl and HBr

    Energy Technology Data Exchange (ETDEWEB)

    Lablanquie, P., E-mail: pascal.lablanquie@upmc.fr [Sorbonne Universités, UPMC Univ Paris 06, LCPMR, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); CNRS, LCPMR (UMR 7614), 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); Iwayama, H. [UVSOR Facility, Institute for Molecular Science, Okazaki 444-8585 (Japan); Penent, F. [Sorbonne Universités, UPMC Univ Paris 06, LCPMR, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); CNRS, LCPMR (UMR 7614), 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); Soejima, K. [Department of Environmental Science, Niigata University, Niigata 950-2181 (Japan); Shigemasa, E. [UVSOR Facility, Institute for Molecular Science, Okazaki 444-8585 (Japan)

    2014-08-15

    Highlights: • Ultrafast dissociation of HCl is triggered by 2p{sub 3/2} → σ* excitation. • Ultrafast dissociation of HBr is triggered by 3d{sub 5/2} → σ* excitation. • Photoelectron spectroscopy reveals sharp vibrational molecular lines and broad atomic lines. • The profiles of the atomic lines are analyzed in detail. • We extract the lifetime of the inner shell hole in the neutral atomic fragment. - Abstract: Ultrafast dissociation of the HCl and HBr molecules excited respectively to the 2p{sub 3/2} → σ* and 3d{sub 5/2} → σ* resonances are studied with high resolution photoelectron spectroscopy. Sharp vibrational molecular lines and broad atomic lines are observed. The analysis of the profile of the atomic lines gives access to the lifetimes of the inner shell 2p{sub 3/2} hole in the Cl* (2p{sub 3/2}){sup −1} 3s{sup 2}3p{sup 6} configuration, and the inner shell 3d{sub 5/2} hole in the Br* (3d{sub 5/2}){sup −1} 4s{sup 2}4p{sup 6} configuration.

  18. Model-independent determination of dissociation energies: method and applications

    International Nuclear Information System (INIS)

    Vogel, Manuel; Hansen, Klavs; Herlert, Alexander; Schweikhard, Lutz

    2003-01-01

    A number of methods are available for the purpose of extracting dissociation energies of polyatomic particles. Many of these techniques relate the rate of disintegration at a known excitation energy to the value of the dissociation energy. However, such a determination is susceptible to systematic uncertainties, mainly due to the unknown thermal properties of the particles and the potential existence of 'dark' channels, such as radiative cooling. These problems can be avoided with a recently developed procedure, which applies energy-dependent reactions of the decay products as an uncalibrated thermometer. Thus, it allows a direct measurement of dissociation energies, without any assumption on properties of the system or on details of the disintegration process. The experiments have been performed in a Penning trap, where both rate constants and branching ratios have been measured. The dissociation energies determined with different versions of the method yield identical values, within a small uncertainty

  19. Deciphering excited state evolution in halorhodopsin with stimulated emission pumping.

    Science.gov (United States)

    Bismuth, Oshrat; Komm, Pavel; Friedman, Noga; Eliash, Tamar; Sheves, Mordechai; Ruhman, Sanford

    2010-03-04

    The primary photochemical dynamics of Hb. pharaonis Halorhodopsin (pHR) are investigated by femtosecond visible pump-near IR dump-hyperspectral probe spectroscopy. The efficiency of excited state depletion is deduced from transient changes in absorption, recorded with and without stimulated emission pumping (SEP), as a function of the dump delay. The concomitant reduction of photocycle population is assessed by probing the "K" intermediate difference spectrum. Results show that the cross section for stimulating emission is nearly constant throughout the fluorescent state lifetime. Probing "K" demonstrates that dumping produces a proportionate reduction in photocycle yields. We conclude that, despite its nonexponential internal conversion (IC) kinetics, the fluorescent state in pHR constitutes a single intermediate in the photocycle. This contrasts with conclusions drawn from the study of primary events in the related chloride pump from Hb. salinarum (sHR), believed to produce the "K" intermediate from a distinct short-lived subpopulation in the excited state. Our discoveries concerning internal conversion dynamics in pHR are discussed in light of recent expectations for similar excited state dynamics in both proteins.

  20. Optical emissions from the dissociative recombination of N{sub 2}H{sup +}, HCO{sup +}, HOC{sup +}, and HNC{sup +}

    Energy Technology Data Exchange (ETDEWEB)

    Johnsen, R [Department of Physics and Astronomy University of Pittsburgh, Pittsburgh, PA 15260 (United States); Golde, M F [Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260 (United States); Rosati, R E [Smithsonian Astrophysical Observatory, 60 Garden St. MS-50 Cambridge, MA, 02138 (United States); Pappas, D [Army Research Laboratory, 4600 Deer Creek Loop, Aberdeen Proving Ground, MD (United States); Skrzypkowski, M P, E-mail: rj@pitt.ed [Prometheus Energy Company, 3311 S. 120th Place Suite 100, Seattle, WA 98168 (United States)

    2009-11-15

    We present recent flowing-afterglow measurements of branching fractions for electronically and vibrationally excited products arising from the dissociative recombination of N{sub 2}H{sup +}, HCO{sup +}, HOC{sup +}, and HNC{sup +} ions with thermal electrons. State-specific yields were derived by fitting the observed, spatially resolved emission band intensities to models that simulate all ion-chemical processes, recombination, diffusion, and gas mixing.

  1. Coherence, energy and charge transfers in de-excitation pathways of electronic excited state of biomolecules in photosynthesis

    DEFF Research Database (Denmark)

    Bohr, Henrik; Malik, F. Bary

    2013-01-01

    The observed multiple de-excitation pathways of photo-absorbed electronic excited state in the peridinin–chlorophyll complex, involving both energy and charge transfers among its constituents, are analyzed using the bio-Auger (B-A) theory. It is also shown that the usually used F¨orster–Dexter...

  2. Numerical simulations of oscillating soliton stars: Excited states in spherical symmetry and ground state evolutions in 3D

    International Nuclear Information System (INIS)

    Balakrishna, Jayashree; Bondarescu, Ruxandra; Daues, Gregory; Bondarescu, Mihai

    2008-01-01

    Excited state soliton stars are studied numerically for the first time. The stability of spherically symmetric S-branch excited state oscillatons under radial perturbations is investigated using a 1D code. We find that these stars are inherently unstable either migrating to the ground state or collapsing to black holes. Higher excited state configurations are observed to cascade through intermediate excited states during their migration to the ground state. This is similar to excited state boson stars [J. Balakrishna, E. Seidel, and W.-M. Suen, Phys. Rev. D 58, 104004 (1998).]. Ground state oscillatons are then studied in full 3D numerical relativity. Finding the appropriate gauge condition for the dynamic oscillatons is much more challenging than in the case of boson stars. Different slicing conditions are explored, and a customized gauge condition that approximates polar slicing in spherical symmetry is implemented. Comparisons with 1D results and convergence tests are performed. The behavior of these stars under small axisymmetric perturbations is studied and gravitational waveforms are extracted. We find that the gravitational waves damp out on a short time scale, enabling us to obtain the complete waveform. This work is a starting point for the evolution of real scalar field systems with arbitrary symmetries

  3. Energy-Looping Nanoparticles: Harnessing Excited-State Absorption for Deep-Tissue Imaging.

    Science.gov (United States)

    Levy, Elizabeth S; Tajon, Cheryl A; Bischof, Thomas S; Iafrati, Jillian; Fernandez-Bravo, Angel; Garfield, David J; Chamanzar, Maysamreza; Maharbiz, Michel M; Sohal, Vikaas S; Schuck, P James; Cohen, Bruce E; Chan, Emory M

    2016-09-27

    Near infrared (NIR) microscopy enables noninvasive imaging in tissue, particularly in the NIR-II spectral range (1000-1400 nm) where attenuation due to tissue scattering and absorption is minimized. Lanthanide-doped upconverting nanocrystals are promising deep-tissue imaging probes due to their photostable emission in the visible and NIR, but these materials are not efficiently excited at NIR-II wavelengths due to the dearth of lanthanide ground-state absorption transitions in this window. Here, we develop a class of lanthanide-doped imaging probes that harness an energy-looping mechanism that facilitates excitation at NIR-II wavelengths, such as 1064 nm, that are resonant with excited-state absorption transitions but not ground-state absorption. Using computational methods and combinatorial screening, we have identified Tm(3+)-doped NaYF4 nanoparticles as efficient looping systems that emit at 800 nm under continuous-wave excitation at 1064 nm. Using this benign excitation with standard confocal microscopy, energy-looping nanoparticles (ELNPs) are imaged in cultured mammalian cells and through brain tissue without autofluorescence. The 1 mm imaging depths and 2 μm feature sizes are comparable to those demonstrated by state-of-the-art multiphoton techniques, illustrating that ELNPs are a promising class of NIR probes for high-fidelity visualization in cells and tissue.

  4. Vibrational excitation in a hydrogen volume source

    International Nuclear Information System (INIS)

    Eenshuistra, P.J.

    1989-01-01

    In this thesis the complex of processes which determines the D - or H - density in a volume source, a hydrogen discharge, is studied. D - beams are of interest for driving the current of a fusion plasma in a TOKAMAK. Densities of vibrationally excited molecules, of H atoms, and of metastable hydrogen molecules were determined using Resonance-Enhanced MultiPhoton Ionization (REMPI). An experiment in which vibrationally highly excited molecules are formed by recombination of atoms in a cold metal surface, is described. The production and destruction of vibrationally excited molecules and atoms in the discharge is discussed. The vibrational distribution for 3≤ν≤5 (ν = vibrational quantumnumber) is strongly super-thermal. This effect is more apparent at higher discharge current and lower gas pressure. The analysis with a model based on rate equations, which molecules are predominantly produced by primary electron excitation of hydrogen molecules and deexcited upon one wall collision. The atom production is compatible with dissociation of molecules by primary electrons, dissociation of molecules on the filaments, and collisions between positive ions and electrons. The electrons are predominantly destroyed by recombination on the walls. Finally the production and destruction of H - in the discharge are discussed. The density of H - in the plasma, the electron density and temperature were determined. H - extraction was measured. The ratio of the extracted H - current and the H - density in the plasma gives an indication of the drift velocity of H - in the plasma. This velocity determines the emittance of the extracted beam. It was found that the H - velocity scales with the square root of the electron temperature. The measured H - densities are compatible with a qualitative model in which dissociative attachment of plasma electrons to vibrationally excited molecules is the most important process. (author). 136 refs.; 39 figs.; 10 tabs

  5. Statistical density of nuclear excited states

    Directory of Open Access Journals (Sweden)

    V. M. Kolomietz

    2015-10-01

    Full Text Available A semi-classical approximation is applied to the calculations of single-particle and statistical level densities in excited nuclei. Landau's conception of quasi-particles with the nucleon effective mass m* < m is used. The approach provides the correct description of the continuum contribution to the level density for realistic finite-depth potentials. It is shown that the continuum states does not affect significantly the thermodynamic calculations for sufficiently small temperatures T ≤ 1 MeV but reduce strongly the results for the excitation energy at high temperatures. By use of standard Woods - Saxon potential and nucleon effective mass m* = 0.7m the A-dependency of the statistical level density parameter K was evaluated in a good qualitative agreement with experimental data.

  6. The eΠ3g state of C2: A pathway to dissociation

    Science.gov (United States)

    Welsh, B. A.; Krechkivska, O.; Nauta, K.; Bacskay, G. B.; Kable, S. H.; Schmidt, T. W.

    2017-07-01

    The lowest 13 vibrational levels, v = 0-12, of the eΠ3g state of the C2 molecule have been measured by laser-induced fluorescence of new bands of the Fox-Herzberg system. The newly observed levels, v = 5-12, which span the eΠ3g electronic state up to and beyond the first dissociation threshold of C2, were analyzed to afford highly accurate molecular constants, including band origins, and rotational and spin-orbit constants. The spin-orbit coupling constants of the previously published lowest five levels are revised in sign and magnitude, requiring an overhaul of previously published molecular constants. The analysis is supported by high level ab initio calculations. Lifetimes of all observed levels were recorded and found to be in excellent agreement with ab initio predicted values up to v = 11. v = 12 was found to exhibit a much reduced lifetime and fluorescence quantum yield, which is attributed to the onset of predissociation. This brackets the dissociation energy of ground state XΣ+1g C2 between 6.1803 and 6.2553 eV, in agreement with the Active Thermochemical Tables.

  7. Interplay between singlet and triplet excited states in a conformationally locked donor–acceptor dyad

    KAUST Repository

    Filatov, Mikhail A.

    2015-10-13

    The synthesis and photophysical characterization of a palladium(II) porphyrin – anthracene dyad bridged via short and conformationally rigid bicyclo[2.2.2]octadiene spacer were achieved. A spectroscopic investigation of the prepared molecule in solution has been undertaken to study electronic energy transfer in excited singlet and triplet states between the anthracene and porphyrin units. By using steady-state and time-resolved photoluminescence spectroscopy it was shown that excitation of the singlet excited state of the anthracene leads to energy transfer to the lower-lying singlet state of porphyrin. Alternatively, excitation of the porphyrin followed by intersystem crossing to the triplet state leads to very fast energy transfer to the triplet state of anthracene. The rate of this energy transfer has been determined by transient absorption spectroscopy. Comparative studies of the dynamics of triplet excited states of the dyad and reference palladium octaethylporphyrin (PdOEP) have been performed.

  8. Interplay between singlet and triplet excited states in a conformationally locked donor–acceptor dyad

    KAUST Repository

    Filatov, Mikhail A.; Etzold, Fabian; Gehrig, Dominik; Laquai, Fré dé ric; Busko, Dmitri; Landfester, Katharina; Baluschev, Stanislav

    2015-01-01

    The synthesis and photophysical characterization of a palladium(II) porphyrin – anthracene dyad bridged via short and conformationally rigid bicyclo[2.2.2]octadiene spacer were achieved. A spectroscopic investigation of the prepared molecule in solution has been undertaken to study electronic energy transfer in excited singlet and triplet states between the anthracene and porphyrin units. By using steady-state and time-resolved photoluminescence spectroscopy it was shown that excitation of the singlet excited state of the anthracene leads to energy transfer to the lower-lying singlet state of porphyrin. Alternatively, excitation of the porphyrin followed by intersystem crossing to the triplet state leads to very fast energy transfer to the triplet state of anthracene. The rate of this energy transfer has been determined by transient absorption spectroscopy. Comparative studies of the dynamics of triplet excited states of the dyad and reference palladium octaethylporphyrin (PdOEP) have been performed.

  9. Dynamics of dissociation versus ionization in strong laser fields

    International Nuclear Information System (INIS)

    DiMauro, L.F.; Yang, B.

    1993-01-01

    In this paper, experimental results are presented which clearly demonstrate the effectiveness that an external field has in altering the dissociation dynamics. The experiment examines the strong-field dissociation dynamics of molecular hydrogen ions and its deuterated isotopes. These studies involve multiphoton excitation in the intensity regime of 10 11-14 W/cm 2 with the fundamental and second harmonic of a ND:YAG or ND:YLF laser system. Measurements include energy resolved electron and mass spectroscopy which provide useful probes in elucidating the interaction dynamics predicted by existing models. The example this in this paper, examines the strong-field dissociation of H 2 + , HD + , and D 2 + at green (0.5 μm) and (1μm) frequencies. The diatomic ions are formed via multiphonon ionization of the neutral precursor which is physically separable from the dissociation process. This study provides the first observation of the dynamics associated with the above threshold dissociation (ATD) process and analogies will be made with the more familiar above threshold ionization (ATI) phenomenon

  10. Study of the Dissociative Processes in O_2 Discharges. Development of an Atomic Oxygen Beam Source

    International Nuclear Information System (INIS)

    Pagnon, Daniel

    1992-01-01

    The first part of this work is devoted to the study of dissociative processes in an oxygen glow discharge at low pressure (0,1-5 Torr, 1-80 mA). The kinetics of oxygen atoms has been determined supported by the measurements of atomic concentrations by VUV absorption spectroscopy and actinometry. The reaction coefficients for dissociative excitation and direct excitation of oxygen atoms have been calculated using the cross sections of the literature and a previously calculated EEDF. It has been demonstrated that dissociative excitation is negligible in respect with direct excitation for dissociation rates smaller than 2,5 %. An upper limit of 20 % for dissociative rates is observed. This limit has been explained by the increase of the atomic recombination at the discharge wall with increasing wall temperature. Using all these results, we have designed and optimized a source of oxygen atoms which has then been adapted on a MBE device. The spatial distribution of the atomic density has been measured in molecular jet by laser induced fluorescence (LIF) and Resonant Multi-Photon Ionization (RMPI). A stimulated emission has been evidenced and the coefficient for this process evaluated. A model for the effusion of atoms has been developed from which the flow of atoms on the sample can be predicted. This source has already been used in industrial MBE devices for in-situ oxidation of copper films, superconductors, and substrates for VLSI high speed applications. The methodology of this work and the diagnostics developed can be applied to other kinds of discharges, of other molecular gases, to design sources of atoms for the treatment of large area samples. (author) [fr

  11. Excited-state formation as H+ and He+ ions scatter from metal surfaces

    International Nuclear Information System (INIS)

    Baird, W.E.; Zivitz, M.; Thomas, E.W.

    1975-01-01

    Impact of 10-to30KeV H + or He + ions on polycrystalline metal surfaces causes some projectiles to be backscattered in a neutral excited state. These projectiles subsequently radiatively decay, emitting Doppler-broadened spectral lines. By analysis of the spectral shape of these lines, we are able to determine the probability of radiationless deexcitation of the excited backscattered atoms. Quantitative measurements of spectral intensity indicate that less than 1% of all projectiles are backscattered in an excited state. The relative variation of total spectral line intensity with angle of projectile incidence and with projectile primary energy has been successfully predicted using a model which assumes that the probability for excited-state formation is independent of the scattered projectile's energy and direction. The variation in total spectral line intensity with target atomic number is predicted, and the sputtering and excitation of Al under He + impact is briefly examined

  12. Di-lepton yield from the decay of excited 28Si states

    International Nuclear Information System (INIS)

    Bacelar, J.C.; Buda, A.; Balanda, A.; Krasznahorkay, A.; Ploeg, H. van der; Sujkowski, Z.; Woude, A. van der

    1994-01-01

    The first dilepton yield measurements from excited nuclear states obtained with a new Positron-Electron Pair Spectroscopic Instrument (PEPSI) are reported. Nuclear states in 28 Si, with an initial excitation energy E * =50 MeV, were populated via the isospin T=0 reaction 4 He+ 24 Mg and the mixed-isospin 3 He+ 25 Mg reaction. In both reactions the dilepton (e + e - ) and photon decay yields were measured concurrently. An excess of counts in the e + e - spectrum, over the converted photon yield, is observed in the energy region above 15 MeV. An analyses is discussed whereby the observed excess counts are assumed to represent the isoscalar E0 strength in excited nuclear states. (orig.)

  13. Excited-state Raman spectroscopy with and without actinic excitation: S{sub 1} Raman spectra of trans-azobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Dobryakov, A. L.; Quick, M.; Ioffe, I. N.; Granovsky, A. A.; Ernsting, N. P.; Kovalenko, S. A. [Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, D-12489 Berlin (Germany)

    2014-05-14

    We show that femtosecond stimulated Raman spectroscopy can record excited-state spectra in the absence of actinic excitation, if the Raman pump is in resonance with an electronic transition. The approach is illustrated by recording S{sub 1} and S{sub 0} spectra of trans-azobenzene in n-hexane. The S{sub 1} spectra were also measured conventionally, upon nπ* (S{sub 0} → S{sub 1}) actinic excitation. The results are discussed and compared to earlier reports.

  14. Superexcited states of molecules

    International Nuclear Information System (INIS)

    Nakamura, Hiroki; Takagi, Hidekazu.

    1990-01-01

    The report addresses the nature and major features of molecule's superexcited states, focusing on their involvement in dynamic processes. It also outlines the quantum defect theory which allows various processes involving these states to be treated in a unified way. The Rydberg state has close relation with an ionized state with a positive energy. The quantum defect theory interprets such relation. Specifically, the report first describes the quantum defect theory focusing on its basic principle. The multi-channel quantum defect theory is then outlined centering on how to describe a Rydberg-type superexcited state. Description of a dissociative double-electron excited state is also discussed. The quantum defect theory is based on the fact that the physics of the motion of a Rydberg electron vary with the region in the electron's coordinate space. Finally, various molecular processes that involve a superexcited state are addressed focusing on autoionization, photoionization, dissociative recombination and bonding ionization of diatomic molecules. (N.K.)

  15. Sensitivity of (α,α') cross sections to excited-state quadrupole moments

    International Nuclear Information System (INIS)

    Baker, F.T.; Scott, A.; Ronningen, R.M.; Hamilton, J.H.; Kruse, T.H.; Suchannek, R.; Savin, W.

    1977-01-01

    Inelastic α particle scattering at 21 and 24 MeV has been used to estimate the electric quadrupole moment of the second 2 + state in 180 Hf. Sensitivity to the assumed quadrupole moment is due almost entirely to reorientation via the nuclear force. Results suggest that the technique may be a useful method of estimating excited state quadrupole moments, particularly for states with high excitation energies or with J greater than 2

  16. Electronic properties of excited states in single InAs quantum dots

    International Nuclear Information System (INIS)

    Warming, Till

    2009-01-01

    The application of quantum-mechanical effects in semiconductor nanostructures enables the realization of novel opto-electronic devices. Examples are given by single-photon emitters and emitters of entangled photon pairs, both being essential for quantum cryptography, or for qubit systems as needed for quantum computing. InAs/GaAs quantum dots are one of the most promising candidates for such applications. A detailed knowledge of the electronic properties of quantum dots is a prerequisite for this development. The aim of this work is an experimental access to the detailed electronic structure of the excited states in single InAs/GaAs quantum dots including few-particle effects and in particular exchange interaction. The experimental approach is micro photoluminescence excitation spectroscopy (μPLE). One of the main difficulties using μPLE to probe single QDs is the unambiguous assignment of the observed resonances in the spectrum to specific transitions. By comparing micro photoluminescence (μPL) and μPLE spectra, the identification of the main resonances becomes possible. The key is given by the fine structure of the hot trion. Excitation spectroscopy on single charged QDs enables for the first time the complete observation of a non-trivial fine structure of an excitonic complex in a QD, the hot trion. Modelling based on eight-band k.p theory in combination with a configuration interaction scheme is in excellent agreement. Therewith the simulation also enables realistic predictions on the fine structure of the ground-state exciton which is of large importance for single quantum dot devices. Theory concludes from the observed transitions that the structural symmetry of the QDs is broken. Micro photoluminescence excitation spectroscopy combined with resonantly excited micro photoluminescence enables an optical access to the single particle states of the hole without the influence of few-particle coulomb interactions. Based on this knowledge the exciton binding

  17. Evidence for stepwise dissociation dynamics in acetone at 248 and 193 nm

    Science.gov (United States)

    North, Simon W.; Blank, David A.; Gezelter, J. Daniel; Longfellow, Cheryl A.; Lee, Yuan T.

    1995-03-01

    The technique of molecular beam photofragment translational spectroscopy has been used to study the dissociation of acetone following S1←S0 (248 nm) and S2←S0 (193 nm) excitation. Excitation at 248 nm resulted in the production of CH3 and CH3CO with 14.2±1.0 kcal/mole on average of the available energy appearing as translation of the photofragments. Comparison of the measured with values reported at 266 nm suggest that the energy partitioning is dominated by the exit barrier caused by an avoided crossing on the potential energy surface. A substantial fraction (30±4%) of the nascent acetyl radicals from the primary dissociation contain sufficient energy to undergo spontaneous secondary decomposition. From the onset of the truncation of the CH3CO P(ET) a threshold of 17.8±3.0 kcal/mole for the dissociation of the acetyl radical has been determined in agreement with recent results on the photodissociation of acetyl chloride. The translational energy release in the dissociation of CH3CO closely matches the experimentally determined exit barrier. At 193 nm the only observed dissociation pathway was the formation of two methyl radicals and carbon monoxide. On average ˜38% of the available energy is found in product translation suggesting that significant internal energy resides in the nascent CH3 fragments consistent with the results of Hall et al. [J. Chem. Phys. 94, 4182 (1991)]. We conclude that the dynamics and energy partitioning for dissociation at 193 nm is similar to that at 248 nm.

  18. Opposite brain emotion-regulation patterns in identity states of dissociative identity disorder: a PET study and neurobiological model.

    Science.gov (United States)

    Reinders, Antje A T S; Willemsen, Antoon T M; den Boer, Johan A; Vos, Herry P J; Veltman, Dick J; Loewenstein, Richard J

    2014-09-30

    Imaging studies in posttraumatic stress disorder (PTSD) have shown differing neural network patterns between hypo-aroused/dissociative and hyper-aroused subtypes. Since dissociative identity disorder (DID) involves different emotional states, this study tests whether DID fits aspects of the differing brain-activation patterns in PTSD. While brain activation was monitored using positron emission tomography, DID individuals (n=11) and matched DID-simulating healthy controls (n=16) underwent an autobiographic script-driven imagery paradigm in a hypo-aroused and a hyper-aroused identity state. Results were consistent with those previously found in the two PTSD subtypes for the rostral/dorsal anterior cingulate, the prefrontal cortex, and the amygdala and insula, respectively. Furthermore, the dissociative identity state uniquely activated the posterior association areas and the parahippocampal gyri, whereas the hyper-aroused identity state uniquely activated the caudate nucleus. Therefore, we proposed an extended PTSD-based neurobiological model for emotion modulation in DID: the hypo-aroused identity state activates the prefrontal cortex, cingulate, posterior association areas and parahippocampal gyri, thereby overmodulating emotion regulation; the hyper-aroused identity state activates the amygdala and insula as well as the dorsal striatum, thereby undermodulating emotion regulation. This confirms the notion that DID is related to PTSD as hypo-aroused and hyper-arousal states in DID and PTSD are similar. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  19. Particle hole excitations coupled to complex states in heavy-ion collisions

    International Nuclear Information System (INIS)

    Jolos, R.V.; Schmidt, R.

    1982-01-01

    The excitation of uncorrelated 1p-1h states in one nucleus due to the action of the time-dependent mean field of the other nucleus was studied earlier. No statistical assumptions or average procedures were made. Such a mechanism can be responsible for an appreciable excitation of the two nuclei during the short approach phase of the reaction (E* approximately> 100 MeV). The reversibility of the equations of motion leads to a deexcitation of the initially stored excitation energy into that of the relative motion for later times. This feedback behaviour of the internal excitation energy which results in particular to the deexcitation of high energetic 1p-1h pairs is probably not realistic due to the coupling of this states to more complex states with high density. It is studied the influence of this coupling due to the residual interaction between the nucleons on the dynamics of two colliding heavy ions

  20. Partial dissociative emission cross sections and product state distributions of the resulting photofragments

    Energy Technology Data Exchange (ETDEWEB)

    Picconi, David; Grebenshchikov, Sergy Yu., E-mail: Sergy.Grebenshchikov@ch.tum.de

    2016-12-20

    This paper relates the partial cross section of a continuous optical emission into a given scattering channel of the lower electronic state to the photofragment population. This allows one to infer partial emission cross sections ‘non-optically’ from product state distributions; in computations, explicit construction of exact scattering states is therefore avoided. Applications to the emission spectra of NaI, CO{sub 2}, and pyrrole are given. It is also demonstrated that a similar relationship holds between partial cross sections of dissociative photoionization and distributions of ionic fragments over final product channels.

  1. Observation of excited state charge transfer with fs/ps-CARS

    International Nuclear Information System (INIS)

    Blom, Alex Jason

    2009-01-01

    Excited state charge transfer processes are studied using the fs/ps-CARS probe technique. This probe allows for multiplexed detection of Raman active vibrational modes. Systems studied include Michler's Ketone, Coumarin 120, 4-dimethylamino-4(prime)-nitrostilbene, and several others. The vibrational spectrum of the para di-substituted benzophenone Michler's Ketone in the first excited singlet state is studied for the first time. It is found that there are several vibrational modes indicative of structural changes of the excited molecule. A combined experimental and theoretical approach is used to study the simplest 7-amino-4-methylcoumarin, Coumarin 120. Vibrations observed in FTIR and spontaneous Raman spectra are assigned using density functional calculations and a continuum solvation model is used to predict how observed modes are affected upon inclusion of a solvent. The low frequency modes of the excited state charge transfer species 4-dimethylamino-4(prime)-nitrostilbene are studied in acetonitrile. Results are compared to previous work on this molecule in the fingerprint region. Finally, several partially completed projects and their implications are discussed. These include the two photon absorption of Coumarin 120, nanoconfinement in cyclodextrin cavities and sensitization of titania nanoparticles

  2. Observation of excited state charge transfer with fs/ps-CARS

    Energy Technology Data Exchange (ETDEWEB)

    Blom, Alex Jason [Iowa State Univ., Ames, IA (United States)

    2009-01-01

    Excited state charge transfer processes are studied using the fs/ps-CARS probe technique. This probe allows for multiplexed detection of Raman active vibrational modes. Systems studied include Michler's Ketone, Coumarin 120, 4-dimethylamino-4'-nitrostilbene, and several others. The vibrational spectrum of the para di-substituted benzophenone Michler's Ketone in the first excited singlet state is studied for the first time. It is found that there are several vibrational modes indicative of structural changes of the excited molecule. A combined experimental and theoretical approach is used to study the simplest 7-amino-4-methylcoumarin, Coumarin 120. Vibrations observed in FTIR and spontaneous Raman spectra are assigned using density functional calculations and a continuum solvation model is used to predict how observed modes are affected upon inclusion of a solvent. The low frequency modes of the excited state charge transfer species 4-dimethylamino-4{prime}-nitrostilbene are studied in acetonitrile. Results are compared to previous work on this molecule in the fingerprint region. Finally, several partially completed projects and their implications are discussed. These include the two photon absorption of Coumarin 120, nanoconfinement in cyclodextrin cavities and sensitization of titania nanoparticles.

  3. Energies and lifetimes of excited states in copperlike Kr VIII

    International Nuclear Information System (INIS)

    Livingston, A.E.; Curtis, L.J.; Schectman, R.M.; Berry, H.G.

    1980-01-01

    The spectrum of Kr VIII has been observed between 180 and 2000 A by using foil excitation of 2.5--3.5-MeV krypton ions. Twenty new transitions have been classified and eleven new excited-state energies have been determined within the n=4 --7 shells. The ionization potential is derived to be 1 015 800 +- 200 cm -1 . The excited-state energies and fine structures are compared with recent relativistic Hartree-Fock calculations. The 4p-state lifetime has been measured by performing a simultaneous analysis of decay data for the 4p level and for its dominant cascade-repopulating levels. The 4p lifetime is found to be 30% shorter than previously measured values and is in excellent agreement with the result of a recent multiconfiguration Hartree-Fock calculation. The source of the discrepancy between this result and earlier measurements is discussed

  4. Cross sections for the vibrational excitation of the H2 X 1Σ+g(v) levels generated by electron collisional excitation of the higher singlet states

    International Nuclear Information System (INIS)

    Hiskes, J.R.

    1991-01-01

    The excitation cross sections, σ(v,v double-prime), for an H 2 molecule initially in any one of the 15 vibrational levels, v belonging to the ground electronic state and excited to a final vibrational level, v double-prime are evaluated for direct excitations via all members of the excited electronic singlet spectrum. Account is taken of predissociation, autoionization, and radiative decay of the excited electronic spectrum that leads to a final population distribution for the ground electronic state, X 1 Σ + g (v double-prime). For v=0, account is taken explicitly of transitions via the B, C, B', and D electronic states in evaluating the cross sections. The additional contribution of excitations via all Rydberg states lying above the D state enhances these cross sections by approximately 10%. For v>0, cross sections are evaluated taking explicit account of transitions through the B and C states; higher singlet excitations enhance these values by 25%. The choice of the reference total cross sections remains a subjective one, causing the values calculated here to have a possible uncertainty of +20% -30% . For excitations occurring within a hydrogen discharge, collisional excitation-ionization events among the intermediate singlet states will effectively quench the v, v double-prime excitation process for discharge densities in excess of the range 10 15 --10 16 electrons/cm -3

  5. Watson-Crick base pairing controls excited-state decay in natural DNA.

    Science.gov (United States)

    Bucher, Dominik B; Schlueter, Alexander; Carell, Thomas; Zinth, Wolfgang

    2014-10-13

    Excited-state dynamics are essential to understanding the formation of DNA lesions induced by UV light. By using femtosecond IR spectroscopy, it was possible to determine the lifetimes of the excited states of all four bases in the double-stranded environment of natural DNA. After UV excitation of the DNA duplex, we detected a concerted decay of base pairs connected by Watson-Crick hydrogen bonds. A comparison of single- and double-stranded DNA showed that the reactive charge-transfer states formed in the single strands are suppressed by base pairing in the duplex. The strong influence of the Watson-Crick hydrogen bonds indicates that proton transfer opens an efficient decay path in the duplex that prohibits the formation or reduces the lifetime of reactive charge-transfer states. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Excited State Chemistry in the Free Stream of the NASA IHF Arc Jet Facility Observed by Emission Spectroscopy

    Science.gov (United States)

    Winter, Michael W.; Prabhu, Dinesh K.

    2011-01-01

    Spectroscopic measurements of non-equilibrium emission were made in the free stream of the 60 megawatts Interaction Heating Facility at NASA Ames Research Center. In the visible near infrared wavelength region, the most prominent emission was from molecular N2, and in the ultra violet region, the spectra were dominated by emission from molecular NO. The only atomic lines observed were those of copper (an erosion product of the electrodes). The bands of the 1st Positive system of N2 (if B is true then A is true) differed significantly from spectra computed spectra assuming only thermal excitation, suggesting overpopulation of the high vibrational states of the B state of N2. Populations of these high vibrational levels (peaking at v (sub upper) equals 13) of the N2 B state were determined by scaling simulated spectra; calculations were performed for each upper vibrational state separately. The experimental-theoretical procedure was repeated for several radial positions away from the nozzle axis to obtain spatial distributions of the upper state populations; rotational symmetry of the flow was assumed in simulations. The overpopulation of the high vibrational levels has been interpreted as the effect of inverse pre-dissociation of neutral atoms in the N2 A state, which populates the N2 B state through a level crossing process at v (sub upper) is greater than 10.

  7. Ioniclike energy structure of neutral core-excited states in free Kr clusters

    International Nuclear Information System (INIS)

    Peredkov, S.; Sorensen, S.L.; Kivimaeki, A.; Schulz, J.; Maartensson, N.; Oehrwall, G.; Lundwall, M.; Rander, T.; Lindblad, A.; Bergersen, H.; Svensson, S.; Bjoerneholm, O.; Tchaplyguine, M.

    2005-01-01

    The development of electronic states in krypton clusters is investigated by high-resolution core-level electron spectroscopy. The energy ordering of bulk versus surface 3d -1 np(n>5) core-excited states in neutral clusters is demonstrated to be reversed to the 3d -1 5p level situation. The cluster 3d -1 6p,7p states are proven to be at a lower energy than the corresponding atomic levels. These findings reveal the ioniclike energy structure of the neutral cluster core-excited levels. The phenomenon is explained by a spatial spread of the excited orbitals over the cluster lattice

  8. Clustered chimera states in systems of type-I excitability

    International Nuclear Information System (INIS)

    Vüllings, Andrea; Omelchenko, Iryna; Hövel, Philipp; Hizanidis, Johanne

    2014-01-01

    The chimera state is a fascinating phenomenon of coexisting synchronized and desynchronized behaviour that was discovered in networks of nonlocally coupled identical phase oscillators over ten years ago. Since then, chimeras have been found in numerous theoretical and experimental studies and more recently in models of neuronal dynamics as well. In this work, we consider a generic model for a saddle-node bifurcation on a limit cycle representative of neural excitability type I. We obtain chimera states with multiple coherent regions (clustered chimeras/multi-chimeras) depending on the distance from the excitability threshold, the range of nonlocal coupling and the coupling strength. A detailed stability diagram for these chimera states and other interesting coexisting patterns (like traveling waves) is presented. (paper)

  9. The triplet excited state of bilirubin

    International Nuclear Information System (INIS)

    Land, E.J.

    1976-01-01

    Pulse radiolysis of benzene solutions of 40 μM bilirubin alone or with 0.1 M biphenyl has yielded evidence for the formation of the triplet excited state of bilirubin. Measurements were made of a number of properties, including the absorption spectrum (lambdasub(max)500nm), lifetime 9μs), extinction coefficient (8800 M -1 cm -1 ), energy level (approximately 150 kJ mol -1 ) and the rate of quenching by oxygen (rate constant, 8.2 x 10 8 M -1 s -1 ). An upper limit of 0.1 has also been obtained for the singlet to triplet crossover efficiency of bilirubin following excitation by 353 nm radiation. Consideration is given to the relevance of these data to the mechanism of bilirubin photo-destruction, both in vivo and in vitro. (U.K.)

  10. Technique for description of nonrotational excited states in a semiphenomenological nuclear theory

    International Nuclear Information System (INIS)

    Krutov, V.A.

    1985-01-01

    A non-standard technique for microscopic description of excited nonrotational states is considered; it is suitable for inseparable force application. Besides, an additional binding operator, mixing quasi-particle excitations and E1-resonance states, is considered. Instead of the standard technique of state ''collectivization'' of the random phase approximation type it is used the so-called ''method of bound amplitudes''

  11. Non-orthogonal configuration interaction for the calculation of multielectron excited states

    Energy Technology Data Exchange (ETDEWEB)

    Sundstrom, Eric J., E-mail: eric.jon.sundstrom@berkeley.edu; Head-Gordon, Martin [Department of Chemistry, University of California Berkeley, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2014-03-21

    We apply Non-orthogonal Configuration Interaction (NOCI) to molecular systems where multielectron excitations, in this case double excitations, play a substantial role: the linear polyenes and β-carotene. We demonstrate that NOCI when applied to systems with extended conjugation, provides a qualitatively correct wavefunction at a fraction of the cost of many other multireference treatments. We also present a new extension to this method allowing for purification of higher-order spin states by utilizing Generalized Hartree-Fock Slater determinants and the details for computing 〈S{sup 2}〉 for the ground and excited states.

  12. Coulomb dissociation of 8B at 254 MeV/u

    International Nuclear Information System (INIS)

    Surowka, G.; Iwasa, N.; Boue, F.

    1999-01-01

    As an alternative method to determine the cross section of 7 Be (p, γ) 8 B, the Coulomb dissociation reaction 8 B → 7 Be + p at E inc = 254 MeV/u was measured. Our preliminary results show the dominant role of the dipole excitation in the Coulomb break-up process. The extracted astrophysical S 17 factor is consistent with the lower-value results both of the direct-capture studies, and the RIKEN Coulomb-dissociation experiment at ∼ 50 MeV/u. (author)

  13. Excited State s-cis Rotamers Produced by Extreme Red Edge Excitation of all-trans-1,4-Diphenyl-1,3-butadiene

    DEFF Research Database (Denmark)

    Wallace-Williams, Stacie E.; Møller, Søren; Goldbeck, Robert A.

    1993-01-01

    with the wavelength independence observed for the excited singlet-state absorption and fluorescence emission spectra of 1,5-diphenyl-2,3,4,6,7,8- hexahydronaphthalene and for the fluorescence emission spectra of 1,4diphenyl-1,3-cyclopentadiene, s-trans and s-cis structural analogs of DPB, respectively. The spectral...... changes in DPB can be explained in terms of an excitation wavelength-dependent production of s-cis and s-trans rotamer populations in the excited state. The DPB fluorescence emission spectrum was resolved into s-cis and s-trans components. The vibronic structure of the s-cis fluorescence spectrum...... is similar to that of s-trans, but the band origin is red-shifted and there is a slightly larger amplitude on the red edge. The excited-state absorption spectrum of s-cis DPB appears to be red-shifted relative to that of s-trans DPB as well....

  14. Study of highly excited high spin states via the (HI, α) reaction

    International Nuclear Information System (INIS)

    Kubono, S.

    1982-01-01

    Three subjects are discussed in this paper. 1) The mechanism of (HI, α) reactions is briefly studied. 2) Possible excitation of molecular resonance states of 12 C- 12 C in 24 Mg through the 12 C( 16 O, α) 24 Mg reaction were investigated. A precise measurement of the level widths in 24 Mg did not support the previous report that the molecular states seen in 12 C + 12 C scattering had been excited in the transfer reaction 12 C( 16 O, α) 24 Mg. 3) Highly excited states in 28 Si, which have a large parentage of 12 C- 16 O, were also studied via the 12 C( 20 Ne, α) 28 Si reaction. An angular correlation measurement revealed the lowest 8 + and 10 + states at 14.00 and 15.97 MeV, respectively, which were selectively excited in the 12 C( 20 Ne, α) reaction. These results suggest a possible new band in 28 Si. (author)

  15. Collision-induced dissociation of diatomic ions

    International Nuclear Information System (INIS)

    Los, J.; Govers, T.R.

    1978-01-01

    An attempt is made to illustrate how mass spectrometric studies of dissociation in diatomic molecular ions can provide information on the dynamics of these collisions and on the predissociative states involved. Restriction is made to primary beam energies of the order of at least keV. The review covers the dynamics of dissociation, experimental techniques, direct dissociation in heavy-particle collisions, and translational spectroscopy. 120 references

  16. Characterising excited states in and around the semi-magic nucleus $^{68}$ Ni using Coulomb excitation and one-neutron transfer

    CERN Multimedia

    It is proposed to investigate the structure of excited states in $^{68, 70}$Ni(Z =28, N=40, 42) via the measurement of electromagnetic matrix elements in a Coulomb excitation experiment in order to study the N = 40 harmonic-oscillator shell and the Z = 28 proton shell closures. The measured B(E2) values connecting low-lying 0$^{+}$ and 2$^{+}$ can be compared to shell-model predictions. It is also proposed to perform the one-neutron transfer reaction ${d}$($^{68}$Ni,$^{69}$Ni)${p}$, with the aim of populating excited states in $^{69}$Ni. Comparisons with the states populated in the recently performed ${d}$($^{66}$Ni,$^{67}$Ni)${p}$ reaction will be useful in determining the role of the neutron $d_{5/2}$ orbital in the semi-magic properties of $^{68}$Ni.

  17. Coherent excitation of a single atom to a Rydberg state

    DEFF Research Database (Denmark)

    Miroshnychenko, Yevhen; Gaëtan, Alpha; Evellin, Charles

    2010-01-01

    We present the coherent excitation of a single Rubidium atom to the Rydberg state 58d3/2 using a two-photon transition. The experimental setup is described in detail, as are experimental techniques and procedures. The coherence of the excitation is revealed by observing Rabi oscillations between...

  18. Some studies on the formation of excited states of aromatic solutes in hydrocarbons and other solvents

    Energy Technology Data Exchange (ETDEWEB)

    Salmon, G A [Leeds Univ. (UK). Cookridge High Energy Radiation Research Centre

    1976-01-01

    This paper reviews the work of the author and his co-workers on the radiation-induced formation of excited states of aromatic compounds in solution. The experimental methods used are surveyed and in particular the method of measuring the yields of triplet and singlet excited states of the solute are described. The problems discussed are: (1) the effect of solvent on the yields of excited states, (2) formation of excited states in cyclohexane and other alicyclic hydrocarbons, (3) the formation of excited states in benzene and (4) the identification of T-T absorption spectra.

  19. Excitation of spin-1 states in 166168170Er using bremsstrahlung

    International Nuclear Information System (INIS)

    Metzger, F.R.

    1976-01-01

    Some 40 states in 166 , 168 , 170 Er, most of them previously unknown, have been excited using bremsstrahlung with < or =4.2 MeV endpoint energy. For all but three of these levels, the angular distribution of the resonantly scattered radiation favors the assignment of spin 1. For some of the strongly excited levels, linear polarization measurements have been performed. They indicate that these levels have positive parity. The branching ratios further characterize them as K=1 excitations

  20. Excited-state dynamics of the medicinal pigment curcumin in a hydrogel.

    Science.gov (United States)

    Harada, Takaaki; Lincoln, Stephen F; Kee, Tak W

    2016-10-12

    Curcumin is a yellow polyphenol with multiple medicinal effects. These effects, however, are limited due to its poor aqueous stability and solubility. A hydrogel of 3% octadecyl randomly substituted polyacrylate (PAAC18) has been shown to provide high aqueous stability for curcumin under physiological conditions, offering a route for photodynamic therapy. In this study, the excited-state photophysics of curcumin in the PAAC18 hydrogel is investigated using a combination of femtosecond transient absorption and fluorescence upconversion spectroscopy. The transient absorption results reveal a multiexponential decay in the excited-state kinetics with fast (1 ps & 15 ps) and slow (110 ps & ≈5 ns) components. The fast decay component exhibits a deuterium isotope effect with D 2 O in the hydrogel, indicating that the 15 ps decay component is attributable to excited-state intramolecular hydrogen atom transfer of curcumin in the PAAC18 hydrogel. In addition, solvent reorganisation of excited-state curcumin is investigated using multiwavelength femtosecond fluorescence upconversion spectroscopy. The results show that the dominant solvation response (τ = 0.08 ps) is a fast inertial motion owing to the presence of bulk-like water in the vicinity of the hydrophobic octadecyl substituents of the PAAC18 hydrogel. The results also show an additional response with longer time constants of 1 and 6 ps, which is attributable to translational diffusion of confined water molecules in the three-dimensional, cross-linking network of the octadecyl substituents of PAAC18. Overall, we show that excited-state intramolecular hydrogen atom transfer and solvent reorganisation are major photophysical events for curcumin in the PAAC18 hydrogel.

  1. Rearrangements in ground and excited states

    CERN Document Server

    de Mayo, Paul

    1980-01-01

    Rearrangements in Ground and Excited States, Volume 2 covers essays on the theoretical approach of rearrangements; the rearrangements involving boron; and the molecular rearrangements of organosilicon compounds. The book also includes essays on the polytopal rearrangement at phosphorus; the rearrangement in coordination complexes; and the reversible thermal intramolecular rearrangements of metal carbonyls. Chemists and people involved in the study of rearrangements will find the book invaluable.

  2. Tracking excited-state charge and spin dynamics in iron coordination complexes

    DEFF Research Database (Denmark)

    Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe

    2014-01-01

    to spin state, can elucidate the spin crossover dynamics of [Fe(2,2'-bipyridine)(3)](2+) on photoinduced metal-to-ligand charge transfer excitation. We are able to track the charge and spin dynamics, and establish the critical role of intermediate spin states in the crossover mechanism. We anticipate......Crucial to many light-driven processes in transition metal complexes is the absorption and dissipation of energy by 3d electrons(1-4). But a detailed understanding of such non-equilibrium excited-state dynamics and their interplay with structural changes is challenging: a multitude of excited...... states and possible transitions result in phenomena too complex to unravel when faced with the indirect sensitivity of optical spectroscopy to spin dynamics(5) and the flux limitations of ultrafast X-ray sources(6,7). Such a situation exists for archetypal poly-pyridyl iron complexes, such as [Fe(2...

  3. Linear-scaling quantum mechanical methods for excited states.

    Science.gov (United States)

    Yam, ChiYung; Zhang, Qing; Wang, Fan; Chen, GuanHua

    2012-05-21

    The poor scaling of many existing quantum mechanical methods with respect to the system size hinders their applications to large systems. In this tutorial review, we focus on latest research on linear-scaling or O(N) quantum mechanical methods for excited states. Based on the locality of quantum mechanical systems, O(N) quantum mechanical methods for excited states are comprised of two categories, the time-domain and frequency-domain methods. The former solves the dynamics of the electronic systems in real time while the latter involves direct evaluation of electronic response in the frequency-domain. The localized density matrix (LDM) method is the first and most mature linear-scaling quantum mechanical method for excited states. It has been implemented in time- and frequency-domains. The O(N) time-domain methods also include the approach that solves the time-dependent Kohn-Sham (TDKS) equation using the non-orthogonal localized molecular orbitals (NOLMOs). Besides the frequency-domain LDM method, other O(N) frequency-domain methods have been proposed and implemented at the first-principles level. Except one-dimensional or quasi-one-dimensional systems, the O(N) frequency-domain methods are often not applicable to resonant responses because of the convergence problem. For linear response, the most efficient O(N) first-principles method is found to be the LDM method with Chebyshev expansion for time integration. For off-resonant response (including nonlinear properties) at a specific frequency, the frequency-domain methods with iterative solvers are quite efficient and thus practical. For nonlinear response, both on-resonance and off-resonance, the time-domain methods can be used, however, as the time-domain first-principles methods are quite expensive, time-domain O(N) semi-empirical methods are often the practical choice. Compared to the O(N) frequency-domain methods, the O(N) time-domain methods for excited states are much more mature and numerically stable, and

  4. Two-electron excitation in slow ion-atom collisions: Excitation mechanisms and interferences among autoionizing states

    International Nuclear Information System (INIS)

    Kimura, M.; Rice Univ., Houston, TX

    1990-01-01

    The two-electron capture or excitation process resulting from collisions of H + and O 6+ ions with He atoms in the energy range from 0.5 keV/amu to 5 keV/amu is studied within a molecular representation. The collision dynamics for formation of doubly excited O 4+ ions and He** atoms and their (n ell, n'ell ') populations are analyzed in conjunction with electron correlations. Autoionizing states thus formed decay through the Auger process. An experimental study of an ejected electron energy spectrum shows ample structures in addition to two characteristic peaks that are identified by atomic and molecular autoionizations. These structures are attributable to various interferences among electronic states and trajectories. We examine the dominant sources of the interferences. 12 refs., 5 figs

  5. Study of dissociative collisions of hydrogen-line ions by mean of angular and energy distributions

    International Nuclear Information System (INIS)

    Martinez, H.; Urquijo, J. de; Cisneros, C.; Alvarez, J.

    1988-01-01

    Angular and energy distribution of fragments produced in a collision, employed in conjunction with the 'step-model' that means excitation and binary dissociation, are used to determine the binding energy of H 3 (D 3 ) and HD + 2 and also to identify the principal channels in the dissociation processes. (A.C.A.S.) [pt

  6. Using narrowband excitation to confirm that the S∗ state in carotenoids is not a vibrationally-excited ground state species

    Science.gov (United States)

    Jailaubekov, Askat E.; Song, Sang-Hun; Vengris, Mikas; Cogdell, Richard J.; Larsen, Delmar S.

    2010-02-01

    The hypothesis that S∗ is a vibrationally-excited ground-state population is tested and discarded for two carotenoid samples: β-carotene in solution and rhodopin glucoside embedded in the light harvesting 2 protein from Rhodopseudomonas acidophila. By demonstrating that the transient absorption signals measured in both systems that are induced by broadband (1000 cm -1) and narrowband (50 cm -1) excitation pulses are near identical and hence bandwidth independent, the impulsive stimulated Raman scattering mechanism proposed as the primary source for S∗ generation is discarded. To support this conclusion, previously published multi-pulse pump-dump-probe signals [17] are revisited to discard secondary mechanisms for S∗ formation.

  7. Can Internal Conversion BE Controlled by Mode-Specific Vibrational Excitation in Polyatomic Molecules

    Science.gov (United States)

    Portnov, Alexander; Epshtein, Michael; Bar, Ilana

    2017-06-01

    Nonadiabatic processes, dominated by dynamic passage of reactive fluxes through conical intersections (CIs) are considered to be appealing means for manipulating reaction paths. One approach that is considered to be effective in controlling the course of dissociation processes is the selective excitation of vibrational modes containing a considerable component of motion. Here, we have chosen to study the predissociation of the model test molecule, methylamine and its deuterated isotopologues, excited to well-characterized quantum states on the first excited electronic state, S_{1}, by following the N-H(D) bond fission dynamics through sensitive H(D) photofragment probing. The branching ratios between slow and fast H(D) photofragments, the internal energies of their counter radical photofragments and the anisotropy parameters for fast H photofragments, confirm correlated anomalies for predissociation initiated from specific rovibronic states, reflecting the existence of a dynamic resonance in each molecule. This resonance strongly depends on the energy of the initially excited rovibronic states, the evolving vibrational mode on the repulsive S_{1} part during N-H(D) bond elongation, and the manipulated passage through the CI that leads to radicals excited with C-N-H(D) bending and preferential perpendicular bond breaking, relative to the photolyzing laser polarization, in molecules containing the NH_{2} group. The indicated resonance plays an important role in the bifurcation dynamics at the CI and can be foreseen to exist in other photoinitiated processes and to control their outcome.

  8. Self-energy correction to the hyperfine splitting for excited states

    International Nuclear Information System (INIS)

    Wundt, B. J.; Jentschura, U. D.

    2011-01-01

    The self-energy corrections to the hyperfine splitting is evaluated for higher excited states in hydrogenlike ions using an expansion in the binding parameter Zα, where Z is the nuclear-charge number and α is the fine-structure constant. We present analytic results for D, F, and G states, and for a number of highly excited Rydberg states, with principal quantum numbers in the range 13≤n≤16, and orbital angular momenta l=n-2 and l=n-1. A closed-form analytic expression is derived for the contribution of high-energy photons, valid for any state with l≥2 and arbitrary n, l, and total angular momentum j. The low-energy contributions are written in the form of generalized Bethe logarithms and evaluated for selected states.

  9. Mechanism for the Excited-State Multiple Proton Transfer Process of Dihydroxyanthraquinone Chromophores.

    Science.gov (United States)

    Zhou, Qiao; Du, Can; Yang, Li; Zhao, Meiyu; Dai, Yumei; Song, Peng

    2017-06-22

    The single and dual cooperated proton transfer dynamic process in the excited state of 1,5-dihydroxyanthraquinone (1,5-DHAQ) was theoretically investigated, taking solvent effects (ethanol) into account. The absorption and fluorescence spectra were simulated, and dual fluorescence exhibited, which is consistent with previous experiments. Analysis of the calculated IR and Raman vibration spectra reveals that the intramolecular hydrogen bonding interactions (O 20 -H 21 ···O 24 and O 22 -H 23 ···O 25 ) are strengthened following the excited proton transfer process. Finally, by constructing the potential energy surfaces of the ground state, first excited singlet state, and triplet state, the mechanism of the intramolecular proton transfer of 1,5-DHAQ can be revealed.

  10. Equations of state for self-excited MHD generator studies

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, F.J.; Ross, M.; Haggin, G.L.; Wong, L.K.

    1980-02-26

    We have constructed a state-of-the-art equation of state (EOS) for argon covering the temperature density range attainable by currently proposed self-excited MHD generators. The EOS for conditions in the flow channel was obtained primarily by a non-ideal plasma code (ACTEX) that is based on a many body activity expansion. For conditions in the driver chamber the EOS was primarily obtained from a fluid code (HDFP) that calculates the fluid properties from perturbation theory based on the insulator interatomic pair potential but including electronic excitations. The results are in agreement with several sets of experimental data in the 0.6 - 91 GPa pressure range.

  11. Bottom-up excited state dynamics of two cinnamate-based sunscreen filter molecules.

    Science.gov (United States)

    Peperstraete, Yoann; Staniforth, Michael; Baker, Lewis A; Rodrigues, Natércia D N; Cole-Filipiak, Neil C; Quan, Wen-Dong; Stavros, Vasilios G

    2016-10-12

    Methyl-E-4-methoxycinnamate (E-MMC) is a model chromophore of the commonly used commercial sunscreen agent, 2-ethylhexyl-E-4-methoxycinnamate (E-EHMC). In an effort to garner a molecular-level understanding of the photoprotection mechanisms in operation with E-EHMC, we have used time-resolved pump-probe spectroscopy to explore E-MMC's and E-EHMC's excited state dynamics upon UV-B photoexcitation to the S 1 (1 1 ππ*) state in both the gas- and solution-phase. In the gas-phase, our studies suggest that the excited state dynamics are driven by non-radiative decay from the 1 1 ππ* to the S 3 (1 1 nπ*) state, followed by de-excitation from the 1 1 nπ* to the ground electronic state (S 0 ). Using both a non-polar-aprotic solvent, cyclohexane, and a polar-protic solvent, methanol, we investigated E-MMC and E-EHMC's photochemistry in a more realistic, 'closer-to-shelf' environment. A stark change to the excited state dynamics in the gas-phase is observed in the solution-phase suggesting that the dynamics are now driven by efficient E/Z isomerisation from the initially photoexcited 1 1 ππ* state to S 0 .

  12. The structure of nuclear states at low, intermediate and high excitation energies

    International Nuclear Information System (INIS)

    Soloviev, V.G.

    1976-01-01

    It is shown that within the model based on the quasiparticle-phonon interaction one can obtain the description of few-quasiparticle components of nuclear states at low, intermediate and high excitation energies. For the low-lying states the energy of each level is calculated. The few-quasiparticle components at intermediate and high excitation energies are represented to be averaged in certain energy intervals and their characteri stics are given as the corresponding strength functions. The fragmentation of single-particle states in deformed nuclei is studied. It is shown that in the distribution of the single-particle strength alongside with a large maximum there appear local maxima and the distribution itself has a long tail. The dependence of neutron strength functions on the excitation energy is investigated for the transfer reaction of the type (d,p) and (d,t). The s,- p,- and d-wave neutron strength functions are calculated at the neutron binding energy Bn. A satisfactory agreement with experiment is obtained. The energies and Elambda-strength functions for giant multipole resonances in deformed nuclei are calculated. The energies of giant quadrupole and octupole resonances are calculated. Their widths and fine structure are being studied. It is stated that to study the structure of highly excited states it is necessary to find the values of many-quasiparticle components of the wave functions. The ways of experimental determination of these components based on the study of γ-transitions between highly excited states are discussed

  13. Evidence for concerted ring opening and C-Br bond breaking in UV-excited bromocyclopropane.

    Science.gov (United States)

    Pandit, Shubhrangshu; Preston, Thomas J; King, Simon J; Vallance, Claire; Orr-Ewing, Andrew J

    2016-06-28

    Photodissociation of gaseous bromocyclopropane via its A-band continuum has been studied at excitation wavelengths ranging from 230 nm to 267 nm. Velocity-map images of ground-state bromine atoms (Br), spin-orbit excited bromine atoms (Br(∗)), and C3H5 hydrocarbon radicals reveal the kinetic energies of these various photofragments. Both Br and Br(∗) atoms are predominantly generated via repulsive excited electronic states in a prompt photodissociation process in which the hydrocarbon co-fragment is a cyclopropyl radical. However, the images obtained at the mass of the hydrocarbon radical fragment identify a channel with total kinetic energy greater than that deduced from the Br and Br(∗) images, and with a kinetic energy distribution that exceeds the energetic limit for Br + cyclopropyl radical products. The velocity-map images of these C3H5 fragments have lower angular anisotropies than measured for Br and Br(∗), indicating molecular restructuring during dissociation. The high kinetic energy C3H5 signals are assigned to allyl radicals generated by a minor photochemical pathway which involves concerted C-Br bond dissociation and cyclopropyl ring-opening following single ultraviolet (UV)-photon absorption. Slow photofragments also contribute to the velocity map images obtained at the C3H5 radical mass, but the corresponding slow Br atoms are not observed. These features in the images are attributed to C3H5 (+) from the photodissociation of the C3H5Br(+) molecular cation following two-photon ionization of the parent compound. This assignment is confirmed by 118-nm vacuum ultraviolet ionization studies that prepare the molecular cation in its ground electronic state prior to UV photodissociation.

  14. Wavepacket theory of collisional dissociation in molecules

    International Nuclear Information System (INIS)

    Kulander, K.

    1980-01-01

    An explicit integration scheme is used to solve the time dependent Schroedinger equation for wavepackets which model collisions in the collinear H + H 2 system. A realistic LEPS-type potential energy surface is used. Collision energies considered are above the dissociation threshold and probabilities for collision induced dissociation are reported. Also quantum mechanical state-to-state transition probabilities are generated. These results are compared to extensive classical trajectory calculations performed on this same system. The time evolution of the wavepacket densities is studied to understand the dynamics of the collinear collisional dissociation process

  15. Ultra-high resolution spectroscopy of the He doubly excited states

    International Nuclear Information System (INIS)

    Bozek, J.D.; Schlachter, A.S.; Kaindl, G.; Schulz, K.

    1995-11-01

    Photoionization spectra of the doubly-excited states of He were measured using beamline 9.0.1 at the Advanced Light Source. The beamline utilizes a 4.5 m long 8 cm period undulator as its source together with a spherical grating monochromator to provide an extremely bright source of photons in the range of 20 - 300 eV. A resolving power (E/ΔE) of 64,000 was obtained from the 1 MeV FWEM (2p,3d) doubly excited state resonance of He at 64.12 eV. The high brightness of the source and the very high quality optical elements of the beamline were all essential for achieving such a high resolution. The beamline components and operation are described and spectra of the double excitation resonances of He presented

  16. Neutral excitations in the Gaffnian state

    Science.gov (United States)

    Kang, Byungmin; Moore, Joel E.

    2017-06-01

    We study a model fractional quantum Hall (FQH) wave function called the Gaffnian state, which is believed to represent a gapless, strongly correlated state that is very different from conventional metals. To understand this exotic gapless state better, we provide a representation based on work of Halperin in which the pairing structure of the Gaffnian state becomes more explicit. We employ the single-mode approximation introduced by Girvin, MacDonald, and Platzman, here extended to three-body interactions, in order to treat a neutral collective excitation mode in order to clarify the physical origin of the gaplessness of the Gaffnian state. We discuss approaches to extract systematically the relevant physics in the long-distance, large-electron-number limit of FQH states using numerical calculations with relatively few electrons. In Appendices, we provide second-quantized expressions for many-body Haldane pseudopotentials in various geometries including the plane, sphere, cylinder, and torus based on the proper definition of the relative angular momentum.

  17. Mechanisms for the Production of Fast HI from Dissociation of H2 on Saturn

    Science.gov (United States)

    Liu, Xianming; Johnson, Paul; Malone, Charles; Young, Jason; Kanik, Isik; Shemansky, Donald

    2010-05-01

    Images of the Saturn system obtained by the Cassini UVIS at a pixel resolution of 0.1 × 0.1 Saturn radii (Rs) reveal atomic hydrogen in ballistic and escaping trajectories sourced at the top of the thermosphere, primarily in the southern sunlit hemisphere. The main feature in the image is a distinctive H Lyman-α plume structure with FWHM of 0.56 Rs at the exobase sub-solar limb at ~ -13.5° latitude constituting the core of the distributed outward flow of atomic hydrogen from the sunlit hemisphere, with a counterpart on the anti-solar side peaking near the equator above the exobase limb. The structure of the image indicates that part of the out-flowing population is sub-orbital and re-enters the thermosphere in ~ 5 hour time scale. A larger and more broadly distributed component fills the magnetosphere to beyond 45 Rs in the orbital plane and 20 Rs latitudinally above and below the plane in an asymmetric distribution in local time. Molecular hydrogen emission in extreme and far ultraviolet regions collected with the H Lyman-α into the image mosaic reveals a distinctive resonance property correlated with the atomic hydrogen plume and shows a strong deviation of H2 X 1Σg+ from local thermodynamic equilibrium in the main source region. The inferred approximate globally averaged energy deposition at the top of the thermosphere from the production of the hot atomic hydrogen accounts for the measured atmospheric temperature. Possible processes for the fast atomic hydrogen formation from dissociation of H2 include the excitation of singlet-ungerade states and doubly excited states by photons and electrons, and the excitation of the singlet-gerade and triplet states by electrons, and chemical reactions involving the formation and dissociative recombination of H3+. Based on the available laboratory measurements and quantum mechanics calculations, the assessment of various mechanisms for H2 - H production, especially those producing H atoms with sufficient energy to

  18. Total photoionization cross-sections of excited electronic states by the algebraic diagrammatic construction-Stieltjes-Lanczos method.

    Science.gov (United States)

    Ruberti, M; Yun, R; Gokhberg, K; Kopelke, S; Cederbaum, L S; Tarantelli, F; Averbukh, V

    2014-05-14

    Here, we extend the L2 ab initio method for molecular photoionization cross-sections introduced in Gokhberg et al. [J. Chem. Phys. 130, 064104 (2009)] and benchmarked in Ruberti et al. [J. Chem. Phys. 139, 144107 (2013)] to the calculation of total photoionization cross-sections of molecules in electronically excited states. The method is based on the ab initio description of molecular electronic states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. The intermediate state representation of the dipole operator in the ADC basis is used to compute the transition moments between the excited states of the molecule. We compare the results obtained using different levels of the many-body theory, i.e., ADC(1), ADC(2), and ADC(2)x for the first two excited states of CO, N2, and H2O both at the ground state and the excited state equilibrium or saddle point geometries. We find that the single excitation ADC(1) method is not adequate even at the qualitative level and that the inclusion of double electronic excitations for description of excited state photoionization is essential. Moreover, we show that the use of the extended ADC(2)x method leads to a substantial systematic difference from the strictly second-order ADC(2). Our calculations demonstrate that a theoretical modelling of photoionization of excited states requires an intrinsically double excitation theory with respect to the ground state and cannot be achieved by the standard single excitation methods with the ground state as a reference.

  19. Dissociation of acetaldehyde in intense laser field: Coulomb explosion or field-assisted dissociation?

    Science.gov (United States)

    Elshakre, Mohamed E.; Gao, Lirong; Tang, Xiaoping; Wang, Sufan; Shu, Yafei; Kong, Fanao

    2003-09-01

    Dissociation of acetaldehyde in moderate strong laser field of 1013-1014W/cm2 was investigated. Singly charged parent ion CH3CHO+ and fragmental ions CH3+, CHO+, C2H4+, O+, CH2CHO+, and H+ were produced by 800 nm laser of 100 fs pulse duration and recorded by time-of-flight mass spectrometer. The CH3+ fragment further dissociated to CH2+, CH+, and C+ ions at higher intensity. Ab initio calculated results show that the singly-, doubly-, and triply charged parent ions are stable. So, the dissociation mechanism was not due to Coulomb explosion of multicharged ion. A field-assisted dissociation (FAD) theory, which assumes that only one bond undergoes dissociation while the rest of the molecular geometry stays unchanged, was employed to treat the dissociation dynamics. Accordingly, the dressed potential energy surfaces of the ground state for the parent and the fragment ions were calculated. Corresponding quasiclassical trajectory calculations show that the bond ruptures take place in the order of C-C, C-O, and C-H, agreeing with the observation. The observed angular dependence and charge distribution of the product ions can also be interpreted by the FAD theory.

  20. Triplet Excited States as a Source of Relevant (Bio)Chemical Information

    OpenAIRE

    Jiménez Molero, María Consuelo; Miranda Alonso, Miguel Ángel

    2014-01-01

    The properties of triplet excited states are markedly medium-dependent, which turns this species into valuable tools for investigating the microenvironments existing in protein binding pockets. Monitoring of the triplet excited state behavior of drugs within transport proteins (serum albumins and alpha(1)-acid glycoproteins) by laser flash photolysis constitutes a valuable source of information on the strength of interaction, conformational freedom and protection from oxygen or other external...

  1. The role of the excited electronic states in the C++H2O reaction

    International Nuclear Information System (INIS)

    Flores, Jesus R.; Gonzalez, Adan B.

    2008-01-01

    The electronic excited states of the [COH 2 ] + system have been studied in order to establish their role in the dynamics of the C + +H 2 O→[COH] + +H reaction, which is a prototypical ion-molecule reaction. The most relevant minima and saddle points of the lowest excited state have been determined and energy profiles for the lowest excited doublet and quartet electronic states have been computed along the fragmentation and isomerization coordinates. Also, nonadiabatic coupling strengths between the ground and the first excited state have been computed where they can be large. Our analysis suggests that the first excited state could play an important role in the generation of the formyl isomer, which has been detected in crossed beam experiments [D. M. Sonnenfroh et al., J. Chem. Phys. 83, 3985 (1985)], but could not be explained in quasiclassical trajectory computations [Y. Ishikawa et al., Chem. Phys. Lett. 370, 490 (2003); J. R. Flores, J. Chem. Phys. 125, 164309 (2006)

  2. Excited states in stochastic electrodynamics

    International Nuclear Information System (INIS)

    Franca, H.M.; Marshall, T.W.

    1987-12-01

    It is shown that the set of Wigner functions associated with the excited states of the harmonic oscillator constitute a complete set of functions over the phase space. An arbitraty distribution can be expanded in terms of these Wigner functions. By studying the time evolution, according to Stochastic Electrodynamics, of the expansion coefficients, becomes feasible to separate explicity the contributionsof the radiative reaction and the vaccuum field to the Einsten. A coefficients for this system. A simple semiclassical explanation of the Weisskopf-Heitler phenomenon in resonance fluorescence is also supplied. (author) [pt

  3. The structure of low-lying states in ${}^{140}$Sm studied by Coulomb excitation

    CERN Document Server

    Klintefjord, M.; Görgen, A.; Bauer, C.; Bello Garrote, F.L.; Bönig, S.; Bounthong, B.; Damyanova, A.; Delaroche, J.P.; Fedosseev, V.; Fink, D.A.; Giacoppo, F.; Girod, M.; Hoff, P.; Imai, N.; Korten, W.; Larsen, A.C.; Libert, J.; Lutter, R.; Marsh, B.A.; Molkanov, P.L.; Naïdja, H.; Napiorkowski, P.; Nowacki, F.; Pakarinen, J.; Rapisarda, E.; Reiter, P.; Renstrøm, T.; Rothe, S.; Seliverstov, M.D.; Siebeck, B.; Siem, S.; Srebrny, J.; Stora, T.; Thöle, P.; Tornyi, T.G.; Tveten, G.M.; Van Duppen, P.; Vermeulen, M.J.; Voulot, D.; Warr, N.; Wenander, F.; De Witte, H.; Zielińska, M.

    2016-05-02

    The electromagnetic structure of $^{140}$Sm was studied in a low-energy Coulomb excitation experiment with a radioactive ion beam from the REX-ISOLDE facility at CERN. The $2^+$ and $4^+$ states of the ground-state band and a second $2^+$ state were populated by multi-step excitation. The analysis of the differential Coulomb excitation cross sections yielded reduced transition probabilities between all observed states and the spectroscopic quadrupole moment for the $2_1^+$ state. The experimental results are compared to large-scale shell model calculations and beyond-mean-field calculations based on the Gogny D1S interaction with a five-dimensional collective Hamiltonian formalism. Simpler geometric and algebraic models are also employed to interpret the experimental data. The results indicate that $^{140}$Sm shows considerable $\\gamma$ softness, but in contrast to earlier speculation no signs of shape coexistence at low excitation energy. This work sheds more light on the onset of deformation and collectivit...

  4. Effects of crossed states on photoluminescence excitation spectroscopy of InAs quantum dots

    Directory of Open Access Journals (Sweden)

    Lin Chien-Hung

    2011-01-01

    Full Text Available Abstract In this report, the influence of the intrinsic transitions between bound-to-delocalized states (crossed states or quasicontinuous density of electron-hole states on photoluminescence excitation (PLE spectra of InAs quantum dots (QDs was investigated. The InAs QDs were different in size, shape, and number of bound states. Results from the PLE spectroscopy at low temperature and under a high magnetic field (up to 14 T were compared. Our findings show that the profile of the PLE resonances associated with the bound transitions disintegrated and broadened. This was attributed to the coupling of the localized QD excited states to the crossed states and scattering of longitudinal acoustical (LA phonons. The degree of spectral linewidth broadening was larger for the excited state in smaller QDs because of the higher crossed joint density of states and scattering rate.

  5. Study of photoionization and dissociative photoionization of carbon monoxide from ionization threshold to 38 eV by using synchrotron radiation

    International Nuclear Information System (INIS)

    Zhao, Yujie; Cao, Maoqi; Li, Yuquan; Shan, Xiaobin; Liu, Fuyi; Sheng, Liusi; Li, Li; Liu, Wanfang

    2014-01-01

    Highlights: • The high resolution photoionization spectrum of carbon monoxide has been investigated using tunable synchrotron radiation. • This work has investigated comprehensively almost all kinds of photo excitation processes of CO in wide photon region. • The mechanisms of photoionization and dissociative photoionization of CO have been researched in detail. - Abstract: The vacuum-ultraviolet photoionization and dissociative photoionization of carbon monoxide in a region 14–38 eV have been investigated with time-of-flight (TOF) photoionization mass spectrometry (PIMS) using tunable synchrotron radiation (SR). The adiabatic ionization energy (IE) of carbon monoxide and appearance energies (AE) for its fragment ions in different states are determined by measurements of photoionization efficiency spectra (PIES). Ab initio calculations have been performed to investigate the reaction mechanism of dissociative photoionization of carbon monoxide. On the basis of experimental and predicted theoretical results, the mechanisms of photoionization and dissociative photoionization of molecular CO are discussed, and sixteen dissociative photoionization processes are proposed. The equilibrium geometries and harmonic vibrational frequencies of CO molecule, and its parent cation were calculated by using MP2 (full) method. The differences of configurations between them are also discussed on the basis of theoretical calculations. According to our results, the experimental IE of CO molecule, and dissociation energies (E d ) of possible dissociative channels are in reasonable agreement with the calculated values of the proposed photodissociation channels

  6. Excited states of 12C above the alpha-decay threshold

    International Nuclear Information System (INIS)

    Freer, M; Ashwood, N I; Barr, M; Curtis, N; Malcolm, J D; Wheldon, C; Ziman, V A; Almaraz-Calderon, S; Aprahamian, A; Bucher, B; Couder, M; Fang, X; Jung, F; Lu, W; Roberts, A; Tan, W P; Copp, P; Lesher, S

    2011-01-01

    The excitation energy spectrum of 12 C is important for both structural and astrophysical reasons; here we present evidence for a new state in 12 C. The two reactions 12 C( 4 He, 4 He+ 4 He+ 4 He) 4 He and 9 Be( 4 He, 4 He+ 4 He+ 4 He)n were measured using an array of four double sided strip detectors. Excited states in 12 C were reconstructed filtered by the condition that the alpha-decay proceeded via the 8 Be ground-state. In both measurements evidence was found for a new state at 13.3(0.2) MeV with a width 1.7(0.2) MeV. Angular correlation measurements from the 12 C( 4 He, 4 He+ 4 He+ 4 He) 4 He reaction indicates that the state may have J π = 4 + .

  7. Calculation of neutral beam deposition accounting for excited states

    International Nuclear Information System (INIS)

    Gianakon, T.A.

    1992-09-01

    Large-scale neutral-beam auxillary heating of plasmas has led to new plasma operational regimes which are often dominated by fast ions injected via the absorption of an energetic beam of hydrogen neutrals. An accurate simulation of the slowing down and transport of these fast ions requires an intimate knowledge of the hydrogenic neutral deposition on each flux surface of the plasma. As a refinement to the present generation of transport codes, which base their beam deposition on ground-state reaction rates, a new set of routines, based on the excited states of hydrogen, is presented as mechanism for computing the attenuation and deposition of a beam of energetic neutrals. Additionally, the numerical formulations for the underlying atomic physics for hydrogen impacting on the constiuent plasma species is developed and compiled as a numerical database. Sample results based on this excited state model are compared with the ground-state model for simple plasma configurations

  8. Dark excited states of carotenoids: Consensus and controversy

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Sundström, V.

    2009-01-01

    Roč. 477, 1-3 (2009), s. 1-11 ISSN 0009-2614 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * excited states * relaxation pathways * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 2.291, year: 2009

  9. Evidence for excited state intramolecular charge transfer in benzazole-based pseudo-stilbenes.

    Science.gov (United States)

    Santos, Fabiano da Silveira; Descalzo, Rodrigo Roceti; Gonçalves, Paulo Fernando Bruno; Benvenutti, Edilson Valmir; Rodembusch, Fabiano Severo

    2012-08-21

    Two azo compounds were obtained through the diazotization reaction of aminobenzazole derivatives and N,N-dimethylaniline using clay montmorillonite KSF as catalyst. The synthesized dyes were characterized using elemental analysis, Fourier transform infrared spectroscopy, and (13)C and (1)H NMR spectroscopy in solution. Their photophysical behavior was studied using UV-vis and steady-state fluorescence in solution. These dyes present intense absorption in the blue region. The spectral features of the azo compounds can be related to the pseudo-stilbene type as well as the E isomer of the dyes. Excitation at the absorption maxima does not produce emissive species in the excited state. However, excitation around 350 nm allowed dual emission of fluorescence, from both a locally excited (LE, short wavelength) and an intramolecular charge transfer (ICT, long wavelength) state, which was corroborated by a linear relation of the fluorescence maximum (ν(max)) versus the solvent polarity function (Δf) from the Lippert-Mataga correlation. Evidence of TICT in these dyes was discussed from the viscosity dependence of the fluorescence intensity in the ICT emission band. Theoretical calculations were also performed in order to study the geometry and charge distribution of the dyes in their ground and excited electronic states. Using DFT methods at the theoretical levels BLYP/Aug-cc-pVDZ, for geometry optimizations and frequency calculations, and B3LYP/6-311+G(2d), for single-point energy evaluations, the calculations revealed that the least energetic and most intense photon absorption leads to a very polar excited state that relaxes non-radioactively, which can be associated with photochemical isomerization.

  10. Radiative and Excited State Charmonium Physics

    Energy Technology Data Exchange (ETDEWEB)

    Jozef Dudek

    2007-07-30

    Renewed interest in the spectroscopy of charmonium has arisen from recent unexpected observations at $e^+e^-$ colliders. Here we report on a series of works from the previous two years examining the radiative physics of charmonium states as well as the mass spectrum of states of higher spin and internal excitation. Using new techniques applied to Domain-Wall and Clover quark actions on quenched isotropic and anisotropic lattices, radiative transitions and two-photon decays are considered for the first time. Comparisons are made with experimental results and with model approaches. Forthcoming application to the light-quark sector of relevance to experiments like Jefferson Lab's GlueX is discussed.

  11. Selective two-photon excitation of a vibronic state by correlated photons.

    Science.gov (United States)

    Oka, Hisaki

    2011-03-28

    We theoretically investigate the two-photon excitation of a molecular vibronic state by correlated photons with energy anticorrelation. A Morse oscillator having three sets of vibronic states is used, as an example, to evaluate the selectivity and efficiency of two-photon excitation. We show that a vibrational mode can be selectively excited with high efficiency by the correlated photons, without phase manipulation or pulse-shaping techniques. This can be achieved by controlling the quantum correlation so that the photon pair concurrently has two pulse widths, namely, a temporally narrow width and a spectrally narrow width. Though this concurrence is seemingly contradictory, we can create such a photon pair by tailoring the quantum correlation between two photons.

  12. Amplitudes and state parameters from ion- and atom-atom excitation processes

    International Nuclear Information System (INIS)

    Andersen, T.; Horsdal-Pedersen, E.

    1984-01-01

    This chapter examines single collisions between two atomic species, one of which is initially in a 1 S state (there is only one initial spin channel). The collisions are characterized by a definite scattering plane and a definite orientation. Topics considered include an angular correlation between scattered particles and autoionization electrons or polarized photons emitted from states excited in atomic collisions (photon emission, electron emission, selectivity excited target atoms), experimental methods for obtaining information on the alignment and orientation parameters of atoms or ions excited in specific collisions, results of experiments and numerical calculations (quasi-oneelectron systems, He + -He collisions, other collision systems), and future aspects and possible applications of the polarizedphoton, scattered-particle coincidence techniques to atomic spectroscopy

  13. Lifetime measurements of excited states in 17C: Possible interplay between collectivity and halo effects

    International Nuclear Information System (INIS)

    Suzuki, D.; Iwasaki, H.; Ong, H.J.; Imai, N.; Sakurai, H.; Nakao, T.; Aoi, N.; Baba, H.; Bishop, S.; Ichikawa, Y.; Ishihara, M.; Kondo, Y.; Kubo, T.; Kurita, K.; Motobayashi, T.; Nakamura, T.; Okumura, T.; Onishi, T.K.; Ota, S.; Suzuki, M.K.

    2008-01-01

    Lifetime measurements were performed on low-lying excited states of the neutron-rich isotope 17 C using the recoil shadow method. The γ-decay mean lifetimes were determined to be 583±21(stat)±35(syst) ps for the first excited state at 212 keV and 18.9±0.6(stat)±4.7(syst) ps for the second excited state at 333 keV. Based on a comparison with the empirical upper limits for the electromagnetic transition strengths, these decays are concluded to be predominantly M1 transitions. The reduced M1 transition probabilities to the ground state were deduced to be (1.0±0.1)x10 -2 μ N 2 and (8.2 -1.8 +3.2 )x10 -2 μ N 2 , respectively, for the first and second excited states. The strongly hindered M1 strength as well as the lowered excitation energy represents unique nature of the 212-keV state

  14. Dissociation kinetics of iodine in oxygen-containing electrical discharge plasmas

    International Nuclear Information System (INIS)

    Zakharov, A.I.; Klopovskii, K.S.; Rakhimova, T.V.; Samorodov, V.A.

    1993-01-01

    Studies of the kinetics of gaseous media containing oxygen and iodine molecules have been stimulated to a substantial degree by the search for ways of improving iodine-oxygen lasers and by the need for information on loss processes for atmospheric ozone. Results are presented from an experimental study and numerical simulations of the kinetics of the dissociation of iodine in self-sustained volume discharges in high-pressure O 2 :Ar:I 2 mixtures. It is shown that the well-studied mechanism for dissociation based on excitation of iodine molecules in successive collisions with singlet oxygen and excited iodine atoms is supplanted by a substantially different mechanism involving the creation and loss of 10 radicals when the densities of atomic oxygen and ozone are high enough. It is also shown that iodine fractions as low as ∼10 -3 in the mixture lead to rapid loss of ozone molecules while less than 18% of the discharge energy is expended in the production of singlet oxygen

  15. Picosecond spectral relaxation of curcumin excited state in toluene–alcohol mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Saini, R.K.; Das, K., E-mail: kaustuv@rrcat.gov.in

    2013-12-15

    Excited state photophysics of Curcumin in a binary solvent mixture of toluene and five different alcohols (Methanol, Ethanol, 1-Propanol, 1-Butanol and 1-Octanol) are compared with an instrument time resolution of ∼40 ps. As the alcohol mole-fraction is varied from zero to unity, the observed trends in the fluorescence quantum yield and lifetime of the pigment in toluene–alcohol mixtures changes significantly in going from Methanol to 1-Octanol. This is attributed to the different degree of modulation of the non-radiative rates associated with the excited state intermolecular H bonding between the pigment and the alcohol. Fluorescence decays taken at the red edge of the emission spectrum started to show measurable rise times (200–30 ps) the magnitude of which decreased gradually with increasing alcohol mole-fraction. As a consequence the solvation times in the binary mixture were observed to slow down considerably at certain solvent compositions compared to that in neat alcohol. However, in toluene-1-Octanol mixture, the rise times and corresponding solvation times did not show a dependence on the 1-Octanol mole-fraction. The observed results suggest that viscosity, polarity and hydrogen bonding property of the alcohol solvent plays an important role in the excited state processes of the pigment in toluene–alcohol mixture. -- Highlights: • Excited state photophysics of Curcumin in a binary solvent mixture of toluene and five different alcohols were studied. • The observed trends in the fluorescence properties are attributed to intermolecular H bonding between the pigment and the alcohol. • Except 1-Octanol, the average solvation times of the pigment were observed to depend upon alcohol mole-fraction. • Viscosity, polarity and hydrogen bonding play an important role in the excited state processes of the pigment.

  16. Picosecond spectral relaxation of curcumin excited state in toluene–alcohol mixtures

    International Nuclear Information System (INIS)

    Saini, R.K.; Das, K.

    2013-01-01

    Excited state photophysics of Curcumin in a binary solvent mixture of toluene and five different alcohols (Methanol, Ethanol, 1-Propanol, 1-Butanol and 1-Octanol) are compared with an instrument time resolution of ∼40 ps. As the alcohol mole-fraction is varied from zero to unity, the observed trends in the fluorescence quantum yield and lifetime of the pigment in toluene–alcohol mixtures changes significantly in going from Methanol to 1-Octanol. This is attributed to the different degree of modulation of the non-radiative rates associated with the excited state intermolecular H bonding between the pigment and the alcohol. Fluorescence decays taken at the red edge of the emission spectrum started to show measurable rise times (200–30 ps) the magnitude of which decreased gradually with increasing alcohol mole-fraction. As a consequence the solvation times in the binary mixture were observed to slow down considerably at certain solvent compositions compared to that in neat alcohol. However, in toluene-1-Octanol mixture, the rise times and corresponding solvation times did not show a dependence on the 1-Octanol mole-fraction. The observed results suggest that viscosity, polarity and hydrogen bonding property of the alcohol solvent plays an important role in the excited state processes of the pigment in toluene–alcohol mixture. -- Highlights: • Excited state photophysics of Curcumin in a binary solvent mixture of toluene and five different alcohols were studied. • The observed trends in the fluorescence properties are attributed to intermolecular H bonding between the pigment and the alcohol. • Except 1-Octanol, the average solvation times of the pigment were observed to depend upon alcohol mole-fraction. • Viscosity, polarity and hydrogen bonding play an important role in the excited state processes of the pigment

  17. Dynamic study of excited state hydrogen-bonded complexes of harmane in cyclohexane-toluene mixtures.

    Science.gov (United States)

    Carmona, Carmen; Balón, Manuel; Galán, Manuel; Guardado, Pilar; Muñoz, María A

    2002-09-01

    Photoinduced proton transfer reactions of harmane or 1-methyl-9H-pyrido[3,4-b]indole (HN) in the presence of the proton donor hexafluoroisopropanol (HFIP) in cyclohexane-toluene mixtures (CY-TL; 10% vol/vol of TL) have been studied. Three excited state species have been identified: a 1:2 hydrogen-bonded proton transfer complex (PTC), between the pyridinic nitrogen of the substrate and the proton donor, a hydrogen-bonded cation-like exciplex (CL*) with a stoichiometry of at least 1:3 and a zwitterionic exciplex (Z*). Time-resolved fluorescence measurements evidence that upon excitation of ground state PTC, an excited state equilibrium is established between PTC* and the cationlike exciplex, CL*, lambdaem approximately/= 390 nm. This excited state reaction is assisted by another proton donor molecule. Further reaction of CL* with an additional HFIP molecule produces the zwitterionic species, Z*, lambda(em) approximately/= 500 nm. From the analysis of the multiexponential decays, measured at different emission wavelengths and as a function of HFIP concentration, the mechanism of these excited state reactions has been established. Thus, three rate constants and three reciprocal lifetimes have been determined. The simultaneous study of 1,9-dimethyl-9H-pyrido[3,4-b]indole (MHN) under the same experimental conditions has helped to understand the excited state kinetics of these processes.

  18. Energy distribution in dissociations of polyatomic molecules

    International Nuclear Information System (INIS)

    Koernig, S.A.

    1989-01-01

    In this thesis studies are reported of fragmentation processes in polyatomic molecules. In order to find out which dessocaciation reactions take place, how they are brought about by the internal energy of the reactant, and to investigate the structure of the dissociating 'transition state', the fragment mass and the corresponding kinetic energy release (KER) are determined by differential translational spectroscopy using a position and time sensitive two-particle coincidence detector. The results are interpreted using the statistical theory of unimolecular dissociation. It turns out that the standard assumptions of the theory, especially in calculating KER-distributions, are not realistic in all molecules considered. Dissociation is induced by the neutralization with alkali metal vapour. In ch. 2 the experimental method and the analysis of the data (dissociation pathways, branching ratios and ε-d-distributions) are introduced and exemplified by measurements of cyclohexane, which represents the upper limit in precursor and fragment mass accessible in the apparatus. In ch. 3 a study is reported of the molecules methylchloride (CH 3 Cl) and the acetylradical (CH 3 CO). In spite of their similar geometric structures, completely different dissociation mechanisms have been found. Methylchloride dissociates via a repulsive state; acetyl radicals show energy scrambling. The energy distribution from dissociating acetyl exemplifies dynamical effects in the dissociation. In ch. 4 an investigation of a number of prototype hydrocarbons is presented. The dissociation pathways of several small linear alkanes indicate that neutralization takes place to unknown repulsive potentials, of which the position and steepness are determined from the kinetic energy release. (author). 118 refs.; 40 figs.; 5 tabs

  19. General active space commutator-based coupled cluster theory of general excitation rank for electronically excited states: implementation and application to ScH.

    Science.gov (United States)

    Hubert, Mickaël; Olsen, Jeppe; Loras, Jessica; Fleig, Timo

    2013-11-21

    We present a new implementation of general excitation rank coupled cluster theory for electronically excited states based on the single-reference multi-reference formalism. The method may include active-space selected and/or general higher excitations by means of the general active space concept. It may employ molecular integrals over the four-component Lévy-Leblond Hamiltonian or the relativistic spin-orbit-free four-component Hamiltonian of Dyall. In an initial application to ground- and excited states of the scandium monohydride molecule we report spectroscopic constants using basis sets of up to quadruple-zeta quality and up to full iterative triple excitations in the cluster operators. Effects due to spin-orbit interaction are evaluated using two-component multi-reference configuration interaction for assessing the accuracy of the coupled cluster results.

  20. Concluding remarks of international symposium on highly excited states in nuclear reactions

    Energy Technology Data Exchange (ETDEWEB)

    Bernstein, A. M.; Ikegami, H.; Muraoka, M. [eds.

    1980-01-01

    This is the concluding remarks in the international symposium on highly excited states in nuclear reactions. The remarks concentrate on the giant quadrupole states. In the framework of the distorted wave Born approximation (DWB), the differential cross section can be deduced. The relevant transition matrix elements are defined, and the quantities which are measured in inelastic hadron (h, h') reactions are shown. These are used to obtain both neutron and proton transition multipole matrix elements. This is equivalent to make the isospin decomposition of the electromagnetic transition matrix elements. The ratios of the transition matrix elements of neutrons and protons of the lowest 2/sup +/ states in even-even single closed shell nuclei are evaluated and compared with experimental results. For each nucleus, the consistency between various measurements is generally good. The effect of the virtual excitation of giant 2/sup +/ states into the ground and first excited states of even-even nuclei is discussed. The accuracy of (h, h') results can be tested.

  1. On satellite lines anomalies in OH excited states

    International Nuclear Information System (INIS)

    Elitzur, M.

    1976-01-01

    It is argued that different pumps produce similar distributions of populations in the first two excited states of OH. The pattern observed recently in G 219.3 - 07 by Whiteoak and Gardner can be due either to radiative or collisional pump. (author)

  2. Calculations of core-excited states in Li

    International Nuclear Information System (INIS)

    Verbockhaven, G.; Hansen, J.E.

    1999-01-01

    We report on progress in the calculation of three-electron states making use of B-spline basis sets. In particular we discuss the advantages and disadvantages of using a Hartree-Fock basis (expanded in B-splines) compared to the use of hydrogenic basis states. Preliminary results are presented for the 2 S terms in Li below the 1s2s 3 S limit at 64.4 eV. The 2 S terms have been studied less extensively than other core-excited states in Li. In this particular case the choice of basis has a large influence on the quality of the results. (orig.)

  3. Electron capture dissociation proceeds with a low degree of intramolecular migration of peptide amide hydrogens

    DEFF Research Database (Denmark)

    Rand, Kasper D; Adams, Christopher M; Zubarev, Roman A

    2008-01-01

    scrambling) that occurs during vibrational excitation of gas-phase ions. Unlike traditional collisional ion activation, electron capture dissociation (ECD) is not associated with substantial vibrational excitation. We investigated the extent of intramolecular backbone amide hydrogen (1H/2H) migration upon...... ECD using peptides with a unique selective deuterium incorporation. Our results show that only limited amide hydrogen migration occurs upon ECD, provided that vibrational excitation prior to the electron capture event is minimized. Peptide ions that are excessively vibrationally excited...

  4. Exact finite volume expectation values of local operators in excited states

    Energy Technology Data Exchange (ETDEWEB)

    Pozsgay, B. [MTA-BME “Momentum” Statistical Field Theory Research Group,Budafoki út 8, 1111 Budapest (Hungary); Szécsényi, I.M. [Department of Mathematical Sciences, Durham University, South Road, Durham, DH1 3LE (United Kingdom); Institute of Theoretical Physics, Eötvös Loránd University,Pázmány Péter sétány 1/A, 1117 Budapest (Hungary); Takács, G. [MTA-BME “Momentum” Statistical Field Theory Research Group,Budafoki út 8, 1111 Budapest (Hungary); Department of Theoretical Physics, Budapest University of Technology and Economics,Budafoki út 8, 1111 Budapest (Hungary)

    2015-04-07

    We present a conjecture for the exact expression of finite volume expectation values in excited states in integrable quantum field theories, which is an extension of an earlier conjecture to the case of general diagonal factorized scattering with bound states and a nontrivial bootstrap structure. The conjectured expression is a spectral expansion which uses the exact form factors and the excited state thermodynamic Bethe Ansatz as building blocks. The conjecture is proven for the case of the trace of the energy-moment tensor. Concerning its validity for more general operators, we provide numerical evidence using the truncated conformal space approach. It is found that the expansion fails to be well-defined for small values of the volume in cases when the singularity structure of the TBA equations undergoes a non-trivial rearrangement under some critical value of the volume. Despite these shortcomings, the conjectured expression is expected to be valid for all volumes for most of the excited states, and as an expansion above the critical volume for the rest.

  5. Exact finite volume expectation values of local operators in excited states

    International Nuclear Information System (INIS)

    Pozsgay, B.; Szécsényi, I.M.; Takács, G.

    2015-01-01

    We present a conjecture for the exact expression of finite volume expectation values in excited states in integrable quantum field theories, which is an extension of an earlier conjecture to the case of general diagonal factorized scattering with bound states and a nontrivial bootstrap structure. The conjectured expression is a spectral expansion which uses the exact form factors and the excited state thermodynamic Bethe Ansatz as building blocks. The conjecture is proven for the case of the trace of the energy-moment tensor. Concerning its validity for more general operators, we provide numerical evidence using the truncated conformal space approach. It is found that the expansion fails to be well-defined for small values of the volume in cases when the singularity structure of the TBA equations undergoes a non-trivial rearrangement under some critical value of the volume. Despite these shortcomings, the conjectured expression is expected to be valid for all volumes for most of the excited states, and as an expansion above the critical volume for the rest.

  6. Formation of excited states in high-Z helium-like systems

    International Nuclear Information System (INIS)

    Fritzsche, S.; Fricke, B.; Brinzanescu, O.

    1999-12-01

    High-Z helium-like ions represent the simplest multi-electron systems for studying the interplay between electron-electron correlations, relativistic as well as quantum electrodynamical effects in strong fields. In contrast to the adjacent lithium-like ions, however, almost no experimental information is available about the excited states in the high-Z domain of the helium sequence. Here, we present a theoretical analysis of the X-ray production and decay dynamics of the excited states in helium-like uranium. Emphasize has been paid particularly to the formation of the 3 P 0 and 3 P 2 levels by using electron capture into hydrogen-like U 91+ . Both states are of interest for precise measurements on high-Z helium-like ions in the future. (orig.)

  7. Direct Electron Impact Excitation of Rydberg-Valence States of Molecular Nitrogen

    Science.gov (United States)

    Malone, C. P.; Johnson, P. V.; Liu, X.; Ajdari, B.; Muleady, S.; Kanik, I.; Khakoo, M. A.

    2012-12-01

    Collisions between electrons and neutral N2 molecules result in emissions that provide an important diagnostic probe for understanding the ionospheric energy balance and the effects of space weather in upper atmospheres. Also, transitions to singlet ungerade states cause N2 to be a strong absorber of solar radiation in the EUV spectral range where many ro-vibrational levels of these Rydberg-valence (RV) states are predissociative. Thus, their respective excitation and emission cross sections are important parameters for understanding the [N]/[N2] ratio in the thermosphere of nitrogen dominated atmospheres. The following work provides improved constraints on absolute and relative excitation cross sections of numerous RV states of N2, enabling more physically accurate atmospheric modeling. Here, we present recent integral cross sections (ICSs) for electron impact excitation of RV states of N2 [6], which were based on the differential cross sections (DCSs) derived from electron energy-loss (EEL) spectra of [5]. This work resulted in electronic excitation cross sections over the following measured vibrational levels: b 1Πu (v‧=0-14), c3 1Πu (v‧=0-3), o3 1Πu (v‧=0-3), b‧ 1Σu+ (v‧=0-10), c‧4 1Σu+ (v‧=0-3), G 3Πu (v‧=0-3), and F 3Πu (v‧=0-3). We further adjusted the cross sections of the RV states by extending the vibronic contributions to unmeasured v‧-levels via the relative excitation probabilities (REPs) as discussed in [6]. This resulted in REP-scaled ICSs over the following vibrational levels for the singlet ungerade states: b(0-19), c3(0-4), o3(0-4), b‧(0-16), and c‧4(0-8). Comparison of the ICSs of [6] with available EEL based measurements, theoretical calculations, and emission based work generally shows good agreement within error estimations, except with the recent reevaluation provided by [1]. Further, we have extended these results, using the recent EEL data of [3], to include the unfolding of better resolved features above ~13

  8. Excited state dynamics of DNA bases

    Czech Academy of Sciences Publication Activity Database

    Kleinermanns, K.; Nachtigallová, Dana; de Vries, M. S.

    2013-01-01

    Roč. 32, č. 2 (2013), s. 308-342 ISSN 0144-235X R&D Projects: GA ČR GAP208/12/1318 Grant - others:National Science Foundation(US) CHE-0911564; NASA (US) NNX12AG77G; Deutsche Forschungsgemeinschaft(DE) SFB 663; Deutsche Forschungsgemeinschaft(DE) KI 531-29 Institutional support: RVO:61388963 Keywords : DNA bases * nucleobases * excited state * dynamics * computations * gas phase * conical intersections Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.920, year: 2013

  9. Excited-state dynamics of mononucleotides and DNA strands in a deep eutectic solvent.

    Science.gov (United States)

    Zhang, Yuyuan; de La Harpe, Kimberly; Hariharan, Mahesh; Kohler, Bern

    2018-04-17

    The photophysics of several mono- and oligonucleotides were investigated in a deep eutectic solvent for the first time. The solvent glyceline, prepared as a 1 : 2 mole ratio mixture of choline chloride and glycerol, was used to study excited-state deactivation in a non-aqueous solvent by the use of steady-state and time-resolved spectroscopy. DNA strands in glyceline retain the secondary structures that are present in aqueous solution to some degree, thus enabling a study of the effects of solvent properties on the excited states of stacked bases and stacked base pairs. The excited-state lifetime of the mononucleotide 5'-AMP in glyceline is 630 fs, or twice as long as in aqueous solution. Even slower relaxation is seen for 5'-TMP in glyceline, and a possible triplet state with a lifetime greater than 3 ns is observed. Circular dichroism spectra show that the single strand (dA)18 and the duplex d(AT)9·d(AT)9 adopt similar structures in glyceline and in aqueous solution. Despite having similar conformations in both solvents, femtosecond transient absorption experiments reveal striking changes in the dynamics. Excited-state decay and vibrational cooling generally take place more slowly in glyceline than in water. Additionally, the fraction of long-lived excited states in both oligonucleotide systems is lower in glyceline than in aqueous solution. For a DNA duplex, water is suggested to favor decay pathways involving intrastrand charge separation, while the deep eutectic solvent favors interstrand deactivation channels involving neutral species. Slower solvation dynamics in the viscous deep eutectic solvent may also play a role. These results demonstrate that the dynamics of excitations in stacked bases and stacked base pairs depend not only on conformation, but are also highly sensitive to the solvent.

  10. On some aspects of Coulomb excitation of nuclear rotational states

    International Nuclear Information System (INIS)

    Massmann, H.; Robotham, H.

    1979-01-01

    The Coulomb excitation of nuclear rotational states is studied with a semiclassical method using classical trajectories and the classical action in order to construct the excitation probabilities. This method allows one to consider the effect on the excitation probabilities of a weak nuclear potential. An explicit expression for the 'safe bombarding energy' that is the largest bombarding energy for which the nuclear force can be neglected, is found. Also the transfer of angular momentum to the projectile's orbit is considered. One finds that the dynamical distortion of the orbit has a measurable effect on the excitation probabilities for the case of very heavy ions. Furthermore, new dimensionless parameters measuring the dynamical distortion and the effect of the adiabaticity of the collision are introduced and discussed. (author)

  11. Diffractive pion dissociation into 5 pion final states at COMPASS

    Energy Technology Data Exchange (ETDEWEB)

    Neubert, Sebastian; Friedrich, Jan; Grabmueller, Stefanie; Haas, Florian; Ketzer, Bernhard; Paul, Stephan; Weitzel, Quirin [Technische Universitaet Muenchen, Physik Department E18, 85748 Garching (Germany); Chung, Suh-Urk [Technische Universitaet Muenchen, Physik Department E18, 85748 Garching (Germany); Brookhaven National Laboratory, Upton, NY 11973 (United States); Ryabchikov, Dimitry [Technische Universitaet Muenchen, Physik Department E18, 85748 Garching (Germany); Institute for High Ernergy Physics, 142284 Protvino (Russian Federation)

    2009-07-01

    COMPASS is a fixed-target experiment at the CERN SPS, which investigates the structure and spectroscopy of hadrons. In 2004, a first run with a 190 GeV/c {pi}{sup -} beam took place using nuclear targets. Diffractive dissociation reactions observed in this run provide clean access to meson resonances with masses up to 3 GeV/c{sup 2}. Exclusive final states with 5 charged pions have been extracted. The covered range in momentum transfer extends from threshold to a few GeV{sup 2}/c{sup 2} allowing to study resonance production in different regimes. We report on the status of the analysis of this unique data set.

  12. Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

    DEFF Research Database (Denmark)

    Zhang, Wenkai; Kjær, Kasper Skov; Alonso-Mori, Roberto

    2017-01-01

    iron complexes with four cyanide (CN-;) ligands and one 2,2′-bipyridine (bpy) ligand. This enables MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL...... state lifetime of iron based complexes due to spin crossover-the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand...

  13. Principal component analysis acceleration of rovibrational coarse-grain models for internal energy excitation and dissociation

    Science.gov (United States)

    Bellemans, Aurélie; Parente, Alessandro; Magin, Thierry

    2018-04-01

    The present work introduces a novel approach for obtaining reduced chemistry representations of large kinetic mechanisms in strong non-equilibrium conditions. The need for accurate reduced-order models arises from compression of large ab initio quantum chemistry databases for their use in fluid codes. The method presented in this paper builds on existing physics-based strategies and proposes a new approach based on the combination of a simple coarse grain model with Principal Component Analysis (PCA). The internal energy levels of the chemical species are regrouped in distinct energy groups with a uniform lumping technique. Following the philosophy of machine learning, PCA is applied on the training data provided by the coarse grain model to find an optimally reduced representation of the full kinetic mechanism. Compared to recently published complex lumping strategies, no expert judgment is required before the application of PCA. In this work, we will demonstrate the benefits of the combined approach, stressing its simplicity, reliability, and accuracy. The technique is demonstrated by reducing the complex quantum N2(g+1Σ) -N(S4u ) database for studying molecular dissociation and excitation in strong non-equilibrium. Starting from detailed kinetics, an accurate reduced model is developed and used to study non-equilibrium properties of the N2(g+1Σ) -N(S4u ) system in shock relaxation simulations.

  14. Shape resonances and the excitation of helium autoionising states by electrons in the 57-66 eV region

    International Nuclear Information System (INIS)

    Burgt, P.J.M. van der; Eck, J. van; Heideman, H.G.M.

    1986-01-01

    Optical excitation functions of singly excited helium states are presented, measured by detecting the yield of emitted photons as a function of the incident electron energy from 56 to 66 eV. Many structures are observed, which are caused by negative-ion resonances and by the decay of autoionising states followed by post-collision interaction. Some of the structures are interpreted as being caused by hitherto unknown shape resonances lying very close to the thresholds of a particular class of autoionising states. As these shape resonances almost exclusively decay to their respective parent (autoionising) states, thereby considerably enhancing the threshold excitation cross sections of these states, they can only be observed via the PCI effect on the excitation functions of (higher lying) singly excited states. Using the recently introduced supermultiplet classification for doubly excited states a selection rule for the near-threshold excitation of doubly excited states by electron impact is deduced from the measurements. Only states with large probabilities in the Wannier region of configuration space (where the two electrons are at nearly equal distances and on opposite sides of the nucleus) are strongly excited. It is pointed out that these states are precisely the states that can support the above mentioned shape resonances at their thresholds. (author)

  15. Dielectronic recombination rate coefficients to the excited states of CIII from CIV

    Energy Technology Data Exchange (ETDEWEB)

    Safronova, U.; Kato, Takako; Ohira, Mituhiko

    1996-07-01

    Energy levels, radiative transition probabilities and autoionization rates for CIII including 1s{sup 2}2pnl` (n=2/6, l`{<=}(n-1)) and 1s{sup 2}3lnl` (n=3/6, l`{<=}(n-1)) states were calculated by using multi-configurational Hartree-Fock (Cowan code) method. Autoionizing levels above the 1s{sup 2}2s and 1s{sup 2}2p thresholds were considered and their contributions were computed. Branching ratios on the autoionization rate to the first threshold and intensity factor were calculated for satellite lines of CIII ion. The dielectronic recombination rate coefficients to the excited states for n=2-6 were calculated. The values for the excited states higher than n=6 were extrapolated and the total dielectronic recombination rate coefficients were also derived. The rate coefficients to the excited states were fitted to an analytical formula and the fitting parameters are given. (author)

  16. Evidence for concerted ring opening and C–Br bond breaking in UV-excited bromocyclopropane

    Energy Technology Data Exchange (ETDEWEB)

    Pandit, Shubhrangshu; Preston, Thomas J.; Orr-Ewing, Andrew J., E-mail: a.orr-ewing@bristol.ac.uk [School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS (United Kingdom); King, Simon J.; Vallance, Claire [Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford OX1 3TA (United Kingdom)

    2016-06-28

    Photodissociation of gaseous bromocyclopropane via its A-band continuum has been studied at excitation wavelengths ranging from 230 nm to 267 nm. Velocity-map images of ground-state bromine atoms (Br), spin-orbit excited bromine atoms (Br{sup ∗}), and C{sub 3}H{sub 5} hydrocarbon radicals reveal the kinetic energies of these various photofragments. Both Br and Br{sup ∗} atoms are predominantly generated via repulsive excited electronic states in a prompt photodissociation process in which the hydrocarbon co-fragment is a cyclopropyl radical. However, the images obtained at the mass of the hydrocarbon radical fragment identify a channel with total kinetic energy greater than that deduced from the Br and Br{sup ∗} images, and with a kinetic energy distribution that exceeds the energetic limit for Br + cyclopropyl radical products. The velocity-map images of these C{sub 3}H{sub 5} fragments have lower angular anisotropies than measured for Br and Br{sup ∗}, indicating molecular restructuring during dissociation. The high kinetic energy C{sub 3}H{sub 5} signals are assigned to allyl radicals generated by a minor photochemical pathway which involves concerted C–Br bond dissociation and cyclopropyl ring-opening following single ultraviolet (UV)-photon absorption. Slow photofragments also contribute to the velocity map images obtained at the C{sub 3}H{sub 5} radical mass, but the corresponding slow Br atoms are not observed. These features in the images are attributed to C{sub 3}H{sub 5}{sup +} from the photodissociation of the C{sub 3}H{sub 5}Br{sup +} molecular cation following two-photon ionization of the parent compound. This assignment is confirmed by 118-nm vacuum ultraviolet ionization studies that prepare the molecular cation in its ground electronic state prior to UV photodissociation.

  17. Application of spectroscopy and super-resolution microscopy: Excited state

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharjee, Ujjal [Iowa State Univ., Ames, IA (United States)

    2016-02-19

    Photophysics of inorganic materials and organic molecules in complex systems have been extensively studied with absorption and emission spectroscopy.1-4 Steady-state and time-resolved fluorescence studies are commonly carried out to characterize excited-state properties of fluorophores. Although steady-state fluorescence measurements are widely used for analytical applications, time-resolved fluorescence measurements provide more detailed information about excited-state properties and the environment in the vicinity of the fluorophore. Many photophysical processes, such as photoinduced electron transfer (PET), rotational reorientation, solvent relaxation, and energy transfer, occur on a nanosecond (10-9 s) timescale, thus affecting the lifetime of the fluorophores. Moreover, time-resolved microscopy methods, such as lifetimeimaging, combine the benefits of the microscopic measurement and information-rich, timeresolved data. Thus, time-resolved fluorescence spectroscopy combined with microscopy can be used to quantify these processes and to obtain a deeper understanding of the chemical surroundings of the fluorophore in a small area under investigation. This thesis discusses various photophysical and super-resolution microscopic studies of organic and inorganic materials, which have been outlined below.

  18. Influence of the excited states on the electron-energy distribution function in low-pressure microwave argon plasmas

    International Nuclear Information System (INIS)

    Yanguas-Gil, A.; Cotrino, J.; Gonzalez-Elipe, A.R.

    2005-01-01

    In this work the influence of the excited states on the electron-energy distribution function has been determined for an argon microwave discharge at low pressure. A collisional-radiative model of argon has been developed taking into account the most recent experimental and theoretical values of argon-electron-impact excitation cross sections. The model has been solved along with the electron Boltzmann equation in order to study the influence of the inelastic collisions from the argon excited states on the electron-energy distribution function. Results show that under certain conditions the excited states can play an important role in determining the shape of the distribution function and the mean kinetic energy of the electrons, deplecting the high-energy tail due to inelastic processes from the excited states, especially from the 4s excited configuration. It has been found that from the populations of the excited states an excitation temperature can be defined. This excitation temperature, which can be experimentally determined by optical emission spectroscopy, is lower than the electron kinetic temperature obtained from the electron-energy distribution function

  19. Photodissociation dynamics of core-excited molecular oxygen

    International Nuclear Information System (INIS)

    Coutinho, L.H.; Homem, M.G.P.; Marinho, R.R.T.; Mocellin, A.; Naves de Brito, A.; Burmeister, F.

    2004-01-01

    Full text: The fragmentation of molecules after the excitation of a core orbital is of particular interest due to the localization of these orbitals and the possibility to observe dissociation in the same time scale as the electronic decay. This process, which occurs in a few femtoseconds and is known as ultrafast dissociation, has been observed for O 2 and the results will be presented. We used the PhotoElectron-PhotoIon COincidence (PEPICO) and PhotoElectron-PhotoIon-PhotoIon COincidence (PEPIPICO) spectroscopy technique to analyze the produced fragments in the 529 to 540 eV photon energy range. Usually Electron Spectroscopy (ES) is employed to establish whether this peculiar phenomenon occurs or not. Here we successfully put forward the use of partial ion yield (PIY) spectroscopy to investigate ultrafast dissociation. The experiment was performed at the Brazilian Synchrotron Light Laboratory (LNLS). The SGM beamline was equipped with an end-station composed by a time-of-flight mass spectrometer able to rotate with respect to the polarization of the exciting beam. The measurements were taken with the TOF axis performing an angle of 54.7 deg with respect to the polarization vector of the light. The data were corrected for non-unitary detection efficiency in the detectors

  20. Excited-State Dynamics of Melamine and Its Lysine Derivative Investigated by Femtosecond Transient Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    Yuyuan Zhang

    2016-11-01

    Full Text Available Melamine may have been an important prebiotic information carrier, but its excited-state dynamics, which determine its stability under UV radiation, have never been characterized. The ability of melamine to withstand the strong UV radiation present on the surface of the early Earth is likely to have affected its abundance in the primordial soup. Here, we studied the excited-state dynamics of melamine (a proto-nucleobase and its lysine derivative (a proto-nucleoside using the transient absorption technique with a UV pump, and UV and infrared probe pulses. For melamine, the excited-state population decays by internal conversion with a lifetime of 13 ps without coupling significantly to any photochemical channels. The excited-state lifetime of the lysine derivative is slightly longer (18 ps, but the dominant deactivation pathway is otherwise the same as for melamine. In both cases, the vast majority of excited molecules return to the electronic ground state on the aforementioned time scales, but a minor population is trapped in a long-lived triplet state.

  1. Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2 '-bipyridine)(CN)4]2-

    DEFF Research Database (Denmark)

    Kjær, Kasper Skov; Kunnus, Kristjan; Harlang, Tobias C. B.

    2018-01-01

    The excited state dynamics of solvated [Fe(bpy)(CN)4]2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer...... the MLCT excited state relaxation dynamics of [Fe(bpy)(CN)4]2- in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state...... developed for solar applications....

  2. Zero photon dissociation of CS2+ in intense ultrashort laser pulses

    Science.gov (United States)

    Severt, Travis; Betsch, K. J.; Zohrabi, M.; Ablikim, U.; Jochim, Bethany; Carnes, K. D.; Esry, B. D.; Ben-Itzhak, I.

    2013-05-01

    We measured the dissociation of a CS2+ molecular ion beam in intense laser pulses ( C+ + S+. We speculate that a pump-dump process occurs whereby the vibrational wavepacket in the electronic ground state of CS2+ is pumped into the electronic first excited state's continuum by a single photon during the laser pulse. Once this continuum vibrational wavepacket passes the potential barrier in the ground electronic potential, the emission of a second photon is stimulated by the same laser pulse, most likely when the wavepacket moves through the internuclear distance where the two electronic states are in resonance with the driving field. A comparison is made to ZPD and ATD in the isovalent CO2+ species. Curiously, ATD is the favored mechanism in CO2+. The underlying molecular structure and dynamics determining this preference will be discussed. Supported by Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy.

  3. Interference spectra induced by a bichromatic field in the excited state of a three-level atom

    International Nuclear Information System (INIS)

    Mavroyannis, C.

    1998-01-01

    The interference spectra for the excited state of a three-level atom have been considered, where the strong and the weak atomic transitions leading to an electric dipole allowed excited state and to a metastable excited state are driven by resonant and nonresonant laser fields, respectively. In the low intensity limit of the strong laser field, there are two short lifetime excitations, the spontaneous one described by the weak signal field and the one induced by the strong laser field, both of which appear at the same frequency, and a long lifetime excitation induced by the weak laser field. The maximum intensities (heights) of the two peaks describing the short lifetime excitations take equal positive and negative values and, therefore, cancel each other out completely, while the long lifetime excitation dominates. This indicates the disappearance of the short lifetime excitations describing the strong atomic transition for a period equal to the lifetime of the long lifetime excitation, which is roughly equal to half of the lifetime of the metastable state. The computed spectra have been graphically presented and discussed at resonance and for finite detunings. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  4. Heat capacity for systems with excited-state quantum phase transitions

    Energy Technology Data Exchange (ETDEWEB)

    Cejnar, Pavel; Stránský, Pavel, E-mail: stransky@ipnp.troja.mff.cuni.cz

    2017-03-18

    Heat capacities of model systems with finite numbers of effective degrees of freedom are evaluated using canonical and microcanonical thermodynamics. Discrepancies between both approaches, which are observed even in the infinite-size limit, are particularly large in systems that exhibit an excited-state quantum phase transition. The corresponding irregularity of the spectrum generates a singularity in the microcanonical heat capacity and affects smoothly the canonical heat capacity. - Highlights: • Thermodynamics of systems with excited-state quantum phase transitions • ESQPT-generated singularities of the microcanonical heat capacity • Non-monotonous dependences of the canonical heat capacity • Discord between canonical and microcanonical pictures in the infinite-size limit.

  5. Theory and computation of triply excited resonances: Application to states of He-

    International Nuclear Information System (INIS)

    Nicolaides, C.A.; Piangos, N.A.; Komninos, Y.

    1993-01-01

    Autoionizing multiply excited states offer unusual challenges to the theory of electronic structure and spectra because of the presence of strong electron correlations, of their occasional weak binding, of their proximity to more than one threshold, and of their degeneracy with many continua. Here we discuss a theory that addresses these difficulties in conjunction with the computation of their wave functions and intrinsic properties. Emphasis is given on the justification of the possible presence of self-consistently obtained open-channel-like (OCL) correlating configurations in the square-integrable representation of such states and on their effect on the energy E and the width Γ. Application of the theory has allowed the prediction of two hitherto unknown He - triply excited resonances, the 2s2p 2 2 P (E=59.71 eV, above the He ground state, Γ=79 meV) and the 2p 3 2 Do (E=59.46 eV, Γ=282 meV) (1 a.u.=27.2116 eV). These resonances are above the singly excited states of He and are embedded in its doubly excited spectrum. The relatively broad 2p 3 2 Do state interacts strongly with the He 2s2p 3 Po εd continuum. The effect of this interaction has been studied in terms of the coupling with fixed core scattering states as well as with a self-consistently computed OCL bound configuration

  6. Ab initio excited states from the in-medium similarity renormalization group

    Science.gov (United States)

    Parzuchowski, N. M.; Morris, T. D.; Bogner, S. K.

    2017-04-01

    We present two new methods for performing ab initio calculations of excited states for closed-shell systems within the in-medium similarity renormalization group (IMSRG) framework. Both are based on combining the IMSRG with simple many-body methods commonly used to target excited states, such as the Tamm-Dancoff approximation (TDA) and equations-of-motion (EOM) techniques. In the first approach, a two-step sequential IMSRG transformation is used to drive the Hamiltonian to a form where a simple TDA calculation (i.e., diagonalization in the space of 1 p 1 h excitations) becomes exact for a subset of eigenvalues. In the second approach, EOM techniques are applied to the IMSRG ground-state-decoupled Hamiltonian to access excited states. We perform proof-of-principle calculations for parabolic quantum dots in two dimensions and the closed-shell nuclei 16O and 22O. We find that the TDA-IMSRG approach gives better accuracy than the EOM-IMSRG when calculations converge, but it is otherwise lacking the versatility and numerical stability of the latter. Our calculated spectra are in reasonable agreement with analogous EOM-coupled-cluster calculations. This work paves the way for more interesting applications of the EOM-IMSRG approach to calculations of consistently evolved observables such as electromagnetic strength functions and nuclear matrix elements, and extensions to nuclei within one or two nucleons of a closed shell by generalizing the EOM ladder operator to include particle-number nonconserving terms.

  7. Luminescent materials: probing the excited state of emission centers by spectroscopic methods

    International Nuclear Information System (INIS)

    Mihóková, E; Nikl, M

    2015-01-01

    We review recent methods employed to study the excited state of rare-earth centers in various luminescent and scintillating materials. The focus is on processes that help determine localization of the excited state within the material band gap, namely photoionization and thermally stimulated ionization. Then the tunneling process between the luminescence center and the trapping state is addressed. We describe the experimental implementation of methods recently developed to study these processes. We report theoretical models helping the data interpretation. We also present application to currently investigated materials. (topical review)

  8. Critical Assessment of TD-DFT for Excited States of Open-Shell Systems: I. Doublet-Doublet Transitions.

    Science.gov (United States)

    Li, Zhendong; Liu, Wenjian

    2016-01-12

    A benchmark set of 11 small radicals is set up to assess the performance of time-dependent density functional theory (TD-DFT) for the excited states of open-shell systems. Both the unrestricted (U-TD-DFT) and spin-adapted (X-TD-DFT) formulations of TD-DFT are considered. For comparison, the well-established EOM-CCSD (equation-of-motion coupled-cluster with singles and doubles) is also used. In total, 111 low-lying singly excited doublet states are accessed by all the three approaches. Taking the MRCISD+Q (multireference configuration interaction with singles and doubles plus the Davidson correction) results as the benchmark, it is found that both U-TD-DFT and EOM-CCSD perform well for those states dominated by singlet-coupled single excitations (SCSE) from closed-shell to open-shell, open-shell to vacant-shell, or closed-shell to vacant-shell orbitals. However, for those states dominated by triplet-coupled single excitations (TCSE) from closed-shell to vacant-shell orbitals, both U-TD-DFT and EOM-CCSD fail miserably due to severe spin contaminations. In contrast, X-TD-DFT provides balanced descriptions of both SCSE and TCSE. As far as the functional dependence is concerned, it is found that, when the Hartree-Fock ground state does not suffer from the instability problem, both global hybrid (GH) and range-separated hybrid (RSH) functionals perform grossly better than pure density functionals, especially for Rydberg and charge-transfer excitations. However, if the Hartree-Fock ground state is instable or nearly instable, GH and RSH tend to underestimate severely the excitation energies. The SAOP (statistically averaging of model orbital potentials) performs more uniformly than any other density functionals, although it generally overestimates the excitation energies of valence excitations. Not surprisingly, both EOM-CCSD and adiabatic TD-DFT are incapable of describing excited states with substantial double excitation characters.

  9. Resonant inelastic x-ray scattering and photoemission measurement of O2: Direct evidence for dependence of Rydberg-valence mixing on vibrational states in O 1s → Rydberg states

    Science.gov (United States)

    Gejo, T.; Oura, M.; Tokushima, T.; Horikawa, Y.; Arai, H.; Shin, S.; Kimberg, V.; Kosugi, N.

    2017-07-01

    High-resolution resonant inelastic x-ray scattering (RIXS) and low-energy photoemission spectra of oxygen molecules have been measured for investigating the electronic structure of Rydberg states in the O 1s → σ* energy region. The electronic characteristics of each Rydberg state have been successfully observed, and new assignments are made for several states. The RIXS spectra clearly show that vibrational excitation is very sensitive to the electronic characteristics because of Rydberg-valence mixing and vibronic coupling in O2. This observation constitutes direct experimental evidence that the Rydberg-valence mixing characteristic depends on the vibrational excitation near the avoided crossing of potential surfaces. We also measured the photoemission spectra of metastable oxygen atoms (O*) from O2 excited to 1s → Rydberg states. The broadening of the 4p Rydberg states of O* has been found with isotropic behavior, implying that excited oxygen molecules undergo dissociation with a lifetime of the order of 10 fs in 1s → Rydberg states.

  10. Studies of the fluorescent excited state of impurities in ionic crystals

    International Nuclear Information System (INIS)

    Romestain, Robert

    1972-01-01

    The author of this research thesis first presents experimental methods used in this research: principles (recall on the optical spectrum of an impurity in a solid, use of fluorescence polarization) and techniques (sample preparation, liquid helium cryostat, application of a disturbance, optical detection). Then, he reports the study of the Mn ++ ion in a tetrahedron crystalline field, the study of the Jahn Teller effect on the excited state of the F + centre in CaO, and the study by double resonance of a specific excited state of this same centre in CaO

  11. Pion inelastic scattering to the first three excited states of lithium-6

    International Nuclear Information System (INIS)

    Kiziah, R.R.

    1984-10-01

    Using the Energetic Pion Channel and Spectrometer system at the Clinton P. Anderson Meson Physics Facility, differential cross sections were measured for π + inelastic scattering to the 3 + , T=0, 2.185-MeV, 0 + , T=1, 3.563-MeV, and 2 + , T=0, 4.25-MeV states of 6 Li at incident pion energies of 120 and 180 MeV and laboratory scattering angles between 15 0 and 47 0 . Excitation functions were measured at a constant momentum transfer of approximately 109 MeV/c for incident pion energies from 100 to 260 MeV. The constant momentum transfer corresponds to the maxima of the angular distributions for π + inelastic scattering to the 3.563-MeV level. Microscopic calculations using the distorted-wave impulse approximation (DWIA) agree well with the measured angular distributions and excitation functions for the 2.185- and 4.25-MeV levels. However, microscopic DWIA calculations do not adequately reproduce the measured angular distributions for the 3.563-MeV level and fail to reproduce the observed anomalous excitation function. The shape of the 3.563-MeV excitation function is similar to that previously observed for π +- inelastic scattering to the 1 + , T=1, 15.11-MeV state of 12 C. The same mechanism may be responsible for the observed excitation functions of both ΔS=ΔT=1 transitions. A possible mechanism is the direct excitation of Δ particle-nucleon hole (Δ-h) components in the final state wave functions. Within the Δ-h model interpretation, the peak of the 3.563-MeV excitation function is reproduced with an estimated probability amplitude for the Δ-h component of the 3.563-MeV state with respect to the ground state of 0.01 less than or equal to β less than or equal to 0.13, a range of values of β consistent with the range estimated for the 15.11-MeV level of 12 C (0.026 less than or equal to β less than or equal to 0.096)

  12. Communication: State mixing by spin-orbit coupling in the anionic chloroiodine dissociations

    Energy Technology Data Exchange (ETDEWEB)

    Xia, L.; Wang, X.-D.; Xuan, C.-J.; Zeng, X.-J.; Li, H.-K.; Tian, S. X., E-mail: sxtian@ustc.edu.cn, E-mail: kaichung@cityu.edu.hk [Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); Pan, Y.; Lau, K.-C., E-mail: sxtian@ustc.edu.cn, E-mail: kaichung@cityu.edu.hk [Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong (China)

    2014-01-28

    Three spin-orbit states, 1{sup 2}Π{sub 1/2}, 2{sup 2}Π{sub 3/2}, and 2{sup 2}Π{sub 1/2}, of chloroiodine anion (ICl{sup −}) formed by low-energy electron attachment in the Franck-Condon region are associated with the dissociative limits of I{sup −} ({sup 1}S{sub 0}) and Cl ({sup 2}P{sub 3/2}) or Cl{sup *} ({sup 2}P{sub 1/2}) fragments. Within the adiabatic scheme, the presumptive Π-symmetry of the fragment angular distributions is dramatically changed to be the Π-Σ mixing symmetry, due to the significant spin-orbit interaction effect on the electronic state couplings of ICl{sup −}. The present experimental approach also enables us to separate the contributions of different electronic states from the mixed states, providing a crucial method for quantitatively evaluating the configuration-interaction wavefunctions.

  13. Effects of excited state mixing on transient absorption spectra in dimers Application to photosynthetic light-harvesting complex II

    CERN Document Server

    Valkunas, L; Trinkunas, G; Müller, M G; Holzwarth, A R

    1999-01-01

    The excited state mixing effect is taken into account considering the difference spectra of dimers. Both the degenerate (homo) dimer as well as the nondegenerate (hetero) dimer are considered. Due to the higher excited state mixing with the two-exciton states in the homodimer, the excited state absorption (or the difference spectrum) can be strongly affected in comparison with the results obtained in the Heitler-London approximation. The difference spectrum of the heterodimer is influenced by two resonance effects (i) mixing of the ground state optical transitions of both monomers in the dimer and (ii) mixing of the excited state absorption of the excited monomer with the ground state optical transition in the nonexcited monomer. These effects have been tested by simulating the difference absorption spectra of the light-harvesting complex of photosystem II (LHC II) experimentally obtained with the 60 fs excitation pulses at zero delay times and various excitation wavelengths. The pairs of coupled chlorophylls...

  14. Measurements of photoionization cross sections from the 4p, 5d and 7s excited states of potassium

    International Nuclear Information System (INIS)

    Amin, Nasir; Mahmood, S.; Haq, S.U.; Kalyar, M.A.; Rafiq, M.; Baig, M.A.

    2008-01-01

    New measurements of the photoionization cross sections from the 4p 2 P 1/2,3/2 , 5d 2 D 5/2,3/2 and 7s 2 S 1/2 excited states of potassium are presented. The cross sections have been measured by two-step excitation and ionization using a Nd:YAG laser in conjunction with a thermionic diode ion detector. By applying the saturation technique, the absolute values of the cross sections from the 4p 2 P 3/2 and 4p 2 P 1/2 states at 355 nm are determined as 7.2±1.1 and 5.6±0.8 Mb, respectively. The photoionization cross section from the 5d 2 D 5/2,3/2 excited state has been measured using two excitation paths, two-step excitation and two-photon excitation from the ground state. The measured values of the cross sections from the 5d 2 D 5/2 state by two-photon excitation from the ground state is 28.9±4.3 Mb, whereas in the two-step excitation, the cross section from the 5d 2 D 3/2 state via the 4p 2 P 1/2 state and from the 5d 2 D 5/2,3/2 states via the 4p 2 P 3/2 state are determined as 25.1±3.8 and 30.2±4.5 Mb, respectively. Besides, we have measured the photoionization cross sections from the 7s 2 S 1/2 excited state using the two-photon excitation from the ground state as 0.61±0.09 Mb

  15. Excitation of atoms and molecules in collisions with highly charged ions

    International Nuclear Information System (INIS)

    Watson, R.L.

    1992-01-01

    This report discusses research of multicharged nitrogen, oxygen and carbon monoxide molecular ions produced with collision with multicharged argon ions. Properties like ionization, dissociation, and excitation are investigated

  16. Pulsed laser study of excited states of aromatic molecules absorbed in globular proteins

    International Nuclear Information System (INIS)

    Cooper, M.; Thomas, J.K.

    1977-01-01

    Pyrene and several derivatives of pyrene such as pyrene sulfonic acid, and pyrene butyric acid were incorporated into bovine serum albumin (BSA) in aqueous solution. The pyrene chromophore was subsequently excited by a pulse of uv light (lambda = 3471 A) from a Q switched frequency doubled ruby laser. The lifetime of the pyrene excited singlet and triplet states were monitored by time resolved spectrophotometry. Various molecules, such as O 2 and I - , dissolved in the aqueous phase, diffused into the protein and quenched pyrene excited states. The rates of these reactions were followed under a variety of conditions such as pH and temperature and in the presence of inert additives. The rates of pyrene excited-state quenching were often considerably smaller than the rates observed in simple solutions. A comparison of the rates in the protein and homogeneous solutions gives information on the factors such as temperature, charge, and pH that control the movement of small molecules in and into BSA

  17. Excited states of ethylene interpreted in terms of perturbed Rydberg series

    International Nuclear Information System (INIS)

    Yamamoto, Shigeyoshi; Tatewaki, Hiroshi

    2003-01-01

    We have investigated the excited states of the ethylene molecule by the multireference configuration interaction (MRCI) method. In particular, the nature of the V state (1 1 B 1u π→π*) was interpreted in terms of perturbed Rydberg series. To clarify the role of the perturbers, we use pseudo-restricted Hartree-Fock natural orbitals (PRHFNO), which would be the most suitable molecular orbital set to describe Rydberg series. It is well known that the expectation value of x 2 for the V state is reduced from 44a 0 2 (RHF) to around 17a 0 2 by considering electron correlation effects, where x is the direction out of the molecular plane. In the present study, a reasonable 2 > value was obtained from small multireference configuration interaction with single excitations (MRCIS), where the π→π* configurations and a few perturbers were assigned as the reference configurations. The major perturbers were found to be five configurations represented by 3a g → 3b 1u , 1b 3g → 3b 2u , 2b 1u → 4a g , 2a g → 3b 1u , and 1b 2u → 2b 3g with respect to the ground state configuration. The V state can therefore be described as a scattering process of the π→π* state by these perturbers. Other low-lying excited states are also investigated by the MRCI method

  18. EPR studies of excited state exchange and crystal-field effects in rare earth compounds

    International Nuclear Information System (INIS)

    Huang, C.Y.; Sugawara, K.; Cooper, B.R.

    1976-01-01

    EPR in excited crystal-field states of Tm 3+ , Pr 3+ , and Tb 3+ in singlet-ground-state systems and in the excited state of Ce 3+ in CeP are reviewed. Because one is looking at a crystal-field excited state resonance, the exchange, even if isotropic, does not act as a secular perturbation. This means that one obtains different effects and has access to more information about the dynamic effects of exchange than in conventional paramagnetic resonance experiments. The Tm and Pr monopnictides studied are paramagnetic at all temperatures. The most striking feature of the behavior of the GAMMA 5 /sup (2)/ EPR in the Tm compounds is the presence of an anomalous maximum in the temperature dependence of the g-factor. The relationship of this effect to anisotropic exchange is discussed. The results of the EPR of the excited GAMMA 5 /sup (2)/ level of Tb 3 + (g-factor becomes very large at T/sub N/ in antiferromagnetic TbX (X = P, As, Sb) and that of the excited GAMMA 8 level of Ce 3+ in antiferromagnetic CeP will also be reported. For sufficient dilution of the Tb 3+ in the terbium monopnictides, the systems become paramagnetic (Van Vleck paramagnets) down to 0 0 K. The Tb 3+ excited state resonance EPR in Tb/sub 0.1/ La/sub 0.9/P was studied as an example of behavior in such systems. 10 fig

  19. Kinetic-energy distributions of O- produced by dissociative electron attachment to physisorbed O2

    International Nuclear Information System (INIS)

    Huels, M.A.; Parenteau, L.; Michaud, M.; Sanche, L.

    1995-01-01

    We report measurements of the kinetic energy (E k ) distributions of O - produced by low-energy electron impact (5.5--19.5 eV) on disordered multilayers of O 2 physisorbed on a polycrystalline Pt substrate. The results confirm that dissociative electron attachment (DEA) proceeds via the formation of the 2 Π u , 2 Σ g + (I), and 2 Σ x + (II) (x=g and/or u) states of O 2 -* . We also find evidence for an additional resonance, namely the 2 Σ u + (I), positioned at about 10 eV above the neutral ground state in the Franck-Condon region, and dissociating into O - +O( 3 P). The measurements suggest that the autodetachment lifetimes of the 2 Σ u + (I) and 2 Σ g + (II) states may be longer than previously suggested. It is also observed that the effects of electron energy loss (EEL) in the solid prior to DEA, O - scattering in the solid after dissociation, and the charge-induced polarization energy of the solid, broaden the E k distributions, shift them to lower anion energies, and result in additional structure in them. The effects of EEL on the desorption dynamics of O - are estimated from high-resolution electron-energy-loss spectra and excitation functions for losses in the vicinity of the Schumann-Runge continuum of the physisorbed O 2 molecules. We find indications for an enhancement of the optically forbidden X 3 Σ g - →A 3 Σ u + transition, and observe that the gas-phase Rydberg bands, for energy losses above 7 eV, are not distinguishable in the condensed phase

  20. Ultrafast dynamics of ligand and substrate interaction in endothelial nitric oxide synthase under Soret excitation.

    Science.gov (United States)

    Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S

    2016-01-01

    Ultrafast transient absorption spectroscopy of endothelial NOS oxygenase domain (eNOS-oxy) was performed to study dynamics of ligand or substrate interaction under Soret band excitation. Photo-excitation dissociates imidazole ligand in 4ps. The eNOS-oxy without additive is partially bound with water molecule, thus its photoexcited dynamics also shows ligand dissociation in <800fs. Then it followed by vibrational cooling coupled with charge transfer in 4.8ps, and recombination of ligand to distal side of heme in 12ps. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Control of HOD photodissociation dynamics via bond-selective infrared multiphoton excitation and a femtosecond ultraviolet laser pulse

    DEFF Research Database (Denmark)

    Amstrup, Bjarne; Henriksen, Niels Engholm

    1992-01-01

    moment, excites the molecule to a dissociative electronic state. We consider the HOD molecule which is ideal due to the local mode structure of the vibrational states. It is shown that selective and localized bond stretching can be created in simple laser fields. When such a nonstationary vibrating HOD...... molecule is photodissociated with a short laser pulse (~5 fs) complete selectivity between the channels H+OD and D+OH is observed over the entire absorption band covering these channels. The Journal of Chemical Physics is copyrighted by The American Institute of Physics....

  2. Analytic energy gradient of excited electronic state within TDDFT/MMpol framework: Benchmark tests and parallel implementation.

    Science.gov (United States)

    Zeng, Qiao; Liang, WanZhen

    2015-10-07

    The time-dependent density functional theory (TDDFT) has become the most popular method to calculate the electronic excitation energies, describe the excited-state properties, and perform the excited-state geometric optimization of medium and large-size molecules due to the implementation of analytic excited-state energy gradient and Hessian in many electronic structure software packages. To describe the molecules in condensed phase, one usually adopts the computationally efficient hybrid Quantum Mechanics/Molecular Mechanics (QM/MM) models. Here, we extend our previous work on the energy gradient of TDDFT/MM excited state to account for the mutual polarization effects between QM and MM regions, which is believed to hold a crucial position in the potential energy surface of molecular systems when the photoexcitation-induced charge rearrangement in the QM region is drastic. The implementation of a simple polarizable TDDFT/MM (TDDFT/MMpol) model in Q-Chem/CHARMM interface with both the linear response and the state-specific features has been realized. Several benchmark tests and preliminary applications are exhibited to confirm our implementation and assess the effects of different treatment of environmental polarization on the excited-state properties, and the efficiency of parallel implementation is demonstrated as well.

  3. Electronically excited and ionized states in condensed phase: Theory and applications

    Science.gov (United States)

    Sadybekov, Arman

    Predictive modeling of chemical processes in silico is a goal of XXI century. While robust and accurate methods exist for ground-state properties, reliable methods for excited states are still lacking and require further development. Electronically exited states are formed by interactions of matter with light and are responsible for key processes in solar energy harvesting, vision, artificial sensors, and photovoltaic applications. The greatest challenge to overcome on our way to a quantitative description of light-induced processes is accurate inclusion of the effect of the environment on excited states. All above mentioned processes occur in solution or solid state. Yet, there are few methodologies to study excited states in condensed phase. Application of highly accurate and robust methods, such as equation-of-motion coupled-cluster theory EOM-CC, is limited by a high computational cost and scaling precluding full quantum mechanical treatment of the entire system. In this thesis we present successful application of the EOM-CC family of methods to studies of excited states in liquid phase and build hierarchy of models for inclusion of the solvent effects. In the first part of the thesis we show that a simple gasphase model is sufficient to quantitatively analyze excited states in liquid benzene, while the latter part emphasizes the importance of explicit treatment of the solvent molecules in the case of glycine in water solution. In chapter 2, we use a simple dimer model to describe exciton formation in liquid and solid benzene. We show that sampling of dimer structures extracted from the liquid benzene is sufficient to correctly predict exited-state properties of the liquid. Our calculations explain experimentally observed features, which helped to understand the mechanism of the excimer formation in liquid benzene. Furthermore, we shed light on the difference between dimer configurations in the first solvation shell of liquid benzene and in unit cell of solid

  4. Lifetime measurements of excited states in 73As

    International Nuclear Information System (INIS)

    Singh, K.P.; Kavakand, T.; Hajivaliei, M.

    2004-01-01

    The excited states of 73 As have been investigated via the 73 Ge(p, nγ) 73 As reaction with proton beam energies from 2.5–4.3 MeV. The lifetimes of the levels at 769.6, 860.5, 1177.8, 1188.7, 1274.9, 1344.1, 1557.1 and 1975.2 keV excitation energies have been measured for the first time using the Doppler shift attenuation method. The angular distributions have been used to assign the spins and the multipole mixing ratios using statistical theory for compound nuclear reactions. The ambiguity in the spin values for the various levels has been removed. The multipole mixing ratios for eight γ-transitions have been newly measured. (author)

  5. Obtaining Hartree-Fock and density functional theory doubly excited states with Car-Parrinello density matrix search

    Science.gov (United States)

    Liang, Wenkel; Isborn, Christine M.; Li, Xiaosong

    2009-11-01

    The calculation of doubly excited states is one of the major problems plaguing the modern day excited state workhorse methodology of linear response time dependent Hartree-Fock (TDHF) and density function theory (TDDFT). We have previously shown that the use of a resonantly tuned field within real-time TDHF and TDDFT is able to simultaneously excite both the α and β electrons to achieve the two-electron excited states of minimal basis H2 and HeH+ [C. M. Isborn and X. Li, J. Chem. Phys. 129, 204107 (2008)]. We now extend this method to many electron systems with the use of our Car-Parrinello density matrix search (CP-DMS) with a first-principles fictitious mass method for wave function optimization [X. Li, C. L. Moss, W. Liang, and Y. Feng, J. Chem. Phys. 130, 234115 (2009)]. Real-time TDHF/TDDFT is used during the application of the laser field perturbation, driving the electron density toward the doubly excited state. The CP-DMS method then converges the density to the nearest stationary state. We present these stationary state doubly excited state energies and properties at the HF and DFT levels for H2, HeH+, lithium hydride, ethylene, and butadiene.

  6. Role of excited state solvent fluctuations on time-dependent fluorescence Stokes shift

    Energy Technology Data Exchange (ETDEWEB)

    Li, Tanping, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu; Kumar, Revati, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States)

    2015-11-07

    We explore the connection between the solvation dynamics of a chromophore upon photon excitation and equilibrium fluctuations of the solvent. Using molecular dynamics simulations, fluorescence Stokes shift for the tryptophan in Staphylococcus nuclease was examined using both nonequilibrium calculations and linear response theory. When the perturbed and unperturbed surfaces exhibit different solvent equilibrium fluctuations, the linear response approach on the former surface shows agreement with the nonequilibrium process. This agreement is excellent when the perturbed surface exhibits Gaussian statistics and qualitative in the case of an isomerization induced non-Gaussian statistics. However, the linear response theory on the unperturbed surface breaks down even in the presence of Gaussian fluctuations. Experiments also provide evidence of the connection between the excited state solvent fluctuations and the total fluorescence shift. These observations indicate that the equilibrium statistics on the excited state surface characterize the relaxation dynamics of the fluorescence Stokes shift. Our studies specifically analyze the Gaussian fluctuations of the solvent in the complex protein environment and further confirm the role of solvent fluctuations on the excited state surface. The results are consistent with previous investigations, found in the literature, of solutes dissolved in liquids.

  7. Structure of excited states in nuclei near doubly magic {sup 100}SN

    Energy Technology Data Exchange (ETDEWEB)

    Gorska, M.

    1998-11-01

    The three neutron-deficient nuclei {sup 94}Pd, {sup 98}Cd and {sup 104}Sn in the vicinity of {sup 100}Sn were investigated by means of in-beam {gamma}-ray spectroscopy of excited states. The isomeric decays in {sup 94}Pd and {sup 98}Cd were studied for the first time with an exclusive experimental setup for delayed {gamma}-ray detection with complete exit channel identification based on information from neutron and charged-particle filter detectors. The structure of excited states of {sup 94}Pd showed the first indication of increasing proton-neutron interaction towards the N=Z line in this region of nuclei, that in turn might be related to increased proton-neutron pairing correlations predicted in T{sub z}=0 nuclei. The closest neighbours of {sup 100}Sn with two active particles, {sup 98}Cd and {sup 102}Sn, are now known with their lowest excited states. The measured reduced transition probabilities for the decay of the isomeric 8{sup +} and 6{sup +} states in {sup 98}Cd and {sup 102}Sn, respectively, allowed to extract an effective quadrupole charge for neutron and proton in this region of nuclei based on the high configurational purity of the states. While the neutron effective charge appeared to be large and in agreement with expectation, the proton effective charge value is very small (e{sub {pi}}{<=}1). This controversial result, which would indicate that {sup 100}Sn is a very good closed shell nucleus with respect to quadrupole excitation, is not understood. An experimental reason for this result, related to existence of a core excited isomer, observed in the experiment by means of its half life but not {gamma}-rays, which may have escaped observation, can not be definitely excluded and is left as possible explanation. (orig.)

  8. An excited-state approach within full configuration interaction quantum Monte Carlo

    International Nuclear Information System (INIS)

    Blunt, N. S.; Smart, Simon D.; Booth, George H.; Alavi, Ali

    2015-01-01

    We present a new approach to calculate excited states with the full configuration interaction quantum Monte Carlo (FCIQMC) method. The approach uses a Gram-Schmidt procedure, instantaneously applied to the stochastically evolving distributions of walkers, to orthogonalize higher energy states against lower energy ones. It can thus be used to study several of the lowest-energy states of a system within the same symmetry. This additional step is particularly simple and computationally inexpensive, requiring only a small change to the underlying FCIQMC algorithm. No trial wave functions or partitioning of the space is needed. The approach should allow excited states to be studied for systems similar to those accessible to the ground-state method due to a comparable computational cost. As a first application, we consider the carbon dimer in basis sets up to quadruple-zeta quality and compare to existing results where available

  9. Lifetime measurements of the excited states in {sup 145} Sm

    Energy Technology Data Exchange (ETDEWEB)

    El-Badry, A M; Abdel Samie, Sh; Ahmad, A A [Depatment of Physics, Faculty of Science, ElMinia University, ElMinia, (Egypt); Kuroyanagi, T; Odahara, A; Gono, Y; Morinobu, S [Tandem Accelerator Laboratory, Department of Physics, Kyushu University, (Japan)

    1997-12-31

    Lifetime of the excited levels in {sup 145} Sm has been measured through the {sup 139} La ({sup 10} B, 4 n){sup 145} Sm nuclear reaction. The optimal beam energy of 49 MeV was determined from the measurements of the excitation function and Cascade program. With the possibility of studying lifetime of this nucleus a conventional plunger system have been designed and constructed at kyushu University tandem accelerator laboratory. A La target of 0.22 mg/cm{sup 2} thickness which was evaporated onto a Au foil of 2 mg/cm{sup 2} thickness was used. Since the recoil velocity was estimated to be 1.76 mm/ns (beta 0.00585), the measurable time range resulted in the range from 5 Ps to 5 ns. The single spectra measurements were performed at the 20 plunger positions in the range from 10 {mu} to 10 mm. Analyses of the data were carried using hypermet and/or GF2 program to obtain the lifetimes. A new list of lifetimes for 12 excited states up to 3.922 MeV excitations for {sup 145} Sm were determined for the first time. Decay curves of the these transitions are discussed. The new lifetimes of excited states in {sup 145} Sm enabled us to understand the electromagnetic properties. The deduced transition probabilities were established and compared with that of N = 83 isotones and the closed shell nucleus {sup 144} Sm. In addition, a nuclear structure of {sup 145} Sm have been discussed and proposed in framework of the shell model. 4 figs., 1 tab.

  10. Describing excited state relaxation and localization in TiO2 nanoparticles using TD-DFT

    International Nuclear Information System (INIS)

    Berardo, Enrico; Hu, Han-Shi; Van Dam, Hubertus J. J.; Shevlin, Stephen A.; Woodley, Scott M.; Kowalski, Karol; Zwijnenburg, Martijn A.

    2014-01-01

    We have investigated the description of excited state relaxation in naked and hydrated TiO 2 nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials; B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to be the inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree-Fock Like Exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT-problems for certain particles. We hypothesize that the spurious stabilization of CT-states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries than those obtained using TD-CAM-B3LYP or TD-BHLYP. In conclusion, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in naked and hydrated TiO 2 nanoparticles is predicted to be associated with a large Stokes' shift

  11. Spectroscopy of weakly-bound complexes in highly excited electronic states: the He-I2(E3Πg) ion-pair state

    International Nuclear Information System (INIS)

    Prosmiti, Rita; Valdés, Álvaro; Kalemost, Apostolos

    2014-01-01

    The study of electronically excited van der Waals (vdW) systems presents a challenge for the theory of intermolecular interactions, and here we show how far ab initio computations can go. We found that the interaction energies for such electronically excited systems can indeed be determined, providing a reliable and accurate description for the E state potential of the HeI 2 , that in combination with the ground X and electronic excited B state of the complex, is useful to model experimental data related with potential minima and also predict higher vibrational vdW states

  12. Excited-State Dynamics of Oxyluciferin in Firefly Luciferase

    KAUST Repository

    Snellenburg, Joris J.; Laptenok, Sergey P.; DeSa, Richard J.; Naumov, Pance; Solntsev, Kyril M.

    2016-01-01

    The color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH dependent emission to a single chemical species would be an oversimplification.

  13. Excited-State Dynamics of Oxyluciferin in Firefly Luciferase

    KAUST Repository

    Snellenburg, Joris J.

    2016-11-23

    The color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH dependent emission to a single chemical species would be an oversimplification.

  14. Strong-field dissociation of CS2+ via a pump/dump-like mechanism

    Science.gov (United States)

    Severt, T.; Zohrabi, M.; Betsch, K. J.; Ablikim, U.; Jochim, Bethany; Carnes, K. D.; Zeng, S.; Esry, B. D.; Ben-Itzhak, I.; Uhlíková, T.

    2014-05-01

    Laser-induced dissociation of the quasi-bound electronic ground state of CS2+ is investigated in intense laser pulses (pump/dump-like mechanism to explain this observed feature. Contrary to the conventional pump/dump control scheme, this process occurs within a single laser pulse, where the time delay is caused by the molecular structure. The process begins when the vibrational wavepacket in the electronic ground state of CS2+ is pumped into the electronic first excited state's continuum by a single photon. After a period of stretching at an energy above the potential barrier, the emission of a second photon is stimulated by the same laser pulse, most likely at the Condon point. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy, Grants DE-FG02-86ER13491 and DE-FG02-09ER16115. TU supported by GACR and MetaCentrum.

  15. Dissociation and psychosis in dissociative identity disorder and schizophrenia.

    Science.gov (United States)

    Laddis, Andreas; Dell, Paul F

    2012-01-01

    Dissociative symptoms, first-rank symptoms of schizophrenia, and delusions were assessed in 40 schizophrenia patients and 40 dissociative identity disorder (DID) patients with the Multidimensional Inventory of Dissociation (MID). Schizophrenia patients were diagnosed with the Structured Clinical Interview for the DSM-IV Axis I Disorders; DID patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised. DID patients obtained significantly (a) higher dissociation scores; (b) higher passive-influence scores (first-rank symptoms); and (c) higher scores on scales that measure child voices, angry voices, persecutory voices, voices arguing, and voices commenting. Schizophrenia patients obtained significantly higher delusion scores than did DID patients. What is odd is that the dissociation scores of schizophrenia patients were unrelated to their reports of childhood maltreatment. Multiple regression analyses indicated that 81% of the variance in DID patients' dissociation scores was predicted by the MID's Ego-Alien Experiences Scale, whereas 92% of the variance in schizophrenia patients' dissociation scores was predicted by the MID's Voices Scale. We propose that schizophrenia patients' responses to the MID do not index the same pathology as do the responses of DID patients. We argue that neither phenomenological definitions of dissociation nor the current generation of dissociation instruments (which are uniformly phenomenological in nature) can distinguish between the dissociative phenomena of DID and what we suspect are just the dissociation-like phenomena of schizophrenia.

  16. Chemical modulation of electronic structure at the excited state

    Science.gov (United States)

    Li, F.; Song, C.; Gu, Y. D.; Saleem, M. S.; Pan, F.

    2017-12-01

    Spin-polarized electronic structures are the cornerstone of spintronics, and have thus attracted a significant amount of interest; in particular, researchers are looking into how to modulate the electronic structure to enable multifunctional spintronics applications, especially in half-metallic systems. However, the control of the spin polarization has only been predicted in limited two-dimensional systems with spin-polarized Dirac structures and is difficult to achieve experimentally. Here, we report the modulation of the electronic structure in the light-induced excited state in a typical half-metal, L a1 /2S r1 /2Mn O3 -δ . According to the spin-transport measurements, there appears a light-induced increase in magnetoresistance due to the enhanced spin scattering, which is closely associated with the excited spin polarization. Strikingly, the light-induced variation can be enhanced via alcohol processing and reduced by oxygen annealing. X-ray photoelectron spectroscopy measurements show that in the chemical process, a redox reaction occurs with a change in the valence of Mn. Furthermore, first-principles calculations reveal that the change in the valence of Mn alters the electronic structure and consequently modulates the spin polarization in the excited state. Our findings thus report a chemically tunable electronic structure, demonstrating interesting physics and the potential for multifunctional applications and ultrafast spintronics.

  17. Triplet excited state properties in variable gap π-conjugated donor–acceptor–donor chromophores

    KAUST Repository

    Cekli, Seda; Winkel, Russell W.; Alarousu, Erkki; Mohammed, Omar F.; Schanze, Kirk S.

    2016-01-01

    A series of variable band-gap donor–acceptor–donor (DAD) chromophores capped with platinum(II) acetylide units has been synthesized and fully characterized by electrochemical and photophysical methods, with particular emphasis placed on probing triplet excited state properties. A counter-intuitive trend of increasing fluorescence quantum efficiency and lifetime with decreasing excited state energy (optical gap) is observed across the series of DAD chromophores. Careful study of the excited state dynamics, including triplet yields (as inferred from singlet oxygen sensitization), reveals that the underlying origin of the unusual trend in the fluorescence parameters is that the singlet–triplet intersystem crossing rate and yield decrease with decreasing optical gap. It is concluded that the rate of intersystem crossing decreases as the LUMO is increasingly localized on the acceptor unit in the DAD chromophore, and this result is interpreted as arising because the extent of spin–orbit coupling induced by the platinum heavy metal centers decreases as the LUMO is more localized on the acceptor. In addition to the trend in intersystem crossing, the results show that the triplet decay rates follow the Energy Gap Law correlation over a 1.8 eV range of triplet energy and 1000-fold range of triplet decay rates. Finally, femtosecond transient absorption studies for the DAD chromophores reveals a strong absorption in the near-infrared region which is attributed to the singlet excited state. This spectral band appears to be general for DAD chromophores, and may be a signature of the charge transfer (CT) singlet excited state.

  18. Triplet excited state properties in variable gap π-conjugated donor–acceptor–donor chromophores

    KAUST Repository

    Cekli, Seda

    2016-02-12

    A series of variable band-gap donor–acceptor–donor (DAD) chromophores capped with platinum(II) acetylide units has been synthesized and fully characterized by electrochemical and photophysical methods, with particular emphasis placed on probing triplet excited state properties. A counter-intuitive trend of increasing fluorescence quantum efficiency and lifetime with decreasing excited state energy (optical gap) is observed across the series of DAD chromophores. Careful study of the excited state dynamics, including triplet yields (as inferred from singlet oxygen sensitization), reveals that the underlying origin of the unusual trend in the fluorescence parameters is that the singlet–triplet intersystem crossing rate and yield decrease with decreasing optical gap. It is concluded that the rate of intersystem crossing decreases as the LUMO is increasingly localized on the acceptor unit in the DAD chromophore, and this result is interpreted as arising because the extent of spin–orbit coupling induced by the platinum heavy metal centers decreases as the LUMO is more localized on the acceptor. In addition to the trend in intersystem crossing, the results show that the triplet decay rates follow the Energy Gap Law correlation over a 1.8 eV range of triplet energy and 1000-fold range of triplet decay rates. Finally, femtosecond transient absorption studies for the DAD chromophores reveals a strong absorption in the near-infrared region which is attributed to the singlet excited state. This spectral band appears to be general for DAD chromophores, and may be a signature of the charge transfer (CT) singlet excited state.

  19. Diffractive dissociation into 3 pion final states at COMPASS

    Energy Technology Data Exchange (ETDEWEB)

    Chung, Suh-Urk [Technische Universitaet Muenchen, Physik Department E18, 85748 Garching (Germany); Brookhaven National Laboratory, Upton, NY 11973 (United States); Friedrich, Jan; Grabmueller, Stefanie; Haas, Florian; Ketzer, Bernhard; Neubert, Sebastian; Paul, Stephan; Weitzel, Quirin [Technische Universitaet Muenchen, Physik Department E18, 85748 Garching (Germany); Ryabchikov, Dimitry [Technische Universitaet Muenchen, Physik Department E18, 85748 Garching (Germany); Institute for High Energy Physics, 142284 Protvino (Russian Federation)

    2009-07-01

    Diffractive dissociation reactions at the COMPASS experiment, CERN, provide access to the meson resonance spectrum. During a pilot run in 2004, using a pion beam on a lead target, a competitive number of {pi}{sup -} {pi}{sup -} {pi}{sup +} final state events with masses below 2.5 GeV/c{sup 2} were recorded. After COMPASS had finished its muon program in 2007, it used in 2008 again a pion beam, but now a liquid hydrogen target, and gathered during several weeks a unique high statistics. A full partial wave analysis of the 2004 data has been performed, with the focus on the kinematic range of a large momentum transfer (0.1 GeV{sup 2}/c{sup 2} {<=} t' {<=} 1.0 GeV{sup 2}/c{sup 2}). In addition first results of the adjacent analysis with 2008 data are presented.

  20. Quantification of entanglement entropies for doubly excited resonance states in two-electron atomic systems

    International Nuclear Information System (INIS)

    Ho, Yew Kam; Lin, Chien-Hao

    2015-01-01

    In this work, we study the quantum entanglement for doubly excited resonance states in two-electron atomic systems such as the H - and Ps - ions and the He atom by using highly correlated Hylleraas type functions The resonance states are determined by calculation of density of resonance states with the stabilization method. The spatial (electron-electron orbital) entanglement entropies (linear and von Neumann) for the low-lying doubly excited states are quantified using the Schmidt-Slater decomposition method. (paper)

  1. Excited states above the proton threshold in {sup 26}Si

    Energy Technology Data Exchange (ETDEWEB)

    Komatsubara, T. [Institute for Basic Science (IBS), Rare Isotope Science Project, Yuseong-gu Daejeon (Korea, Republic of); Kubono, S.; Ito, Y. [RIKEN, Saitama (Japan); Hayakawa, T.; Shizuma, T. [Japan Atomic Energy Agency, Tokai, Ibaraki (Japan); Ozawa, A.; Ishibashi, Y. [University of Tsukuba, Institute of Physics, Tsukuba, Ibaraki (Japan); Moriguchi, T. [National Cerebral and Cardiovascular Center Research Institute, Suita, Osaka (Japan); Yamaguchi, H.; Kahl, D. [University of Tokyo, Wako Branch, Center for Nuclear Study (CNS), Wako, Saitama (Japan); Hayakawa, S. [Laboratori Nazionali del Sud-INFN, Catania (Italy); Nguyen Binh, Dam [Vietnamese Academy for Science and Technology, Institute of Physics, Hanoi (Viet Nam); Chen, A.A.; Chen, J. [McMaster University, Hamilton, Ontario (Canada); Setoodehnia, K. [University of Notre Dame, Department of Physics, Notre Dame, Indiana (United States); Kajino, T. [National Astronomical Observatory, Tokyo (Japan); University of Tokyo, Department of Astronomy, Graduate School of Science, Tokyo (Japan)

    2014-09-15

    The level scheme above the proton threshold in {sup 26}Si is crucial for evaluating the {sup 25}Al(p, γ){sup 26}Si stellar reaction, which is important for understanding the astrophysical origin of the long-lived cosmic radioactivity {sup 26}Al(T{sub 1/2} = 7.17 x 10{sup 5} y) in the Galaxy. The excited states in {sup 26}Si have been studied using an in-beam γ-ray spectroscopy technique with the {sup 24}Mg({sup 3}He, nγ){sup 26}Si reaction. γ-rays with energies up to 4.6 MeV emitted from excited states in {sup 26}Si have been measured using large volume HPGe detectors. The spin-parity of one of the most important states reported recently at 5890.0keV has been assigned as 0{sup +} by γ-γ angular correlation measurements in this work. (orig.)

  2. Excited state intramolecular charge transfer reaction in non-aqueous ...

    Indian Academy of Sciences (India)

    polar phase and thus leading to less swelling of reverse .... ues were restricted up to the limit at which no phase separation was ..... The lower panel of figure 1 also indicates that the slopes of ... probe in its ground and excited states.55.

  3. Pressure dependence of excited-state charge-carrier dynamics in organolead tribromide perovskites

    Science.gov (United States)

    Liu, X. C.; Han, J. H.; Zhao, H. F.; Yan, H. C.; Shi, Y.; Jin, M. X.; Liu, C. L.; Ding, D. J.

    2018-05-01

    Excited-state charge-carrier dynamics governs the performance of organometal trihalide perovskites (OTPs) and is strongly influenced by the crystal structure. Characterizing the excited-state charge-carrier dynamics in OTPs under high pressure is imperative for providing crucial insights into structure-property relations. Here, we conduct in situ high-pressure femtosecond transient absorption spectroscopy experiments to study the excited-state carrier dynamics of CH3NH3PbBr3 (MAPbBr3) under hydrostatic pressure. The results indicate that compression is an effective approach to modulate the carrier dynamics of MAPbBr3. Across each pressure-induced phase, carrier relaxation, phonon scattering, and Auger recombination present different pressure-dependent properties under compression. Responsiveness is attributed to the pressure-induced variation in the lattice structure, which also changes the electronic band structure. Specifically, simultaneous prolongation of carrier relaxation and Auger recombination is achieved in the ambient phase, which is very valuable for excess energy harvesting. Our discussion provides clues for optimizing the photovoltaic performance of OTPs.

  4. Excitation of the lowest 1- state in 18O by scattering from 16O

    International Nuclear Information System (INIS)

    Carter, J.; Sellschop, J.P.F.; Clarkson, R.G.; Hnizdo, V.; Osterfeld, F.; Frahn, W.E.; Richter, A.

    1981-01-01

    The 1 - (4.45 MeV) state in 18 O, together with the 2 + (1.98 MeV) and 3 - (5.09 MeV) states, were excited by inelastic scattering from 16 O at E(lab)=35 MeV. In an attempt to understand the 1 - excitation, various macroscopic models, including a ralationship derived recently by Frahn, were considered. However, this excitation was found to be best explained by a microscopic description. A comparison is made with inelastic α-scattering from 18 O [af

  5. Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.

    Science.gov (United States)

    Ghosh, Soumen; Sonnenberger, Andrew L; Hoyer, Chad E; Truhlar, Donald G; Gagliardi, Laura

    2015-08-11

    The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.

  6. Methane dissociation on the steps and terraces of Pt(211) resolved by quantum state and impact site

    Science.gov (United States)

    Chadwick, Helen; Guo, Han; Gutiérrez-González, Ana; Menzel, Jan Paul; Jackson, Bret; Beck, Rainer D.

    2018-01-01

    Methane dissociation on the step and terrace sites of a Pt(211) single crystal was studied by reflection absorption infrared spectroscopy (RAIRS) at a surface temperature of 120 K. The C—H stretch RAIRS signal of the chemisorbed methyl product species was used to distinguish between adsorption on step and terrace sites allowing methyl uptake to be monitored as a function of incident kinetic energy for both sites. Our results indicate a direct dissociation mechanism on both sites with higher reactivity on steps than on terraces consistent with a difference in an activation barrier height of at least 30 kJ/mol. State-specific preparation of incident CH4 with one quantum of antisymmetric (ν3) stretch vibration further increases the CH4 reactivity enabling comparison between translational and vibrational activation on both steps and terraces. The reaction is modeled with first principles quantum theory that accurately describes dissociative chemisorption at different sites on the surface.

  7. Generalized Bethe-Negele inequalities for excited states in muonic atoms

    International Nuclear Information System (INIS)

    Klarsfeld, S.

    1976-11-01

    Rigorous upper and lower bounds are derived for the Bethe logarithms in excited states of muonic atoms. Comparison with previous empirical estimates shows that the latter are inadequate in certain cases

  8. Isoelectronic study of triply excited Li-like states

    International Nuclear Information System (INIS)

    Benis, E P; Zouros, T J M; Gorczyca, T W; Zamkov, M; Richard, P

    2003-01-01

    Absolute doubly differential cross sections (DDCSs) for the production and Auger decay of the intra-shell 2s2p 22 D triply excited state formed in collisions of He-like ions (Z = 5-9) with H 2 were determined experimentally, using zero-degree Auger projectile electron spectroscopy. The 2 D e state was directly produced by 180 deg. resonant scattering of the quasi-free H 2 electrons from the 1s2s 3 S metastable state of the ion. Resonant energies and DDCSs calculated using the R-matrix approach within the electron scattering model were found to be in good overall agreement with experiment. (letter to the editor)

  9. Excited states by analytic continuation of TBA equations

    International Nuclear Information System (INIS)

    Dorey, P.; Tateo, R.

    1996-01-01

    We suggest an approach to the problem of finding integral equations for the excited states of an integrable model, starting from the thermodynamic Bethe ansatz equations for its ground state. The idea relies on analytic continuation through complex values of the coupling constant, and an analysis of the monodromies that the equations and their solutions undergo. For the scaling Lee-Yang model, we find equations in this way for the one- and two-particle states in the spin-zero sector, and suggest various generalisations. Numerical results show excellent agreement with the truncated conformal space approach, and we also treat some of the ultraviolet and infrared asymptotics analytically. (orig.)

  10. Effect of xanthophyll composition on the chlorophyll excited state lifetime in plant leaves and isolated LHCII

    International Nuclear Information System (INIS)

    Johnson, Matthew P.; Zia, Ahmad; Horton, Peter; Ruban, Alexander V.

    2010-01-01

    Xanthophyll excited states have been implicated by transient absorption and two-photon excitation studies in playing a key role in the regulation of photosynthetic light harvesting via photoprotective energy dissipation. For any proposed quenching mechanism to be effective it must reduce the chlorophyll excited state lifetime from 2 ns to ∼0.5-0.4 ns. In the presented study the effect of xanthophyll composition on the chlorophyll excited state lifetime in Arabidopsis leaves in the light harvesting (F m ) and photoprotective (NPQ) states was determined. The data was compared to the chlorophyll excited state lifetime of native isolated LHCII and CP26 in detergent micelles with varying xanthophyll composition. It was found that although the differences in xanthophyll composition between LHC complexes from various Arabidopsis mutants were sufficient to explain the varying F m lifetime (and varying PSII efficiency), they were not of a sufficient scale to fully explain the observed differences in the NPQ lifetimes. Only when the LHC complexes were exposed to a low detergent/low pH media, a condition known to mimic the conformational state of LHCII associated with NPQ in vivo, were variations in excited state lifetime large enough to explain the differences observed in leaves. Furthermore, the data reveal that the replacement of lutein by either zeaxanthin or violaxanthin in the internal xanthophyll binding sites of LHCII and CP26 reduces the efficiency of energy dissipation in the photoprotective state in leaves and isolated complexes.

  11. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    International Nuclear Information System (INIS)

    Tomin, Vladimir I.; Ushakou, Dzmitryi V.

    2015-01-01

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited-state

  12. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Tomin, Vladimir I., E-mail: tomin@apsl.edu.pl; Ushakou, Dzmitryi V.

    2015-10-15

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited-state

  13. Studies of isotopic effects in the excited electronic states of molecular systems

    International Nuclear Information System (INIS)

    1982-01-01

    Rare gas halogen (RGH) lasers serve as convenient tools for a range of photophysical processes which exhibit isotope effects. This document summarizes progress in the production of molecular systems in their electronic excited states with the aid of RGH lasers, and the various isotopic effects one can study under these conditions. We conclude that the basic physical mechanisms involved in the isotopically sensitive characteristics of excited molecular electronic states are sufficiently selective to be useful in both the detection and separation of many atomic materials

  14. Studies of photoionization processes from ground-state and excited-state atoms and molecules

    International Nuclear Information System (INIS)

    Ederer, D.L.; Parr, A.C.; West, J.B.

    1982-01-01

    Recent triply-differential photoelectron spectroscopy experiments designed for the study of correlation effects in atoms and molecules are described. Final-state symmetry of the n=2 state of helium has been determined. The non-Franck-Condon behavior of vibrational branching ratios and large variations of the angular asymmetry parameter has been observed for shape resonances and autoionizing resonances in CO and other molecules. Recent observations of the photoionization of excited sodium atoms are also described

  15. Pushing the limits of excited-state g-factor measurements

    Science.gov (United States)

    Stuchbery, Andrew E.; McCormick, Brendan P.; Gray, Timothy J.; Coombes, Ben J.

    2018-05-01

    Current developments in excited-state g-factor measurements are discussed with an emphasis on cases where the experimental methodology is being extended into new regimes. The transient-field technique, the recoil in vacuum method, and moment measurements with LaBr3 detectors are discussed.

  16. Electronic excitation and deexcitation of atoms and molecules in nonequilibrium plasmas; Hiheiko plasma chu no denshi reiki ryushi hanno katei

    Energy Technology Data Exchange (ETDEWEB)

    Shimamori, H. [Fukui University of Technology, Fukui (Japan)

    1997-05-20

    Regarding excitation and deexcitation due to collision of electrons and deexcitation due to collision of baryons in nonequilibrium plasma, explanation is made about the general characteristics of the elementary processes involving their formation and disappearance and about the prediction of their sectional areas and velocity constants. As for the process of the formation of excited atoms and molecules by collision of electrons, it may be divided into the direct excitation in the ground state, excitation and light emission toward the resonance state, reexcitation and transformation of excited particles, recombination of electrons and positive atomic ions, and dissociation and recombination of electrons and positive molecular ions. As for the process of the disappearance of excited particles, there exist various courses it may follow, and it is quite complicated because it is dependent on the types of particles involved and the conditions the process proceeds under. Although the skeleton has been built of the theory of derivation of the sectional area of excitation due to collision of electrons and atoms/molecules, yet it is accurate enough only when applied to simple atomic/molecular systems, is far from satisfying in general, and is to be augmented by data from future experiments. 22 refs., 3 figs., 1 tab.

  17. Triplet excited States as a source of relevant (bio)chemical information.

    Science.gov (United States)

    Jiménez, M Consuelo; Miranda, Miguel A

    2014-01-01

    The properties of triplet excited states are markedly medium-dependent, which turns this species into valuable tools for investigating the microenvironments existing in protein binding pockets. Monitoring of the triplet excited state behavior of drugs within transport proteins (serum albumins and α1-acid glycoproteins) by laser flash photolysis constitutes a valuable source of information on the strength of interaction, conformational freedom and protection from oxygen or other external quenchers. With proteins, formation of spatially confined triplet excited states is favored over competitive processes affording ionic species. Remarkably, under aerobic atmosphere, the triplet decay of drug@protein complexes is dramatically longer than in bulk solution. This offers a convenient dynamic range for assignment of different triplet populations or for stereochemical discrimination. In this review, selected examples of the application of the laser flash photolysis technique are described, including drug distribution between the bulk solution and the protein cavities, or between two types of proteins, detection of drug-drug interactions inside proteins, and enzyme-like activity processes mediated by proteins. Finally, protein encapsulation can also modify the photoreactivity of the guest. This is illustrated by presenting an example of retarded photooxidation.

  18. Ferenczi's concept of identification with the aggressor: understanding dissociative structure with interacting victim and abuser self-states.

    Science.gov (United States)

    Howell, Elizabeth F

    2014-03-01

    No one has described more passionately than Ferenczi the traumatic induction of dissociative trance with its resulting fragmentation of the personality. Ferenczi introduced the concept and term, identification with the aggressor in his seminal "Confusion of Tongues" paper, in which he described how the abused child becomes transfixed and robbed of his senses. Having been traumatically overwhelmed, the child becomes hypnotically transfixed by the aggressor's wishes and behavior, automatically identifying by mimicry rather than by a purposeful identification with the aggressor's role. To expand upon Ferenczi's observations, identification with the aggressor can be understood as a two-stage process. The first stage is automatic and initiated by trauma, but the second stage is defensive and purposeful. While identification with the aggressor begins as an automatic organismic process, with repeated activation and use, gradually it becomes a defensive process. Broadly, as a dissociative defense, it has two enacted relational parts, the part of the victim and the part of the aggressor. This paper describes the intrapersonal aspects (how aggressor and victim self-states interrelate in the internal world), as well as the interpersonal aspects (how these become enacted in the external). This formulation has relevance to understanding the broad spectrum of the dissociative structure of mind, borderline personality disorder, and dissociative identity disorder.

  19. Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

    Science.gov (United States)

    2016-06-03

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9681 Calculation of Vibrational and Electronic Excited -State Absorption Spectra...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited -State Absorption Spectra of Arsenic-Water Complexes Using...Unclassified Unlimited Unclassified Unlimited 59 Samuel G. Lambrakos (202) 767-2601 Calculations are presented of vibrational and electronic excited -state

  20. Unique insula subregion resting-state functional connectivity with amygdala complexes in posttraumatic stress disorder and its dissociative subtype.

    Science.gov (United States)

    Nicholson, Andrew A; Sapru, Iman; Densmore, Maria; Frewen, Paul A; Neufeld, Richard W J; Théberge, Jean; McKinnon, Margaret C; Lanius, Ruth A

    2016-04-30

    The insula and amygdala are implicated in the pathophysiology of posttraumatic stress disorder (PTSD), where both have been shown to be hyper/hypoactive in non-dissociative (PTSD-DS) and dissociative subtype (PTSD+DS) PTSD patients, respectively, during symptom provocation. However, the functional connectivity between individual insula subregions and the amygdala has not been investigated in persons with PTSD, with or without the dissociative subtype. We examined insula subregion (anterior, mid, and posterior) functional connectivity with the bilateral amygdala using a region-of-interest seed-based approach via PickAtlas and SPM8. Resting-state fMRI was conducted with (n=61) PTSD patients (n=44 PTSD-DS; n=17 PTSD+DS), and (n=40) age-matched healthy controls. When compared to controls, the PTSD-DS group displayed increased insula connectivity (bilateral anterior, bilateral mid, and left posterior) to basolateral amygdala clusters in both hemispheres, and the PTSD+DS group displayed increased insula connectivity (bilateral anterior, left mid, and left posterior) to the left basolateral amygdala complex. Moreover, as compared to PTSD-DS, increased insula subregion connectivity (bilateral anterior, left mid, and right posterior) to the left basolateral amygdala was found in PTSD+DS. Depersonalization/derealization symptoms and PTSD symptom severity correlated with insula subregion connectivity to the basolateral amygdala within PTSD patients. This study is an important first step in elucidating patterns of neural connectivity associated with unique symptoms of arousal/interoception, emotional processing, and awareness of bodily states, in PTSD and its dissociative subtype. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  1. An excited state underlies gene regulation of a transcriptional riboswitch

    Science.gov (United States)

    Zhao, Bo; Guffy, Sharon L.; Williams, Benfeard; Zhang, Qi

    2017-01-01

    Riboswitches control gene expression through ligand-dependent structural rearrangements of the sensing aptamer domain. However, we found that the Bacillus cereus fluoride riboswitch aptamer adopts identical tertiary structures in solution with and without ligand. Using chemical exchange saturation transfer (CEST) NMR spectroscopy, we revealed that the structured ligand-free aptamer transiently accesses a low-populated (~1%) and short-lived (~3 ms) excited conformational state that unravels a conserved ‘linchpin’ base pair to signal transcription termination. Upon fluoride binding, this highly localized fleeting process is allosterically suppressed to activate transcription. We demonstrated that this mechanism confers effective fluoride-dependent gene activation over a wide range of transcription rates, which is essential for robust toxicity response across diverse cellular conditions. These results unveil a novel switching mechanism that employs ligand-dependent suppression of an aptamer excited state to coordinate regulatory conformational transitions rather than adopting distinct aptamer ground-state tertiary architectures, exemplifying a new mode of ligand-dependent RNA regulation. PMID:28719589

  2. Isospin quantum number and structure of the excited states in halo nuclei. Halo-isomers

    International Nuclear Information System (INIS)

    Izosimov, I.N.

    2015-01-01

    It has been shown that isobar-analog (IAS), double isobar-analog (DIAS), configuration (CS), and double configuration states (DCS) can simultaneously have n-n, n-p, and p-p halo components in their wave functions. Differences in halo structure of the excited and ground states can result in the formation of isomers (halo-isomers). Both the Borromean and tango halo types can be observed for n-p configurations of atomic nuclei. The structure of the ground and excited states with different isospin quantum number in halo-like nuclei is discussed. B(Mλ) and B(Eλ) for γ-transitions in 6-8 Li, 8-10 Be, 8,10,11 B, 10-14 C, 13-17 N, 15-17,19 O, and 17 F are analyzed. Special attention is given to nuclei whose ground state does not exhibit halo structure, but the excited state may have one.

  3. The (2p, 2p) 11Δg state of 6Li2: Fourier transform spectrum of the 11Δg-B1IIu transition

    International Nuclear Information System (INIS)

    Linton, C.; Martin, F.; Crozet, P.; Ross, A.J.; Bacis, R.

    1993-01-01

    The 1 1 Δ g -B 1 II u transition of 6 Li 2 has been observed in collisionally induced fluorescence following single frequency optical-optical double resonance excitation of the F 1 Σ g + state using a ring dye laser with DCM dye. Spectra of the s and a symmetry levels were obtained separately, at high resolution, in the near-infrared region using a Fourier transform spectrometer. The molecular constants (Dunham coefficients) of the 1 1 Δ g state have been calculated. Comparison of the constants and dissociation energy with ab initio calculations has shown that the 1 1 Δ g state correlates with Li(2p) + Li(2p) and has a dissociation energy of 9,579 ± 1 cm -1 . The energy transfer process responsible for excitation of the 1 1 Δ g state is discussed

  4. Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution

    Energy Technology Data Exchange (ETDEWEB)

    Imanbaew, D.; Nosenko, Y. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Kerner, C. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Chevalier, K.; Rupp, F. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Riehn, C., E-mail: riehn@chemie.uni-kl.de [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Thiel, W.R. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Diller, R. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany)

    2014-10-17

    Graphical abstract: - Highlights: • Ultrafast dynamics of new Ru(II) catalysts investigated in gas phase and solution. • Catalyst activation (HCl loss) achieved in ion trap by UV photoexcitation. • Electronic relaxation proceeds by IVR and IC followed by ground state dissociation. • No triplet formation in contrast to other Ru-polypyridine complexes. • Solvent prohibits catalyst activation in solution by fast vibrational cooling. - Abstract: We report studies on the excited state dynamics of new ruthenium(II) complexes [(η{sup 6}-cymene)RuCl(apypm)]PF{sub 6} (apypm=2-NR{sub 2}-4-(pyridine-2-yl)-pyrimidine, R=CH{sub 3} (1)/H (2)) which, in their active form [1{sup +}-HCl] and [2{sup +}-HCl], catalyze the transfer hydrogenation of arylalkyl ketones in the absence of a base. The investigations encompass femtosecond pump–probe transient mass spectrometry under isolated conditions and transient absorption spectroscopy in acetonitrile solution, both on the cations [(η{sup 6}-cymene)RuCl(apypm)]{sup +} (1{sup +}, 2{sup +}). Gas phase studies on mass selected ions were performed in an ESI ion trap mass spectrometer by transient photofragmentation, unambiguously proving the formation of the activated catalyst species [1{sup +}-HCl] or [2{sup +}-HCl] after photoexcitation being the only fragmentation channel. The primary excited state dynamics in the gas phase could be fitted to a biexponential decay, yielding time constants of <100 fs and 1–3 ps. Transient absorption spectroscopy performed in acetonitrile solution using femtosecond UV/Vis and IR probe laser pulses revealed additional deactivation processes on longer time scales (∼7–12 ps). However, the formation of the active catalyst species after photoexcitation could not be observed in solution. The results from both studies are compared to former CID investigations and DFT calculations concerning the activation mechanism.

  5. Dissociative symptoms in kleptomania.

    Science.gov (United States)

    Grant, Jon E

    2004-02-01

    Many patients with kleptomania report an altered state of consciousness during acts of theft. The purpose of this investigation was to clarify a possible link between dissociation and kleptomania, a disabling disorder whose phenomenology remains understudied. 26 adult outpatients who met DSM-IV criteria for kleptoania were administered the Dissociative Experiences Scale and compared to 22 normal controls. The patients with kleptomania had scores that differed significantly from those reported by normal controls. There were no statistically significant differences by sex. Because kleptomania patients seeking treatment with medication may differ from others with kleptomania, further studies are needed.

  6. Orientation and alignment of the first excited p state in Li+He and Na+He scattering

    International Nuclear Information System (INIS)

    Archer, B.J.; Lane, N.F.; Kimura, M.

    1990-01-01

    Orientation and alignment parameters for the first excited p state of Li and Na in collisions with He through direct excitation from the ground state are studied theoretically in the energy region up to E c.m. =100 keV by using a quasi-one-electron theory. Scattering states are expanded in terms of molecular orbitals, which are calculated by using the pseudopotential method and include electron translation factors. The approach appears to work well for Li+He, giving good agreement for the 2p excitation probability and orientation. For alignment, the situation is less clear because of difficulty in experimental measurement. Two-electron effects and cascades from more highly excited states cause our description of Na+He collisions to be less satisfactory. However, agreement with the experimental 3p excitation probability and orientation parameters where all data are available is fairly good at lower energies (E c.m. 1.25 a.u.)

  7. Search for two-neutrino double-β decay of 96Zr to excited states of 96Mo

    Science.gov (United States)

    Finch, S. W.; Tornow, W.

    2015-10-01

    Background: Double-β decay is a rare second-order nuclear decay. The importance of this decay stems from the possibility of neutrinoless double-β decay and its applications to neutrino physics. Purpose: A search was conducted for the 2 ν β β decay of 96Zr to excited final states of the daughter nucleus, 96Mo. Measurements of this decay are important to test nuclear matrix element calculations, which are necessary to extract the neutrino mass from a measurement of the neutrinoless double-β decay half-life. Method: Two coaxial high-purity germanium detectors were used in coincidence to detect γ rays produced by the daughter nucleus as it de-excited to the ground state. The experiment was carried out at the Kimballton Underground Research Facility and produced 685.7 d of data with a 17.91 g enriched sample. Results: No counts were seen above background. For the decay to the first excited 0+ state, a limit of T1 /2>3.1 ×1020 yr was produced. Limits to higher excited states are also reported. Conclusion: The new limits on double-β decay are an improvement over previous experiments by a factor of 2 to 5 for the various excited states. The nuclear matrix element for the double-β decay to the first excited 0+ state is found to be <0.13 .

  8. Nonlinear phenomena in the highly excited state of C60

    International Nuclear Information System (INIS)

    Byrne, H.J.; Maser, W.K.; Kaiser, M.; Akselrod, L.; Anders, J.; Ruehle, W.W.; Zhou, X.Q.; Mittelbach, A.; Roth, S.

    1993-01-01

    Under high intensity illumination, the optical and electronic properties of fullerenes are seen to undergo dramatic, nonlinear changes. The photoluminescence emission is seen to increase with approximately the third power of the input intensity above an apparent threshold intensity. Associated with this nonlinear increase is the emergence of a long lifetime emission component and a redshifting of the emission spectrum. Above the threshold intensity the photoconductive response increases with approximately the cube of the input power. In the highly excited state, the photoconductive response becomes relatively temperature independent compared to the thermally activated behaviour observed at low intensities. The characteristics of the temperature dependence are associated with a metallic-like phase in the highly excited state and therefore an optically driven insulator to metal transition is proposed as a description of the observed phenomena. (orig.)

  9. Excited state redox properties of phthalocyanines: influence of the axial ligand on the rates of relaxation and electron-transfer quenching of the lowest /sup 3/. pi pi. /sup */ excited state

    Energy Technology Data Exchange (ETDEWEB)

    Ferraudi, G J; Prasad, D R

    1874-01-01

    Laser flash excitations at 640 nm have been used to generate the transient spectra of the lowest-lying /sup 3/..pi pi../sup */ state of phthalocyaninatoruthenium(II) complexes. The properties of this excited state such as the properties of the maxima, lambda/sub max/ = 500 +/- 30 nm, and lifetimes, t/sub 1/2/ = 70-4500 ns, exhibit a large dependence on the electron-accepting and electron-withdrawing tendencies of the axial ligands. A similar influence was observed upon the rate of electron-transfer quenching of the /sup 3/..pi pi../sup */ state. Values between 10/sup 6/ and 10/sup 7/ dm/sup 3/ mol/sup -1/ s/sup -1/ for the self-exchange rate constant have been obtained, according to Marcus-Hush theoretical treatments, for (Ru(pc.)LL')/sup +//(/sup 3/..pi pi../sup */)(Ru(pc)LL') (L and L' = neutral axial ligands; pc = phthalocyaninate (2-)) and isoelectronic cobalt(III) and rhodium(III) couples. The redox properties of the ground and excited states are correlated with axial ligand-induced perturbations of the electronic structure.

  10. Collective and single-particle states at high excitation energy

    International Nuclear Information System (INIS)

    Van den Berg, A.M.; Van der Molen, H.K.T.; Harakeh, M.N.; Akimune, H.; Daito, I.; Fujimura, H.; Fujiwara, M.; Ihara, F.; Inomata, T.

    2000-01-01

    Complete text of publication follows. Damping of high-lying single-particle states was investigated by the study of proton decay from high-lying states in 91 Nb, populated by the 90 Zr(α,t) reaction with E α = 180 MeV. In addition to decay to the ground state of 90 Zr, semi-direct decay was observed to the low-lying (2 + and 3 - ) phonon states, confirming the conclusion from other experiments that these phonon states play an important role in the damping process of the single-particle states. Furthermore, the population and decay of Isobaric Analogue States of 91 Zr, which are located at an excitation energy of about 10 - 12 MeV in 91 Nb, has been studied in the same reaction. (author)

  11. Cortisone Dissociates the Shaker Family K Channels from their Beta Subunit

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Y.; Weng, J; Kabaleeswaran, V; Li, H; Cao, Y; Bholse, R; Zhou, M

    2008-01-01

    The Shaker family voltage-dependent potassium channels (Kv1) are expressed in a wide variety of cells and are essential for cellular excitability. In humans, loss-of-function mutations of Kv1 channels lead to hyperexcitability and are directly linked to episodic ataxia and atrial fibrillation. All Kv1 channels assemble with {Beta} subunits (Kv{Beta}s), and certain Kv{Beta}s, for example Kv{Beta}1, have an N-terminal segment that closes the channel by the N-type inactivation mechanism. In principle, dissociation of Kv{Beta}1, although never reported, should eliminate inactivation and thus potentiate Kv1 current. We found that cortisone increases rat Kv1 channel activity by binding to Kv{Beta}1. A crystal structure of the K{Beta}v-cortisone complex was solved to 1.82-{angstrom}resolution and revealed novel cortisone binding sites. Further studies demonstrated that cortisone promotes dissociation of Kv{Beta}. The new mode of channel modulation may be explored by native or synthetic ligands to fine-tune cellular excitability.

  12. Photoemission from excited states in rare gas solids by combining synchrotronradiation with a laser

    International Nuclear Information System (INIS)

    Bernstorff, S.

    1984-09-01

    A new spectroscopic method has been developed to study excited states in rare gas solids: Excitons and conductionband-states are populated by synchrotron radiation (photon energy hw SR =5 - 30 eV). Subsequently electrons from these bound or conduction band-states are excited above the vacuum level of the solid by a pulsed dye laser (hw L =1.9 - 3.7 eV). This experimental technique was applied to solid Xe, Kr, Ar and Ne. (orig./GSCH)

  13. Excited states in 146Sm and 147Sm

    International Nuclear Information System (INIS)

    Kownacki, J.; Sujkowski, Z.; Hammaren, E.; Liukkonen, E.; Piiparinen, M.; Lindblad, Th.; Ryde, H.

    1979-10-01

    The sup(144,146)Nd(α,xn) and sup(146,148)Nd( 3 He,xn) reactions with Esub(α) = 20 - 43 MeV and E 3 sub(He) = 19 - 27 MeV are used to investigate excited states in the isotopes 146 Sm and 147 Sm. The experiments involve measurements of singles γ-ray spectra and conversion electron spectra, γ-ray angular distributions and three parameter (E sub(γ)E sub(γ) time) coincidences. From these experiments information is obtained for states with spin up to I = 13 + and I = 27/2 - , respectively, These states are interpeted within the framework of the cluster-vibration model (CVM) as well as the shell model. (author)

  14. Using Images, Metaphor, and Hypnosis in Integrating Multiple Personality and Dissociative States: A Review of the Literature.

    Science.gov (United States)

    Crawford, Carrie L.

    1990-01-01

    Reviews literature on hypnosis, imagery, and metaphor as applied to the treatment and integration of those with multiple personality disorder (MPD) and dissociative states. Considers diagnostic criteria of MPD; explores current theories of etiology and treatment; and suggests specific examples of various clinical methods of treatment using…

  15. Highly selective population of two excited states in nonresonant two-photon absorption

    International Nuclear Information System (INIS)

    Zhang Hui; Zhang Shi-An; Sun Zhen-Rong

    2011-01-01

    A nonresonant two-photon absorption process can be manipulated by tailoring the ultra-short laser pulse. In this paper, we theoretically demonstrate a highly selective population of two excited states in the nonresonant two-photon absorption process by rationally designing a spectral phase distribution. Our results show that one excited state is maximally populated while the other state population is widely tunable from zero to the maximum value. We believe that the theoretical results may play an important role in the selective population of a more complex nonlinear process comprising nonresonant two-photon absorption, such as resonance-mediated (2+1)-three-photon absorption and (2+1)-resonant multiphoton ionization. (atomic and molecular physics)

  16. Size dependent deactivation of the excited state of DHICA

    DEFF Research Database (Denmark)

    Gauden, Magdalena; Pezzella, Alessandro; Panzella, Lucia

    2008-01-01

    Melanin is a natural pigment mainly responsible for the protection of skin and eyes from UV damage. 5,6- dihydroxyindole- 2 carboxylic acid (DHICA) is a key melanin building block. We have investigated the excited state dynamics of DHICA as well as its derivatives and oligomeric units using...

  17. Vibrational frequencies and dephasing times in excited electronic states by femtosecond time-resolved four-wave mixing

    Science.gov (United States)

    Joo, Taiha; Albrecht, A. C.

    1993-06-01

    Time-resolved degenerate four-wave mixing (TRDFWM) for an electronically resonant system in a phase-matching configuration that measures population decay is reported. Because the spectral width of input light exceeds the vibrational Bohr frequency of a strong Raman active mode, the vibrational coherence produces strong oscillations in the TRDFWM signal together with the usual population decay from the excited electronic state. The data are analyzed in terms of a four-level system: ground and excited electronic states each split by a vibrational quantum of a Raman active mode. Absolute frequencies and their dephasing times of the vibrational modes at ≈590 cm -1 are obtained for the excited as well as the ground electronic state. The vibrational dephasing rate in the excited electronic state is about an order of magnitude faster than that in the ground state, the origin of which is speculated upon.

  18. Dynamics of excited-state intramolecular proton transfer reactions in piroxicam. Role of triplet states

    Science.gov (United States)

    Cho, Dae Won; Kim, Yong Hee; Yoon, Minjoong; Jeoung, Sae Chae; Kim, Dongho

    1994-08-01

    The picosecond time-resolved fluorescence and transient absorption behavior of piroxicam at room temperature are reported. The keto tautomer in the excited singlet state ( 1K*) formed via the fast intramolecular proton transfer (≈ 20 ps) is observed. The short-lived (7.5 ns) triplet state of keto tauomer ( 3K*) is generated from 1K * in toluene whereas it is hardly observed in ethanol. Consequently, rapid reverse proton transfer takes place from 3K * to the enol triplet state ( 3E *.

  19. Comparing the symptoms and mechanisms of "dissociation" in dissociative identity disorder and borderline personality disorder.

    Science.gov (United States)

    Laddis, Andreas; Dell, Paul F; Korzekwa, Marilyn

    2017-01-01

    A total of 75 patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised as having dissociative identity disorder (DID), and 100 patients were diagnosed with the Structured Interview for DSM-IV Personality as having borderline personality disorder (BPD). Both groups were administered the Multidimensional Inventory of Dissociation (MID). DID patients had significantly higher MID scores than BPD patients, different distributions of MID scores, and different MID subscale profiles in 3 ranges of MID scores (0-15, 15-30, 30-45). The core MID symptoms-exhibited at all ranges of MID scores-for DID patients (the presence of alters, identity confusion, and memory problems) and BPD patients (flashbacks, identity confusion, and memory problems) were ostensibly similar but were considered to be mostly produced by different underlying processes. Multiple regression analyses showed that the core MID symptoms of DID patients had different predictors than did the core MID symptoms of BPD patients. Alter identities seemed to generate most-but not all-dissociative phenomena in DID patients, whereas only the 24% highest scoring BPD patients (MID ≥45) seemed to manifest alter-driven dissociative experiences. Most BPD dissociative experiences appeared to be due to 5 other mechanisms: (a) BPD-specific, stress-driven, rapid shifts of self-state; (b and c) nondefensive disruptions of the framework of perceptual organization with or without an accompanying BPD-specific, dissociation-like disintegration of affective/neurocognitive functioning; (d) a defensive distancing or detachment from distress (i.e., simple depersonalization); and (e) Allen, Console, and Lewis's (1999) severe absorptive detachment.

  20. Fluorescent molecular probes based on excited state prototropism in lipid bilayer membrane

    Science.gov (United States)

    Mohapatra, Monalisa; Mishra, Ashok K.

    2012-03-01

    Excited state prototropism (ESPT) is observed in molecules having one or more ionizable protons, whose proton transfer efficiency is different in ground and excited states. The interaction of various ESPT molecules like naphthols and intramolecular ESPT (ESIPT) molecules like hydroxyflavones etc. with different microheterogeneous media have been studied in detail and excited state prototropism as a probe concept has been gaining ground. The fluorescence of different prototropic forms of such molecules, on partitioning to an organized medium like lipid bilayer membrane, often show sensitive response to the local environment with respect to the local structure, physical properties and dynamics. Our recent work using 1-naphthol as an ESPT fluorescent molecular probe has shown that the incorporation of monomeric bile salt molecules into lipid bilayer membranes composed from dipalmitoylphosphatidylcholine (DPPC, a lung surfactant) and dimyristoylphosphatidylcholine (DMPC), in solid gel and liquid crystalline phases, induce appreciable wetting of the bilayer up to the hydrocarbon core region, even at very low (fisetin, an ESIPT molecule having antioxidant properties, in lipid bilayer membrane has been sensitively monitored from its intrinsic fluorescence behaviour.