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Sample records for electronic excitation transfer

  1. Ground and excited state electron transfer dynamics

    OpenAIRE

    Brennan, Jennifer L.

    2002-01-01

    The focus of this work is the investigation of the factors controlling electron transfer in molecular electronic systems, in particular those affecting electron transfer to and from electronically excited states. To achieve this, a number of mono- and trimetallic osmium and ruthenium complexes were synthesised and characterised. Monolayers of an osmium polypyridyl complex bound to a platinum microelectrode via a ¿rara-l,2-bis-(4-pyridyl)ethylene bridge were formed to probe ground state electr...

  2. Electronic and Nuclear Factors in Charge and Excitation Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Piotr Piotrowiak

    2004-09-28

    We report the and/or state of several subprojects of our DOE sponsored research on Electronic and Nuclear Factors in Electron and Excitation Transfer: (1) Construction of an ultrafast Ti:sapphire amplifier. (2) Mediation of electronic interactions in host-guest molecules. (3) Theoretical models of electrolytes in weakly polar media. (4) Symmetry effects in intramolecular excitation transfer.

  3. Electron transfer, ionization, and excitation atomic collisions

    International Nuclear Information System (INIS)

    Basic atomic-collision processes at intermediate and high energies are being studied theoretically at Penn State by Alston and Winter. In the high velocity regime, single-electron capture is treated using a high order multiple-scattering approach; extensive comparison with experiment and analysis of mechanisms have been made. Fitting the calculated amplitude with a simple analytic form, the asymptotic velocity dependence of the cross section is obtained. The effect on the capture amplitude of altering the inner part of the internuclear potential has also been explored. In the intermediate velocity regime, earlier work on collisions between protons and hydrogenic-ion targets using a coupled-state approach is being extended to the two-electron helium target. 29 refs

  4. [Electron transfer, ionization, and excitation in atomic collisions]: Progress report

    International Nuclear Information System (INIS)

    The fundamental processes of electron transfer, ionization, and excitation in ion-atom collisions are being studied. These collision processes are treated in the context of simple one- or two-electron systems in order to provide unambiguous results and reveal more clearly the collisional mechanisms. As outlined in the original proposal, three coupled-state calculations are being carried out over the present three-year period: a Sturmian-pseudostate study of ionization in collisions between protons and the hydrogenic ions He+, Li2+, Be3+, ...; a triple-center, atomic-state study of ionization in collisions between ? particles and H(ls) atoms and between protons and He+(ls) ions; and an atomic-state study of electron transfer and excitation in collisions between protons and neutral He atoms. 12 refs

  5. Electron excitation and energy transfer rates for H2O in the upper atmosphere

    OpenAIRE

    Brunger Michael; Campbell Laurence; Thorn Penny

    2009-01-01

    Abstract Recent measurements of the cross sections for electronic state excitations in H2O have made it possible to calculate rates applicable to these excitation processes. We thus present here calculations of electron energy transfer rates for electronic and vibrational state excitations in H2O, as well as rates for excitation of some of these states by atmospheric thermal and auroral secondary electrons. The calculation of these latter rates is an important first step towards our aim of in...

  6. Electronic excitation energy transfer between quasi-zero-dimensional systems.

    Czech Academy of Sciences Publication Activity Database

    Král, Karel; Menšík, Miroslav

    Ostrava : Tanger, 2013. ISBN 978-80-87294-44-4. [International Conference NANOCON 2013 /5./. Brno (CZ), 16.10.2013-18.10.2013] R&D Pro jects: GA MŠk LH12236; GA MŠk LH12186 Institutional support: RVO:68378271 ; RVO:61389013 Keywords : quantum dots * energy transfer * electron-phonon interaction Subject RIV: BM - Solid Matter Physics ; Magnetism

  7. Electron excitation and energy transfer rates for H2O in the upper atmosphere

    Directory of Open Access Journals (Sweden)

    Brunger Michael

    2009-01-01

    Full Text Available Abstract Recent measurements of the cross sections for electronic state excitations in H2O have made it possible to calculate rates applicable to these excitation processes. We thus present here calculations of electron energy transfer rates for electronic and vibrational state excitations in H2O, as well as rates for excitation of some of these states by atmospheric thermal and auroral secondary electrons. The calculation of these latter rates is an important first step towards our aim of including water into a statistical equilibrium model of the atmosphere under auroral conditions. PACS Codes: 34.50.Gb 34.50.Ez

  8. 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 theory, which does not allow for charge transfer, is a special case of B-A theory. The latter could, under appropriate circumstances, lead to excimers.

  9. Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes

    Energy Technology Data Exchange (ETDEWEB)

    Westlake, Brittany C.; Brennaman, Kyle M; Concepcion, Javier J; Paul, Jared J.; Bettis, Stephanie E; Hampton, Shaun D; Miller, Stephen A.; Lebedeva, Natalia V.; Forbes, Malcolm D. E.; Moran, Andrew M.; Meyer, Thomas J.; Papanikolas, John M.

    2011-05-24

    The simultaneous, concerted transfer of electrons and protons—electron-proton transfer (EPT)—is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4'-biphenylphenol. Femtosecond transient absorption spectral measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H? is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck–Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated ?H–B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.

  10. Electronic excitation energy transfer between quasi-zero-dimensional systems.

    Czech Academy of Sciences Publication Activity Database

    Král, Karel; Menšík, Miroslav; Mao, H.

    Tokyo : The Surface Science Society of Japan, 2014, s. 11-17. ISSN 1348-0391. [International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures /12/ - International Colloquium on Scanning Probe Microscopy /21./. Tsukuba (JP), 04.11.2013-08.11.2013] R&D Projects: GA MŠk LH12236; GA MŠk LH12186 Institutional support: RVO:68378271 ; RVO:61389013 Keywords : quantum dots * energy transfer * electron-phonon interaction Subject RIV: BM - Solid Matter Physics ; Magnetism https://www.jstage.jst.go.jp/result?item1=4&word1=Atomically+Controlled+Surfaces+AND+kral

  11. Ab initio study on electron excitation and electron transfer in tryptophan-tyrosine system

    International Nuclear Information System (INIS)

    In this article, ab initio calculation has been performed to evaluate the transition energy of electronic excitation in tryptophan and tyrosine by using semiempirical molecular orbital method AM1 and complete active space self-consistent field method. The solvent effect has been considered by means of the conductor-like screening model. After geometric optimizations of isolated tryptophan and tyrosine, and their corresponding radicals and cations, reaction heat of these electron transfer reactions have been obtained by the means of complete active space self-consistent field method. The transition energies from the ground state, respectively, to the lowest excited state and to the lowest triplet state of these two amino acids are also calculated and compared with the experimentally observed values. The ionization potential and electron affinity are also calculated for tryptophan and tyrosine employing Koopmans' theorem and ab initio calculation. Compared with the experimental measurements, the theoretical results are found satisfactory. Theoretical results give good explanations on the experimental phenomena that N3· can preferably oxide the side chain of tryptophan residue and then the electron transfer from tyrosine residue to tryptophan residue follows in peptides involving tryptophan and tyrosine

  12. Excitation of the ligand-to-metal charge transfer band induces electron tunnelling in azurin

    Energy Technology Data Exchange (ETDEWEB)

    Baldacchini, Chiara [Biophysics and Nanoscience Centre, DEB-CNISM, Università della Tuscia, I-01100 Viterbo (Italy); Institute of Agro-environmental and Forest Biology, National Research Council, I-05010 Porano (Italy); Bizzarri, Anna Rita; Cannistraro, Salvatore, E-mail: cannistr@unitus.it [Biophysics and Nanoscience Centre, DEB-CNISM, Università della Tuscia, I-01100 Viterbo (Italy)

    2014-03-03

    Optical excitation of azurin blue copper protein immobilized on indium-tin oxide, in resonance with its ligand-to-metal charge transfer absorption band, resulted in a light-induced current tunnelling within the protein milieu. The related electron transport rate is estimated to be about 10{sup 5}?s{sup ?1}. A model based on resonant tunnelling through an azurin excited molecular state is proposed. The capability of controlling electron transfer processes through light pulses opens interesting perspectives for implementation of azurin in bio-nano-opto-electronic devices.

  13. Nonlinear response of metal nanoparticles: Double plasmon excitation and electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Shiwu [Beijing Computational Science Research Center, Zhongguancun Software Park II, 100094, Beijing (China)

    2015-06-21

    We investigate the dynamical response of a metal nanoparticle and the electron transfer to a molecule near its surface using time-dependent density functional theory. In addition to the linear response of the Mie resonance, double plasmon excitations and a low-frequency charge transfer band emerge and become prominent at high laser intensities. Both modes are nonlinear processes, which are derived from the re-excitation and decay of the primary plasmon mode, respectively. Our results shed light on the localised characters of the plasmon-molecule coupling and hot electron distributions. These findings have general implications to photoinduced phenomena in nanosystems.

  14. Effect of the excitation pulse frequency on the ultrafast photoinduced electron transfer dynamics

    International Nuclear Information System (INIS)

    The dependence of the ultrafast photoinduced electron transfer dynamics in donor-acceptor complexes on the excitation pulse carrier frequency (spectral effect) has been investigated in the framework of a model involving three electronic state. The spectral effect has been shown to strongly depend on the angle ? between the reaction coordinate directions corresponding to optical and charge transfer transitions. Describing the solvent as a linear homogenous polar medium and accounting for Coulombic interaction of the transferred charge with the medium polarization fluctuations, the angle ? has been found out to be typically in the area 40 deg. -85 deg. Exactly in this area of ? the spectral effect is predicted to be most pronounced

  15. Photo- and radiation chemical studies of intermediates involved in excited-state electron-transfer reactions

    International Nuclear Information System (INIS)

    Excited-state inter- and intramolecular electron-transfer reactions lie at the heart of the most photochemical solar energy conversion schemes. The authors research, which has utilized the techniques of continuous and pulsed photolysis and radiolysis, has focused on three general aspects of these reactions involving transition metal coordination complexes and electron donor-acceptor complexes: i) the effect of solution medium on the properties and quenching of the excited states; ii) the control of the quantum yields of formation of redox products; iii) the mechanism by which reduced species interact with water to yield H2 homogeneously and heterogeneously. EDTA is among the most popular sacrificial electron donors used in model systems. Its role is to scavenge the oxidized form of the photosensitizer in order to prevent its rapid reaction with the reduced form of the electron relay species that results from the electron-transfer quenching of the excited photosensitizer. In systems involving MV2+, the radicals resulting from the oxidation of EDTA can eventually lead to the generation of a second equivalent of MV+; the reducing agent is believed to be a radical localized on the carbon atom alpha to the carboxylate group. The reaction of radiolytically-generated OH/H with EDTA produces this radical directly via H-abstraction or indirectly via deprotonation of the carbon atom adjacent to the nitrogen radical site in the oxidized amine moiety; it reduces MV2+ with rate constants of 2.8 x 109, 7.6 x 109, and 8.5 x 106M-1s-1 at pH 12.5, 8.3, and 4.7, respectively. Degradative decarboxylation of EDTA-radicals and their back electron-transfer reactions are enhanced in acidic solution causing the yield of MV+ to be severely diminished

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

    KAUST Repository

    Alsam, Amani A.

    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.

  17. Laser-assisted ionization-excitation of helium by electron impact at large momentum transfer

    Science.gov (United States)

    Bulychev, Andrey A.; Kouzakov, Konstantin A.

    2014-11-01

    Ionization of a helium atom by electron impact in the presence of laser radiation is studied theoretically. The kinematic regime of high impact energy and large momentum transfer is considered. The S-matrix of the process is treated within the first Born and binary-encounter approximations. Triple differential cross sections are calculated for the cases when the residual He+ ion is left both in the ground ( n = 1) and in the first excited ( n = 2) states in the presence of a laser field with frequency ? = 1.55 eV and intensity I = 5 × 1011 W/cm2. The laser-assisted cross sections corresponding to n = 2 are found to be more sensitive to the electron-electron correlations in helium than the field-free ones.

  18. Laser-assisted ionization-excitation of helium by electron impact at large momentum transfer

    International Nuclear Information System (INIS)

    Ionization of a helium atom by electron impact in the presence of laser radiation is studied theoretically. The kinematic regime of high impact energy and large momentum transfer is considered. The S-matrix of the process is treated within the first Born and binary-encounter approximations. Triple differential cross sections are calculated for the cases when the residual He+ ion is left both in the ground (n=1) and in the first excited (n=2) states in the presence of a laser field with frequency ? = 1.55 eV and intensity I = 5*1011 W/cm2. The laser-assisted cross sections corresponding to n=2 are found to be more sensitive to the electron-electron correlations in helium than the field-free ones. (authors)

  19. Triple-center treatment of electron transfer and excitation in p-H collisions

    International Nuclear Information System (INIS)

    Cross sections have been calculated for electron transfer into the 1s, 2s, and 2p states and for excitation into the 2s and 2p states in collisions between 1.5--15-keV protons and hydrogen atoms. The triple-center, coupled-state method of Anderson, Antal, and McElroy has been used: Bound atomic states are centered on each nucleus and on a third center (the center of charge) in order to simulate the molecular character of slow collisions. Convergence of cross sections (and molecular potential-energy curves) with respect to the size of the basis has been studied; the present basis includes up to 36 states (16 gerade, 20 ungerade states). The 1s capture cross section is estimated to be converged, and the 2p and 2s cross sections are estimated to be converged to about 10% and 20%, respectively. Dips are observed in the 2s and 2p excitation cross sections at about 10 keV and in the 2p capture cross section at about 5 keV. Results have been compared with atomic-state, pseudostate, and molecular-state results, as well as with experimental results. The results agree fairly closely with the related AO+ pseudostate results of Fritsch and Lin at the lowest calculated energy, although there are differences at higher energies. There are differences from some of the many experimental results, but overall there is agreement within the experimental error limits

  20. Ab initio study of the excited-state coupled electron-proton-transfer process in the 2-aminopyridine dimer

    International Nuclear Information System (INIS)

    The low-lying 1??* excited states of the 2-aminopyridine dimer have been investigated with multi-reference ab initio methods (CASSCF and MRMP2). The 2-aminopyridine dimer can be considered as a mimetic model of Watson-Crick DNA base pairs. The reaction path and the energy profile for single proton transfer in the lowest 1??* inter-monomer charge-transfer state have been obtained. A weakly avoided crossing of the 1??* surface with the electronic ground-state surface has been found near the single-proton-transfer minimum of the 1??* surface. From the splitting of the adiabatic surfaces at the avoided crossing, an internal-conversion lifetime of the excited state of <100 ps has been estimated. The potential relevance of these results for the rationalization of radiation-induced mutations and the photostability of the genetic code is briefly discussed

  1. Resonant electron transfer and L-shell excitation for 26Fe19+ and 30Zn23+ ions

    OpenAIRE

    RAMADAN, Hassan

    2012-01-01

    Resonant transfer and excitation (RTE) involving simultaneous electron capture and projectile L-shell excitation has been calculated for Fe19+ and Zn23+ ions, in charge states ranging from nitrogen-like to oxygen-like incident on molecular hydrogen over an energy range 0--250 MeV. By the same way the calculations have been performed with helium over an energy range 0--300 MeV. The calculations are carried out using the angular momentum average (AMA) scheme in the isolated resonance app...

  2. Photochemistry and electron-transfer mechanism of transition metal oxalato complexes excited in the charge transfer band

    OpenAIRE

    Chen, Jie; Zhang, Hua; Tomov, Ivan V.; Ding, Xunliang; Rentzepis, Peter M.

    2008-01-01

    The photoredox reaction of trisoxalato cobaltate (III) has been studied by means of ultrafast extended x-ray absorption fine structure and optical transient spectroscopy after excitation in the charge-transfer band with 267-nm femtosecond pulses. The Co–O transient bond length changes and the optical spectra and kinetics have been measured and compared with those of ferrioxalate. Data presented here strongly suggest that both of these metal oxalato complexes operate under similar photoredox r...

  3. Electron transfer collisions between sulfur dioxide clusters and laser-excited Rydberg atoms

    Energy Technology Data Exchange (ETDEWEB)

    Desfrancois, C.; Khelifa, N.; Lisfi, A.; Schermann, J.P. (Paris-13 Univ., 93 - Villetaneuse (France). Lab. de Physique des Lasers)

    1991-08-01

    Electron attachment to SO{sub 2} clusters is studied in a pulsed crossed beam apparatus, using laser-excited nf Rydberg atoms as a low energy electron source. The results are interpreted as an attachment to a dimer subcluster followed by a rapid impulsive dissociation of the nascent dimer anion. The remaining cluster anions possess a large amount of internal energy. At low principal quantum numbers n, the influence of the Rydberg ionic core leads to an important evaporation process interpreted with simple model calculations. (orig.).

  4. Electron transfer collisions between sulfur dioxide clusters and laser-excited Rydberg atoms

    International Nuclear Information System (INIS)

    Electron attachment to SO2 clusters is studied in a pulsed crossed beam apparatus, using laser-excited nf Rydberg atoms as a low energy electron source. The results are interpreted as an attachment to a dimer subcluster followed by a rapid impulsive dissociation of the nascent dimer anion. The remaining cluster anions possess a large amount of internal energy. At low principal quantum numbers n, the influence of the Rydberg ionic core leads to an important evaporation process interpreted with simple model calculations. (orig.)

  5. Exciton delocalization, charge transfer, and electronic coupling for singlet excitation energy transfer between stacked nucleobases in DNA: An MS-CASPT2 study

    Energy Technology Data Exchange (ETDEWEB)

    Blancafort, Lluís, E-mail: lluis.blancafort@udg.edu [Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071 Girona (Spain); Voityuk, Alexander A., E-mail: alexander.voityuk@icrea.cat [Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071 Girona (Spain); Institució Catalana de Recerca i Estudis Avançats (ICREA), Barcelona 08010 (Spain)

    2014-03-07

    Exciton delocalization and singlet excitation energy transfer have been systematically studied for the complete set of 16 DNA nucleobase dimers in their ideal, single-strand stacked B-DNA conformation, at the MS-CASPT2 level of theory. The extent of exciton delocalization in the two lowest (?,?{sup *}) states of the dimers is determined using the symmetrized one-electron transition density matrices between the ground and excited states, and the electronic coupling is calculated using the delocalization measure and the energy splitting between the states [see F. Plasser, A. J. A. Aquino, W. L. Hase, and H. Lischka, J. Phys. Chem. A 116, 11151–11160 (2012)]. The calculated couplings lie between 0.05 eV and 0.14 eV. In the B-DNA conformation, where the interchromophoric distance is 3.38 Å, our couplings deviate significantly from those calculated with the transition charges, showing the importance of orbital overlap components for the couplings in this conformation. The calculation of the couplings is based on a two-state model for exciton delocalization. However, in three stacks with a purine in the 5{sup ?} position and a pyrimidine in the 3{sup ?} one (AT, GC, and GT), there is an energetically favored charge transfer state that mixes with the two lowest excited states. In these dimers we have applied a three-state model that considers the two locally excited diabatic states and the charge transfer state. Using the delocalization and charge transfer descriptors, we obtain all couplings between these three states. Our results are important in the context of DNA photophysics, since the calculated couplings can be used to parametrize effective Hamiltonians to model extended DNA stacks. Our calculations also suggest that the 5{sup ?}-purine-pyrimidine-3{sup ?} sequence favors the formation of charge transfer excited states.

  6. [Electron transfer, ionization, and excitation in atomic collisions]. Final technical report, June 15, 1986 - June 14, 1998

    International Nuclear Information System (INIS)

    The research on theoretical atomic collisions that was funded at The Pennsylvania State University's Wilkes-Barre Campus by DOE from 1986 to 1998 was carried out by Winger from 1986 to 1989 and by Winter and Alston from 1989 to 1998. The fundamental processes of electron transfer, ionization, and excitation in ion-ion, ion-atom, and, more recently, ion-molecule collisions were addressed. These collision processes were treated in the context of simple one-electron, quasi-one-electron, or two-electron systems in order to provide unambiguous results and reveal more clearly the collisional mechanisms. Winter's work generally focused on the intermediate projectile-energy range corresponding to proton energies from about ten to a few hundred keV. In this velocity-matching energy range, the electron-transfer cross section reaches a peak, and many states, including electron-transfer and ionization states, contribute to the overall electron-cloud distribution and transition probabilities; a large number of states are coupled, and therefore perturbative approaches are generally inappropriate. These coupled-state calculations were sometimes also extended to higher energies to join with perturbative results. Alston concentrated on intermediate-energy asymmetric collision systems, for which coupling with the projectile is weaker, but many target states are included, and on high energies (MeV energies). Thus, while perturbation theory for electron transfer is valid, it is not adequate to first order. The studies by Winter and Alston described were often done in parallel. Alston also developed formal perturbative approaches not tied to any particular system. Materials studied included He+, Li2+, Be3+, B4+, C5+, and the H+ + Na system

  7. Study of intermediates from transition metal excited-state electron-transfer reactions. Final report, August 4, 1986--August 31, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Hoffman, M.Z.

    1997-12-31

    The techniques of continuous photolysis and pulsed laser flash photolysis, continuous and pulse radiolysis, fast-scan cyclic voltammetry, and time-resolved fluorimetry have been used to examine intramolecular electron transfer within the solvent quenching cage, photodynamics of quenching of the excited states of transition-metal photosensitizers, the properties of excites states and one-electron reduced forms, ground- and excited-state interactions with solutes, and photoinduced oxidations of organic solutes in aqueous solution. The following specific areas were examined: (1) the parameters that govern the yields of redox products from excited-state electron-transfer quenching reactions; (2) the mediation of the properties of excited states and one-electron reduced forms by the ligands and the solution medium; (3) the effect of the interactions between the ground state of the complex and the solution components on the behavior of the excited state; (4) the yields of singlet oxygen from excited-state energy-transfer quenching by O{sub 2}; and (5) the oxidations of solutes by singlet oxygen, excited-state electron-transfer quenching, and free radicals. This report contains the abstracts of 50 publications describing the studies.

  8. Mechanism of electronic-excitation transfer in organic light-emitting devices based on semiconductor quantum dots

    International Nuclear Information System (INIS)

    The results of an experimental study of organic light-emitting diodes (LEDs) with luminescent layers based on two types of CdSe/CdS semiconductor quantum dots (QDs) with an average CdSe core diameter of 3 and 5 nm and a characteristic CdS shell thickness of 0.5 nm are presented. The dependences of the LED efficiency on the QD concentration are determined. The experimental data are used to determine the mechanism of electronic-excitation transfer from the organic matrix to the semiconductor QDs. Ways of optimizing the design of the LEDs in order to improve their efficiency are suggested on this basis

  9. Evidence for resonance electron transfer in photon excited X-ray satellite spectra of fluorine compounds

    Indian Academy of Sciences (India)

    K Ram Narayana; B Seetharami Reddy; S S Raju; T Seshi Reddy; S Lakshmi Narayana; K Premachand; B M Rao; M V R Murti; L S Mombasawala

    2005-08-01

    The K$\\alpha$L1/K$\\alpha$L0 intensity ratio of fluorine is measured in five fluorine compounds with a crystal spectrometer. An anomalous reduction of this intensity ratio was observed in KF and SrF2, which is attributed to resonance electron transfer from the metal ion to the spectator vacancy in the fluorine ion. K$\\alpha$L2/K$\\alpha$L0 intensity ratio of fluorine is also measured. The measured relative intensities are compared with the theoretical estimates of Aberg.

  10. Inelastic scattering of high transfer moment electrons to the first excited state (Jsup(?)=3-) of 208Pb

    International Nuclear Information System (INIS)

    A determination was made of an angular distribution of the inelastic scattering cross-sections of electrons by the first excited state (Jsup(?)=3-, E*=2.615 MeV) of 208Pb. The statistical accuracy of previous data was improved between 2 and 2.7 fm-1 and the area of transfer of moment was extended up to qsub(max)=3.4 fm-1. Cross-sections up to 10-37cm2/sr were determined whereas the limit reached before was 7x10-35 cm2/sr. In order to determine the transition charge density, it was put into parametric form by a Fourier-Bessel development using 12 coefficients and an 11 fm cut-off radius. The model error inherent in this method is reduced to an insignificant contribution by the sufficiently high transfer of moment. The experimental transition charge density was compared with the theoretical predictions

  11. Ultrafast Excited-State Dynamics of Diketopyrrolopyrrole (DPP)-Based Materials: Static versus Diffusion-Controlled Electron Transfer Process

    KAUST Repository

    Alsulami, Qana A.

    2015-06-25

    Singlet-to-triplet intersystem crossing (ISC) and photoinduced electron transfer (PET) of platinum(II) containing diketopyrrolopyrrole (DPP) oligomer in the absence and presence of strong electron-acceptor tetracyanoethylene (TCNE) were investigated using femtosecond and nanosecond transient absorption spectroscopy with broadband capabilities. The role of platinum(II) incorporation in those photophysical properties was evaluated by comparing the excited-state dynamics of DPP with and without the metal centers. The steady-state measurements reveal that platinum(II) incorporation facilitates dramatically the interactions between DPP-Pt(acac) and TCNE, resulting in charge transfer (CT) complex formation. The transient absorption spectra in the absence of TCNE reveal ultrafast ISC of DPP-Pt(acac) followed by their long-lived triplet state. In the presence of TCNE, PET from the excited DPP-Pt(acac) and DPP to TCNE, forming the radical ion pairs. The ultrafast PET which occurs statically from DPP-Pt(acac) to TCNE in picosecond regime, is much faster than that from DPP to TCNE (nanosecond time scale) which is diffusion-controlled process, providing clear evidence that PET rate is eventually controlled by the platinum(II) incorporation.

  12. The Fate of Electronically Excited States : Ultrafast Electron and Energy Transfer in Solvated Donor-Acceptor Systems

    OpenAIRE

    Wallin, Staffan

    2005-01-01

    Processes where a molecule absorbs visible light and then disposes of the excess energy via electron/energy transfer reactions have an important role both in nature (e.g. in photosynthesis) and in many technical applications (e.g. in photography and photovoltaics). This thesis uses different spectroscopical techniques, mainly ultrafast transient absorption, to study such processes. The thesis can roughly be divided into three parts. In the first part, donor-acceptor systems linked by differen...

  13. Description of electron transfer in the ground and excited states of organic donor–acceptor systems by single-reference and multi-reference density functional methods

    International Nuclear Information System (INIS)

    Electron transfer in the ground and excited states of a model donor–acceptor (D–A) system is investigated using the single-reference and multi-reference density functional theory (DFT) methods. To analyze the results of the calculations, a simple two-site multi-reference model was derived that predicts a stepwise electron transfer in the S0 state and a wave-like dependence of the S1 electron transfer on the external stimulus. The standard single-reference Kohn-Sham (KS) DFT approach and the time-dependent DFT (TDDFT) method failed to describe the correct dependence of the S0 and S1 electron transfer on the external electric field applied along the donor–acceptor system. The multi-reference DFT approach, the spin-restricted ensemble-referenced KS (REKS) method, was able to successfully reproduce the correct behavior of the S0 and S1 electron transfer on the applied field. The REKS method was benchmarked against experimentally measured gas phase charge transfer excitations in a series of organic donor–acceptor complexes and displayed its ability to describe this type of electronic transitions with a very high accuracy, mean absolute error of 0.05 eV with the use of the standard range separated density functionals. On the basis of the calculations undertaken in this work, it is suggested that the non-adiabatic coupling between the S0 and S1 states may interfere with the electron transfer in a weakly coupled donor–acceptor system. It is also suggested that the electronic excitation of a D+–A? system may play a dual role by assisting the further electron transfer at certain magnitudes of the applied electric field and causing the backward transfer at lower electric field strengths

  14. Description of electron transfer in the ground and excited states of organic donor–acceptor systems by single-reference and multi-reference density functional methods

    Energy Technology Data Exchange (ETDEWEB)

    Filatov, Michael, E-mail: mike.filatov@gmail.com [Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstr. 4, D-53115 Bonn (Germany)

    2014-09-28

    Electron transfer in the ground and excited states of a model donor–acceptor (D–A) system is investigated using the single-reference and multi-reference density functional theory (DFT) methods. To analyze the results of the calculations, a simple two-site multi-reference model was derived that predicts a stepwise electron transfer in the S{sub 0} state and a wave-like dependence of the S{sub 1} electron transfer on the external stimulus. The standard single-reference Kohn-Sham (KS) DFT approach and the time-dependent DFT (TDDFT) method failed to describe the correct dependence of the S{sub 0} and S{sub 1} electron transfer on the external electric field applied along the donor–acceptor system. The multi-reference DFT approach, the spin-restricted ensemble-referenced KS (REKS) method, was able to successfully reproduce the correct behavior of the S{sub 0} and S{sub 1} electron transfer on the applied field. The REKS method was benchmarked against experimentally measured gas phase charge transfer excitations in a series of organic donor–acceptor complexes and displayed its ability to describe this type of electronic transitions with a very high accuracy, mean absolute error of 0.05 eV with the use of the standard range separated density functionals. On the basis of the calculations undertaken in this work, it is suggested that the non-adiabatic coupling between the S{sub 0} and S{sub 1} states may interfere with the electron transfer in a weakly coupled donor–acceptor system. It is also suggested that the electronic excitation of a D{sup +}–A{sup ?} system may play a dual role by assisting the further electron transfer at certain magnitudes of the applied electric field and causing the backward transfer at lower electric field strengths.

  15. Excitation energy transfer in the photosystem I

    Energy Technology Data Exchange (ETDEWEB)

    Webber, Andrew N

    2012-09-25

    Photosystem I is a multimeric pigment protein complex in plants, green alage and cyanobacteria that functions in series with Photosystem II to use light energy to oxidize water and reduce carbon dioxide. The Photosystem I core complex contains 96 chlorophyll a molecules and 22 carotenoids that are involved in light harvesting and electron transfer. In eucaryotes, PSI also has a peripheral light harvesting complex I (LHCI). The role of specific chlorophylls in excitation and electron transfer are still unresolved. In particular, the role of so-called bridging chlorophylls, located between the bulk antenna and the core electron transfer chain, in the transfer of excitation energy to the reaction center are unknown. During the past funding period, site directed mutagenesis has been used to create mutants that effect the physical properties of these key chlorophylls, and to explore how this alters the function of the photosystem. Studying these mutants using ultrafast absorption spectroscopy has led to a better understanding of the process by which excitation energy is transferred from the antenna chlorophylls to the electron transfer chain chlorophylls, and what the role of connecting chlorophylls and A_0 chlorophylls is in this process. We have also used these mutants to investigate whch of the central group of six chlorophylls are involved in the primary steps of charge separation and electron transfer.

  16. Theoretical investigation of electronic excitation transfer between chlorophylls in light-harvesting antenna of photosystem ii using quantum computers

    Scientific Electronic Library Online (English)

    Maryam, Dehestani; Somaie, Shojaei; Azita, Khosravan.

    Full Text Available The excitation energy transfer between chlorophylls in major and minor antenna complexes of photosystem II (PSII) was investigated using quantum Fourier transforms. These transforms have an important role in the efficiency of quantum algorithms of quantum computers. The equation 2n=N was used to mak [...] e the connection between excitation energy transfers using quantum Fourier transform, where n is the number of qubits required for simulation of transfers and N is the number of chlorophylls in the antenna complexes.

  17. Influence of macromolecule main chain structure on electron excitation energy transfer in carbazole-containing polymers

    International Nuclear Information System (INIS)

    Efficiencies of energy transfer from singlet excitons to rubrene in poly-N-epoxypropylcarbazole (PEPC) and from triplet excitons to pyrene in poly-N-vinylcarbazole (PVC) were found to increase on heating from 5 to 295 K. At the same time, the transfer efficiency in PVC at rubrene concentration 2x10-3 M decreased in the range T = 100-295 K, which correlated with a rise in the intensity of the fluorescence band of the matrix sandwich-like excimers. However, the transfer efficiency increased upon increasing the concentration, which caused the maximum donor-acceptor distance to approach the critical radius of the Forster model. The observed effects were explained by the fact that the free-path lengths of singlet excitons in PEPC and triplet excitons in PVC increased with increasing temperature and, correspondingly, the probability of them approaching the acceptor within distances where energy transfer was possible increased. Singlet-exciton self-trapping at excimer-forming sites and formation of sandwich-like excimers competed in PVC with energy transfer to rubrene. (authors)

  18. Influence of macromolecule main chain structure on electron excitation energy transfer in carbazole-containing polymers

    Science.gov (United States)

    Skryshevski, Yu. A.

    2013-05-01

    Efficiencies of energy transfer from singlet excitons to rubrene in poly- N-epoxypropylcarbazole (PEPC) and from triplet excitons to pyrene in poly- N-vinylcarbazole (PVC) were found to increase on heating from 5 to 295 K. At the same time, the transfer efficiency in PVC at rubrene concentration 2•10-3 M decreased in the range T = 100-295 K, which correlated with a rise in the intensity of the fluorescence band of the matrix sandwich-like excimers. However, the transfer efficiency increased upon increasing the concentration, which caused the maximum donor-acceptor distance to approach the critical radius of the Forster model. The observed effects were explained by the fact that the free-path lengths of singlet excitons in PEPC and triplet excitons in PVC increased with increasing temperature and, correspondingly, the probability of them approaching the acceptor within distances where energy transfer was possible increased. Singlet-exciton self-trapping at excimer-forming sites and formation of sandwich-like excimers competed in PVC with energy transfer to rubrene.

  19. Influence of macromolecule main chain structure on electron excitation energy transfer in carbazole-containing polymers

    International Nuclear Information System (INIS)

    Efficiencies of energy transfer from singlet excitons to rubrene in poly-N-epoxypropylcarbazole (PEPC) and from triplet excitons to pyrene in poly-N-vinylcarbazole (PVC) were found to increase on heating from 5 to 295 K. At the same time, the transfer efficiency in PVC at rubrene concentration 2*10-3 M decreased in the range T = 100-295 K, which correlated with a rise in the intensity of the fluorescence band of the matrix sandwich-like excimers.However, the transfer efficiency increased upon increasing the concentration, which caused the maximum donor-acceptor distance to approach the critical radius of the Forster model. The observed effects were explained by the fact that the free-path lengths of singlet excitons in PEPC and triplet excitons in PVC increased with increasing temperature and, correspondingly, the probability of them approaching the acceptor within distances where energy transfer was possible increased.Singlet-exciton self-trapping at excimer-forming sites and formation of sandwich-like excimers competed in PVC with energy transfer to rubrene. (author)

  20. Study of photo-activated electron transfer reactions in the first excited singlet state by picosecond and nanosecond laser spectroscopy

    International Nuclear Information System (INIS)

    Picosecond laser spectroscopy has been used to study two photo-activated electron transfer reactions: - a bimolecular electron transfer reaction between a sensitizer, DODCI, and an electron acceptor, methylviologen. The two radical ions created with an electron transfer efficiency ? ? 0.07 have been identified in picosecond and nanosecond laser absorption spectroscopy by adding selective solutes such as para-benzoquinone (an electron acceptor) or L(+) ascorbic acid (an electron donor). - an intramolecular electron transfer reaction in a triad molecule consisting of a tetra-aryl-porphyrin covalently linked to both a carotenoid and a quinone. The photoinduced charge separation occurs within 30 ps and leads, with a yield of 25 pc, to the formation of a zwitterion whose half-life is 2.5 ?s. The experimental results obtained in these two studies show an effective decrease in the recombination rate of the two radical ions created in the encounter pair. (author)

  1. Controlling fast electron transfer at the nano-scale by solitonic excitations along crystallographic axes

    Science.gov (United States)

    Chetverikov, A. P.; Ebeling, W.; Velarde, M. G.

    2012-08-01

    We present computational evidence of the possibility of fast, supersonic or subsonic, nearly loss-free transport of electrons bound to lattice solitons along crystallographic axes in two-dimensional anharmonic crystal lattices.

  2. Investigations of heme distortion, low-frequency vibrational excitations, and electron transfer in cytochrome c

    OpenAIRE

    Sun, Yuhan; Benabbas, Abdelkrim; Zeng, Weiqiao; Kleingardner, Jesse G.; Bren, Kara L.; Champion, Paul M.

    2014-01-01

    To probe the effect of heme ruffling on electron transport, we studied three cytochromes that display wide variation in the heme ruffling distortion. Ruffling is characterized by a low-frequency heme mode in the region 45–60 cm?1 and by a photoreduction cross-section that displays strong variation as a function of the magnitude of the distortion. Given the similarity in the distance between the heme and the nearest aromatic amino acid for all three proteins, the order-of-magnitude changes in ...

  3. Excited-state intramolecular hydrogen transfer (ESIHT) of 1,8-Dihydroxy-9,10-anthraquinone (DHAQ) characterized by ultrafast electronic and vibrational spectroscopy and computational modeling

    KAUST Repository

    Mohammed Abdelsaboor, Omar F.

    2014-05-01

    We combine ultrafast electronic and vibrational spectroscopy and computational modeling to investigate the photoinduced excited-state intramolecular hydrogen-transfer dynamics in 1,8-dihydroxy-9,10-anthraquinone (DHAQ) in tetrachloroethene, acetonitrile, dimethyl sulfoxide, and methanol. We analyze the electronic excited states of DHAQ with various possible hydrogen-bonding schemes and provide a general description of the electronic excited-state dynamics based on a systematic analysis of femtosecond UV/vis and UV/IR pump-probe spectroscopic data. Upon photoabsorption at 400 nm, the S 2 electronic excited state is initially populated, followed by a rapid equilibration within 150 fs through population transfer to the S 1 state where DHAQ exhibits ESIHT dynamics. In this equilibration process, the excited-state population is distributed between the 9,10-quinone (S2) and 1,10-quinone (S1) states while undergoing vibrational energy redistribution, vibrational cooling, and solvation dynamics on the 0.1-50 ps time scale. Transient UV/vis pump-probe data in methanol also suggest additional relaxation dynamics on the subnanosecond time scale, which we tentatively ascribe to hydrogen bond dynamics of DHAQ with the protic solvent, affecting the equilibrium population dynamics within the S2 and S1 electronic excited states. Ultimately, the two excited singlet states decay with a solvent-dependent time constant ranging from 139 to 210 ps. The concomitant electronic ground-state recovery is, however, only partial because a large fraction of the population relaxes to the first triplet state. From the similarity of the time scales involved, we conjecture that the solvent plays a crucial role in breaking the intramolecular hydrogen bond of DHAQ during the S2/S1 relaxation to either the ground or triplet state. © 2014 American Chemical Society.

  4. Excited-state intramolecular hydrogen transfer (ESIHT) of 1,8-dihydroxy-9,10-anthraquinone (DHAQ) characterized by ultrafast electronic and vibrational spectroscopy and computational modeling.

    Science.gov (United States)

    Mohammed, Omar F; Xiao, Dequan; Batista, Victor S; Nibbering, Erik T J

    2014-05-01

    We combine ultrafast electronic and vibrational spectroscopy and computational modeling to investigate the photoinduced excited-state intramolecular hydrogen-transfer dynamics in 1,8-dihydroxy-9,10-anthraquinone (DHAQ) in tetrachloroethene, acetonitrile, dimethyl sulfoxide, and methanol. We analyze the electronic excited states of DHAQ with various possible hydrogen-bonding schemes and provide a general description of the electronic excited-state dynamics based on a systematic analysis of femtosecond UV/vis and UV/IR pump-probe spectroscopic data. Upon photoabsorption at 400 nm, the S2 electronic excited state is initially populated, followed by a rapid equilibration within 150 fs through population transfer to the S1 state where DHAQ exhibits ESIHT dynamics. In this equilibration process, the excited-state population is distributed between the 9,10-quinone (S2) and 1,10-quinone (S1) states while undergoing vibrational energy redistribution, vibrational cooling, and solvation dynamics on the 0.1-50 ps time scale. Transient UV/vis pump-probe data in methanol also suggest additional relaxation dynamics on the subnanosecond time scale, which we tentatively ascribe to hydrogen bond dynamics of DHAQ with the protic solvent, affecting the equilibrium population dynamics within the S2 and S1 electronic excited states. Ultimately, the two excited singlet states decay with a solvent-dependent time constant ranging from 139 to 210 ps. The concomitant electronic ground-state recovery is, however, only partial because a large fraction of the population relaxes to the first triplet state. From the similarity of the time scales involved, we conjecture that the solvent plays a crucial role in breaking the intramolecular hydrogen bond of DHAQ during the S2/S1 relaxation to either the ground or triplet state. PMID:24684387

  5. Electron-excited molecule interactions

    International Nuclear Information System (INIS)

    In this paper the limited but significant knowledge to date on electron scattering from vibrationally/rotationally excited molecules and electron scattering from and electron impact ionization of electronically excited molecules is briefly summarized and discussed. The profound effects of the internal energy content of a molecule on its electron attachment properties are highlighted focusing in particular on electron attachment to vibrationally/rotationally and to electronically excited molecules. The limited knowledge to date on electron-excited molecule interactions clearly shows that the cross sections for certain electron-molecule collision processes can be very different from those involving ground state molecules. For example, optically enhanced electron attachment studies have shown that electron attachment to electronically excited molecules can occur with cross sections 106 to 107 times larger compared to ground state molecules. The study of electron-excited molecule interactions offers many experimental and theoretical challenges and opportunities and is both of fundamental and technological significance. 54 refs., 15 figs

  6. Calculations of nonlinear wave-packet interferometry signals in the pump-probe limit as tests for vibrational control over electronic excitation transfer

    Science.gov (United States)

    Biggs, Jason D.; Cina, Jeffrey A.

    2009-12-01

    The preceding paper [J. D. Biggs and J. A. Cina, J. Chem. Phys. 131, 224101 (2009)] (referred to here as Paper 1), describes a strategy for externally influencing the course of short-time electronic excitation transfer (EET) in molecular dimers and observing the process by nonlinear wave-packet interferometry (nl-WPI). External influence can, for example, be exerted by inducing coherent intramolecular vibration in one of the chromophores prior to short-pulse electronic excitation of the other. Within a sample of isotropically oriented dimers having a specified internal geometry, a vibrational mode internal to the acceptor chromophore can be preferentially driven by electronically nonresonant impulsive stimulated Raman (or resonant infrared) excitation with a short polarized "control" pulse. A subsequent electronically resonant polarized pump then preferentially excites the donor, and EET ensues. Paper 1 investigates control-pulse-influenced nl-WPI as a tool for the spectroscopic evaluation of the effect of coherent molecular vibration on excitation transfer, presenting general expressions for the nl-WPI difference signal from a dimer following the action of a control pulse of arbitrary polarization and shape. Electronic excitation is to be effected and its interchromophore transfer monitored by resonant pump and probe "pulses," respectively, each consisting of an optical-phase-controlled ultrashort pulse-pair having arbitrary polarization, duration, center frequency, and other characteristics. Here we test both the control strategy and its spectroscopic investigation—with some sacrifice of amplitude-level detail—by calculating the pump-probe difference signal. That signal is the limiting case of the control-influenced nl-WPI signal in which the two pulses in the pump pulse-pair coincide, as do the two pulses in the probe pulse-pair. We present calculated pump-probe difference signals for (1) a model excitation-transfer complex in which two equal-energy monomers each support one moderately Franck-Condon active intramolecular vibration; (2) a simplified model of the covalent dimer dithia-anthracenophane, representing its EET dynamics following selective impulsive excitation of the weakly Franck-Condon active ?12 anthracene vibration at 385 cm-1; and (3) a model complex featuring moderate electronic-vibrational coupling in which the site energy of the acceptor chromophore is lower than that of the donor.

  7. Role of electron-driven proton-transfer processes in the excited-state deactivation of the adenine-thymine base pair.

    Science.gov (United States)

    Perun, Serhiy; Sobolewski, Andrzej L; Domcke, Wolfgang

    2006-07-27

    Exploratory electronic structure calculations have been performed with the CC2 (simplified singles and doubles coupled-cluster) method for two conformers of the adenine (A)-thymine (T) base pair, with emphasis on excited-state proton-transfer reactions. The Watson-Crick conformer and the most stable (in the gas-phase) conformer of the A-T base pair have been considered. The equilibrium geometries of the ground state and of the lowest excited electronic states have been determined with the MP2 (second-order Møller-Plesset) and CC2 methods, respectively. Vertical and adiabatic excitation energies, oscillator strengths, and dipole moments of the excited states are reported. Of particular relevance for the photochemistry of the A-T base pair are optically dark (1)pipi* states of charge-transfer character. Although rather high in energy at the ground-state equilibrium geometry, these states are substantially lowered in energy by the transfer of a proton, which thus neutralizes the charge separation. A remarkable difference of the energetics of the proton-transfer reaction is predicted for the two tautomers of A-T: in the Watson-Crick conformer, but not in the most stable conformer, a sequence of conical intersections connects the UV-absorbing (1)pipi* state in a barrierless manner with the electronic ground state. These conical intersections allow a very fast deactivation of the potentially reactive excited states in the Watson-Crick conformer. The results provide evidence that the specific hydrogen-bonding pattern of the Watson-Crick conformer endows this structure with a greatly enhanced photostability. This property of the Watson-Crick conformer of A-T may have been essential for the selection of this species as carrier of genetic information in early stages of the biological evolution. PMID:16854013

  8. Efficiency of intramolecular charge separation from the second excited state: suppression of the hot charge recombination by electron transfer to the secondary acceptor.

    Science.gov (United States)

    Feskov, Serguei V; Ivanov, Anatoly I

    2013-11-14

    Ultrafast intramolecular charge transfer induced by the Soret-band excitation of the donor-acceptor1-acceptor2 molecular triads has been explored within the stochastic point-transition model. It is shown that nonthermal (hot) charge transfer from the primary to the secondary acceptor, assisted by relaxation of solvent polarization, can effectively screen ultrafast back electron transfer into the first excited state of the donor. Ways to increase the quantum yield of the charge-separated states are discussed. The dependencies of the quantum yield of the charge-separated states on the main electron transfer parameters: the free energy gaps, the reorganization energy of the solvent and intramolecular vibrational modes, the electronic couplings, and the solvent relaxation timescale are revealed. The important role of the geometry of the donor-acceptor1-acceptor2 triad in charge separation effectiveness is emphasized. For the zinc-porphyrin-imide1-imide2 triad, the charge-transfer parameters maximizing the quantum yield of the charge separated states are estimated. PMID:24102350

  9. Study of intermediates from transition metal excited-state electron-transfer reactions: Progress report, August 1, 1986--December 31, 1988

    International Nuclear Information System (INIS)

    During the period covered by this progress report, the examination of intermediates from transition metal excited-state electron-transfer reactions followed certain well-defined themes; the techniques of conventional and time-resolved spectrofluorimetry, continuous and pulsed laser flash photolysis, and continuous and pulse radiolysis were employed. Research involves Ru(II) complexes and Cr(III) complexes. 23 refs., 2 tabs

  10. Tautomeric selectivity of the excited-state lifetime of guanine/cytosine base pairs: the role of electron-driven proton-transfer processes.

    Science.gov (United States)

    Sobolewski, Andrzej L; Domcke, Wolfgang; Hättig, C

    2005-12-13

    The UV spectra of three different conformers of the guanine/cytosine base pair were recorded recently with UV-IR double-resonance techniques in a supersonic jet [Abo-Riziq, A., Grace, L., Nir, E., Kabelac, M., Hobza, P. & de Vries, M. S. (2005) Proc. Natl. Acad. Sci. USA 102, 20-23]. The spectra provide evidence for a very efficient excited-state deactivation mechanism that is specific for the Watson-Crick structure and may be essential for the photostability of DNA. Here we report results of ab initio electronic-structure calculations for the excited electronic states of the three lowest-energy conformers of the guanine/cytosine base pair. The calculations reveal that electron-driven interbase proton-transfer processes play an important role in the photochemistry of these systems. The exceptionally short lifetime of the UV-absorbing states of the Watson-Crick conformer is tentatively explained by the existence of a barrierless reaction path that connects the spectroscopic (1)pi pi * excited state with the electronic ground state via two electronic curve crossings. For the non-Watson-Crick structures, the photochemically reactive state is located at higher energies, resulting in a barrier for proton transfer and, thus, a longer lifetime of the UV-absorbing (1)pi pi * state. The computational results support the conjecture that the photochemistry of hydrogen bonds plays a decisive role for the photostability of the molecular encoding of the genetic information in isolated DNA base pairs. PMID:16330778

  11. Charge-Transfer Versus Charge-Transfer-Like Excitations Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Moore, Barry; Sun, Haitao; Govind, Niranjan; Kowalski, Karol; Autschbach, Jochen

    2015-07-14

    Criteria to assess charge-transfer (CT) and `CT-like' character of electronic excitations are examined. Time-dependent density functional theory (TDDFT) with non-hybrid, hybrid, and tuned long-range corrected (LC) functionals is compared with with coupled-cluster (CC) benchmarks. The test set includes an organic CT complex, two `push-pull' donor-acceptor chromophores, a cyanine dye, and several polycyclic aromatic hydrocarbons. Proper CT is easily identified. Excitations with significant density changes upon excitation within regions of close spatial proximity can also be diagnosed. For such excitations, the use of LC functionals in TDDFT sometimes leads to dramatic improvements of the singlet energies, similar to proper CT, which has led to the concept of `CT-like' excitations. However, `CT-like' excitations are not like charge transfer, and the improvements are not obtained for the right reasons. The triplet excitation energies are underestimated for all systems, often severely. For the `CT-like' candidates, when going from a non-hybrid to an LC functional the error in the singlet-triplet (S/T) separation changes from negative to positive, providing error compensation. For the cyanine, the S/T separation is too large with all functionals, leading to the best error compensation for non-hybrid functionals.

  12. Exogenous quinones inhibit photosynthetic electron transfer in Chloroflexus aurantiacus by specific quenching of the excited bacteriochlorophyll c antenna

    DEFF Research Database (Denmark)

    Frigaard, N-U; Tokita, S; Matsuura, K

    1999-01-01

    In the photosynthetic green filamentous bacterium Chloroflexus aurantiacus, excitation energy is transferred from a large bacteriochlorophyll (BChl) c antenna via smaller BChl a antennas to the reaction center. The effects of substituted 1,4-naphthoquinones on BChl c and BChl a fluorescence and on flash-induced cytochrome c oxidation were studied in whole cells under aerobic conditions. BChl c fluorescence in a cell suspension with 5.4 microM BChl c was quenched to 50% by addition of 0.6 microM ...

  13. Materials modification by electronic excitation

    OpenAIRE

    A.M. Stoneham; ITOH, N.

    2000-01-01

    Electronic excitation by lasers or electron beams can modify the properties of materials. The changes are not just due to heat, nor do they result from the well-known collision dynamics of much radiation damage. Everyday examples of modification by electronic excitation include photography, and photochromics (such as sunglasses) which change colour. In the last few years it has become clear that excitation can offer novel types of modification, with better-controlled changes. The field has ev...

  14. The electron-electron interaction studied in strong central fields by resonant transfer and excitation with H-like U ions

    CERN Document Server

    Ma, X; Gumberidze, A; Kozhuharov, C; Liesen, D; Mokler, P H; Sierpowski, D; Stachura, Z; Stöhlker, T; Warczak, A

    2003-01-01

    Electron-electron interaction is studied in the strongest possible atomic fields (Z.alpha => 1) in the presence of only two electrons. A quasi-free electron from a hydrogen gas target is resonantly captured into a L sub j subshell of a fast H-like U sup 9 sup 1 sup + ion by simultaneous excitation of the strongly bound K electron also into a L sub j sub ' subshell of the projectile, with j and j' the total angular momenta of 1/2 or 3/2 for the electron of concern. This resonant capture and excitation process, KL sub j L sub j sub ' -RTE, is mediated by electron-electron interaction. It is equivalent to dielectronic recombination (DR) in ion-electron collisions and leads to a doubly excited He-like U sup 9 sup 0 sup + sup * sup * ion, which stabilizes - almost exclusively - via the emission of two successive K X-rays, first a K hypersatellite (K alpha i-H) and then a K satellite (K alpha i'-S) transition. The K X-ray emission characteristics associated with one-electron capture in collisions of U sup 9 sup 1 s...

  15. Electron transfer reactions

    CERN Document Server

    Cannon, R D

    2013-01-01

    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  16. Electron-excited molecule interactions

    Energy Technology Data Exchange (ETDEWEB)

    Christophorou, L.G. (Oak Ridge National Lab., TN (USA) Tennessee Univ., Knoxville, TN (USA). Dept. of Physics)

    1991-01-01

    In this paper the limited but significant knowledge to date on electron scattering from vibrationally/rotationally excited molecules and electron scattering from and electron impact ionization of electronically excited molecules is briefly summarized and discussed. The profound effects of the internal energy content of a molecule on its electron attachment properties are highlighted focusing in particular on electron attachment to vibrationally/rotationally and to electronically excited molecules. The limited knowledge to date on electron-excited molecule interactions clearly shows that the cross sections for certain electron-molecule collision processes can be very different from those involving ground state molecules. For example, optically enhanced electron attachment studies have shown that electron attachment to electronically excited molecules can occur with cross sections 10{sup 6} to 10{sup 7} times larger compared to ground state molecules. The study of electron-excited molecule interactions offers many experimental and theoretical challenges and opportunities and is both of fundamental and technological significance. 54 refs., 15 figs.

  17. Theoretical study of intermolecular energy transfer involving electronically excited molecules: He(1S) + H2(B 1?/sub u/+)

    International Nuclear Information System (INIS)

    To further understanding of gas phase collision dynamics involving electronically-excited molecules, a fully quantum mechanical study of He + H2(B 1?/sub u/+) was undertaken. Iterative natural orbital configuration interaction (CI) calculations were performed to obtain the interaction potential between He and H2(B 1?/sub u/+). The potential energy surface (PES) is highly anisotropic and has a van der Waals well of about 0.03 eV for C/sub 2v/ approach. Avoided PES crossings occur with He + H2(E,F 1?/sub g/+) and with He + H2(X 1?/sub g/+) and cause a local maximum and a deep minimum in the He + H2(B 1?/sub u/+) PES, respectively. The crossing with He + H2(X 1?/sub g/+) provides a mechanism for fluorescence quenching. The computed CI energies were combined with previous multi-reference double excitation CI calculations and fit with analytic functions for convenience in scattering calculations. Accurate dipole polarizabilities and quadrupole moment of H2(B 1?/sub u/+) were computed for use in the multipole expansion, which is the analytic form of the long-range PES. 129 refs., 28 figs., 35 tabs

  18. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1995-01-01

    Advances in Electron Transfer Chemistry, Volume 4 presents the reaction mechanisms involving the movement of single electrons. This book discusses the electron transfer reactions in organic, biochemical, organometallic, and excited state systems. Organized into four chapters, this volume begins with an overview of the photochemical behavior of two classes of sulfonium salt derivatives. This text then examines the parameters that control the efficiencies for radical ion pair formation. Other chapters consider the progress in the development of parameters that control the dynamics and reaction p

  19. Intramolecular electron transfer rates

    Science.gov (United States)

    Hupp, Joseph T.

    The initial goals of this project were: (1) to construct pulsed-accelerated-flow and pulsed-laser (transient absorbance) instruments for intramolecular electron-transfer rate measurements, (2) to design and synthesize appropriate molecules and perform such measurements, (3) to develop further an electrochemical method for gauging site-to-site electronic coupling, and (4) to apply time-dependent Raman scattering theory to the problem of inner-shell reorganization in charge-transfer reactions. Although all four goals were met, we also found it necessary to pursue studies in some unforeseen directions. For example, early on we discovered that medium effects (aggregation and ion pairing) could play a very large, and previously unrecognized, role in some optical intervalence reactions. Given the importance of the effects to the areas above, we chose to map them in a fairly complete fashion. Also, in anticipation of possible renewal we initiated studies in a new area: bimolecular photoredox kinetics in supercritical media. Finally, in a small project carried out largely by undergraduates we examined solvent tuning effects upon lifetimes of photo-excited ruthenium am(m)ine bipyridine complexes. The key new findings and other highlights of these studies are outlined.

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

    CERN Document Server

    Theophilou, Iris; 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 accurate and computationally inexpensive treatment of charge transfer excitations is a topic that attracts nowadays 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. For the description of an excitation where an electron is transferred from a donor system to an acceptor one, it is necessary to keep the excited state orthogonal to the ground sate in order to avoid variational collapse. These conditions are achieved by decomposing the subspace spanned by the Hartree-Fock (HF) ground state orbitals to four subspaces: The subspace spanned ...

  1. The electron-electron interaction studied in strong central fields by resonant transfer and excitation with H-like U ions. - Angular distribution of hypersatellite and satellite radiation emitted after resonant and excitation into U91+ ions

    International Nuclear Information System (INIS)

    Electron-electron interaction is studied in the strongest possible atomic fields (Z.? => 1) in the presence of only two electrons. A quasi-free electron from a hydrogen gas target is resonantly captured into a Lj subshell of a fast H-like U91+ ion by simultaneous excitation of the strongly bound K electron also into a Lj' subshell of the projectile, with j and j' the total angular momenta of 1/2 or 3/2 for the electron of concern. This resonant capture and excitation process, KLjLj'-RTE, is mediated by electron-electron interaction. It is equivalent to dielectronic recombination (DR) in ion-electron collisions and leads to a doubly excited He-like U90+** ion, which stabilizes - almost exclusively - via the emission of two successive K X-rays, first a K hypersatellite (K?i-H) and then a K satellite (K?i'-S) transition. The K X-ray emission characteristics associated with one-electron capture in collisions of U91+ ions with a hydrogen target is studied for the three resonance groups of the KLjLj'-RTE and one off-resonance energy, i.e. in the energy range between 100 and 135 MeV/u. The total cross section for the first resonance group KL1/2L1/2 confirms the importance of the Breit contribution to the interaction. The angular distribution for the K?2-H transition (j=1/2) is isotropic in the projectile system whereas the K?1-H transition (j=3/2) indicates a strong alignment for the 3/2 electrons in the doubly excited states for the second resonance group KL1/2L3/2. The experimental results are in agreement with fully relativistic calculations including the generalized Breit interaction. (orig.)

  2. Proton-Coupled Electron Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Weinberg, Dave; Gagliardi, Christopher J.; Hull, Jonathan F; Murphy, Christine Fecenko; Kent, Caleb A.; Westlake, Brittany C.; Paul, Amit; Ess, Daniel H; McCafferty, Dewey Granville; Meyer, Thomas J

    2012-07-11

    Proton-Coupled Electron Transfer (PCET) describes reactions in which there is a change in both electron and proton content between reactants and products. It originates from the influence of changes in electron content on acid-base properties and provides a molecular-level basis for energy transduction between proton transfer and electron transfer. Coupled electron-proton transfer or EPT is defined as an elementary step in which electrons and protons transfer from different orbitals on the donor to different orbitals on the acceptor. There is (usually) a clear distinction between EPT and H-atom transfer (HAT) or hydride transfer, in which the transferring electrons and proton come from the same bond. Hybrid mechanisms exist in which the elementary steps are different for the reaction partners. EPT pathways such as PhO•/PhOH exchange have much in common with HAT pathways in that electronic coupling is significant, comparable to the reorganization energy with H{sub DA} ~ ?. Multiple-Site Electron-Proton Transfer (MS-EPT) is an elementary step in which an electron-proton donor transfers electrons and protons to different acceptors, or an electron-proton acceptor accepts electrons and protons from different donors. It exploits the long-range nature of electron transfer while providing for the short-range nature of proton transfer. A variety of EPT pathways exist, creating a taxonomy based on what is transferred, e.g., 1e-/2H+ MS-EPT. PCET achieves “redox potential leveling” between sequential couples and the buildup of multiple redox equivalents, which is of importance in multielectron catalysis. There are many examples of PCET and pH-dependent redox behavior in metal complexes, in organic and biological molecules, in excited states, and on surfaces. Changes in pH can be used to induce electron transfer through films and over long distances in molecules. Changes in pH, induced by local electron transfer, create pH gradients and a driving force for long-range proton transfer in Photosysem II and through other biological membranes. In EPT, simultaneous transfer of electrons and protons occurs on time scales short compared to the periods of coupled vibrations and solvent modes. A theory for EPT has been developed which rationalizes rate constants and activation barriers, includes temperature- and driving force (?G)-dependences implicitly, and explains kinetic isotope effects. The distance-dependence of EPT is dominated by the short-range nature of proton transfer, with electron transfer being far less demanding.Changes in external pH do not affect an EPT elementary step. Solvent molecules or buffer components can act as proton donor acceptors, but individual H2O molecules are neither good bases (pKa(H3O+) = -1.74) nor good acids (pKa(H2O) = 15.7). There are many examples of mechanisms in chemistry, in biology, on surfaces, and in the gas phase which utilize EPT. PCET and EPT play critical roles in the oxygen evolving complex (OEC) of Photosystem II and other biological reactions by decreasing driving force and avoiding high-energy intermediates.

  3. An efficient computational scheme for electronic excitation spectra of molecules in solution using the symmetry-adapted cluster-configuration interaction method: The accuracy of excitation energies and intuitive charge-transfer indices

    Science.gov (United States)

    Fukuda, Ryoichi; Ehara, Masahiro

    2014-10-01

    Solvent effects on electronic excitation spectra are considerable in many situations; therefore, we propose an efficient and reliable computational scheme that is based on the symmetry-adapted cluster-configuration interaction (SAC-CI) method and the polarizable continuum model (PCM) for describing electronic excitations in solution. The new scheme combines the recently proposed first-order PCM SAC-CI method with the PTE (perturbation theory at the energy level) PCM SAC scheme. This is essentially equivalent to the usual SAC and SAC-CI computations with using the PCM Hartree-Fock orbital and integrals, except for the additional correction terms that represent solute-solvent interactions. The test calculations demonstrate that the present method is a very good approximation of the more costly iterative PCM SAC-CI method for excitation energies of closed-shell molecules in their equilibrium geometry. This method provides very accurate values of electric dipole moments but is insufficient for describing the charge-transfer (CT) indices in polar solvent. The present method accurately reproduces the absorption spectra and their solvatochromism of push-pull type 2,2'-bithiophene molecules. Significant solvent and substituent effects on these molecules are intuitively visualized using the CT indices. The present method is the simplest and theoretically consistent extension of SAC-CI method for including PCM environment, and therefore, it is useful for theoretical and computational spectroscopy.

  4. Electron transfer in proteins

    DEFF Research Database (Denmark)

    Farver, O; Pecht, I

    1991-01-01

    Electron migration between and within proteins is one of the most prevalent forms of biological energy conversion processes. Electron transfer reactions take place between active centers such as transition metal ions or organic cofactors over considerable distances at fast rates and with remarkable specificity. The electron transfer is attained through weak electronic interaction between the active sites, so that considerable research efforts are centered on resolving the factors that control th...

  5. Collisional excitation transfer between lithium isotopes

    International Nuclear Information System (INIS)

    Excitation transfer between the 3S1/2 states of the lithium isotopes 6Li and 7Li is measured in a thermionic diode. The 3S level is excited by off-resonant two-photon transitions with a single mode cw laser. The relative densities of the directly excited and collisionally populated levels are probed by further laser excitation to the 12P levels. An energy transfer cross section of 585 A2 ± 160 A2 is found at the experimental temperature of about 850 K. A simple semiclassical calculation yields a cross section of 450 A2. (orig.)

  6. Resonant electron transfer and L-shell excitation at 3.6 MeV/u 62Smsup(q+) -> Xe collisions, q=35-52

    International Nuclear Information System (INIS)

    For 3.6 MeV/u Smsup(q+) projectiles a hump in the projectile (Lsub(l)+Lsub(?)) X-ray emission cross section is seen as a function of charge state q for high q with 463-shell electron to the M-shell. The cross section for this L3-shell RTE process gives values of up to 2 . 10-19 cm2 which is seen in single spectra already. To demonstrate the strong existence of the L-shell RTE process for the studied collision system, extensive calculations have been carried out. This concerns especially the L3-shell fluorescence yields for the radiative stabilization process in the highly charged projectile, when simultaneous transfer and excitation has taken place. Our calculated q-dependent cross sections for the RTE process support the given interpretation. (orig.)

  7. Systems approach to excitation-energy and electron transfer reaction networks in photosystem II complex: model studies for chlorophyll a fluorescence induction kinetics.

    Science.gov (United States)

    Matsuoka, Takeshi; Tanaka, Shigenori; Ebina, Kuniyoshi

    2015-09-01

    Photosystem II (PS II) is a protein complex which evolves oxygen and drives charge separation for photosynthesis employing electron and excitation-energy transfer processes over a wide timescale range from picoseconds to milliseconds. While the fluorescence emitted by the antenna pigments of this complex is known as an important indicator of the activity of photosynthesis, its interpretation was difficult because of the complexity of PS II. In this study, an extensive kinetic model which describes the complex and multi-timescale characteristics of PS II is analyzed through the use of the hierarchical coarse-graining method proposed in the authors? earlier work. In this coarse-grained analysis, the reaction center (RC) is described by two states, open and closed RCs, both of which consist of oxidized and neutral special pairs being in quasi-equilibrium states. Besides, the PS II model at millisecond scale with three-state RC, which was studied previously, could be derived by suitably adjusting the kinetic parameters of electron transfer between tyrosine and RC. Our novel coarse-grained model of PS II can appropriately explain the light-intensity dependent change of the characteristic patterns of fluorescence induction kinetics from O-J-I-P, which shows two inflection points, J and I, between initial point O and peak point P, to O-J-D-I-P, which shows a dip D between J and I inflection points. PMID:26025316

  8. Electron excitation of dielectric wedges

    International Nuclear Information System (INIS)

    Recent experimental data of Electron Energy Loss Spectrometry of the interaction between small crystallites and beams travelling at a fixed beam-solid surface distance are analyzed in terms of the surface and bulk excitation modes of parabolically shaped wedges. The probability of excitation of the surface modes is calculated for an electron travelling parallel to the wedge surface, either outside or inside the dielectric wedge. The main features of available experimental data for MgO crystallites can be explained by the theory. 8 figures

  9. An accurate full-dimensional potential energy surface for H-Au(111): Importance of nonadiabatic electronic excitation in energy transfer and adsorption

    Science.gov (United States)

    Janke, Svenja M.; Auerbach, Daniel J.; Wodtke, Alec M.; Kandratsenka, Alexander

    2015-09-01

    We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H-Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension, not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ?3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab.

  10. An accurate full-dimensional potential energy surface for H-Au(111): Importance of nonadiabatic electronic excitation in energy transfer and adsorption.

    Science.gov (United States)

    Janke, Svenja M; Auerbach, Daniel J; Wodtke, Alec M; Kandratsenka, Alexander

    2015-09-28

    We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H-Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension, not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ?3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab. PMID:26429033

  11. Calculation of electronic coupling matrix elements for ground and excited state electron transfer reactions: Comparison of the generalized Mulliken-Hush and block diagonalization methods

    Science.gov (United States)

    Cave, Robert J.; Newton, Marshall D.

    1997-06-01

    Two independent methods are presented for the nonperturbative calculation of the electronic coupling matrix element (Hab) for electron transfer reactions using ab initio electronic structure theory. The first is based on the generalized Mulliken-Hush (GMH) model, a multistate generalization of the Mulliken Hush formalism for the electronic coupling. The second is based on the block diagonalization (BD) approach of Cederbaum, Domcke, and co-workers. Detailed quantitative comparisons of the two methods are carried out based on results for (a) several states of the system Zn2OH2+ and (b) the low-lying states of the benzene-Cl atom complex and its contact ion pair. Generally good agreement between the two methods is obtained over a range of geometries. Either method can be applied at an arbitrary nuclear geometry and, as a result, may be used to test the validity of the Condon approximation. Examples of nonmonotonic behavior of the electronic coupling as a function of nuclear coordinates are observed for Zn2OH2+. Both methods also yield a natural definition of the effective distance (rDA) between donor (D) and acceptor (A) sites, in contrast to earlier approaches which required independent estimates of rDA, generally based on molecular structure data.

  12. Efficient excited-state deactivation of the Gly-Phe-Ala tripeptide via an electron-driven proton-transfer process.

    Science.gov (United States)

    Shemesh, Dorit; Sobolewski, Andrzej L; Domcke, Wolfgang

    2009-02-01

    Ab initio electronic-structure calculations indicate a mechanism for efficient excited-state deactivation of a low-energy conformer of the Gly-Phe-Ala tripeptide. The particularly short excited-state lifetime can explain the unexpected absence of this conformer in resonant two-photon ionization spectra. It is suggested that these ultrafast electronic deactivation processes provide specific conformers of peptides with a high degree of photostability. PMID:19140760

  13. Phonons and charge-transfer excitations in HTS superconductors

    International Nuclear Information System (INIS)

    Some of the experimental and theoretical evidence implicating phonons and charge-transfer excitations in HTS superconductors is reviewed. It is suggested that superconductivity may be driven by a synergistic interplay of (anharmonic) phonons and electronic degrees of freedom (e.g., charge fluctuations, excitons). 47 refs., 5 figs

  14. Excitation and charge transfer in He+ + H collisions. A molecular approach including two-electron translation factors

    International Nuclear Information System (INIS)

    In a previous paper we have pointed out that the common-translation-factor (CTF) method is the only one which, at present, and within the framework of the molecular model of atomic collisions, can be shown to be both convergent and computationally fast, even for many-electron systems. In this Communication we check that this second statement is correct, presenting, for the first time, a molecular calculation involving two-electron translation factors, for He+ + H collisions. A careful study of the sensitivity of the calculated cross sections to the choice of the CTF is performed, and conclusions on that sensitivity are drawn, for several types of processes

  15. Excitation and charge transfer in He/sup +/ + H collisions. A molecular approach including two-electron translation factors

    Energy Technology Data Exchange (ETDEWEB)

    Errea, L.F.; Mendez, L.; Riera, A.

    1983-06-01

    In a previous paper we have pointed out that the common-translation-factor (CTF) method is the only one which, at present, and within the framework of the molecular model of atomic collisions, can be shown to be both convergent and computationally fast, even for many-electron systems. In this Communication we check that this second statement is correct, presenting, for the first time, a molecular calculation involving two-electron translation factors, for He/sup +/ + H collisions. A careful study of the sensitivity of the calculated cross sections to the choice of the CTF is performed, and conclusions on that sensitivity are drawn, for several types of processes.

  16. Charge Transfer Excitations in Insulating Copper Oxides

    CERN Document Server

    Moskvin, A S; Hayn, R; Malek, J

    2005-01-01

    A semi-quantitative cluster approach is developed to describe the charge transfer (CT) electron-hole excitations in insulating cuprates in a rather wide energy range up to 10- 15 eV. It generalizes the Zhang-Ng (ZN) model of CT excitons by considering the complete set of Cu3d and O2p orbitals within the CuO4 embedded molecular cluster method and by introducing one-center (intra-center) Frenkel-like and two-center (inter-center) excitons. Special attention is paid to the transition matrix element effects both in optical and electron energy loss spectra (EELS). In the latter case we obtain the momentum dependence of matrix elements both for intra-center and inter-center transitions. We are able to give a semi-quantitative description of the optical and EELS spectra for a large number of 0D (like CuB2O4), 1D (Sr2CuO3) and 2D (like Sr2CuO2Cl2) insulating cuprates in a unifying manner. By comparing our analysis with the experimental data we find that the CT gap in insulating cuprates is determined by nearly degene...

  17. Relations among theories of excitation transfer

    International Nuclear Information System (INIS)

    Recent applications of the generalized master equation (GME) theory for the transfer of excitation interacting linearly with phonons results in revision of some previous conclusions about relations between GME and other advanced theories: Haken-Strobl-Reineker (HSR) stochastic Liouville equation (SLE) theory, Grover-Silbey (GS) microscopic theory and Continuous Time Random Walk (CTRW) method. Two-channel memory functions (MF) derived from first principles relate entirely to those corresponding to GS and HRS approaches and unify theories of the excitation transfer. Trapping effects have pronounced influence on MFs. Coherence effects in the excitation transfer lead to a strange behaviour of ''probabilities'' in CTRW. Kenkre-Knox (KK) correspondence between MF and spectral properties has a limited applicability. Decay time obtained in such a manner could have nothing to do with much longer real coherence time. (author). 69 refs

  18. Vibrational control of electron-transfer reactions: a feasibility study for the fast coherent transfer regime.

    Science.gov (United States)

    Antoniou, P; Ma, Z; Zhang, P; Beratan, D N; Skourtis, S S

    2015-11-18

    Molecular vibrations and electron-vibrational interactions are central to the control of biomolecular electron and energy-transfer rates. The vibrational control of molecular electron-transfer reactions by infrared pulses may enable the precise probing of electronic-vibrational interactions and of their roles in determining electron-transfer mechanisms. This type of electron-transfer rate control is advantageous because it does not alter the electronic state of the molecular electron-transfer system or irreversibly change its molecular structure. For bridge-mediated electron-transfer reactions, infrared (vibrational) excitation of the bridge linking the electron donor to the electron acceptor was suggested as being capable of influencing the electron-transfer rate by modulating the bridge-mediated donor-to-acceptor electronic coupling. This kind of electron-transfer experiment has been realized, demonstrating that bridge-mediated electron-transfer rates can be changed by exciting vibrational modes of the bridge. Here, we use simple models and ab initio computations to explore the physical constraints on one's ability to vibrationally perturb electron-transfer rates using infrared excitation. These constraints stem from the nature of molecular vibrational spectra, the strengths of the electron-vibrational coupling, and the interaction between molecular vibrations and infrared radiation. With these constraints in mind, we suggest parameter regimes and molecular architectures that may enhance the vibrational control of electron transfer for fast coherent electron-transfer reactions. PMID:25909507

  19. Collective Excitations in Electron-Hole Bilayers

    International Nuclear Information System (INIS)

    We report a combined analytic and molecular dynamics analysis of the collective mode spectrum of a bipolar (electron-hole) bilayer in the strong coupling classical limit. A robust, isotropic energy gap is identified in the out-of-phase spectra, generated by the combined effect of correlations and of the excitation of the bound dipoles. In the in-phase spectra we identify longitudinal and transverse acoustic modes wholly maintained by correlations. Strong nonlinear generation of higher harmonics of the fundamental dipole oscillation frequency and the transfer of harmonics between different modes is observed

  20. Electron impact excitation of methane

    Science.gov (United States)

    Vuskovic, L.; Trajmar, S.

    1983-01-01

    A crossed molecular beam-electron beam apparatus was employed to examine the excitation cross-sections of CH4. Attention was given to 20, 30, and 200 eV impact energies at angles from 8-130 deg. Spectra were obtained in the elastic and inelastic realms as well as in the ionization continuum in the 12.99-15.0 eV energy-loss range. Differential cross-sections were also determined. The results are useful for modeling the behavior of CH4 in planetary atmospheres.

  1. Excited state Intramolecular Proton Transfer in Anthralin

    DEFF Research Database (Denmark)

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

    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 unusually large fluorescence Stokes shift of 10500 cm?1. The emission appears as a broad band with a maximum at 17500 cm?1 and is characterized by a low and nearly temperature-independent quantum yield. The ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Theophilou, Iris, E-mail: i.theophilou@fz-juelich.de [Peter Grunberg Institut (PGI) Forschungszentrum Jülich, D-52425 Jülich (Germany); Tassi, M.; Thanos, S. [Institute for Advanced Materials, Physicochemical Processes, Nanotechnology and Microsystems, ‘Demokritos’ National Center for Scientific Research, 15310 Athens (Greece)

    2014-04-28

    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.

  3. Excitation energy transfer from dye molecules to doped graphene

    Indian Academy of Sciences (India)

    R S Swathi; K L Sebastian

    2012-01-01

    Recently, we have reported theoretical studies on the rate of energy transfer from an electronically excited molecule to graphene. It was found that graphene is a very efficient quencher of the electronically excited states and that the rate $\\alpha z^{?4}$. The process was found to be effective up to 30 $nm$ which is well beyond the traditional FRET limit. In this report, we study the transfer of an amount of energy $\\hbar \\Omega$ from a dye molecule to doped graphene. We find a crossover of the distance dependence of the rate from $z^{?4}$ to exponential as the Fermi level is increasingly shifted into the conduction band, with the crossover occurring at a shift of the Fermi level by an amount $\\hbar \\Omega/2$.

  4. Electron transfer in biology

    Science.gov (United States)

    Williams, R. J. P.

    Electron transfer is one of the key reactions of biology not just in catalysis of oxidation/reduction reactions but in the conversion of sources of energy such as light to usable form for chemical transformations. There are then two intriguing problems. What is the nature of the matrix in which electrons flow in a biological cell after the initial charge separation due for example to the absorption of light. Here we are examining biological structures similar to man's electronic wires and the construction must be of low resistance in what are apparently insulators - organic polymers. It has been found that the electronic conduction system is largely made from metallo-proteins associated with lipid membranes. We understand much about these biological wires today. The second problem concerns the conversion of the energy captured from the light into usable chemical form. The major synthetic step in the production of biological polymers, including proteins, DNA, RNA, polysaccharides and fats, is condensation, i.e. the removal of water in the formation of amides, esters and so on. Now these condensation reactions are driven in biology by using a drying agent in water, namely the anhydride, pyrophosphate, in a special compound ATP, adenosine triphosphate. The central problem is to discover exactly how the flow of electrons can be related to the synthesis of (bound) pyrophosphate. (In a thermodynamic sense pyrophosphate is a water soluble kinetically stable drying agent comparable with solid P2O5.) In the biological systems the connection between these different classes of reaction, electron transfer and condensation, is known to be via the production of an energized gradient of protons across the biological membrane which arises from the flow of electrons across the same membrane in the electron transport wires of biology. However we do not understand thoroughly the steps which lead from electron flow in a membrane to proton gradients in that membrane, i.e. electron/proton coupling. Again we do not understand thoroughly how subsequently the proton gradient across a membrane makes ATP, pyrophosphate. Today there is good experimental evidence as to the likely answers in principle. These analyse the coupling devices in mechanical terms. In this article I describe at first the 'wires' of biology, uncoupled simple electron flow, and then go on to the ways in which electron flow could be transduced by mechanical devices, also proteins, into proton gradients and then ATP. This will be termed coupled electron flow. The objective of the article is to stimulate participation by physical chemists in the further description of biological energy capture from light or the oxidation of hydrocarbons to a form suitable for driving chemical syntheses in a controlled manner.

  5. Theoretical studies of electronically excited states

    Energy Technology Data Exchange (ETDEWEB)

    Besley, Nicholas A. [School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom)

    2014-10-06

    Time-dependent density functional theory is the most widely used quantum chemical method for studying molecules in electronically excited states. However, excited states can also be computed within Kohn-Sham density functional theory by exploiting methods that converge the self-consistent field equations to give excited state solutions. The usefulness of single reference self-consistent field based approaches for studying excited states is demonstrated by considering the calculation of several types of spectroscopy including the infrared spectroscopy of molecules in an electronically excited state, the rovibrational spectrum of the NO-Ar complex, core electron binding energies and the emission spectroscopy of BODIPY in water.

  6. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1993-01-01

    Advances in Electron Transfer Chemistry, Volume 3 presents studies that discuss findings in the various aspects of electron chemistry. The book is comprised of four chapters; each chapter reviews a work that tackles an issue in electron transfer chemistry. Chapter 1 discusses the photoinduced electron transfer in flexible biaryl donor-acceptor molecules. Chapter 2 tackles light-induced electron transfer in inorganic systems in homogeneous and heterogeneous phases. The book also covers internal geometry relaxation effects on electron transfer rates of amino-centered systems. The sequential elec

  7. Cold transfer between deformed, Coulomb excited nuclei

    International Nuclear Information System (INIS)

    The scattering system 162Dy ? 116Sn has been examined at energies in the vicinity of the Coulomb barrier using the Heidelberg-Darmstadt Crystal Ball spectrometer combined with 5 Germanium-CLUSTER detectors. In order to study pairing correlations as a function of angular momentum cold events were selected in the 2n stripping channel by identifying and suppressing the dominant hot part of the transfer with the Crystal Ball. The CLUSTER detectors with their high ?-efficiency were used to identify the transfer channel and to resolve individual final states. Cross sections for the population of individual yrast states in a cold transfer reaction have been measured for the first time indicating the strong influence of higher transfer multipolarities. At small surface distances Coulomb-nuclear interferences were found to be responsible for the stronger decline of the population of higher yrast states in the transfer channel as compared to the Coulex channel. As a preparatory study for 2n transfer measurements between high spin yrast states in the backbending region of deformed nuclei the Coulomb excitation process in the crossing region of two bands in 162Dy has been analyzed. The gross properties of the measured population probabilities could be interpreted in a simple band mixing model. (orig.)

  8. Excitation transfer, charge transfer and hydrogen abstraction reaction, kinetics studies of modification of DNA components

    International Nuclear Information System (INIS)

    Laser induced acetone-sensitized excitation of DNA components offered, for the first time, T-T absorption spectra and direct triplet states kinetics of cytosine, cytidine, and dCMP, adenine, adenosine and dAMP and guanosine. Mechanisms and kinetics of electron transfer reactions between triplet acetone and purine bases and triplet thymine and electroaffinic modifiers have been elucidated. Rapid electron transfer from hydroxycinnamic acid derivatives to oxidizing OH adducts of pyrimidines have been performed. Fast reduction and repair of oxidizing damage of pyrimidines have been achieved accordingly. (author)

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

    International Nuclear Information System (INIS)

    The time evolution of electronically excited vitamin B12 (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

  10. Ultrafast electronic relaxation of excited state vitamin B{sub 12} in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Shafizadeh, Niloufar [Laboratoire de Photophysique Moleculaire, U.P.R. 3361 CNRS Bat 210, Universite de Paris-Sud, 91405 Orsay, Cedex (France)], E-mail: Niloufar.Shafizadeh@u-psud.fr; Poisson, Lionel; Soep, Benoit [Laboratoire Francis Perrin, CEA/DSM/DRECAM/SPAM - CNRS URA 2453, CEA Saclay, 91191 Gif-sur-Yvette Cedex (France)

    2008-06-23

    The time evolution of electronically excited vitamin B{sub 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. Electron transfer reactions of excited dyes with metal complexes. Progress report, March 1, 1978-February 28, 1979. [Iron-methylene blue

    Energy Technology Data Exchange (ETDEWEB)

    Lichtin, N.N.

    1979-03-15

    An intense absorption band of /sup 3/MBH/sup 2 +/ at 700nm was characterized in several media and its pK/sub A/ was measured to be 7.17 +- .1 in water. Flash photolysis show that semiethylene blue, MBH/sup +/, formed by quenching /sup 3/MBH/sup 2 +/ with Fe/sub II/(H/sub 2/O)/sub 6//sup 2 +/, decays by disproportionation at a diffusion-controlled rate. Rates of decay of the photostationary state of solutions of MB/sup +/ and Fe/sup II/(H/sub 2/O)/sub 6//sup 2 +/ in acidic media were measured using crossed beams to yield specific rates of oxidation of leucomethylene blue (MBH/sub 3//sup 2 +/) by MB/sup +/ (synproportionation) and by Fe(III). Laser flash-photolysis shows that quenching of MB/sup +/(S/sub 1/) by Fe(H/sub 2/O)/sub 6//sup 2 +/ can result in electron transfer to give MBH/sup +/. Profound differences between processes initiated by quenching triplet methylene blue with Fe(H/sub 2/O)/sub 6//sup 2 +/ and with stable coordination complexes of Fe(II) were found. Quenchers included (Fe/sup II/(CN)/sub 6/)/sup 4 -/, (Fe/sup II/(CN)/sub 4/(bpy)/sub 2/)/sup 2 -/, (Fe/sup II/(CN)/sub 2/(bpy))/sup 0/, and (Fe/sup II/(bpy)/sub 3/)/sup 2 +/. Measurements were made in aqueous and aqueous-alcoholic solutions at pH 2, 4.4, and 8.2. Quenching of /sup 3/MBH/sup 2 +/ or /sup 3/MB/sup +/ by a stable complex of Fe(II) is diffusion-controlled and 10/sup 2/ to 10/sup 3/ times the rate at which Fe(H/sub 2/O)/sub 6//sup 2 +/ quenches /sup 3/MBH/sup 2 +/. Net electron transfer accounts for less than 1/3 of total quenching by complexed Fe(II). In contrast, quenching by Fe(H/sub 2/O)/sub 6//sup 2 +/ goes essentially entirely with net electron transfer. It is concluded that quenching of triplet methylene blue by complexes proceeds via electron transfer which is reversible in the encounter complex. The MBH/sup +/ which results from net electron transfer from complexes of Fe(II) decays essentially entirely to MB/sup +/ via oxidation by complexed Fe(III); no disproportionation has been observed.

  12. Electron transfer at nickel electrode

    International Nuclear Information System (INIS)

    There is considerable contemporary interest in the electron transfer reaction. at active (transition) metal electrodes. this work reports the electrochemical behavior of potassium ferrocyanide at nickel electrode in aqueous potassium nitrate solution. Potassium ferrocyanide is frequently employed to probe one-electron transfer reactions at solid, electrodes. It was found that the voltammetric oxidation of ferrocyanide at nickel is a simple electron transfer reaction. Normal pulse voltammetry revealed similar behavior. (author)

  13. Electron transfer reactions of excited dyes with metal complexes. Progress report, May 1, 1976--January 31, 1977. [Fe(III)--thionine reaction

    Energy Technology Data Exchange (ETDEWEB)

    Lichtin, N.N.

    1977-02-01

    A study was initiated of the factors which determine quantum efficiency of transfer of reducing equivalents between excited dye molecules and metal complexes in their ground state and composition and dynamics of formation and decay of related photostationary states. A ruby laser capable of delivering a 3.6 J, 19 nsec flash was acquired and assembly of an apparatus for laser flash photolysis begun. At the same time, conventional flash photolysis was used to pursue investigation of the dependence upon solvent, anions, pH, and ionic strength of the kinetics of the spontaneous dark reaction of Fe(H/sub 2/O)/sup 3 +//sub 6/ with leucothionine and with semithionine, reactions which contribute to the composition and dynamics of formation and decay of the photostationary state of the iron-thionine photoredox reaction. Results are consistent with formation of an intermediate complex between leucothionine and Fe(III), K/sub A/ = 380 M/sup -1/ and k(elec. transfer) = 0.88 s/sup -1/ at approximately 22/sup 0/ in water solution at pH2, with sulfate as anion and ..mu.. = .05 - .1 M. Under similar conditions in 50 v/v percent aqueous CH/sub 3/CN, K/sub A/ = 780 M/sup -1/, k(elec. transfer) = 0.55 s/sup -1/. In both solvents, sulfate produces a large positive salt effect. Intermediacy of a complex was not established for the faster reaction of Fe(III) with semithionine under similar conditions: K/sub A/ . k(elec. transfer) approximately 3.5 x 10/sup 5/ M/sup -1/s/sup -1/ in H/sub 2/O, approximately 1.0 x 10/sup 4/ in 50 v/v percent aqueous CH/sub 3/CN.

  14. Symmetry characterization of electrons and lattice excitations

    Directory of Open Access Journals (Sweden)

    Schober H.

    2012-03-01

    Full Text Available Symmetry concerns all aspects of a physical system from the electronic orbitals to structural and magnetic excitations. In this article we will try to elaborate the fundamental connection between symmetry and excitations. As excitations are manyfold in physical systems it is impossible to treat them exhaustively. We thus concentrate on the two topics of Bloch electrons and phonons. These two examples are complementary in the sense that Bloch electrons describe single particles in an external periodic potential while phonons exemplify a decoupled system of interacting particles. The way we develop the argument gives as by-product a short account of molecular orbitals and molecular vibrations.

  15. Electron-impact excitation of silver

    Science.gov (United States)

    Toši?, S. D.; Pej?ev, V.; Ševi?, D.; McEachran, R. P.; Stauffer, A. D.; Marinkovi?, B. P.

    2015-05-01

    We measure the differential cross sections (DCSs) for the electron-impact excitation of the combined (two fine-structure levels) resonant 4 d105 p P 1 /2 ,3 /2 2 and 4 d95 s2D 5 /2 2 states in silver from the 4 d105 s S 1 /2 2 ground state. A comparison with the predictions of the relativistic distorted-wave (RDW) approximation model is carried out. Relativistic distorted-wave calculations are performed for each level separately and are combined to compare with the measurements. Both the experimental and theoretical results are obtained at incident electron energies E0 of 10, 20, 40, 60, 80, and 100 eV and scattering angles ? from 10° up to 150° (experiment) and from 0° to 180° (calculations). Absolute values for the experimental DCSs are obtained by normalizing relative DCSs to theoretical RDW results at 40° at all energies except at 10 eV, where we performed the normalization of the relative DCSs at 10° to our previous small-angle experimental DCS values [S. D. Toši? et al., Nucl. Instrum. Methods Phys. Res. Sect. B 279, 53 (2012), 10.1016/j.nimb.2011.10.066]. The integrated cross sections, which include integral QI, momentum transfer QM, and viscosity QV cross sections, are determined by numerical integration of the absolute DCSs.

  16. Medium effects in photoinduced electron transfer reactions

    International Nuclear Information System (INIS)

    The transfer of an electron between two molecules is a fundamental chemical process of great significance in biochemistry as well as in general chemistry. Electron transfer reactions can be induced by the absorption of light - as in photosynthesis - so that one of the molecules reacts through an electronically excited state; a net storage of chemical energy may then take place. When electron transfer involves molecules in condensed phase, the role of the liquid or solid medium must be considered. In the first place, a polar solvent may promote electron transfer through the stabilization of ion pairs and the separation of ions; but if the polar solvent must reorganize prior to the reaction, then an activation barrier will exist against electron transfer in polar solvents. This article gives a citical review of this field, with some novel ideas concerning the role of the medium (liquid solvent or solid matrix) in the overall energy balance of electron transfer, in the kinetics of the reaction, and in the further process of charge separation. It is suggested in particular that no dielectric screening by a polar solvent can exist when ions are formed in direct contact; and that the extensive reorganization of the solvent prior to electron transfer is so unlikely as to be discounted. In these respects the model presented in this article diverges from the commonly accepted model of Weller and of Marcus and Hush. In the Conclusion section some areas of particular importance for further research in this field are outlined. (author) 28 refs., 20 figs., 2 tabs

  17. Resonant electron transfer between quantum dots

    OpenAIRE

    Openov, Leonid A.

    1999-01-01

    An interaction of electromagnetic field with a nanostructure composed of two quantum dots is studied theoretically. An effect of a resonant electron transfer between the localized low-lying states of quantum dots is predicted. A necessary condition for such an effect is the existence of an excited bound state whose energy lies close to the top of the barrier separating the quantum dots. This effect may be used to realize the reversible quantum logic gate NOT if the superposi...

  18. Rate expressions for excitation transfer I. Radiationless transition theory perspective

    Science.gov (United States)

    Scholes, Gregory D.; Ghiggino, Kenneth P.

    1994-07-01

    The ideas concerning preparation of an initial state and its subsequent temporal evolution are discussed with reference to interchromophore electronic excitation (energy) transfer (EET), particularly the ``resonance'' case. The cases of strong and weak coupling, and their consequences, are discussed. It is shown that when the interactions between two identical chromophores lie in the weak coupling regime, then a rate of excitation transfer may be defined on an experimental time scale and is given by a Fermi golden rule expression; the quasicontinuous final state being provided primarily by nonradiative line broadening. In general, such a rate expression applies so long as the donor-acceptor electronic coupling is less than the vibronic band width. The strong coupling limit is shown to result in excimer or exciplex-type emission. A rate equation formalizing donor-acceptor EET in general is determined by consideration of the Green's function methods of scattering theory. The role of nuclear coordinates, including the possibility of Herzberg-Teller coupling, and the influence of nonradiative processes are examined.

  19. High resolution studies of electron capture and excitation by 00 projectile electron spectroscopy

    International Nuclear Information System (INIS)

    A tandem 450 parallel-plate spectrometer has been developed for high resolution electron studies of atomic collision processes using the method of 00 electron spectroscopy. High resolution projectile K-Auger electron spectra have been obtained in a state-selective study of transfer-excitation (TE) and single excitation in collisions of 4.5-33 MeV F6+ with He and H2 targets. A high resolution measurement of 9.5 MeV F7+ with He yielded preliminary information on state-selective capture to the metastable F7+ (1s2s) state. Future plans include studies of Fq+ + T (q: 6-9; T: H2, He, Ne) to determine absolute state-selective cross sections for transfer-excitation, single and double electron capture. (orig.)

  20. Electron-beam-excited gas laser research

    International Nuclear Information System (INIS)

    Net energy gain in laser fusion places requirements on the laser that are not realized by any existing laser. Utilization of relativistic electron beams (REB's), a relatively new source for the excitation of gas laser media, may lead to new lasers that could satisfy these requirements. Already REB's have been utilized to excite gas laser media and produce gas lasers that have not been produced as successfully any other way. Electron-beam-excitation has produced electronic-transition dimer lasers that have not yet been produced by any other excitation scheme (for example, Xe2/ sup *(1)/, Kr:O(21S)/sup 2/, KrF/sup *(3)/). In addition, REB's have initiated chemical reactions to produce HF laser radiation with unique and promising results. Relativistic-electron-beam gas-laser research is continuing to lead to new lasers with unique properties. Results of work carried out at Sandia Laboratories in this pioneering effort of electron-beam-excited-gas lasers are reviewed. (U.S.)

  1. Photoinduced energy and electron transfer in rubrene-benzoquinone and rubrene-porphyrin systems

    KAUST Repository

    Khan, Jafar Iqbal

    2014-11-01

    Excited-state electron and energy transfer from singlet excited rubrene (Ru) to benzoquinone (BQ) and tetra-(4-aminophenyl) porphyrin (TAPP) were investigated by steady-state absorption and emission, time-resolved transient absorption, and femtosecond (fs)-nanosecond (ns) fluorescence spectroscopy. The low reduction potential of BQ provides the high probability of electron transfer from the excited Ru to BQ. Steady-state and time-resolved results confirm such an excited electron transfer scenario. On the other hand, strong spectral overlap between the emission of Ru and absorption of TAPP suggests that energy transfer is a possible deactivation pathway of the Ru excited state.

  2. Excitations and benchmark ensemble density functional theory for two electrons

    Energy Technology Data Exchange (ETDEWEB)

    Pribram-Jones, Aurora; Burke, Kieron [Department of Chemistry, University of California-Irvine, Irvine, California 92697 (United States); Yang, Zeng-hui; Ullrich, Carsten A. [Department of Physics and Astronomy, University of Missouri, Columbia, Missouri 65211 (United States); Trail, John R.; Needs, Richard J. [Theory of Condensed Matter Group, Cavendish Laboratory, University of Cambridge, Cambridge CB3 0HE (United Kingdom)

    2014-05-14

    A new method for extracting ensemble Kohn-Sham potentials from accurate excited state densities is applied to a variety of two-electron systems, exploring the behavior of exact ensemble density functional theory. The issue of separating the Hartree energy and the choice of degenerate eigenstates is explored. A new approximation, spin eigenstate Hartree-exchange, is derived. Exact conditions that are proven include the signs of the correlation energy components and the asymptotic behavior of the potential for small weights of the excited states. Many energy components are given as a function of the weights for two electrons in a one-dimensional flat box, in a box with a large barrier to create charge transfer excitations, in a three-dimensional harmonic well (Hooke's atom), and for the He atom singlet-triplet ensemble, singlet-triplet-singlet ensemble, and triplet bi-ensemble.

  3. Excitations and benchmark ensemble density functional theory for two electrons

    CERN Document Server

    Pribram-Jones, Aurora; Trail, John R; Burke, Kieron; Needs, Richard J; Ullrich, Carsten A

    2014-01-01

    A new method for extracting ensemble Kohn-Sham potentials from accurate excited state densities is applied to a variety of two electron systems, exploring the behavior of exact ensemble density functional theory. The issue of separating the Hartree energy and the choice of degenerate eigenstates is explored. A new approximation, spin eigenstate Hartree-exchange (SEHX), is derived. Exact conditions that are proven include the signs of the correlation energy components, the virial theorem for both exchange and correlation, and the asymptotic behavior of the potential for small weights of the excited states. Many energy components are given as a function of the weights for two electrons in a one-dimensional flat box, in a box with a large barrier to create charge transfer excitations, in a three-dimensional harmonic well (Hooke's atom), and for the He atom singlet-triplet ensemble, singlet-triplet-singlet ensemble, and triplet bi-ensemble.

  4. Neutral excitations in quasi-1D strongly correlated electron systems

    International Nuclear Information System (INIS)

    Novel neutral spin-0 excitation for quasi-1D systems with one electron per site are obtained within a localized scheme. Our ground state wave-function is defined by a variational localized - site cluster - expanded ansatz and these excitations are naturally built upon it. All computations are easily carried out by a transfer matrix technique that enables explicit inclusion of electron - correlation effects and, at the same time, provides a quasi - particle band - theoretic picture of these excitations. This treatment is applied, in particular, to a polyphene strip. At k=0 the energy gap corresponds to a dipole-allowed transition in the visible region, our result compares fairly well with observed decreasing transitions for finite polyphene strips. (author). 14 refs, 1 fig

  5. Electron impact excitation of helium atoms

    International Nuclear Information System (INIS)

    Two experiments have been conducted in an apparatus which was designed and constructed to study interactions between electrons and atoms. (1) The polarisation fraction of the ultra violet radiation emitted following electron impact excitation of the n1P states of helium atoms has been deduced from measurements of the angular distribution of the photons for incident electron energies from 40eV to 300eV. (2) Angular correlations between the scattered electrons resulting from the excitation of the 21P state of helium and the photons emitted in the decay of this state have been measured using the delayed coincidence technique for an incident energy of 81.2eV. The measurements extend over the electron scattering angles from 10 deg to 130 deg. (author)

  6. Electronic excitation of Na atom by electron impact

    International Nuclear Information System (INIS)

    Electronic excitation of the 3s-3p transition in the Na atom was studied by intermediate energy electron impact spectroscopy. Differential Cross Sections (DCS) and Generalized Oscillator Strenghts (GOS) were determined experimentally for 1 KeV electrons. Theoretical results within the First Born Approximation as well as Glauber theory, were also performed. (A.C.A.S.)

  7. Coherence in electron-impact excitation of helium

    International Nuclear Information System (INIS)

    This thesis describes an experimental study into the electron-impact excitation to the 33P, 31D and 33D states of Helium. The scattered electron and the photon, emitted by the excited atom, are measured in coincidence. The parameters, which can be varied, are the scattering angle and the kinetic energy of the projectile. Two parameters, which are used to characterize the excited state, are the angular momentum transferred to the atom, L perpendicular, and the alignment angle ?. It is shown that results of measurements on 31D excitation with photon detection perpendicular to the scattering plane do not agree in the small scattering angle region with any of the model calculations currently available. Remarkable is the sign of L perpendicular, which appears to start of negatively at 60 eV. It is shown that for 33P excitation the predicted large value of ? is indeed found experimentally. This supports the suggestion that exchange scattering is underestimated in model calculations for 1P excitation. Another result is that for 1P and 3P excitation the behaviour of L perpendicular as a function of the scattering angle can be related at different impact energies with the help of a partial wave expansion. A scaling relation can be formulated for the behaviour of L perpendicular. The influence of a negative ion resonance to excitation of the 33D state is investigated. Both in coincidence and non-coincidence measurements the presence of the resonance yields information on both the direct and indirect excitation of the 33D state. It is shown that the coincident measurement gives an unique opportunity to determine the excited 33D state completely. Results of measurements with photon detection in the scattering plane are given. They supplement previous 31D and 33D results and allow physical parameters, such as L perpendicular and ?, to be obtained. (H.W.). 132 refs.; 20 figs.; 18 tabs

  8. Electron-impact vibrational excitation of cyclopropane

    Science.gov (United States)

    ?urík, R.; ?ársky, P.; Allan, M.

    2015-04-01

    We report a very detailed test of the ab initio discrete momentum representation (DMR) method of calculating vibrational excitation of polyatomic molecules by electron impact, by comparison of its results with an extensive set of experimental data, covering the entire range of scattering angles from 10? to 180? and electron energies from 0.4 to 20 eV. The DMR calculations were carried out by solving the two-channel Lippmann-Schwinger equation in the momentum space, and the interaction between the scattered electron and the target molecule was described by exact static-exchange potential corrected by a density functional theory (DFT) correlation-polarization interaction that models target's response to the field of incoming electron. The theory is found to quantitatively reproduce the measured spectra for all normal modes, even at the difficult conditions of extreme angles and at low energies, and thus provides full understanding of the excitation mechanism. It is shown that the overlap of individual vibrational bands caused by limited experimental resolution and rotational excitation must be properly taken into account for correct comparison of experiment and theory. By doing so, an apparent discrepancy between published experimental data could be reconciled. A substantial cross section is found for excitation of the non-symmetric HCH twisting mode ?4 of A1 ? symmetry by the 5.5 eV A2 ' resonance, surprisingly because the currently accepted selection rules predict this process to be forbidden. The DMR theory shows that the excitation is caused by an incoming electron in an f-wave of A2 ' symmetry which causes excitation of the non-symmetric HCH twisting mode ?4 of the A1 ? symmetry and departs in p- and f-waves of A2 ? symmetry.

  9. How Geometric Distortions Scatter Electronic Excitations in Conjugated Macromolecules.

    Science.gov (United States)

    Shi, Tian; Li, Hao; Tretiak, Sergei; Chernyak, Vladimir Y

    2014-11-20

    Effects of disorder and exciton-phonon interactions are the major factors controlling photoinduced dynamics and energy-transfer processes in conjugated organic semiconductors, thus defining their electronic functionality. All-atom quantum-chemical simulations are potentially capable of describing such phenomena in complex "soft" organic structures, yet they are frequently computationally restrictive. Here we efficiently characterize how electronic excitations in branched conjugated molecules interact with molecular distortions using the exciton scattering (ES) approach as a fundamental principle combined with effective tight-binding models. Molecule geometry deformations are incorporated to the ES view of electronic excitations by identifying the dependence of the Frenkel-type exciton Hamiltonian parameters on the characteristic geometry parameters. We illustrate our methodology using two examples of intermolecular distortions, bond length alternation and single bond rotation, which constitute vibrational degrees of freedom strongly coupled to the electronic system in a variety of conjugated systems. The effect on excited-state electronic structures has been attributed to localized variation of exciton on-site energies and couplings. As a result, modifications of the entire electronic spectra due to geometric distortions can be efficiently and accurately accounted for with negligible numerical cost. The presented approach can be potentially extended to model electronic structures and photoinduced processes in bulk amorphous polymer materials. PMID:26276475

  10. Femtosecond Timescale Evolution of Pyrrole Electronic Excitation

    Science.gov (United States)

    Montero, Raul; Conde, Alvaro Peralta; Ovejas, Virginia; Castano, Fernando; Longarte, Asier

    2012-06-01

    Pyrrole is a simple aromatic molecule with relevantchromophoric properties in biology. Although its apparent simplicity, it shows a complicated dynamics after excitation in the near part of the UV absorption spectrum, which results from the interplay between the bright ??^* and the dark dissociative ??^* electronic transitions. Herein, we present a time resolved study with ultrafast resolution on the relaxation dynamics of isolated pyrrole, after excitation in the 265-217 nm range. Two lifetimes of 19 and 15 fs, which are associated with the internal conversion from the bright 1B2 ??^* state and the propagation of the wavepacket on the ??^* state, respectively, are found in the studied energy interval. The work also explores the consequences of non resonant adiabatic excitation of the system when broadband femtosecond pulses are employed to prepare the molecule in the targeted electronic states, revealing the key implication of this type of coherent phenomena. The collected data reveal that the bright 1B2 ??^* state is adiabatically populated at excitation wavelengths far away from resonance, providing an efficient way to reach the ??^* state. The recorded transients are fit employing a coherent model that provides a comprehensive view of the dynamical processes pyrrole undergoes after excitation by ultrashort light pulses. M. N. R. Ashfold, B. Cronin, A. L. Devine, R. N. Dixon and M. G. D. Nix Science, 312, 1637-1640, 2006.

  11. Electronic excitation of methane molecule by electron impact

    International Nuclear Information System (INIS)

    In this work, it is presented elastic and inelastic differential cross sections for the electronic excitation of the Triplet (3T2) of CH4 molecule calculated for electron incident energies of 20 and 30 eV. It is employed the Schwinger multichannel method and these results are compared to the ones available in the literature. (A.C.A.S.)

  12. Electron spectroscopy of collisional excited atoms

    International Nuclear Information System (INIS)

    In this thesis measurements are described in which coincidences are detected between scattered projectiles and emitted electrons. This yields information on two-electron excitation processes. In order to show what can be learnt from coincidence experiments a detailed theoretical analysis is given. The transition amplitudes, which contain all the information, are introduced (ch.2). In ch.3 the experimental set-up is shown. The results for the Li+-He system are shown in ch. 7 and are compared with predictions based on the Molecular-Orbitalmodel which however does not account for two-excitation mechanisms. With the transition amplitudes also the wave function of the excited atom has been completely determined. In ch.8 the shape of the electron cloud, induced by the collision, is derived from the amplitudes. The relation between the oscillatory motion of this cloud after the collision and the correlation between the two electrons of the excited atom is discussed. In ch. 6 it is shown that the broad structures in the non-coincident energy spectra of the Li+-He system are erroneously interpretated as a result of electron emission from the (Li-He)+-quasimolecule. A model is presented which explains, based on the results obtained from the coincidence measurements, these broad structures. In ch. 4 the Post-Collision Interaction process is treated. It is shown that for high-energy collisions, in contrast with general assumptions, PCI is important. In ch. 5 the importance of PCI-processes in photoionization of atoms, followed by Auger decay, are studied. From the formulas derived in ch. 4 simple analytical results are obtained. These are applied to recent experiments and good agreement is achieved. 140 refs.; 55 figs.; 9 tabs

  13. An excitable electronic circuit as a sensory neuron model

    CERN Document Server

    Medeiros, Bruno N S; Mindlin, Gabriel B; Copelli, Mauro; Leite, José R Rios

    2011-01-01

    An electronic circuit device, inspired on the FitzHugh-Nagumo model of neuronal excitability, was constructed and shown to operate with characteristics compatible with those of biological sensory neurons. The nonlinear dynamical model of the electronics quantitatively reproduces the experimental observations on the circuit, including the Hopf bifurcation at the onset of tonic spiking. Moreover, we have implemented an analog noise generator as a source to study the variability of the spike trains. When the circuit is in the excitable regime, coherence resonance is observed. At sufficiently low noise intensity the spike trains have Poisson statistics, as in many biological neurons. The transfer function of the stochastic spike trains has a dynamic range of 6 dB, close to experimental values for real olfactory receptor neurons.

  14. Electronic excitation as a mode of heat dissipation in laser-driven cluster plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Rajeev, R.; Rishad, K. P. M.; Madhu Trivikram, T.; Krishnamurthy, M. [Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai-5 (India)

    2013-12-15

    Electrons streaming out of laser plasma are known for non-local heat transport and energy deposition by the ionization wave. At 100 eV electron temperature, since the electronic excitation cross section is comparable to that of ionization for Ar and CO{sub 2}, a non-local excitation wave akin to the ionization wave is envisaged where energy deposition in excitations forms a excited cluster sheath beyond the laser focus. Here, we show that nano-cluster systems have the right parameters to form such an exciton sheath and experimentally demonstrate this via charge transfer reactions.

  15. Electron impact excitation of SF6

    Science.gov (United States)

    Trajmar, S.; Chutjian, A.

    1977-01-01

    A study of the electron impact energy-loss spectrum of SF6 under both optical (low scattering angle, high impact energy) and non-optical conditions (high scattering angle, low impact energy) has revealed a number of electronic excitation processes. With the help of theoretical calculations, several of these transitions have been assigned and approximate cross sections associated with four features have been determined. In addition, a strong resonance at 12 eV has been observed in both elastic and vibrationally inelastic (delta E = 0.092 eV) channels.

  16. Theory of plasmon enhanced interfacial electron transfer

    Science.gov (United States)

    Wang, Luxia; May, Volkhard

    2015-04-01

    A particular attempt to improve the efficiency of a dye sensitized solar cell is it's decoration with metal nano-particles (MNP). The MNP-plasmon induced enhancement of the local field enlarges the photoexcitation of the dyes and a subsequent improvement of the charge separation efficiency may result. In a recent work (2014 J. Phys. Chem. C 118 2812) we presented a theory of plasmon enhanced interfacial electron transfer for perylene attached to a TiO2 surface and placed in the proximity of a spherical MNP. These earlier studies are generalized here to the coupling of to up to four MNPs and to the use of somewhat altered molecular parameters. If the MNPs are placed close to each other strong hybridization of plasmon excitations appears and a broad resonance to which molecular excitations are coupled is formed. To investigate this situation the whole charge injection dynamics is described in the framework of the density matrix theory. The approach accounts for optical excitation of the dye coupled to the MNPs and considers subsequent electron injection into the rutile TiO2-cluster. Using a tight-binding model for the TiO2-system with about 105 atoms the electron motion in the cluster is described. We again consider short optical excitation which causes an intermediate steady state with a time-independent overall probability to have the electron injected into the cluster. This probability is used to introduce an enhancement factor which rates the influence of the MNP. Values larger than 500 are obtained.

  17. Testing time-dependent density functional theory with depopulated molecular orbitals for predicting electronic excitation energies of valence, Rydberg, and charge-transfer states and potential energies near a conical intersection

    International Nuclear Information System (INIS)

    Kohn-Sham (KS) time-dependent density functional theory (TDDFT) with most exchange-correlation functionals is well known to systematically underestimate the excitation energies of Rydberg and charge-transfer excited states of atomic and molecular systems. To improve the description of Rydberg states within the KS TDDFT framework, Gaiduk et al. [Phys. Rev. Lett. 108, 253005 (2012)] proposed a scheme that may be called HOMO depopulation. In this study, we tested this scheme on an extensive dataset of valence and Rydberg excitation energies of various atoms, ions, and molecules. It is also tested on a charge-transfer excitation of NH3-F2 and on the potential energy curves of NH3 near a conical intersection. We found that the method can indeed significantly improve the accuracy of predicted Rydberg excitation energies while preserving reasonable accuracy for valence excitation energies. However, it does not appear to improve the description of charge-transfer excitations that are severely underestimated by standard KS TDDFT with conventional exchange-correlation functionals, nor does it perform appreciably better than standard TDDFT for the calculation of potential energy surfaces

  18. Testing time-dependent density functional theory with depopulated molecular orbitals for predicting electronic excitation energies of valence, Rydberg, and charge-transfer states and potential energies near a conical intersection

    Energy Technology Data Exchange (ETDEWEB)

    Li, Shaohong L.; Truhlar, Donald G., E-mail: truhlar@umn.edu [Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455 (United States)

    2014-09-14

    Kohn-Sham (KS) time-dependent density functional theory (TDDFT) with most exchange-correlation functionals is well known to systematically underestimate the excitation energies of Rydberg and charge-transfer excited states of atomic and molecular systems. To improve the description of Rydberg states within the KS TDDFT framework, Gaiduk et al. [Phys. Rev. Lett. 108, 253005 (2012)] proposed a scheme that may be called HOMO depopulation. In this study, we tested this scheme on an extensive dataset of valence and Rydberg excitation energies of various atoms, ions, and molecules. It is also tested on a charge-transfer excitation of NH{sub 3}-F{sub 2} and on the potential energy curves of NH{sub 3} near a conical intersection. We found that the method can indeed significantly improve the accuracy of predicted Rydberg excitation energies while preserving reasonable accuracy for valence excitation energies. However, it does not appear to improve the description of charge-transfer excitations that are severely underestimated by standard KS TDDFT with conventional exchange-correlation functionals, nor does it perform appreciably better than standard TDDFT for the calculation of potential energy surfaces.

  19. Tautomeric selectivity of the excited-state lifetime of guanine/cytosine base pairs: The role of electron-driven proton-transfer processes

    OpenAIRE

    Sobolewski, Andrzej L.; Domcke, Wolfgang; Hättig, C.

    2005-01-01

    The UV spectra of three different conformers of the guanine/cytosine base pair were recorded recently with UV-IR double-resonance techniques in a supersonic jet [Abo-Riziq, A., Grace, L., Nir, E., Kabelac, M., Hobza, P. & de Vries, M. S. (2005) Proc. Natl. Acad. Sci. USA 102, 20–23]. The spectra provide evidence for a very efficient excited-state deactivation mechanism that is specific for the Watson–Crick structure and may be essential for the photostability of DNA. Here we report results of...

  20. Motional effects on the efficiency of excitation transfer

    CERN Document Server

    Asadian, Ali; Guerreschi, Gian Giacomo; Cai, Jianming; Popescu, Sandu; Briegel, Hans J

    2010-01-01

    Energy transfer plays a vital role in many natural and technological processes. In this work, we study the effects of mechanical motion on the excitation transfer through a chain of interacting molecules with application to the biological scenario of energy transfer in $\\alpha$-helices. Our investigation demonstrates that, for various types of mechanical oscillations, the transfer efficiency is significantly enhanced over that of comparable static configurations. This enhancement is a genuine quantum signature, and requires the collaborative interplay between the quantum-coherent evolution of the excitation and the mechanical motion of the molecules via their distance-dependent coupling; it has no analogue in the classical incoherent energy transfer. This effect may not only occur naturally, but it could be exploited in artificially designed systems to optimize transport processes. As an application, we discuss simple and hence robust control techniques.

  1. Motional effects on the efficiency of excitation transfer

    International Nuclear Information System (INIS)

    Energy transfer plays a vital role in many natural and technological processes. In this work, we study the effects of mechanical motion on the excitation transfer through a chain of interacting molecules with applications to biological scenarios of transfer processes. Our investigation demonstrates that, for various types of mechanical oscillations, the transfer efficiency is significantly enhanced over that of comparable static configurations. This enhancement is a genuine quantum signature and requires the collaborative interplay between the quantum-coherent evolution of the excitation and the mechanical motion of the molecules; it has no analogue in the classical incoherent energy transfer. This effect may not only occur naturally but also be exploited in artificially designed systems to optimize transport processes. As an application, we discuss a simple and hence robust control technique.

  2. Motional effects on the efficiency of excitation transfer

    Energy Technology Data Exchange (ETDEWEB)

    Asadian, Ali; Tiersch, Markus; Guerreschi, Gian Giacomo; Cai, Jianming; Briegel, Hans J [Institut fuer Theoretische Physik, Universitaet Innsbruck, Technikerstrasse 25, A-6020 Innsbruck (Austria); Popescu, Sandu, E-mail: hans.briegel@uibk.ac.a [H H Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom)

    2010-07-15

    Energy transfer plays a vital role in many natural and technological processes. In this work, we study the effects of mechanical motion on the excitation transfer through a chain of interacting molecules with applications to biological scenarios of transfer processes. Our investigation demonstrates that, for various types of mechanical oscillations, the transfer efficiency is significantly enhanced over that of comparable static configurations. This enhancement is a genuine quantum signature and requires the collaborative interplay between the quantum-coherent evolution of the excitation and the mechanical motion of the molecules; it has no analogue in the classical incoherent energy transfer. This effect may not only occur naturally but also be exploited in artificially designed systems to optimize transport processes. As an application, we discuss a simple and hence robust control technique.

  3. Combustion enhancement through electronically excited oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Zaehringer, K.; Thevenin, D. [Otto-von-Guericke-Universitaet, Magdeburg (Germany). Lehrstuhl fuer Stroemungsmechanik und Stroemungstechnik; Bourig, A.; Martin, J.P. [ICARE, CNRS, Orleans (France)

    2009-07-01

    The promoting action of electrical discharges on combustion processes results in the reduction of the ignition delay, improvement of flame stability as well as extension of the flammability limits. These features are key technical issues for combustion improvement. One particularly promising approach consists of plasma-enhanced activation of the oxidizing substance, such as when transforming molecular oxygen into its electronically excited singlet delta O{sub 2}(a{sup 1}{delta}{sub g}) and singlet sigma O{sub 2}(b{sup 1}{sigma}{sub g}{sup +}) states. In contrast with non-excited reactants, singlet oxygen molecules display a higher chemical activity and can affect reaction kinetics due to a decrease of the energy barrier associated with endo-energetic reactions, as demonstrated theoretically and numerically [1]. The aim of the present study is to understand experimentally why and how combustion processes are modified in the presence of electronically-excited oxygen molecules, using spontaneous emission of typical flame front marker molecules. (orig.)

  4. Orbital-selective electronic excitations in iron arsenides revealed by simulated nonresonant inelastic x-ray scattering

    Science.gov (United States)

    Tsutsui, Kenji; Kaneshita, Eiji; Tohyama, Takami

    2015-11-01

    Nonresonant inelastic x-ray scattering (NIXS) is a possible tool to detect charge excitations in electron systems. In addition, multipole transitions at high-momentum-transfer regions open a new possibility to determine orbital-selective electronic excitations in multiorbital itinerant 3 d electron systems. As a theoretical example, we choose the antiferromagnetic state of iron arsenides and demonstrate that the orbital-selective excitations are detectable by choosing appropriate momentum transfer in NIXS. We propose that both NIXS and resonant inelastic x-ray scattering are complementary to each other for fully understanding the nature of orbital excitations in multiorbital itinerant electron systems.

  5. Reactive scattering of electronically excited alkali atoms with molecules

    Energy Technology Data Exchange (ETDEWEB)

    Mestdagh, J.M.; Balko, B.A.; Covinsky, M.H.; Weiss, P.S.; Vernon, M.F.; Schmidt, H.; Lee, Y.T.

    1987-06-01

    Representative families of excited alkali atom reactions have been studied using a crossed beam apparatus. For those alkali-molecule systems in which reactions are also known for ground state alkali and involve an early electron transfer step, no large differences are observed in the reactivity as Na is excited. More interesting are the reactions with hydrogen halides (HCl): it was found that adding electronic energy into Na changes the reaction mechanism. Early electron transfer is responsible of Na(5S, 4D) reactions, but not of Na(3P) reactions. Moreover, the NaCl product scattering is dominated by the HCl/sup -/ repulsion in Na(5S, 4D) reactions, and by the NaCl-H repulsion in the case of Na(3P). The reaction of Na with O/sub 2/ is of particular interest since it was found to be state specific. Only Na(4D) reacts, and the reaction requires restrictive constraints on the impact parameter and the reactants' relative orientation. The reaction with NO/sub 2/ is even more complex since Na(4D) leads to the formation of NaO by two different pathways. It must be mentioned however, that the identification of NaO as product in these reactions has yet to be confirmed.

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

    Science.gov (United States)

    Egidi, Franco; Segado, Mireia; Koch, Henrik; Cappelli, Chiara; Barone, Vincenzo

    2014-12-01

    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-?*, ?-?*, 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.

  7. 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-?{sup *}, ?-?{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.

  8. Efficiency of excitation transfer in photosynthesis under quantum coherence

    CERN Document Server

    Olaya-Castro, Alexandra; Fassioli-Olsen, Francesca; Johnson, Neil F

    2007-01-01

    We investigate the role of quantum coherence in the efficiency of excitation transfer in a spin-star arrangement of interacting two-level systems, mimicking a light-harvesting antenna connected to a reaction center, similar to a photosynthetic system in nature. By using the quantum jump approach, we show that the efficiency depends intimately on the quantum interference among states in which the excitation is localized on individual sites in the antenna. Our results indicate how efficiency may be used as an indication of quantum coherence in energy transfer.

  9. Convoy electrons emitted from resonant coherently excited ions

    Energy Technology Data Exchange (ETDEWEB)

    Kimura, K.; Gibbons, J.P.; Elston, S.B.; Biedermann, C.; DeSerio, R.; Keller, N.; Levin, J.C.; Breinig, M.; Burgdoerfer, J.; Sellin, I.A. (Department of Physics, University of Tennessee, Knoxville, Tennessee 37996-1200 an (US) Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6377)

    1991-01-07

    We demonstrate the use of selective excitation of fast ions by resonant coherent excitation as a new technique to study convoy electron production. It is shown that electron loss from excited states plays an important role in convoy electron production by fast-channeled ions. The absolute cross section for convoy production by hydrogenic ions in {ital n}=2 states is derived from the dtaa, as is an estimate of the absolute probability of resonant coherent excitation as a function of ion energy.

  10. Efficient deactivation of a model base pair via excited-state hydrogen transfer.

    Science.gov (United States)

    Schultz, Thomas; Samoylova, Elena; Radloff, Wolfgang; Hertel, Ingolf V; Sobolewski, Andrzej L; Domcke, Wolfgang

    2004-12-01

    We present experimental and theoretical evidence for an excited-state deactivation mechanism specific to hydrogen-bonded aromatic dimers, which may account, in part, for the photostability of the Watson-Crick base pairs in DNA. Femtosecond time-resolved mass spectroscopy of 2-aminopyridine clusters reveals an excited-state lifetime of 65 +/- 10 picoseconds for the near-planar hydrogen-bonded dimer, which is significantly shorter than the lifetime of either the monomer or the 3- and 4-membered nonplanar clusters. Ab initio calculations of reaction pathways and potential-energy profiles identify the mechanism of the enhanced excited-state decay of the dimer: Conical intersections connect the locally excited 1pipi* state and the electronic ground state with a 1pipi* charge-transfer state that is strongly stabilized by the transfer of a proton. PMID:15576616

  11. Theoretical characterization of excitation energy transfer in chlorosome light-harvesting antennae from green sulfur bacteria

    CERN Document Server

    Fujita, Takatoshi; Saikin, Semion K; Brookes, Jennifer C; Aspuru-Guzik, Alan

    2013-01-01

    Chlorosomes are the largest and most efficient natural light-harvesting antenna systems. They contain thousands of pigment molecules - bacteriochlorophylls (BChls)- that are organized into supramolecular aggregates and form a very efficient network for excitonic energy migration. Here, we present a theoretical study of excitation energy transfer (EET) in the chlorosome based on experimental evidence of the molecular assembly. Our model for the exciton dynamics throughout the antenna combines a stochastic time propagation of the excitonic wave function with molecular dynamics simulations of supramolecular structure, and electronic structure calculations of the excited states. The simulation results reveal a detailed picture of the EET in the chlorosome. Coherent energy transfer is significant only for the first 50 fs after the initial excitation, and the wavelike motion of the exciton is completely damped at 100 fs. Characteristic time constants of incoherent energy transfer, subsequently, vary from 1 ps to se...

  12. Excitation transfer in atom collisions in helium-neon plasma

    International Nuclear Information System (INIS)

    Due to creation of new types of lasers experimental data on inelastic He* + Ne collisions and results of a theoretic analysis of processes of excitation transfer under atomic collisions in neon-helium plasma are presented. 94 refs., 10 figs., 7 tabs

  13. Electron-electron interactions in K-shell excitation of F6+ ions in fast collisions with H2 targets

    International Nuclear Information System (INIS)

    K-shell excitation of F6+(1s22s) projectile ions in collisions with H2 targets has been studied by measuring 0 degree state-resolved Auger electron production cross sections in the projectile energy range of 0.25 to 2 MeV/u. Projectile 1s?2p excitation due to the interaction with a ''target electron'' (electron-electron Excitation1 [eeE]) has been observed in the production of the 1s(2s2p3P)2P- and 1s(2s2p1P)2P+ states as well as 1s2s2p4P state above the electron impact threshold. Projectile excitation is also produced by the target nucleus (electron-nucleus Excitation [enE]) for the 2P± states. The eeE and enE cross sections were evaluated by Impulse Approximation (IA) and PWBA, respectively. The total KLL Auger electron production cross sections were also determined and exhibited the overall electron-electron interaction effects of eeE and Resonant-Transfer Excitation (RTE) which, in particular, is the 1s?2p excitation with 2p capture to result in 1s2s2p23,1D states

  14. Excited-state intramolecular charge transfer in 9-aminoacridine derivative.

    Science.gov (United States)

    Pereira, Robson Valentim; Garcia Ferreira, Ana Paula; Gehlen, Marcelo Henrique

    2005-07-14

    A new fluorochromic dye was obtained from the reaction of 9-aminoacridine with ethyl-2-cyano-3-ethoxyacrylate. It displays complex fluorescence that is ascribed to normal emission from the acridine chromophore in addition to excited-state intramolecular charge transfer (ESICT) formed upon light excitation. The analysis of the fluorescence decays in different solvents reveals two short-lived components in the range of 80-450 ps and 0.7-3.2 ns, ascribed to the formation and decay of the intramolecular charge transfer (ICT) state, in addition to a third component of about 9.0 ns, which is related to the normal emission from the acridine singlet excited state, probably in an enol-imine tautomeric form. The ICT emission is readily quenched by water addition to polar solvents, and this effect is ascribed to changes in the keto-amine/enol-imine equilibrium of this fluorochromic dye. PMID:16833932

  15. An Accurate and Linear Scaling Method to Calculate Charge-Transfer Excitation Energies and Diabatic Couplings

    CERN Document Server

    Pavanello, Michele; Visscher, Lucas; Neugebauer, Johannes

    2012-01-01

    Quantum--Mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those charge transfer excitations that take place between non-covalently bound molecules. In particular, we present a method that scales linearly with the number of non-covalently bound molecules in the system and is based on a two-pronged approach: The molecular electronic structure of broken-symmetry charge-localized states is obtained with the Frozen Density Embedding formulation of subsystem Density-Functional Theory; subsequently, in a post-SCF calculation, the full-electron Hamiltonian and overlap matrix elements among the charge-localized states are evaluated with an algorithm which takes full advantage of the subsystem DFT density partitioning technique. The method is benchmarked against Coupled-Cluster calculations and achieves chemical accuracy for the systems considered...

  16. Light induced electron transfer reactions of metal complexes

    International Nuclear Information System (INIS)

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

  17. Separating annihilation and excitation energy transfer dynamics in light harvesting systems.

    Science.gov (United States)

    Vengris, Mikas; Larsen, Delmar S; Valkunas, Leonas; Kodis, Gerdenis; Herrero, Christian; Gust, Devens; Moore, Thomas; Moore, Ana; van Grondelle, Rienk

    2013-09-26

    The dependence of excitation energy transfer kinetics on the electronic state of the acceptor (ground vs excited) has been resolved with a novel multipulse prePump-Pump-Probe spectroscopy. The primary energy transfer and annihilation dynamics in two model light-harvesting systems were explored: an artificially synthesized carotenoid-zinc-phthalocyanine dyad and a naturally occurring light-harvesting peridinin-chlorophyll protein complex from Amphidinium carterae. Both systems use carotenoid as the primary excitation energy donor with porphyrin chromophores as the acceptor molecules. The prePump-Pump-Probe transient signals were analyzed with Monte Carlo modeling to explicitly address the underlying step-by-step kinetics involved in both excitation migration and annihilation processes. Both energy transfer and annihilation dynamics were demonstrated to occur with approximately the same rate in both systems, regardless of the excitation status of the acceptor pigments. The possible reasons for these observations are discussed in the framework of the Förster energy transfer model. PMID:23662680

  18. Energy traps of excited energy transfer processes in polymer solids

    International Nuclear Information System (INIS)

    In this report, the singlet and triplet exciton behaviors of the polymers containing carbazole (Cz) or phenanthrene (Ph) chromophores as the side group were studied in the solid state. The role of electronic energy traps in energy transfer process will be discussed and controlling factors of energy transfer processes will be given

  19. Vibration-translation energy transfer in vibrationally excited diatomic molecules

    International Nuclear Information System (INIS)

    A semiclassical collision model is applied to the study of energy transfer rates between a vibrationally excited diatomic molecule and a structureless atom. The molecule is modeled as an anharmonic oscillator with a multitude of dynamically coupled vibrational states. Three main aspects in the prediction of vibrational energy transfer rates are considered. The applicability of the semiclassical model to an anharmonic oscillator is first evaluated for collinear encounters. Second, the collinear semiclassical model is applied to obtain numerical predictions of the vibrational energy transfer rate dependence on the initial vibrational state quantum number. Thermally averaged vibration-translation rate coefficients are predicted and compared with CO-He experimental values for both ground and excited initial states. The numerical model is also used as a basis for evaluating several less complete but analytic models. Third, the role of rational motion in the dynamics of vibrational energy transfer is examined. A three-dimensional semiclassical collision model is constructed with coupled rotational motion included. Energy transfer within the molecule is shown to be dominated by vibration-rotation transitions with small changes in angular momentum. The rates of vibrational energy transfer in molecules with rational frequencies that are very small in comparison to their vibrational frequency are shown to be adequately treated by the preceding collinear models

  20. Intra- and intermolecular energy transfer in highly excited ozone complexes.

    Science.gov (United States)

    Ivanov, Mikhail V; Grebenshchikov, Sergy Yu; Schinke, Reinhard

    2004-06-01

    The energy transfer of highly excited ozone molecules is investigated by means of classical trajectories. Both intramolecular energy redistribution and the intermolecular energy transfer in collisions with argon atoms are considered. The sign and magnitude of the intramolecular energy flow between the vibrational and the rotational degrees of freedom crucially depend on the projection K(a) of the total angular momentum of ozone on the body-fixed a axis. The intermolecular energy transfer in single collisions between O(3) and Ar is dominated by transfer of the rotational energy. In accordance with previous theoretical predictions, the direct vibrational de-excitation is exceedingly small. Vibration-rotation relaxation in multiple Ar+O(3) collisions is also studied. It is found that the relaxation proceeds in two clearly distinguishable steps: (1) During the time between collisions, the vibrational degrees of freedom are "cooled" by transfer of energy to rotation; even at low pressure equilibration of the internal energy is slow compared to the time between collisions. (2) In collisions, mainly the rotational modes are "cool" by energy transfer to argon. PMID:15268022

  1. Electron transfer by singlet excited state of porphyn and electron acceptor affinity in rigid medium: photoacoustic phase angle analysis / Transferência de elétrons via estado singleto excitado de porfirina de base livre e afinidade de elétrons por aceitadores em meio rígido: análise fotoacústica do ângulo de fase

    Scientific Electronic Library Online (English)

    Marinônio Lopes, CORNÉLIO.

    Full Text Available A espectroscopia fotoacústica obtém informações sobre amplitude e fase, da resposta de um sistema submetido a excitação por luz. Este artigo apresenta estudos do ângulo de fase no processo de transfereência de elétrons entre octaetilporfirina (OEP) e derivados de quinona ambos dispersos em uma matri [...] z polimérica. Observou-se uma tendência no comportamento da fase para valores menores na região espectral próximo de 620 nm. Enquanto que para comprimentos de onda menores este efeito não foi apresentado. Estas medidas sugerem que a transferência de elétrons para o aceitador ocorreu com a participação do estado singleto excitado da octaetilporfirina. Abstract in english Photoacoustic spectroscopy provides information about both amplitude and phase of the response of a system to an optical excitation process. This paper presents the studies of the phase in the electron transfer process between octaethylporphyn (OEP) and quinone molecules dispersed in a polymeric mat [...] rix. It was observed a tendency in the phase behavior to small values only in the spectral region near to 620 nm, while for shorter wavelength did not show any tendency. These measurements suggested that the electron transfer to acceptor occurred with the participation of octaethylporphyn singlet excited state.

  2. Electron Impact Excitation of Noble Gases

    Science.gov (United States)

    Zeman, Vlado; Bartschat, Klaus

    1998-05-01

    We have extended our Breit-Pauli R-matrix work [1,2] to model electron impact excitation of the [np^5(n+1)s] and [np^5(n+1)p] states in the noble gases Ne--Xe. Total and differential cross sections, the polarization of emitted light, and spin asymmetry parameters will be presented for incident electron energies between threshold and 30 eV. The results will be analyzed and compared with a large amount of recent experimental data [3--8]. 1. V. Zeman et al., Phys. Rev. Lett. 79, 1825 (1997) 2. V. Zeman and K. Bartschat, J. Phys. B 30, 4609 (1997) 3. C. Norén et al., Phys. Rev. A53, 3253 (1996) and 54, 510 (1996) 4. T.J. Gay et al., Phys. Rev. A53, 1623 (1996) 5. D.H. Yu et al., Phys. Rev. Lett. 78, 2724 (1997); J. Phys. B 30, L461 5. (1997); J. Phys. B 30, 1799 (1997) 6. J.E. Chilton et al., Phys. Rev. A57, 267 (1998) 7. M.A. Khakoo, private communication (1998) 8. M. Dümmler, G.F. Hanne and J. Kessler, J. Phys. B 28, 2985 (1995)

  3. Collective electronic excitation modes in a superlattice

    International Nuclear Information System (INIS)

    Collective excitation (plasmon) modes of an electron gas in a multilayer system (superlattice) have been studied in great detail in recent years. One important aspect of this fermion system is that the dispersion relation of the plasma frequency shows transitional behavior between the two- and three-dimensional character. An inelastic light scattering experiment was recently conducted in which the intermediate dispersion was observed for a superlattice. The results of the light scattering experiment and earlier calculations based on a superlattice of two-dimensional layers model developed by Fetter and Das Sarma and Quinn are in qualitatively good agreement. Nevertheless there are discrepancies between this theory and experiment, especially for increasing values of q. The objective of this work was to improve Fetter and Das Sarma and Quinn's theory to include the effect of finite thickness of the plasma layers with the objective of better understanding the systematic discrepancy and to describe electronic correlations in a superlattice in a more general way. It proceeds by the determination of the particle-hole channel of the two particle Green's function in the random phase approximation

  4. Nanostructuring graphene by dense electronic excitation

    Science.gov (United States)

    Ochedowski, O.; Lehtinen, O.; Kaiser, U.; Turchanin, A.; Ban-d’Etat, B.; Lebius, H.; Karluši?, M.; Jakši?, M.; Schleberger, M.

    2015-11-01

    The ability to manufacture tailored graphene nanostructures is a key factor to fully exploit its enormous technological potential. We have investigated nanostructures created in graphene by swift heavy ion induced folding. For our experiments, single layers of graphene exfoliated on various substrates and freestanding graphene have been irradiated and analyzed by atomic force and high resolution transmission electron microscopy as well as Raman spectroscopy. We show that the dense electronic excitation in the wake of the traversing ion yields characteristic nanostructures each of which may be fabricated by choosing the proper irradiation conditions. These nanostructures include unique morphologies such as closed bilayer edges with a given chirality or nanopores within supported as well as freestanding graphene. The length and orientation of the nanopore, and thus of the associated closed bilayer edge, may be simply controlled by the direction of the incoming ion beam. In freestanding graphene, swift heavy ion irradiation induces extremely small openings, offering the possibility to perforate graphene membranes in a controlled way.

  5. Local operator partitioning of electronic energy for electronic energy transfer: An efficient algorithm

    CERN Document Server

    Nagesh, Jayashree; Brumer, Paul

    2013-01-01

    An efficient computational algorithm to implement a local operator approach to partitioning electronic energy in general molecular systems is presented. This approach, which rigorously defines the electronic energy on any subsystem within a molecule, gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. We apply the technique to the $9-$(($1-$naphthyl)$-$methyl)-anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH$_2-$naphthyl groups as subsystems, and examine their electronic energies and populations for several excited states using Configuration Interaction Singles method. The implemented approach shows a wide variety of different behaviors amongst these excited electronic states.

  6. Measurement of the electronic excitation of atoms in atom-molecule collisions near threshold

    International Nuclear Information System (INIS)

    In first part of the paper the measurement of scattering cross sections is described and the energy transfer in molecule-alkali systems is investigated. The influence of translational and vibrational energy could be separated near the excitation threshold. In the second part of the work measurements are reported on the electronic excitation of the work measurements are reported on the electronic excitation of Xe in Xe-Xe-collisions. The experimental data are compared with theoretical calculations. (KBE) 891 KBE/KBE 892 HIS

  7. Electronic excited states of protonated aromatic molecules: Protonated Fluorene

    Energy Technology Data Exchange (ETDEWEB)

    Alata, Ivan [CLUPS (Centre Laser de l' Universite Paris Sud / LUMAT FR 2764) Bat. 106, Univ Paris-Sud 11, 91405 Orsay Cedex (France) and Atomic Energy Commission of Syria, Damascus, P.O. Box 6091 (Syrian Arab Republic); Broquier, Michel; Dedonder, Claude [CLUPS (Centre Laser de l' Universite Paris Sud / LUMAT FR 2764) Bat. 106, Univ Paris-Sud 11, 91405 Orsay Cedex (France); Institut des Sciences Moleculaires d' Orsay (ISMO, UMR8624 CNRS) Bat. 210, Univ Paris-Sud 11, 91405 Orsay Cedex (France); Jouvet, Christophe, E-mail: christophe.jouvet@u-psud.fr [CLUPS (Centre Laser de l' Universite Paris Sud / LUMAT FR 2764) Bat. 106, Univ Paris-Sud 11, 91405 Orsay Cedex (France); Institut des Sciences Moleculaires d' Orsay (ISMO, UMR8624 CNRS) Bat. 210, Univ Paris-Sud 11, 91405 Orsay Cedex (France); Marceca, Ernesto [INQUIMAE-FCEN, UBA, Ciudad Universitaria, 3er piso, Pab. II, 1428 Buenos Aires (Argentina)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer We report the vibrationally resolved electronic spectrum of protonated fluorene. Black-Right-Pointing-Pointer The ground and excited states of the x possible isomers have been calculated ab initio. Black-Right-Pointing-Pointer Among these isomers, only two may contribute to the two band systems observed. Black-Right-Pointing-Pointer Franck Condon simulations are used to assign the active vibrations. - Abstract: The photo-fragmentation spectrum of protonated fluorene has been recorded in the visible spectral region, evidencing an absorption that appears largely red shifted in comparison to that of the neutral molecule fluorene. The spectrum shows two different vibrational progressions, separated by 0.19 eV. As in the case of protonated linear polycyclic aromatic hydrocarbons (PAHs), comparison of the measured spectra with ab initio calculations allows to associate the observed absorption shift with the charge transfer character of the excited state. The spectra can be properly simulated by geometry optimization of the ground and excited states, followed by Franck Condon analysis. The two vibrational bands progressions observed are assigned, with relatively good confidence, to the existence of two different conformers.

  8. Dynamics of Energy Transfer in a Conjugated Dendrimer Driven by Ultrafast Localization of Excitations.

    Science.gov (United States)

    Galindo, Johan F; Atas, Evrim; Altan, Aysun; Kuroda, Daniel G; Fernandez-Alberti, Sebastian; Tretiak, Sergei; Roitberg, Adrian E; Kleiman, Valeria D

    2015-09-16

    Solar energy conversion starts with the harvest of light, and its efficacy depends on the spatial transfer of the light energy to where it can be transduced into other forms of energy. Harnessing solar power as a clean energy source requires the continuous development of new synthetic materials that can harvest photon energy and transport it without significant losses. With chemically-controlled branched architectures, dendrimers are ideally suited for these initial steps, since they consist of arrays of chromophores with relative positioning and orientations to create energy gradients and to spatially focus excitation energies. The spatial localization of the energy delimits its efficacy and has been a point of intense research for synthetic light harvesters. We present the results of a combined theoretical experimental study elucidating ultrafast, unidirectional, electronic energy transfer on a complex molecule designed to spatially focus the initial excitation onto an energy sink. The study explores the complex interplay between atomic motions, excited-state populations, and localization/delocalization of excitations. Our findings show that the electronic energy-transfer mechanism involves the ultrafast collapse of the photoexcited wave function due to nonadiabatic electronic transitions. The localization of the wave function is driven by the efficient coupling to high-frequency vibrational modes leading to ultrafast excited-state dynamics and unidirectional efficient energy funneling. This work provides a long-awaited consistent experiment-theoretical description of excited-state dynamics in organic conjugated dendrimers with atomistic resolution, a phenomenon expected to universally appear in a variety of synthetic conjugated materials. PMID:26122872

  9. The mechanism of electronic excitation in the bacterial bioluminescent reaction

    International Nuclear Information System (INIS)

    The current state of the problem of formation of the electron-excited product in the chemiluminescent reaction that underlies the bacterial luminescence is analysed. Various schemes of chemical transformations capable of producing a bacterial bioluminescence emitter are presented. The problem of excitation of secondary emitters is considered; two possible mechanisms of their excitation are analysed.

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

    International Nuclear Information System (INIS)

    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

  11. K- and L-shell resonant transfer and excitation in ion-atom collisions

    International Nuclear Information System (INIS)

    Recent experimental studies of resonant transfer and excitation (RTE) in ion-atom collisions are reviewed. In the RTE process correlated electron capture and projectile excitation occur together in a single encounter with a target atom. Measurements of Caq+ + H2 (q=10-19) from 100 to 370 MeV establish the projectile charge-state dependence of K-shell RTE and provide a detailed collision system. A comparison of the Ca17+ + H2 data with previous results for Ca17+ + He demonstrates the effect of the target-electron momentum distribution on the RTE process. Studies of 230-610 MeV Nb31+ + H2 provide information about RTE involing projectile L-shell excitation. All the measurements are in reasonable agreement wit theoretical calculations. (orig.)

  12. Correlated electron capture and inner-shell excitation measurements in ion-atom collisions

    International Nuclear Information System (INIS)

    In an ion-atom collision projectile excitation and charge transfer (electron capture) may occur together in a single encounter. If the excitation and capture are correlated, then the process is called resonant transfer and excitation (RTE); if they are uncorrelated, then the process is termed nonresonant transfer and excitation (NTE). Experimental work to date has shown the existence of RTE and provided strong evidence for NTE. Results presented here provide information on the relative magnitudes of RTE and NTE, the charge state dependence of RTE, the effect of the target momentum distribution on RTE, the magnitude of L-shell RTE compared to K-shell RTE, and the target Z dependences of RTE and NTE. 15 refs., 5 figs

  13. Fishbone instability excited by electrons in a tokamak

    International Nuclear Information System (INIS)

    Fishbone instability in Tokamak plasma is often produced by deeply trapped suprathermal ions. Theoretical analysis indicates that the instability can be excited by barely trapped suprathermal electrons. Negative magnetic shear help exciting electron fishbone or suppress ion one, while positive shear is opposite. The fishbone instability purely driven by suprathermal trapped electrons is firstly identified by using electron cyclotron resonance heating (ECRH) in the HL-1M Tokamak

  14. Search for Excited Electrons in ep Collisions at HERA

    CERN Document Server

    Aaron, F D; Andreev, V; Antunovic, B; Aplin, S; Asmone, A; Astvatsatourov, A; Bacchetta, A; Backovic, S; Baghdasaryan, A; Baranov, P; Barrelet, E; Bartel, Wulfrin; Beckingham, M; Begzsuren, K; Behnke, O; Belousov, A; Berger, N; Bizot, J C; Boenig, M O; Boudry, V; Bozovic-Jelisavcic, I; Bracinik, J; Brandt, G; Brinkmann, M; Brisson, V; Bruncko, D; Bunyatyan, A; Buschhorn, G; Bystritskaya, L; Campbell, A J; Cantun Avila, K B; Cassol-Brunner, F; Cerny, K; Cerny, V; Chekelian, V; Cholewa, A; Contreras, J G; Coughlan, J A; Cozzika, G; Cvach, J; Dainton, J B; Daum, K; Deák, M; De Boer, Y; Delcourt, B; Del Degan, M; Delvax, J; de Roeck, A; De Wolf, E A; Diaconu, C; Dodonov, V; Dossanov, A; Dubak, A; Eckerlin, G; Efremenko, V; Egli, S; Eliseev, A; Elsen, E; Essenov, S; Falkiewicz, A; Faulkner, P J W; Favart, L; Fedotov, A; Felst, R; Feltesse, J; Ferencei, J; Finke, L; Fleischer, M; Fomenko, A; Gabathuler, E; Gayler, J; Ghazaryan, S; Glazov, A; Glushkov, I; Görlich, L; Goettlich, M; Gogitidze, N; Gouzevitch, M; Grab, C; Greenshaw, T; Grell, B R; Grindhammer, G; Habib, S; Haidt, D; Hansson, M; Helebrant, C; Henderson, R C W; Henschel, H; Herrera-Corral, G; Hildebrandt, M; Hiller, K H; Hoffmann, D; Horisberger, R; Hovhannisyan, A; Hreus, T; Jacquet, M; Janssen, M E; Janssen, X; Jemanov, V; Jonsson, L; Johnson, D P; Jung, A W; Jung, H; Kapichine, M; Katzy, J; Kenyon, I R; Kiesling, C; Klein, M; Kleinwort, C; Klimkovich, T; Kluge, T; Knutsson, A; Kogler, R; Korbel, V; Kostka, P; Krämer, M; Krastev, K; Kretzschmar, J; Kropivnitskaya, A; Krüger, K; Kutak, K; Landon, M P J; Lange, W; Lastoviicka-Medin, G; Laycock, P; Lebedev, A; Leibenguth, G; Lendermann, V; Levonian, S; Li, G; Lipka, K; Liptaj, A; List, B; List, J; Loktionova, N; López-Fernandez, R; Lubimov, V; Lucaci-Timoce, A I; Lytkin, L; Makankine, A; Malinovski, E; Marage, P; Marti, L; Martyn, H U; Maxfield, S J; Mehta, A; Meier, K; Meyer, A B; Meyer, H; Meyer, J; Michels, V; Mikocki, S; Milcewicz-Mika, I; Moreau, F; Morozov, A; Morris, J V; Mozer, M U; Mudrinic, M; Müller, K; Murn, P; Nankov, K; Naroska, B; Naumann, T; Newman, P R; Niebuhr, C; Nikiforov, A; Nowak, G; Nowak, K; Nozicka, M; Olivier, B; Olsson, J E; Osman, S; Ozerov, D; Palichik, V; Panagouliasl, I; Pandurovic, M; Papadopouloul, T; Pascaud, C; Patel, G D; Pejchal, O; Peng, H; Pérez, E; Petrukhin, A; Picuric, I; Piec, S; Pitzl, D; Placakyte, R; Polifka, R; Povh, B; Preda, T; Radescu, V; Rahmat, A J; Raicevic, N; Raspiareza, A; Ravdandorj, T; Reimer, P; Rizvi, E; Robmann, P; Roland, B; Roosen, R; Rostovtsev, A; Rotaru, M; Ruiz Tabasco, J E; Rurikova, Z; Rusakov, S; Salek, D; Salvaire, F; Sankey, D P C; Sauter, M; Sauvan, E; Schmidt, S; Schmitt, S; Schmitz, C; Schoeffel, L; Schöning, A; Schultz-Coulon, H C; Sefkow, F; Shaw-West, R N; Shevyakov, I; Shtarkov, L N; Shushkevich, S; Sloan, T; Smiljanic, I; Smirnov, P; Soloviev, Yu; Sopicki, P; South, D; Spaskov, V; Specka, A; Staykova, Z; Steder, M; Stella, B; Straumann, U; Sunar, D; Sykora, T; Tchoulakov, V; Thompson, G; Thompson, P D; Toll, T; Tomasz, F; Tran, T H; Traynor, D; Trinh, T N; Truöl, P; Tsakov, I; Tseepeldorj, B; Tsurin, I; Turnau, J; Tzamariudaki, E; Urban, K; Valkárová, A; Vallée, C; Van Mechelen, P; VargasTrevino, A; Vazdik, Ya; Vinokurova, S; Volchinski, V; Wegener, D; Wessels, M; Wissing, C; Wünsch, E; Yeganov, V; Zácek, J; Zaleisak, J; Zhang, Z; Zhelezov, A; Zhokin, A; Zhu, Y C; Zimmermann, T; Zohrabyan, H; Zomer, F; 10.1016/j.physletb.2008.07.014

    2008-01-01

    A search for excited electrons is performed using the full $e^{\\pm}p$ data sample collected by the H1 experiment at HERA, corresponding to a total luminosity of 475 pb$^{-1}$. The electroweak decays of excited electrons ${e}^{*}\\to{e}{\\gamma}$, ${e}^{*}\\to{e}Z$ and ${e}^{*}{\\to}\

  15. Theory of nuclear excitation by electron capture for heavy ions

    OpenAIRE

    Gagyi-Palffy, Adriana

    2006-01-01

    The resonant process of nuclear excitation by electron capture (NEEC) in collisions involving highly-charged ions has been investigated theoretically. NEEC is a rare recombination process in which a free electron is captured into a bound shell of an ion with the simultaneous excitation of the nucleus. Total cross sections for NEEC followed by the radiative decay of the excited nucleus are presented for various collision systems. The possibility to observe the NEEC in scattering experiments wi...

  16. Matrix photochemistry of small molecules: Influencing reaction dynamics on electronically excited hypersurfaces

    International Nuclear Information System (INIS)

    Investigations of chemical reactions on electronically excited reaction surfaces are presented. The role of excited-surface multiplicity is of particular interest, as are chemical reactivity and energy transfer in systems in which photochemistry is initiated through a metal atom ''sensitizer.'' Two approaches are employed: A heavy-atom matrix affords access to forbidden triplet reaction surfaces, eliminating the need for a potentially reactive sensitizer. Later, the role of the metal atom in the photosensitization process is examined directly

  17. Excitation transfer through open quantum networks: a few basic mechanisms

    CERN Document Server

    Venuti, Lorenzo Campos

    2011-01-01

    A variety of open quantum networks are currently under intense examination to model energy transport in photosynthetic systems. Here we study the coherent transfer of a quantum excitation over a network incoherently coupled with a structured and small environment that effectively models the photosynthetic reaction center. Our goal is to distill a few basic, possibly universal, mechanisms or "effects" that are featured in simple energy-transfer models. In particular, we identify three different phenomena: the congestion effect, the asymptotic unitarity and the staircase effects. We begin with few-site models, in which these effects can be fully understood, and then proceed to study more complex networks similar to those employed to model energy transfer in light-harvesting complexes. Our numerical studies on such networks seem to suggest that some of the effects observed in simple networks may be of relevance for biological systems, or artificial analogues of them as well.

  18. The separation of vibrational coherence from ground- and excited-electronic states in P3HT film

    International Nuclear Information System (INIS)

    Concurrence of the vibrational coherence and ultrafast electron transfer has been observed in polymer/fullerene blends. However, it is difficult to experimentally investigate the role that the excited-state vibrational coherence plays during the electron transfer process since vibrational coherence from the ground- and excited-electronic states is usually temporally and spectrally overlapped. Here, we performed 2-dimensional electronic spectroscopy (2D ES) measurements on poly(3-hexylthiophene) (P3HT) films. By Fourier transforming the whole 2D ES datasets (S(?1,T~2,?3)) along the population time (T~2) axis, we develop and propose a protocol capable of separating vibrational coherence from the ground- and excited-electronic states in 3D rephasing and nonrephasing beating maps (S(?1,?~2,?3)). We found that the vibrational coherence from pure excited electronic states appears at positive frequency (+?~2) in the rephasing beating map and at negative frequency (??~2) in the nonrephasing beating map. Furthermore, we also found that vibrational coherence from excited electronic state had a long dephasing time of 244 fs. The long-lived excited-state vibrational coherence indicates that coherence may be involved in the electron transfer process. Our findings not only shed light on the mechanism of ultrafast electron transfer in organic photovoltaics but also are beneficial for the study of the coherence effect on photoexcited dynamics in other systems

  19. The separation of vibrational coherence from ground- and excited-electronic states in P3HT film.

    Science.gov (United States)

    Song, Yin; Hellmann, Christoph; Stingelin, Natalie; Scholes, Gregory D

    2015-06-01

    Concurrence of the vibrational coherence and ultrafast electron transfer has been observed in polymer/fullerene blends. However, it is difficult to experimentally investigate the role that the excited-state vibrational coherence plays during the electron transfer process since vibrational coherence from the ground- and excited-electronic states is usually temporally and spectrally overlapped. Here, we performed 2-dimensional electronic spectroscopy (2D ES) measurements on poly(3-hexylthiophene) (P3HT) films. By Fourier transforming the whole 2D ES datasets (S(?1,T?2,?3)) along the population time (T?2) axis, we develop and propose a protocol capable of separating vibrational coherence from the ground- and excited-electronic states in 3D rephasing and nonrephasing beating maps (S(?1,??2,?3)). We found that the vibrational coherence from pure excited electronic states appears at positive frequency (+??2) in the rephasing beating map and at negative frequency (-??2) in the nonrephasing beating map. Furthermore, we also found that vibrational coherence from excited electronic state had a long dephasing time of 244 fs. The long-lived excited-state vibrational coherence indicates that coherence may be involved in the electron transfer process. Our findings not only shed light on the mechanism of ultrafast electron transfer in organic photovoltaics but also are beneficial for the study of the coherence effect on photoexcited dynamics in other systems. PMID:26049430

  20. Electron - phonon interaction influence on electron and phonon excitations in amorphous metals

    International Nuclear Information System (INIS)

    The influence of electron-phonon interaction on electron and phonon excitations in amorphous metals is examined. The equation for the gap in the electron spectrum for the transition to the superconducting state is obtained. The renormalization of the energy spectrum and damping of electron and phonon excitations due to electron-phonon interaction is considered. (orig.)

  1. Initial state dependence of convoy electrons emitted from the excited ions by resonant coherent excitation

    Energy Technology Data Exchange (ETDEWEB)

    Azuma, T; Nakano, Y; Metoki, K [Department of Physics, Tokyo Metropolitan University, Hachioji, Tokyo (Japan); Hatakeyama, A [Department of Applied Physics, Tokyo University of Agriculture and Technology, Koganei, Tokyo (Japan); Nakai, Y [Radioactive Isotope Physics Laboratory, RIKEN Nishina Center, Wako, Saitama (Japan); Komaki, K; Yamazaki, Y [Graduate School of Arts and Sciences, University of Tokyo, Komaba, Meguro, Tokyo (Japan); Takada, E; Murakami, T, E-mail: azuma@phys.metro-u.ac.j [National Institute of Radiological Sciences, Inage, Chiba (Japan)

    2009-11-01

    Convoy electrons emitted from 416 MeV/u heliumlike Ar{sup 16+} ions excited by three-dimensional resonant coherent excitation (3D-RCE) have been explored. The 1s electron in the ground state was excited to the 2p state by a periodic crystal field during the passage through a Si crystal and released into the continuum by collisions with target atoms to form a cusp-shaped peak in the energy distribution, referred to as convoy electron. Under the resonance condition, we found not only enhancement of the convoy electron yield but also significant narrowing in the energy distribution, reflecting the initial bound state momentum distribution of the excited ions. This suggests that RCE is well-suited to study fast ion collisions involving the specific excited state.

  2. Enhanced luminescence excitation via efficient optical energy transfer (Presentation Recording)

    Science.gov (United States)

    Aad, Roy; Nomenyo, Komla D.; Bercu, Bogdan; Couteau, Christophe; Sallet, Vincent; Rogers, David J.; Molinari, Michael; Lérondel, Gilles

    2015-10-01

    Luminescent nanoscale materials (LNMs) have received widespread interest in sensing and lighting applications due to their enhanced emissive properties. For sensing applications, LNMs offer improved sensitivity and fast response time which allow for lower limits of detection. Meanwhile, for lighting applications, LNMs, such as quantum dots, offer an improved internal quantum efficiency and controlled color rendering which allow for better lighting performances. Nevertheless, due to their nanometric dimensions, nanoscale materials suffer from extremely weak luminescence excitation (i.e. optical absorption) limiting their luminescence intensity, which in turn results in a downgrade in the limits of detection and external quantum efficiencies. Therefore, enhancing the luminescence excitation is a major issue for sensing and lighting applications. In this work, we report on a novel photonic approach to increase the luminescence excitation of nanoscale materials. Efficient luminescence excitation increase is achieved via a gain-assisted waveguided energy transfer (G-WET). The G-WET concept consists on placing nanoscale materials atop of a waveguiding active (i.e. luminescent) layer with optical gain. Efficient energy transfer is thus achieved by exciting the nanoscale material via the tail of the waveguided mode of the active layer emission. The G-WET concept is demonstrated on both a nanothin layer of fluorescent sensitive polymer and on CdSe/ZnS quantum dots coated on ZnO thin film, experimentally proving up to an 8-fold increase in the fluorescence of the polymer and a 3-fold increase in the luminescence of the CdSe/ZnS depending of the active layer emission regime (stimulated vs spontaneous emission). Furthermore, we will discuss on the extended G-WET concept which consists on coating nanoscale materials on a nanostructured active layer. The nanostructured active layer offers the necessary photonic modulation and a high specific surface which can presumably lead to a more efficient G-WET concept. Finally, the efficiency as well as the observation conditions of the GWET will be discussed and compared with more conventional charge transfer or dipole-dipole energy transfer.

  3. Two-photon Induced Hot Electron Transfer to a Single Molecule in a Scanning Tunneling Microscope

    OpenAIRE

    Wu, Shiwei; Ho, Wilson

    2010-01-01

    The junction of a scanning tunneling microscope (STM) operating in the tunneling regime was irradiated with femtosecond laser pulses. A photo-excited hot electron in the STM tip resonantly tunnels into an excited state of a single molecule on the surface, converting it from the neutral to the anion. The electron transfer rate depends quadratically on the incident laser power, suggesting a two-photon excitation process. This nonlinear optical process is further confirmed by t...

  4. Contribution of excited electrons to the e+e- ? ?? process

    International Nuclear Information System (INIS)

    We have calculated the scattering cross-section of the e+e-??? process in the lowest order of QED. In addition to the single electron exchange diagram we have considered the possible contribution of heavy excited electrons. A symbolic manipulation program, REDUCE, is used for algebraic calculation of the cross section. Illustrations are given or QED tests for possible compositeness of leptons. Also we have studied the QED cuttoff parameters for the excited electrons search. (Author)

  5. Search for excited electrons using the ZEUS detector

    International Nuclear Information System (INIS)

    This paper reports a search for excited electrons at the HERA electron-proton collider. In a sample corresponding to an integrated luminosity of 26 nb-1, no evidence was found for any resonant state decaying into e-?, ?W- or e-Z0. Limits on the coupling strength of an excited electron have been determined for masses between 45 and 225 GeV. This study also reports the observation of the wide-angle e? Compton scattering process. (orig.)

  6. SEARCH FOR EXCITED ELECTRONS USING THE ZEUS DETECTOR

    OpenAIRE

    ARZARELLO, F; Basile, M.; Bruni, G.; Bruni, P.; Lin, Q; Diekmann, B; Hilger, E; MENGEL, S; MOLLEN, J; SCHRAMM, D; Wedemeyer, R; Heath, H.; MALOS, J; TAPPER, R; Barillari, T.

    1993-01-01

    This paper reports a search for excited electrons at the HERA electron-proton collider. In a sample corresponding to an integrated luminosity of 26 nb-1, no evidence was found for any resonant state decaying into e-?, ?W- or e-Z0. Limits on the coupling strength of an excited electron have been determined for masses between 45 and 225 GeV. This study also reports the observation of the wide-angle e? Compton scattering process.

  7. Computer simulation of electron transfer in molecular electronic devices

    OpenAIRE

    Correia, Helena M. G.; Ramos, Marta M. D.

    2005-01-01

    The study of electron transfer through individual molecules bound to metal electrodes has become important due to the potential application in molecular electronic devices. Since the electronic and atomic motions in these molecules influence each other they need to be treated self-consistently. We have used self-consistent quantum chemistry molecular dynamics calculations to discuss some of the issues related to electron transfer through a spatially symmetric [9,10-Bis((2???-para-mercaptophen...

  8. The role of electron-electron interactions in the excitation of fast, highly charged projectile ions

    International Nuclear Information System (INIS)

    The excitation of highly charged projectiles is usually dominated by interactions with the target nucleus, with the target electrons contributing only by screening the nucleus. At high energies, however, the target electrons have enough energy to independently excite the projectile. At the threshold energy, the target electrons give up all of their energy in the projectile frame in order to perform the excitation. These target electrons thereby end up in the continuum of the projectile and can be observed in the laboratory frame as cusp electrons. The authors are studying the electrons' role in these collisions by observing cusp electrons in coincidence with photons emitted from the excited projectiles in collisions of Si13+ with Ar, Ne, and H2, targets. They separate the electron-electron contribution by measuring these coincidences across the threshold energy (? 102 MeV). Initial data indicate that electron-electron interactions do not make a significant contribution in excitation due to the heavy targets

  9. Observation of proton transfer in 2-aminopyridine dimer by electron and mass spectroscopy.

    Science.gov (United States)

    Samoylova, Elena; Radloff, Wolfgang; Ritze, Hans-Hermann; Schultz, Thomas

    2009-07-23

    A photoinitiated intermolecular electron-proton transfer reaction in 2-aminopyridine dimer was investigated by femtosecond pump-probe electron-ion coincidence spectroscopy and accompanying theory. Excited-state population dynamics were observed in real time by time-resolved mass spectroscopy, and the respective excited-state character of locally excited and proton/hydrogen transfer states was identified in coincident electron spectra. Two reaction channels for an ultrafast (sub-50 fs) and a slower (approximately 75 ps) proton/hydrogen transfer were observed and indicate that vibrational energy redistribution may lead to efficient population trapping in the excited state. Spectroscopic evidence of an unexpected hydrogen-transfer reaction in photoexcited aminopyridine monomer is also presented. PMID:19569694

  10. Attenuation of excited electrons at crystal surfaces

    International Nuclear Information System (INIS)

    Attenuation of the electron current determines surface sensitivity of electron spectroscopies. Pronounced energy and directional dependencies of the electron attenuation in crystals differ strongly from those commonly used for amorphous solids. Quantum descriptions of the electron attenuation can be obtained from the complex band structure of crystal surfaces at energies above the vacuum level. Contributions, specific for concrete processes, are obtained from theoretical description of photoelectron spectroscopy and of electron diffraction.

  11. Theoretical Studies of Chemical Reactions following Electronic Excitation

    Science.gov (United States)

    Chaban, Galina M.

    2003-01-01

    The use of multi-configurational wave functions is demonstrated for several processes: tautomerization reactions in the ground and excited states of the DNA base adenine, dissociation of glycine molecule after electronic excitation, and decomposition/deformation of novel rare gas molecules HRgF. These processes involve bond brealung/formation and require multi-configurational approaches that include dynamic correlation.

  12. Electronic and rotational excitation of H2 by positron impact

    International Nuclear Information System (INIS)

    The body frame fixed nuclei and the laboratory frame rotational close coupling approximations have been employed to calculate electronic excitation of H2 (X 1?+g ? B 1?+u) by positron impact. Two electronic states (X 1?+g and B 1?+u) and three rotational states in both the elastic and excitation channels are retained in the calculations. Results are reported for electronically elastic, excitation and rotational cross sections up to the incident energy 75.0 eV. The elastic cross sections are found to be influenced significantly with the addition of B 1?+u state in the expansion scheme, in both the models used. Above the incident energy of 25.0 eV, the electronic excitation cross sections using the laboratory frame differ significantly from those of the fixed nuclei model. (orig.)

  13. Search for excited electrons in ep collisions at HERA

    International Nuclear Information System (INIS)

    A search for excited electrons is performed using the full e±p data sample collected by the H1 experiment at HERA, corresponding to a total luminosity of 475 pb-1. The electroweak decays of excited electrons e* ?e?, e* ?eZ and e* ??W with subsequent hadronic or leptonic decays of the W and Z bosons are considered. No evidence for excited electron production is found. Mass dependent exclusion limits on e* production cross sections and on the ratio f/? of the coupling to the compositeness scale are derived within gauge mediated models. These limits extend the excluded region compared to previous excited electron searches. The e* production via contact interactions is also addressed for the first time in ep collisions. (orig.)

  14. Ultrafast tryptophan-to-heme electron transfer in myoglobins revealed by UV 2D spectroscopy.

    Science.gov (United States)

    Consani, Cristina; Auböck, Gerald; van Mourik, Frank; Chergui, Majed

    2013-03-29

    Tryptophan is commonly used to study protein structure and dynamics, such as protein folding, as a donor in fluorescence resonant energy transfer (FRET) studies. By using ultra-broadband ultrafast two-dimensional (2D) spectroscopy in the ultraviolet (UV) and transient absorption in the visible range, we have disentangled the excited state decay pathways of the tryptophan amino acid residues in ferric myoglobins (MbCN and metMb). Whereas the more distant tryptophan (Trp(7)) relaxes by energy transfer to the heme, Trp(14) excitation predominantly decays by electron transfer to the heme. The excited Trp(14)?heme electron transfer occurs in edge-to-edge distance below ~10 angstroms, outcompeting the FRET process. Our results raise the question of whether such electron transfer pathways occur in a larger class of proteins. PMID:23393092

  15. Ultrafast coherent dynamics of nonadiabatically coupled quasi-degenerate excited states in molecules: Population and vibrational coherence transfers

    International Nuclear Information System (INIS)

    Graphical abstract: Temporal behaviors due to quantum mechanical interferences between the nonadiabatically coupled quasi-degenerate excited states (b and c) after a coherent excitation. Highlights: ? A nonadiabatic theory of quasi-degenerate ?-electronic states in aromatic molecules. ? Quantum interferences between the nonadiabatically-coupled ?-electronic states. ? Analysis of time-dependent vibrational coherence transfer via nonadiabatic couplings. - Abstract: Results of a theoretical study of ultrafast coherent dynamics of nonadiabatically coupled quasi-degenerate ?-electronic excited states of molecules were presented. Analytical expressions for temporal behaviors of population and vibrational coherence were derived using a simplified model to clarify the quantum mechanical interferences between the two coherently excited electronic states, which appeared in the nuclear wavepacket simulations [M. Kanno, H. Kono, Y. Fujimura, S.H. Lin, Phys. Rev. Lett 104 (2010) 108302]. The photon-polarization direction of the linearly polarized laser, which controls the populations of the two quasi-degenerate electronic states, determines constructive or destructive interference. Features of the vibrational coherence transfer between the two coupled quasi-electronic states through nonadiabatic couplings are also presented. Information on both the transition frequency and nonadiabatic coupling matrix element between the two states can be obtained by analyzing signals of two kinds of quantum beats before and after transfer through nonadiabatic coupling.

  16. Anomalous temperature dependence of excitation transfer betweenquantum dots.

    Czech Academy of Sciences Publication Activity Database

    Král, Karel; Menšík, Miroslav

    Praha : Czechoslovak Association for Crystal Growth (CSACG), 2014 - (Kožíšek, Z.; Nitsch, K.). s. 25-25 ISBN 978-80-260-6599-9. [Joint Seminar Development of Materials Science in Research and Education /24./. 08.09.2014-12.09.2014, Lednice] R&D Pro jects: GA MŠk LH12186 Institutional support: RVO:68378271 Keywords : quantum dots * nanoparticles * electron-phonon interaction * energy transfer Subject RIV: BM - Solid Matter Physics ; Magnetism

  17. Role of excited-state hydrogen detachment and hydrogen-transfer processes for the excited-state deactivation of an aromatic dipeptide: N-acetyl tryptophan methyl amide.

    Science.gov (United States)

    Shemesh, Dorit; Sobolewski, Andrzej L; Domcke, Wolfgang

    2010-05-21

    The excited-state electronic potential-energy surfaces of the three conformers of the capped dipeptide N-acetyl tryptophan methyl amide (NATMA), for which UV and IR spectra have been reported by Dian et al. [J. Chem. Phys., 2003, 118, 2696], have been explored with ab initio electronic-structure methods. The results provide insight into the nonadiabatic electronic coupling mechanisms which are responsible for the pronounced and conformer-specific perturbations of the spectra, such as broad and congested UV spectra as well as the deletion of certain fundamentals in the IR spectrum of the S(1) state. It is shown that the photophysical dynamics of NATMA is governed by at least five excited singlet electronic states: the two spectroscopic (1)L(b) and (1)L(a) states and the dissociative (1)pisigma* state of the indole chromophore, as well as a locally-excited state and a charge-transfer state of the peptide backbone. For the conformer NATMA C, which exhibits a gamma-turn of the backbone, a potentially very efficient excited-state deactivation mechanism to the electronic ground state via three conical intersections has been revealed. The results confirm the important role of hydrogen bonds for rapid excited-state deactivation of peptides, which enhances their photostability. PMID:20445897

  18. Excitation energy transfer in the antenna system with divinyl-chlorophylls in the vinyl reductase-expressing Arabidopsis

    Science.gov (United States)

    Akimoto, Seiji; Yokono, Makio; Ohmae, Maiko; Yamazaki, Iwao; Nagata, Nozomi; Tanaka, Ryouichi; Tanaka, Ayumi; Mimuro, Mamoru

    2005-06-01

    We examined the excitation energy transfer and electron transfer processes in Arabidopsis thaliana thylakoid membranes following replacement of chlorophyll (Chl) molecules by expression of the vinyl reductase: monovinyl (MV)-Chl was replaced with divinyl (DV)-Chl and the DV-Chl a/DV-Chl b ratio was higher than that of control cells. By this replacement, energy transfer within the photosystem (PS) II became faster, whereas the PS II-to-PS I energy transfer was slower. In the DV-Chl mutant system, the delayed fluorescence from PS II was not resolved. Alternations of the antenna system and the reaction center are discussed in relation to Chl replacement.

  19. Double-electron excitation above Xe K-edge

    International Nuclear Information System (INIS)

    When X-rays fall on any substance, whether solid, liquid, or gaseous, a photoabsorption occurs. Photoabsorption in atoms has been generally treated as a single-electron excitation process. However, the existence of the multi-electron excitation process, where the removal of a core electron by photoabsorption causes excitation of additional electrons in the same atoms, has been known in x-ray absorption spectra for a long time. In x-ray absorption spectra, experimental investigations of the shake processes in inner-shell ionization phenomena have been performed by detecting discontinuities. The shake effect which is a consequence of rearrangement of the atomic electrons, occurs in association with inner-shell excitation and ionization phenomena in x-ray absorption. The shake process has been studied extensively in various gases, because it is usually considered that the measurement of the multi-electron excitation is only possible for monatomic gases or vapors. The x-ray absorption spectra in Kr gas were measured by Ito et al. in order to observe precisely x-ray absorption spectra and to investigate the multi-electron excitation cross sections in Kr as a function of photon energy using synchrotron radiation. However, no suitable measured K x-ray absorption spectra was available to elucidate the shake processes. In the present work, the photoabsorption cross sections in Xe have been precisely measured in order to determine the features on the shake processes resulting from multiple electron excitations as a function of photon energy. Double-electron transitions of [1s4d], [1s4p], [1s4s], and [1s3d] are first detected. (author)

  20. Reaction dynamics of electronically excited alkali atoms with simpler molecules

    International Nuclear Information System (INIS)

    The reactions of electronically excited sodium atoms with simple molecules have been studied in crossed molecular beams experiments. Electronically excited Na(32P/sub 3/2/, 42D/sub 5/2/, and 52S/sub 1/2/) were produced by optical pumping using single frequency dye lasers. The effects of the symmetry, and the orientation and alignment of the excited orbital on the chemical reactivity, and detailed information on the reaction dynamics were derived from measurements of the product angular and velocity distributions. 12 refs., 9 figs

  1. Excitation energy transfer in the peridinin-chlorophyll a-protein complex modeled using configuration interaction.

    Science.gov (United States)

    Bricker, William P; Lo, Cynthia S

    2014-08-01

    We modeled excitation energy transfer (EET) in the peridinin-chlorophyll a-protein (PCP) complex of dinoflagellate Amphidinium carterae to determine which pathways contribute dominantly to the high efficiency of this process. We used complete active space configuration interaction (CAS-CI) to calculate electronic structure properties of the peridinin (PID) and chlorophyll a (CLA) pigments in PCP and the transition density cube (TDC) method to calculate Coulombic couplings between energy transfer donors and acceptors. Our calculations show that the S1 ? Qy EET pathway from peridinin to chlorophyll a is the dominant energy transfer pathway in PCP, with two sets of interactions-between PID612 and CLA601 and between PID622 and CLA602-contributing most strongly. EET lifetimes for these two interactions were calculated to be 2.66 and 2.90, with quantum efficiencies of 85.75 and 84.65%, respectively. The calculated Coulombic couplings for EET between two peridinin molecules in the strongly allowed S2 excited states are extremely large and suggest excitonic coupling between pairs of peridinin S2 states. This methodology is also broadly applicable to the study of EET in other photosynthetic complexes and/or organic photovoltaics, where both single and double excitations are present and donor and acceptor molecules are tightly packed. PMID:25007401

  2. Advances in electron transfer chemistry, v.6

    CERN Document Server

    Mariano, PS

    1999-01-01

    It is clear that electron transfer chemisty is now one of the most active areas of chemical study. Advances in Electron Transfer Chemistry has been designed to allow scientists who are developing new knowledge in this rapidly expanding area to describe their most recent research findings. This volume will serve those interested in learning about current breakthroughs in this rapidly expanding area of chemical research.

  3. Describing excited state intramolecular proton transfer in dual emissive systems: a density functional theory based analysis.

    Science.gov (United States)

    Wilbraham, Liam; Savarese, Marika; Rega, Nadia; Adamo, Carlo; Ciofini, Ilaria

    2015-02-12

    The excited state intramolecular proton transfer (ESIPT) reaction taking place within 2-(2-hydroxyphenyl)benzoxazole (HBT) and two recently experimentally characterized napthalimide derivatives-known as N-1 and N-4-has been investigated in order to identify and test a possible protocol for the description and complete mechanistic and electronic characterization of the reaction at the excited state. This protocol is based on density functional theory, time-dependent density functional theory, and a recently proposed electron density based index (DCT). This method is able to identify all stable species involved in the reaction, discriminate between possible reaction pathways over potential energy surfaces (PES), which are intrinsically very flat and difficult to characterize, and quantitatively measure the excited state charge transfer character throughout the reaction. The photophysical properties of the molecules (i.e., absorption and emission wavelength) are also quantitatively determined via the implicit inclusion of solvent effects in the case of toluene and, the more polar, tetrahydrofuran. The accuracy obtained with this protocol then opens up the possibility of the ab initio design of molecules exhibiting ESIPT for tailored applications such as highly selective molecular sensors. PMID:25208048

  4. A stochastic reorganizational bath model for electronic energy transfer

    CERN Document Server

    Fujita, Takatoshi; Aspuru-Guzik, Alan

    2014-01-01

    The fluctuations of optical gap induced by the environment play crucial roles in electronic energy transfer dynamics. One of the simplest approaches to incorporate such fluctuations in energy transfer dynamics is the well known Haken-Strobl-Reineker model, in which the energy-gap fluctuation is approximated as a white noise. Recently, several groups have employed molecular dynamics simulations and excited-state calculations in conjunction to take the thermal fluctuation of excitation energies into account. Here, we discuss a rigorous connection between the stochastic and the atomistic bath models. If the phonon bath is treated classically, time evolution of the exciton-phonon system can be described by Ehrenfest dynamics. To establish the relationship between the stochastic and atomistic bath models, we employ a projection operator technique to derive the generalized Langevin equations for the energy-gap fluctuations. The stochastic bath model can be obtained as an approximation of the atomistic Ehrenfest equ...

  5. Electronic and vibrational excitations in adsorbed metalorganic molecules

    International Nuclear Information System (INIS)

    HREELS has been used to probe the vibrational and electronic properties of metalorganic molecules adsorbed on III-V semiconductor surfaces. Following adsorbate characterisation, the HREELS electron beam is used to investigate possible resonant vibrational excitation for a range of alkyl-based molecules adsorbed on GaAs(100) and InSb(100). By varying the electron beam energy of the HREEL spectrometer, resonant vibrational excitation is demonstrated at discrete energies in all the molecules studied. This excitation mechanism is confirmed by obtaining adsorbate excitation functions, the observation of enhanced overtone and combination bands at the resonant energies, the measurement of angular distributions that are not consistent with dipole scattering, and by comparison of reflectivity measurements from both the clean and adsorbate covered surfaces. Resonant vibrational excitation is strong in the methyl-based molecules studied (Me3Al and Me3In), but even higher resonant cross-sections are evident in the larger alkyl-based metalorganics (Et3Ga and Np3Ga). The resonant behaviour is generally independent of substrate, although electronic excitation of the InSb(100) surface appears to prevent higher energy resonances (>10 eV) being observed for the methyl-based molecules. The incident HREELS electron beam causes dissociation of Me3Al and Me3In adsorbed on either surface, with a threshold energy of ? 10 eV; an energy close to the ionisation potential of the molecules. An electron impact ionisation dissociation mechanism is inferred, with chemisorbed Me groups decomposing to surface CH2 species. Electron induced dissociation rarely occurs for molecules chemisorbed on metal surfaces due to the efficient quenching of the excited states on these substrates. No dissociation is observed for Et3Ga or NP3Ga, even above their ionisation potential. It is suggested that the time taken to form stable species in these larger compounds following ionisation is much longer than the quenching time and decomposition cannot occur. (author)

  6. Ultrafast coherent dynamics of nonadiabatically coupled quasi-degenerate excited states in molecules: Population and vibrational coherence transfers

    Science.gov (United States)

    Mineo, H.; Kanno, M.; Kono, H.; Chao, S. D.; Lin, S. H.; Fujimura, Y.

    2012-01-01

    Results of a theoretical study of ultrafast coherent dynamics of nonadiabatically coupled quasi-degenerate ?-electronic excited states of molecules were presented. Analytical expressions for temporal behaviors of population and vibrational coherence were derived using a simplified model to clarify the quantum mechanical interferences between the two coherently excited electronic states, which appeared in the nuclear wavepacket simulations [M. Kanno, H. Kono, Y. Fujimura, S.H. Lin, Phys. Rev. Lett 104 (2010) 108302]. The photon-polarization direction of the linearly polarized laser, which controls the populations of the two quasi-degenerate electronic states, determines constructive or destructive interference. Features of the vibrational coherence transfer between the two coupled quasi-electronic states through nonadiabatic couplings are also presented. Information on both the transition frequency and nonadiabatic coupling matrix element between the two states can be obtained by analyzing signals of two kinds of quantum beats before and after transfer through nonadiabatic coupling.

  7. Ultrafast electron diffraction studies of optically excited thin bismuth films

    International Nuclear Information System (INIS)

    This thesis contains work on the design and the realization of an experimental setup capable of providing sub-picosecond electron pulses for ultrafast electron diffraction experiments, and performing the study of ultrafast dynamics in bismuth after optical excitation using this setup. (orig.)

  8. Ultrafast electron diffraction studies of optically excited thin bismuth films

    Energy Technology Data Exchange (ETDEWEB)

    Rajkovic, Ivan

    2008-10-21

    This thesis contains work on the design and the realization of an experimental setup capable of providing sub-picosecond electron pulses for ultrafast electron diffraction experiments, and performing the study of ultrafast dynamics in bismuth after optical excitation using this setup. (orig.)

  9. Excitation of metastable argon and helium atoms by electron impact

    Science.gov (United States)

    Borst, W. L.

    1974-01-01

    Using a time-of-flight method, the excitation of argon and helium metastables by electron impact is investigated in the energy range from threshold to about 50 eV. The secondary-electron yields of the metastable detector used are reviewed in detail. The effect of metastable recoil is also discussed. Comparisons with data from other investigators are presented.

  10. Excited baryon program at the Bonn electron stretcher accelerator ELSA

    International Nuclear Information System (INIS)

    The Bonn electron stretcher accelerator ELSA is the first of a new generation of continuous beam machines in the GeV region. It is qualified for experiments with tagged photons and with polarized electrons on polarized nucleons to investigate the electromagnetic properties of excited baryon resonances

  11. Electron-driven excitations and dissociation of molecules

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Greg [Univ. of California, Davis, CA (United States); Orel, Ann E. [Univ. of California, Davis, CA (United States)

    2015-02-13

    This program studied how energy is interchanged in electron and photon collisions with molecules leading to ex-citation and dissociation. Modern ab initio techniques, both for the photoionization and electron scattering, and the subsequent nuclear dynamics studies, are used to accurately treat these problems. This work addresses vibrational ex-citation and dissociative attachment following electron impact, and the dynamics following inner shell photoionzation. These problems are ones for which a full multi-dimensional treatment of the nuclear dynamics is essential and where non-adiabatic effects are expected to be important.

  12. Peculiarities of electron excitations decay in ion-molecular crystals

    International Nuclear Information System (INIS)

    Ionic-molecular crystals (IMC) have wide application in various optical devices. Its are using in capacity of solid state dosimetric materials and isolators. Peculiarities of chemical and energetic states of IMC lead to following number of features of electron excitation decay in comparison with alkaline-halogen crystals: - both an electrons and a holes simultaneously could be captured and localized either on anion or on cation complexes; - in-molecular forces arising in result of charge capture could conduct to decay of anion or cation complex; - decay products od anion or cation complex could participate in following reaction of new products formation. All these processes and new products of electron excitation decay exert strong effect on optical, magnetic and electrical characteristics of IMC. Knowledge of way and mechanisms of electron excitation decay in IMC could allow to control of radiation stability of crystals with help of impurities participating in different channels of solid state reactions

  13. Electron-impact excitation of ions

    International Nuclear Information System (INIS)

    A review of electron-ion beam experiments is given. Techniques, difficulties, and present trends in this area are discussed. Measured cross sections are compared with theoretical results and the current level of agreement is assessed. 74 references

  14. DCS - a program for calculating differential cross sections for the electronic excitation of diatomic molecules at fixed nuclei

    International Nuclear Information System (INIS)

    The program DSC computes differential cross sections for the electron-impact electronic excitation of diatomic molecules from the corresponding fixed-nuclei T-matrices. The momentum-transfer formalism is used to derive a convenient expression of the differential cross section. (orig.)

  15. Single Molecule Spectroscopy of Electron Transfer

    International Nuclear Information System (INIS)

    The objectives of this research are threefold: (1) to develop methods for the study electron transfer processes at the single molecule level, (2) to develop a series of modifiable and structurally well defined molecular and nanoparticle systems suitable for detailed single molecule/particle and bulk spectroscopic investigation, (3) to relate experiment to theory in order to elucidate the dependence of electron transfer processes on molecular and electronic structure, coupling and reorganization energies. We have begun the systematic development of single molecule spectroscopy (SMS) of electron transfer and summaries of recent studies are shown. There is a tremendous need for experiments designed to probe the discrete electronic and molecular dynamic fluctuations of single molecules near electrodes and at nanoparticle surfaces. Single molecule spectroscopy (SMS) has emerged as a powerful method to measure properties of individual molecules which would normally be obscured in ensemble-averaged measurement. Fluctuations in the fluorescence time trajectories contain detailed molecular level statistical and dynamical information of the system. The full distribution of a molecular property is revealed in the stochastic fluctuations, giving information about the range of possible behaviors that lead to the ensemble average. In the case of electron transfer, this level of understanding is particularly important to the field of molecular and nanoscale electronics: from a device-design standpoint, understanding and controlling this picture of the overall range of possible behaviors will likely prove to be as important as designing ia the ideal behavior of any given molecule.

  16. Charge-Transfer Excited States in Aqueous DNA: Insights from Many-Body Green's Function Theory

    Science.gov (United States)

    Yin, Huabing; Ma, Yuchen; Mu, Jinglin; Liu, Chengbu; Rohlfing, Michael

    2014-06-01

    Charge-transfer (CT) excited states play an important role in the excited-state dynamics of DNA in aqueous solution. However, there is still much controversy on their energies. By ab initio many-body Green's function theory, together with classical molecular dynamics simulations, we confirm the existence of CT states at the lower energy side of the optical absorption maximum in aqueous DNA as observed in experiments. We find that the hydration shell can exert strong effects (˜1 eV) on both the electronic structure and CT states of DNA molecules through dipole electric fields. In this case, the solvent cannot be simply regarded as a macroscopic screening medium as usual. The influence of base stacking and base pairing on the CT states is also discussed.

  17. Electronic excitation and charge transfer processes in collisions of H{sup +}, H{sub 2}{sup +}, and H{sub 3}{sup +} ions with carbon monoxide at typical solar-wind velocities

    Energy Technology Data Exchange (ETDEWEB)

    Werbowy, S.; Pranszke, B., E-mail: dokws@univ.gda.pl [Institute of Experimental Physics, University of Gdansk, ul. Wita Stwosza 57, PL-80-952 Gdansk (Poland)

    2014-01-10

    Luminescence in the 200-580 nm spectral region was observed in the collisions of H{sup +}, H{sub 2}{sup +}, and H{sub 3}{sup +} with CO in the 50-1000 eV projectile energy range. Using computer simulations, we have identified emission of the following products in the observed spectra: the CO{sup +}(A-X) comet-tail system, CO{sup +}(B-X) first negative system, CO{sup +}(B-A) Baldet-Johnson system, and CO(b-a) third positive system. Also, an emission from atomic hydrogen (H{sub ?} line at 486nm) has been observed. From the analysis of the experimental spectra, we have determined the absolute emission cross-sections for the formation of the observed products. Computer simulations gave the excited-product population distributions over vibrational and rotational energy levels. The vibrational level distribution from the CO{sup +}(A-X) comet-tail system is compared with the data for CO excited by 100 eV electrons and extreme ultraviolet radiation (XUV) photons. We have used these data to analyze the excitation conditions in the comet Humason (1961e). From the vibrational population distributions observed in the comet, we found that this distribution can be reproduced if electrons produce 25%, protons 70%, and XUV photons produce 5% of the emitting molecules. We find that the ratio of the CO{sup +}(B-X) emission to the sum of two main emissions (CO{sup +}(A-X)+CO{sup +}(B-X)) is velocity dependent and does not depend on the projectile ion type. For small velocities (below 100 km s{sup –1}) the ratio is about 5%, while for higher velocities it increases to 30%. For these data, we have found an empirical formula that satisfactorily describes the experimental data: R = R {sub max}(1 – v {sub th}/v), (where R {sub max} = 33%, v {sub th} = 87 km s{sup –1}). This could be used to infer the velocity of ions producing the observed emission of CO{sup +} products.

  18. An Exciting Aspect of Nanotechnology: Unimolecular Electronics

    Directory of Open Access Journals (Sweden)

    Metzger R. M.

    2013-08-01

    Full Text Available This is a brief update on our experimental work towards better one-molecule-thick monolayer rectifiers of electrical current, and on theoretical progress towards a one-molecule amplifier of electrical current. This program aims to provide electronic devices at the 2 to 3 nm level, as a dramatic advance towards practical integrated circuits of the future.

  19. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    2013-01-01

    The step from ab initio atomic and molecular properties to thermodynamic - or macroscopic - properties requires the combination of several theoretical tools. This dissertation presents constant temperature molecular dynamics with bond length constraints, a hybrid quantum mechanics-molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems to show general (or expected) properties. Properties such as in the physical and (semi-)chemical interface between classical and quantum systems and the effects of molecular bond length constraints on the temperature during simulations. As a second step the methodology is applied to the symmetric and asymmetric charge transfer reactions between several first-row transition metals in water. The results are compared to experiments and rationalised with classical analytic expressions. Shortcomings of the methods are accounted for with clear steps towards improved accuracy. Later the analysis is extended to more complex systems composed of a larger osmium complex in solution and at the solute-substrate interfaces, where in particular the redox state of the complex is controlled through chemical means. The efficiency of the hybrid-classical and quantum mechanics method is used to generate adequate statistics and a simple post-sampling scheme used to generate free energy surfaces - which compare to full ab initio calculations. In the last part both the molecular dynamics and hybrid classical and quantum mechanics method are used to generate a vast data set for the accurate analysis of dynamical structure modes. This is for a large iridium-iridium dimer complex which shows a dramatic structural (and vibrational) change upon electronic excitation.

  20. The particle-hole map: a computational tool to visualize electronic excitations

    CERN Document Server

    Li, Yonghui

    2015-01-01

    We introduce the particle-hole map (PHM), a visualization tool to analyze electronic excitations in molecules in the time or frequency domain, to be used in conjunction with time-dependent density-functional theory (TDDFT) or other ab initio methods. The purpose of the PHM is to give detailed insight into electronic excitation processes which is not obtainable from local visualization methods such as transition densities, density differences, or natural transition orbitals. The PHM is defined as a nonlocal function of two spatial variables and provides information about the origins, destinations, and connections of charge fluctuations during an excitation process; it is particularly valuable to analyze charge-transfer excitonic processes. In contrast with the transition density matrix, the PHM has a statistical interpretation involving joint probabilities of individual states and their transitions, it satisfies several sum rules and exact conditions, and it is easier to read and interpret. We discuss and illu...

  1. Measuring excitation-energy transfer with a real-time time-dependent density functional theory approach

    CERN Document Server

    Hofmann, Dirk; Di Ventra, Massimiliano; Kümmel, Stephan

    2012-01-01

    We investigate the time an electronic excitation travels in a supermolecular setup using a measurement process in an open quantum-system framework. The approach is based on the stochastic Schr\\"odinger equation and uses a Hamiltonian from time-dependent density functional theory (TDDFT). It treats electronic-structure properties and intermolecular coupling on the level of TDDFT, while it opens a route to the description of dissipation and relaxation via a bath operator that couples to the dipole moment of the density. Within our study, we find that in supermolecular setups small deviations of the electronic structure from the perfectly resonant case have only minor influence on the pathways of excitation-energy transfer, thus lead to similar transfer times. Yet, sizable defects cause notable slowdown of the energy spread.

  2. Vibrational excitation of molecules by resonant electron scattering

    International Nuclear Information System (INIS)

    A formalism to describe the vibrational excitation of molecules via resonances is presented. For the limiting cases of short and long lifetime of the negative ion the excitation probability can be calculated using a golden rule expression and a simple Hamiltonian. The intensity distribution of the electron energy loss spectrum is expressed in terms of electron-vibration coupling constants which depend on the lifetime of the negative ion. Spectra for resonant scattering on benzene-d6 are calculated and good agreement with experiment is obtained. (orig.)

  3. Structural Phase Transition of Aluminum Induced by Electronic Excitation

    International Nuclear Information System (INIS)

    The dynamics of a structural phase transition induced by interband electronic excitation in aluminum is studied by determining the time evolution of the dielectric constant at 1.55 eV through the measurement of the transient reflectivity induced by an ultrafast pump pulse. The threshold fluence and the time scale for this transition are significantly less than the values necessary for ultrafast heat-induced melting, indicating that this phase change is caused by band structure collapse and lattice instability resulting from strong electronic excitation. (c) 2000 The American Physical Society

  4. Collective modes of laser excited electrons in clusters

    International Nuclear Information System (INIS)

    Complete text of publication follows. Clusters of material at solid state densities can form nanoplasmas after intense laser irradiation. The time evolution of the electron ion system is simulated using semi classical molecular dynamics (MD) simulations. Plasma properties like temperature and density are discussed as function of time. In order to investigated dynamical correlations for finite systems the method of restricted MD simulations has been developed. In this context, we investigate the bi-local frequency dependent structure factor for excited clusters. Within the resonance structure found, different collective excitations have been identified and characterized via the spatial distribution of the momentum auto-correlation function. For demonstration of the applicability of restricted MD simulations, results for resonances in a linear 1D chain are discussed. A systematic behaviour of a dispersion relation typical for plasmon excitations is obtained and agrees well with the bulk limit of an infinite chain. Collective electron excitation modes of 3D clusters are analysed using spherical harmonics. The spatially resolved momentum auto-correlation spectrum is interpreted in terms of collective electron excitation modes. Resonance frequencies of the modes are calculated and identified, for instance as a rigid collective oscillation of all electrons as well as a plane wave like oscillation. Damping rates are discussed. In order to compare with bulk properties, size effects of dynamical properties are investigated. Comparing different cluster sizes at similar ionization degrees, temperatures and densities, we found systematic changes for the Mie mode and the bulk plasmon excitations. In particular, the damping rates are increasing with the cluster size. As already shown for bulk plasmas, the dynamical bi-local structure factor, in particular the current auto-correlation function, is related to optical properties. Scattering as well as absorption of light in excited clusters is influenced by the corresponding collision frequency and subsequently affects the dielectric response function.

  5. 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.

  6. Emission Spectroscopy as a Probe into Photoinduced Intramolecular Electron Transfer in Polyazine Bridged Ru(II,Rh(III Supramolecular Complexes

    Directory of Open Access Journals (Sweden)

    Karen J. Brewer

    2010-08-01

    Full Text Available Steady-state and time-resolved emission spectroscopy are valuable tools to probe photochemical processes of metal-ligand, coordination complexes. Ru(II polyazine light absorbers are efficient light harvesters absorbing in the UV and visible with emissive 3MLCT excited states known to undergo excited state energy and electron transfer. Changes in emission intensity, energy or band-shape, as well as excited state lifetime, provide insight into excited state dynamics. Photophysical processes such as intramolecular electron transfer between electron donor and electron acceptor sub-units may be investigated using these methods. This review investigates the use of steady-state and time-resolved emission spectroscopy to measure excited state intramolecular electron transfer in polyazine bridged Ru(II,Rh(III supramolecular complexes. Intramolecular electron transfer in these systems provides for conversion of the emissive 3MLCT (metal-to-ligand charge transfer excited state to a non-emissive, but potentially photoreactive, 3MMCT (metal-to-metal charge transfer excited state. The details of the photophysics of Ru(II,Rh(III and Ru(II,Rh(III,Ru(II systems as probed by steady-state and time-resolved emission spectroscopy will be highlighted.

  7. Vibrationally Assisted Electron Transfer Mechanism of Olfaction: Myth or Reality?

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Chang, Po-Yao

    2012-01-01

    Smell is a vital sense for animals. The mainstream explanation of smell is based on recognition of the odorant molecules through characteristics of their surface, e.g., shape, but certain experiments suggest that such recognition is complemented by recognition of vibrational modes. According to this suggestion an olfactory receptor is activated by electron transfer assisted through odorant vibrational excitation. The hundreds to thousands of different olfactory receptors in an animal recognize odorants over a discriminant landscape with surface properties and vibrational frequencies as the two major dimensions. In the present paper we introduce the vibrationally assisted mechanism of olfaction and demonstrate for several odorants that, indeed, a strong enhancement of an electron tunneling rate due to odorant vibrations can arise. We discuss in this regard the influence of odorant deuteration and explain, thereby, recent experiments performed on Drosophila melanogaster. Our demonstration is based on known physical properties of biological electron transfer and on ab initio calculations on odorants carried out for the purpose of the present study. We identify a range of physical characteristics which olfactory receptors and odorants must obey for the vibrationally assisted electron transfer mechanism to function. We argue that the stated characteristics are feasible for realistic olfactory receptors, noting, though, that the receptor structure presently is still unknown, but can be studied through homology modeling.

  8. Vibrational energy transfer in selectively excited diatomic molecules

    International Nuclear Information System (INIS)

    Single rovibrational states of HCl(v=2), HBr(v=2), DCl(v=2), and CO(v=2) were excited with a pulsed optical parametric oscillator (OPO). Total vibrational relaxation rates near - resonance quenchers were measured at 2950K using time resolved infrared fluorescence. These rates are attributed primarily to V - V energy transfer, and they generally conform to a simple energy gap law. A small deviation was found for the CO(v) + DCl(v') relaxation rates. Upper limits for the self relaxation by V - R,T of HCl(v=2) and HBr(v=2) and for the two quantum exchange between HCl and HBr were determined. The HF dimer was detected at 2950K and 30 torr HF pressure with an optoacoustic spectrometer using the OPO. Pulsed and chopped, resonant and non-resonant spectrophones are analyzed in detail. From experiments and first order perturbation theory, these V - V exchange rates appear to behave as a first order perturbation in the vibrational coordinates. The rotational dynamics are known to be complicated however, and the coupled rotational - vibrational dynamics were investigated theoreticaly in infinite order by the Dillon and Stephenson and the first Magnus approximations. Large ?J transitions appear to be important, but these calculations differ by orders of magnitude on specific rovibrational transition rates. Integration of the time dependent semiclassical equations by a modified Gordon method and a rotationally distorted wave approximation are discussed as methods which would treat the rotational motion more accurately. 225 references

  9. Monte Carlo generators for excited electron and neutrino production

    International Nuclear Information System (INIS)

    'EPEX' and 'NUPEX' are monte carlo event generators, written in standard FORTRAN 77, being able to simulate the production and the decay of the excited leptons e* and ?e* at the electron-proton-colliders HERA and LHC+LEP. A further option of the program 'EPEX' is to simulate the inelastic electron-proton-scattering via contact interactions as: e + p ? e + X. (orig./HSI)

  10. Excitation of He(31D) by electron impact

    International Nuclear Information System (INIS)

    We report new results of the Stokes parameters P1 to P4 and of the coherence parameters Plin, ?a, ?00 and Lperpendicularto for He(31D) excitation by electron impact in the energy range 40 eV to 81.6 eV obtained by the scattered electron-polarized photon coincidence technique. The present results are, where available, in fair agreement with previous meaasurements of other groups but disagree with the available calculations based on different models. (orig.)

  11. Study of excitation transfer in laser dye mixtures by direct measurement of fluorescence lifetime

    Science.gov (United States)

    Lin, C.; Dienes, A.

    1973-01-01

    By directly measuring the donor fluorescence lifetime as a function of acceptor concentration in the laser dye mixture Rhodamine 6G-Cresyl violet, we found that the Stern-Volmer relation is obeyed, from which the rate of excitation transfer is determined. The experimental results indicate that the dominant mechanism responsible for the efficient excitation transfer is that of resonance transfer due to long range dipole-dipole interaction.

  12. Promoting Knowledge Transfer with Electronic Note Taking

    Science.gov (United States)

    Katayama, Andrew D.; Shambaugh, R. Neal; Doctor, Tasneem

    2005-01-01

    We investigated the differences between (a) copying and pasting text versus typed note-taking methods of constructing study notes simultaneously with (b) vertically scaffolded versus horizontally scaffold notes on knowledge transfer. Forty-seven undergraduate educational psychology students participated. Materials included 2 electronic

  13. Quantum effects in biological electron transfer.

    Czech Academy of Sciences Publication Activity Database

    de la Lande, A.; Babcock, N. S.; ?ezá?, Jan; Levy, B.; Sanders, B. C.; Salahub, D.

    2012-01-01

    Ro?. 14, ?. 17 (2012), s. 5902-5918. ISSN 1463-9076 Institutional research plan: CEZ:AV0Z40550506 Keywords : electron transfer * tunnelling * decoherence * semi-classical molecular dynamics * density functional theory Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.829, year: 2012

  14. Molecular dynamics simulation of electronically excited polyatomic molecules

    International Nuclear Information System (INIS)

    A computer simulation method is proposed for MD study of the photoinduced intramolecular dynamics in polyatomic molecules electronically excited by ultrashort laser pulses. An efficient, partially analytical procedure for calculation of the absorption (emission) spectra is developed and used for determination of molecular potentials in accordance with the experimental supersonic jets spectra. (author). 21 refs, 4 figs, 1 tab

  15. Excitation of electron Langmuir frequency harmonics in the solar atmosphere

    International Nuclear Information System (INIS)

    An alternative mechanism for the excitation of electron Langmuir frequency harmonics as a result of the development of explosive instability in a weakly relativistic beam-plasma system in the solar atmosphere is proposed. The efficiency of the new mechanism as compared to the previously discussed ones is analyzed.

  16. Cyclotron electron beam excited surface plasmon polaritons coherent radiation

    Science.gov (United States)

    Sen, Gong; Tao, Zhao; Min, Hu; Renbin, Zhong; Xiaoxing, Chen; Diwei, Liu; Ping, Zhang; Chao, Zhang; Jian, Chen; Biaobin, Jin; Huabing, Wang; Peiheng, Wu; Shenggang, Liu

    2015-07-01

    A physical mechanism of electron beam excitation of surface plasmon polaritons (SPPs) on the circular cylindrical structure and transformation into coherent radiation is proposed. Here SPPs on the circular cylindrical structures are excited by a cyclotron electron beam (CEB) rather than by the linearly moving electron beam (LEB). This change leads to an essential consequence due to the natural periodicity of 2? in structure and CEB, and this dual natural periodicity makes the SPPs transformation possible and brings significant excellences. HEM hybrid modes and \\text{TM}0n modes SPPs can be excited and propagate along a cyclotron trajectory together with the CEB to attract energy from CEB continuously to compensate the energy loss; the phase velocity of SPPs synchronizes the CEB; the process of the excitation and transformation is longer. Therefore, the transformed power density is enhanced and reaches up to 1010 \\text{W/cm}2 . The cyclotron frequency of the electron beam is 1 THz, but the frequency regime of the SPPs and the radiation are much higher, up to hundreds of terahertz. The mechanism presented in this letter opens the way for developing the desired room temperature, powerful and coherent light radiation sources from the infrared to the ultraviolet frequency regime.

  17. Defect production and annihilation in metals through electronic excitation by energetic heavy ion bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Iwase, Akihiro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1997-03-01

    Defect production, radiation annealing and defect recovery are studied in Ni and Cu irradiated with low-energy ({approx}1-MeV) and high-energy ({approx}100-MeV) ions. Irradiation of Ni with {approx}100-MeV ions causes an anomalous reduction, or even a complete disappearance of the stage-I recovery. This result shows that the energy transferred from excited electrons to lattice atoms through the electron-lattice interaction contributes to the annihilation of the stage-I interstitials. This effect is also observed in Ni as a large radiation annealing during 100-MeV heavy ion irradiation. On the other hand, in Cu thin foils, we find the defect production process strongly associated with electron excitation, where the defect production cross section is nearly proportional to S{sub e}{sup 2}. (author)

  18. Localised to intraligand charge-transfer states in cyclometalated platinum complexes: an experimental and theoretical study into the influence of electron-rich pendants and modulation of excited states by ion binding.

    Science.gov (United States)

    Rochester, David L; Develay, Stéphanie; Zális, Stanislav; Williams, J A Gareth

    2009-03-14

    The neopentyl ester of 1,3-di(2-pyridyl)benzene-5-boronic acid (dpy-B) is a useful intermediate in the divergent synthesis of N;C;N-coordinating, 1,3-di(2-pyridyl)benzene ligands, HL(n), that carry aryl substituents at the 5-position of the central ring. The platinum(ii) complexes, PtL(n)Cl, of several such ligands have been prepared, incorporating pendant anisoles, arylamines, an oxacrown, and an azacrown, all of which are strongly luminescent in solution at 298 K. The emission of the complexes is partially quenched by oxygen, and all of the compounds are very efficient sensitisers of singlet oxygen. The quantum yields of (1)O(2) formation have been measured on the basis of the intensity of the O(2)(1)Delta(g) emission at 1270 nm, and are in the range 0.25-0.65. Density functional theory (DFT) calculations have been carried out that include the effect of the solvent, on the unsubstituted complex PtL(1)Cl and on the derivatives incorporating p-dimethylaminophenyl and phenyl-15-mono-N-azacrown-5 pendants (PtL(9)Cl and PtL(12)Cl respectively). Absorption spectra have been simulated on the basis of the calculated singlet excitations: they closely resemble the experimental spectra. In particular, the DFT successfully accounts for the appearance of low-energy absorption bands that accompany the introduction of the aryl pendants, indicating the participation of the aryl group in the HOMO but not significantly in the LUMO. The calculated lowest energy triplet excitation of PtL(1)Cl is close to the observed 0-0 emission maximum of this complex in solution. Taking together data for this series of complexes and related compounds previously studied, the energies of the lowest-energy spin-allowed absorption bands are shown to correlate approximately linearly with the oxidation peak potential. The emission energies show a similar correlation in toluene, but in CH2Cl2 the value for PtL(9)Cl is anomalously low. The differing emission properties of this complex in the two solvents suggest a switch to a TICT-like state in CH2Cl2 (TICT = twisted intramolecular charge transfer), stabilised in the more polar environment. Transient DC photoconductivity measurements confirm that the dipole moment of the triplet excited state is larger in CH2Cl2 than in toluene. The azacrown PtL(12)Cl displays similar behaviour. Binding of metal ions such as Ca2+ to the azacrown unit of this complex leads to a pronounced blue shift in the emission, which can be readily understood in terms of the large increase in the TICT energy that will accompany the binding of the metal ion to the lone pair of the azacrown nitrogen atom. PMID:19240906

  19. Excited-state kinetics of the carotenoid S//1 state in LHC II and two-photon excitation spectra of lutein and beta-carotene in solution Efficient Car S//1 yields Chl electronic energy transfer via hot S//1 states?

    CERN Document Server

    Walla, P J; Linden, Patricia A; Ohta, Kaoru

    2002-01-01

    The excited-state dynamics of the carotenoids (Car) in light- harvesting complex II (LHC II) of Chlamydomonas reinhardtii were studied by transient absorption measurements. The decay of the Car S //1 population ranges from similar to 200 fs to over 7 ps, depending on the excitation and detection wavelengths. In contrast, a 200 fs Car S//1 yields Chlorophyll (Chl) energy transfer component was the dominant time constant for our earlier two-photon fluorescence up- conversion measurements (Walla, P.J. ; et al. J. Phys. Chem. B 2000, 104, 4799-4806). We also present the two-photon excitation (TPE) spectra of lutein and beta-carotene in solution and compare them with the TPE spectrum of LHC II. The TPE-spectrum of LHC II has an onset much further to the blue and a width that is narrower than expected from comparison to the S//1 fluorescence of lutein and beta-carotene in solution. Different environments may affect the shape of the S//1 spectrum significantly. To explain the blue shift of the TPE spectrum and the d...

  20. Excitation of magnesium ions in slow electron-ion collisions

    International Nuclear Information System (INIS)

    Using the method of crossing modulated beams, the absolute excitation functions for the transitions 3s-3p and 3p-4s in Mg 2 taking place in collisions between electrons and magnesium ions have been measured. The study has been carried out by measuring the flux of photons excited in the transitions indicated. The estimated error of the determination of the absolute cross sections is about 25%. The energy dependences of the cross sections have been investigated from the threshold of excitation to 100 eV. In both cases, an abrupt increase in the effectiveness of excitation can be observed in the near-threshold region, which is consistent (if the electron energy straggling is taken into account) with the concept that at threshold the cross section is finite. As the electron energy increases, one can observe a steady decrease of the above characteristic. At an energy of 11 eV, the resonance doublet excitation functions have a bench, which may be accounted for the cascade contribution to the 3p-state population. The greatest effectiveness of excitation of the 3p-4s transition is attained just at the energy of 11 eV, amounting to about 4% of that for the 3s-3p transition. For comparison also the results of theoretical calculations of the cross sections for excitation of the 3p- and 4s-configurations, have been given, performed in a modified Coulomb-Born approximation. At electron energies of 80 eV and above one observes a reasonable agreement between theory and experiment. The experimental results on the resonance doublet excitation are also compared with the results of calculations of the 3s-3p excitation carried out in the Bethe approximation. The strong-coupling calculations yield the cross-sectional values close to the experimental ones measured in the corresponding energy region. The slope of the theoretical curves is, however, different from that of the experimental ones. The Bethe approximation has been used also at the higher energies

  1. An efficient implementation of the localized operator partitioning method for electronic energy transfer

    International Nuclear Information System (INIS)

    The localized operator partitioning method [Y. Khan and P. Brumer, J. Chem. Phys. 137, 194112 (2012)] rigorously defines the electronic energy on any subsystem within a molecule and gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. However, an efficient implementation of this approach has been hindered by complicated one- and two-electron integrals arising in its formulation. Using a resolution of the identity in the definition of partitioning, we reformulate the method in a computationally efficient manner that involves standard one- and two-electron integrals. We apply the developed algorithm to the 9 ? ((1 ? naphthyl) ? methyl) ? anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH2 ? naphthyl groups as subsystems and examine their electronic energies and populations for several excited states using configuration interaction singles method. The implemented approach shows a wide variety of different behaviors amongst the excited electronic states

  2. Electron emission and electron transfer processes in proton-naphthalene collisions at intermediate velocities

    Science.gov (United States)

    Mishra, P. M.; Rajput, J.; Safvan, C. P.; Vig, S.; Kadhane, U.

    2013-11-01

    We investigate the fragmentation and ionization of naphthalene by protons at intermediate velocities (between 1.41 and 2.68 a.u.). Relative cross sections for electron capture (EC), electron emission (EE), and capture ionization are measured. The EC cross sections decrease rapidly over the energy range under consideration (50-150 keV) and are lower than EE cross sections. The EE cross sections, on the other hand, change very slowly in this energy range. The energetics of interactions is quantified by comparing the mass spectra with the photodissociation breakdown curves from literature. In the case of single capture, resonant electron transfer to n = 1 state in H+ is seen to dominate the interaction but is shown to be accompanied by a small amount of electronic energy loss. In the EE mode, two mechanisms are shown to be active in the collision process: large impact parameter plasmon excitation mode, and closer encounters with higher amounts of electronic energy loss.

  3. Dynamic correlation of photo-excited electrons: Anomalous levels induced by light–matter coupling

    International Nuclear Information System (INIS)

    Nonlinear light–matter coupling plays an important role in many aspects of modern physics, such as spectroscopy, photo-induced phase transition, light-based devices, light-harvesting systems, light-directed reactions and bio-detection. However, excited states of electrons are still unclear for nano-structures and molecules in a light field. Our studies unexpectedly present that light can induce anomalous levels in the electronic structure of a donor–acceptor nanostructure with the help of the photo-excited electrons transferring dynamically between the donor and the acceptor. Furthermore, the physics underlying is revealed to be the photo-induced dynamical spin–flip correlation among electrons. These anomalous levels can significantly enhance the electron current through the nanostructure. These findings are expected to contribute greatly to the understanding of the photo-excited electrons with dynamic correlations, which provides a push to the development and application of techniques based on photosensitive molecules and nanostructures, such as light-triggered molecular devices, spectroscopic analysis, bio-molecule detection, and systems for solar energy conversion.

  4. Dynamics of two-electron excitations in helium

    Energy Technology Data Exchange (ETDEWEB)

    Caldwell, C.D.; Menzel, A.; Frigo, S.P. [Univ. of Central Florida, Orlando, FL (United States)] [and others

    1997-04-01

    Excitation of both electrons in helium offers a unique window for studying electron correlation at the most basic level in an atom in which these two electrons and the nucleus form a three-body system. The authors utilized the first light available at the U-8 undulator-SGM monochromator beamline to investigate the dynamic parameters, partial cross sections, differential cross sections, and photoelectron angular distribution parameters ({beta}), with a high resolving power for the photon beam and at the highly differential level afforded by the use of their electron spectrometer. In parallel, they carried out detailed calculations of the relevant properties by a theoretical approach that is based on the hyperspherical close-coupling method. Partial photoionization cross sections {sigma}{sub n}, and photoelectron angular distributions {beta}{sub n} were measured for all possible final ionic states He{sup +}(n) in the region of the double excitations N(K,T){sup A} up to the N=5 threshold. At a photon energy bandpass of 12 meV below the thresholds N=3, 4, and 5, this level of differentiation offers the most critical assessment of the dynamics of the two-electron excitations to date. The experimental data were seen to be very well described by the most advanced theoretical calculations.

  5. Statistics of excitations in the electron glass model

    Science.gov (United States)

    Palassini, Matteo

    2011-03-01

    We study the statistics of elementary excitations in the classical electron glass model of localized electrons interacting via the unscreened Coulomb interaction in the presence of disorder. We reconsider the long-standing puzzle of the exponential suppression of the single-particle density of states near the Fermi level, by measuring accurately the density of states of charged and electron-hole pair excitations via finite temperature Monte Carlo simulation and zero-temperature relaxation. We also investigate the statistics of large charge rearrangements after a perturbation of the system, which may shed some light on the slow relaxation and glassy phenomena recently observed in a variety of Anderson insulators. In collaboration with Martin Goethe.

  6. A quadrature excitation coil for longitudinally detected electron spin resonance

    Science.gov (United States)

    Resmer, Frank; Nicholson, Ian; Hutchison, James M. S.

    2001-07-01

    Longitudinally detected electron spin resonance (LODESR) is an alternative method to conventional continuous wave (cw) ESR with transverse detection. LODESR has some practical advantages over cw-ESR for in vivo experiments carried out with excitation at radio frequencies. Sample losses, however, can be a problem and generally limit the LODESR signal to noise ratio for biological samples. We have developed a LODESR coil system with quadrature excitation circuit in order to decrease the sample power deposition. The coil system consists of a high pass birdcage excitation coil operated in quadrature (320 MHz) and a solenoidal coil (325 kHz) for signal detection. Methods of decoupling the excitation and detection circuits are described. Results reported here show the effectiveness of the LODESR coil system with quadrature excitation in reducing the sample power deposition by a factor of 2. The quadrature excitation coil assembly we have described here could be used, without further modification, for LODESR imaging. The coil assembly, including rf screen, could be placed inside the field gradient coils. LODESR imaging, in contrast to nuclear magnetic resonance imaging, uses continuous rather than pulsed gradient wave forms and the copper foil used for the rf screen would not significantly distort the gradients.

  7. Ultrafast Intramolecular Electron and Proton Transfer in Bis(imino)isoindole Derivatives.

    Science.gov (United States)

    Driscoll, Eric; Sorenson, Shayne; Dawlaty, Jahan M

    2015-06-01

    Concerted motion of electrons and protons in the excited state is pertinent to a wide range of chemical phenomena, including those relevant for solar-to-fuel light harvesting. The excited state dynamics of small proton-bearing molecules are expected to serve as models for better understanding such phenomena. In particular, for designing the next generation of multielectron and multiproton redox catalysts, understanding the dynamics of more than one proton in the excited state is important. Toward this goal, we have measured the ultrafast dynamics of intramolecular excited state proton transfer in a recently synthesized dye with two equivalent transferable protons. We have used a visible ultrafast pump to initiate the proton transfer in the excited state, and have probed the transient absorption of the molecule over a wide bandwidth in the visible range. The measurement shows that the signal which is characteristic of proton transfer emerges within ?710 fs. To identify whether both protons were transferred in the excited state, we have measured the ultrafast dynamics of a related derivative, where only a single proton was available for transfer. The measured proton transfer time in that molecule was ?427 fs. The observed dynamics in both cases were reasonably fit with single exponentials. Supported by the ultrafast observations, steady-state fluorescence, and preliminary computations of the relaxed excited states, we argue that the doubly protonated derivative most likely transfers only one of its two protons in the excited state. We have performed calculations of the frontier molecular orbitals in the Franck-Condon region. The calculations show that in both derivatives, the excitation is primarily from the HOMO to LUMO causing a large rearrangement of the electronic charge density immediately after photoexcitation. In particular, charge density is shifted away from the phenolic protons and toward the proton acceptor nitrogens. The proton transfer is hypothesized to occur both due to enhanced acidity of the phenolic proton and enhanced basicity of the nitrogen in the excited state. We hope this study can provide insight for better understanding of the general class of excited state concerted electron-proton dynamics. PMID:25932563

  8. Excitation transfer pathways in excitonic aggregates revealed by the stochastic Schrödinger equation

    Energy Technology Data Exchange (ETDEWEB)

    Abramavicius, Vytautas, E-mail: vytautas.ab@gmail.com; Abramavicius, Darius, E-mail: darius.abramavicius@ff.vu.lt [Faculty of Physics, Department of Theoretical Physics, Vilnius University, Saul?tekio 9, LT-10222 Vilnius (Lithuania)

    2014-02-14

    We derive the stochastic Schrödinger equation for the system wave vector and use it to describe the excitation energy transfer dynamics in molecular aggregates. We suggest a quantum-measurement based method of estimating the excitation transfer time. Adequacy of the proposed approach is demonstrated by performing calculations on a model system. The theory is then applied to study the excitation transfer dynamics in a photosynthetic pigment-protein Fenna-Matthews-Olson (FMO) aggregate using both the Debye spectral density and the spectral density obtained from earlier molecular dynamics simulations containing strong vibrational high-frequency modes. The obtained results show that the excitation transfer times in the FMO system are affected by the presence of the vibrational modes; however, the transfer pathways remain the same.

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

    International Nuclear Information System (INIS)

    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.)

  10. Excitement tem-horn antenna by impulsive relativistic electron beam

    CERN Document Server

    Balakirev, V A; Egorov, A M; Lonin, Y F

    2000-01-01

    In the given operation the opportunity of reception powerful electromagnetic irradiation (EMI) is observationally explored by excitation by a impulsive relativistic electronic beam (IREB) of a TEM-horn antenna. It is revealed, that at such expedient of excitation of the TEM-horn antenna, the signal of radiation of the antenna contains three various components caused by oscillation of radiation by forward front IREB, high-voltage discharge between plates irradiation of TEM-horn antenna a and resonant properties of the antenna devices.

  11. Charge-Transfer Excitations in the Model Superconductor HgBa$_2$CuO$_{\\bf 4+\\delta}$

    OpenAIRE

    Lu, L.; Zhao , X.; Chabot-Couture, G.; Hancock, J. N.; Kaneko, N.; Vajk, O. P.; Yu, G; Grenier, S.; Kim, Y.J.; Casa, D.; Gog, T.; Greven, M.

    2005-01-01

    We report a Cu $K$-edge resonant inelastic x-ray scattering (RIXS) study of charge-transfer excitations in the 2-8 eV range in the structurally simple compound HgBa$_2$CuO$_{4+\\delta}$ at optimal doping ($T_{\\rm c} = 96.5 $ K). The spectra exhibit a significant dependence on the incident photon energy which we carefully utilize to resolve a multiplet of weakly-dispersive ($ < 0.5$ eV) electron-hole excitations, including a mode at 2 eV. The observation of this 2 eV excitatio...

  12. Spectroscopy of nitrophenolates in vacuo: effect of spacer, configuration, and microsolvation on the charge-transfer excitation energy

    DEFF Research Database (Denmark)

    Nielsen, Steen Brøndsted; Nielsen, Mogens Brøndsted; Rubio, Angel

    2014-01-01

    Conspectus In a charge-transfer (CT) transition, electron density moves from one end of the molecule (donor) to the other end (acceptor). This type of transition is of paramount importance in nature, for example, in photosynthesis, and it governs the excitation of several protein biochromophores and luminophores such as the oxyluciferin anion that accounts for light emission from fireflies. Both transition energy and oscillator strength are linked to the coupling between the donor and acceptor g...

  13. Local electron distributions and diffusion in anharmonic lattices mediated by thermally excited solitons

    Science.gov (United States)

    Chetverikov, A. P.; Ebeling, W.; Velarde, M. G.

    2009-07-01

    We study the excitation of solitons in lattices with Morse interactions in a wide temperature range and their influence on (free) electrons moving in the lattice. The lattice units (considered as “atoms" or “screened ion cores") are treated by classical Langevin equations. For visualizations the densities of the core (valence) electrons are in a first estimate represented by Gaussian densities, thus permitting to visualize lattice compressions. The evolution of the (free) electrons is modelled in the tight binding approximation first using Schrödinger equation and, subsequently, a stochastic description of the evolution as a Markov process. We investigate electron transfer assisted by solitons and solitonic influences on macroscopic transport in particular on diffusion. Then we consider the electron-lattice interaction and obtain numerical solutions of the simultaneously evolving Langevin and Pauli master equations. We show that the proposed mechanism of riding on thermal solitons is relatively fast (of the order of the sound velocity).

  14. Neutral histidine and photoinduced electron transfer in DNA photolyases.

    Science.gov (United States)

    Domratcheva, Tatiana

    2011-11-16

    The two major UV-induced DNA lesions, the cyclobutane pyrimidine dimers (CPD) and (6-4) pyrimidine-pyrimidone photoproducts, can be repaired by the light-activated enzymes CPD and (6-4) photolyases, respectively. It is a long-standing question how the two classes of photolyases with alike molecular structure are capable of reversing the two chemically different DNA photoproducts. In both photolyases the repair reaction is initiated by photoinduced electron transfer from the hydroquinone-anion part of the flavin adenine dinucleotide (FADH(-)) cofactor to the photoproduct. Here, the state-of-the-art XMCQDPT2-CASSCF approach was employed to compute the excitation spectra of the respective active site models. It is found that protonation of His365 in the presence of the hydroquinone-anion electron donor causes spontaneous, as opposed to photoinduced, coupled proton and electron transfer to the (6-4) photoproduct. The resulting neutralized biradical, containing the neutral semiquinone and the N3'-protonated (6-4) photoproduct neutral radical, corresponds to the lowest energy electronic ground-state minimum. The high electron affinity of the N3'-protonated (6-4) photoproduct underlines this finding. Thus, it is anticipated that the (6-4) photoproduct repair is assisted by His365 in its neutral form, which is in contrast to the repair mechanisms proposed in the literature. The repair via hydroxyl group transfer assisted by neutral His365 is considered. The repair involves the 5'base radical anion of the (6-4) photoproduct which in terms of electronic structure is similar to the CPD radical anion. A unified model of the CPD and (6-4) photoproduct repair is proposed. PMID:21970417

  15. The role of electron-impact vibrational excitation in electron transport through gaseous tetrahydrofuran

    International Nuclear Information System (INIS)

    In this paper, we report newly derived integral cross sections (ICSs) for electron impact vibrational excitation of tetrahydrofuran (THF) at intermediate impact energies. These cross sections extend the currently available data from 20 to 50 eV. Further, they indicate that the previously recommended THF ICS set [Garland et al., Phys. Rev. A 88, 062712 (2013)] underestimated the strength of the electron-impact vibrational excitation processes. Thus, that recommended vibrational cross section set is revised to address those deficiencies. Electron swarm transport properties were calculated with the amended vibrational cross section set, to quantify the role of electron-driven vibrational excitation in describing the macroscopic swarm phenomena. Here, significant differences of up to 17% in the transport coefficients were observed between the calculations performed using the original and revised cross section sets for vibrational excitation

  16. Electronic transfer between low-dimensional nanosystems.

    Czech Academy of Sciences Publication Activity Database

    Král, Karel

    Hoboken : Wiley, 2011 - (Nair, K.; Priya, S.; Jia, Q.), s. 33-40 ISBN 9781118059999. - (Ceramic Transactions. vol. 226). [Materials Science and Technology meeting 2010 (MS&T'10). Dielectric Ceramic Materials and Electronic Devices .. Houston (US), 17.10.2010-21.10.2010] R&D Projects: GA MŠk(CZ) OC10007 Institutional research plan: CEZ:AV0Z10100520 Keywords : electron transfer * nanostructures quantum dots Subject RIV: BM - Solid Matter Physics ; Magnetism http://eu.wiley.com/WileyCDA/WileyTitle/productCd-1118059999,descCd-tableOfContents.html

  17. Bonding electrons visualization in photo-excited state using synchrotron x-ray powder diffractometry

    International Nuclear Information System (INIS)

    The synchrotron X-ray powder diffractometry has been recognized as one of powerful methods for materials science research. By using Maximum Entropy Method (MEM) as an analytical method for the powder diffraction data, bonding electrons can be visualized to reveal the structure-property relationship. The reliability of the MEM change density depends on 'accuracy' and precision' of experimental data. In present studies, we have succeeded in visualizing bonding electrons in the photo-excited state. So far the accuracy of structural analysis under photo irradiation has not reached bonding electrons level. That can be attributed to inhomogeneous excitation caused by large difference between probe light (X-ray) and excitation light (visible laser) energy. In order to overcome the difficulties, we designed sample packing method into a capillary and photo irradiation system for homogeneous excitation. As a result charge density analysis under photo irradiation was successfully achieved in one of spin crossover complexes, Fe(phen)2(NCS)2, which shows a dynamical photo-induced phase transition (PIPT). The bonding nature between Fe and N under photo irradiation is clearly suppressed compared with both ground low-spin phase and temperature induced high-spin phase. The bonding nature created by visible laser may characterize the faster relaxation process of the dynamical PIPT. In my talk, charge density study of persistent PIPT materials (transition metal cyanides) and transient PIPT materials (charge transfer organic materials) will be presented with the dynamical PIPT material. (author)

  18. Extremely confined gap surface-plasmon modes excited by electrons.

    DEFF Research Database (Denmark)

    Raza, SØren; Stenger, Nicolas

    2014-01-01

    High-spatial and energy resolution electron energy-loss spectroscopy (EELS) can be used for detailed characterization of localized and propagating surface-plasmon excitations in metal nanostructures, giving insight into fundamental physical phenomena and various plasmonic effects. Here, applying EELS to ultra-sharp convex grooves in gold, we directly probe extremely confined gap surface-plasmon (GSP) modes excited by swift electrons in nanometre-wide gaps. We reveal the resonance behaviour associated with the excitation of the antisymmetric GSP mode for extremely small gap widths, down to ~5 nm. We argue that excitation of this mode, featuring very strong absorption, has a crucial role in experimental realizations of non-resonant light absorption by ultra-sharp convex grooves with fabrication-induced asymmetry. The occurrence of the antisymmetric GSP mode along with the fundamental GSP mode exploited in plasmonic waveguides with extreme light confinement is a very important factor that should be taken into account in the design of nanoplasmonic circuits and devices.

  19. Promoting interspecies electron transfer with biochar

    DEFF Research Database (Denmark)

    Chen, Shanshan; Rotaru, Amelia-Elena; Shrestha, Pravin Malla; Malvankar, Nikhil S.; Liu, Fanghua; Fan, Wei; Nevin, Kelly P.; Lovley, Derek R.

    2014-01-01

    Biochar, a charcoal-like product of the incomplete combustion of organic materials, is an increasingly popular soil amendment designed to improve soil fertility. We investigated the possibility that biochar could promote direct interspecies electron transfer (DIET) in a manner similar to that previously reported for granular activated carbon (GAC). Although the biochars investigated were 1000 times less conductive than GAC, they stimulated DIET in co-cultures of Geobacter metallireducens with Ge...

  20. Electron transfer in branched expanded pyridinium molecules.

    Czech Academy of Sciences Publication Activity Database

    Hromadová, Magdaléna; Lachmanová, Št?pánka; Pospíšil, Lubomír; Fortage, J.; Dupeyre, G.; Perruchot, Ch.; Lainé, P. P.

    Aveiro : DEMAC - Universidade de Aveiro, 2014. s. 99-99. [Meeting of the Portuguese Electrochemical Society /19./. Iberian Meeting of Electrochemistry /16./. 30.06.2014-02.07.2014, Aveiro] R&D Projects: GA ?R(CZ) GA14-05180S Grant ostatní: Rada Programu interní porpory projekt? mezinárodní spolupráce AV ?R M200401202 Institutional support: RVO:61388955 Keywords : electron transfer * electrochemistry * pyridinium Subject RIV: CG - Electrochemistry

  1. Quantum coherent contributions in biological electron transfer

    OpenAIRE

    Dorner, Ross; Goold, John; Heaney, Libby; Farrow, Tristan; Roberts, Philippa G.; Hirst, Judy; Vedral, Vlatko

    2011-01-01

    Many biological electron transfer (ET) reactions are mediated by metal centres in proteins. NADH:ubiquinone oxidoreductase (complex I) contains an intramolecular chain of seven iron-sulphur (FeS) clusters, one of the longest chains of metal centres in biology and a test case for physical models of intramolecular ET. In biology, intramolecular ET is commonly described as a diffusive hopping process, according to the semi-classical theories of Marcus and Hopfield. However, rec...

  2. Promoting Interspecies Electron Transfer with Biochar

    OpenAIRE

    Chen, Shanshan; Rotaru, Amelia-Elena; Shrestha, Pravin Malla; Nikhil S. Malvankar; Liu, Fanghua; Fan, Wei; Nevin, Kelly P; Derek R. Lovley

    2014-01-01

    Biochar, a charcoal-like product of the incomplete combustion of organic materials, is an increasingly popular soil amendment designed to improve soil fertility. We investigated the possibility that biochar could promote direct interspecies electron transfer (DIET) in a manner similar to that previously reported for granular activated carbon (GAC). Although the biochars investigated were 1000 times less conductive than GAC, they stimulated DIET in co-cultures of Geobacter metallireducens with...

  3. Vibrational relaxation pathways in the electronic excited state of carotenoid

    International Nuclear Information System (INIS)

    The intra- and inter-molecular vibrational relaxation in the electronic excited state (1Bu+) of spheroidene derivative (the number of conjugated double bonds, n=8) has been investigated at room temperature by means of femtosecond time-resolved fluorescence spectroscopy based on an optical-Kerr-gate technique. Depending on the photo-excitation either to the 1Bu+(v=1) or 1Bu+(v=2) vibronic level, remarkable differences were observed in hot luminescence spectra related to the vibrational relaxation process of high- and low-frequency modes. Under the excitation to the 1Bu+(v=2) state hot luminescence from the 1Bu+(v=1) state was observed as a dominant feature of the time-resolved spectra while the dynamic Stokes shift originating from the low-frequency-modes dynamics was clearly observed under the excitation to the 1Bu+(v=1). These observations of the excitation energy dependence of time-resolved fluorescence spectra were discussed by analyzing the Franck-Condon factors of transitions from v=0,1, and 2 levels of high-frequency modes

  4. Hot-electron-mediated desorption rates calculated from excited-state potential energy surfaces

    DEFF Research Database (Denmark)

    Olsen, Thomas; Gavnholt, Jeppe

    2009-01-01

    We present a model for desorption induced by (multiple) electronic transitions [DIET (DIMET)] based on potential energy surfaces calculated with the delta self-consistent field extension of density-functional theory. We calculate potential energy surfaces of CO and NO molecules adsorbed on various transition-metal surfaces and show that classical nuclear dynamics does not suffice for propagation in the excited state. We present a simple Hamiltonian describing the system with parameters obtained from the excited-state potential energy surface and show that this model can describe desorption dynamics in both the DIET and DIMET regimes and reproduce the power-law behavior observed experimentally. We observe that the internal stretch degree of freedom in the molecules is crucial for the energy transfer between the hot electrons and the molecule when the coupling to the surface is strong.

  5. Energy shift of collective electron excitations in highly corrugated graphitic nanostructures: Experimental and theoretical investigation

    Energy Technology Data Exchange (ETDEWEB)

    Sedelnikova, O. V., E-mail: o.sedelnikova@gmail.com; Bulusheva, L. G.; Okotrub, A. V. [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Science, 3 Acad. Lavrentiev Ave., Novosibirsk 630090 (Russian Federation); Novosibirsk State University, 2 Pirogov Str., Novosibirsk 630090 (Russian Federation); Tomsk State University, 36 Lenina Ave., Tomsk 634050 (Russian Federation); Asanov, I. P. [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Science, 3 Acad. Lavrentiev Ave., Novosibirsk 630090 (Russian Federation); Novosibirsk State University, 2 Pirogov Str., Novosibirsk 630090 (Russian Federation); Yushina, I. V. [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Science, 3 Acad. Lavrentiev Ave., Novosibirsk 630090 (Russian Federation)

    2014-04-21

    Effect of corrugation of hexagonal carbon network on the collective electron excitations has been studied using optical absorption and X-ray photoelectron spectroscopy in conjunction with density functional theory calculations. Onion-like carbon (OLC) was taken as a material, where graphitic mantle enveloping agglomerates of multi-shell fullerenes is strongly curved. Experiments showed that positions of ? and ??+?? plasmon modes as well as ? ? ?* absorption peak are substantially redshifted for OLC as compared with those of highly ordered pyrolytic graphite and thermally exfoliated graphite consisted of planar sheets. This effect was reproduced in behavior of dielectric functions of rippled graphite models calculated within the random phase approximation. We conclude that the energy of electron excitations in graphitic materials could be precisely tuned by a simple bending of hexagonal network without change of topology. Moreover, our investigation suggests that in such materials optical exciton can transfer energy to plasmon non-radiatively.

  6. Hot electron mediated desorption rates calculated from excited state potential energy surfaces

    CERN Document Server

    Olsen, Thomas; Schiøtz, Jakob

    2008-01-01

    We present a model for Desorption Induce by (Multiple) Electronic Transitions (DIET/DIMET) based on potential energy surfaces calculated with the Delta Self-Consistent Field extension of Density Functional Theory. We calculate potential energy surfaces of CO and NO molecules adsorbed on various transition metal surfaces, and show that classical nuclear dynamics does not suffice for propagation in the excited state. We present a simple Hamiltonian describing the system, with parameters obtained from the excited state potential energy surface, and show that this model can describe desorption dynamics in both the DIET and DIMET regime, and reproduce the power law behavior observed experimentally. We observe that the internal stretch degree of freedom in the molecules is crucial for the energy transfer between the hot electrons and the molecule when the coupling to the surface is strong.

  7. Electron energy distributions and excitation rates in high-frequency argon discharges

    International Nuclear Information System (INIS)

    The electron energy distribution functions and rate coefficients for excitation and ionisation in argon under the action of an uniform high-frequency electric field were calculated by numerically solving the homogeneous Boltzmann equation. Analytic calculations in the limiting cases ?>>?sub(c) and ?<electron-neutral collision frequency for momentum transfer, are also presented and shown to be in very good agreement with the numerical computations. The results reported here are relevant for the modelling of high-frequency discharges in argon and, in particular, for improving recent theoretical descriptions of a plasma column sustained by surface microwaves. The properties of surface wave produced plasmas make them interesting as possible substitutes for other more conventional plasma sources for such important applications as plasma chemistry laser excitation, plasma etching spectroscopic sources etc...

  8. Electron densities and the excitation of CN in molecular clouds

    Science.gov (United States)

    Black, John H.; Van Dishoeck, Ewine F.

    1991-01-01

    In molecular clouds of modest density and relatively high fractional ionization, the rotational excitation of CN is controlled by a competition among electron impact, neutral impact and the interaction with the cosmic background radiation. The degree of excitation can be measured through optical absorption lines and millimeter-wave emission lines. The available, accurate data on CN in diffuse and translucent molecular clouds are assembled and used to determine electron densities. The derived values, n(e) = roughly 0.02 - 0.5/cu cm, imply modest neutral densities, which generally agree well with determinations by other techniques. The absorption- and emission-line measurements of CN both exclude densities higher than n(H2) = roughly 10 exp 3.5/cu cm on scales varying from 0.001 to 60 arcsec in these clouds.

  9. Regulation of excitation energy transfer in diatom PSII dimer: How does it change the destination of excitation energy?

    Science.gov (United States)

    Yokono, Makio; Nagao, Ryo; Tomo, Tatsuya; Akimoto, Seiji

    2015-10-01

    Energy transfer dynamics in dimeric photosystem II (PSII) complexes isolated from four diatoms, Chaetoceros gracilis, Cyclotella meneghiniana, Thalassiosira pseudonana, and Phaeodactylum tricornutum, are examined. Time-resolved fluorescence measurements were conducted in the range of 0-80ns. Delayed fluorescence spectra showed a clear difference between PSII monomer and PSII dimer isolated from the four diatoms. The difference can be interpreted as reflecting suppressed energy transfer between PSII monomers in the PSII dimer for efficient energy trapping at the reaction center. The observation was especially prominent in C. gracilis and T. pseudonana. The pathways seem to be suppressed under a low pH condition in isolated PSII complexes from C. gracilis, and excitation energy may be quenched with fucoxanthin chlorophyll a/c-binding protein (FCP) that was closely associated with PSII in C. gracilis. The energy transfer between PSII monomers in the PSII dimer may play a role in excitation energy regulation in diatoms. PMID:26188377

  10. The [(NH3)5Ru-Pyz-Ru(NH3)5]5+ complex: electronic structure, spectrum and modeling of intramolecular electron transfer

    International Nuclear Information System (INIS)

    Semiempirical method INDO+CI was used to calculate the electronic structure of base and excited states of binuclear mixed-valent complex [Ru(NH3)5]2(Pyz)5+. Referral of electron spectra was given. Theoretical model of electron transfer between Ru(2) and Ru(3) metal centers was approved on the basis of multielectron wave functions

  11. Stepwise vs concerted excited state tautomerization of 2-hydroxypyridine: Ammonia dimer wire mediated hydrogen/proton transfer

    Science.gov (United States)

    Esboui, Mounir

    2015-07-01

    The stepwise and concerted excited state intermolecular proton transfer (PT) and hydrogen transfer (HT) reactions in 2-hydroxypyridine-(NH3)2 complex in the gas phase under Cs symmetry constraint and without any symmetry constraints were performed using quantum chemical calculations. It shows that upon excitation, the hydrogen bonded in 2HP-(NH3)2 cluster facilitates the releasing of both hydrogen and proton transfer reactions along ammonia wire leading to the formation of the 2-pyridone tautomer. For the stepwise mechanism, it has been found that the proton and the hydrogen may transfer consecutively. These processes are distinguished from each other through charge translocation analysis and the coupling between the motion of the proton and the electron density distribution along ammonia wire. For the complex under Cs symmetry, the excited state HT occurs on the A?(1???) and A'(1n??) states over two accessible energy barriers along reaction coordinates, and excited state PT proceeds mainly through the A'(1???) and A?(1n??) potential energy surfaces. For the unconstrained complex, potential energy profiles show two 1???-1??? conical intersections along enol ? keto reaction path indicating that proton and H atom are localized, respectively, on the first and second ammonia of the wire. Moreover, the concerted excited state PT is competitive to take place with the stepwise process, because it proceeds over low barriers of 0.14 eV and 0.11 eV with respect to the Franck-Condon excitation of enol tautomer, respectively, under Cs symmetry and without any symmetry constraints. These barriers can be probably overcome through tunneling effect.

  12. Stepwise vs concerted excited state tautomerization of 2-hydroxypyridine: Ammonia dimer wire mediated hydrogen/proton transfer.

    Science.gov (United States)

    Esboui, Mounir

    2015-07-21

    The stepwise and concerted excited state intermolecular proton transfer (PT) and hydrogen transfer (HT) reactions in 2-hydroxypyridine-(NH3)2 complex in the gas phase under Cs symmetry constraint and without any symmetry constraints were performed using quantum chemical calculations. It shows that upon excitation, the hydrogen bonded in 2HP-(NH3)2 cluster facilitates the releasing of both hydrogen and proton transfer reactions along ammonia wire leading to the formation of the 2-pyridone tautomer. For the stepwise mechanism, it has been found that the proton and the hydrogen may transfer consecutively. These processes are distinguished from each other through charge translocation analysis and the coupling between the motion of the proton and the electron density distribution along ammonia wire. For the complex under Cs symmetry, the excited state HT occurs on the A?((1)??*) and A'((1)n?*) states over two accessible energy barriers along reaction coordinates, and excited state PT proceeds mainly through the A'((1)??*) and A?((1)n?*) potential energy surfaces. For the unconstrained complex, potential energy profiles show two (1)??*-(1)??* conical intersections along enol ? keto reaction path indicating that proton and H atom are localized, respectively, on the first and second ammonia of the wire. Moreover, the concerted excited state PT is competitive to take place with the stepwise process, because it proceeds over low barriers of 0.14 eV and 0.11 eV with respect to the Franck-Condon excitation of enol tautomer, respectively, under Cs symmetry and without any symmetry constraints. These barriers can be probably overcome through tunneling effect. PMID:26203026

  13. Comparative study on contribution of charge-transfer collision to excitations of iron ion between argon radio-frequency inductively-coupled plasma and nitrogen microwave induced plasma

    Science.gov (United States)

    Satoh, Kozue; Wagatsuma, Kazuaki

    2015-06-01

    This paper describes an ionization/excitation phenomenon of singly-ionized iron occurring in an Okamoto-cavity microwave induced plasma (MIP) as well as an argon radio-frequency inductively-coupled plasma (ICP), by comparing the Boltzmann distribution among iron ionic lines (Fe II) having a wide range of the excitation energy from 4.76 to 9.01 eV. It indicated in both the plasmas that plots of Fe II lines having lower excitation energies (4.76 to 5.88 eV) were fitted on each linear relationship, implying that their excitations were caused by a dominant thermal process such as collision with energetic electron. However, Fe II lines having higher excitation energies (more than 7.55 eV) had a different behavior from each other. In the ICP, Boltzmann plots of Fe II lines assigned to the higher excited levels also followed the normal Boltzmann relationship among the low-lying excited levels, even including a deviation from it in particular excited levels having an excitation energy of ca. 7.8 eV. This deviation can be attributed to a charge-transfer collision with argon ion, which results in the overpopulation of these excited levels, but the contribution is small. On the other hand, the distribution of the high-lying excited levels was non-thermal in the Okamoto-cavity MIP, which did not follow the normal Boltzmann relationship among the low-lying excited levels. A probable reason for the non-thermal characteristics in the MIP is that a charge-transfer collision with nitrogen molecule ion having many vibrational/rotational levels could work for populating the 3d64p (3d54s4p) excited levels of iron ion broadly over an energy range of 7.6-9.0 eV, while collisional excitation by energetic electron would occur insufficiently to excite these high-energy levels.

  14. Quantifying electron transfer reactions in biological systems: what interactions play the major role?

    Science.gov (United States)

    Sjulstok, Emil; Olsen, Jógvan Magnus Haugaard; Solov’yov, Ilia A.

    2015-01-01

    Various biological processes involve the conversion of energy into forms that are usable for chemical transformations and are quantum mechanical in nature. Such processes involve light absorption, excited electronic states formation, excitation energy transfer, electrons and protons tunnelling which for example occur in photosynthesis, cellular respiration, DNA repair, and possibly magnetic field sensing. Quantum biology uses computation to model biological interactions in light of quantum mechanical effects and has primarily developed over the past decade as a result of convergence between quantum physics and biology. In this paper we consider electron transfer in biological processes, from a theoretical view-point; namely in terms of quantum mechanical and semi-classical models. We systematically characterize the interactions between the moving electron and its biological environment to deduce the driving force for the electron transfer reaction and to establish those interactions that play the major role in propelling the electron. The suggested approach is seen as a general recipe to treat electron transfer events in biological systems computationally, and we utilize it to describe specifically the electron transfer reactions in Arabidopsis thaliana cryptochrome–a signaling photoreceptor protein that became attractive recently due to its possible function as a biological magnetoreceptor. PMID:26689792

  15. Theory of nuclear excitation by electron capture for heavy ions

    International Nuclear Information System (INIS)

    The resonant process of nuclear excitation by electron capture (NEEC) in collisions involving highly-charged ions has been investigated theoretically. NEEC is a rare recombination process in which a free electron is captured into a bound shell of an ion with the simultaneous excitation of the nucleus. Total cross sections for NEEC followed by the radiative decay of the excited nucleus are presented for various collision systems. The possibility to observe the NEEC in scattering experiments with trapped or stored ions was discussed focusing on the cases with the largest calculated resonance strength. As the photons emitted in different channels of the electron recombination process are indistinguishable in the total cross section, the interference between NEEC followed by the radiative decay of the nucleus and radiative recombination was investigated. The angular distribution of the emitted photons in the recombination process provides means to discern the two processes. Angular differential cross sections for the emitted photons in the case of E2 nuclear transitions were presented for several heavy elements. (orig.)

  16. Theory of nuclear excitation by electron capture for heavy ions

    Energy Technology Data Exchange (ETDEWEB)

    Gagyi-Palffy, A.

    2006-07-01

    The resonant process of nuclear excitation by electron capture (NEEC) in collisions involving highly-charged ions has been investigated theoretically. NEEC is a rare recombination process in which a free electron is captured into a bound shell of an ion with the simultaneous excitation of the nucleus. Total cross sections for NEEC followed by the radiative decay of the excited nucleus are presented for various collision systems. The possibility to observe the NEEC in scattering experiments with trapped or stored ions was discussed focusing on the cases with the largest calculated resonance strength. As the photons emitted in different channels of the electron recombination process are indistinguishable in the total cross section, the interference between NEEC followed by the radiative decay of the nucleus and radiative recombination was investigated. The angular distribution of the emitted photons in the recombination process provides means to discern the two processes. Angular differential cross sections for the emitted photons in the case of E2 nuclear transitions were presented for several heavy elements. (orig.)

  17. Indistinguishability in electron-impact excitation-ionization of helium

    International Nuclear Information System (INIS)

    We present fully differential cross section (FDCS) calculations for electron-impact excitation-ionization of helium using the four-body distorted wave-exchange (4DWE) model. This model includes both the direct and exchange amplitudes, which account for the indistinguishability of the free electrons in the final state. The results of the 4DWE model are compared with absolute experimental results, and we find that the exchange amplitude has a minimal impact in determining the shape and magnitude of the FDCS.

  18. Electron plasma dynamics during autoresonant excitation of the diocotron mode

    Energy Technology Data Exchange (ETDEWEB)

    Baker, C. J., E-mail: cbaker@physics.ucsd.edu; Danielson, J. R., E-mail: jrdanielson@ucsd.edu; Hurst, N. C., E-mail: nhurst@physics.ucsd.edu; Surko, C. M., E-mail: csurko@ucsd.edu [Physics Department, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093 (United States)

    2015-02-15

    Chirped-frequency autoresonant excitation of the diocotron mode is used to move electron plasmas confined in a Penning-Malmberg trap across the magnetic field for advanced plasma and antimatter applications. Plasmas of 10{sup 8} electrons, with radii small compared to that of the confining electrodes, can be moved from the magnetic axis to ?90% of the electrode radius with near unit efficiency and reliable angular positioning. Translations of ?70% of the wall radius are possible for a wider range of plasma parameters. Details of this process, including phase and displacement oscillations in the plasma response and plasma expansion, are discussed, as well as possible extensions of the technique.

  19. Dynamical response function of transverse excitations in electron fluid

    International Nuclear Information System (INIS)

    Dynamical response function of transverse excitations in 3D electron fluid has been studied within moment conserving method by including the effect of many-body correlations beyond the random approximation for various electron densities. It is found that correlation effects bring about qualitative as well as quantitative changes in the behavior of transverse response function as compared to the corresponding non-interacting system. The imaginary part of transverse response function becomes flatter with increase in rs and shows signature of the presence of double peak structure. On the other hand. the width at half maximum of real part decreases with increase in rs. (author)

  20. Theory of resonance and threshold effects in the electronic excitation of molecules by electron impact

    International Nuclear Information System (INIS)

    A simple model of electron scattering resonances near electronic excitation thresholds is discussed. The model consists of a single discrete electronic state coupled to several electronic continua. The vibrational dynamics in the resonance state is treated, taking proper account of non-Born-Oppenheimer effects in near-threshold electron-molecule scattering. The effect of long-range potentials is included via the threshold expansion of the partial decay widths of the resonance. The analytic properties of the fixed-nuclei S matrix are analyzed in detail for two special cases (s-wave scattering in the absence of long-range potentials and scattering from a strongly polar target molecule). The dipole potential is shown to lead to a qualitatively new behavior of the trajectories of resonance poles near excitation thresholds. The model yields a qualitative description of the measured excitation function of the B 1?+ state of the CO molecule, where a strong and narrow threshold peak is observed

  1. Many-body approach to electronic excitations concepts and applications

    CERN Document Server

    Bechstedt, Friedhelm

    2015-01-01

    The many-body-theoretical basis and applications of theoretical spectroscopy of condensed matter, e.g. crystals, nanosystems, and molecules are unified in one advanced text for readers from graduate students to active researchers in the field. The theory is developed from first principles including fully the electron-electron interaction and spin interactions. It is based on the many-body perturbation theory, a quantum-field-theoretical description, and Green's functions. The important expressions for ground states as well as electronic single-particle and pair excitations are explained. Based on single-particle and two-particle Green's functions, the Dyson and Bethe-Salpeter equations are derived. They are applied to calculate spectral and response functions. Important spectra are those which can be measured using photoemission/inverse photoemission, optical spectroscopy, and electron energy loss/inelastic X-ray spectroscopy. Important approximations are derived and discussed in the light of selected computa...

  2. Electron transfer and reaction mechanism of laccases.

    Science.gov (United States)

    Jones, Stephen M; Solomon, Edward I

    2015-03-01

    Laccases are part of the family of multicopper oxidases (MCOs), which couple the oxidation of substrates to the four electron reduction of O2 to H2O. MCOs contain a minimum of four Cu's divided into Type 1 (T1), Type 2 (T2), and binuclear Type 3 (T3) Cu sites that are distinguished based on unique spectroscopic features. Substrate oxidation occurs near the T1, and electrons are transferred approximately 13 Å through the protein via the Cys-His pathway to the T2/T3 trinuclear copper cluster (TNC), where dioxygen reduction occurs. This review outlines the electron transfer (ET) process in laccases, and the mechanism of O2 reduction as elucidated through spectroscopic, kinetic, and computational data. Marcus theory is used to describe the relevant factors which impact ET rates including the driving force, reorganization energy, and electronic coupling matrix element. Then, the mechanism of O2 reaction is detailed with particular focus on the intermediates formed during the two 2e(-) reduction steps. The first 2e(-) step forms the peroxide intermediate, followed by the second 2e(-) step to form the native intermediate, which has been shown to be the catalytically relevant fully oxidized form of the enzyme. PMID:25572295

  3. Electronic excitations from a linear-response range-separated hybrid scheme

    CERN Document Server

    Rebolini, Elisa; Toulouse, Julien

    2013-01-01

    We study linear-response time-dependent density-functional theory (DFT) based on the single-determinant range-separated hybrid (RSH) scheme, i.e. combining a long-range Hartree-Fock exchange kernel with a short-range DFT exchange-correlation kernel, for calculating electronic excitation energies of molecular systems. It is an alternative to the long-range correction (LC) scheme which has a standard full-range DFT correlation kernel instead of only a short-range one. We discuss the local-density approximation (LDA) to the short-range exchange-correlation kernel, and assess the performance of the linear-response RSH scheme for singlet-singlet and singlet-triplet valence and Rydberg excitations in the N2, CO, H2CO, C2H4, and C6H6 molecules, and for the first charge-transfer excitation in the C2H4-C2F4 dimer. The introduction of long-range HF exchange corrects the underestimation of charge-transfer and high-lying Rydberg excitation energies obtained with standard (semi)local density-functional approximations, but...

  4. Promoting interspecies electron transfer with biochar

    DEFF Research Database (Denmark)

    Chen, Shanshan; Rotaru, Amelia-Elena

    2014-01-01

    Biochar, a charcoal-like product of the incomplete combustion of organic materials, is an increasingly popular soil amendment designed to improve soil fertility. We investigated the possibility that biochar could promote direct interspecies electron transfer (DIET) in a manner similar to that previously reported for granular activated carbon (GAC). Although the biochars investigated were 1000 times less conductive than GAC, they stimulated DIET in co-cultures of Geobacter metallireducens with Geobacter sulfurreducens or Methanosarcina barkeri in which ethanol was the electron donor. Cells were attached to the biochar, yet not in close contact, suggesting that electrons were likely conducted through the biochar, rather than biological electrical connections. The finding that biochar can stimulate DIET may be an important consideration when amending soils with biochar and can help explain why biochar may enhance methane production from organic wastes under anaerobic conditions.

  5. 77 FR 34127 - Financial Management Service; Proposed Collection of Information: Electronic Transfer Account...

    Science.gov (United States)

    2012-06-08

    ...Collection of Information: Electronic Transfer Account...on a continuing information collection. By...FMS-111, ``Electronic Transfer Account...collection of information described below: Title: Electronic Transfer...

  6. The reaction dynamics of alkali dimer molecules and electronically excited alkali atoms with simple molecules

    Energy Technology Data Exchange (ETDEWEB)

    Hou, H [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1995-12-01

    This dissertation presents the results from the crossed molecular beam studies on the dynamics of bimolecular collisions in the gas phase. The primary subjects include the interactions of alkali dimer molecules with simple molecules, and the inelastic scattering of electronically excited alkali atoms with O2. The reaction of the sodium dimers with oxygen molecules is described in Chapter 2. Two reaction pathways were observed for this four-center molecule-molecule reaction, i.e. the formations of NaO2 + Na and NaO + NaO. NaO2 products exhibit a very anisotropic angular distribution, indicating a direct spectator stripping mechanism for this reaction channel. The NaO formation follows the bond breaking of O2, which is likely a result of a charge transfer from Na2 to the excited state orbital of O2-. The scattering of sodium dimers from ammonium and methanol produced novel molecules, NaNH3 and Na(CH3OH), respectively. These experimental observations, as well as the discussions on the reaction dynamics and the chemical bonding within these molecules, will be presented in Chapter 3. The lower limits for the bond dissociation energies of these molecules are also obtained. Finally, Chapter 4 describes the energy transfer between oxygen molecules and electronically excited sodium atoms.

  7. Simulação Monte Carlo de mecanismo de transferência de energia de excitação eletrônica: modelo de Perrin para a supressão estática da luminescência / Monte Carlo simulation of electronic excitation energy transfer: Perrin´s model for static luminescence quenching

    Scientific Electronic Library Online (English)

    João Batista Marques, Novo; Lauro Camargo, Dias Júnior.

    Full Text Available [...] Abstract in english A software based in the Monte Carlo method has been developed aiming the teaching of the Perrin´s model for static luminescence quenching. This software allows the student to easily simulate the luminescence decays of emissive molecules in the presence of quenching ones. The software named PERRIN wa [...] s written for FreeBASIC compiler and it can be applied for systems where the molecules remain static during its excited state lifetime. The good agreement found between the simulations and the expected theoretical results shows that it can be used for the luminescence and excited states decay kinetic teaching.

  8. Direct electron transfer from photosystem II to hematite in a hybrid photoelectrochemical cell.

    Science.gov (United States)

    Wang, Wangyin; Wang, Zhiliang; Zhu, Qingjun; Han, Guangye; Ding, Chunmei; Chen, Jun; Shen, Jian-Ren; Li, Can

    2015-11-17

    A hybrid photoanode integrating the cyanobacterial photosystem II (PSII) with a hematite film for water oxidation is constructed. Direct electron transfer from PSII to the excited Ti/Fe2O3 electrode occurs under light irradiation, resulting in a significant improvement of the photocurrent. PMID:26443427

  9. Interplay between particle-hole excitation and nucleon transfer in deep-inelastic collisions

    International Nuclear Information System (INIS)

    The interplay between particle-hole excitation and nucleon transfer in deep-inelastic collisions is studied within an independent-particle model in which the relative motion is treated classically. The energy and angular momentum loss are evaluated selfconsistently in the model. The results show that the inclusion of the ph excitation strongly affects the transfer mode giving rise to a drift of the charge centroid towards charge asymmetry. The model predicts a roughly equal excitation energy for the two fragments rather than one proportional to their masses. (orig.)

  10. Application of Degenerately Doped Metal Oxides in the Study of Photoinduced Interfacial Electron Transfer.

    Science.gov (United States)

    Farnum, Byron H; Morseth, Zachary A; Brennaman, M Kyle; Papanikolas, John M; Meyer, Thomas J

    2015-06-18

    Degenerately doped In2O3:Sn semiconductor nanoparticles (nanoITO) have been used to study the photoinduced interfacial electron-transfer reactivity of surface-bound [Ru(II)(bpy)2(4,4'-(PO3H2)2-bpy)](2+) (RuP(2+)) molecules as a function of driving force over a range of 1.8 eV. The metallic properties of the ITO nanoparticles, present within an interconnected mesoporous film, allowed for the driving force to be tuned by controlling their Fermi level with an external bias while their optical transparency allowed for transient absorption spectroscopy to be used to monitor electron-transfer kinetics. Photoinduced electron transfer from excited-state -RuP(2+*) molecules to nanoITO was found to be dependent on applied bias and competitive with nonradiative energy transfer to nanoITO. Back electron transfer from nanoITO to oxidized -RuP(3+) was also dependent on the applied bias but without complication from inter- or intraparticle electron diffusion in the oxide nanoparticles. Analysis of the electron injection kinetics as a function of driving force using Marcus-Gerischer theory resulted in an experimental estimate of the reorganization energy for the excited-state -RuP(3+/2+*) redox couple of ?* = 0.83 eV and an electronic coupling matrix element, arising from electronic wave function overlap between the donor orbital in the molecule and the acceptor orbital(s) in the nanoITO electrode, of Hab = 20-45 cm(-1). Similar analysis of the back electron-transfer kinetics yielded ? = 0.56 eV for the ground-state -RuP(3+/2+) redox couple and Hab = 2-4 cm(-1). The use of these wide band gap, degenerately doped materials provides a unique experimental approach for investigating single-site electron transfer at the surface of oxide nanoparticles. PMID:25668488

  11. Influence of multiphonon excitations and transfer on the fusion of Ca+Zr

    CERN Document Server

    Esbensen, H

    2014-01-01

    Fusion data for $^{48}$Ca+$^{90,96}$Zr are analyzed by coupled-channels calculations that are based on the M3Y+repulsion, double-folding potential. By applying a previously determined nuclear density of $^{48}$Ca, the neutron densities of the zirconium isotopes are adjusted to optimize the fit to the fusion data, whereas the proton densities are determined by electron scattering experiments. It is shown that the fusion data can be explained fairly well by including couplings to one- and two-phonon excitations of the reacting nuclei and to one- and two-nucleon transfer reactions but there is also some sensitivity to multiphonon excitations. The neutron skin thicknesses extracted for the two zirconium isotopes are consistent with anti-proton measurements. The densities of the zirconium isotopes are used together with the previously determined nuclear density of $^{40}$Ca to calculate the M3Y+repulsion potentials and predict the fusion cross sections of $^{40}$Ca+$^{90,96}$Zr. The predicted cross sections for $^...

  12. Direct heterogeneous electron transfer of theophylline oxidase

    OpenAIRE

    Christenson, Andreas; Dock, Eva; Gorton, Lo; Ruzgas, Tautgirdas

    2004-01-01

    Direct electron transfer (DET) was shown between the heme containing enzyme theophylline oxidase (ThO) and the surface of both graphite and gold electrodes. As proof on graphite a steady state current for theophylline was recorded using the electrode modified with adsorbed ThO. The electrode showed a Michaelis–Menten-like response to theophylline with a detection limit of 0.2 mM and a Michaelis–Menten constant equal to 3.2 mM. These initial results open up a possibility for the development of...

  13. Effect of electronic excitation on high-temperature flows behind strong shock waves

    Science.gov (United States)

    Istomin, V. A.; Kustova, E. V.

    2014-12-01

    In the present paper, a strongly non-equilibrium one-dimensional steady-state flow behind the plane shock wave is studied. We consider a high-temperature chemically reacting five-component ionized mixture of nitrogen species (N2/N22/N/N+/e-) taking into account electronic degrees of freedom in N and N+ (170 and 625 electronic energy levels respectively), and electronic-rotational-vibrational modes in N2 and N2+ (5 and 7 electronic terms). Non-equilibrium reactions of ionization, dissociation, recombination and charge-transfer are included to the kinetic scheme. The system of governing equations is written under the assumption that translation and internal energy relaxation is fast whereas chemical reactions and ionization proceed on the macroscopic gas-dynamics time-scale. The developed model is applied to simulate the flow behind a plane shock wave under initial conditions characteristic for the spacecraft re-entry from an interplanetary flight (Hermes and Fire II experiments). Fluid-dynamic parameters behind the shock wave as well as transport coefficients and the heat flux are calculated for the (N2/N2+/N/N+/e-) mixture. The effect of electronic excitation on kinetics, dynamics and heat transfer is analyzed. Whereas the contribution of electronic degrees of freedom to the flow macroparameters is negligible, their influence on the heat flux is found to be important under conditions of Hermes re-entry.

  14. Effect of electronic excitation on high-temperature flows behind strong shock waves

    International Nuclear Information System (INIS)

    In the present paper, a strongly non-equilibrium one-dimensional steady-state flow behind the plane shock wave is studied. We consider a high-temperature chemically reacting five-component ionized mixture of nitrogen species (N2/N22/N/N+/e?) taking into account electronic degrees of freedom in N and N+ (170 and 625 electronic energy levels respectively), and electronic-rotational-vibrational modes in N2 and N2+ (5 and 7 electronic terms). Non-equilibrium reactions of ionization, dissociation, recombination and charge-transfer are included to the kinetic scheme. The system of governing equations is written under the assumption that translation and internal energy relaxation is fast whereas chemical reactions and ionization proceed on the macroscopic gas-dynamics time-scale. The developed model is applied to simulate the flow behind a plane shock wave under initial conditions characteristic for the spacecraft re-entry from an interplanetary flight (Hermes and Fire II experiments). Fluid-dynamic parameters behind the shock wave as well as transport coefficients and the heat flux are calculated for the (N2/N2+/N/N+/e?) mixture. The effect of electronic excitation on kinetics, dynamics and heat transfer is analyzed. Whereas the contribution of electronic degrees of freedom to the flow macroparameters is negligible, their influence on the heat flux is found to be important under conditions of Hermes re-entry

  15. Solvent effects on electron-driven proton-transfer processes: adenine-thymine base pairs.

    Science.gov (United States)

    Dargiewicz, Monika; Biczysko, Malgorzata; Improta, Roberto; Barone, Vincenzo

    2012-07-01

    Time-Dependent Density Functional Theory (TD-DFT) computations, with M05-2X and PBE0 functionals, have been employed for a detailed study of the Electron-Driven Proton-Transfer (PT) processes in an Adenine-Thymine Watson-Crick Base Pair in the gas phase and in solution, with the bulk solvent described by the polarizable continuum model. In the gas phase, TD-DFT computations predict that the Adenine ? Thymine Charge Transfer (CT) excited state undergoes a barrierless PT reaction, in agreement with CC2 computations (S. Perun, A. Sobolewski, W. Domcke, J. Phys. Chem. A, 2006, 110, 9031.). The good agreement between the TD-DFT approach and CC2 results validates the former for the studies of excited state properties, excited state proton transfer reaction, and deactivation mechanisms in the DNA base pairs. Next, it is shown that inclusion of solvent effects significantly influences the possibility of both barrier-less excited state proton transfer and radiation-less deactivation through conical intersection with the ground state, affecting the energy of the CT excited state in the Franck-Condon region, the energy barrier associated to the PT process and the energy gap with the ground electronic state. These findings clearly indicate that environmental effects, with a special attention to proper treatment of dynamical solvation effects, have to be included for reliable computational analysis of photophysical and photochemical processes occurring in condensed phases. PMID:22398748

  16. Simulação Monte Carlo de mecanismo de transferência de energia de excitação eletrônica: modelo de Perrin para a supressão estática da luminescência Monte Carlo simulation of electronic excitation energy transfer: Perrin´s model for static luminescence quenching

    OpenAIRE

    João Batista Marques Novo; Lauro Camargo Dias Júnior

    2011-01-01

    A software based in the Monte Carlo method has been developed aiming the teaching of the Perrin´s model for static luminescence quenching. This software allows the student to easily simulate the luminescence decays of emissive molecules in the presence of quenching ones. The software named PERRIN was written for FreeBASIC compiler and it can be applied for systems where the molecules remain static during its excited state lifetime. The good agreement found between the simulations and the expe...

  17. A bifurcated molecular pentad capable of sequential electronic energy transfer and intramolecular charge transfer.

    Science.gov (United States)

    Harriman, Anthony; Stachelek, Patrycja; Sutter, Alexandra; Ziessel, Raymond

    2015-10-21

    An extended molecular array, comprising three distinct types of chromophores and two additional redox-active subunits, that harvests photons over most of the visible spectral range has been synthesized and characterised. The array exhibits a rich variety of electrochemical waves when examined by cyclic voltammetry but assignment can be made on the basis of control compounds and molecular orbital calculations. Stepwise electronic energy transfer occurs along the molecular axis, corresponding to a gradient of excitation energies, to populate the lowest-energy excited state of the ultimate acceptor. The latter species, which absorbs and emits in the far-red region, enters into light-induced charge transfer with a terminal amine group. The array is relatively stable under illumination with white light but degrades slowly via a series of well-defined steps, the first of which is autocatalytic. One of the main attributes of this system is the capability to harvest an unusually high fraction of sunlight while providing protection against exposure to UV light. PMID:26381219

  18. Computer simulation of electronic excitation in atomic collision cascades

    International Nuclear Information System (INIS)

    The impact of an keV atomic particle onto a solid surface initiates a complex sequence of collisions among target atoms in a near-surface region. The temporal and spatial evolution of this atomic collision cascade leads to the emission of particles from the surface - a process usually called sputtering. In modern surface analysis the so called SIMS technology uses the flux of sputtered particles as a source of information on the microscopical stoichiometric structure in the proximity of the bombarded surface spots. By laterally varying the bombarding spot on the surface, the entire target can be scanned and chemically analyzed. However, the particle detection, which bases upon deflection in electric fields, is limited to those species that leave the surface in an ionized state. Due to the fact that the ionized fraction of the total flux of sputtered atoms often only amounts to a few percent or even less, the detection is often hampered by rather low signals. Moreover, it is well known, that the ionization probability of emitted particles does not only depend on the elementary species, but also on the local environment from which a particle leaves the surface. Therefore, the measured signals for different sputtered species do not necessarily represent the stoichiometric composition of the sample. In the literature, this phenomenon is known as the Matrix Effect in SIMS. In order to circumvent this principal shortcoming of SIMS, the present thesis develops an alternative computer simulation concept, which treats the electronic energy losses of all moving atoms as excitation sources feeding energy into the electronic sub-system of the solid. The particle kinetics determining the excitation sources are delivered by classical molecular dynamics. The excitation energy calculations are combined with a diffusive transport model to describe the spread of excitation energy from the initial point of generation. Calculation results yield a space- and time-resolved excitation energy density profile E(r,t) within the volume affected by the atomic collision cascade.The distribution E(r,t) is then converted into an electron temperature, which in a further step can be utilized to calculate the ionization probabilities of sputtered atoms using published theory. (orig.)

  19. Computer simulation of electronic excitation in atomic collision cascades

    Energy Technology Data Exchange (ETDEWEB)

    Duvenbeck, A.

    2007-04-05

    The impact of an keV atomic particle onto a solid surface initiates a complex sequence of collisions among target atoms in a near-surface region. The temporal and spatial evolution of this atomic collision cascade leads to the emission of particles from the surface - a process usually called sputtering. In modern surface analysis the so called SIMS technology uses the flux of sputtered particles as a source of information on the microscopical stoichiometric structure in the proximity of the bombarded surface spots. By laterally varying the bombarding spot on the surface, the entire target can be scanned and chemically analyzed. However, the particle detection, which bases upon deflection in electric fields, is limited to those species that leave the surface in an ionized state. Due to the fact that the ionized fraction of the total flux of sputtered atoms often only amounts to a few percent or even less, the detection is often hampered by rather low signals. Moreover, it is well known, that the ionization probability of emitted particles does not only depend on the elementary species, but also on the local environment from which a particle leaves the surface. Therefore, the measured signals for different sputtered species do not necessarily represent the stoichiometric composition of the sample. In the literature, this phenomenon is known as the Matrix Effect in SIMS. In order to circumvent this principal shortcoming of SIMS, the present thesis develops an alternative computer simulation concept, which treats the electronic energy losses of all moving atoms as excitation sources feeding energy into the electronic sub-system of the solid. The particle kinetics determining the excitation sources are delivered by classical molecular dynamics. The excitation energy calculations are combined with a diffusive transport model to describe the spread of excitation energy from the initial point of generation. Calculation results yield a space- and time-resolved excitation energy density profile E(r,t) within the volume affected by the atomic collision cascade.The distribution E(r,t) is then converted into an electron temperature, which in a further step can be utilized to calculate the ionization probabilities of sputtered atoms using published theory. (orig.)

  20. Compilation of electron collision excitation cross sections for neutro argon

    International Nuclear Information System (INIS)

    The present work presents a compilation and critical analysis of the available data on electron collision excitation cross sections for neutral Argon levels. This study includes: 1.- A detailed description in intermediate coupling for all the levels belonging the 20 configurations 3p''5 ns(n=4 to 12), np(n=4 to 8) and nd(n=3 to 8) of neutral Argon. 2.- Calculation of the electron collision excitation cross sections in Born and Born-Oppenheimer-Ochkur approximations for all the levels in the 14 configurations 3p''5 ns(n=4 to 7), np(n=4 to 7) and nd(n=3 to 8). 3.- Comparison and discussion of the compiled data. These are the experimental and theoretical values available from the literature, and those from this work. 4.- Analysis of the regularities and systematic behaviors in order to determine which values can be considered more reliable. It is show that the concept of one electron cross section results quite useful for this purpose. In some cases it has been possible to obtain in this way approximate analytical expressions interpolating the experimental data. 5.- All the experimental and theoretical values studied are graphically presented and compared. 6.- The last part of the work includes a listing of several general purpose programs for Atomic Physics calculations developed for this work. (Author)

  1. Effect of Electronic Excitation on Thin Film Growth

    Energy Technology Data Exchange (ETDEWEB)

    Elsayed-Ali, Hani E. [Old Dominion University

    2011-01-31

    The effect of nanosecond pulsed laser excitation on surface diffusion during growth of Ge on Si(100) at 250 degrees C was studied. In Situ reflection high-energy electron diffraction (RHEED) was used to measure the surface diffusion coefficient while ex situ atomic force microscopy (AFM) was used to probe the structure and morphology of the grown quantum dots. The results show that laser excitation of the substrate increases the surface diffusion during growth of Ge on Si(100), changes the growth morphology, improves crystalline structure of the grown quantum dots, and decreases their size distribution. A purely electronic mechanism of enhanced surface diffusion of the deposited Ge is proposed. Ge quantum dots were grown on Si(100)-(2x1) by pulsed laser deposition at various substrate temperatures using a femtosecond Ti:sapphire laser. In-situ reflection high-energy electron diffraction and ex-situ atomic force microscopy were used to analyze the fim structure and morphology. The morphology of germanium islands on silicon was studied at differect coverages. The results show that femtosecond pulsed laser depositon reduces the minimum temperature for epitaxial growth of Ge quantum dots to ~280 degrees C, which is 120 degrees C lower then previously observed in nanosecond pulsed laser deposition and more than 200 degrees C lower than that reported for molecular beam epitaxy and chemical vapor deposition.

  2. Excimer Emission using 20keV Electron Beam Excitation

    Science.gov (United States)

    Wieser, J.; Ulrich, A.; Murnick, D. E.

    1996-10-01

    A small, continuously emitting rare gas excimer light source has been developed. The gas is excited by a 20keV dc-electron beam. A 300nm thick, 1×1mm^2 SiNx foil sustaining a pressure difference up to 2bar, separates the target volume from the high vacuum part of the electron gun. Spectra of the rare gases Ar, Kr, and Xe have been studied. The monochromator detector system was intensity calibrated in the wavelength range from 115nm to 320nm. Electron beam currents of typically 1?A were used for excitation. When used as a VUV lamp on the second excimer continua, energy conversion efficiencies of 30% were obtained. Emissions originating from the so called left turning points have been clearly observed at 155, 173, and 222nm in Ar_2^*, Kr_2^*, and Xe_2^*, respectively. The so called third continua between 185nm and 240nm (Ar), 220nm and 250nm (Kr), and at 270nm (Xe) have been studied. A new continuum in Xe at 280nm was found. (Funded by the A.v.Humboldt Foundation and NSF (CTS 94-19440). The authors acknowledge support by H. Huggins, A. Liddle and W.L. Brown (Bell Laboratories, Lucent Technologies))

  3. Complex frequency-dependent polarizability through the ? ? ?* excitation energy of azobenzene molecules by a combined charge-transfer and point-dipole interaction model.

    Science.gov (United States)

    Haghdani, Shokouh; Davari, Nazanin; Sandnes, Runar; Åstrand, Per-Olof

    2014-11-26

    The complex frequency-dependent polarizability and ? ? ?* excitation energy of azobenzene compounds are investigated by a combined charge-transfer and point-dipole interaction (CT/PDI) model. To parametrize the model, we adopted time-dependent density functional theory (TDDFT) calculations of the frequency-dependent polarizability extended with excited-state lifetimes to include also its imaginary part. The results of the CT/PDI model are compared with the TDDFT calculations and experimental data demonstrating that the CT/PDI model is fully capable to reproduce the static polarizability as well as the ? ? ?* excitation energy for these compounds. In particular, azobenzene molecules with different functional groups in the para-position have been included serving as a severe test of the model. The ? ? ?* excitation is to a large extent localized to the azo bond, and substituting with electron-donating or electron-attracting groups on the phenyl rings results in charge-transfer effects and a shift in the excitation energy giving rise to azobenzene compounds with a range of different colors. In the CT/PDI model, the ? ? ?* excitation in azobenzenes is manifested as drastically increasing atomic induced dipole moments in the azo group as well as in the adjacent carbon atoms, whereas the shifts in the excitation energies are due to charge-transfer effects. PMID:25356936

  4. Electron scattering by magnesium: excitation of the 3s3p 1P1 state

    International Nuclear Information System (INIS)

    Differential cross sections (DCS) for electron-impact excitation of the 3s3p 1P1 state in magnesium at incident electron energies E0 = 10, 15, 20, 40, 60, 80 and 100 eV have been measured and corresponding calculations carried out. Scattered-electron intensities were measured over a wide range of scattering angles (100-1500) and normalized to the DCSs at 100 experimentally obtained by Filipovic et al (2006 Int. J. Mass Spectrom. 251 66). Corresponding calculations have been conducted in the relativistic distorted-wave approximation. Integrated (integral, momentum transfer and viscosity) cross sections are determined by numerical integration of our DCSs. The results are analysed and compared with previous experimental data and theoretical calculations

  5. Quantum tunneling resonant electron transfer process in Lorentzian plasmas

    International Nuclear Information System (INIS)

    The quantum tunneling resonant electron transfer process between a positive ion and a neutral atom collision is investigated in nonthermal generalized Lorentzian plasmas. The result shows that the nonthermal effect enhances the resonant electron transfer cross section in Lorentzian plasmas. It is found that the nonthermal effect on the classical resonant electron transfer cross section is more significant than that on the quantum tunneling resonant charge transfer cross section. It is shown that the nonthermal effect on the resonant electron transfer cross section decreases with an increase of the Debye length. In addition, the nonthermal effect on the quantum tunneling resonant electron transfer cross section decreases with increasing collision energy. The variation of nonthermal and plasma shielding effects on the quantum tunneling resonant electron transfer process is also discussed

  6. Electron transfer pathways in microbial oxygen biocathodes

    Energy Technology Data Exchange (ETDEWEB)

    Freguia, Stefano, E-mail: stefano@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan); Tsujimura, Seiya, E-mail: seiya@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan); Kano, Kenji, E-mail: kkano@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan)

    2010-01-01

    The ability of some bacteria to enhance the rate of cathodic oxygen reduction to water has been recently discovered, opening the way to an entirely renewable and environmentally friendly concept of biocathode. In this study we reveal that several mechanisms may induce catalytic effects by bacteria. These comprise mechanisms that are putatively beneficial to the bacteria as well as mechanisms which are merely side effects, including quinone autoxidation and direct O{sub 2} reduction by heme compounds. Here we showed that 1 muM of ACNQ is able to generate a significant catalytic wave for oxygen reduction, with onset at approximately 0 V vs. SHE. Similarly, adsorption of hemin on a carbon surface catalyses O{sub 2} reduction to H{sub 2}O{sub 2} with an onset of +0.2 V vs. SHE. To evaluate the catalytic pathways of live cells on cathodic oxygen reduction, two species of electrochemically active bacteria were selected as pure cultures, namely Acinetobacter calcoaceticus and Shewanella putrefaciens. The former appears to exploit a self-excreted redox compound with redox characteristics matching those of pyrroloquinoline quinone (PQQ) for extracellular electron transfer. The latter appears to utilise outer membrane-bound redox compounds. Interaction of quinones and cytochromes with the membrane-bound electron transfer chain is yet to be proven.

  7. Investigations of bimolecular photoinduced electron transfer reactions in polar solvents using ultrafast spectroscopy

    OpenAIRE

    Vauthey, Eric

    2006-01-01

    Several controversial questions in the field of bimolecular photoinduced electron transfer reactions in polar solvents are first briefly reviewed. Results obtained in our group using ultrafast spectroscopy and giving a new insight into these problems will then be described. They concern the driving force dependence of the charge separation distance, the formation of the reaction product in an electronic excited state, the absence of normal region for weakly exergonic charge recombination proc...

  8. Transfer line TT70 (electrons from PS to SPS)

    CERN Multimedia

    1981-01-01

    As injectors for LEP, PS and SPS had to be converted to the acceleration of electrons and positrons. So far, only positively charged particles had been transferred from the PS to the SPS, for the negatively charged electrons a new transfer line, TT70, had to be built. Due to the difference in level of the two machines, the transfer line slopes and tilts.

  9. Directed excitation transfer in vibrating chains by external fields

    CERN Document Server

    Muelken, Oliver

    2010-01-01

    We study the coherent dynamics of excitations on vibrating chains. By applying an external field and matching the field strength with the oscillation frequency of the chain it is possible to obtain an (average) transport of an initial Gaussian wave packet. We distinguish between a uniform oscillation of all nodes of the chain and the chain being in its lowest eigenmode. Both cases can lead to directed transport.

  10. Inelastic electron and light scattering from the elementary electronic excitations in quantum wells: Zero magnetic field

    Directory of Open Access Journals (Sweden)

    Manvir S. Kushwaha

    2012-09-01

    Full Text Available The most fundamental approach to an understanding of electronic, optical, and transport phenomena which the condensed matter physics (of conventional as well as nonconventional systems offers is generally founded on two experiments: the inelastic electron scattering and the inelastic light scattering. This work embarks on providing a systematic framework for the theory of inelastic electron scattering and of inelastic light scattering from the electronic excitations in GaAs/Ga1?xAlxAs quantum wells. To this end, we start with the Kubo's correlation function to derive the generalized nonlocal, dynamic dielectric function, and the inverse dielectric function within the framework of Bohm-Pines’ random-phase approximation. This is followed by a thorough development of the theory of inelastic electron scattering and of inelastic light scattering. The methodological part is then subjected to the analytical diagnoses which allow us to sense the subtlety of the analytical results and the importance of their applications. The general analytical results, which know no bounds regarding, e.g., the subband occupancy, are then specified so as to make them applicable to practicality. After trying and testing the eigenfunctions, we compute the density of states, the Fermi energy, the full excitation spectrum made up of intrasubband and intersubband – single-particle and collective (plasmon – excitations, the loss functions for all the principal geometries envisioned for the inelastic electron scattering, and the Raman intensity, which provides a measure of the real transitions induced by the (laser probe, for the inelastic light scattering. It is found that the dominant contribution to both the loss peaks and the Raman peaks comes from the collective (plasmon excitations. As to the single-particle peaks, the analysis indicates a long-lasting lack of quantitative comparison between theory and experiments. It is inferred that the inelastic electron scattering can be a potential alternative of the inelastic light scattering for investigating elementary electronic excitations in quantum wells.

  11. An efficient implementation of the localized operator partitioning method for electronic energy transfer

    CERN Document Server

    Nagesh, Jayashree; Brumer, Paul

    2014-01-01

    The localized operator partitioning method [Y. Khan and P. Brumer, J. Chem. Phys. 137, 194112 (2012)] rigorously defines the electronic energy on any subsystem within a molecule and gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. However, an efficient implementation of this approach has been hindered by complicated one- and two-electron integrals arising in its formulation. Using a resolution of the identity in the definition of partitioning we reformulate the method in a computationally e?cient manner that involves standard one- and two-electron integrals. We apply the developed algorithm to the 9-((1-naphthyl)-methyl)-anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH2-naphthyl groups as subsystems, and examine their electronic energies and populations for several excited states using Configuration Interaction Singles method. The implemented approach shows a wide variety o...

  12. Electronically excited states and photochemical reaction mechanisms of ?-glucose.

    Science.gov (United States)

    Tuna, Deniz; Sobolewski, Andrzej L; Domcke, Wolfgang

    2014-01-01

    Carbohydrates are important molecular components of living matter. While spectroscopic and computational studies have been performed on carbohydrates in the electronic ground state, the lack of a chromophore complicates the elucidation of the excited-state properties and the photochemistry of this class of compounds. Herein, we report on the first computational investigation of the singlet photochemistry of ?-glucose. It is shown that low-lying singlet excited states are of n?* nature. Our computations of the singlet vertical excitation energies predict absorption from 6.0 eV onward. Owing to a dense manifold of weakly-absorbing states, a sizable and broad absorption in the ultraviolet-C range arises. We have explored two types of photochemical reaction mechanisms: hydrogen-detachment processes for each of the five O-H groups and a C-O ring-opening process. Both types of reactions are driven by repulsive n?* states that are readily accessible from the Franck-Condon region and lead to conical intersections in a barrierless fashion. We have optimized the geometries of the conical intersections involved in these photochemical processes and found that these intersections are located around 5.0 eV for the O-H hydrogen-detachment reactions and around 4.0 eV for the C-O ring-opening reaction. The energies of all conical intersections are well below the computed absorption edge. The calculations were performed using linear-response methods for the computation of the vertical excitation energies and multiconfigurational methods for the optimization of conical intersections and the computation of energy profiles. PMID:23959595

  13. Electron transfer and ionization in collisions of highly stripped ions with neutral targets at intermediate velocities

    International Nuclear Information System (INIS)

    A highly-charged ion impinging upon a neutral target atom will capture electrons into excited states of the projectile. If the velocity is much less than that of the target electrons, little direct ionization is expected, although appreciable target ionization has been reported for very highly charged ions. Recent studies on both transfer and ionization for Arq+ (6?q?17) and O+8,7 on Ar and He target shave been performed for projectile velocities between 0.2 and 1.7 a.u. The measured quantities include charge-state-correlated differential cross sections, K-x-ray emission, and longitudinal recoil- ion momentum transfer, from which Q values can be deduced. Non-negligible direct ionization is observed. Information is extracted on both the primary transfer process and the decay of the multiply excited projectile states formed. Comparisons with model predictions will be made

  14. Excitation of solid electron by proton and hydrogen molecular ions

    International Nuclear Information System (INIS)

    An electric stopping power of solid for hydrogen molecular ion (H2+, H3+) and ion cluster (2H+, 3H+) which lost the bounded electron from the former, were estimated and compared with the value of proton. The spacial distribution of the bounded electron of hydrogen molecular ions such as H2+ and H3+ was assumed by the molecular orbital on the basis of gauss function. In calculating the electric stopping power, a conduction electron is modelled on the free electron gas model and an exitation of bounded electron on the wave packet model. In any cases, the excitation of electron is described by the dielectric function. An effective charge Zeff, the index of the amount of stopping power S, is defined as Zeff = (s/sp)2/1 where Sp represents the stopping power for proton running with the same velocity in the same solid. This effective charge is a useful physical parameter to arrange the stopping power data, because it shows the practical charge number of the injection ion with bounded electron to be reduced to the point charge. The effective charges of H2+ and He+ in low energy field are different depend on the orientations when they transmitted through the carbon film. The effective charge of H2+ was less than 1 if the molecular axis was parallel to the running direction. In high energy field, the dependence of orientation was not observed. The differences of effective charges of H3+ passing through the carbon, aluminium and krypton gas were about 0.2, the small value indicating the small dependence of value on the materials. (S.Y.)

  15. Excitation of kinetic Alfvén waves by fast electron beams

    Energy Technology Data Exchange (ETDEWEB)

    Chen, L.; Wu, D. J.; Zhao, G. Q. [Purple Mountain Observatory, CAS, Nanjing (China); Tang, J. F. [Xinjiang Astronomical Observatory, CAS, Urumqi 830011 (China); Huang, J., E-mail: clvslc214@pmo.ac.cn, E-mail: djwu@pmo.ac.cn, E-mail: gqzhao@pmo.ac.cn, E-mail: jftang@xao.ac.cn, E-mail: huangj@bao.ac.cn [Key Laboratory of Solar Activity, National Astronomical Observatories, Chinese Academy of Sciences, Beijing (China)

    2014-09-20

    Energetic electron beams, which are ubiquitous in a large variety of active phenomena in space and astrophysical plasmas, are one of the most important sources that drive plasma instabilities. In this paper, taking account of the return-current effect of fast electron beams, kinetic Alfvén wave (KAW) instability driven by a fast electron beam is investigated in a finite-? plasma of Q < ? < 1 (where ? is the kinetic-to-magnetic pressure ratio and Q ? m{sub e} /m{sub i} is the mass ratio of electrons to ions). The results show that the kinetic resonant interaction of beam electrons is the driving source for KAW instability, unlike the case driven by a fast ion beam, where both the kinetic resonant interaction of beam ions and the return-current are the driving source for the KAW instability. KAW instability has a nonzero growth rate in the range of the perpendicular wave number, 0electron beam v{sub b} , and the most favorable beam velocity occurs between 8v{sub A} < v{sub b} < 10v{sub A} . On the other hand, the excited KAWs are weakly dispersive with k ? {sub i} < 1 and have the maximum growth rate at relatively low perpendicular wave numbers in the range 0.3electron beams in the terrestrial magnetosphere is briefly discussed.

  16. Proton transfer in phenol-amine complexes: phenol electronic effects on free energy profile in solution.

    Science.gov (United States)

    Aono, Shinji; Kato, Shigeki

    2010-12-01

    Free energy profiles for the proton transfer reactions in hydrogen-bonded complex of phenol with trimethylamine in methyl chloride solvent are studied with the reference interaction site model self-consistent field method. The reactions in both the electronic ground and excited states are considered. The second-order Møller-Plesset perturbation (MP) theory or the second-order multireference MP theory is used to evaluate the effect of the dynamical electron correlation on the free energy profiles. The free energy surface in the ground state shows a discrepancy with the experimental results for the related hydrogen-bonded complexes. To resolve this discrepancy, the effects of chloro-substitutions in phenol are examined, and its importance in stabilizing the ionic form is discussed. The temperature effect is also studied. In contrast to the ground state, the ??* excited state of phenol-trimethylamine complex exhibits the proton transfer reaction with a low barrier. The reaction is almost thermoneutral. This is attributed to the reduction of proton affinity of phenol by the ??* electronic excitation. We further examine the possibility of the electron-proton-coupled transfer in the ??* state through the surface crossing with the charge transfer type ??* state. PMID:20602442

  17. Electron transfer reaction in the Marcus inverted region: Role of high frequency vibrational modes

    International Nuclear Information System (INIS)

    A theoretical study of the dynamics of photo-electron transfer reactions in the Marcus inverted regime is presented. This study is motivated partly by the recent proposal of Barbara et al. (J. Phys. Chem. 96, 3728, 1991) that a minimal model of an electron transfer reaction should consist of a polar solvent mode (X), a low frequency vibrational mode (Q) and one high frequency mode (q). Interplay between these modes may be responsible for the crossover observed in the dynamics from a solvent controlled to a vibrational controlled electron transfer. The following results have been obtained. (i) In the case of slowly relaxing solvents, the proximity of the point of excitation to an effective sink on the excited surface is critical in determining the decay of the reactant population. This is because the Franck-Condon overlap between the reactant ground and the product excited states decreases rapidly with increase in the quantum number of the product vibrational state. (ii) Non-exponential solvation dynamics has an important effect in determining the rates of electron transfer. Especially, a biphasic solvation and a large coupling between the reactant and the product states both may be needed to explain the experimental results

  18. Coupling of radiation, excited states and electron energy distribution function in non equilibrium hydrogen plasmas

    International Nuclear Information System (INIS)

    Some of the recent efforts in the state-to-state modeling of H/H2-based plasma are considered, with particular concern to the aspects of self-consistent coupling between the chemical kinetics, electron kinetics and radiation. These aspects are first illustrated in the case of a 0-dimensional model considering both optically thin and optically thick cases in recombining and ionizing regimes. In the second part of the paper, a 1-dimensional extension of the model is applied to study a steady normal shock generated in an H2/He plasma of interest in atmospheric entry problems. A radiation transfer equation is coupled to the model as well, to analyze the effect of radiation transfer on chemical kinetics and compare to the commonly used thin and thick plasma approximations. The most significant result is the influence of reabsorption on the concentration of excited states, which in turn creates additional structure on the electron energy distribution function through second kind collisions. - Highlights: • We review our recent efforts in modeling of H2/H plasmas. • We stress the couplings between state-to-state chemical kinetics, electron kinetics and radiation. • These issues are illustrated using a 0-d and 1-d models. • The effect of radiation transfer on chemical kinetics is considered

  19. Electron Spin Excited States Spectroscopy in a Quantum Dot Probed by QPC Back-action

    OpenAIRE

    Li, HaiOu; Xiao, Ming; Cao, Gang; Zhou, Cheng; Shang, RuNan; Tu, Tao; Guo, GuangCan; Jiang, Hongwen; Guo, Guoping

    2011-01-01

    The quantum point contact (QPC) back-action has been found to cause non-thermal-equilibrium excitations to the electron spin states in a quantum dot (QD). Here we use back-action as an excitation source to probe the spin excited states spectroscopy for both the odd and even electron numbers under a varying parallel magnetic field. For a single electron, we observed the Zeeman splitting. For two electrons, we observed the splitting of the spin triplet states $|T^{+}>$ and $|T...

  20. Selection rules for transport excitation spectroscopy of few-electron quantum dots

    CERN Document Server

    Pfannkuche, D; Pfannkuche, Daniela; Ulloa, Sergio E

    1995-01-01

    Tunneling of electrons traversing a few-electron quantum dot is strongly influenced by the Coulomb interaction leading to Coulomb blockade effects and single-electron tunneling. We present calculations which demonstrate that correlations between the electrons cause a strong suppression of most of the energetically allowed tunneling processes involving excited dot states. The excitation of center-of-mass modes, in contrast, is unaffected by the Coulomb interaction. Therefore, channels connected to these modes dominate the excitation spectra in transport measurements.

  1. Transfer of excitation between 2p levels of neon induced by collisions with neutral neon atoms

    International Nuclear Information System (INIS)

    The reaction coefficients for transfer of excitation between 2p atoms of neon induced by collisions with neutral neon atoms have been determined for nine 2p states. By means of a continuous dye laser 1s atoms of neon in a plasma generated by a 20-MeV proton beam in 110 torr neon, were excited to a specific 2p state. The relative population density of 2p states produced via collisional transfer of excitation was determined from the spectrum of the induced fluorescence light. This has been carried out for laser excitation to eight 2p levels. The reaction coefficients were calculated after inserting the observed population densities in a set of balance equations. The ratios of the experimental values of the reaction coefficients for collisional coupling between each two 2p states appeared to be consistent with a relation following from the principle of detailed balancing. (Auth.)

  2. Decision making based on optical excitation transfer via near-field interactions between quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Naruse, Makoto, E-mail: naruse@nict.go.jp [Photonic Network Research Institute, National Institute of Information and Communications Technology, 4-2-1 Nukui-kita, Koganei, Tokyo 184-8795 (Japan); Nomura, Wataru; Ohtsu, Motoichi [Department of Electrical Engineering and Information Systems, Graduate School of Engineering, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-8656 (Japan); Aono, Masashi [Earth-Life Science Institute, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguru-ku, Tokyo 152-8550 (Japan); PRESTO, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi-shi, Saitama 332-0012 (Japan); Sonnefraud, Yannick; Drezet, Aurélien; Huant, Serge [Université Grenoble Alpes, Inst. NEEL, F-38000 Grenoble (France); CNRS, Inst. NEEL, F-38042 Grenoble (France); Kim, Song-Ju [WPI Center for Materials Nanoarchitectonics, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)

    2014-10-21

    Optical near-field interactions between nanostructured matters, such as quantum dots, result in unidirectional optical excitation transfer when energy dissipation is induced. This results in versatile spatiotemporal dynamics of the optical excitation, which can be controlled by engineering the dissipation processes and exploited to realize intelligent capabilities such as solution searching and decision making. Here, we experimentally demonstrate the ability to solve a decision making problem on the basis of optical excitation transfer via near-field interactions by using colloidal quantum dots of different sizes, formed on a geometry-controlled substrate. We characterize the energy transfer behavior due to multiple control light patterns and experimentally demonstrate the ability to solve the multi-armed bandit problem. Our work makes a decisive step towards the practical design of nanophotonic systems capable of efficient decision making, one of the most important intellectual attributes of the human brain.

  3. Decision making based on optical excitation transfer via near-field interactions between quantum dots

    International Nuclear Information System (INIS)

    Optical near-field interactions between nanostructured matters, such as quantum dots, result in unidirectional optical excitation transfer when energy dissipation is induced. This results in versatile spatiotemporal dynamics of the optical excitation, which can be controlled by engineering the dissipation processes and exploited to realize intelligent capabilities such as solution searching and decision making. Here, we experimentally demonstrate the ability to solve a decision making problem on the basis of optical excitation transfer via near-field interactions by using colloidal quantum dots of different sizes, formed on a geometry-controlled substrate. We characterize the energy transfer behavior due to multiple control light patterns and experimentally demonstrate the ability to solve the multi-armed bandit problem. Our work makes a decisive step towards the practical design of nanophotonic systems capable of efficient decision making, one of the most important intellectual attributes of the human brain.

  4. Decision making based on optical excitation transfer via near-field interactions between quantum dots

    CERN Document Server

    Naruse, Makoto; Aono, Masashi; Ohtsu, Motoichi; Sonnefraud, Yannick; Drezet, Aurélien; Huant, Serge; Kim, Song-Ju

    2014-01-01

    Optical near-field interactions between nanostructured matter, such as quantum dots, result in unidirectional optical excitation transfer when energy dissipation is induced. This results in versatile spatiotemporal dynamics of the optical excitation, which can be controlled by engineering the dissipation processes and exploited to realize intelligent capabilities such as solution searching and decision making. Here we experimentally demonstrate the ability to solve a decision making problem on the basis of optical excitation transfer via near-field interactions by using colloidal quantum dots of different sizes, formed on a geometry-controlled substrate. We characterize the energy transfer behavior due to multiple control light patterns and experimentally demonstrate the ability to solve the multi-armed bandit problem. Our work makes a decisive step towards the practical design of nanophotonic systems capable of efficient decision making, one of the most important intellectual attributes of the human brain.

  5. Surface excitations in the modelling of electron transport for electron- beam-induced deposition experiments

    OpenAIRE

    Salvat-Pujol, Francesc; Valenti, Roser; Werner, Wolfgang S.

    2015-01-01

    The aim of the present overview article is to raise awareness of an essential aspect that is usually not accounted for in the modelling of electron transport for focused-electron-beam-induced deposition (FEBID) of nanostructures: surface excitations are on the one hand responsible for a sizeable fraction of the intensity in reflection-electron-energy-loss spectra for primary electron energies of up to a few keV and, on the other hand, they play a key role in the emission of ...

  6. Two-Photon Excitation of trans-Stilbene: Spectroscopy and Dynamics of Electronically Excited States above S1.

    Science.gov (United States)

    Houk, Amanda L; Zheldakov, Igor L; Tommey, Tyler A; Elles, Christopher G

    2015-07-23

    The photoisomerization dynamics of trans-stilbene have been well studied in the lowest excited state, but much less is known about the behavior following excitation to higher-lying electronically excited states. This contribution reports a combined study of the spectroscopy and dynamics of two-photon accessible states above S1. Two-photon absorption (2PA) measurements using a broadband pump-probe technique reveal distinct bands near 5.1 and 6.4 eV. The 2PA bands have absolute cross sections of 40 ± 16 and 270 ± 110 GM, respectively, and a pump-probe polarization dependence that suggests both of the transitions access Ag-symmetry excited states. Separate transient absorption measurements probe the excited-state dynamics following two-photon excitation into each of the bands using intense pulses of 475 and 380 nm light, respectively. The initially excited states rapidly relax via internal conversion, leading to the formation of an S1 excited-state absorption band that is centered near 585 nm and evolves on a time scale of 1-2 ps due to intramolecular vibrational relaxation. The subsequent evolution of the S1 excited-state absorption is identical to the behavior following direct one-photon excitation of the lowest excited state at 4.0 eV. The complementary spectroscopy and dynamics measurements provide new benchmarks for computational studies of the electronic structure and dynamics of this model system on excited states above S1. Probing the dynamics of molecules in their higher-lying excited states is an important frontier in chemical reaction dynamics. PMID:25369524

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

    Science.gov (United States)

    Neves, R. F. C.; Jones, D. B.; Lopes, M. C. A.; Blanco, F.; García, G.; Ratnavelu, K.; Brunger, M. J.

    2015-05-01

    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.

  8. EXCITATION TRANSFER WITHIN THE OPTICALLY EXCITED DOUBLET ?(2E) IN RUBY

    OpenAIRE

    Van Miltenburg, J.; Jongerden, G.; Dijkhuis, J.; De Wijn, H.

    1985-01-01

    Phonon-assisted spectral transport mediated by Orbach processes via 2?(2E) is demonstrated to occur within the inhomogeneously broadened transition between the Zeeman components of the ?(2E) state in 130 at.ppm ruby at 1.5 K. The experimental method is hole burning with microwave excitation over a variable band-width. The homgeneous width of the transition was found to be 6.0 ± 0.5 MHz.

  9. Analytical model for rates of electron attachment and intramolecular electron transfer in electron transfer dissociation mass spectrometry.

    Science.gov (United States)

    Simons, Jack

    2010-05-26

    A new physical model is put forth to allow the prediction of electron transfer rates and distances for (i) intramolecular transfer from an n > or = 3 Rydberg orbital on a positive site to a disulfide or amide bond site and (ii) intermolecular transfer from an anion donor to an n > or = 3 Rydberg orbital of a positively charged polypeptide. Although ab initio methods have proven capable of handling such electron transfer events when the Rydberg orbital has principal quantum number n = 3, they have proven to be incapable of handling Rydberg states having quantum number n > 3, so having a new tool capable of handling n > 3 Rydberg states is important. The model (i) focuses on each Rydberg orbital's large peak of high amplitude, (ii) approximates the electron density within this peak as constant within a radial shell characterized by a radius and thickness T both of which depend on the quantum number n, and (iii) assumes that strong coupling (either with an orbital of an anion donor or to a disulfide sigma* or a backbone amide pi* orbital) occurs when the valence orbital penetrates fully within the radial shell of the Rydberg orbital. These assumptions permit a derivation of the ratios of rates of electron transfer for n > 3 to those for n = 3. Combining these ratios with ab initio rates for n = 3 allows one to make rate predictions for inter- and intramolecular electron transfer involving Rydberg orbitals appropriate to the electron transfer dissociation process. One important prediction of this model is that the combination of large-penetration and Landau-Zener surface-crossing conditions places very severe limitations on which Rydberg levels can initially be populated in electron transfer dissociation. Another prediction is that a Rydberg orbital of a given principal quantum number n has a limited range of distances over which it can transfer an electron; sigma* or pi* orbitals either too far from or too close to a given Rydberg orbital cannot accept an electron from that orbital. PMID:20438123

  10. Direct electron transfer based enzymatic fuel cells

    International Nuclear Information System (INIS)

    In this mini-review we briefly describe some historical developments made in the field of enzymatic fuel cells (FCs), discussing important design considerations taken when constructing mediator-, cofactor-, and membrane-less biological FCs (BFCs). Since the topic is rather extensive, only BFCs utilizing direct electron transfer (DET) reactions on both the anodic and cathodic sides are considered. Moreover, the performance of mostly glucose/oxygen biodevices is analyzed and compared. We also present some unpublished results on mediator-, cofactor-, and membrane-less glucose/oxygen BFCs recently designed in our group and tested in different human physiological fluids, such as blood, plasma, saliva, and tears. Finally, further perspectives for BFC applications are highlighted.

  11. Plugging in or going wireless: strategies for interspecies electron transfer

    OpenAIRE

    PravinMallaShrestha; Amelia-ElenaRotaru

    2014-01-01

    Interspecies exchange of electrons enables a diversity of microbial communities to gain energy from reactions that no one microbe can catalyze. The first recognized strategies for interspecies electron transfer were those that relied on chemical intermediates that are recycled through oxidized and reduced forms. Well-studied examples are interspecies H2 transfer and the cycling of sulfur intermediates in anaerobic photosynthetic communities. Direct interspecies electron transfer (DIET) in whi...

  12. Electron transfer reactions of metal complexes in solution

    International Nuclear Information System (INIS)

    A few representative electron-transfer reactions are selected and their kinetic parameters compared with the predictions of activated complex models. Since Taube has presented an elegant treatment of intramolecular electron-transfer reactions, emphasis is on bimolecular reactions. The latter electron-transfer reactions are more complicated to treat theoretically since the geometries of their activated complexes are not as well known as for the intramolecular case. In addition in biomolecular reactions, the work required to bring the two reactants together needs to be calculated. Since both reactants generally carry charges this presents a non-trivial problem at the ionic strengths usually used to study bimolecular electron transfer

  13. Photoinduced electron transfer in donor-acceptor complexes of ethylene with molecular and atomic iodine.

    Science.gov (United States)

    Kalume, Aimable; George, Lisa; Powell, Andrew D; Dawes, Richard; Reid, Scott A

    2014-08-28

    Building upon our recent studies of radical addition pathways following excitation of the I2 chromophore in the donor-acceptor complex of ethylene and I2 (C2H4···I2), in this article, we extend our studies to examine photoinduced electron transfer. Thus, irradiation into the intense charge-transfer band of the complex (?max = 247 nm) gave rise to a band at 366 nm that is assigned to the bridged ethylene-I radical complex on the basis of our prior work. The formation of the radical complex is explained by a mechanism that involves rapid back electron transfer leading to I-I bond fission. Excitation into the charge-transfer band of the radical complex led to regeneration of the parent complex and the formation of the final photoproduct, anti- and gauche-1,2-diiodoethane, which confirms that the reaction proceeds ultimately by a radical addition mechanism. This finding is contrasted with our previous study of the C2H4···Br2 complex, where CT excitation led to only one product, anti-1,2-dibromoethane, a result explained by a single electron-transfer mechanism proceeding via a bridged bromonium ion intermediate. For the I2 complex, the breakup of the photolytically generated I2(-•) anion radical is apparently sufficiently slow to render it uncompetitive with back electron transfer. Finally, we report a detailed computational examination of the parent and radical complexes of both bromine and iodine, using high-level single- and multireference methods, which provide insight into the different behaviors of the charge-transfer states of the two radicals and the role of spin-orbit coupling. PMID:25075444

  14. The population transfer of high excited states of Rydberg lithium atoms in a microwave field

    International Nuclear Information System (INIS)

    Using the time-dependent multilevel approach (TDMA), the properties of high excited Rydberg lithium atom have been obtained in the microwave field. The population transfer of lithium atom are studied on numerical calculation, quantum states are controlled and manipulated by microwave field. It shows that the population can be completely transferred to the target state by changing the chirped rate and field amplitude. (authors)

  15. Experimental study on the kinetically induced electronic excitation in atomic collisional cascades

    International Nuclear Information System (INIS)

    the present thesis deals with the ion-collision-induced electronic excitation of metallic solids. For this for the first time metal-insulator-metal layer systems are used for the detection of this electronic excitation. The here applied aluminium/aluminium oxide/silver layer sytems have barrier heights of 2.4 eV on the aluminium respectively 3.3 eV on the silver side. With the results it could uniquely be shown that the electronic excitation is generated by kinetic processes, this excitation dependenc on the kinetic energy of the colliding particles, and the excitation dependes on the charge state of the projectile

  16. Vibrational excitations in molecular layers probed by ballistic electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kajen, Rasanayagam Sivasayan; Chandrasekhar, Natarajan [Institute of Materials Research and Engineering, 3 Research Link, 117602 (Singapore); Feng Xinliang; Muellen, Klaus [Max-Planck-Institut fuer Polymerforschung, Postfach 3148, D-55021 Mainz (Germany); Su Haibin, E-mail: n-chandra@imre.a-star.edu.sg, E-mail: muellen@mpip-mainz.mpg.de, E-mail: hbsu@ntu.edu.sg [Division of Materials Science, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore)

    2011-10-28

    We demonstrate the information on molecular vibrational modes via the second derivative (d{sup 2}I{sub B}/dV{sup 2}) of the ballistic electron emission spectroscopy (BEES) current. The proposed method does not create huge fields as in the case of conventional derivative spectroscopy and maintains a zero bias across the device. BEES studies carried out on three different types of large polycyclic aromatic hydrocarbon (PAH) molecular layers show that the d{sup 2}I{sub B}/dV{sup 2} spectra consist of uniformly spaced peaks corresponding to vibronic excitations. The peak spacing is found to be identical for molecules within the same PAH family though the BEES onset voltage varies for different molecules. In addition, injection into a particular orbital appears to correspond to a specific vibrational mode as the manifestation of the symmetry principle.

  17. Electron impact excitation of carbon and oxygen ions

    International Nuclear Information System (INIS)

    This report is an attempt at a comprehensive compilation of currently available theoretical data on electron impact excitation of carbon and oxygen ions. It is designed to be of use primarily to theoretical atomic physicists, allowing them a broader than usual view of how various approximations compare. We do not attempt to place an estimate on the accuracy to which any of the collision strengths are known. The reader may obtain some idea of the accuracy from the spread in the calculations. Further, we do not evaluate rate coefficients or make any comparison with observed results. We do provide simple analytic fits to the data, where possible, thus allowing the reader to make comparison with observation or evaluate rate coefficients if he desires. The present data contains little about resonance effects, due to the difficulty of their presentation. It is possible that resonances could make a considerable change in the average collision strength near threshold, and this topic requires further study

  18. Investigation of the charge-transfer in photo-excited nanoparticles for CO2 reduction in non-aqueous media

    Directory of Open Access Journals (Sweden)

    Dimitrijevi? Nada M.

    2013-01-01

    Full Text Available Photoinduced charge separation in TiO2 and Cu2O semiconductor nanoparticles was examined using Electron Paramagnetic Resonance spectroscopy in order to get insight into the photocatalytic reduction of CO2 in nonaqueous media. For dissolution/grafting of CO2 we have used carboxy-PEG4-amine, and as a solvent poly(ethylene glycol 200. We have found that, in this system, reduction of CO2 starts at potential of -0.5 V vs Ag/AgCl, which is significantly more positive than the potential for electrochemical reduction of CO2 in most organic solvents and water (-2.0 V vs. Ag/AgCl. The electron transfer from excited nanoparticles to CO2 is governed both by thermodynamic and kinetic parameters, namely by the redox potential of conduction band electrons and adsorption/binding of CO2 on the surface of nanoparticles.

  19. Ultrafast excited state dynamics of the bi- and termolecular stilbene-viologen charge-transfer complexes assembled via host-guest interactions

    International Nuclear Information System (INIS)

    Excited state dynamics of the highly stable 1:1 and 2:1 charge-transfer (CT) complexes assembled via host-guest interactions between a biscrown stilbene and a viologen vinylog was studied using transient pump-supercontinuum probe spectroscopy. In acetonitrile, both complexes showed ultrafast two-component transient absorption dynamics after excitation in the CT absorption band by a 616 nm, 70 fs laser pulse. The faster component (?<200 fs) is assigned to relaxation processes in the lowest CT excited state. The second component is due to the back electron transfer (ET) reaction leading to the ground state. The measured ET time constants for the 1:1 and 2:1 CT complexes are about 540 fs and 1.08 ps, respectively. Excitation of the bimolecular complex by a 308 nm laser pulse gave rise to three-component transient absorption dynamics. The fastest transient (??150 fs) is assigned to relaxation processes in the high-lying excited states of the complex. The high-amplitude rise component with a time constant of about 300 fs is due to the internal conversion from the high-lying excited states to the lowest CT excited state. The latter decayed to the ground state via the back ET with a time constant very close to that measured when the complex was excited in the CT absorption band

  20. Collective two-particle excitations in cuprates and manganites: Resonant inelastic x-ray scattering and electron energy loss spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Geck, Jochen; Krauss, Roberto; Schuster, Roman; Knupfer, Martin; Ribeiro, Patrick; Buechner, Bernd [IFW Dresden (Germany); Glatzel, Pieter; Herrero-Martin, Javier [European Synchrotron Radiation Facility (France); Garcia-Ruiz, Joaquin [Universidad de Zaragoza (Spain); Casa, Diego; Gog, Thomas [Advanced Photon Source (United States); Wadati, Hiroki; Sawatzky, George A. [University of British Columbia (Canada)

    2009-07-01

    The two-particle charge excitations of Sr{sub 2}CuO{sub 3}, which contains one-dimensional corner-sharing CuO{sub 2}-chains, were studied by Resonant Inelastic X-ray Scattering (RIXS) at the Cu K-edge. At the center of the Brillouin zone, the dependence of the various charge-transfer excitations on the incident photon energy E{sub i} was studied in detail. The different charge transfer excitations resonate for different intermediate states, i.e., different E{sub i}, which allows to draw conclusions about the symmetry of the created excitations. Further, the RIXS results are discussed in comparison to previous Electron Energy Loss Spectroscopy (EELS) studies. A similar approach was then used to investigate the two-particle excitations (La,Sr){sub 2}MnO{sub 4}. Surprisingly, the excitations observed for the doped manganite materials share similar traits with the ones observed for the doped cuprates.

  1. Interfacial electron transfer dynamics of ru(II)-polypy6ridine sensitized TiO2

    Energy Technology Data Exchange (ETDEWEB)

    Jakubikova, Elena [Los Alamos National Laboratory; Martin, Richard L [Los Alamos National Laboratory; Batista, Enrique R [Los Alamos National Laboratory; Snoeberger, Robert C [YALE UNIV.; Batista, Victor S [YALE UNIV.

    2009-01-01

    Quantum dynamics simulations combined with density functional theory calculations are applied to study interfacial electron transfer (IET) from pyridine-4-phosphonic acid, [Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 2+} and [Ru(tpy)(bpy)(H{sub 2}O)-Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 4+} into the (101) surface of anatase TiO{sub 2}. IET rate from pyridine-4-phosphonic acid attached to the nanoparticle in bidentate mode ({tau} {approx} 100 fs) is an order of magnitude faster than the IET rate of the adsorbate attached in the monodentate mode ({tau} {approx} 1 ps). Upon excitation with visible light, [Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 2+} attached to TiO{sub 2} in bidentate binding mode will undergo IET with the rate of {approx} 1-10 ps, which is competitive with the excited state decay into the ground state. The probability of electron injection from [Ru(tpy)(bpy)(H{sub 2}O)-Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 4+} is rather low, as the excitation with visible light localizes the excited electron in the tpy-tpy bridge, which does not have favorable coupling with the TiO{sub 2} nanoparticle. The results are relevant to better understanding of the adsorbate features important for promoting efficient interfacial electron transfer into the semiconductor.

  2. Excited-State Proton Transfer in Resveratrol and Proposed Mechanism for Plant Resistance to Fungal Infection.

    Science.gov (United States)

    Simkovitch, Ron; Huppert, Dan

    2015-09-01

    Steady-state and time-resolved fluorescence techniques were employed to study the photophysics and photochemistry of trans-resveratrol. trans-Resveratrol is found in large quantities in fungi-infected grapevine-leaf tissue and plays a direct role in the resistance to plant disease. We found that trans-resveratrol in liquid solution undergoes a trans-cis isomerization process in the excited state at a rate that depends partially on the solvent viscosity, as was found in previous studies on trans-stilbene. The hydroxyl groups of the phenol moieties in resveratrol are weak photoacids. In water and methanol solutions containing weak bases such as acetate, a proton is transferred to the base within the lifetime of the excited state. When resveratrol is adsorbed on cellulose (also a component of the plant's cell wall), the cis-trans process is slow and the lifetime of the excited state increases from several tens of picoseconds in ethanol to about 1.5 ns. Excited-state proton transfer occurs when resveratrol is adsorbed on cellulose and acetate ions are in close proximity to the phenol moieties. We propose that proton transfer from excited resveratrol to the fungus acid-sensing chemoreceptor is one of the plant's resistance mechanisms to fungal infection. PMID:26247232

  3. 77 FR 71035 - Financial Management Service; Proposed Collection of Information: Electronic Funds Transfer (EFT...

    Science.gov (United States)

    2012-11-28

    ...Collection of Information: Electronic Funds Transfer...on a continuing information collection. By...concerning the ``Electronic Funds Transfer...collection of information described below: Title: Electronic Funds...

  4. 77 FR 22066 - Proposed Collection of Information: “Notice of Reclamation Electronic Funds Transfer, Federal...

    Science.gov (United States)

    2012-04-12

    ...Collection of Information: ``Notice of Reclamation Electronic Funds Transfer...continuing information collection...Reclamation. Electronic Funds Transfer...collection of information described...Reclamation, Electronic Funds...

  5. Computer modelling of coherence effects in excitation transfer in hexagonal PSU

    International Nuclear Information System (INIS)

    The time development of the site occupation probabilities in the hexagonal model of photosynthetic units is investigated. The method based on Stochastic Liouville Equations allows us to describe the excitation transfer with a trap (reaction center) in coherent, quasicoherent and incoherent regimes. (author). 26 refs, 9 figs

  6. Elastic, excitation, ionization and charge transfer cross sections of current interest in fusion energy research

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, D.R.; Krstic, P.S. [Oak Ridge National Lab. TN (United States). Physics Div.

    1997-01-01

    Due to the present interest in modeling and diagnosing the edge and divertor plasma regions in magnetically confined fusion devices, we have sought to provide new calculations regarding the elastic, excitation, ionization, and charge transfer cross sections in collisions among relevant ions, neutrals, and isotopes in the low-to intermediate-energy regime. We summarize here some of our recent work. (author)

  7. Elastic, excitation, ionization and charge transfer cross sections of current interest in fusion energy research

    International Nuclear Information System (INIS)

    Due to the present interest in modeling and diagnosing the edge and divertor plasma regions in magnetically confined fusion devices, we have sought to provide new calculations regarding the elastic, excitation, ionization, and charge transfer cross sections in collisions among relevant ions, neutrals, and isotopes in the low- to intermediate-energy regime. We summarize here some of our recent work

  8. On the rate of triplet excitation transfer in the diffuse limit

    International Nuclear Information System (INIS)

    The usefulness of spectral data in estimating intermolecular triplet excitation transfer rates in found to be rather limited and to depend explicitly on the mechaisms which allow the optical transitions. Necessary conditions for the validity of such use of spectra are given, and the otherwise required correction factors are discussed and estimated. (Author)

  9. Rate of Excitation Energy Transfer between Fluorescent Dyes and Nanoparticles

    CERN Document Server

    Saini, S; Shenoy, V B; Bagchi, B; Saini, Sangeeta; Bhowmick, Somnath; Shenoy, Vijay B.; Bagchi, Biman

    2006-01-01

    Long range resonance energy transfer (RET) between a donor and an acceptor molecule is increasingly being used in many areas of biological and material science. The phenomenon is used to monitor the in vivo separation between different (bio) polymers/units of (bio) polymers and hence the dynamics of various biomolecular processes. Because of the sensitivity of the rate on to the distance between the donor (D) and the acceptor (A), the technique is popularly termed as "spectroscopic ruler". In this work we examine the distance and orientation dependence of RET in three different systems: (i) between a conjugated polymer and a fluorescent dye, (ii) between a nanometal particle (NMP) and a fluorescent dye and (iii) between two NMP. We show that in all the three cases, the rate of RET follows a distance dependence of d^(- sigma) where exponent sigma approaches 6 at large d (F"orster type dependence) but has a value varying from 3-4 at short to intermediate distance. At short separation, the amplitude of rate is c...

  10. Nonlocality in the excitation energy transfer in the Fenna-Matthews-Olson complex

    CERN Document Server

    Bengtson, Charlotta; Sjöqvist, Erik

    2015-01-01

    Pigment protein complexes involved in photosynthesis are remarkably efficient in transferring excitation energy from light harvesting antenna molecules to a reaction centre where it is converted to and stored as chemical energy. Recent experimental and theoretical studies suggest that quantum coherence and correlations may play a role in explaining this efficiency. We examine whether bipartite nonlocality, a property that verifies a strong correlation between two quantum systems, exists between different pairs of chromophore states in the Fenna-Matthews-Olson (FMO) complex and how this is connected to the amount of bipartite entanglement. In particular, it is tested in what way these correlation properties are affected by different initial conditions (i.e., which chromophore is initially excited). When modeling the excitation energy transfer (EET) in the FMO complex with the hierarchically coupled equations of motions (HEOM), it is found that bipartite nonlocality indeed exists for some pairs of chromophore s...

  11. Electromagnetically induced electron transfer between quantum dots via conduction band

    International Nuclear Information System (INIS)

    The Stark-like mechanism of electron transfer between quantum dots under the influence of electromagnetic field is considered. Analytical estimations and numerical simulation results clarifying the special role of conduction band are adduced. Two-photon mechanism of electron transfer between quantum dots via conduction band is suggested

  12. Photoinduced Electron-transfer Reaction of Pentafluoroiodobenzene with Alkenes

    Directory of Open Access Journals (Sweden)

    Qing-Yun Chen

    1997-01-01

    Full Text Available Irradiation of pentafluoroiodobenzene and alkenes gave the corresponding adducts. The presence of single electron-transfer scavengers, (p-dinitrobenzene and t-Bu2NO and the free radical inhibitor (hydroquinone suppressed the reaction. A photoinduced electron-transfer mechanism is proposed.

  13. Modeling time-coincident ultrafast electron transfer and solvation processes at molecule-semiconductor interfaces

    International Nuclear Information System (INIS)

    Kinetic models based on Fermi's Golden Rule are commonly employed to understand photoinduced electron transfer dynamics at molecule-semiconductor interfaces. Implicit in such second-order perturbative descriptions is the assumption that nuclear relaxation of the photoexcited electron donor is fast compared to electron injection into the semiconductor. This approximation breaks down in systems where electron transfer transitions occur on 100-fs time scale. Here, we present a fourth-order perturbative model that captures the interplay between time-coincident electron transfer and nuclear relaxation processes initiated by light absorption. The model consists of a fairly small number of parameters, which can be derived from standard spectroscopic measurements (e.g., linear absorbance, fluorescence) and/or first-principles electronic structure calculations. Insights provided by the model are illustrated for a two-level donor molecule coupled to both (i) a single acceptor level and (ii) a density of states (DOS) calculated for TiO2 using a first-principles electronic structure theory. These numerical calculations show that second-order kinetic theories fail to capture basic physical effects when the DOS exhibits narrow maxima near the energy of the molecular excited state. Overall, we conclude that the present fourth-order rate formula constitutes a rigorous and intuitive framework for understanding photoinduced electron transfer dynamics that occur on the 100-fs time scale

  14. Oxygen uncouples light absorption by the chlorosome antenna and photosynthetic electron transfer in the green sulfur bacterium Chlorobium tepidum

    DEFF Research Database (Denmark)

    Frigaard, N-U; Matsuura, K

    1999-01-01

    In photosynthetic green sulfur bacteria excitation energy is transferred from large bacteriochlorophyll (BChl) c chlorosome antennas via small BChl a antennas to the reaction centers which then transfer electrons from cytochrome c to low-potential iron-sulfur proteins. Under oxidizing conditions a reversible mechanism is activated in the chlorosomes which quenches excited BChl c. We used flash-induced cytochrome c oxidation to investigate the effect of this quenching on photosynthetic electron t...

  15. Light-induced electron transfer vs. energy transfer in molecular thin-film systems

    International Nuclear Information System (INIS)

    Quenching of fluoranthene (FA) singlets by tetrabromo-o-benzoquinone (TBBQ) and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) was studied both in xylene solutions and in spin-cast polystyrene (PS) films. Emphasis was placed on time-resolved fluorescence transients resulting from pulsed excitation. Linear Stern-Volmer plots were obtained for quenching in solution and gave diffusion-controlled rate constants, of 1.45 x 1010 M-1 sec-1 and 1.53 x 1010 M-1 sec-1 for TBBQ and TMPD, respectively. TBBQ was found to quench FA singlets in PS over the studied concentration range 12 mM 0 was experimentally determined to be 24.3 A, which is in good agreement with the theoretical value of 23 A calculated from spectral data. Quenching of FA singlets in PS films was found to be independent of FA concentration over a 300 mM to 1200 mM FA concentration range for a constant TBBQ concentration of 24.0 mM. TMPD was only slightly effective as a quencher of FA singlets in PS because it apparently behaves strictly as a contact quencher based on reversible charge transfer. The implications of these results for the design of systems intended to exploit light-induced electron transfer are discussed

  16. A DFT/TDDFT investigation of the excited state proton transfer reaction of fisetin chromophore.

    Science.gov (United States)

    Yang, Dapeng; Zhao, Jinfeng; Zheng, Rui; Wang, Yusheng; Lv, Jian

    2015-12-01

    In the present work, 3, 3', 4', 7-tetrahydroxyflavone (fisetin), as one of the most extensive distributed flavonoids, has been investigated on the excited state proton transfer (ESPT) based on the time-dependent density functional theory (TDDFT) method. The calculated absorption and fluorescence spectra based on the TDDFT method are in agreement with the experimental results. Two kinds of structures of fisetin chromophore are found in the first excited (S1) state, which may be due to the proton transfer reactive. Hydrogen bond strengthening has been testified in the S1 state based on comparing staple bond lengths and bond angles involved in hydrogen bonding between the S0 state and the S1 state. In addition, the calculated infrared spectra at the O-H stretching vibrational region and calculated hydrogen bond energy also declare the phenomenon of hydrogen bond strengthening. The frontier molecular orbitals (MOs) analysis and Natural bond orbital (NBO) manifest the intramolecular charge transfer of fisetin chromophore, which reveals the tendency of proton transfer. The potential energy surfaces of the S0 and S1 states are constructed to explain the mechanism of the proton transfer in excited state in detail. PMID:26143329

  17. Computer Simulation of Electron Transfer at Hematite Surfaces

    International Nuclear Information System (INIS)

    Molecular dynamics simulations in combination with ab initio calculations were carried out to determine the rate of electron transfer in bulk hematite (?-Fe2O3) and at two low-index surfaces, namely the (012) and (001) surfaces. The electron transfer reactions considered here involve the II/III valence interchange between nearest-neighbor iron atoms. Two electron transfer directions were investigated namely the basal plane and c direction charge transfers. Electron transfer rates obtained in bulk hematite were in good agreement with ab initio electronic structure calculations thus validating the potential model. The surfaces were considered both in vacuum and in contact with an equilibrated aqueous solution. The reorganization energy is found to increase significantly at the first surface layer and this value is little affected by the presence of water. In addition, in the case of the (012) surface, the electronic coupling matrix element for the topmost basal plane transfer was calculated at the Hartree-Fock level and was found to be weak compared to the corresponding charge transfer in the bulk. Therefore, most surfaces show a decrease in the rate of charge transfer at the surface. However, where iron atoms involved in the charge transfer reaction are directly coordinated to water molecules, water lowers the free energy of activation to a great extent and provides a large driving force for electrons to diffuse toward the bulk thus opposing the intrinsic surface effect. The surfaces considered in this work show different charge transfer properties. Hematite has been shown to exhibit anisotropic conductivity and thus different surfaces will show different intra- and inter-layer rates depending on their orientation. Moreover, the calculations of charge transfers at the hydroxyl- and iron-terminated (001) surfaces revealed that surface termination has a significant effect on the charge transfer parameters in the vicinity of the surface. Finally, our findings indicate that undercoordinated terminal iron atoms could act as electron traps at the surface

  18. Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles

    DEFF Research Database (Denmark)

    Gilbert, Benjamin; Katz, Jordan E.

    2013-01-01

    An emerging area in chemical science is the study of solid-phase redox reactions using ultrafast time-resolved spectroscopy. We have used molecules of the photoactive dye 2?,7?-dichlorofluorescein (DCF) anchored to the surface of iron(iii) oxide nanoparticles to create iron(ii) surface atoms via photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(iii) oxide nanoparticles has not been reported. We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(iii)–dye complex. Following light absorption, excited state relaxation times of the dye of 115–310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye–oxide energy transfer is energetically forbidden) even though the acceptor states are different. Comparison of the alignment of the excited states of the dye and the unoccupied states of these oxides showed that the dye injects into acceptor states of different symmetry (Ti t2g vs. Fe eg).

  19. Photoredox Reaction of Cobalticinium Pentacarbonylmanganate(-I) induced by Outer-Sphere Metal to Metal Charge Transfer Excitation

    OpenAIRE

    Kunkely, Horst; Vogler, Arnd

    1989-01-01

    The salts [Co(C5H5)2]+ wavelength absorptions at [Mn(CO)5]- and [Cr(C6H6)2]+ [Mn(CO)5]- show longwavelength absorptions at ?max 740 nm and 665 nm. These bands assigned to metal to metal charge transfer (MMCT) transitions from Mn-I to CoIII and CrI. Upon MMCT excitation the former ion pair is converted to Co(C5H5)2 and Mn 2(CO)10. The latter ion pair undergoes an analogous redox reaction as a thermal process. The thermal and the light-induced electron transfer are explained on the basis of th...

  20. Electronic transfer of sensitive patient data.

    Science.gov (United States)

    Detterbeck, A M W; Kaiser, J; Hirschfelder, U

    2015-01-01

    The purpose of this study was to develop decision-making aids and recommendations for dental practitioners regarding the utilization and sharing of sensitive digital patient data. In the current environment of growing digitization, healthcare professionals need detailed knowledge of secure data management to maximize confidentiality and minimize the risks involved in both archiving patient data and sharing it through electronic channels. Despite well-defined legal requirements, an all-inclusive technological solution does not currently exist. The need for a preliminary review and critical appraisal of common practices of data transfer prompted a search of the literature and the Web to identify viable methods of secure data exchange and to develop a flowchart. A strong focus was placed on the transmission of datasets both smaller than and larger than 10 MB, and on secure communication by smartphone. Although encryption of patient-related data should be routine, it is often difficult to implement. Pretty Good Privacy (PGP) and Secure/Multipurpose Internet Mail Extensions (S/MIME) are viable standards for secure e-mail encryption. Sharing of high-volume data should be accomplished with the help of file encryption. Careful handling of sensitive patient data is mandatory, and it is the end-user's responsibility to meet any requirements for encryption, preferably by using free, open-source (and hence transparent) software. PMID:25911828

  1. Quantum coherent contributions in biological electron transfer

    CERN Document Server

    Dorner, Ross; Heaney, Libby; Farrow, Tristan; Roberts, Philippa G; Hirst, Judy; Vedral, Vlatko

    2011-01-01

    Many biological electron transfer (ET) reactions are mediated by metal centres in proteins. NADH:ubiquinone oxidoreductase (complex I) contains an intramolecular chain of seven iron-sulphur (FeS) clusters, one of the longest chains of metal centres in biology and a test case for physical models of intramolecular ET. In biology, intramolecular ET is commonly described as a diffusive hopping process, according to the semi-classical theories of Marcus and Hopfield. However, recent studies have raised the possibility that non-trivial quantum mechanical effects play a functioning role in certain biomolecular processes. Here, we extend the semi-classical model for biological ET to incorporate both semi-classical and coherent quantum phenomena using a quantum master equation based on the Holstein Hamiltonian. We test our model on the structurally-defined chain of FeS clusters in complex I. By exploring a wide range of realistic parameters we and that, when the energy profile for ET along the chain is relatively at, ...

  2. Electron Transfer Dissociation of Milk Oligosaccharides

    Science.gov (United States)

    Han, Liang; Costello, Catherine E.

    2011-06-01

    For structural identification of glycans, the classic collision-induced dissociation (CID) spectra are dominated by product ions that derived from glycosidic cleavages, which provide only sequence information. The peaks from cross-ring fragmentation are often absent or have very low abundances in such spectra. Electron transfer dissociation (ETD) is being applied to structural identification of carbohydrates for the first time, and results in some new and detailed information for glycan structural studies. A series of linear milk sugars was analyzed by a variety of fragmentation techniques such as MS/MS by CID and ETD, and MS3 by sequential CID/CID, CID/ETD, and ETD/CID. In CID spectra, the detected peaks were mainly generated via glycosidic cleavages. By comparison, ETD generated various types of abundant cross-ring cleavage ions. These complementary cross-ring cleavages clarified the different linkage types and branching patterns of the representative milk sugar samples. The utilization of different MS3 techniques made it possible to verify initial assignments and to detect the presence of multiple components in isobaric peaks. Fragment ion structures and pathways could be proposed to facilitate the interpretation of carbohydrate ETD spectra, and the main mechanisms were investigated. ETD should contribute substantially to confident structural analysis of a wide variety of oligosaccharides.

  3. Direct observation of multistep energy transfer in LHCII with fifth-order 3D electronic spectroscopy

    Science.gov (United States)

    Zhang, Zhengyang; Lambrev, Petar H.; Wells, Kym L.; Garab, Gy?z?; Tan, Howe-Siang

    2015-07-01

    During photosynthesis, sunlight is efficiently captured by light-harvesting complexes, and the excitation energy is then funneled towards the reaction centre. These photosynthetic excitation energy transfer (EET) pathways are complex and proceed in a multistep fashion. Ultrafast two-dimensional electronic spectroscopy (2DES) is an important tool to study EET processes in photosynthetic complexes. However, the multistep EET processes can only be indirectly inferred by correlating different cross peaks from a series of 2DES spectra. Here we directly observe multistep EET processes in LHCII using ultrafast fifth-order three-dimensional electronic spectroscopy (3DES). We measure cross peaks in 3DES spectra of LHCII that directly indicate energy transfer from excitons in the chlorophyll b (Chl b) manifold to the low-energy level chlorophyll a (Chl a) via mid-level Chl a energy states. This new spectroscopic technique allows scientists to move a step towards mapping the complete complex EET processes in photosynthetic systems.

  4. Integral cross sections for electron impact excitation of electronic states of N2

    International Nuclear Information System (INIS)

    We report integral cross sections (ICSs) for electron impact excitation of the A 3?u+, B 3?g, W 3?u, B' 3?y-, a' 1?u-, a 1?g, ? 1?u, C 3?u, E 3?g+ and a'' 1?g+ electronic states of N2. The present data, for each state, were derived at five incident electron energies in the range 15-50 eV, from the earlier crossed-beam differential cross section (DCS) measurements of our group. This was facilitated by using a molecular phase shift analysis technique to extrapolate the measured DCSs to 0 deg. and 180 deg., before performing the integration. A comprehensive comparison of the present ICSs with the results of earlier experimental studies, both crossed beam and electron swarm, and theoretical calculations is provided. This comparison clearly indicates that some of the previous estimates for these excited electronic-state cross sections need to be reassessed. In addition, we have used the present ICSs in a Monte Carlo simulation for modelling the behaviour of an electron swarm in the bulk of a low current N2 discharge. The macroscopic transport parameters determined from this simulation are compared against those measured from independent swarm-based experiments and the self-consistency of our ICSs evaluated. (author)

  5. TD-DFT study on electron transfer mobility and intramolecular hydrogen bond of substituted indigo derivatives

    Science.gov (United States)

    Ma, Chi; Li, Hui; Yang, Yonggang; Li, Donglin; Liu, Yufang

    2015-10-01

    The density functional theory (DFT) and time-dependent density functional theory (TDDFT) method were carried out to investigate the ground and excited states of indigo and its derivative molecules. The results demonstrate that the intramolecular hydrogen bond I is weakened and the intramolecular hydrogen bond II is strengthened upon photo-excitation to the S1 state. In the absorption spectra, the substitution at R4R4, of indigo causes a significant redshift. In addition, the halogen substitution obviously increases the electron transfer mobility of indigo. It is proved that the halogen substitution may be a new method to design high performance organic semiconductors.

  6. Ab initio nonadiabatic molecular dynamics of the ultrafast excitation energy transfer in small semiconducting carbon nanotube aggregates

    Science.gov (United States)

    Postupna, Olena; Long, Run; Prezhdo, Oleg

    2012-02-01

    Outstanding physical properties of carbon nanotubes (CNTs), such as well-defined optical resonance and ultrafast nonlinear response, result in CNTs gaining popularity in academic and industrial endeavors as potential effective energy generating devices. Following recent experiments on ultrafast excitation energy transfer in small semiconducting carbon nanotube aggregates [1], we report results of ab initio nonadiabatic molecular dynamics simulation of the energy transfer taking place in two carbon nanotube systems. We investigate the energy transfer between (8,4) and (10,0) CNTs, as well as (8,4) and (13,0) CNTs. In both cases, the CNTs are orthogonal to each other. Luer et al. in [1] elucidate the second excitonic transitions followed by fast intratube relaxation and energy transfer from the (8,4) CNT toward other acceptor tubes. Our project aims to provide a better understanding of the energy transfer mechanism in the given systems, which should foster development of a theory for the electronic structure and dynamics of CNT networks, hence enhancing their tailoring and application in the future. References 1.Larry Luer, Jared Crochet, Tobias Hertel, Giulio Cerullo, Gugliermo Lanzani. ACSNano. Vol.4, No. 7, 4265-4273

  7. Resonant transfer excitation of fluorine-like Mo{sup 33+} ion

    Energy Technology Data Exchange (ETDEWEB)

    Ramadan, Hassan [Ain Shams Univ., Cairo (Egypt). Dept. of Basic Sciences; Elkilany, Sabbah [Kafr El-sheikh Univ. (Egypt). Dept. of Mathematics

    2010-06-15

    Dielectronic recombination (DR) cross sections (anti {sigma}{sup DR}) and rate coefficients ({alpha}{sup DR}) for Mo{sup 33+} are calculated using the angular momentum average scheme (AMA). Moreover, the resonant transfer excitation followed by X-ray emission (RTEX) cross sections ({sigma}{sup RTEX}) for the collision of Mo{sup 33+} with H{sub 2} and He targets are calculated and studied. The calculations of the cross sections are performed for both K- and L-shell excitations. A smooth change with the temperatures for {alpha}{sup DR} is found for all kinds of excitations. The rates for K-shell excitation are very small in comparison with the rates for L-shell excitation. The RTEX cross sections for Mo{sup 33+} ions are obtained from their corresponding DR cross sections by the method of folding in the impulse approximation (IMA). {sigma}{sup RTEX} for the K-shell excitation shows two overlapped peaks which may be attributed to the two groups in this excitation process. The present calculations are considered as a database for future comparison with theoretical and experimental data using other coupling schemes. Multiple Auger channels are complicating the dependence of the cross sections on principal quantum numbers. (orig.)

  8. Spin-Orbital Excitation Continuum and Anomalous Electron-Phonon Interaction in the Mott Insulator LaTiO_{3}.

    Science.gov (United States)

    Ulrich, C; Khaliullin, G; Guennou, M; Roth, H; Lorenz, T; Keimer, B

    2015-10-01

    Raman scattering experiments on stoichiometric, Mott-insulating LaTiO_{3} over a wide range of excitation energies reveal a broad electronic continuum which is featureless in the paramagnetic state, but develops a gap of ?800??cm^{-1} upon cooling below the Néel temperature T_{N}=146??K. In the antiferromagnetic state, the spectral weight below the gap is transferred to well-defined spectral features due to spin and orbital excitations. Low-energy phonons exhibit pronounced Fano anomalies indicative of strong interaction with the electron system for T>T_{N}, but become sharp and symmetric for Telectronic continuum and the marked renormalization of the phonon lifetime by the onset of magnetic order are highly unusual for Mott insulators and indicate liquidlike correlations between spins and orbitals. PMID:26550738

  9. Spin-Orbital Excitation Continuum and Anomalous Electron-Phonon Interaction in the Mott Insulator LaTiO3

    Science.gov (United States)

    Ulrich, C.; Khaliullin, G.; Guennou, M.; Roth, H.; Lorenz, T.; Keimer, B.

    2015-10-01

    Raman scattering experiments on stoichiometric, Mott-insulating LaTiO3 over a wide range of excitation energies reveal a broad electronic continuum which is featureless in the paramagnetic state, but develops a gap of ˜800 cm-1 upon cooling below the Néel temperature TN=146 K . In the antiferromagnetic state, the spectral weight below the gap is transferred to well-defined spectral features due to spin and orbital excitations. Low-energy phonons exhibit pronounced Fano anomalies indicative of strong interaction with the electron system for T >TN , but become sharp and symmetric for T electronic continuum and the marked renormalization of the phonon lifetime by the onset of magnetic order are highly unusual for Mott insulators and indicate liquidlike correlations between spins and orbitals.

  10. Charge transfer dynamics from adsorbates to surfaces with single active electron and configuration interaction based approaches

    International Nuclear Information System (INIS)

    Highlights: • We model electron dynamics across cyano alkanethiolates attached to gold cluster. • We present electron transfer time scales from TD-DFT and TD-CI based simulations. • Both DFT and CI methods qualitatively predict the trend in time scales. • TD-CI predicts the experimental relative time scale very accurately. - Abstract: We employ wavepacket simulations based on many-body time-dependent configuration interaction (TD-CI), and single active electron theories, to predict the ultrafast molecule/metal electron transfer time scales, in cyano alkanethiolates bonded to model gold clusters. The initial states represent two excited states where a valence electron is promoted to one of the two virtual ?? molecular orbitals localized on the cyanide fragment. The ratio of the two time scales indicate the efficiency of one charge transfer channel over the other. In both our one-and many-electron simulations, this ratio agree qualitatively with each other as well as with the previously reported experimental time scales (Blobner et al., 2012), measured for a macroscopic metal surface. We study the effect of cluster size and the description of electron correlation on the charge transfer process

  11. Excitation and ionization of highly charged ions by electron impact

    International Nuclear Information System (INIS)

    Two approaches for very rapid calculation of atomic data for high temperature plasma modeling have been developed. The first uses hydrogenic basis states and has been developed and applied in many papers discussed in previous progress reports. Hence, it is only briefly discussed here. The second is a very rapid, yet accurate, fully relativistic approach that has been developed over the past two or three years. It is described in more detail. Recently it has been applied to large scale production of atomic data. Specifically, it has been used to calculate relativistic distorted wave collision strengths and oscillator strengths for the following: all transitions from the ground level to the n=3 and 4 excited levels in the 71 Neon-like ions with nuclear charge number Z in the range 22 ? Z ? 92; all transitions among the 2s1/2, 2p1/2 and 2p3/2 levels and from them to all nlj levels with n=3,4 and 5 in the 85 Li-like ions with 8 ? Z ? 92; all transitions among the 3s1/2, 3p3/2, 3d3/2 and 3d5/2 levels and from them to all nlj levels with n=4 and 5 in the 71 Na-like ions with 22 ? Z ? 92; and all transitions among 4s1/2, 4p1/2, 4p3/2, 4d3/2, 4d5/2, 4f5/2 and 4f7/2 levels and from them to all nlj levels with n=5 in the 33 Cu-like ions with 60 ? Z ? 92. Also the program has been extended to give cross-sections for excitation to specific magnetic sublevels of the target ion by an electron beam and very recently it has been extended to give relativistic distorted wave cross sections for ionization of highly charged ions by electron impact

  12. Analytic approximations for integrated electron-atom excitations

    International Nuclear Information System (INIS)

    Accurate calculations of atomic excitations require estimates of the effect of higher excitations on the effective (optical) potential coupling various reaction channels. The total cross section for a particular excitation is proportional to the maximum contribution of that excitation to the imaginary part of the elastic momentum-space optical potential, and is typical of the contribution to the potential in general. Analytic expressions relevant to the calculation of optical potentials are given. Their validity is estimated by comparison with more-accurate calculations and with experimental excitation cross sections

  13. A model for energy transfer in collisions of atoms with highly excited molecules.

    Science.gov (United States)

    Houston, Paul L; Conte, Riccardo; Bowman, Joel M

    2015-05-21

    A model for energy transfer in the collision between an atom and a highly excited target molecule has been developed on the basis of classical mechanics and turning point analysis. The predictions of the model have been tested against the results of trajectory calculations for collisions of five different target molecules with argon or helium under a variety of temperatures, collision energies, and initial rotational levels. The model predicts selected moments of the joint probability distribution, P(Jf,?E) with an R(2) ? 0.90. The calculation is efficient, in most cases taking less than one CPU-hour. The model provides several insights into the energy transfer process. The joint probability distribution is strongly dependent on rotational energy transfer and conservation laws and less dependent on vibrational energy transfer. There are two mechanisms for rotational excitation, one due to motion normal to the intermolecular potential and one due to motion tangential to it and perpendicular to the line of centers. Energy transfer is found to depend strongly on the intermolecular potential and only weakly on the intramolecular potential. Highly efficient collisions are a natural consequence of the energy transfer and arise due to collisions at "sweet spots" in the space of impact parameter and molecular orientation. PMID:25907301

  14. Ultrafast excited-state charge-transfer dynamics in laccase type I copper site.

    Science.gov (United States)

    Delfino, Ines; Viola, Daniele; Cerullo, Giulio; Lepore, Maria

    2015-01-01

    Femtosecond pump-probe spectroscopy was used to investigate the excited state dynamics of the T1 copper site of laccase from Pleurotus ostreatus, by exciting its 600 nm charge transfer band with a 15-fs pulse and probing over a broad range in the visible region. The decay of the pump-induced ground-state bleaching occurs in a single step and is modulated by clearly visible oscillations. Global analysis of the two-dimensional differential transmission map shows that the excited state exponentially decays with a time constant of 375 fs, thus featuring a decay rate slower than those occurring in quite all the investigated T1 copper site proteins. The ultrashort pump pulse induces a vibrational coherence in the protein, which is mainly assigned to ground state activity, as expected in a system with fast excited state decay. Vibrational features are discussed also in comparison with the traditional resonance Raman spectrum of the enzyme. The results indicate that both excited state dynamics and vibrational modes associated with the T1 Cu laccase charge transfer have main characteristics similar to those of all the T1 copper site-containing proteins. On the other hand, the differences observed for laccase from P. ostreatus further confirm the peculiar hypothesized trigonal T1 Cu site geometry. PMID:25819432

  15. Photoinduced charge accumulation by metal ion-coupled electron transfer.

    Science.gov (United States)

    Bonn, Annabell G; Wenger, Oliver S

    2015-10-01

    An oligotriarylamine (OTA) unit, a Ru(bpy)3(2+) photosensitizer moiety (Ru), and an anthraquinone (AQ) entity were combined to a molecular dyad (Ru-OTA) and a molecular triad (AQ-Ru-OTA). Pulsed laser excitation at 532 nm led to the formation of charge-separated states of the type Ru(-)-OTA(+) and AQ(-)-Ru-OTA(+) with lifetimes of ?10 ns and 2.4 ?s, respectively, in de-aerated CH3CN at 25 °C. Upon addition of Sc(OTf)3, very long-lived photoproducts were observed. Under steady-state irradiation conditions using a flux of (6.74 ± 0.21) × 10(15) photons per second at 450 nm, the formation of twofold oxidized oligotriarylamine (OTA(2+)) was detected in aerated CH3CN containing 0.02 M Sc(3+), as demonstrated unambiguously by comparison with UV-Vis absorption spectra obtained in the course of chemical oxidation with Cu(2+). Photodriven charge accumulation on the OTA unit of Ru-OTA and AQ-Ru-OTA is possible due to the lowering of the O2 reduction potential caused by the interaction of superoxide with the strong Lewis acid Sc(3+). The presence of the anthraquinone unit in AQ-Ru-OTA accelerates the rate-determining reaction step for charge accumulation by a factor of 10 compared to the Ru-OTA dyad. This is attributed to the formation of Sc(3+)-stabilized anthraquinone radical anion intermediates in the triad. Possible mechanistic pathways leading to charge accumulation are discussed. Photodriven charge accumulation is of key importance for solar fuels because their production will have to rely on multi-electron chemistry rather than single-electron reaction steps. Our study is the first to demonstrate that metal ion-coupled electron transfer (MCET) can be exploited to accumulate charges on a given molecular unit using visible light as an energy input. The approach of using a combination of intra- and intermolecular electron transfer reactions which are enabled by MCET is conceptually novel, and the fundamental insights gained from our study are relevant in the greater context of solar energy conversion. PMID:26312416

  16. Differential cross sections for electron impact excitation of the electronic bands of phenol

    Science.gov (United States)

    Neves, R. F. C.; Jones, D. B.; Lopes, M. C. A.; Nixon, K. L.; da Silva, G. B.; Duque, H. V.; de Oliveira, E. M.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Lima, M. A. P.; Ratnavelu, K.; García, G.; Brunger, M. J.

    2015-03-01

    We report results from a joint theoretical and experimental investigation into electron scattering from the important organic species phenol (C6H5OH). Specifically, differential cross sections (DCSs) have been measured and calculated for the electron-impact excitation of the electronic states of C6H5OH. The measurements were carried out at energies in the range 15-40 eV, and for scattered-electron angles between 10? and 90?. The energy resolution of those experiments was typically ˜80 meV. Corresponding Schwinger multichannel method with pseudo-potentials calculations, with and without Born-closure, were also performed for a sub-set of the excited electronic-states that were accessed in the measurements. Those calculations were conducted at the static exchange plus polarisation (SEP)-level using a minimum orbital basis for single configuration interaction (MOBSCI) approach. Agreement between the measured and calculated DCSs was typically fair, although to obtain quantitative accord, the theory would need to incorporate even more channels into the MOBSCI.

  17. Differential cross sections for electron impact excitation of the electronic bands of phenol

    International Nuclear Information System (INIS)

    We report results from a joint theoretical and experimental investigation into electron scattering from the important organic species phenol (C6H5OH). Specifically, differential cross sections (DCSs) have been measured and calculated for the electron-impact excitation of the electronic states of C6H5OH. The measurements were carried out at energies in the range 15–40 eV, and for scattered-electron angles between 10? and 90?. The energy resolution of those experiments was typically ?80 meV. Corresponding Schwinger multichannel method with pseudo-potentials calculations, with and without Born-closure, were also performed for a sub-set of the excited electronic-states that were accessed in the measurements. Those calculations were conducted at the static exchange plus polarisation (SEP)-level using a minimum orbital basis for single configuration interaction (MOBSCI) approach. Agreement between the measured and calculated DCSs was typically fair, although to obtain quantitative accord, the theory would need to incorporate even more channels into the MOBSCI

  18. Optically forbidden excitations of 2s electron of neon studied by fast electron impact

    International Nuclear Information System (INIS)

    The electron energy loss spectrum in the energy region of 42-48.5 eV of neon is measured with an angle-resolved fast-electron energy-loss spectrometer at an incident electron energy of 2500 eV. Besides the dipole-allowed autoionization transitions of 2s-1 np (n = 3,4) and 2p-2 3s3p, the dipole-forbidden ones of 2s-1 ns (n = 3-6) and 2s-1 3d are observed. The line profile parameters, i.e. Er, ? and q for these transitions, are determined, and the momentum transfer dependence behaviour is discussed. (authors)

  19. Electron-phonon contribution to the phonon and excited electron (hole) linewidths in bulk Pd

    International Nuclear Information System (INIS)

    We present an ab initio study of the electron-phonon (e-ph) coupling and its contribution to the phonon linewidths and to the lifetime broadening of excited electron and hole states in bulk Pd. The calculations, based on density-functional theory, were carried out using a linear-response approach in the plane-wave pseudopotential representation. The obtained results for the Eliashberg spectral function ?2F(?), e-ph coupling constant ?, and the contribution to the lifetime broadening, ?e-ph, show strong dependence on both the energy and momentum of an electron (hole) state. The calculation of phonon linewidths gives, in agreement with experimental observations, an anomalously large broadening for the transverse phonon mode T1 in the ? direction. In addition, this mode is found to contribute most strongly to the electron-phonon scattering processes on the Fermi surface

  20. A Simple Marcus-Theory Type Model for Hydrogen Atom Transfer/Proton-Coupled Electron Transfer

    OpenAIRE

    MAYER, JAMES M.

    2011-01-01

    Hydrogen atom transfer reactions are the simplest class of proton-coupled electron transfer (PCET) processes. These reactions involve transfer of one electron and one proton from one reagent to another, in the same kinetic step: XH + Y ? X + HY. A predictive model for these reactions based on the Marcus cross relation is described. The model predicts rate constants within one or two orders of magnitude in most cases, over a very wide range of reactants and solvents. This remarkable result imp...

  1. Assessment of asymptotically corrected model potential scheme for charge-transfer-like excitations in oligoacenes

    CERN Document Server

    Peng, Wei-Tao

    2014-01-01

    We examine the performance of the asymptotically corrected model potential scheme on the two lowest singlet excitation energies of acenes with different number of linearly fused benzene rings (up to 5), employing both the real-time time-dependent density functional theory and the frequency-domain formulation of linear-response time-dependent density functional theory. The results are compared with the experimental data and those calculated by long-range corrected hybrid functionals and others. The long-range corrected hybrid scheme is shown to outperform the asymptotically corrected model potential scheme for charge-transfer-like excitations.

  2. Optimized excitation energy transfer in a three-dye luminescent solar concentrator

    Energy Technology Data Exchange (ETDEWEB)

    Bailey, Sheldon T.; Lokey, Gretchen E.; Hanes, Melinda S.; McLafferty, Jason B.; Beaumont, Gregg T.; Wittmershaus, Bruce P. [School of Science, Pennsylvania State University: Erie, The Behrend College, Erie, PA 16563-0203 (United States); Shearer, John D.M.; Baseler, Timothy T.; Layhue, Joshua M.; Broussard, Dustin R. [School of Engineering, Pennsylvania State University: Erie, The Behrend College, Erie, PA 16563-1701 (United States); Zhang, Yu-Zhong [Molecular Probes Inc., 4849 Pitchford Ave., Eugene, OR 97402-9165 (United States)

    2007-01-05

    The spectral range of sunlight absorbed by a luminescent solar concentrator (LSC) is increased by using multiple dyes. Absorption, fluorescence, and fluorescence excitation spectra, and relative light output are reported for LSCs made with one, two, or three BODIPY dyes in a thin polymer layer on glass. Losses caused by multiple emission and reabsorption events are minimized by optimizing resonance excitation energy transfer between dyes. Increases in the outputs from the multiple-dye LSCs are directly proportional to increases in the number of photons absorbed. The output of the three-dye LSC is 45-170% higher than those of the single-dye LSCs. (author)

  3. Electromagnetic field excitation by an electron bunches in a partially filled cylindrical dielectric resonator

    International Nuclear Information System (INIS)

    A nonlinear self-consistent theory of wakefield excitation by an electron bunches in cylindrical resonator with longitudinally nonuniform filling by dielectric is constructed. A bunch-excited field are presented in the form of superposition solenoidal and potential fields. The formulated nonlinear theory allows carrying out numerical analysis of resonator excitation by electron bunches for the best interpretation of the results received in experiment

  4. Probing and Exploiting the Interplay between Nuclear and Electronic Motion in Charge Transfer Processes.

    Science.gov (United States)

    Delor, Milan; Sazanovich, Igor V; Towrie, Michael; Weinstein, Julia A

    2015-04-21

    The Born-Oppenheimer approximation refers to the assumption that the nuclear and electronic wave functions describing a molecular system evolve and can be determined independently. It is now well-known that this approximation often breaks down and that nuclear-electronic (vibronic) coupling contributes greatly to the ultrafast photophysics and photochemistry observed in many systems ranging from simple molecules to biological organisms. In order to probe vibronic coupling in a time-dependent manner, one must use spectroscopic tools capable of correlating the motions of electrons and nuclei on an ultrafast time scale. Recent developments in nonlinear multidimensional electronic and vibrational spectroscopies allow monitoring both electronic and structural factors with unprecedented time and spatial resolution. In this Account, we present recent studies from our group that make use of different variants of frequency-domain transient two-dimensional infrared (T-2DIR) spectroscopy, a pulse sequence combining electronic and vibrational excitations in the form of a UV-visible pump, a narrowband (12 cm(-1)) IR pump, and a broadband (400 cm(-1)) IR probe. In the first example, T-2DIR is used to directly compare vibrational dynamics in the ground and relaxed electronic excited states of Re(Cl)(CO)3(4,4'-diethylester-2,2'-bipyridine) and Ru(4,4'-diethylester-2,2'-bipyridine)2(NCS)2, prototypical charge transfer complexes used in photocatalytic CO2 reduction and electron injection in dye-sensitized solar cells. The experiments show that intramolecular vibrational redistribution (IVR) and vibrational energy transfer (VET) are up to an order of magnitude faster in the triplet charge transfer excited state than in the ground state. These results show the influence of electronic arrangement on vibrational coupling patterns, with direct implications for vibronic coupling mechanisms in charge transfer excited states. In the second example, we show unambiguously that electronic and vibrational movement are coupled in a donor-bridge-acceptor complex based on a Pt(II) trans-acetylide design motif. Time-resolved IR (TRIR) spectroscopy reveals that the rate of electron transfer (ET) is highly dependent on the amount of excess energy localized on the bridge following electronic excitation. Using an adaptation of T-2DIR, we are able to selectively perturb bridge-localized vibrational modes during charge separation, resulting in the donor-acceptor charge separation pathway being completely switched off, with all excess energy redirected toward the formation of a long-lived intraligand triplet state. A series of control experiments reveal that this effect is mode specific: it is only when the high-frequency bridging C?C stretching mode is pumped that radical changes in photoproduct yields are observed. These experiments therefore suggest that one may perturb electronic movement by stimulating structural motion along the reaction coordinate using IR light. These studies add to a growing body of evidence suggesting that controlling the pathways and efficiency of charge transfer may be achieved through synthetic and perturbative approaches aiming to modulate vibronic coupling. Achieving such control would represent a breakthrough for charge transfer-based applications such as solar energy conversion and molecular electronics. PMID:25789559

  5. A molecular shift register based on electron transfer.

    Science.gov (United States)

    Hopfield, J J; Onuchic, J N; Beratan, D N

    1988-08-12

    An electronic shift-register memory at the molecular level is described. The memory elements are based on a chain of electron-transfer molecules and the information is shifted by photoinduced electron-transfer reactions. This device integrates designed electronic molecules onto a very large scale integrated (silicon microelectronic) substrate, providing an example of a "molecular electronic device" that could actually be made. The design requirements for such a device and possible synthetic strategies are discussed. Devices along these lines should have lower energy usage and enhanced storage density. PMID:17829175

  6. Solar energy conversion dynamics of interfacial electron and excitation transfer

    CERN Document Server

    Piotrowiak, Piotr

    2013-01-01

    The importance of developing new, clean and renewable sources of energy will continue to grow in the foreseeable future and so will the need for the education of researchers in this field of research. The interest and challenges of the field continue to shift from simple homogeneous solutions to increasingly more complex heterogeneous systems and interfaces. Over the past decade there have been numerous theoretical and experimental breakthroughs many of which still exist only in the primary literature. The aim of this book is to gather in one volume the description of modern, sometimes explora

  7. Differential and integrated cross sections for the electron excitation of the 4 1Po state of calcium atom

    International Nuclear Information System (INIS)

    Differential cross section (DCS) data for excitation of the 4 1Po state (2.93 eV) of Ca atoms by electrons have been obtained using a crossed electron-atom beam technique. The measurements were divided into two groups. The first one consists of measurements at 10, 20, 40, 60 and 100 eV impact electron energies from 10 to 100 scattering angle interval. The second group of measurements are those at larger scattering angles (100-1500) at the same energies except 100 eV. Absolute values have been obtained by normalizing generalized oscillator strengths (GOS) to optical oscillator strength (OOS) in the minimum momentum transfer squared (K2) limit. Integral, momentum transfer and viscosity cross sections have been determined from DCSs. A comparison is made with existing relativistic distorted wave calculation

  8. Modulating the electronic structure of chromophores by chemical substituents for efficient energy transfer: application to fluorone.

    Science.gov (United States)

    Sand, Andrew M; Liu, Claire; Valentine, Andrew J S; Mazziotti, David A

    2014-08-01

    Strong electron correlation within a quasi-spin model of chromophores was recently shown to enhance exciton energy transfer significantly. Here we investigate how the modulation of the electronic structure of the chromophores by chemical substitution can enhance energy-transfer efficiency. Unlike previous work that does not consider the direct effect of the electronic structure on exciton dynamics, we add chemical substituents to the fluorone dimer to study the effect of electron-donating and electron-withdrawing substituents on exciton energy transfer. The exciton dynamics are studied from the solution of a quantum Liouville equation for an open system whose model Hamiltonian is derived from excited-state electronic structure calculations. Both van der Waals energies and coupling energies, arising from the Hellmann-Feynman force generated upon transferring the dimers from infinity to a finite separation, are built into the model Hamiltonian. Though these two effects are implicitly treated in dipole-based models, their explicit and separate treatment as discussed here is critical to forging the correct connection with the electronic structure calculations. We find that the addition of electron-donating substituents to the fluorone system results in an increase in exciton-transfer rates by factors ranging from 1.3-1.9. The computed oscillator strength is consistent with the recent experimental results on a larger heterodimer system containing fluorone. The oscillator strength increases with the addition of electron-donating substituents. Our results indicate that the study of chromophore networks via electronic structure will help in the future design of efficient synthetic light-harvesting systems. PMID:25062094

  9. Theoretical study of Raman chirped adiabatic passage by X-ray absorption spectroscopy: Highly excited electronic states and rotational effects

    International Nuclear Information System (INIS)

    Raman Chirped Adiabatic Passage (RCAP) is an efficient method to climb the vibrational ladder of molecules. It was shown on the example of fixed-in-space HCl molecule that selective vibrational excitation can thus be achieved by RCAP and that population transfer can be followed by X-ray Photoelectron spectroscopy [S. Engin, N. Sisourat, P. Selles, R. Taïeb, and S. Carniato, Chem. Phys. Lett. 535, 192–195 (2012)]. Here, in a more detailed analysis of the process, we investigate the effects of highly excited electronic states and of molecular rotation on the efficiency of RCAP. Furthermore, we propose an alternative spectroscopic way to monitor the transfer by means of X-ray absorption spectra

  10. Effect of the chirality of residues and ?-turns on the electronic excitation spectra, excited-state reaction paths and conical intersections of capped phenylalanine-alanine dipeptides.

    Science.gov (United States)

    Shemesh, Dorit; Domcke, Wolfgang

    2011-07-11

    The capped dipeptides Ac-L-Phe-Xxx-NH(2) , Xxx=L-Ala, D-Ala, Aib, where Aib (aminoisobutyric acid) is a non-chiral amino acid, have been investigated by means of UV/IR double-resonance spectroscopy in supersonic jets and density functional theory calculations by Gloaguen et al. [Phys. Chem. Chem. Phys. 2007, 9, 4491]. The UV and IR spectra of five different species were observed and their structures assigned by comparison with calculated vibrational frequencies in the NH-stretching region. The peptides with two chiral residues can form homochiral or heterochiral species. In addition, ?-turns exist as two helical forms (?(D), ?(L)) of opposite handedness. Herein, we explore the excited-state potential-energy surfaces of these dipeptides with ab initio calculations. Vertical and adiabatic excitation energies, excited-state reaction paths and conical intersections are characterized with the ADC(2) propagator method. It is shown that electron/proton transfer along the hydrogen bond of the ?-turn gives rise to efficient radiationless deactivation of the (1)??* state of the chromophore via several conical intersections. While the homo/hetero chirality of the residues appears to have a negligible effect on the photophysical dynamics, we found evidence that the ?(L) conformers may have shorter excited-state lifetimes (and thus higher photostability) than the ?(D) conformers. PMID:21488142

  11. Electronic Excitation Processes in Single-Strand and Double-Strand DNA: A Computational Approach.

    Czech Academy of Sciences Publication Activity Database

    Plasser, F.; Aquino, A. J. A.; Lischka, H.; Nachtigallová, Dana

    Cham : Springer, 2015 - (Barbatti, M.; Borin, A.; Ullrich, S.), s. 1-37 ISBN 978-3-319-13271-6. - (Topics in Current Chemistry . 356) Institutional support: RVO:61388963 Keywords : ab initio calculations * charge transfer excited states * excitonic states * interaction of excited state nucleic acid bases * photodynamics * UV absorption spectra Subject RIV: CF - Physical ; Theoretical Chemistry

  12. Electron transfer in SmHfCo alloys

    International Nuclear Information System (INIS)

    The rare-earth electron-transfer concept in the rare-earth--transition-metal compounds was evaluated for the binary compounds Sm2Co17 and Sm1Co5 from published data. The cobalt moment was found to be consistent with a two-transferred-electron rigid-band model. These results were verified by saturation magnetization measurements on the mixed-valence pseudobinary Sm/sub 2(1-x)/Hf/sub 2x/Co17 alloys where the moment per cobalt atom was consistent with a tetravalent-hafnium divalent-samarium electron-transfer mechanism

  13. Prototropic studies in vitreous and in solid phases: Pyranine and 2-naphthol excited state proton transfer

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Fátima Aparecida das Chagas [Departamento de Química Fundamental, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Rezende, Eduardo Triboni [Universidade Nove de Julho, São Paulo, SP (Brazil); Filho, Décio Briotto [Departamento de Bioquímica Instituto de Química, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Brito Rezende, Daisy de [Departamento de Química Fundamental, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Cuccovia, Iolanda Midea [Departamento de Bioquímica Instituto de Química, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Gome, Ligia Ferreira [Departamento de Análises Clínicas, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Silva, Mauro Francisco Pinheiro da [Departamento de Química Fundamental, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); and others

    2014-02-15

    Excited state proton transfer processes in vitreous glasses and in solid mixtures are investigated by steady state fluorimetry and laser flash photolysis kinetic studies with the photoacids pyranine and 2-naphthol. Glasses were derived from TEOS by the sol–gel condensation process and hydrated solid mixtures from NaCl or KH{sub 2}PO{sub 4}/K{sub 2}HPO{sub 4} crystals. The extent of the water content necessary for the reaction is determined. Shrinkage of TEOS derived monoliths from water loss leads to an increase in proton transfer extent due to the increase in local concentrations of accepting and donor buffer species, but the concomitant increase in the ionic strength actuates in an opposite direction. Furthermore, water losses by aging of air-exposed gel goes to a critical 20% weight fraction, beyond it proton transfer reactions are hindered. Similar studies with solid NaCl or solid phosphate buffer mixtures demonstrated the same critical water level indicating that free water molecules are crucial for the proton to escape from the original cage where the geminate ion pair [–||RO{sup ??}H{sup +}||–] is formed and can undergo coupled proton transfer reactions. -- Highlights: • Pyranine and 2-naphthol excited state proton transfer in SiO{sub 2} gel, solid phosphate buffer and NaCl. • Sol–gel formation leads to contraction and concentration of donor and accepting species. • 20% weight fraction water is required for the ESPT to go forward.

  14. Excited-state proton transfer from pyranine to acetate in methanol

    Indian Academy of Sciences (India)

    Sudip Kumar Mondal; Subhadip Ghosh; Kalyanasis Sahu; Pratik Sen; Kankan Bhattacharyya

    2007-03-01

    Excited-state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulphonate, HPTS) to acetate in methanol has been studied by steady-state and time-resolved fluorescence spectroscopy. The rate constant of direct proton transfer from pyranine to acetate ($k_1$) is calculated to be $\\sim 1 \\times 10^9$ M-1 s-1. This is slower by about two orders of magnitude than that in bulk water ($8 \\times 10^{10}$ M-1 s-1) at 4 M acetate.

  15. Environment-assisted Quantum Critical Effect for Excitation Energy Transfer in a LH2-type Trimer

    Science.gov (United States)

    Xu, Lan; Xu, Bo

    2015-10-01

    In this article, we are investigating excitation energy transfer (EET) in a basic unit cell of light-harvesting complex II (LH2), named a LH2-type trimer. Calculation of energy transfer efficiency (ETE) in the framework of non-Markovian environment is also implemented. With these achievements, we theoretically predict the environment-assisted quantum critical effect, where ETE exhibits a sudden change at the critical point of quantum phase transition (QPT) for the LH2-type trimer. It is found that highly efficient EET with nearly unit efficiency may occur in the vicinity of the critical point of QPT.

  16. 76 FR 35219 - Federal Acquisition Regulation; Information Collection; Payment by Electronic Fund Transfer

    Science.gov (United States)

    2011-06-16

    ...Regulation; Information Collection; Payment by Electronic Fund Transfer...previously approved information collection...payment by electronic fund transfer...contract by electronic fund transfer (EFT). The information necessary...

  17. 48 CFR 52.232-38 - Submission of Electronic Funds Transfer Information with Offer.

    Science.gov (United States)

    2010-10-01

    ...false Submission of Electronic Funds Transfer Information with Offer. 52...232-38 Submission of Electronic Funds Transfer Information with Offer. As... Submission of Electronic Funds Transfer Information With Offer...

  18. Detailed theoretical investigation of excited-state intramolecular proton transfer mechanism of a new chromophore II.

    Science.gov (United States)

    Cui, Yanling; Li, Yafei; Dai, Yumei; Verpoort, Francis; Song, Peng; Xia, Lixin

    2016-02-01

    In the present work, TDDFT has been used to investigate the excited state intramolecular proton transfer (ESIPT) mechanism of a new chromophore II [Sensors and Actuators B: Chemical. 202 (2014) 1190]. The calculated absorption and fluorescence spectra agree well with experimental results. In addition, two types of II configurations are found in the first excited state (S1), which can be ascribed to the ESIPT reaction. Based on analysis of the calculated infrared (IR) spectra of O-H stretching vibration as well as the hydrogen bonding energies, the strengthening of the hydrogen bond in the S1 state has been confirmed. The frontier molecular orbitals (MOs), Hirshfeld charge distribution and the Natural bond orbital (NBO) have also been analyzed, which displays the tendency of the ESIPT process. Finally, potential energy curves of the S0 and S1 states were constructed, demonstrating that the ESIPT reaction can be facilitated based on the photo-excitation. PMID:26523683

  19. Photodynamics of excitation energy transfer in self-assembled dyads. Evidence for back transfer.

    Science.gov (United States)

    Leray, Isabelle; Valeur, Bernard; Paul, Dharam; Regnier, Emilie; Koepf, Matthieu; Wytko, Jennifer A; Boudon, Corinne; Weiss, Jean

    2005-03-01

    Three self-assembled photonic dyads comprising a zinc porphyrin donor and a free base acceptor have been studied by time-resolved fluorescence spectroscopy. The driving force of the assembly is the site selective binding of an imidazole connected to a free base porphyrin. Three spacers have been incorporated between the imidazole connector and the free base porphyrin, providing three different distances separating the donor and the acceptor. The high efficiencies and the rates of energy transfer in the set of dyads is consistent with the Forster energy transfer mechanism. Evidence for Forster back transfer has been obtained, and its efficiency and rate have been quantitatively evaluated for the first time. PMID:15738996

  20. Excited-State Proton Transfer in Chiral Environments: Photoracemization of BINOLs1

    OpenAIRE

    Solntsev, Kyril M.; Bartolo, Elizabeth-Ann; Pan, George; MULLER, GILLES; BOMMIREDDY, SHRUTHI; Huppert, Dan; Tolbert, Laren M.

    2009-01-01

    We have studied excited-state proton transfer (ESPT) from chiral proton donors to chiral and achiral acceptors. The key role of the exergonicity of the reaction and the transition-state position along the reaction coordinate for the existence of an enantiomeric effect was established. This effect was observed for “super” photoacids (?G ? 0) and vanished for endergonic reactions (?G > 0) where a “late” transition state similar to planar achiral binaphtholate anion occurs. As a result, photorac...

  1. Substituent and Solvent Effects on Excited State Charge Transfer Behavior of Highly Fluorescent Dyes Containing Thiophenylimidazole-Based Aldehydes

    Science.gov (United States)

    Santos, Javier; Bu, Xiu R.; Mintz, Eric A.

    2001-01-01

    The excited state charge transfer for a series of highly fluorescent dyes containing thiophenylimidazole moiety was investigated. These systems follow the Twisted Intramolecular Charge Transfer (TICT) model. Dual fluorescence was observed for each substituted dye. X-ray structures analysis reveals a twisted ground state geometry for the donor substituted aryl on the 4 and 5 position at the imidazole ring. The excited state charge transfer was modeled by a linear solvation energy relationship using Taft's pi and Dimroth's E(sub T)(30) as solvent parameters. There is linear relation between the energy of the fluorescence transition and solvent polarity. The degree of stabilization of the excited state charge transfer was found to be consistent with the intramolecular molecular charge transfer. Excited dipole moment was studied by utilizing the solvatochromic shift method.

  2. Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

    Energy Technology Data Exchange (ETDEWEB)

    Van Tassle, Aaron Justin

    2006-09-01

    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.

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

    International Nuclear Information System (INIS)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Blom, Alex Jason

    2009-08-01

    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.

  5. Electron emission from fast heavy ions associated with resonant coherent excitation

    Energy Technology Data Exchange (ETDEWEB)

    Suda, S; Metoki, K; Azuma, T [Department of Physics, Tokyo Metropolitan University (Japan); Nakano, Y [AMO Physics Laboratory, RIKEN (Japan); Takano, Y [Graduate School of Arts and Sciences, University of Tokyo (Japan); Hatakeyama, A [Department of Applied Physics, Tokyo University of Agriculture and Technology (Japan); Nakai, Y [RI Physics Laboratory, RIKEN Nishina Center (Japan); Komaki, K [Atomic Physics Laboratory, RIKEN (Japan); Takada, E; Murakami, T, E-mail: suda-shintaro@ed.tmu.ac.jp [National Institute of Radiological Sciences (Japan)

    2011-06-15

    We observed convoy electrons emitted from 416 MeV/u He-like Ar{sup 16+} passing through a thin Si crystal under the condition of three-dimensional resonant coherent excitation (3D-RCE). The convoy electrons, which originate from electrons released from ions into the continuum by collisions with target atoms, emerged in the forward direction and formed a cusp-shaped peak in the energy distribution. We selectively controlled the population of the ground and excited states of ions traveling through the crystal by using 3D-RCE, where the 1s electron was excited to the 2p state by a periodic crystal field. Under the resonance condition, we found an enhancement of the convoy electrons with a narrowing in the energy distribution, which reflects the electron momentum distribution of the initial bound state of the excited ions.

  6. Production of excited electrons at TESLA and CLIC based egamma colliders

    CERN Document Server

    Kirca, Z; Cakir, O

    2003-01-01

    We analyze the potential of TESLA and CLIC based electron-photon colliders to search for excited spin-1/2 electrons. The production of excited electrons in the resonance channel through the electron- photon collision and their subsequent decays to leptons and electroweak gauge bosons are investigated. We study in detail the three signal channels of excited electrons and the corresponding backgrounds through the reactions egamma yields egamma, egamma yields eZ and egamma yields vW. Excited electrons with masses up to about 90% of the available collider energy can be probed down to the coupling f = f prime = 0.05(0.1) at TESLA(CLIC) based egamma colliders. 22 Refs.

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

    International Nuclear Information System (INIS)

    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(2p43s2)1D and He(2p2)1D, were completely determined and possible excitation mechanisms are described. (Auth.)

  8. Excitation and charge transfer in hydrogen-proton collisions at 5--80 keV and application to astrophysical shocks

    CERN Document Server

    Tseliakhovich, Dmitriy; Heng, Kevin

    2012-01-01

    In astrophysical regimes where the collisional excitation of hydrogen atoms is relevant, the cross sections for the interactions of hydrogen atoms with electrons and protons are necessary for calculating line profiles and intensities. In particular, at relative velocities exceeding ~1000 km/s, collisional excitation by protons dominates over that by electrons. Surprisingly, the hydrogen-proton cross sections at these velocities do not exist for atomic levels of n >= 4, forcing researchers to utilize extrapolation via inaccurate scaling laws. In this study, we present a faster and improved algorithm for computing cross sections for the hydrogen-proton collisional system, including excitation and charge transfer to the n >= 2 levels of the hydrogen atom. We develop a code named BDSCx which directly solves the Schrodinger equation with variable (but non-adaptive) resolution and utilizes a hybrid spatial-Fourier grid. Our novel hybrid grid reduces the number of grid points needed from ~4000 n^6 (for a "brute forc...

  9. Excited-state charge coupled proton transfer reaction in dipole-functionalized salicylideneaniline

    International Nuclear Information System (INIS)

    Based on design and synthesis of salicylideneaniline derivatives 1–4, we demonstrate an exceedingly useful system to investigate the excited-state intramolecular charge transfer (ESICT) coupled with excited-state intramolecular proton transfer (ESIPT) reaction via the dipolar functionality of Schiff base salicylideneaniline. In solid and aprotic solvents 1–4 exist mainly as E conformers that possess a strong intramolecular six-membered-ring hydrogen bond. Compounds 2–4 exhibit solely a long-wavelength proton-transfer tautomer emission, while dipole-functionalized Schiff base 1 exhibits remarkable dual emission due to the different solvent-polarity environments between ESICT and ESIPT states. Moreover, the geometric structures, frontier molecular orbitals (MOs) and the potential energy curves for 1–4 in the ground and the first singlet excited state were fully rationalized by density functional theory (DFT) and time-dependent DFT calculations. - Highlights: • A dipole-functionalized salicylideneaniline derivative was synthesized. • The Schiff base exhibits remarkable dual emission. • A novel ESICT/ESIPT coupled system was created

  10. Excited-state charge coupled proton transfer reaction in dipole-functionalized salicylideneaniline

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Kew-Yu, E-mail: kyuchen@fcu.edu.tw; Hu, Jiun-Wei

    2015-03-15

    Based on design and synthesis of salicylideneaniline derivatives 1–4, we demonstrate an exceedingly useful system to investigate the excited-state intramolecular charge transfer (ESICT) coupled with excited-state intramolecular proton transfer (ESIPT) reaction via the dipolar functionality of Schiff base salicylideneaniline. In solid and aprotic solvents 1–4 exist mainly as E conformers that possess a strong intramolecular six-membered-ring hydrogen bond. Compounds 2–4 exhibit solely a long-wavelength proton-transfer tautomer emission, while dipole-functionalized Schiff base 1 exhibits remarkable dual emission due to the different solvent-polarity environments between ESICT and ESIPT states. Moreover, the geometric structures, frontier molecular orbitals (MOs) and the potential energy curves for 1–4 in the ground and the first singlet excited state were fully rationalized by density functional theory (DFT) and time-dependent DFT calculations. - Highlights: • A dipole-functionalized salicylideneaniline derivative was synthesized. • The Schiff base exhibits remarkable dual emission. • A novel ESICT/ESIPT coupled system was created.

  11. 76 FR 709 - Electronic Funds Transfer of Depository Taxes; Correction

    Science.gov (United States)

    2011-01-06

    ...Funds Transfer of Depository Taxes; Correction AGENCY: Internal...guidance relating to Federal tax deposits (FTDs) by Electronic...202) 622-4910 (not a toll-free number). SUPPLEMENTARY...Subjects 26 CFR Part 40 Excise taxes, Reporting and...

  12. Combining UV photodissociation with electron transfer for peptide structure analysis.

    Czech Academy of Sciences Publication Activity Database

    Shaffer, C. J.; Marek, Aleš; Pepin, R.; Slováková, K.; Ture?ek, F.

    2015-01-01

    Ro?. 50, ?. 3 (2015), s. 470-475. ISSN 1076-5174 Institutional support: RVO:61388963 Keywords : electron transfer dissociation * laser photodissociation * peptide ions * cation radical * chromophores * isomer distinction Subject RIV: CE - Biochemistry Impact factor: 2.379, year: 2014

  13. Electron-Transfer Acceleration Investigated by Time Resolved Infrared Spectroscopy.

    Czech Academy of Sciences Publication Activity Database

    Vl?ek Jr., Antonín; Kvapilová, Hana; Towrie, M.; Záliš, Stanislav

    2015-01-01

    Ro?. 48, ?. 3 (2015), s. 868-876. ISSN 0001-4842 Institutional support: RVO:61388955 Keywords : electron transfer * infrared spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 22.323, year: 2014

  14. Dynamics of double auger excitation of Er3+ f-electron in semiconductor heterostructures

    International Nuclear Information System (INIS)

    In this paper, we present a process by which inverse distribution of Er3+ f-electrons can be created in semiconductors which quantum wells. It is shown that if the electrons are localized in quantum wells, the coulomb excitation of Er3+ f-electrons by electrons of the semiconductor has resonant nature. The double coulomb excitation of f-electrons, I15/2 ? I11/21 and I15/2 ? I13/2 produce electron population inversion for the I13/2 level. (author)

  15. Subphthalocyanines: tuneable molecular scaffolds for intramolecular electron and energy transfer processes.

    Science.gov (United States)

    González-Rodríguez, David; Torres, Tomás; Guldi, Dirk M; Rivera, José; Herranz, Maria Angeles; Echegoyen, Luis

    2004-05-26

    A series of four subphthalocyanine-C(60) fullerene dyads have been prepared through axial functionalization of the macrocycle with m-hydroxybenzaldehyde and a subsequent dipolar cycloaddition reaction. The subphthalocyanine moiety has been peripherally functionalized with substituents of different electronic character, namely fluorine or iodine atoms and ether or amino groups, thus reaching a control over its electron-donating properties. This is evidenced in cyclic voltammetry experiments by a progressive shift to lower potentials, by ca. 200 mV, of the first oxidation event of the SubPc unit in the dyads. As a consequence, the energy level of the SubPc(*)(+)-C(60)(*)(-) charge-transfer state may be tuned so as to compete with energy transfer deactivation pathways upon selective excitation of the SubPc component. For instance, excitation of those systems where the level of the radical pair lies high in energy triggers a sequence of exergonic photophysical events that comprise (i) nearly quantitative singlet-singlet energy transfer to the C(60) moiety, (ii) fullerene intersystem crossing, and (iii) triplet-triplet energy transfer back to the SubPc. On the contrary, the stabilization of the SubPc(*)(+)-C(60)(*)(-) radical pair state by increasing the polarity of the medium or by lowering the donor-acceptor redox gap causes charge transfer to dominate. In the case of 1c in benzonitrile, the thus formed radical pair has a lifetime of 0.65 ns and decays via the energetically lower lying triplet excited state. Further stabilization is achieved for dyad 1d, whose charge-transfer state would lie now below both triplets. The radical pair lifetime consequently increases in more than 2 orders of magnitude with respect to 1c and presents a significant stabilization in less polar solvents, revealing a low reorganization energy for this kind of SubPc-C(60) systems. PMID:15149228

  16. Electron impact excitation of the gamma bands of nitric oxide

    International Nuclear Information System (INIS)

    The excitation of several pronounced ? bands of NO by electron impact was studied from threshold to 1000 eV. A high optical efficiency was achieved by using an ellipsoidal collision chamber with mirrored interior surfaces. The interaction volume viewed was located at one of the foci of the ellipsoid. A 0.25 m double monochromator and single photon counting techniques were employed to monitor molecular band intensities. The optical sensitivity between 2000 and 4000 A was obtained with the molecular branching ratio method by monitoring 1NG CO+, 1NG N+2, 2PG N2 band intensities and suitable progressions in the ? system of NO. Second order effects were avoided by low NO densities (approx.10-1 torr) in the collision chamber. No ionization gauges were used during measurement, thus eliminating the possible dissociation of NO and subsequent formation of N2. Absolute cross sections for ? bands were obtained by normalizing to the 2PG (0,0) band of N2. For this purpose, a known mixture of NO and N2 was prepared in a gas handling manifold using a manometer. For the unambiguously identifiable (0,1), (0,2), (1,0), (1,5), and (2,7) ? bands of NO, the cross sections peaked near 18 eV and had values of 2.2, 1.8, 6.3, 1.3, and 0.57times10-19 cm2, respectively, with a possible error of 25%. The relative peak cross sections agree with calculated band intensities within 20%

  17. Theoretical aspects of electron transfer reactions of complex molecules

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    2001-01-01

    Features of electron transfer involving complex molecules are discussed. This notion presently refers to molecular reactants where charge transfer is accompanied by large molecular reorganization, and commonly used displaced harmonic oscillator models do not apply. It is shown that comprehensive theory of charge transfer in polar media offers convenient tools for the treatment of experimental data for such systems, with due account of large-amplitude strongly anharmonic intramolecular reorganiza...

  18. Frontier orbital symmetry control of intermolecular electron transfer. Final report, September 15, 1988--December 31, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Stevens, B.

    1997-07-01

    This report discusses the following topics: the recovery of intermolecular transfer parameters from fluorescence quenching in liquids; photoinduced intramolecular electron transfer in flexible donor/space/acceptor systems containing an extended unsaturated spacer; electron transfer sensitized reaction; the recovery of solute and fractal dimensions from electron transfer quenching data; and frontier orbital symmetry control of back electron transfer.

  19. Electron-impact core excitation of SF6. II. Generalized oscillator strengths in the S 2p region

    International Nuclear Information System (INIS)

    The generalized oscillator strengths (GOSs) for discrete and continuum S 2p excitations of SF6 have been derived in the momentum transfer range (K2) of 1--20 a.u.-2 from the angular variation of the relative differential cross section for inelastic electron scattering. The experimental techniques and data processing procedures used to obtain reliable, absolute GOS values are documented. The GOS results are compared to recent literature results [J. F. Ying, C. P. Mathers, and K. T. Leung, Phys. Rev. A 47, R5 (1993)]. Some discrepancies are noted. These are found to arise largely, but not completely, from differences in the data analysis procedures used. The Bethe surface for SF6 in the region of S 2p excitation is derived and the important role of Compton scattering by valence electrons is illustrated

  20. Theory of interrelated electron and proton transfer processes

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2003-01-01

    A simple theory of elementary act of interrelated reactions of electron and proton transfer is developed. Mechanisms of synchronous and multistage transfer and coherent transitions via a dynamically populated intermediate state are discussed. Formulas for rate constants of adiabatic and nonadiabatic reactions are derived.

  1. Transcriptomic and genetic analysis of direct interspecies electron transfer

    DEFF Research Database (Denmark)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena; Summers, Zarath M; Shrestha, Minita; Liu, Fanghua; Lovley, Derek R

    2013-01-01

    The possibility that metatranscriptomic analysis could distinguish between direct interspecies electron transfer (DIET) and H2 interspecies transfer (HIT) in anaerobic communities was investigated by comparing gene transcript abundance in cocultures in which Geobacter sulfurreducens was the electron-accepting partner for either Geobacter metallireducens, which performs DIET, or Pelobacter carbinolicus, which relies on HIT. Transcript abundance for G. sulfurreducens uptake hydrogenase genes was 7...

  2. Observation of a collective excitation in the ejected-electron spectra of Yb and Ba

    International Nuclear Information System (INIS)

    Ejected-electron spectra of Yb and Ba are presented. In both spectra, structure was seen which is attributable to autoionization to ground and excited states of M+ (M=Ba or Yb), and to Auger decay of highly excited M*+ states to the ground state of M2+. In Yb, Auger decay was also observed to populate excited states of M2+. Both spectra are strongly affected by a collective resonance in the excitation of a 5p electron. For energies above the 5p ionization threshold, two-step autoionization to M2+ was found to be dominant

  3. Scanning electron microscopy of Rydberg-excited Bose-Einstein condensates

    International Nuclear Information System (INIS)

    We report on the realization of high resolution electron microscopy of Rydberg-excited ultracold atomic samples. The implementation of an ultraviolet laser system allows us to excite the atom, with a single-photon transition, to Rydberg states. By using the electron microscopy technique during the Rydberg excitation of the atoms, we observe a giant enhancement in the production of ions. This is due to l-changing collisions, which broaden the Rydberg level and therefore increase the excitation rate of Rydberg atoms. Our results pave the way for the high resolution spatial detection of Rydberg atoms in an atomic sample. (paper)

  4. Electron-beam-sustained discharge revisited - light emission from combined electron beam and microwave excited argon at atmospheric pressure

    CERN Document Server

    Dandl, T; Neumeier, A; Wieser, J; Ulrich, A

    2015-01-01

    A novel kind of electron beam sustained discharge is presented in which a 12keV electron beam is combined with a 2.45GHz microwave power to excite argon gas at atmospheric pressure in a continuous mode of operation. Optical emission spectroscopy is performed over a wide wavelength range from the vacuum ultraviolet (VUV) to the near infrared (NIR). Several effects which modify the emission spectra compared to sole electron beam excitation are observed and interpreted by the changing plasma parameters such as electron density, electron temperature and gas temperature.

  5. Peroxyacetyl radical: Electronic excitation energies, fundamental vibrational frequencies, and symmetry breaking in the first excited state

    International Nuclear Information System (INIS)

    Peroxyacetyl radical [CH3C(O)O2] is among the most abundant peroxy radicals in the atmosphere and is involved in OH-radical recycling along with peroxyacetyl nitrate formation. Herein, the ground (X~) and first (A~) excited state surfaces of cis and trans peroxyacetyl radical are characterized using high-level ab initio methods. Geometries, anharmonic vibrational frequencies, and adiabatic excitation energies extrapolated to the complete basis-set limit are reported from computations with coupled-cluster theory. Excitation of the trans conformer is found to induce a symmetry-breaking conformational change due to second-order Jahn-Teller interactions with higher-lying excited states. Additional benchmark computations are provided to aid future theoretical work on peroxy radicals

  6. Multiple electron capture, excitation, and fragmentation in C6+-C-60 collisions

    DEFF Research Database (Denmark)

    da Silva, Humberto; Oller, Javier

    2014-01-01

    We present experimental and theoretical results on single- and multiple-electron capture, and fragmentation, in C6+ + C-60 collisions at velocities in the v(col) = 0.05 - 0.4 a.u. range. We use time-of-flight mass spectrometry and coincidence detection of charged fragments to separate pure target ionization from processes in which the C-60 target is both ionized and fragmented. The coincidence technique allows us to identify different types of fragmentation processes such as C-60(q+) -> C-58(q+) + C-2 and C-60(q+) -> C-58((q-1)+) + C-2(+). A quasimolecular approach is employed to calculate charge transfer and target excitation cross sections. First-order time-dependent perturbation and statistical methods are used to treat the postcollisional processes: the calculated rate constants for C-2 and C-2(+) emission from the excited and charged fullerene are then used to evaluate the fragmentation dynamics. We show that the target ionization cross section decreases with the induced target charge state and the impact energy. C-2 emission from C-60(q+) is found to dominate when q = 5, in agreement with the present and previous experimental results.

  7. Energy transfer from excited cyclobutane-t chemically activated by nuclear recoil reaction

    International Nuclear Information System (INIS)

    Relative energy transfer efficiencies were determined for collisions between highly excited cyclobutane-t and a number of thermal bath gases, including nitrogen, tetrafluoromethane, the noble gases, and cyclobutane. The excited cyclobutane-t was produced with a broad spectrum of energies about a mean energy of 5 eV by replacement of hydrogen with nuclear recoil tritium. The distribution of cyclobutane-t included a fraction produced at such low energies that it was not subjected to unimolecular decomposition, a fraction always found as the decomposition product, ethylene-t, and a fraction subject to competitive stabilization-decomposition reactions. The fraction of cyclobutane-t produced at such extreme energies that it was not subject to competitive unimolecular reaction was determined by curve-fitting the pressure dependence of ratio of cyclobutane-t to ethylene-t. Subsequent examination of the composition dependence of the ratio of competitive cyclobutane-t and ethylene-t yields gave energy transfer efficiencies for C4H8, CF4, N2, He, Ne, Ar, Kr, and Xe of 1.00:1.05:0.40, 0.12, 0.23, 0.24, 0.31, 0.39. The relative efficiencies found in this system are similar to those found in high energy conventional chemical activation systems, supporting this method for determination of energy transfer efficiencies following nuclear recoil activation. Cascade deactivation is demonstrated for this system and discussed with respect to energy transfer in hot atom activated systems

  8. Electronic reorganization triggered by electron transfer: the intervalence charge transfer of a Fe³?/Fe²? bimetallic complex.

    Science.gov (United States)

    Domingo, Alex; Angeli, Celestino; de Graaf, Coen; Robert, Vincent

    2015-04-30

    The key role of the molecular orbitals in describing electron transfer processes is put in evidence for the intervalence charge transfer (IVCT) of a synthetic nonheme binuclear mixed-valence Fe(3+)/Fe(2+) compound. The electronic reorganization induced by the IVCT can be quantified by controlling the adaptation of the molecular orbitals to the charge transfer process. We evaluate the transition energy and its polarization effects on the molecular orbitals by means of ab initio calculations. The resulting energetic profile of the IVCT shows strong similarities to the Marcus' model, suggesting a response behaviour of the ensemble of electrons analogue to that of the solvent. We quantify the extent of the electronic reorganization induced by the IVCT process to be 11.74 eV, a very large effect that induces the crossing of states reducing the total energy of the transfer to 0.89 eV. PMID:25739890

  9. On the validity of the electron transfer model in photon emission from ion bombarded vanadium surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ait El Fqih, M.; El Boujlaidi, A.; Jourdani, R.; Kaddouri, A. [Equipe de Spectroscopie and Imagerie Atomiques des Materiaux, Universite Cadi Ayyad, Marrakech (Morocco); Ait El Fqih, M. [Faculte Polydisciplinaire, Universite Chouaib Doukkali, B.P. 2390 El Jadida (Morocco)

    2011-06-15

    The spectral structure of the radiation (250-500 nm) emitted during sputtering of clean and oxygen-covered polycrystalline vanadium and V{sub 2}O{sub 5} by 5 keV Kr{sup +} ions is presented. The optical spectra obtained by bombarding the vanadium target consist of series of sharp lines, which are attributed to neutral and ionic excited V. The same lines are observed in the spectra of V{sub 2}O{sub 5} and vanadium when oxygen is present. The absolute intensities of VI and VII lines are measured under similar conditions for all spectra. The difference in photon yield from the clean and oxide vanadium targets is discussed in terms of the electron-transfer processes between the excited sputtered and electronic levels of the two types of surfaces. We have examined the existing models of ionisation, excitation, neutralisation and de-excitation of atomic particles in the vicinity of solid surfaces. Continuum radiation was also observed and interpreted as a result of the emission of excited molecules of the metal-oxide. (authors)

  10. Electron Transfer Dissociation: Effects of Cation Charge State on Product Partitioning in Ion/Ion Electron Transfer to Multiply Protonated Polypeptides

    OpenAIRE

    Liu, Jian; McLuckey, Scott A.

    2012-01-01

    The effect of cation charge state on product partitioning in the gas-phase ion/ion electron transfer reactions of multiply protonated tryptic peptides, model peptides, and relatively large peptides with singly charged radical anions has been examined. In particular, partitioning into various competing channels, such as proton transfer (PT) versus electron transfer (ET), electron transfer with subsequent dissociation (ETD) versus electron transfer with no dissociation (ET,noD), and fragmentati...

  11. The use of MIM tunnel junctions to investigate kinetic electron excitation in atomic collision cascades

    International Nuclear Information System (INIS)

    A novel technique is introduced to investigate the kinetic excitation of electrons in a solid by bombardment with energetic ions. The sample is prepared as a metal-insulator-metal (MIM) tunnel junction which opens the possibility to detect hot electrons with excitation energies well below the vacuum barrier. The excitations produced by the projectile impact onto the top electrode are detected as a tunnel current into the underlying base electrode. By varying the top electrode thickness, the elastic transport of hot electrons towards the tunnel junction can be studied

  12. Nuclear fission fragment excitation of electronic transition laser media

    Science.gov (United States)

    Lorents, D. C.; Mccusker, M. V.; Rhodes, C. K.

    1976-01-01

    Specific characteristics of the media including density, excitation rates, wavelength, kinetics, fissile material, scale size, and medium uniformity are assessed. The use of epithermal neutrons, homogeneously mixed fissile material, and special high cross section nuclear isotopes to optimize coupling of the energy to the medium are shown to be important considerations maximizing the scale size, energy deposition, and medium uniformity. It is demonstrated that e-beam excitation can be used to simulate nuclear pumping conditions to facilitate the search for candidate media.

  13. Electron and proton transfer in chemistry and biology

    International Nuclear Information System (INIS)

    This book constitutes the proceedings of an international meeting held in September 19-21, 1990, at Zentrum fuer Interdisziplinaere Forschung, Universitaet Bielefeld, Germany. It describes various aspects of electron and proton transfer in chemistry and biology. The book starts with a survey of physiochemical principles of electron transfer in the gas and the solid phase, with thermodynamic and photochemical driving force. Inner and outer sphere mechanisms and the coupling of electron transfer to nuclear rearrangements are reviewed. These principles are applied to construct artificial photosynthesis. This leads to biological electron transfer involving proteins with transition metal and/or organic redox centres. The tuning of the free energy profile on the reaction trajectory through the protein by single amino acids or by the larger ensemble that determines the electrostatic properties of the reaction path is one major issue. Another one is the transformation of one-electron to paired-electron steps with protection against hazardous radical intermediates. The diversity of electron transport systems is represented in some chapters with emphasis on photosynthesis, respiration and nitrogenases. In photosynthesis of green plants light driven vectorial electron transfer is coupled to protolytic reactions, with about one quarter of the useful work derived from light quanta utilized for proton pumping across a coupling membrane. That is where the interchange of electrochemical (Dm) and chemical (ATP) forms of free energy storage and transfer in cellular energetics starts. The proton is distinguished from other reactants by an extremely small diameter and the ability of tunneling at reasonable rates. This is the basis for particular polarization, solvent and isotope effects as well as for hydrogen-bonded networks that are suited to long-range proton-transfer. (author). refs.; figs.; tabs

  14. Contribution of electronically excited states to the radiation chemistry of organic systems. Progress report, December 1, 1981-November 30, 1984

    International Nuclear Information System (INIS)

    The fluorescence of saturated hydrocarbon liquids excited by 85Kr beta particles has been studied as a function of the concentration of electron scavenger. It has been possible to extract the probability, p+, that the scavengers attach a geminate electron. The effect of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) to scavenge geminate positive ions in irradiated hydrocarbon liquids has been studied via examination of the recombination fluorescence of TMPD+ + e- as a function of TMPD concentration. The scavenging probability p+ is found to be simply proportional to c. An effect of electron scavengers to reduce the photocurrent from TMPD excited optically above its ionization threshold in nonpolar liquids has been observed and explained in terms of interaction of the scavenger with epithermal electrons. The field and temperature dependences of the photocurrent has been studied in the presence and absence of electron scavengers and the results support the epithermal model. The fractional reduction in TMPD fluorescence in liquid tetramethylsilane caused by imposition of an electric field has been studied as a function of excitation energy (above the photoionization threshold) and as a function of field strength. It has been possible to extract the photoionization quantum yield and the electron thermalization range from approx. = 5.5 eV to 7.5 eV. From an absolute measurement of the yield of excited solute states in irradiated benzene and comparison with optical measurements, it is concluded that the energy transfer efficiency is representable by a Stern-Volmer function that extrapolates to unity at infinite solute concentration. The excimer to monomer ratio in photoexcited polystyrene in solution is found not to depend on polystyrene concentration

  15. Microscopic simulations of electronic excitations in donor-acceptor heterojunctions of small-molecule based solar cells

    Science.gov (United States)

    Baumeier, Bjoern

    2015-03-01

    Fundamental processes involving electronic excitations govern the functionality of molecular materials in which the dynamics of excitons and charges is determined by an interplay of molecular electronic structure and morphological order. To understand, e.g., charge separation and recombination at donor-acceptor heterojunctions in organic solar cells, knowledge about the microscopic details influencing these dynamics in the bulk and across the interface is required. For a set of prototypical heterojunctions of small-molecule donor materials with C60, we employ a hybrid QM/MM approach linking density-functional and many-body Green's functions theory and analyze the charged and neutral electronic excitations therein. We pay special attention the spatially-resolved electron/hole transport levels, as well as the relative energies of Frenkel and charge-transfer excitations at the interface. Finally, we link the molecular architecture of the donor material, its orientation on the fullerene substrate as well as mesoscale order to the solar cell performance.

  16. Electronic energy transfer involving carotenoid pigments in chlorosomes of two green bacteria: Chlorobium tepidum and Chloroflexus aurantiacus

    DEFF Research Database (Denmark)

    Melø, T B; Frigaard, N-U; Matsuura, K; Razi Naqvi, K

    2000-01-01

    Electronic energy transfer processes in chlorosomes isolated from the green sulphur bacterium Chlorobium tepidum and from the green filamentous bacterium Chloroflexus aurantiacus have been investigated. Steady-state fluorescence excitation spectra and time-resolved triplet-minus-singlet (TmS) spectra, recorded at ambient temperature and under non-reducing or reducing conditions, are reported. The carotenoid (Car) pigments in both species transfer their singlet excitation to bacteriochlorophyll c...

  17. Direct simulation of electron transfer reactions in DNA radical cations.

    Science.gov (United States)

    Steinbrecher, Thomas; Koslowski, Thorsten; Case, David A

    2008-12-25

    The electron transfer properties of DNA radical cations are important in DNA damage and repair processes. Fast long-range charge transfer has been demonstrated experimentally, but the subtle influences that experimental conditions as well as DNA sequences and geometries have on the details of electron transfer parameters are still poorly understood. In this work, we employ an atomistic QM/MM approach, based on a one-electron tight binding Hamiltonian and a classical molecular mechanics forcefield, to conduct nanosecond length MD simulations of electron holes in DNA oligomers. Multiple spontaneous electron transfer events were observed in 100 ns simulations with neighboring adenine or guanine bases. Marcus parameters of charge transfer could be extracted directly from the simulations. The reorganization energy lambda for hopping between neighboring bases was found to be ca. 25 kcal/mol and charge transfer rates of 4.1 x 10(9) s(-1) for AA hopping and 1.3 x 10(9) s(-1) for GG hopping were obtained. PMID:19049302

  18. Electron transfer in the Hf1Co6 magnetic alloy

    International Nuclear Information System (INIS)

    The cobalt atomic magnetic moment in Hf1Co6 was determined from the measured saturation magnetization and compared with predictions of an electron transfer model. Good agreement was found when hafnium contributes only two of its four valence electrons to the empty states in the minority spin band of cobalt

  19. Breit-Pauli R-matrix electron-impact excitation calculations along the argon isonuclear sequence

    International Nuclear Information System (INIS)

    Electron-impact excitation of argon ions is a vital component in the modelling of fusion tokamak experiments. Currently the available electron-impact excitation rates for the argon isonuclear sequence are a collection of isolated calculations carried out within various theoretical scattering models. With the development of our parallel suite of Breit-Pauli codes and the accessibility of massively parallel architectures, there was the opportunity to calculate the entire argon isonuclear sequence and provide a single, comprehensive and complete excitation data set. These data will subsequently be archived as Maxwellian averaged rate coefficients. We report on Breit-Pauli R-matrix electron-impact excitation calculations that have been performed for Ar3+, Ar4+, Ar5+, Ar7+, Ar8+, Ar10+, Ar11+, Ar12+, Ar13+, Ar14+ and Ar17+. Together with existing R-matrix calculations, this completes the generation of excitation data for the argon isonuclear sequence.

  20. Two-Photon Study on the Electronic Interactions between the First Excited Singlet States in Carotenoid-Tetrapyrrole Dyads

    Energy Technology Data Exchange (ETDEWEB)

    Liao, Pen-Nan [Technische Universitat Braunschweig (Germany); Pillai, Smitha [Arizona State Univ., Tempe, AZ (United States); Gust, Devens [Arizona State Univ., Tempe, AZ (United States); Moore, Thomas A. [Arizona State Univ., Tempe, AZ (United States); Moore, Ana L. [Arizona State Univ., Tempe, AZ (United States); Walla, Peter J. [Technische Universitat Braunschweig (Germany)

    2011-03-22

    Electronic interactions between the first excited states (S1) of carotenoids (Car) of different conjugation lengths (8-11 double bonds) and phthalocyanines (Pc) in different Car-Pc dyad molecules were investigated by two-photon spectroscopy and compared with Car S1-chlorophyll (Chl) interactions in photosynthetic light harvesting complexes (LHCs). The observation of Chl/Pc fluorescence after selective two-photon excitation of the Car S1 state allowed sensitive monitoring of the flow of energy between Car S1 and Pc or Chl. It is found that two-photon excitation excites to about 80% to 100% exclusively the carotenoid state Car S1 and that only a small fraction of direct tetrapyrrole two-photon excitation occurs. Amide-linked Car-Pc dyads in tetrahydrofuran demonstrate a molecular gear shift mechanism in that effective Car S1 ? Pc energy transfer is observed in a dyad with 9 double bonds in the carotenoid, whereas in similar dyads with 11 double bonds in the carotenoid, the Pc fluorescence is strongly quenched by Pc ? Car S1 energy transfer. In phenylamino-linked Car-Pc dyads in toluene extremely large electronic interactions between the Car S1 state and Pc were observed, particularly in the case of a dyad in which the carotenoid contained 10 double bonds. This observation together with previous findings in the same system provides strong evidence for excitonic Car S1-Pc Qy interactions. Very similar results were observed with photosynthetic LHC II complexes in the past, supporting an important role of such interactions in photosynthetic down-regulation.

  1. Coulomb Excitation and Transfer Reactions with Rare Neutron-Rich Isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Radford, David C [ORNL; Baktash, Cyrus [ORNL; Barton, C. J. [University of York, UK; Batchelder, J. C. [Oak Ridge Associated Universities (ORAU); Beene, James R [ORNL; Bingham, C. R. [University of Tennessee, Knoxville (UTK); Caprio, M. A. [Yale University; Danchev, M. [University of Tennessee, Knoxville (UTK); Fuentes, B. [ORNL/Facultad de Ciencias, UNAM, Mexico; Galindo-Uribarri, Alfredo {nmn} [ORNL; Gomez Del Campo, Jorge [ORNL; Gross, Carl J [ORNL; Halbert, Melvyn L [ORNL; Hartley, D. J. [University of Tennessee, Knoxville (UTK); Hausladen, Paul [ORNL; Hwang, J. K. [Vanderbilt University; Krolas, W. [Joint Institute for Heavy Ion Research, Oak Ridge; Larochelle, Y [University of Tennessee; Liang, J Felix [ORNL; Mueller, Paul Edward [ORNL; Padilla, E. [ORNL/Instituto de Ciencias Nucleares, UNAM, Mexico; Pavan, John R [ORNL; Piechaczek, A. [Louisiana State University; Shapira, Dan [ORNL; Stracener, Daniel W [ORNL; Varner Jr, Robert L [ORNL; Woehr, Andreas [ORNL; Yu, Chang-Hong [ORNL; Zamfir, Nicolae Victor [ORNL

    2005-04-01

    Neutron-rich radioactive ion beams available from the HRIBF allow a variety of measurements around the {sup 132}Sn region, including Coulomb excitation, fusion-evaporation, and neutron transfer. The B(E2;0{sup +}{yields}2{sup +}) value for first 2{sup +} excited states of even-even neutron-rich {sup 132-136}Te and {sup 126-134}Sn have been measured by Coulomb excitation in inverse kinematics. The results are discussed in terms of the shell model and the quasiparticle random phase approximation. Neutron transfer onto a {sup 134}Te beam, from {sup 9}Be and {sup 13}C targets to populate single-particle states in {sup 135}Te, has also been studied. Gamma rays from the {sup 13}C({sup 134}Te, {sup 12}C) reaction were used to identify the ?i{sub 13/2} state in {sup 135}Te, at an energy of 2109 keV. These and other results, and plans for future experiments with these neutron-rich beams, are presented.

  2. Two-level systems coupled to an oscillator: Excitation transfer and energy exchange

    CERN Document Server

    Hagelstein, P L; Hagelstein, Peter L.; Chaudhary, Irfan U.

    2006-01-01

    We consider models in which two sets of matched two-level systems are coupled to a common oscillator in the case where the oscillator energy is small relative to the two-level transition energies. Since the two sets of two-level systems are coupled indirectly through the oscillator, excitation transfer from one set of two-level systems to the other is possible. In addition, the excitation energy from the two-level systems may be exchanged with the oscillator coherently, even though the oscillator energy may be orders of magnitude smaller than the two-level system transition energy. In the lossless case, we demonstrate these effects numerically, and also use an approximate diagonalization to show that these effects are expected from the model Hamiltonian. We augment the model to include loss effects, and show that loss enhances the excitation transfer effect by breaking the severe cancelation between different paths that occurs in the lossless case. We describe a simple approximate model wavefunction appropria...

  3. Peculiar effects from number theory for doubly excited Rydberg states of two-electron ions

    International Nuclear Information System (INIS)

    Without electron repulsion there were accidental degeneracies between some of the excited states of two- (or more-) electron atoms among themselves and also with ionization threshold. The effects of these degeneracies on resonances of highly ionized atoms decaying by the Auger effect of autoionization, are investigated by treating the repulsion between the electrons as a perturbation. (author)

  4. A new technique for excitation studies in electron-ion collisions

    International Nuclear Information System (INIS)

    A new technique based on an electron energy-loss technique is being developed to measure absolute total cross sections for ion excitation by electron impact. Novel aspects of the instrument include collection of the electrons in the backward direction, and the use of curved trochoidal plates to minimise distortion of the inelastically scattered beam during analysis. (orig.)

  5. Electron spectroscopy studies of argon K-shell excitation and vacancy cascades

    International Nuclear Information System (INIS)

    Electron spectroscopy combined with tunable synchrotron radiation has been used for studies of Ar K-shell excitation and vacancy decay processes. In addition, electrons and fluorescent X-rays have been recorded in coincidence to select subsets of the ejected electron spectra. Examples are presented for Ar 1s photoelectrons and KLL and LMM Auger spectra

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

    International Nuclear Information System (INIS)

    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.)

  7. Spectral heterogeneity and time-resolved spectroscopy of excitation energy transfer in membranes of Heliobacillus mobilis at low temperatures.

    OpenAIRE

    Lin, S; Kleinherenbrink, F A; Chiou, H. C.; Blankenship, R. E.

    1994-01-01

    Transient absorption difference spectra in the Qy absorption band from membranes of Heliobacillus mobilis were recorded at 140 and 20 K upon 200 fs laser pulse excitation at 590 nm. Excitation transfer from short wavelength absorbing forms of bacteriochlorophyll g to long wavelength bacteriochlorophyll g occurred within 1-2 ps at both long wavelength bacteriochlorophyll g occurred within 1-2 ps at both temperatures. In addition, a slower energy transfer process with a time constant of 15 ps w...

  8. Resonant hot charge-transfer excitations in fullerene-porphyrin complexes: a many-body Bethe-Salpeter study

    OpenAIRE

    Duchemin, Ivan; Blase, Xavier

    2013-01-01

    We study within the many-body Green's function GW and Bethe-Salpeter approaches the neutral singlet excitations of the zinctetraphenylporphyrin and C70 fullerene donor-acceptor complex. The lowest transition is a charge-transfer excitation between the donor and the acceptor with an energy in excellent agreement with recent constrained density functional theory calculations. Beyond the lowest charge-transfer state, of which the energy can be determined with simple electrostat...

  9. Effect of strong coupling on interfacial electron transfer dynamics in dye-sensitized TiO2 semiconductor nanoparticles

    Indian Academy of Sciences (India)

    Hirendra N Ghosh

    2007-03-01

    Dynamics of interfacial electron transfer (ET) in ruthenium polypyridyl complex [{bis-(2,2'-bpy)-(4-[2-(4'-methyl-[2,2']bipyridinyl-4-yl)-vinyl]-benzene-1,2-diol)}ruthenium(II) hexafluorophosphate] (Ru-cat) and 5,10,15-tris phenyl-20-(3,4-dihydroxy benzene) porphyrin (TPP-cat)-sensitized TiO2 nanoparticles have been investigated using femtosecond transient absorption spectroscopic detection in the visible and near-infrared region. We have observed that both Ru-cat and TPP-cat are coupled strongly with the TiO2 nanoparticles through their pendant catechol moieties. We have observed a single exponential and pulse-width limited (<100 fs) electron injection from nonthermalized-excited states of Ru-complex. Here electron injection competes with the singlet-triplet manifold relaxation due to strong coupling of catecholate binding, which is a unique observation. Optical absorption measurements indicate that the catechol moiety interacts with TiO2 nanoparticles showing the characteristic pure catechol-TiO2 charge-transfer (CT) band in the visible region. Transient absorption studies on TPP-cat/TiO2 system exciting both the Soret band at 400 nm and the Q-band at 800 nm have been carried out to determine excitation wavelength-dependence on ET dynamics. The reaction channel for the electron-injection process has been found to be different for both the excitation wavelengths. Excitation at 800 nm, is found directly populate directly the excited CT state from where diffusion of electrons into the conduction band takes place. On the other hand, excitation at 400 nm light excites both the CT band of cat-TiO2 and also Soret band of TPP-cat.

  10. Lewis Acid Coupled Electron Transfer of Metal-Oxygen Intermediates.

    Science.gov (United States)

    Fukuzumi, Shunichi; Ohkubo, Kei; Lee, Yong-Min; Nam, Wonwoo

    2015-12-01

    Redox-inactive metal ions and Brønsted acids that function as Lewis acids play pivotal roles in modulating the redox reactivity of metal-oxygen intermediates, such as metal-oxo and metal-peroxo complexes. The mechanisms of the oxidative C?H bond cleavage of toluene derivatives, sulfoxidation of thioanisole derivatives, and epoxidation of styrene derivatives by mononuclear nonheme iron(IV)-oxo complexes in the presence of triflic acid (HOTf) and Sc(OTf)3 have been unified as rate-determining electron transfer coupled with binding of Lewis acids (HOTf and Sc(OTf)3 ) by iron(III)-oxo complexes. All logarithms of the observed second-order rate constants of Lewis acid-promoted oxidative C?H bond cleavage, sulfoxidation, and epoxidation reactions of iron(IV)-oxo complexes exhibit remarkably unified correlations with the driving forces of proton-coupled electron transfer (PCET) and metal ion-coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes were taken into account. The binding of HOTf and Sc(OTf)3 to the metal-oxo moiety has been confirmed for Mn(IV) -oxo complexes. The enhancement of the electron-transfer reactivity of metal-oxo complexes by binding of Lewis acids increases with increasing the Lewis acidity of redox-inactive metal ions. Metal ions can also bind to mononuclear nonheme iron(III)-peroxo complexes, resulting in acceleration of the electron-transfer reduction but deceleration of the electron-transfer oxidation. Such a control on the reactivity of metal-oxygen intermediates by binding of Lewis acids provides valuable insight into the role of Ca(2+) in the oxidation of water to dioxygen by the oxygen-evolving complex in photosystem?II. PMID:26404482

  11. Effect of electronic and nuclear factors on the dynamics of dye-to-semiconductor electron transfer

    OpenAIRE

    Wenger, Bernard

    2006-01-01

    Dye-to-semiconductor electron transfer is the initial step in many processes where light is used for the storage of information (e. g. color photography) or converted into electricity as in dye-sensitized solar cells. In the latter, interfacial charge injection occurs on a timescale spanning from tens of femtoseconds (10-15 s) to several picoseconds (10-12 s), with an efficiency approaching 100 %. In standard electron transfer theory, the parameters controlling charge transfer dynamics are di...

  12. On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

    International Nuclear Information System (INIS)

    The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S0) and first singlet excited (S1) electronic states. In S0 the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S1. The ab initio configuration interaction singles (CIS) method overestimates the energy of S1 and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S1 and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media

  13. On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Casadesus, Ricard [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States); Vendrell, Oriol [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Moreno, Miquel [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain)], E-mail: mmf@klingon.uab.es; Lluch, Jose M. [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Morokuma, Keiji [Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States)

    2006-06-20

    The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S{sub 0}) and first singlet excited (S{sub 1}) electronic states. In S{sub 0} the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S{sub 1}. The ab initio configuration interaction singles (CIS) method overestimates the energy of S{sub 1} and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S{sub 1} and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media.

  14. Production processes of excited hydrogen (H and D) by electron impacts

    International Nuclear Information System (INIS)

    By the collision of molecules with electrons, the molecules are excited easily to the state of high excitation above10 eV. As the result, the excited hydrogen atoms formed by the electron impact dissociation of the molecules containing hydrogen atoms have large translation energy, and the Balmer line has large Doppler width. In order to determine the anisotropy and orientation of spatial distribution and the magnetic quantum number distribution of the excited hydrogen atoms formed by the electron impact of H2 and D2, the author devised the methods of measurement and analysis of various Doppler profiles, and elucidated the dynamics of the dissociation of hydrogen molecules in high excitation state by electron impact. The research on the orientation quantum number distribution of the dissociated atoms by pulsed electron impact is reported, in which the Balmer beta line formed from H2 by pulsed electron beam impact was measured by time separation. The polarized light emission of the excited hydrogen atoms formed by the electron impact of H2 and D2 was measured, and the degree of polarization was separated for each component. (K.I.)

  15. The EMP excitation of radiation by the pulsed relativistic electron beam

    International Nuclear Information System (INIS)

    The mechanisms of excitation of ultra-wideband electromagnetic pulses (EMP) by short pulses of high-current relativistic electron beams were proposed and investigated. It is shown that the transformation efficiency of the bunch kinetic energy to the excited energy of the EMP can be very significant. (author). 2 figs., 4 refs

  16. Absolute amplitude and growth time of electron plasma waves excited by two laser beams

    International Nuclear Information System (INIS)

    Excitation of electron plasma waves in a hot and fully ionized plasma by two laser beams is presented. The growth time and absolute amplitude of the excited waves, measured by light scattering, indicate very strong coupling of the laser light with the plasma

  17. Rapid bond rearrangement in molecules after core-electron excitation

    International Nuclear Information System (INIS)

    Experimental studies of core-excited molecules using three-dimensional multi particle momentum imaging are presented where bond rearrangement processes in dication species are analysed. The aim of the study is to understand the relation between the geometric changes associated with core-excited states and the kinetic energy released in particular molecular dissociation processes. The kinematics of individual fragmentation channels are studied by fully three-dimensional momentum imaging of fragments in coincidence. Examples are presented where the high efficiency of the instrument and the fully three-dimensional momentum capabilities are exploited to understand nuclear motion leading to bond rearrangement in core-excited states. We identify bond-rearrangement processes in water, carbonyl sulphide and acetylene which are initiated in the core-excited state. In water this is evidenced by the H+2/O+ ion pair, and in carbonyl sulphide the OS++C+ pair is the fingerprint of this reaction. In acetylene the H+2 + C+2 ion pair indicates a molecular geometry that changes from linear to strongly bent. We measure the angular distribution of all fragments and fragment pairs and for the bond rearrangement processes in water and in core-excited acetylene the angular distribution of fragments suggests that the bond rearrangement is very rapid

  18. Electron emission from collective excitation of solids by heavy ion impact

    International Nuclear Information System (INIS)

    Collective excitation of the electron plasma of a solid by a penetrating heavy ion can lead to the emission of low energy electrons. In double differential energy- and angular distributions of secondary electrons from sputter-cleaned solid surfaces from heavy ion impact structures are observed which can be related to 1. wake-induced shock electrons and 2. electrons resulting from the decay of plasmons. The emission of these electrons is strongly influenced by both surface contamination and structure. The directed emission of shock electrons offers the possibility to study the refraction of low energy electrons by the surface potential barrier. 14 refs., 4 figs

  19. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    2013-01-01

    The step from ab initio atomic and molecular properties to thermodynamic - or macroscopic - properties requires the combination of several theoretical tools. This dissertation presents constant temperature molecular dynamics with bond length constraints, a hybrid quantum mechanics-molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical en...

  20. Electron transfer from nucleobase electron adducts to 5-bromouracil: a radiation chemical study

    International Nuclear Information System (INIS)

    Electron transfer to 5-bromouracil from their nucleobase electron adducts and their protonated forms has been studied by product analysis. When an electron is transferred to 5-bromouracil, the ensuing 5-bromouracil radical anion rapidly loses a bromide ion. The uracilyl radical thus formed reacts with added t-butanol, yielding uracil. From the uracil yields measured as a function of (N)/(5-BrU) after ?-radiolysis of Ar-saturated solutions it is concluded that the hetero atom protonated forms transfer electron quantitatively to 5-bromouracil. (author). 3 refs., 1 fig

  1. Modifications of poly (vinilydene fluoride) under electronic excitations produced by charged particles (heavy ions and electrons)

    International Nuclear Information System (INIS)

    Some of the physico-chemical properties of organic solids like conductivity or permeation can be improved by irradiation. The aim of this work is to characterize modifications induced in poly (vinylidene fluoride) films (PVDF) by charged particles (ions and electrons), with electronic stopping power, for doses ranging from zero to twenty G-Grays. Influence of dose, density of electronic excitations, and flux (in particles per square centimeter), and the nature of defects induced by the beam, were studied with two methods: X-ray Photoelectron Spectroscopy (or XPS) for surface analysis, and electron Spin Resonance (or ESR) to probe the bulk of the film. Three ranges of doses are revealed in view of experimental results. At lower doses, PVDF undergoes deshydrofluorination induced by desorption; it is a low modifications regime. For intermediate range doses, conjugated carbon backbones of polyene compounds are produced. At higher doses, intermolecular interactions between the resulting fragments give a crosslinked network. For the upper limit of doses used, bond breaking results in a non reversible degradation of PVDF. In this last situation, direct atomic displacement of target atoms, is not negligible

  2. Differential cross sections for electron-impact excitation of the electronic states of pyrimidine

    Science.gov (United States)

    Brunger, Michael; Jones, Darryl; Bellm, Susan

    2012-06-01

    Pyrimidine (C4N2H4) is an important molecule, as it forms the basis of larger biomolecules, such as the DNA bases thymine, cytosine and uracil. There is a pressing demand for low-energy electron scattering data from such biological analogs in order to model radiation induced damage [1]. We therefore present the first measurements for absolute differential cross section data for low-energy electron-impact excitation of the electronic states of pyrimidine. The present measurements were performed using a crossed-beam apparatus [2] for incident electron energies ranging between 15 to 50eV while covering a 10 to 90^o angular range. Here the absolute scale has been determined through a normalisation to the recently measured elastic scattering differential cross section data for pyrimidine [3]. [1] F. Ferreira da Silva, D. Almeida, G. Martins, A. R. Milosavljevic, B. P. Marinkovic, S. V. Hoffmann, N. J. Mason, Y. Nunes, G. Garcia and P. Limao-Vieira, Phys Chem Chem Phys 12, 6717 (2010). [2] M. J. Brunger and P. J. O. Teubner, Phys Rev A 41, 1413 (1990). [3] P. Palihawadana, J. Sullivan, M. Brunger, C. Winstead, V. McKoy, G. Garcia, F. Blanco and S. Buckman, Phys Rev A 84, 062702 (2011).

  3. What we do and not know about electron impact excitation of atomic hydrogen

    International Nuclear Information System (INIS)

    The present state of knowledge derived from both theoretical and experimental information on electron impact excitation of atomic hydrogen is briefly reviewed. Suggestions are made for further calculations and for additional experiments. (author)

  4. Creation and evolution of excited states in anthracene crystals bombarded by electrons

    International Nuclear Information System (INIS)

    A qualitative description of the kinematics of excited states in anthracene crystals bombarded by electrons is given. It is compared with experimental results concerning scintillation decay curves, and magnetic field effects on the prompt and delayed components of the scintillation

  5. Surface plasmon excitations in cylindrical nanorods by electron-hole pair creation.

    Science.gov (United States)

    García Gallardo, J A; Gervasoni, J L; Kövér, L

    2012-12-01

    In this work we study the effect of the excitation of surface plasmons in a metallic cylindrical nanorod by a suddenly created electron-hole pair, using a classical model for the emerging electron and a quantum-mechanical model for the plasmon field in the cylinder. The electron and the hole interact independently with the plasmon field, generating electron density oscillations. Two different trajectories for the emerging electron (parallel to the axis and radial) are studied in an aluminum nanorod. The average number of excited plasmons indicates how important is the role of the hole in the excitation process. We found that the results can be very different according to the trajectory of the emerging electron. We also found that the distinction between intrinsic and extrinsic process is sometimes not applicable. PMID:23447988

  6. Demonstration of Lignin-to-Peroxidase Direct Electron Transfer

    Science.gov (United States)

    Sáez-Jiménez, Verónica; Baratto, Maria Camilla; Pogni, Rebecca; Rencoret, Jorge; Gutiérrez, Ana; Santos, José Ignacio; Martínez, Angel T.; Ruiz-Dueñas, Francisco Javier

    2015-01-01

    Versatile peroxidase (VP) is a high redox-potential peroxidase of biotechnological interest that is able to oxidize phenolic and non-phenolic aromatics, Mn2+, and different dyes. The ability of VP from Pleurotus eryngii to oxidize water-soluble lignins (softwood and hardwood lignosulfonates) is demonstrated here by a combination of directed mutagenesis and spectroscopic techniques, among others. In addition, direct electron transfer between the peroxidase and the lignin macromolecule was kinetically characterized using stopped-flow spectrophotometry. VP variants were used to show that this reaction strongly depends on the presence of a solvent-exposed tryptophan residue (Trp-164). Moreover, the tryptophanyl radical detected by EPR spectroscopy of H2O2-activated VP (being absent from the W164S variant) was identified as catalytically active because it was reduced during lignosulfonate oxidation, resulting in the appearance of a lignin radical. The decrease of lignin fluorescence (excitation at 355 nm/emission at 400 nm) during VP treatment under steady-state conditions was accompanied by a decrease of the lignin (aromatic nuclei and side chains) signals in one-dimensional and two-dimensional NMR spectra, confirming the ligninolytic capabilities of the enzyme. Simultaneously, size-exclusion chromatography showed an increase of the molecular mass of the modified residual lignin, especially for the (low molecular mass) hardwood lignosulfonate, revealing that the oxidation products tend to recondense during the VP treatment. Finally, mutagenesis of selected residues neighboring Trp-164 resulted in improved apparent second-order rate constants for lignosulfonate reactions, revealing that changes in its protein environment (modifying the net negative charge and/or substrate accessibility/binding) can modulate the reactivity of the catalytic tryptophan. PMID:26240145

  7. Spectroscopy of nitrophenolates in vacuo: effect of spacer, configuration, and microsolvation on the charge-transfer excitation energy

    DEFF Research Database (Denmark)

    Nielsen, Steen BrØndsted; Nielsen, Mogens BrØndsted

    2014-01-01

    Conspectus In a charge-transfer (CT) transition, electron density moves from one end of the molecule (donor) to the other end (acceptor). This type of transition is of paramount importance in nature, for example, in photosynthesis, and it governs the excitation of several protein biochromophores and luminophores such as the oxyluciferin anion that accounts for light emission from fireflies. Both transition energy and oscillator strength are linked to the coupling between the donor and acceptor groups: The weaker the coupling, the smaller the excitation energy. But a weak coupling necessarily also causes a low oscillator strength possibly preventing direct excitation (basically zero probability in the noncoupling case). The coupling is determined by the actual spacer between the two groups, and whether the spacer acts as an insulator or a conductor. However, it can be difficult or even impossible to distinguish the effect of the spacer from that of local solvent molecules that often cause large solvent shifts due to different ground-state and excited-state stabilization. This calls for gas-phase spectroscopy experiments where absorption by the isolated molecule is identified to unequivocally establish the intrinsic molecular properties with no perturbations from a microenvironment. From such insight, the effect of a protein microenvironment on the CT excited state can be deduced. In this Account, we review our results over the last 5 years from mass spectroscopy experiments using specially designed apparatus on several charged donor-acceptor ions that are based on the nitrophenolate moiety and ?-extended derivatives, which are textbook examples of donor-acceptor chromophores. The phenolate oxygen is the donor, and the nitro group is the acceptor. The choice of this system is also based on the fact that phenolate is a common structural motif of biochromophores and luminophores, for example, it is a constituent of the oxyluciferin anion. A presentation of the setups used for gas-phase ion spectroscopy in Aarhus is given, and we address issues of whether double bonds or triple bonds best convey electronic coupling between the phenolate oxygen and the nitro group, the significance of separating the donor and acceptor spatially, the influence of cross-conjugation versus linear conjugation, and along this line ortho versus meta versus para configuration, and not least the effect of a single solvent molecule (water, methanol, or acetonitrile). From systematic studies, a clear picture has emerged that has been supported by high-level calculations of electronically excited states. Our work shows that CC2 coupled-cluster calculations of vertical excitation energies are within 0.2 eV of experimental band maxima, and importantly, that the theoretical method is excellent in predicting the relative order of excitation energies of a series of nitrophenolates. Finally, we discuss future challenges such as following the change in absorption as a function of the number of solvent molecules and when gradually approaching the bulk limit.

  8. Surface chemical reactions induced by molecules electronically-excited in the gas

    DEFF Research Database (Denmark)

    Petrunin, Victor V.

    2011-01-01

    We present a model suggesting high chemical activity of electronically-excited molecules colliding with an isolator surface. Initial photochemical event is accounted for as the result of molecular evolution on the electronically-excited potential energy surface (PES), where acceleration and alignment are taking place, guiding all the molecules towards the intersections with the ground state PES, where transitions to the ground state PES will occur with minimum energy dissipation. The accumulated...

  9. Effect of vacuum polarization on the excitation of hydrogen atom by electron impact

    Directory of Open Access Journals (Sweden)

    T. Roy

    1981-09-01

    Full Text Available The vacuum polarization potential is included in the interaction Hamiltonian for 1S−2S excitation of the hydrogen atom by electron impact. The excitation amplitude calculated field theoretically is found to be lowered by 0.47t2/(t2+93 where t2=4|P−Q|2, P and Q being the momenta of the incident and scattered electrons respectively.

  10. Collisional ionization and excitation of H2: Two-electron processes

    International Nuclear Information System (INIS)

    The cross sections for the double ionization, ionization plus excitation, and double excitation of H2 by electrons and protons in the range of 350 to 3500 keV/amu have been measured. In all cases, the cross section for electron bombardment was greater than that for equivelocity proton bombardment. The results are discussed in terms of first and second Born processes and interferences between the two

  11. Excitation and relaxation of the electronic subsystem in solids after high energy deposition

    OpenAIRE

    Medvedev, Nikita

    2011-01-01

    The present dissertation contains the theoretical studies performed on the topic of a high energy deposition in matter. The work focuses on electronic excitation and relaxation processes on ultrafast timescales. Energy deposition by means of intense ultrashort (femtosecond) laser pulses or by means of swift heavy ions irradiation have a certain similarities: the final observable material modifications result from a number of processes on different timescales. First, the electronic excitation ...

  12. Electron transfer reactions in microporous solids

    Energy Technology Data Exchange (ETDEWEB)

    Mallouk, T.E.

    1993-01-01

    Basic thrust the research program involves use of microporous solids (zeolites, clays, layered and tunnel structure oxide semiconductors) as organizing media for artificial photosynthetic systems. Purpose of the microporous solid is twofold. First, it induces spatial organization of photoactive and electroactive components (sensitizers, semiconductor particles, electron relays, and catalysts) at the solid-solution interface, enhancing the quantum efficiency of charge separation and separating physically the ultimate electron donor and acceptor in the electron transport chain. Second, since the microcrystalline solid admits only molecules of a certain charge and size, it is possible to achieve permanent charge separation by sieving chemical photoproducts (e.g., H[sub 2] and I[sub 3][sup [minus

  13. Plugging in or Going Wireless: Strategies for Interspecies Electron Transfer

    Directory of Open Access Journals (Sweden)

    PravinMallaShrestha

    2014-05-01

    Full Text Available Interspecies exchange of electrons enables a diversity of microbial communities to gain energy from reactions that no one microbe can catalyze. The first recognized strategies for interspecies electron transfer were those that relied on chemical intermediates that are recycled through oxidized and reduced forms. Well-studied examples are interspecies H2 transfer and the cycling of sulfur intermediates in anaerobic photosynthetic communities. Direct interspecies electron transfer (DIET in which two species establish electrical contacts is an alternative. Electrical contacts documented to date include electrically conductive pili, as well as conductive iron minerals and conductive carbon moieties such as activated carbon and biochar. It seems likely that there are additional alternative strategies for interspecies electrical connections that have yet to be discovered. Interspecies electron transfer is central to the functioning of methane-producing microbial communities. The importance of interspecies H2 transfer in many methanogenic communities is clear, but under some circumstances DIET predominates. It is expected that further mechanistic studies and broadening investigations to a wider range of environments will help elucidate the factors that favor specific forms of interspecies electron exchange under different environmental conditions.

  14. Plugging in or going wireless: strategies for interspecies electron transfer.

    Science.gov (United States)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena

    2014-01-01

    Interspecies exchange of electrons enables a diversity of microbial communities to gain energy from reactions that no one microbe can catalyze. The first recognized strategies for interspecies electron transfer were those that relied on chemical intermediates that are recycled through oxidized and reduced forms. Well-studied examples are interspecies H2 transfer and the cycling of sulfur intermediates in anaerobic photosynthetic communities. Direct interspecies electron transfer (DIET) in which two species establish electrical contact is an alternative. Electrical contacts documented to date include electrically conductive pili, as well as conductive iron minerals and conductive carbon moieties such as activated carbon and biochar. Interspecies electron transfer is central to the functioning of methane-producing microbial communities. The importance of interspecies H2 transfer in many methanogenic communities is clear, but under some circumstances DIET predominates. It is expected that further mechanistic studies and broadening investigations to a wider range of environments will help elucidate the factors that favor specific forms of interspecies electron exchange under different environmental conditions. PMID:24904551

  15. Plugging in or Going Wireless : Strategies for Interspecies Electron Transfer

    DEFF Research Database (Denmark)

    Shrestha, Pravin; Rotaru, Amelia-Elena

    2014-01-01

    Interspecies exchange of electrons enables a diversity of microbial communities to gain energy from reactions that no one microbe can catalyze. The first recognized strategies for interspecies electron transfer were those that relied on chemical intermediates that are recycled through oxidized and reduced forms. Well-studied examples are interspecies H2 transfer and the cycling of sulfur intermediates in anaerobic photosynthetic communities. Direct interspecies electron transfer (DIET) in which two species establish electrical contact is an alternative. Electrical contacts documented to date include electrically conductive pili, as well as conductive iron minerals and conductive carbon moieties such as activated carbon and biochar. Interspecies electron transfer is central to the functioning of methane-producing microbial communities. The importance of interspecies H2 transfer in many methanogenic communities is clear, but under some circumstances DIET predominates. It is expected that further mechanistic studies and broadening investigations to a wider range of environments will help elucidate the factors that favor specific forms of interspecies electron exchange under different environmental conditions.

  16. Surface excitations in electron backscattering from silicon surfaces.

    Czech Academy of Sciences Publication Activity Database

    Zemek, Josef; Ji?í?ek, Petr; Lesiak, B.; Jablonski, A.

    2004-01-01

    Ro?. 562, - (2004), s. 92-100. ISSN 0039-6028 R&D Projects: GA ?R GA202/02/0237 Institutional research plan: CEZ:AV0Z1010914 Keywords : electron-solid interactions * electron-solid scattering and transmission-elastic * electron-solid scattering and transmission-inelastic * Monte Carlo simulation * electron bombardment * silicon Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.168, year: 2004

  17. A combined experimental and DFT-TDDFT study of the excited-state intramolecular proton transfer (ESIPT) of 2-(2'-hydroxyphenyl) imidazole derivatives.

    Science.gov (United States)

    Padalkar, Vikas S; Ramasami, Ponnadurai; Sekar, Nagaiyan

    2013-09-01

    We report a combined experimental and computational study of the effect of electron donor and acceptor groups on the excited state intramolecular proton transfer of 2-(2'-hydroxyphenyl) imidazole derivatives in solvents of different polarities. The changes in fluorescence properties, electronic transitions and energy levels are analyzed and discussed. The study was complemented using the Density Functional Theory (DFT)-Time Dependent DFT [B3LYP/6-31G(d)] computations. The calculated absorption and emission spectra of the imidazole derivatives are in good agreement with the experiments, thus allowing an assignment of the UV-vis spectra. PMID:23613133

  18. Photoinduced intra- and intermolecular electron transfer in solutions and in solid organized molecular assemblies.

    Science.gov (United States)

    Lemmetyinen, Helge; Tkachenko, Nikolai V; Efimov, Alexander; Niemi, Marja

    2011-01-14

    The present paper highlights results of a systematic study of photoinduced electron transfer, where the fundamental aspects of the photochemistry occurring in solutions and in artificially or self-assembled molecular systems are combined and compared. In photochemical electron transfer (ET) reactions in solutions the electron donor, D, and acceptor, A, have to be or to diffuse to a short distance, which requires a high concentration of quencher molecules and/or long lifetimes of the excited donor or acceptor, which cannot always be arranged. The problem can partly be avoided by linking the donor and acceptor moieties covalently by a single bond, molecular chain or chains, or rigid bridge, forming D-A dyads. The covalent combination of porphyrin or phthalocyanine donors with an efficient electron acceptor, e.g. fullerene, has a two-fold effect on the electron transfer properties. Firstly, the electronic systems of the D-A pair result in a formation of an exciplex intermediate upon excitation both in solutions and in solid phases. The formation of the exciplex accelerates the ET rate, which was found to be as fast as >10(12) s(-1). Secondly, the total reorganization energy can be as small as 0.3 eV, even in polar solvents, which allows nanosecond lifetimes for the charge separated (CS) state. Molecular assemblies can form solid heterogeneous, but organized systems, e.g. molecular layers. This results in more complex charge separation and recombination dynamics. A distinct feature of the ET in organized assemblies is intermolecular interactions, which open a possibility for a charge migration both in the acceptor and in the donor layers, after the primary intramolecular exciplex formation and charge separation in the D-A dyad. The intramolecular ET is fast (35 ps) and efficient, but the formed interlayer CS states have lifetimes in microsecond or even second time domain. This is an important result considering possible applications. PMID:21031207

  19. Light- induced electron transfer and ATP synthesis in a carotene synthesizing insect

    Science.gov (United States)

    Valmalette, Jean Christophe; Dombrovsky, Aviv; Brat, Pierre; Mertz, Christian; Capovilla, Maria; Robichon, Alain

    2012-08-01

    A singular adaptive phenotype of a parthenogenetic insect species (Acyrthosiphon pisum) was selected in cold conditions and is characterized by a remarkable apparition of a greenish colour. The aphid pigments involve carotenoid genes well defined in chloroplasts and cyanobacteria and amazingly present in the aphid genome, likely by lateral transfer during evolution. The abundant carotenoid synthesis in aphids suggests strongly that a major and unknown physiological role is related to these compounds beyond their canonical anti-oxidant properties. We report here that the capture of light energy in living aphids results in the photo induced electron transfer from excited chromophores to acceptor molecules. The redox potentials of molecules involved in this process would be compatible with the reduction of the NAD+ coenzyme. This appears as an archaic photosynthetic system consisting of photo-emitted electrons that are in fine funnelled into the mitochondrial reducing power in order to synthesize ATP molecules.

  20. Collisional and radiative relaxation of the first excited states of rare gases. Energy transfer from argon excited atoms to different molecules and fluorescence of molecular xenon excited by synchrotron radiation

    International Nuclear Information System (INIS)

    In the first section, the measurement of total deexcitation cross sections of the 3P2,1,0 and 1P1 argon states by N2, H2, CO and SF6 using a pulsed gas radiolysis technique and 600 keV electrons is discussed. The energy transfer from the resonant states 3P1 and 1P1 of argon (as excited selectively by synchrotron radiation) to the C3?u state of nitrogen has been studied in more detail. On the basis of these results, the different theoretical models for these reactions have been discussed. In the second section, the fluorescence of the second continuum of molecular xenon at around 1700 A, as excited by synchrotron radiation in the region of the 3P1 1S0 resonance line at 1470 A, is considered. A short lived component of the fluorescence decay has been observed; this is attributed to emission at short interatomic distances from the high vibrational levels of Xe2+ (Ou+). The emissions at the left turning point of the potential curve of the Ou+ state has been observed at ? > 2000 A. From these results, the potential curves for the states Xe2 (Og+) and Xe2* (Ou+) have been estimated and the Franck-Condon factors have also been calculated as a function of the wavelength of the fluorescence. (author)

  1. Electron Transport, Energy Transfer, and Optical Response in Single Molecule Junctions

    Science.gov (United States)

    White, Alexander

    2015-03-01

    The field of molecular electronics has grown significantly since the first measurements of single molecule conductance. The single molecule junction, a device in which two conducting leads are spanned by a single molecule, has become a powerful tool for studying charge transfer at the molecular level. While early experiments were focused on elastic electron conductance, today measurements of vibronic effects, molecular optical response, spintronics, thermal conductance, and quantum interference and decoherence effects are prominent areas of research. These new experimental advancements demand improved theoretical treatments which properly account for the interactions between different degrees of freedom: charge, electronic, vibrational, spin, etc.; all in physically relevant parameter ranges. This talk focuses on using a many-body states based approach to investigate the regime of strong interaction between these degrees of freedom, with relatively weak coupling between the molecule and the electric reservoirs created by the conducting leads. We focused on three related processes, electron transfer, electronic energy transfer and molecular excitation. In collaboraton with Boris Fainberg, Faculty of Sciences, Holon Institute of Technology; Sergei Tretiak, Theoretical Division, Center for Integrated Nanotechnologies, Los Alamos National Laboratory; and Michael Galperin, Department of Chemistry and Biochemistry, University of California San Diego.

  2. Electron-impact excitation of low-lying preionization-edge electronic and Rydberg transitions of fluoroform and chloroform: Bethe surfaces and absolute generalized oscillator strengths

    International Nuclear Information System (INIS)

    Absolute generalized oscillator strengths (GOSs) of valence-shell electronic transitions of CHF3 and CHCl3 as functions of energy loss (0 endash 150 eV) and momentum transfer (i.e., the Bethe surfaces) have been determined using angle-resolved electron energy-loss spectroscopy at an impact energy of 2.5 keV. The assignments for the prominent low-lying preionization-edge energy-loss features of CHF3 and CHCl3 were inferred from the term values reported previously and from their characteristic experimental GOS profiles. In particular, the GOS profiles of the low-lying Rydberg transitions (which originated from the nonbonding highest occupied molecular orbitals) below the ionization edge at 11.1, 11.9, 12.7, and 13.7 eV in CHF3 and at 8.5, 9.6, and 10.6 eV in CHCl3 were determined. These GOS profiles were found to be dominated by a strong maximum at zero-momentum transfer, which is characteristic of dipole interaction. Weak secondary maxima (and minima) were also observed and could be interpreted qualitatively in terms of the spatial overlaps between the initial-state and final-state orbital wave functions. In addition, the low-lying feature at 7.2 eV in CHCl3 could be attributed predominantly to electronic excitations from the Cl 3p nonbonding (n) orbitals (2a2, 9e, 9a1, and 8e) to a C-Cl ?* antibonding orbital (10a1), according to a single-excitation configuration-interaction (CI) excited-state calculation. The experimental GOS profile of this low-lying feature was found to have a shape that is characteristic of a mixture of dipole-allowed and nondipole interactions, with maxima at momentum transfers of 0 and ?0.9 a.u., respectively. (Abstract Truncated)

  3. Differential cross sections for electron-impact vibrational-excitation of tetrahydrofuran at intermediate impact energies

    Science.gov (United States)

    Do, T. P. T.; Duque, H. V.; Lopes, M. C. A.; Konovalov, D. A.; White, R. D.; Brunger, M. J.; Jones, D. B.

    2015-03-01

    We report differential cross sections (DCSs) for electron-impact vibrational-excitation of tetrahydrofuran, at intermediate incident electron energies (15-50 eV) and over the 10°-90° scattered electron angular range. These measurements extend the available DCS data for vibrational excitation for this species, which have previously been obtained at lower incident electron energies (?20 eV). Where possible, our data are compared to the earlier measurements in the overlapping energy ranges. Here, quite good agreement was generally observed where the measurements overlapped.

  4. Differential cross sections for electron-impact vibrational-excitation of tetrahydrofuran at intermediate impact energies

    International Nuclear Information System (INIS)

    We report differential cross sections (DCSs) for electron-impact vibrational-excitation of tetrahydrofuran, at intermediate incident electron energies (15-50 eV) and over the 10°-90° scattered electron angular range. These measurements extend the available DCS data for vibrational excitation for this species, which have previously been obtained at lower incident electron energies (?20 eV). Where possible, our data are compared to the earlier measurements in the overlapping energy ranges. Here, quite good agreement was generally observed where the measurements overlapped

  5. Failures of TDDFT in describing the lowest intramolecular charge-transfer excitation in para-nitroanilin

    DEFF Research Database (Denmark)

    Eriksen, J.J.; Sauer, S.P.A.; Mikkelsen, K.V.; Christiansen, O.; Jensen, Hans Jørgen Aagaard; Kongsted, Jacob

    2013-01-01

    We investigate the failure of Time{Dependent Density Functional Theory (TDDFT) with the CAM{B3LYP exchange{correlation (xc) functional coupled to the Polarizable Embedding (PE) scheme (PE-CAM-B3LYP) in reproducing the solvatochromic shift of the lowest intense charge{transfer excitation in para{nitroaniline (pNA) in water by comparing with results obtained with the Coupled Cluster Singles and Doubles (CCSD) model also coupled to the Polarizable Embedding scheme (PE-CCSD). We determine the amount...

  6. Photoredox Reaction of [Cr(CO)?I] induced by Ligand to Metal Charge Transfer Excitation

    OpenAIRE

    Kunkely, Horst; Vogler, Arnd

    1989-01-01

    The complex [CrI(CO)5I] is characterized by a long-wavelength absorption at ?max 638 nm. This band is assigned to a ligand to metal charge transfer (LMCT) transition from iodide (?) to CrI (t2g). Upon LMCT excitation the complex undergoes a photoredox reaction with a quantum yield ? 0.01 according to the equation: [CrI(CO)5I] + CH3CN ? [Cr0(CO)5CH3CN] + I/2 I2. This reaction takes place also thermally.

  7. Excited state intramolecular charge transfer reaction in 4-(1-azetidinyl)benzonitrile: Solvent isotope effects

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Piue Ghoshal; Ranjit Biswas

    2009-01-01

    Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several other properties such as quantum yield and radiative rates have been found to be insensitive to the solvent isotope substitution in all these solvents. The origin of the solvent isotope insensitivity of the reaction is discussed and correlated with the observed slowing down of the solvation dynamics upon isotope substitution.

  8. Nonlinear Ultrafast Spectroscopy of Electron and Energy Transfer in Molecule Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Mukamel, Shaul

    2006-02-09

    The proposed research program will focus on the development of a unified dynamical theoretical framework for calculating the optical response of molecular assemblies and applying it towards studying the interplay of energy and charge transfer in artificial chromophore-aggregate complexes. Applications will be made to poly (p phenylene vinylene), (PPV) oligomers, several families of stilbenoid aggregates with stacking through a cyclophane group, coupled porphyrin arrays, and energy funneling in phenylacetylene dendrimers. The approach is based on formulating the problem using the density- matrix and developing Liouville-space techniques which provide physical insight and are particularly suitable for computing both coherent and incoherent transport. A physical picture based on collective electronic normal modes which represent the dynamics of the optically-driven reduced single electron density matrix will be established. Femtosecond signals and optical properties will be directly related to the motions of electron-hole pairs in real space, completely avoiding the calculation of many-electron excited-state wavefunctions, thus, considerably reducing computational effort. Vibrational and solvent effects will be incorporated. Guidelines for the synthesis of new donor/bridge/acceptor molecules with desired properties such as carrier transport, optical response time scales and fluorescence quantum yields will be developed. The analogy with Thz emission spectroscopy which probes charge carrier dynamic is in semiconductor superlattices will be explored. A systematic procedure for identifying the electronic coherence sizes which control the transport and optical properties will be developed. Localization of electronic transition density matrices of large molecules will be used to break the description of their optical response into coupled chromophores. The proposal is divided into four parts: (i) Collective-Oscillator Representation of Electronic Excitations in Molecular Assemblies; (ii) Nonlinear Optical Spectroscopy of Coupled Chromophores; (iii) Long-Range Electron Transfer and Transport in Solvents with Complex Spectral Densities; (iv) Probing Exciton-Migration by Coherent Femtosecond Spectroscopies.

  9. Photocurrent generation by direct electron transfer using photosynthetic reaction centres

    International Nuclear Information System (INIS)

    Photosynthetic reaction centres (RCs) convert light into separated charges with nearly perfect quantum efficiency, and have been used to generate photocurrent. Previous work has shown that electron tunnelling rates between redox centres in proteins depend exponentially on the tunnelling distance. In this work the RC from Rhodobacter sphaeroides was genetically modified with the aim of achieving the shortest tunnelling distances yet demonstrated between the RC's electron-accepting P site and underlying graphite and gold electrodes, and between the electron donor Q site and graphite electrodes. Opposite charges are carried to counter electrodes using mobile mediators, as in dye-sensitised solar cells. Native RCs are bound to graphite surfaces through N-(1-pyrene)iodoacetamide. Although the linker's length is only 4 Å, the electron transfer pathway between the Q electron donor site on the RC and the electrode surface is still too large for current to be significant. A mutant version with the electron acceptor P side close to the graphite surface produced currents of 15 nA cm?2 upon illumination. Direct binding of RCs to a gold surface is shown, resulting in currents of 5 nA cm?2. In both cases the current was unaffected by mediator concentration but increased with illumination, suggesting that direct electron transfer was achieved. The engineering of an RC to achieve direct electron transfer will help with long term efforts to demonstrate RC-based photovoltaic devices

  10. DFT and time-resolved IR investigation of electron transfer between photogenerated 17- and 19-electron organometallic radicals

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James B.; Kling, Matthias F.; Sawyer, Karma R.; Andersen, Lars K.; Harris, Charles B.

    2008-04-30

    The photochemical disproportionation mechanism of [CpW(CO){sub 3}]{sub 2} in the presence of Lewis bases PR{sub 3} was investigated on the nano- and microsecond time-scales with Step-Scan FTIR time-resolved infrared spectroscopy. 532 nm laser excitation was used to homolytically cleave the W-W bond, forming the 17-electron radicals CpW(CO){sub 3} and initiating the reaction. With the Lewis base PPh{sub 3}, disproportionation to form the ionic products CpW(CO){sub 3}PPh{sub 3}{sup +} and CpW(CO){sub 3}{sup -} was directly monitored on the microsecond time-scale. Detailed examination of the kinetics and concentration dependence of this reaction indicates that disproportionation proceeds by electron transfer from the 19-electron species CpW(CO){sub 3}PPh{sub 3} to the 17-electron species CpW(CO){sub 3}. This result is contrary to the currently accepted disproportionation mechanism which predicts electron transfer from the 19-electron species to the dimer [CpW(CO){sub 3}]{sub 2}. With the Lewis base P(OMe){sub 3} on the other hand, ligand substitution to form the product [CpW(CO){sub 2}P(OMe){sub 3}]{sub 2} is the primary reaction on the microsecond time-scale. Density Functional Theory (DFT) calculations support the experimental results and suggest that the differences in the reactivity between P(OMe){sub 3} and PPh{sub 3} are due to steric effects. The results indicate that radical-to-radical electron transfer is a previously unknown but important process for the formation of ionic products with the organometallic dimer [CpW(CO){sub 3}]{sub 2} and may also be applicable to the entire class of organometallic dimers containing a single metal-metal bond.

  11. Electronic excitation of H2 by positron impact using the CCA

    International Nuclear Information System (INIS)

    The close coupling approximation has been employed in positron-hydrogen molecule collision in the fixed nuclei formulation to obtain the electronic excitation cross section of the B 1?u+ state up to the incident energy 75 eV. The elastic cross sections are found to be influenced significantly when compared with the static results. The effect of the excited state on the elastic channel enhances the elastic cross section. In the absence of any other theoretical results or measured values, excitation cross sections are compared with the corresponding electron results. (author)

  12. Electron-impact multiple ionization of Baq+ ions (1?q?13) via resonant 3d excitation

    International Nuclear Information System (INIS)

    One ionization mechanism of barium ions is the resonant excitation of a 3d inner-shell electron with the subsequent decay of the resulting highly excited intermediate state by multiple autoionization processes. We have experimentally studied this process by observing associated resonance structures - in the energy range 700-800 eV - in the multiple (up to sevenfold) ionization cross-sections of Baq+ ions with 1?q?13. The 3d-resonance strength is determined quantitatively as a function of initial and final ion charge state. The results suggest a statistical description of multiple ionization via the excitation of inner-shell electrons

  13. Intersystem collisional transfer of excitation in the mesosphere and in the laboratory. Final report, 3 November 1983-31 December 1986

    Energy Technology Data Exchange (ETDEWEB)

    Benesch, W.; Carragher, B.; Morrill, J.

    1987-03-01

    The report describes a program of experimentation involving the emission spectra of auroral species and the processes and mechanisms leading to the production of their spectra. Emphasis is on the temporal evolution of the spectrum, particularly as brought about by the intersystem collisional transfer of excitation. This latter process becomes important in auroral spectra at or near mesospheric altitudes where the collision frequency becomes comparable with the transition probability from the excited state of the auroral emitter. The experiments have been undertaken in several modes, but in every case the observational technique is that of time-resolved spectroscopy by means of which we are able to detect changes in the emitted spectrum of a collision-by-collision basis. Previously unreported effects are described which fall in the category of molecular excitation energy storage and release. Examples are given of possible superradiance where particular vibrational levels of molecular nitrogen become temporarily overpopulated with respect to those in adjacent electronic states.

  14. [Solvent effect of europium (III) complex sensitized by charge transfer excited state of functional cation].

    Science.gov (United States)

    Fu, Shi-rong; Shi, Meng; Han, Pei-gao; Zhang, Bei-bei; Yan, Ke-zhu

    2013-09-01

    Abstract In the novel europium (IIl) complex of the form [Eu(tta)4 . DEASPI], the sensitization of lanthanide luminescence is via functional cation The photophysical sensitization process of Eu(tta)4 . DEASPI involves an energy transfer from charge transfer excited state of hemicyanine (aminostyrylpyridinium) cation, and the sensitization mechanism follows Förster resonance energy mechanism. The solvent effect on this new kind of europium (III) complex was investigated in the present work. The europium (III) complex was dissolved in a variety of solvents, i.e., acetone, DMF, ethanol and acetonitrile, and the emission intensity of europium (III) complex in acetonitrile is much higher than in other solvents. The detailed discussion about solvent effect is provided in this paper. PMID:24369661

  15. Environmental correlation effects on excitation energy transfer in photosynthetic light harvesting

    CERN Document Server

    Sarovar, Mohan; Whaley, K Birgitta

    2009-01-01

    Several recent studies of energy transfer in photosynthetic light harvesting complexes have revealed a subtle interplay between coherent and decoherent dynamic contributions to the overall transfer efficiency in these open quantum systems. In this work we systematically investigate the impact of temporal and spatial correlations in environmental fluctuations on excitation transport in the Fenna-Matthews-Olson photosynthetic complex. We demonstrate that the exact nature of the correlations can have a large impact on the efficiency of light harvesting. In particular, we find that spatial correlations can enhance coherences in the site basis while at the same time slowing transport, and that the overall efficiency of transport is maximized at a finite temporal correlation that results in optimal driving of transitions between excitonic states.

  16. Coherent excitation transferring via dark state in light-harvesting process

    CERN Document Server

    Dong, H; Sun, C P

    2011-01-01

    We study the light absorption and energy transferring in a donor-acceptor system with a bionic structure. In the optimal case with uniform couplings, it is found that the quantum dynamics of this seemingly complicated system is reduced as a three-level system of $\\Lambda$-type. With this observation, we show that the dark state based electromagnetically-induced transparency (EIT) effect could enhance the energy transfer efficiency, through a quantum interference effect suppressing the excited population of the donors. We estimate the optimal parameters of the system to achieve the maximum output power. The splitting behavior of maximum power may be used to explain the phenomenon that the photosynthesis systems mainly absorb two colors of light.

  17. Contribution of electronically excited states to the radiation chemistry of organic systems. Progress report, July 1, 1985-February 28, 1986

    International Nuclear Information System (INIS)

    The attachment of thermal electrons by cyclic perfluorocarbons has been shown to enhance the photocurrent from TMPD in solvents in which the electron thermalization range is low. The effect has been studied with perfluorodecalin and perfluoromethylcyclohexane in n-pentane and n-hexane as a function of scavenger concentration, excitation energy and applied electric field strength. The mechanism of the effect suggests a technique for separating epithermal from thermal electron scavenging processes. Contact charge transfer absorption maxima have been located in six hydrocarbon-cyclic perfluorocarbon systems, and correlate well with the known gas-phase ionization potentials of the hydrocarbon. Concentration studies indicate one to one complexes when the hydrocarbon is dissolved in a perfluorocarbon solvent. Fluorescence quantum yields and fluorescence spectra have been obtained for cyclopentane, cycloheptane, cyclooctane, cyclodecane and a number of their alkyl derivatives

  18. Electron capture and excitation in slow H+ + He*(n) collisions

    International Nuclear Information System (INIS)

    Electron capture and excitation (de-excitation) processes in slow collisions of protons with excited helium, H++He*(1s, NL)?H*(nl)+He+(1s) or ?H++He*(1s, N'L'), are studied by using the close coupling of the states {N, n}=2, 3, 4 within the approach described in a previous paper. At small collision velocities, 106 cm s-17 cm s-1, the cross sections for excitation (de-excitation) are very large, due to the importance of two-step transitions. The coupling of the states with different principal quantum numbers significantly increases the cross sections for electron capture at adiabatically small collision velocities

  19. Electron-impact excitation of Ti{sup 21+} in Debye plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Li, B.W.; Dong, C.Z.; Jiang, J. [College of Physics and Electronics Engineering, Northwest Normal University, Lanzhou, P.R. (China); Wang, J.G. [Institute of Applied Physics and Computational Mathematic, Beijing, P.R. (China)

    2010-08-15

    The plasma screening effect on electron-impact excitation is studied by using the relativistic distorted-wave description and exemplified by the excitation of Ti{sup 21+} ion. The total and differential cross sections for the 1s-2s and 1s-2p excitations are calculated in the energy range from threshold to 5 times threshold energy, and the magnetic sub-level cross sections are also given. Comparison of present calculations with other results, when available, is made. The results show that plasma screening effects decrease the binding energies and broadens the wavefunction of bound states. Continuum wavefunctions are also modified by plasma effects. These effects reduce the electron-impact excitation cross sections and cross sections for excitation to the magnetic sublevels. Particularly, for differential cross sections, we found that it decreases for small angle scattering while it increases at large angle scattering for low energy scattering in plasma environment

  20. Direct evidences for inner-shell electron-excitation by laser induced electron recollision

    CERN Document Server

    Deng, Yunpei; Jia, Zhengmao; Komm, Pavel; Zheng, Yinhui; Ge, Xiaochun; Li, Ruxin; Marcus, Gilad

    2015-01-01

    Extreme ultraviolet (XUV) attosecond pulses, generated by a process known as laser-induced electron recollision, are a key ingredient for attosecond metrology, providing a tool to precisely initiate and probe sub-femtosecond dynamics in the microcosms of atoms, molecules and solids[1]. However, with the current technology, extending attosecond metrology to scrutinize the dynamics of the inner-shell electrons is a challenge, that is because of the lower efficiency in generating the required soft x-ray \\hbar\\omega>300 eV attosecond bursts and the lower absorption cross-sections in this spectral range. A way around this problem is to use the recolliding electron to directly initiate the desired inner-shell process, instead of using the currently low flux x-ray attosecond sources.Such an excitation process occurs in a sub-femtosecond timescale, and may provide the necessary "pump" step in a pump-probe experiment[2]. Here we used a few cycle infrared \\lambda_{0}~1800nm source[3] and observed direct evidences for i...

  1. Heavy particle interference and diffraction in fast electron transfer collisions

    OpenAIRE

    Gudmundsson, Magnus

    2011-01-01

    This thesis presents experimental results from the synchrotron cooler and storage ring CRYRING on charge transfer processes in fast electron transfer collisions using high-resolution cold target recoil-ion momentum spectroscopy. The main focus of these studies was to investigate a key concept of quantum mechanics: the wave-particle duality. One series of experiments has been dedicated to the study of heavy particle de Broglie wave interference due to scattering on a molecular ’double slit’. T...

  2. Study of magnetic excitations in sup(42,44,48)Ca by high-resolution electron scattering

    International Nuclear Information System (INIS)

    In electron scattering experiments with high energy resolution in the nuclei 42Ca, 44Ca, and 48Ca magnetic dipole and quadrupole excitations were looked for. For this at the Darmstadt electron linear accelerator spectra at incident energies E0=30-58 MeV under scattering angles of theta=1050, 1170, and 1650 were taken up at low momentum transfer q-1 and continued at the nucleus 48Ca to larger momentum transfer up to q=1.4 fm-1 at the 350-MeV electron accelerator in Mainz. These measurements led to the discovery of a magnetic dipole transition in 48Ca at the excitation energy Esub(x)=10.23 MeV which is with the transition strength B(M1)up=(3.9+-0.3) ?sub(N)2 the strongest M1-transition in a nucleus heavier than 28Si. Beside this prominent M1-excitation in 48Ca further weaker magnetic dipole transitions are observed. Also in 42Ca and 44Ca a strong fragmentation of the M1 strength occurs. While in 44Ca and 48Ca scattering experiments with electrons and protons yield agreeing results for Jsup(?)=1+ states in 42Ca in the electron scattering the excitation of a Jsup(?)=1+ state at Esub(x)=11.24 MeV is observed which is not populated in (p, n) and (p, p') experiments. The magnetic quadrupole strength in the calcium isotopes exhibits a similarly strong fragmentation as the M1-strength. With the results of an earlier work on 48Ca up to Esub(x)=17 MeV the M2 sum strength exhausts 23% of an energy-weighted sum rule. In 42Ca and 44Ca at Esub(x)=9.75 and 14.43 MeV the excitation of the Jsup(?); T=2-; Tsub(>) analog states of the ground states of 42K and 44K is observed. (orig./HSI)

  3. Methods, algorithms and computer codes for calculation of electron-impact excitation parameters

    CERN Document Server

    Bogdanovich, P; Stonys, D

    2015-01-01

    We describe the computer codes, developed at Vilnius University, for the calculation of electron-impact excitation cross sections, collision strengths, and excitation rates in the plane-wave Born approximation. These codes utilize the multireference atomic wavefunctions which are also adopted to calculate radiative transition parameters of complex many-electron ions. This leads to consistent data sets suitable in plasma modelling codes. Two versions of electron scattering codes are considered in the present work, both of them employing configuration interaction method for inclusion of correlation effects and Breit-Pauli approximation to account for relativistic effects. These versions differ only by one-electron radial orbitals, where the first one employs the non-relativistic numerical radial orbitals, while another version uses the quasirelativistic radial orbitals. The accuracy of produced results is assessed by comparing radiative transition and electron-impact excitation data for neutral hydrogen, helium...

  4. Numerical modeling of fast electron energy transfer

    International Nuclear Information System (INIS)

    In this paper methods of calculating energy transport by fast electrons that are currently used in the ''Diana'' program are described; this program is intended to address issues in laser thermonuclear fusion. A method is proposed for solving a kinetic equation which has the following properties: conservativeness, the absence of constraints on the grid spacing relation, monitonicity, and second order approximation. The applicability of a ''front-back'' approximation is analyzed

  5. Back-action-induced excitation of electrons in a silicon quantum dot with a single-electron transistor charge sensor

    International Nuclear Information System (INIS)

    Back-action in the readout of quantum bits is an area that requires a great deal of attention in electron spin based-quantum bit architecture. We report here back-action measurements in a silicon device with quantum dots and a single-electron transistor (SET) charge sensor. We observe the back-action-induced excitation of electrons from the ground state to an excited state in a quantum dot. Our measurements and theoretical fitting to the data reveal conditions under which both suitable SET charge sensor sensitivity for qubit readout and low back-action-induced transition rates (less than 1?kHz) can be achieved

  6. Electron transfer statistics and thermal fluctuations in molecular junctions

    International Nuclear Information System (INIS)

    We derive analytical expressions for probability distribution function (PDF) for electron transport in a simple model of quantum junction in presence of thermal fluctuations. Our approach is based on the large deviation theory combined with the generating function method. For large number of electrons transferred, the PDF is found to decay exponentially in the tails with different rates due to applied bias. This asymmetry in the PDF is related to the fluctuation theorem. Statistics of fluctuations are analyzed in terms of the Fano factor. Thermal fluctuations play a quantitative role in determining the statistics of electron transfer; they tend to suppress the average current while enhancing the fluctuations in particle transfer. This gives rise to both bunching and antibunching phenomena as determined by the Fano factor. The thermal fluctuations and shot noise compete with each other and determine the net (effective) statistics of particle transfer. Exact analytical expression is obtained for delay time distribution. The optimal values of the delay time between successive electron transfers can be lowered below the corresponding shot noise values by tuning the thermal effects

  7. Measurements and analysis of excitation coefficients and secondary electron yields in Townsend dark discharges

    International Nuclear Information System (INIS)

    In this paper, we review our study of excitation coefficients in rare gases and in methane, some of the excitation cross sections that were obtained, the spatial profiles of emission (with absolute calibration) and secondary electron yields. The data for excitation coefficients have been analysed to produce the cross section data in some cases. The spatial profiles of emission at the low currents were used to establish the importance of the non-hydrodynamic relaxation and the contributions of heavy particles and reflected electrons. These data were also used to get more reliable secondary electron yields for rare gases. The spatial emission profiles at higher currents have been applied to obtain field profiles and make comparisons with hybrid models. In particular, we present in this paper, the emission coefficients in krypton and we discuss the wide range of interconnected applications of excitation coefficients and spatial emission profiles

  8. Electron impact excitation of helium in Debye plasma

    Energy Technology Data Exchange (ETDEWEB)

    Diallo, S.; Gomis, L.; Faye, I. G.; Tall, M. S.; Diédhiou, I. [Département de Physique, Faculté des Sciences and Techniques, Université Cheikh Anta Diop, Dakar-Fann (Senegal); Diatta, C. S. [Institut International des Sciences et de Technologie, 28 Avenue des Ambassadeurs Dakar-Fann (Senegal); Zammit, M. [ARC Centre for Antimatter-Matter Studies, Curtin University, GPO Box U1987, Perth, Western Australia 6845 (Australia)

    2015-03-15

    The probability, differential, and integral scattering cross sections of the 1{sup 1}S?2{sup 1}S and 1{sup 1}S?2{sup 1}P transitions of helium have been calculated in the first Born approximation. The projectile-target interactions depending on the temperature and the density of plasma are described by the Debye-Hückel model. Wave functions of the target before and after collision were modeled by non orthogonal Hartree-Fock orbitals. The wave functions parameters are calculated with the Ritz variational method. We improve our unscreened first Born approximation integral cross sections by using the BE-scaled (B stands for binding energy and E excitation energy) method. The second Born approximation has also been used to calculate the excitation cross sections in Debye plasma. Our calculations are compared to other theoretical and experimental results where applicable.

  9. Electron impact excitation of helium in Debye plasma

    Science.gov (United States)

    Diallo, S.; Gomis, L.; Faye, I. G.; Tall, M. S.; Diédhiou, I.; Diatta, C. S.; Zammit, M.

    2015-03-01

    The probability, differential, and integral scattering cross sections of the 11S ?21S and 11S ?21P transitions of helium have been calculated in the first Born approximation. The projectile-target interactions depending on the temperature and the density of plasma are described by the Debye-Hückel model. Wave functions of the target before and after collision were modeled by non orthogonal Hartree-Fock orbitals. The wave functions parameters are calculated with the Ritz variational method. We improve our unscreened first Born approximation integral cross sections by using the BE-scaled (B stands for binding energy and E excitation energy) method. The second Born approximation has also been used to calculate the excitation cross sections in Debye plasma. Our calculations are compared to other theoretical and experimental results where applicable.

  10. Photoinduced electron transfer in some photosensitive molecules-incorporated semiconductor/zeolites: New photocatalytic systems

    Indian Academy of Sciences (India)

    Minjoong Yoon; Devendra P S Negi

    2002-12-01

    An intramolecular charge transfer (ICT) molecule, -N,N-dimethylaminobenzoic acid (DMABA) has been studied in zeolite and colloidal media. The ratio of ICT to normal emission (ICT/LE) is greatly enhanced in zeolites compared to that in polar solvents. The ICT emission of DMABA was quenched by increasing the concentration of TiO2 colloids, while the normal emission was slightly enhanced. Upon illumination of the heteropoly acid (HPA) incorporated TiO2 colloids, interfacial electron transfer takes place from the conduction band of TiO2 to the incorporated HPA which is also excited to catalyze the photoreduction of Methyl Orange. It is found that the interfacial electron transfer mechanism of HPA/TiO2 is quite analogous to the Z-scheme mechanism for plant photosynthetic systems. In DMABA-adsorbed TiO2/Y-zeolite the ICT/LE ratio of DMABA is quite small implying that electron transfer takes place from DMABA to the conduction band of TiO2. This results in drastic enhancement in the photocatalytic activity of DMABA-adsorbed TiO2/Y-zeolite compared to free TiO2/Y-zeolite.

  11. Marcus Electron Transfer Reactions with Bulk Metallic Catalysis

    CERN Document Server

    Widom, A; Srivastava, Y N

    2015-01-01

    Electron transfer organic reaction rates are considered employing the classic physical picture of Marcus wherein the heats of reaction are deposited as the energy of low frequency mechanical oscillations of reconfigured molecular positions. If such electron transfer chemical reaction events occur in the neighborhood of metallic plates, then electrodynamic interface fields must also be considered in addition to mechanical oscillations. Such electrodynamic interfacial electric fields in principle strongly effect the chemical reaction rates. The thermodynamic states of the metal are unchanged by the reaction which implies that metallic plates are purely catalytic chemical agents.

  12. Electron Transfer Dissociation Mass Spectrometry of Hemoglobin on Clinical Samples

    Science.gov (United States)

    Coelho Graça, Didia; Lescuyer, Pierre; Clerici, Lorella; Tsybin, Yury O.; Hartmer, Ralf; Meyer, Markus; Samii, Kaveh; Hochstrasser, Denis F.; Scherl, Alexander

    2012-10-01

    A mass spectrometry-based assay combining the specificity of selected reaction monitoring and the protein ion activation capabilities of electron transfer dissociation was developed and employed for the rapid identification of hemoglobin variants from whole blood without previous proteolytic cleavage. The analysis was performed in a robust ion trap mass spectrometer operating at nominal mass accuracy and resolution. Subtle differences in globin sequences, resulting with mass shifts of about one Da, can be unambiguously identified. These results suggest that mass spectrometry analysis of entire proteins using electron transfer dissociation can be employed on clinical samples in a workflow compatible with diagnostic applications.

  13. Electron-photon polarization correlation study of Ne, Ar and Kr excitation by electron impact

    International Nuclear Information System (INIS)

    The electron impact excitation of the 3s' [1/2]01 state in neon, the 4s' [1/2]O1 state in argon and the 5s[3/2]01 state in krypton have been studied using the electron-photon polarization correlation technique. The two linear coherence parameters P1 and P2 have been measured and the alignment angle ? and the linear polarization P+lin of the angular part of the collisionally induced excited state charge cloud were extracted from the measured P1 and P2 parameters. The authors measured P1 and P2 in neon at an impact energy of 50 eV, in argon at impact energies of 50 eV, 40 eV, 30 eV and 25 eV, and in krypton at impact energies of 50 eV and 30 eV and electron scattering angles up to 55 degrees in all cases. A comparison with theoretical predictions from first-order perturbative theories such as a Distorted Wave Born Approximation (DWBA) and a First Order Many Body Theory (FOMBT) was made. At 50 eV in neon and argon, the agreement between experiment and theory is generally good at small scattering angles up to 25 degrees and somewhat poorer at larger scattering angles. At 50 eV in krypton, the agreement between experiment and theory is generally good at scattering angles up to 40 degrees. The measurements in argon (40 eV, 30 eV, and 25 eV) generally follow the trend of the theoretical predictions, but it was found that the experimentally measured coherence parameters appear to be shifted towards larger scattering angles compared to the theoretical predictions as the impact energy is decreased. At 30 eV in krypton, very good agreement between experiment and theory was found over the entire range of electron scattering angles (up to 55 degrees). The level of agreement between experiment and theory indicates that the DWBA and FOMBT appear to provide a better description of the collision process for a more complex target

  14. Electron transfer and fragmentation in fullerene collisions

    OpenAIRE

    Zettergren, Henning

    2005-01-01

    In this thesis, we present results from detailed gas phase studies of intrinsic properties of fullerenes (C60) and clusters of fullerenes as probed by slow multiply charged (atomic or cluster) ions in combination with coincidence time-of-flight mass spectrometry. We have investigated the structures, stabilities, and the electron mobilities of multiply charged clusters of fullerenes, (C60)nr+ (r=2-5). We found that the (C60)nr+ cluster ions are weakly bound by van der Waals forces and the elec...

  15. The investigation of excited state proton transfer mechanism in water-bridged 7-azaindole.

    Science.gov (United States)

    Zhang, Yong-Jia; Zhao, Jin-Feng; Li, Yong-Qing

    2016-01-15

    Based on the time-dependent density functional theory (TDDFT), the excited-state intermolecular proton transfer (ESIPT) mechanism of water-bridged 7-azaindole has been investigated theoretically. The calculations of primary bond lengths and the IR vibrational spectra between the S0 state and the S1 state that verified the intramolecular hydrogen bond were strengthened. The fact that reproduced experimental absorbance and fluorescence emission spectra well theoretically demonstrate that the TDDFT theory we adopted is reasonable and effective. In addition, intramolecular charge transfer based on the frontier molecular orbitals demonstrated the indication of the ESIPT reaction. The constructed potential energy curves of ground state and the first excited state based on keeping the H2···O3 and H6···N7 distances fixed at a series of values have been used to illustrate the ESIPT process. A relative lower barrier of 5.94kcal/mol in the S1 state potential energy curve for type II (lower than that of 9.82kcal/mol in the S1 state for type I) demonstrates that type II ESIPT process occurs firstly in 7Al-2H2O complex. PMID:26301539

  16. T-3 electron-beam-excited laser system

    International Nuclear Information System (INIS)

    A laser system specifically designed to study the kinetics of electron-beam driven systems is described. Details of the system are given along with measurements of the electron-beam uniformity and deposition in the laser medium. Some HF laser results obtained with this system are also given

  17. Excitation of the surface flute waves in electron cyclotron frequency range by internal rotating electron beam in a coaxial waveguide

    Science.gov (United States)

    Blednov, O.; Girka, I.; Girka, V.; Pavlenko, I.; Sydora, R.

    2014-12-01

    The initial stage of interaction between a gyrating beam of electrons, which move along Larmor orbits in a narrow gap between a cylindrical plasma layer and an internal screen of a metal coaxial waveguide and electromagnetic eigen waves, is studied theoretically. These waves are extraordinary polarized ones; they propagate along the azimuthal angle across an axial external steady magnetic field in the electron cyclotron frequency range. The numerical analysis shows that the excitation process is stable enough in respect to changing plasma waveguide parameters. The wider the plasma layer, the broader the range of plasma waveguide parameters within which effective wave excitation takes place. The main influence on the excitation of these modes is performed by the applied axial magnetic field, namely: its increase leads to an increase of growth rate and a broadening of the range of the waveguide parameters within which wave excitation is effective.

  18. Excitation energy transfer in natural photosynthetic complexes and chlorophyll trefoils: hole-burning and single complex/trefoil spectroscopic studies

    Energy Technology Data Exchange (ETDEWEB)

    Ryszard Jankowiak, Kansas State University, Department of Chemistry, CBC Bldg., Manhattan KS, 66505; Phone: (785) 532-6785

    2012-09-12

    In this project we studied both natural photosynthetic antenna complexes and various artificial systems (e.g. chlorophyll (Chl) trefoils) using high resolution hole-burning (HB) spectroscopy and excitonic calculations. Results obtained provided more insight into the electronic (excitonic) structure, inhomogeneity, electron-phonon coupling strength, vibrational frequencies, and excitation energy (or electron) transfer (EET) processes in several antennas and reaction centers. For example, our recent work provided important constraints and parameters for more advanced excitonic calculations of CP43, CP47, and PSII core complexes. Improved theoretical description of HB spectra for various model systems offers new insight into the excitonic structure and composition of low-energy absorption traps in very several antenna protein complexes and reaction centers. We anticipate that better understanding of HB spectra obtained for various photosynthetic complexes and their simultaneous fits with other optical spectra (i.e. absorption, emission, and circular dichroism spectra) provides more insight into the underlying electronic structures of these important biological systems. Our recent progress provides a necessary framework for probing the electronic structure of these systems via Hole Burning Spectroscopy. For example, we have shown that the theoretical description of non-resonant holes is more restrictive (in terms of possible site energies) than those of absorption and emission spectra. We have demonstrated that simultaneous description of linear optical spectra along with HB spectra provides more realistic site energies. We have also developed new algorithms to describe both nonresonant and resonant hole-burn spectra using more advanced Redfield theory. Simultaneous description of various optical spectra for complex biological system, e.g. artificial antenna systems, FMO protein complexes, water soluble protein complexes, and various mutants of reaction centers continues; this work is supported by the new DOE BES grant.

  19. Quantum Mechanical Hysteresis and the Electron Transfer Problem

    CERN Document Server

    Etchegoin, P G

    2004-01-01

    We study a simple quantum mechanical symmetric donor-acceptor model for electron transfer (ET) with coupling to internal deformations. The model contains several basic properties found in biological ET in enzymes and photosynthetic centers; it produces tunnelling with hysteresis thus providing a simple explanation for the slowness of the reversed rate and the near 100% efficiency of ET in many biological systems. The model also provides a conceptual framework for the development of molecular electronics memory elements based on electrostatic architectures.

  20. Carboxylate Shifts Steer Interquinone Electron Transfer in Photosynthesis*

    OpenAIRE

    Chernev, Petko; Zaharieva, Ivelina; Dau, Holger; Haumann, Michael

    2010-01-01

    Understanding the mechanisms of electron transfer (ET) in photosynthetic reaction centers (RCs) may inspire novel catalysts for sunlight-driven fuel production. The electron exit pathway of type II RCs comprises two quinone molecules working in series and in between a non-heme iron atom with a carboxyl ligand (bicarbonate in photosystem II (PSII), glutamate in bacterial RCs). For decades, the functional role of the iron has remained enigmatic. We tracked the iron site using microsecond-resolu...