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Sample records for excited transient molecules

  1. Spectroscopy and reactions of vibrationally excited transient molecules

    Energy Technology Data Exchange (ETDEWEB)

    Dai, H.L. [Univ. of Pennsylvania, Philadelphia (United States)

    1993-12-01

    Spectroscopy, energy transfer and reactions of vibrationally excited transient molecules are studied through a combination of laser-based excitation techniques and efficient detection of emission from the energized molecules with frequency and time resolution. Specifically, a Time-resolved Fourier Transform Emission Spectroscopy technique has been developed for detecting dispersed laser-induced fluorescence in the IR, visible and UV regions. The structure and spectroscopy of the excited vibrational levels in the electronic ground state, as well as energy relaxation and reactions induced by specific vibronic excitations of a transient molecule can be characterized from time-resolved dispersed fluorescence in the visible and UV region. IR emissions from highly vibrational excited levels, on the other hand, reveal the pathways and rates of collision induced vibrational energy transfer.

  2. Electron-excited molecule interactions

    International Nuclear Information System (INIS)

    Christophorou, L.G.; Tennessee Univ., Knoxville, TN

    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 6 to 10 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

  3. Isotope separation using vibrationally excited molecules

    International Nuclear Information System (INIS)

    Woodroffe, J.A.; Keck, J.C.

    1979-01-01

    Vibrational excitation of molecules having components of a selected isotope type is used to produce a conversion from vibrational to translational excitation of the molecules by collision with the molecules of a heavy carrier gas. The resulting difference in translaton between the molecules of the selected isotope type and all other molecules of the same compound permits their separate collection. When applied to uranium enrichment, a subsonic cryogenic flow of molecules of uranium hexafluoride in combination with an argon carrier gas is directed through a cooled chamber that is illuminated by laser radiaton tuned to vibrationally excite the uranium hexafluoride molecules of a specific uranium isotope. The excited molecules collide with carrier gas molecules, causing a conversion of the excitation energy into a translation of the excited molecule, which results in a higher thermal energy or diffusivity than that of the other uranium hexafluoride molecules. The flowing molecules including the excited molecules directly enter a set of cryogenically cooled channels. The higher thermal velocity of the excited molecules increases the probability of their striking a collector surface. The molecules which strike this surface immediately condense. After a predetermined thickness of molecules is collected on the surface, the flow of uranium hexafluoride is interrupted and the chamber heated to the point of vaporization of the collected hexafluoride, permitting its removal. (LL)

  4. Vibrational-rotational excitation: chemical reactions of vibrationally excited molecules

    International Nuclear Information System (INIS)

    Moore, C.B.; Smith, I.W.M.

    1979-03-01

    This review considers a limited number of systems, particularly gas-phase processes. Excited states and their preparation, direct bimolecular reactions, reactions of highly excited molecules, and reactions in condensed phases are discussed. Laser-induced isotope separation applications are mentioned briefly. 109 references

  5. Isotope separation using vibrationally excited molecules

    International Nuclear Information System (INIS)

    Woodroffe, J.A.; Keck, J.C.

    1977-01-01

    A system for isotope separation or enrichment wherein molecules of a selected isotope type in a flow of molecules of plural isotope types are vibrationally excited and collided with a background gas to provide enhanced diffusivity for the molecules of the selected isotope type permitting their separate collection. The system typically is for the enrichment of uranium using a uranium hexafluoride gas in combination with a noble gas such as argon. The uranium hexafluoride molecules having a specific isotope of uranium are vibrationally excited by laser radiation. The vibrational energy is converted to a translation energy upon collision with a particle of the background gas and the added translation energy enhances the diffusivity of the selected hexafluoride molecules facilitating its condensation on collection surfaces provided for that purpose. This process is periodically interrupted and the cryogenic flow halted to permit evaporation of the collected molecules to provide a distinct, enriched flow

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

    CERN Document Server

    Lim, Edward C

    2013-01-01

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

  7. Studies of interstellar vibrationally-excited molecules

    International Nuclear Information System (INIS)

    Ziurys, L.M.; Snell, R.L.; Erickson, N.R.

    1986-01-01

    Several molecules thus far have been detected in the ISM in vibrationally-excited states, including H 2 , SiO, HC 3 N, and CH 3 CN. In order for vibrational-excitation to occur, these species must be present in unusually hot and dense gas and/or where strong infrared radiation is present. In order to do a more thorough investigation of vibrational excitation in the interstellar medium (ISM), studies were done of several mm-wave transitions originating in excited vibrational modes of HCN, an abundant interstellar molecule. Vibrationally-excited HCN was recently detected toward Orion-KL and IRC+10216, using a 12 meter antenna. The J=3-2 rotational transitions were detected in the molecule's lowest vibrational state, the bending mode, which is split into two separate levels, due to l-type doubling. This bending mode lies 1025K above ground state, with an Einstein A coefficient of 3.6/s. The J=3-2 line mode of HCN, which lies 2050K above ground state, was also observed toward IRC+10216, and subsequently in Orion-KL. Further measurements of vibrationally-excited HCN were done using a 14 meter telescope, which include the observations of the (0,1,0) and (0,2,0) modes towards Orion-KL, via their J=3-2 transitions at 265-267 GHz. The spectrum of the J=3-2 line in Orion taken with the 14 meter telescope, is shown, along with a map, which indicates that emission from vibrationally-excited HCN arises from a region probably smaller than the 14 meter telescope's 20 arcsec beam

  8. Photodissociation and excitation of interstellar molecules

    International Nuclear Information System (INIS)

    Dishoeck, E.F. van.

    1984-01-01

    Apart from a rather long introduction containing some elementary astrophysics, quantum chemistry and spectroscopy and an incomplete, historical review of molecular observations, this thesis is divided into three sections. In part A, a rigorous quantum chemical and dynamical study is made of the photodissociation processes in the OH and HCl molecules. In part B, the cross sections obtained in part A are used in various astrophysical problems such as the study of the abundances of the OH and HCl molecules in interstellar clouds, the use of the OH abundance as a measure of the cosmic ray ionization rate, the lifetime of the OH radical in comets and the abundance of OH in the solar photosphere. Part C discusses the excitation of the C 2 molecule under interstellar conditions, its use as a diagnostic probe of the temperature, density and strength of the radiation field in interstellar clouds. Quadrupole moments and oscillator strengths are analyzed. (Auth.)

  9. The photodissociation and reaction dynamics of vibrationally excited molecules

    Energy Technology Data Exchange (ETDEWEB)

    Crim, F.F. [Univ. of Wisconsin, Madison (United States)

    1993-12-01

    This research determines the nature of highly vibrationally excited molecules, their unimolecular reactions, and their photodissociation dynamics. The goal is to characterize vibrationally excited molecules and to exploit that understanding to discover and control their chemical pathways. Most recently the author has used a combination of vibrational overtone excitation and laser induced fluorescence both to characterize vibrationally excited molecules and to study their photodissociation dynamics. The author has also begun laser induced grating spectroscopy experiments designed to obtain the electronic absorption spectra of highly vibrationally excited molecules.

  10. Electron Impact Excitation-Ionization of Molecules

    Science.gov (United States)

    Ali, Esam Abobakr A.

    In the last few decades, the study of atomic collisions by electron-impact has made significant advances. The most difficult case to study is electron impact ionization of molecules for which many approximations have to be made and the validity of these approximations can only be checked by comparing with experiment. In this thesis, I have examined the Molecular three-body distorted wave (M3DW) or Molecular four-body distorted wave (M4DW) approximations for electron-impact ionization. These models use a fully quantum mechanical approach where all particles are treated quantum mechanically and the post collision interaction (PCI) is treated to all orders of perturbation. These electron impact ionization collisions play central roles in the physics and chemistry of upper atmosphere, biofuel, the operation of discharges and lasers, radiation induced damage in biological material like damage to DNA by secondary electrons, and plasma etching processes. For the M3DW model, I will present results for electron impact single ionization of small molecules such as Water, Ethane, and Carbon Dioxide and the much larger molecules Tetrahydrofuran, phenol, furfural, 1-4 Benzoquinone. I will also present results for the four-body problem in which there are two target electrons involved in the collision. M4DW results will be presented for dissociative excitation-ionization of orientated D2. I will show that M4DW calculations using a variational wave function for the ground state that included s- and p- orbital states give better agreement to the experimental measurements than a ground state approximated as a product of two 1s-type Dyson orbitals.

  11. Isotope separation using vibrationally excited molecules

    International Nuclear Information System (INIS)

    1979-01-01

    This invention relates to isotope separation employing isotopically selective vibrational excitation and vibration-translation reactions of the excited particles. Uranium enrichment, using uranium hexafluoride, is a particular embodiment. (U.K.)

  12. Core excitation and de-excitation spectroscopies of free atoms and molecules

    International Nuclear Information System (INIS)

    Ueda, Kiyoshi

    2006-01-01

    This article provides a review of the current status of core excitation and de-excitation spectroscopy studies of free atoms molecules using a high-resolution soft X-ray monochromator and a high-resolution electron energy analyzer, installed in the soft X-ray photochemistry beam line at SPring-8. Experimental results are discussed for 1s excitation of Ne, O 1s excitation of CO and H 2 O, and F 1s excitation of CF 4 . (author)

  13. Excitation of neutron flux waves in reactor core transients

    International Nuclear Information System (INIS)

    Carew, J.F.; Neogy, P.

    1983-01-01

    An analysis of the excitation of neutron flux waves in reactor core transients has been performed. A perturbation theory solution has been developed for the time-dependent thermal diffusion equation in which the absorption cross section undergoes a rapid change, as in a PWR rod ejection accident (REA). In this analysis the unperturbed reactor flux states provide the basis for the spatial representation of the flux solution. Using a simplified space-time representation for the cross section change, the temporal integrations have been carried out and analytic expressions for the modal flux amplitudes determined. The first order modal excitation strength is determined by the spatial overlap between the initial and final flux states, and the cross section perturbation. The flux wave amplitudes are found to be largest for rapid transients involving large reactivity perturbations

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-12-01

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

  15. Multiply excited molecules produced by photon and electron interactions

    International Nuclear Information System (INIS)

    Odagiri, T.; Kouchi, N.

    2006-01-01

    The photon and electron interactions with molecules resulting in the formation of multiply excited molecules and the subsequent decay are subjects of great interest because the independent electron model and Born-Oppenheimer approximation are much less reliable for the multiply excited states of molecules than for the ground and lower excited electronic states. We have three methods to observe and investigate multiply excited molecules: 1) Measurements of the cross sections for the emission of fluorescence emitted by neutral fragments in the photoexcitation of molecules as a function of incident photon energy [1-3], 2) Measurements of the electron energy-loss spectra tagged with the fluorescence photons emitted by neutral fragments [4], 3) Measurements of the cross sections for generating a pair of photons in absorption of a single photon by a molecule as a function of incident photon energy [5-7]. Multiply excited states degenerate with ionization continua, which make a large contribution in the cross section curve involving ionization processes. The key point of our methods is hence that we measure cross sections free from ionization. The feature of multiply excited states is noticeable in such a cross section curve. Recently we have measured: i) the cross sections for the emission of the Lyman- fluorescence in the photoexcitation of CH 4 as a function of incident photon energy in the range 18-51 eV, ii) the electron energy-loss spectrum of CH 4 tagged with the Lyman-photons at 80 eV incident electron energy and 10 electron scattering angle in the range of the energy loss 20-45 eV, in order to understand the formation and decay of the doubly excited methane in photon and electron interactions. [8] The results are summarized in this paper and the simultaneous excitation of two electrons by electron interaction is compared with that by photon interaction in terms of the oscillator strength. (authors)

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

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  17. Millimeterwave spectroscopy of transient molecules produced in a ...

    Indian Academy of Sciences (India)

    The construction of a millimeterwave spectrometer to study the pure rotational spectra of transient molecules in the gas phase is presented. The spectrometer is a source-modulated system combined with a free space glass discharge cell. Millimeterwave radiation has been produced using a frequency multiplier, the ...

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

    International Nuclear Information System (INIS)

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

    1985-05-01

    The reactions of electronically excited sodium atoms with simple molecules have been studied in crossed molecular beams experiments. Electronically excited Na(3 2 P/sub 3/2/, 4 2 D/sub 5/2/, and 5 2 S/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

  19. Non-adiabatic rotational excitation of dipolar molecule under the ...

    Indian Academy of Sciences (India)

    J. Chem. Sci. Vol. 125, No. 5, September 2013, pp. 1213–1221. c Indian Academy of Sciences. ... The rotational wave packets of LiCl molecule excited non-adiabatically by half cycle pulse. (HCP) is .... pared to the intensities required for the ionization of ..... out and with delayed ultrashort HCP at different initial pulse dura-.

  20. Neutral molecules in tokamak edge plasma - role of vibrationally excited hydrogen molecules

    International Nuclear Information System (INIS)

    Cadez, I.; Cercek, M.; Pelicon, P.; Razpet, A.

    2003-01-01

    The role of neutral molecules in edge plasma is discussed with special emphasis on the vibrationally excited hydrogen. Neutral molecules are formed mostly by surface processes on the walls and then released to the edge plasma where they take part in volumetric reactions with other particles. Typically these molecules are formed in excited states and data are needed for their reactions on the wall and in the volume. Processes in edge plasma determine particle and energy flux what is especially critical issue in tokamak divertor region. Various cross sections and reaction rates are needed for modelling edge plasma and its interaction with walls. (author)

  1. Study on the excited diatomic molecules of rare gas

    International Nuclear Information System (INIS)

    Kasama, Kunihiko; Arai, Shigeyoshi

    1981-01-01

    The study on the excited diatomic molecules of rare gas is presented. The absorption spectra, the mechanism of formation and attenuation and the reactions with other molecules are described. The excitation of rare gas was made by using a pulsed electron beam generator. The absorption of excited diatomic molecules was measured as the functions of time. Two absorption peaks were observed. The electron states of rare gases were estimated. The observed and calculated transition values were given for each peak. The absorption spectra of Ne change with time. The spectra of Ar do not change with time. Four and eleven absorption maxima were seen in the spectra of Kr and Xe, respectively. In the case of Ar, the thermal equilibrium existed. The constants of the production and attenuation rates were obtained as the functions of Ar gas pressure. In the case of Ne, there wad definitely the time dependence of absorption spectra. The attenuation constant was obtained for each transition between various vibration levels. It is necessary to consider the relaxation from high vibrational levels. The energy transfer between vibrational levels hardly occurred in Ne because the intervals are large. When there are other molecules, the attnuation was accelerated. (Kato, T.)

  2. Excited-State Dynamics of Melamine and Its Lysine Derivative Investigated by Femtosecond Transient Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    Yuyuan Zhang

    2016-11-01

    Full Text Available Melamine may have been an important prebiotic information carrier, but its excited-state dynamics, which determine its stability under UV radiation, have never been characterized. The ability of melamine to withstand the strong UV radiation present on the surface of the early Earth is likely to have affected its abundance in the primordial soup. Here, we studied the excited-state dynamics of melamine (a proto-nucleobase and its lysine derivative (a proto-nucleoside using the transient absorption technique with a UV pump, and UV and infrared probe pulses. For melamine, the excited-state population decays by internal conversion with a lifetime of 13 ps without coupling significantly to any photochemical channels. The excited-state lifetime of the lysine derivative is slightly longer (18 ps, but the dominant deactivation pathway is otherwise the same as for melamine. In both cases, the vast majority of excited molecules return to the electronic ground state on the aforementioned time scales, but a minor population is trapped in a long-lived triplet state.

  3. A study of vibrational relaxation of electronically-excited molecules

    International Nuclear Information System (INIS)

    Datsyuk, V.V.; Izmailov, I.A.; Kochelap, V.A.

    1992-09-01

    The time kinetics of the vibrational relaxation of excimers is studied in the diffusional approximation. Simple formulae for functions of nonstationary vibrational distribution are found for the electronically excited molecules. Some spectral-kinetic dependencies of the excimer luminescence are explained in a new way. The possibilities of the determination of excimer parameters are discussed. The dependence of energetical characteristics of excimer lasers on these parameters is particularly emphasized. (author). 22 refs, 5 figs

  4. Transient absorption study of two-photon excitation mechanism in the LH2 complex from purple bacterium Rhodobacter sphaeroides.

    Science.gov (United States)

    Stepanenko, Ilya; Kompanetz, Viktor; Makhneva, Zoya; Chekalin, Sergey; Moskalenko, Andrei; Razjivin, Andrei

    2012-03-08

    The mechanism of two-photon excitation of a peripheral light-harvesting complex LH2 (B800-850) from purple bacterium Rhodobacter sphaeroides was explained on the basis of femtosecond transient absorption data. Fast bleaching of the B850 absorption band was measured under two-photon excitation by 1350 nm femtosecond pulses, showing fast subpicosecond arrival of excitation energy to B850 circular aggregates. Any spectral changes connected with the B800 absorption band of B800-BChl molecules were absent. A similar picture was observed under one-photon excitation of the LH2 complex by 675 nm femtosecond pulses. We believe these effects may be attributed to direct excitation of high-energy excitonic states of a B850 circular aggregate or its vibrational manifold in accordance with the model of Abe [Chem. Phys. 2001, 264, 355-363].

  5. Ultrafast dynamics of electronically excited molecules and clusters

    International Nuclear Information System (INIS)

    Lietard, Aude

    2014-01-01

    This PhD thesis investigated the ultrafast dynamics of photo-chromic molecules and argon clusters in the gas phase at the femtosecond timescale. Pump-probe experiments are performed in a set-up which associates a versatile pulsed molecular beam coupled to a photoelectron/photoion velocity map imager (VMI) and a time-of-flight mass spectrometer (TOF-MS). Theses pump-probe experiments provides the temporal evolution of the electronic distribution for each system of interest. Besides, a modelization has been performed in order to characterize the density and the velocity distribution in the pulsed beam. Regarding the photo-chromic di-thienyl-ethene molecules, parallel electronic relaxation pathways were observed. This contrasts with the observation of sequential relaxation processes in most molecules studied so far. In the present case, the initial wave packet splits in two parts. One part is driven to the ground state at the femtosecond time scale through a conical intersection, and the second part remains for ps in the excited state and experiences oscillations in a suspended well. This study has shed light into the intrinsic dynamics of the molecules under study and a general relaxation mechanism has been proposed, which applies to the whole family of di-thienyl-ethene molecules whatever the state of matter (gas phase or solution) in which they have been investigated. Concerning argon clusters excited at about 14 eV, two behaviors of different time scale have been observed at different time scales. The first one occurs in the first picoseconds of the dynamics. It corresponds to the electronic relaxation of an excitonic state at a rate of 1 eV.ps -1 . The second phenomenon corresponds to the localization of the exciton on the excimer Ar 2 *. This phenomenon is observed 4-5 ps after the excitation. In this study, we also observed the ejection of excited argon atoms, addressing the lifetime of the delocalized excitonic state. This work provide additional informations

  6. The origin of small and large molecule behavior in the vibrational relaxation of highly excited molecules

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1990-01-01

    An explanation is proposed for the qualitatively different types of behavior that have been reported for the vibrational relaxation of highly excited diatomic and polyatomic molecules. It is argued that all of the diatomic molecules that have been studied in bulk relax adiabatically at room temperature. In contrast, large polyatomic molecules have low frequency modes which act at ''doorway'' modes for the rest of the molecules, producing an impulsive relaxation mechanism. The theoretical work of Nesbitt and Hynes showed that impulsive collisions result in an exponential decay of the average vibrational energy of a Morse oscillator, whereas adiabatic collisions produce nonexponential power law behavior. We propose that this result explains a large body of data for the vibrational relaxation of small and large molecules

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

    NARCIS (Netherlands)

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

    2003-01-01

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

  8. Inner-shell excitation and ionic fragmentation of molecules

    International Nuclear Information System (INIS)

    Hitchcock, A.P.; Tyliszczak, T.; Cavell, R.G.

    1997-01-01

    Inner-shell excitation and associated decay spectroscopies are site specific probes of electronic and geometrical structure and photoionization dynamics. X-ray absorption probes the geometric and electronic structure, while time-of-flight mass spectrometry with multi-coincidence detection provides information on the photofragmentation dynamics of the initially produced inner-shell state. Auger decay of inner-shell excited and ionised states is an efficient source of multiply charged ions. The charge separation and fragmentation of these species, studied by photoelectron-photoion-photoion coincidence (also called charge separation mass spectrometry) gives insights into bonding and electronic structure. In molecules, the dependence of the fragmentation process on the X-ray energy can reveal cases of site and/or state selective fragmentation. At the ALS the authors have examined the soft X-ray spectroscopy and ionic fragmentation of a number of molecules, including carboranes, silylenes, phosphorus halides, SF 6 and CO 2 . Their work is illustrated using results from the carborane and PF 3 studies

  9. Inner-shell excitation and ionic fragmentation of molecules

    Energy Technology Data Exchange (ETDEWEB)

    Hitchcock, A.P.; Tyliszczak, T. [McMaster Univ., Hamilton, Ontario (Canada); Cavell, R.G. [Univ. of Alberta, Edmonton (Canada)] [and others

    1997-04-01

    Inner-shell excitation and associated decay spectroscopies are site specific probes of electronic and geometrical structure and photoionization dynamics. X-ray absorption probes the geometric and electronic structure, while time-of-flight mass spectrometry with multi-coincidence detection provides information on the photofragmentation dynamics of the initially produced inner-shell state. Auger decay of inner-shell excited and ionised states is an efficient source of multiply charged ions. The charge separation and fragmentation of these species, studied by photoelectron-photoion-photoion coincidence (also called charge separation mass spectrometry) gives insights into bonding and electronic structure. In molecules, the dependence of the fragmentation process on the X-ray energy can reveal cases of site and/or state selective fragmentation. At the ALS the authors have examined the soft X-ray spectroscopy and ionic fragmentation of a number of molecules, including carboranes, silylenes, phosphorus halides, SF{sub 6} and CO{sub 2}. Their work is illustrated using results from the carborane and PF{sub 3} studies.

  10. Excited Atoms and Molecules in High Pressure Gas Discharges

    International Nuclear Information System (INIS)

    Vuskovic, L.; Popovic, S.

    2003-01-01

    Various types of high-pressure non-thermal discharges are increasingly drawing attention in view of many interesting applications. These, partially ionized media in non-equilibrium state, tend to generate complex effects that are difficult to interpret without a detailed knowledge of elementary processes involved. Electronically excited molecules and atoms may play an important role as intermediate states in a wide range of atomic and molecular processes, many of which are important in high-pressure discharges. They can serve also as reservoirs of energy or as sources of high energy electrons either through the energy pooling or through superelastic collisions. By presenting the analysis of current situation on the processes involving excited atoms and molecules of interest for high-pressure gas discharges, we will attempt to draw attention on the insufficiency of available data. In the same time we will show how to circumvent this situation and still be able to develop accurate models and interpretations of the observed phenomena

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

    International Nuclear Information System (INIS)

    Lee, Ingu; Pang, Yoonsoo; Lee, Sebok

    2014-01-01

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

  12. Transient computational homogenization for heterogeneous materials under dynamic excitation

    NARCIS (Netherlands)

    Pham, N.K.H.; Kouznetsova, V.; Geers, M.G.D.

    2013-01-01

    This paper presents a novel transient computational homogenization procedure that is suitable for the modelling of the evolution in space and in time of materials with non-steady state microstructure, such as metamaterials. This transient scheme is an extension of the classical (first-order)

  13. Process and system for isotope separation using the selective vibrational excitation of molecules

    International Nuclear Information System (INIS)

    Woodroffe, J.A.; Keck, J.C.

    1976-01-01

    This invention concerns the separation of isotopes by using the isotopically selective vibrational excitation and the vibration-translation reactions of the excited particles. UF 6 molecular mixed with a carrier gas, such as argon, are directed through a refrigerated chamber lighted by a laser radiation tuned to excite vibrationally the uranium hexafluoride molecules of a particular uranium isotope. The density of the carrier gas is preferably maintained above the density of the uranium hexafluoride to allow a greater collision probability of the vibrationally excited molecules with a carried molecule. In such a case, the vibrationally excited uranium hexafluoride will collide with a carrier gas molecule provoking the conversion of the excitation energy into a translation of the excited molecule, resulting in thermal energy or greater diffusibility than that of the other uranium hexafluoride molecules [fr

  14. Reactive scattering of electronically excited alkali atoms with molecules

    International Nuclear Information System (INIS)

    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 - repulsion in Na(5S, 4D) reactions, and by the NaCl-H repulsion in the case of Na(3P). The reaction of Na with O 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 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

  15. Impact Assessment of Various Methods for Control of Synchronous Generator Excitation on Quality of Transient Processes

    Directory of Open Access Journals (Sweden)

    Y. D. Filipchik

    2011-01-01

    Full Text Available The paper considers an impact of various methods for control of an exciting current pertaining to a synchronous generator on the nature of transient processes. A control algorithm for the exciting current in relation to changes in sliding and acceleration of a generator rotor has been proposed in the paper. The algorithm makes it possible to improve quality of the transient processes due to reduction of oscillation range concerning as an active power so a δ-angle as well.

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

    International Nuclear Information System (INIS)

    Ducas, T.W.

    1978-01-01

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

  17. Versatile single-molecule multi-color excitation and detection fluorescence setup for studying biomolecular dynamics

    KAUST Repository

    Sobhy, M. A.; Elshenawy, M. M.; Takahashi, Masateru; Whitman, B. H.; Walter, N. G.; Hamdan, S. M.

    2011-01-01

    Single-molecule fluorescence imaging is at the forefront of tools applied to study biomolecular dynamics both in vitro and in vivo. The ability of the single-molecule fluorescence microscope to conduct simultaneous multi-color excitation

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-05-07

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

  19. selective excitation of vibrational modes of polyatomic molecule

    Indian Academy of Sciences (India)

    Abstract. Mode-selective dynamics of triatomic molecule in the electronic ground state under continuous wave laser pulse is investigated for the discrete vibrational bound states. A non-perturbative approach has been used to analyse the vibrational couplings and dynamics of the molecule. Keywords. Polyatomic molecule ...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-03-15

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

  1. Desorption of large organic molecules by laser-induced plasmon excitation

    International Nuclear Information System (INIS)

    Lee, I.; Callcott, T.A.

    1991-01-01

    Ejection of large organic molecules from surfaces by laser-induced electronic-excited desorption has attracted considerable interest in recent years. In addition to the importance of this effect for fundamental investigations of the ejection process, this desorption technique has been applied to the study of large, fragile molecules by mass spectrometry. In this paper, we present a new method to induce electronic excitation on the metal surface for the desorption of large organic molecules. 3 refs., 3 figs

  2. Features of Chaotic Transients in Excitable Media Governed by Spiral and Scroll Waves

    Science.gov (United States)

    Lilienkamp, Thomas; Christoph, Jan; Parlitz, Ulrich

    2017-08-01

    In excitable media, chaotic dynamics governed by spiral or scroll waves is often not persistent but transient. Using extensive simulations employing different mathematical models we identify a specific type-II supertransient by an exponential increase of transient lifetimes with the system size in 2D and an investigation of the dynamics (number and lifetime of spiral waves, Kaplan-Yorke dimension). In 3D, simulations exhibit an increase of transient lifetimes and filament lengths only above a critical thickness. Finally, potential implications for understanding cardiac arrhythmias are discussed.

  3. Near field imaging of transient collisional excitation x-ray laser

    International Nuclear Information System (INIS)

    Tanaka, Momoko; Kado, Masataka; Hasegawa, Noboru; Kawachi, Tetsuya; Sukegawa, Kouta; Lu, Peixiang; Nagashima, Akira; Kato, Yoshiaki

    2001-01-01

    We observed the spatial profile of the transient collisional excitation Ni-like Ag laser (λ=13.9 nm) for various plasma lengths using the near field imaging method. The gain coefficient of the x-ray laser was estimated as 24 cm -1 . The gain region was a 50 μm crescent shape and included localized high gain areas. (author)

  4. Progressive practice promotes motor learning and repeated transient increases in corticospinal excitability across multiple days

    DEFF Research Database (Denmark)

    Christiansen, Lasse; Madsen, Mads Alexander Just; Bojsen-Møller, Emil

    2018-01-01

    Background: A session of motor skill learning is accompanied by transient increases in corticospinal excitability (CSE), which are thought to reflect acute changes in neuronal connectivity associated with improvements in sensorimotor performance. Factors influencing changes in excitability...... and motor skill with continued practice remain however to be elucidated. Objective/Hypothesis: Here we investigate the hypothesis that progressive motor practice during consecutive days can induce repeated transient increases in corticospinal excitability and promote motor skill learning. Methods: Changes...... in motor performance and CSE were assessed during 4 consecutive days of skill learning and 8 days after the last practice session. CSE was assessed as area under recruitment curves (RC) using transcranial magnetic stimulation (TMS). Two groups of participants (n = 12) practiced a visuomotor tracking...

  5. Picosecond transient absorption spectra of aminosalicylates in confirmation of the triple excitation mechanism

    International Nuclear Information System (INIS)

    Gormin, D.

    1989-01-01

    Using picosecond transient absorption studies, it is shown that the twisted intramolecular charge-transfer state (TICT) and the excited intramolecular proton-transfer state (ESIPT or PT) of specific aminosalicylates both contribute to the long-wavelength fluorescence band, F 2 , observed as an unresolved band to the red of the normal fluorescence band, F 1 . The transient absorption band for 2-hydroxy-4-(dimethylamino)benzoic acid methyl ester (PDASE) is shown to be a composite of the two excited-state absorption modes: S n double-prime(TICT) left-arrow S 1 double-prime (TICT) and S n '(PT)left-arrow S 1 '(PT). This corroborates previous steady-state fluorescence studies of the unresolved F 2 band. The assignments are based on comparison with the excited-state absorption spectra of various substituted aminosalicylates in polar and nonpolar solvents

  6. Spin fine structure of optically excited quantum dot molecules

    Science.gov (United States)

    Scheibner, M.; Doty, M. F.; Ponomarev, I. V.; Bracker, A. S.; Stinaff, E. A.; Korenev, V. L.; Reinecke, T. L.; Gammon, D.

    2007-06-01

    The interaction between spins in coupled quantum dots is revealed in distinct fine structure patterns in the measured optical spectra of InAs/GaAs double quantum dot molecules containing zero, one, or two excess holes. The fine structure is explained well in terms of a uniquely molecular interplay of spin-exchange interactions, Pauli exclusion, and orbital tunneling. This knowledge is critical for converting quantum dot molecule tunneling into a means of optically coupling not just orbitals but also spins.

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

    International Nuclear Information System (INIS)

    Smirnov, Yu.M.

    1998-01-01

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

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

    International Nuclear Information System (INIS)

    Nubbemeyer, T; Eichmann, U; Sandner, W

    2009-01-01

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

  9. Catalytic synthesis of ammonia using vibrationally excited nitrogen molecules

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Henriksen, Niels Engholm; Billing, Gert D.

    1992-01-01

    The dissociation of nitrogen is the rate-limiting step in the catalytic synthesis of ammonia. Theoretical calculations have shown that the dissociative sticking probability of molecular nitrogen on catalytic active metal surfaces is enhanced by orders of magnitude when the molecules...

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

    International Nuclear Information System (INIS)

    Verhaart, G.J.

    1980-01-01

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

  11. Vibrational energy transfer in selectively excited diatomic molecules

    International Nuclear Information System (INIS)

    Dasch, C.J.

    1978-09-01

    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 295 0 K 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 295 0 K 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 ΔJ 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

  12. Investigation of Multiconfigurational Short-Range Density Functional Theory for Electronic Excitations in Organic Molecules

    DEFF Research Database (Denmark)

    Hubert, Mickaël; Hedegård, Erik D.; Jensen, Hans Jørgen Aa

    2016-01-01

    -srDFT for a selected benchmark set of electronic excitations of organic molecules, covering the most common types of organic chromophores. This investigation confirms the expectation that the MC-srDFT method is accurate for a broad range of excitations and comparable to accurate wave function methods such as CASPT2......Computational methods that can accurately and effectively predict all types of electronic excitations for any molecular system are missing in the toolbox of the computational chemist. Although various Kohn-Sham density-functional methods (KS-DFT) fulfill this aim in some cases, they become...... and double excitations have been promising, it is nevertheless important that the accuracy of MC-srDFT is at least comparable to the best KS-DFT methods also for organic molecules that are typically of single-reference character. In this paper we therefore systematically investigate the performance of MC...

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

    International Nuclear Information System (INIS)

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

    2004-01-01

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

  14. Ultrashort-pulse-train pump and dump excitation of a diatomic molecule

    OpenAIRE

    de Araujo, LEE

    2010-01-01

    An excitation scheme is proposed for transferring population between ground-vibrational levels of a molecule. The transfer is accomplished by pumping and dumping population with a pair of coherent ultrashort-pulse trains via a stationary state. By mismatching the teeth of the frequency combs associated with the pulse trains to the vibrational levels, high selectivity in the excitation, along with high transfer efficiency, is predicted. The pump-dump scheme does not suffer from spontaneous emi...

  15. Study on infrared multiphoton excitation of the linear triatomic molecule by the Lie-algebra approach

    International Nuclear Information System (INIS)

    Feng, H.; Zheng, Y.; Ding, S.

    2007-01-01

    Infrared multiphoton vibrational excitation of the linear triatomic molecule has been studied using the quadratic anharmonic Lie-algebra model, unitary transformations, and Magnus approximation. An explicit Lie-algebra expression for the vibrational transition probability is obtained by using a Lie-algebra approach. This explicit Lie-algebra expressions for time-evolution operator and vibrational transition probabilities make the computation clearer and easier. The infrared multiphoton vibrational excitation of the DCN linear tri-atomic molecule is discussed as an example

  16. Multiple scattering approach to the vibrational excitation of molecules by slow electrons

    International Nuclear Information System (INIS)

    Drukarev, G.

    1976-01-01

    Another approach to the problem of vibrational excitation of homonuclear two-atomic molecules by slow electrons possibly accompanied by rotational transitions is presented based on the picture of multiple scattering of an electron inside the molecule. The scattering of two fixed centers in the zero range potential model is considered. The results indicate that the multiple scattering determines the order of magnitude of the vibrational excitation cross sections in the energy region under consideration even if the zero range potential model is used. Also the connection between the multiple scattering approach and quasi-stationary molecular ion picture is established. 9 refs

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

    International Nuclear Information System (INIS)

    Kazanskii, A.K.

    1982-01-01

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

  18. Optical excitation cross-sections for electron collisions with atoms and molecules

    International Nuclear Information System (INIS)

    McConkey, J.W.; Univ. of Windsor, Ontario)

    1983-01-01

    A brief review of the status of absolute electron-impact excitation cross-section measurements for atoms and molecules is presented. Some of the reasons for the wide discrepancies which exist in the published data are discussed. Tables are presented of recent publications in the field which are not included in the J.I.L.A. compilations. A tabular compilation of the existing data for e-impact on H 2 O is also given and discussed. Some recent experiments of particular interest to the development of the theory of electron-molecule excitation are mentioned. 112 references, 3 figures, 3 tables

  19. Structure and conformational dynamics of molecules in the excited electronic states: theory and experiment

    International Nuclear Information System (INIS)

    Godunov, I.A.; Bataev, V.A.; Maslov, D.V.; Yakovlev, N.N.

    2017-01-01

    The structure of conformational non-rigid molecules in the excited electronic states are investigated by joint theoretical and experimental methods. The theoretical part of work consist of two stages. In first stage the ab initio quantum-chemical calculations are carried out using high level methods. In second stage the vibrational problems of the various dimensions are solved by variational method for vibrations of large amplitude. In experimental part of work the vibronic spectra are investigated: gas-phase absorption and also, fluorescence excitation spectra of jet-cooled molecules. Some examples are considered.

  20. Effect resonance radiation transfer of excitation porous silicon to I sub 2 molecules sorbed in pores

    CERN Document Server

    Zakharchenko, K V; Kuznetsov, M B; Chistyakov, A A; Karavanskij, V A

    2001-01-01

    One studies the effect of resonance radiation-free transfer of electronic excitation between silicon nanocrystals and iodine molecules sorbed in pores. The experiment procedure includes laser-induced luminescence and laser desorption mass spectrometry. One analyzes photoluminescence spectra prior to and upon iodine sorption. Excitation of iodine through the mechanism of resonance transfer is determined to result in desorption of the iodine sorbed molecules with relatively high kinetic energies (3-1 eV). One evaluated the peculiar distance of resonance transfer the approximate value of which was equal to 2 nm

  1. Influence of excited molecules on electron swarm transport coefficients and gas discharge kinetics

    International Nuclear Information System (INIS)

    Petrovic, Z.L.; Jovanovic, J.V.; Raspopovic, Z.M.; Bzenic, S.A.; Vrhovac, S.B.

    1997-01-01

    In this paper we study different effects of excited molecules on swarm parameters, electron energy distribution functions and gas discharge modeling. First we discuss a possible experiment in parahydrogen to resolve the discrepancy in hydrogen vibrational excitation cross section data. Negative differential conductivity (NDC) is a kinetic phenomenon which manifests itself in a particular dependence of the drift velocity on E=N and it is affected by superelastic collisions with excited states. A complete kinetic scheme for argon required to model excited state densities in gas discharges is also described. These results are used to explain experiments in capacitively and inductively coupled RF plasmas used for processing. The paper illustrates the application of atomic and molecular collision data, swarm data and the theoretical techniques in modeling of gas discharges with large abundances of excited molecules. It is pointed out that swarm experiments with excited molecules are lacking and that there is a shortage of reliable data, while the numerical procedures are sufficiently developed to include all the important effects. (authors). 59 refs., 12 figs

  2. Rydberg excitation of neutral nitric oxide molecules in strong UV and near-IR laser fields

    International Nuclear Information System (INIS)

    Lv Hang; Zhang Jun-Feng; Zuo Wan-Long; Xu Hai-Feng; Jin Ming-Xing; Ding Da-Jun

    2015-01-01

    Rydberg state excitations of neutral nitric oxide molecules are studied in strong ultraviolet (UV) and near-infra-red (IR) laser fields using a linear time-of-flight (TOF) mass spectrometer with the pulsed electronic field ionization method. The yield of Rydberg molecules is measured as a function of laser intensity and ellipticity, and the results in UV laser fields are compared with those in near-IR laser fields. The present study provides the first experimental evidence of neutral Rydberg molecules surviving in a strong laser field. The results indicate that a rescattering-after-tunneling process is the main contribution to the formation of Rydberg molecules in strong near-IR laser fields, while multi-photon excitation may play an important role in the strong UV laser fields. (paper)

  3. Absolute carrier phase effects in the two-color excitation of dipolar molecules

    International Nuclear Information System (INIS)

    Brown, Alex; Meath, W.J.; Kondo, A.E.

    2002-01-01

    The pump-probe excitation of a two-level dipolar (d≠0) molecule, where the pump frequency is tuned to the energy level separation while the probe frequency is extremely small, is examined theoretically as an example of absolute phase control of excitation processes. The state populations depend on the probe field's absolute carrier phase but are independent of the pump field's absolute carrier phase. Interestingly, the absolute phase effects occur for pulse durations much longer and field intensities much weaker than those required to see such effects in single pulse excitation

  4. Studies of photoionization processes from ground-state and excited-state atoms and molecules

    International Nuclear Information System (INIS)

    Ederer, D.L.; Parr, A.C.; West, J.B.

    1982-01-01

    Recent triply-differential photoelectron spectroscopy experiments designed for the study of correlation effects in atoms and molecules are described. Final-state symmetry of the n=2 state of helium has been determined. The non-Franck-Condon behavior of vibrational branching ratios and large variations of the angular asymmetry parameter has been observed for shape resonances and autoionizing resonances in CO and other molecules. Recent observations of the photoionization of excited sodium atoms are also described

  5. Can Internal Conversion BE Controlled by Mode-Specific Vibrational Excitation in Polyatomic Molecules

    Science.gov (United States)

    Portnov, Alexander; Epshtein, Michael; Bar, Ilana

    2017-06-01

    Nonadiabatic processes, dominated by dynamic passage of reactive fluxes through conical intersections (CIs) are considered to be appealing means for manipulating reaction paths. One approach that is considered to be effective in controlling the course of dissociation processes is the selective excitation of vibrational modes containing a considerable component of motion. Here, we have chosen to study the predissociation of the model test molecule, methylamine and its deuterated isotopologues, excited to well-characterized quantum states on the first excited electronic state, S_{1}, by following the N-H(D) bond fission dynamics through sensitive H(D) photofragment probing. The branching ratios between slow and fast H(D) photofragments, the internal energies of their counter radical photofragments and the anisotropy parameters for fast H photofragments, confirm correlated anomalies for predissociation initiated from specific rovibronic states, reflecting the existence of a dynamic resonance in each molecule. This resonance strongly depends on the energy of the initially excited rovibronic states, the evolving vibrational mode on the repulsive S_{1} part during N-H(D) bond elongation, and the manipulated passage through the CI that leads to radicals excited with C-N-H(D) bending and preferential perpendicular bond breaking, relative to the photolyzing laser polarization, in molecules containing the NH_{2} group. The indicated resonance plays an important role in the bifurcation dynamics at the CI and can be foreseen to exist in other photoinitiated processes and to control their outcome.

  6. Enhanced Electron Attachment to Highly-Excited Molecules and Its Applications in Pulsed Plasmas

    International Nuclear Information System (INIS)

    Ding, W.X.; Ma, C.Y.; McCorkle, D.L.; Pinnaduwage, L.A.

    1999-01-01

    Studies conducted over the past several years have shown that electron attachment to highly-excited states of molecules have extremely large cross sections. We will discuss the implications of this for pulsed discharges used for H - generation, material processing, and plasma remediation

  7. Bibliography on electron collisions with molecules: rotational and vibrational excitations, 1980-2000

    International Nuclear Information System (INIS)

    Itikawa, Yukikazu

    2001-04-01

    A list of papers reporting cross sections for electron-impact excitations of rotational and vibrational states of molecules is presented. The list includes both the theoretical and the experimental papers published in 1980-2000. An index by molecular species is provided at the end of the bibliography. (author)

  8. Vibrational excitation of hydrogen molecules by two-photon absorption and third-harmonic generation

    Science.gov (United States)

    Miyamoto, Yuki; Hara, Hideaki; Hiraki, Takahiro; Masuda, Takahiko; Sasao, Noboru; Uetake, Satoshi; Yoshimi, Akihiro; Yoshimura, Koji; Yoshimura, Motohiko

    2018-01-01

    We report the coherent excitation of the vibrational state of hydrogen molecules by two-photon absorption and the resultant third-harmonic generation (THG). Parahydrogen molecules cooled by liquid nitrogen are irradiated by mid-infrared nanosecond pulses at 4.8 μm with a nearly Fourier-transform-limited linewidth. The first excited vibrational state of parahydrogen is populated by two-photon absorption of the mid-infrared photons. Because of the narrow linewidth of the mid-infrared pulses, coherence between the ground and excited states is sufficient to induce higher-order processes. Near-infrared photons from the THG are observed at 1.6 μm. The dependence of the intensity of the near-infrared radiation on mid-infrared pulse energy, target pressure, and cell length is determined. We used a simple formula for THG with consideration of realistic experimental conditions to explain the observed results.

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

    Science.gov (United States)

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

    2018-04-01

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

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

    Science.gov (United States)

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

    1987-01-01

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

  11. Short-Lived Electronically-Excited Diatomic Molecules Cooled via Supersonic Expansion from a Plasma Microjet

    Science.gov (United States)

    Houlahan, Thomas J., Jr.; Su, Rui; Eden, Gary

    2014-06-01

    Using a pulsed plasma microjet to generate short-lived, electronically-excited diatomic molecules, and subsequently ejecting them into vacuum to cool via supersonic expansion, we are able to monitor the cooling of molecules having radiative lifetimes as low as 16 ns. Specifically, we report on the rotational cooling of He_2 molecules in the d^3Σ_u^+, e^3Π_g, and f^3Σ_u^+ states, which have lifetimes of 25 ns, 67 ns, and 16 ns, respectively. The plasma microjet is driven with a 2.6 kV, 140 ns high-voltage pulse (risetime of 20 ns) which, when combined with a high-speed optical imaging system, allows the nonequilibrium rotational distribution for these molecular states to be monitored as they cool from 1200 K to below 250 K with spatial and temporal resolutions of below 10 μm and 10 ns, respectively. The spatial and temporal resolution afforded by this system also allows the observation of excitation transfer between the f^3Σ_u^+ state and the lower lying d^3Σ_u^+ and e^3Π_g states. The extension of this method to other electronically excited diatomics with excitation energies >5 eV will also be discussed.

  12. Versatile single-molecule multi-color excitation and detection fluorescence setup for studying biomolecular dynamics

    KAUST Repository

    Sobhy, M. A.

    2011-11-07

    Single-molecule fluorescence imaging is at the forefront of tools applied to study biomolecular dynamics both in vitro and in vivo. The ability of the single-molecule fluorescence microscope to conduct simultaneous multi-color excitation and detection is a key experimental feature that is under continuous development. In this paper, we describe in detail the design and the construction of a sophisticated and versatile multi-color excitation and emission fluorescence instrument for studying biomolecular dynamics at the single-molecule level. The setup is novel, economical and compact, where two inverted microscopes share a laser combiner module with six individual laser sources that extend from 400 to 640 nm. Nonetheless, each microscope can independently and in a flexible manner select the combinations, sequences, and intensities of the excitation wavelengths. This high flexibility is achieved by the replacement of conventional mechanical shutters with acousto-optic tunable filter (AOTF). The use of AOTF provides major advancement by controlling the intensities, duration, and selection of up to eight different wavelengths with microsecond alternation time in a transparent and easy manner for the end user. To our knowledge this is the first time AOTF is applied to wide-field total internal reflection fluorescence (TIRF) microscopy even though it has been commonly used in multi-wavelength confocal microscopy. The laser outputs from the combiner module are coupled to the microscopes by two sets of four single-mode optic fibers in order to allow for the optimization of the TIRF angle for each wavelength independently. The emission is split into two or four spectral channels to allow for the simultaneous detection of up to four different fluorophores of wide selection and using many possible excitation and photoactivation schemes. We demonstrate the performance of this new setup by conducting two-color alternating excitation single-molecule fluorescence resonance energy

  13. Impact of nuclear lattice relaxation on the excitation energy transfer along a chain of pi-conjugated molecules

    NARCIS (Netherlands)

    Schmid, S.A.; Abbel, R.J.; Schenning, A.P.H.J.; Meijer, E.W.; Herz, L.M.

    2010-01-01

    We have investigated the extent to which delocalization of the ground-state and excited-state wave functions of a p-conjugated molecule affects the excitation energy transfer (EET) between such molecules. Using femtosecond photoluminescence spectroscopy, we experimentally monitored the EET along

  14. Electronic excitation of atoms and molecules by electron impact in a linear algebraic, separable potential approach

    International Nuclear Information System (INIS)

    Collins, L.A.; Schneider, B.I.

    1984-01-01

    The linear algebraic, separable potential approach is applied to the electronic excitation of atoms and molecules by electron impact. By representing the exchange and off-diagonal direct terms on a basis, the standard set of coupled inelastic equations is reduced to a set of elastic inhomogeneous equations. The procedure greatly simplifies the formulation by allowing a large portion of the problem to be handled by standard bound-state techniques and by greatly reducing the order of the scattering equations that must be solved. Application is made to the excitation of atomic hydrogen in the three-state close-coupling (1s, 2s, 2p) approximation. (author)

  15. Ultrashort-pulse-train pump and dump excitation of a diatomic molecule

    Science.gov (United States)

    de Araujo, Luís E. E.

    2010-09-01

    An excitation scheme is proposed for transferring population between ground-vibrational levels of a molecule. The transfer is accomplished by pumping and dumping population with a pair of coherent ultrashort-pulse trains via a stationary state. By mismatching the teeth of the frequency combs associated with the pulse trains to the vibrational levels, high selectivity in the excitation, along with high transfer efficiency, is predicted. The pump-dump scheme does not suffer from spontaneous emission losses, it is insensitive to the pump-dump-train delay, and it requires only basic pulse shaping.

  16. Ultrafast single-molecule photonics: Excited state dynamics in coherently coupled complexes

    International Nuclear Information System (INIS)

    Hernando, Jordi; Hoogenboom, Jacob; Dijk, Erik van; Garcia-Parajo, Maria; Hulst, Niek F. van

    2008-01-01

    We present a single-molecule study on femtosecond dynamics in multichromophoric systems, combining fs pump-probe, emission-spectra and fluorescence-lifetime analysis. The ultrafast fs approach gives direct information on the initial exciton dynamics after excitation. The lifetime data show superradiance, a direct measure for the extent of the coherent coupling and static disorder. The spectra finally reveal the role of exciton-phonon coupling. At the single-molecule level a wide range of exciton delocalization lengths and energy redistribution times is revealed

  17. Ultrafast single-molecule photonics: Excited state dynamics in coherently coupled complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hernando, Jordi [Dept. de Quimica, Universitat Autonoma Barcelona, 08193 Cerdanyola del Valles (Spain); Hoogenboom, Jacob [ICFO-Institut de Ciencies Fotoniques, Mediterranean Technology Park, 08860 Castelldefels, Barcelona (Spain); Dijk, Erik van [Applied Optics Group, MESA Institute for Nanotechnology, University of Twente, 7500AE Enschede (Netherlands); Garcia-Parajo, Maria [IBEC-Institute of BioEngineering of Catalunya, 08028 Barcelona (Spain); ICREA-Institucio Catalana de Recerca i Estudis Avancats, 08015 Barcelona (Spain); Hulst, Niek F. van [ICFO-Institut de Ciencies Fotoniques, Mediterranean Technology Park, 08860 Castelldefels, Barcelona (Spain) and ICREA-Institucio Catalana de Recerca i Estudis Avancats, 08015 Barcelona (Spain)], E-mail: Niek.vanHulst@ICFO.es

    2008-05-15

    We present a single-molecule study on femtosecond dynamics in multichromophoric systems, combining fs pump-probe, emission-spectra and fluorescence-lifetime analysis. The ultrafast fs approach gives direct information on the initial exciton dynamics after excitation. The lifetime data show superradiance, a direct measure for the extent of the coherent coupling and static disorder. The spectra finally reveal the role of exciton-phonon coupling. At the single-molecule level a wide range of exciton delocalization lengths and energy redistribution times is revealed.

  18. Experimental studies of processes with vibrationally excited hydrogen molecules that are important for tokamak edge plasma

    International Nuclear Information System (INIS)

    Cadez, I.; Markelj, S.; Rupnik, Z.; Pelicon, P.

    2006-01-01

    We are currently conducting a series of different laboratory experimental studies of processes involving vibrationally excited hydrogen molecules that are relevant to fusion edge plasma. A general overview of our activities is presented together with results of studies of hydrogen recombination on surfaces. This includes vibrational spectroscopy of molecules formed by recombination on metal surfaces exposed to the partially dissociated hydrogen gas and recombination after hydrogen permeation through metal membrane. The goal of these studies is to provide numerical parameters needed for edge plasma modelling and better understanding of plasma wall interaction processes. (author)

  19. Analytical calculation of spin tunneling effect in single molecule magnet Fe8 with considering quadrupole excitation

    OpenAIRE

    Y Yousefi; H Fakhari; K Muminov; M R Benam

    2018-01-01

    Spin tunneling effect in Single Molecule Magnet Fe8 is studied by instanton calculation technique using SU(3) generalized spin coherent state in real parameter as a trial function. For this SMM, tunnel splitting arises due to the presence of a Berry like phase in action, which causes interference between tunneling trajectories (instantons). For this SMM, it is established that the use of quadrupole excitation (g dependence) changes not only the location of the quenching points, but also the n...

  20. (e, 2e) ionization-excitation experiment with fixed-in-space H2 molecules

    International Nuclear Information System (INIS)

    Takahashi, M.; Watanabe, N.; Khajuria, Y.; Udagawa, Y.; Eland, J.H.D.

    2005-01-01

    This report will introduce an electron-electron-fragment ion triple coincidence spectrometer to the readers with our recent collision dynamics study on ionization-excitation processes of the hydrogen molecule. Following a description of the working principle of the spectrometer, results of the study will be discussed; this includes molecular frame (e, 2e) cross sections that have been observed for the first time. (author)

  1. Charge exchange of excited mesic atoms of hydrogen isotopes in triple collisions with molecules

    International Nuclear Information System (INIS)

    Men'shikov, L.I.; Ponomarev, L.I.

    1985-01-01

    At high densities of deuterium-tritium mixture the probability for the occurrence of the isotope-exchange reaction (dμ)/sub n/+t → d+(tμ)/sub n/ from the excited states of n mesic atoms of deuterium is high in the triple collisions of mesic atoms with the molecules of hydrogen isotopes. This reaction should be taken into account in describing the kinetics of muon catalysis

  2. Convergence problems and energetic regions in π excited states of certain conjugated molecules

    International Nuclear Information System (INIS)

    Giambiagi, M.S. de; Giambiagi, M.; Barros, H.G. de P.L. de.

    1980-01-01

    When calculating π bond orders of excited and superexcited states of conjugated molecules, difficulties arise in applying the variation method; besides, the convergence problems involved are well known. For pyridazine, chosen for discussion, 27 states are considered; the convergence problem is envisaged through two criteria in the choice of a parameter introduced in the compromise Hamiltonian. This convergence parameter is related to the variation method. There exist three particular solutions for bond orders, which divide the 27 states into energetical regions. (Author) [pt

  3. Influence of capture to excited states of multiply charged ion beams colliding with small molecules

    International Nuclear Information System (INIS)

    Montenegro, P; Monti, J M; Fojón, O A; Hanssen, J; Rivarola, R D

    2015-01-01

    Electron capture by multiply charged ions impacting on small molecules is theoretically investigated. Particular attention is paid to the case of biological targets. The interest is focused on the importance of the transition to excited final states which can play a dominant role on the total capture cross sections. Projectiles at intermediate and high collision energies are considered. Comparison with existing experimental data is shown. (paper)

  4. Development of transient collisional excitation x-ray laser with ultra short-pulse laser

    International Nuclear Information System (INIS)

    Kado, Masataka; Kawachi, Tetsuya; Hasegawa, Noboru; Tanaka, Momoko; Sukegawa, Kouta; Nagashima, Keisuke; Kato, Yoshiaki

    2001-01-01

    We have observed lasing on Ne-like 3s-3p line from titanium (32.4 nm), Ni-like 4p-4d line from silver (13.9 nm) and tin (11.9 nm) with the transient collisional excitation (TCE) scheme that uses combination of a long pre-pulse (∼ns) and a short main pulse (∼ps). A gain coefficient of 23 cm -1 was measured for plasma length up to 4 mm with silver slab targets. We have also observed lasing on Ne-like and Ni-like lines with new TCE scheme that used pico-seconds laser pulse to generate plasma and observed strong improvement of x-ray laser gain coefficient. A gain coefficient of 14 cm -1 was measured for plasma length up to 6 mm with tin targets. (author)

  5. Cometary models - excitation of molecules at radio wavelengths and thermodynamics of the coma

    International Nuclear Information System (INIS)

    Crovisier, J.

    1987-01-01

    Models for molecular excitation under physical conditions of cometary atmospheres are obviously a requisite for interpreting radio spectroscopic observations of comets. A review of such models is presented. The prevailing excitation mechanism for the rotational lines of parent molecules is pumping of the fundamental vibrational bands by the solar infrared radiation field, followed by spontaneous decay; the molecular rotational population is then at fluorescence equilibrium. Another competing mechanism in the inner coma is thermal excitation by collisions. Its evaluation needs the knowledge of the coma kinetic temperature law, which up to now can only be achieved by modeling the coma thermodynamics. A review of cometary thermodynamical models is also given here, and the relations between such models and cometary molecular observations are discussed. 50 references

  6. Pulsed laser study of excited states of aromatic molecules absorbed in globular proteins

    International Nuclear Information System (INIS)

    Cooper, M.; Thomas, J.K.

    1977-01-01

    Pyrene and several derivatives of pyrene such as pyrene sulfonic acid, and pyrene butyric acid were incorporated into bovine serum albumin (BSA) in aqueous solution. The pyrene chromophore was subsequently excited by a pulse of uv light (lambda = 3471 A) from a Q switched frequency doubled ruby laser. The lifetime of the pyrene excited singlet and triplet states were monitored by time resolved spectrophotometry. Various molecules, such as O 2 and I - , dissolved in the aqueous phase, diffused into the protein and quenched pyrene excited states. The rates of these reactions were followed under a variety of conditions such as pH and temperature and in the presence of inert additives. The rates of pyrene excited-state quenching were often considerably smaller than the rates observed in simple solutions. A comparison of the rates in the protein and homogeneous solutions gives information on the factors such as temperature, charge, and pH that control the movement of small molecules in and into BSA

  7. Retrieving transient conformational molecular structure information from inner-shell photoionization of laser-aligned molecules

    Science.gov (United States)

    Wang, Xu; Le, Anh-Thu; Yu, Chao; Lucchese, R. R.; Lin, C. D.

    2016-01-01

    We discuss a scheme to retrieve transient conformational molecular structure information using photoelectron angular distributions (PADs) that have averaged over partial alignments of isolated molecules. The photoelectron is pulled out from a localized inner-shell molecular orbital by an X-ray photon. We show that a transient change in the atomic positions from their equilibrium will lead to a sensitive change in the alignment-averaged PADs, which can be measured and used to retrieve the former. Exploiting the experimental convenience of changing the photon polarization direction, we show that it is advantageous to use PADs obtained from multiple photon polarization directions. A simple single-scattering model is proposed and benchmarked to describe the photoionization process and to do the retrieval using a multiple-parameter fitting method. PMID:27025410

  8. An exactly solvable model for multiphoton excitation of polyatomic molecules in the presence of collisions

    International Nuclear Information System (INIS)

    Strekalov, M L

    2013-01-01

    A theoretical study has been made on the non-stationary phenomena in the relaxation of highly vibrationally excited molecules under laser radiation giving rise to these molecules. An exact analytical solution to the master equation has been obtained in terms of Meixner polynomials with regard to VV and VT processes. The time-dependent vibrational distribution is used to obtain analytical expressions for the mean number of photons, stored on the vibrational degrees of freedom and transferred to a thermal bath. Using the latter result, an explicit expression is given for the average energy transfer as a function of time. Its dependence on the partial pressure of absorbing molecules has also been established. (paper)

  9. Collision dynamics of methyl radicals and highly vibrationally excited molecules using crossed molecular beams

    International Nuclear Information System (INIS)

    Chu, P.M.Y.

    1991-10-01

    The vibrational to translational (V→T) energy transfer in collisions between large highly vibrationally excited polyatomics and rare gases was investigated by time-of-flight techniques. Two different methods, UV excitation followed by intemal conversion and infrared multiphoton excitation (IRMPE), were used to form vibrationally excited molecular beams of hexafluorobenzene and sulfur hexafluoride, respectively. The product translational energy was found to be independent of the vibrational excitation. These results indicate that the probability distribution function for V→T energy transfer is peaked at zero. The collisional relaxation of large polyatomic molecules with rare gases most likely occurs through a rotationally mediated process. Photodissociation of nitrobenzene in a molecular beam was studied at 266 nm. Two primary dissociation channels were identified including simple bond rupture to produce nitrogen dioxide and phenyl radical and isomerization to form nitric oxide and phenoxy radical. The time-of-flight spectra indicate that simple bond rupture and isomerization occurs via two different mechanisms. Secondary dissociation of the phenoxy radicals to carbon monoxide and cyclopentadienyl radicals was observed as well as secondary photodissociation of phenyl radical to give H atom and benzyne. A supersonic methyl radical beam source is developed. The beam source configuration and conditions were optimized for CH 3 production from the thermal decomposition of azomethane. Elastic scattering of methyl radical and neon was used to differentiate between the methyl radicals and the residual azomethane in the molecular beam

  10. 48-spot single-molecule FRET setup with periodic acceptor excitation

    Science.gov (United States)

    Ingargiola, Antonino; Segal, Maya; Gulinatti, Angelo; Rech, Ivan; Labanca, Ivan; Maccagnani, Piera; Ghioni, Massimo; Weiss, Shimon; Michalet, Xavier

    2018-03-01

    Single-molecule Förster resonance energy transfer (smFRET) allows measuring distances between donor and acceptor fluorophores on the 3-10 nm range. Solution-based smFRET allows measurement of binding-unbinding events or conformational changes of dye-labeled biomolecules without ensemble averaging and free from surface perturbations. When employing dual (or multi) laser excitation, smFRET allows resolving the number of fluorescent labels on each molecule, greatly enhancing the ability to study heterogeneous samples. A major drawback to solution-based smFRET is the low throughput, which renders repetitive measurements expensive and hinders the ability to study kinetic phenomena in real-time. Here we demonstrate a high-throughput smFRET system that multiplexes acquisition by using 48 excitation spots and two 48-pixel single-photon avalanche diode array detectors. The system employs two excitation lasers allowing separation of species with one or two active fluorophores. The performance of the system is demonstrated on a set of doubly labeled double-stranded DNA oligonucleotides with different distances between donor and acceptor dyes along the DNA duplex. We show that the acquisition time for accurate subpopulation identification is reduced from several minutes to seconds, opening the way to high-throughput screening applications and real-time kinetics studies of enzymatic reactions such as DNA transcription by bacterial RNA polymerase.

  11. The mechanism of three-body process of energy transfer from excited xenon atoms to molecules

    International Nuclear Information System (INIS)

    Wojciechowski, K.; Forys, M.

    1999-01-01

    The mechanism of energy transfer from Xe(6 s[3/2] 1 ) resonance state (E=8.44 eV) and higher excited Xe(6p, 6p', 6 d) atoms produced in pulse radiolysis to molecules have been discussed. The analysis of the kinetic data for these processes shows that in the sensitized photolysis and radiolysis of Xe-M mixtures the excited atoms decay in 'ordinary' two-body reaction: Xe(6s[3/2] 1 0 )+M→products (r.1) and in fast 'accelerated' third order process: Xe(6s[3/2] 1 0 )+M+Xe→products (r.2) The discussion shows that three-body process occurs via reactions: Xe(6s[3/2] 1 0 )+Xe k w ↔ k d Xe 2 ** (r.2a) Xe 2 **+M k q →[Xe 2 M]*→products (r.2b) It was shown that this mechanism concerns also higher excited Xe atoms and can explain a similar process in He-M mixtures and suggests that it is a general mechanism of energy transfer in all irradiated rare gas-molecule systems

  12. Twistacene contained molecule for optical nonlinearity: Excited-state based negative refraction and optical limiting

    Science.gov (United States)

    Wu, Xingzhi; Xiao, Jinchong; Sun, Ru; Jia, Jidong; Yang, Junyi; Ao, Guanghong; Shi, Guang; Wang, Yuxiao; Zhang, Xueru; Song, Yinglin

    2018-06-01

    Spindle-type molecules containing twisted acenes (PyBTA-1 &PyBTA-2) are designed, synthesized characterized. Picosecond Z-scan experiments under 532 nm show reverse saturable absorption and negative nonlinear refraction, indicating large third-order optical nonlinearity in PyBTA-1. The mechanism of the optical nonlinearity is investigated and the results show that the nonlinear absorption and refraction in PyBTA-1 originates from a charge transfer (CT) state. Furthermore, relatively long lifetime and absorptive cross section of the CT state are measured. Based on the excited state absorption in PyBTA-1, strong optical limiting with ∼0.3 J/cm2 thresholds are obtained when excited by picoseconds and nanoseconds pulses. The findings on nonlinear optics suggest PyBTA-1 a promising material of all optical modulation and laser protection, which enrich the potential applications of these spindle-type molecules. Comparing to the previously reported spindle-type molecules with analogous structures, the introduction of ICT in PyBTA-1 &PyBTA-2 dramatically decreases the two-photon absorption while enhances the nonlinear refraction. The results could be used to selectively tailor the optical nonlinearity in such kind of compounds.

  13. Analytical calculation of spin tunneling effect in single molecule magnet Fe8 with considering quadrupole excitation

    Directory of Open Access Journals (Sweden)

    Y Yousefi

    2018-02-01

    Full Text Available Spin tunneling effect in Single Molecule Magnet Fe8 is studied by instanton calculation technique using SU(3 generalized spin coherent state in real parameter as a trial function. For this SMM, tunnel splitting arises due to the presence of a Berry like phase in action, which causes interference between tunneling trajectories (instantons. For this SMM, it is established that the use of quadrupole excitation (g dependence changes not only the location of the quenching points, but also the number of these points. Also, these quenching points are the steps in hysteresis loops of this SMM. If dipole and quadrupole excitations in classical energy considered, the number of these steps equals to the number that obtained from experimental data.

  14. High mass-resolution electron-ion-ion coincidence measurements on core-excited organic molecules

    CERN Document Server

    Tokushima, T; Senba, Y; Yoshida, H; Hiraya, A

    2001-01-01

    Total electron-ion-ion coincidence measurements on core excited organic molecules have been carried out with high mass resolution by using multimode (reflectron/linear) time-of-flight mass analyzer. From the ion correlation spectra of core excited CH sub 3 OH and CD sub 3 OH, the reaction pathway to form H sub 3 sup + (D sub 3 sup +) is identified as the elimination of three H (D) atoms from the methyl group, not as the inter-group (-CH sub 3 and -OH) interactions. In a PEPIPICO spectrum of acetylacetone (CH sub 3 COCH sub 2 COCH sub 3) measured by using a reflectron TOF, correlations between ions up to mass number 70 with one-mass resolution was recorded.

  15. Time delay for resonant vibrational excitation in electron--molecule collisions

    International Nuclear Information System (INIS)

    Gauyacq, J.P.

    1990-01-01

    An analysis of the time delay associated with vibrational excitation in electron--molecule collision is presented. It consists of a direct study of the time dependence of the process for three model systems. An electron wave packet, that is narrow in time, is sent on the target and the amplitudes in the different inelastic channels are studied as functions of time. The time delay is found to correspond to very different time effects: broadenings, shifts in time of the wave packet, but also complex distortions that cannot be represented by a time delay. The direct analysis of the scattered wave also provides new insights into the vibrational excitation process. It should be a useful tool to analyze complex collision processes

  16. Three exciting areas of experimental physical sciences : high temperature superconductors, metal clusters and super molecules of carbon

    International Nuclear Information System (INIS)

    Rao, C.N.

    1992-01-01

    The author has narrated his experience in carrying out research in three exciting areas of physical sciences. These areas are : high temperature superconductors, metal clusters and super molecules of carbon. (M.G.B.)

  17. Selective excitation of a vibrational level within the electronic ground state of a polyatomic molecule with ultra pulses

    CSIR Research Space (South Africa)

    de Clercq, L

    2010-09-01

    Full Text Available Coherent control of the upper vibrational level populations in the electronic ground state of a polyatomic molecule was simulated. Results indicate that selective excitation of a specific upper state level is possible...

  18. Linear-algebraic approach to electronic excitation of atoms and molecules by electron impact

    International Nuclear Information System (INIS)

    Collins, L.A.; Schneider, B.I.

    1983-01-01

    A linear-algebraic method, based on an integral equations formulation, is applied to the excitation of atoms and molecules by electron impact. Various schemes are devised for treating the one-electron terms that sometimes cause instabilities when directly incorporated into the solution matrix. These include introducing Lagrange undetermined multipliers and correlation terms. Good agreement between the method and other computational techniques is obtained for electron scattering for hydrogenic and Li-like atomic ions and for H 2 + in two- to five-state close-coupling calculations

  19. ESR measurement of the concentration of vibrationally excited hydrogen and deuterium molecules

    International Nuclear Information System (INIS)

    Gershenzon, Yu.M.; Ivanov, A.V.; Il'in, S.D.; Kucheryavyi, S.I.; Rozenshtein, V.B.

    1988-01-01

    A method is described for measuring the concentration of vibrationally excited H 2 and D 2 molecules using an ESR microwave spectrometer. The essence of the method is the titration of H 2 (v = 1) and D 2 (v = 1) with D and H atoms and measurement of the concentrations of the titration products H and D, respectively. Stoichiometric titration coefficients were determined in the form of proportionality coefficients between the titration signals Δ[H], Δ[D] and the concentrations of H 2 (v = 1), D 2 (v = 1)

  20. Electronic excitation and ionic dissociation of the vanillin molecule: photoionization with flavor

    International Nuclear Information System (INIS)

    Betancourt, A Moreno; De Souza, G G B; Bernini, R B; Coutinho, L H

    2015-01-01

    The electronic properties of vanillin molecule were investigated by different excitation and ionization techniques. The Ionic fragmentation mechanisms were studied using time-of-flight mass spectrometry as a function of the energy of the incident radiation in the valence energy region and the inner and core levels. It was stablished as a general feature that the ruptures related to the oxygen atoms are predominant at all energies. The resonances and ionization potential of the oxygen 1s was also determined by NEXAFS spectra. (paper)

  1. Observation of the adsorption and desorption of vibrationally excited molecules on a metal surface

    Science.gov (United States)

    Shirhatti, Pranav R.; Rahinov, Igor; Golibrzuch, Kai; Werdecker, Jörn; Geweke, Jan; Altschäffel, Jan; Kumar, Sumit; Auerbach, Daniel J.; Bartels, Christof; Wodtke, Alec M.

    2018-06-01

    The most common mechanism of catalytic surface chemistry is that of Langmuir and Hinshelwood (LH). In the LH mechanism, reactants adsorb, become thermalized with the surface, and subsequently react. The measured vibrational (relaxation) lifetimes of molecules adsorbed at metal surfaces are in the range of a few picoseconds. As a consequence, vibrational promotion of LH chemistry is rarely observed, with the exception of LH reactions occurring via a molecular physisorbed intermediate. Here, we directly detect adsorption and subsequent desorption of vibrationally excited CO molecules from a Au(111) surface. Our results show that CO (v = 1) survives on a Au(111) surface for 1 × 10-10 s. Such long vibrational lifetimes for adsorbates on metal surfaces are unexpected and pose an interesting challenge to the current understanding of vibrational energy dissipation on metal surfaces. They also suggest that vibrational promotion of surface chemistry might be more common than is generally believed.

  2. Calculation of the ground and excited states of the Ne2 molecule by the variational cellular method

    International Nuclear Information System (INIS)

    Dias, A.M.; Rosato, A.

    1981-07-01

    The potential curves for the ground state 1 Σ + sub(g) and for the first singlet excited state 1 Σ + sub (u) of the Ne 2 molecule are determined by the Variational Cellular Method. From these curves some spectroscopical constants are obtained. Ionization energies of the excited state 1 Σ + sub (u) are calculated. (Author) [pt

  3. Calculation of the ground and excited states of the Ne2 molecule by the Variational Cellular Method

    International Nuclear Information System (INIS)

    Dias, A.M.; Rosato, A.

    1982-01-01

    The potential curves for the ground 1 μ + sub(g) and for the first singlet excited state 1 μ + sub(u) of the Ne 2 molecule are determined by the Variational Cellular Method. From these curves some spectroscopical constants are obtained. Ionization energies of the excited state 1 μ + sub(u) are calculated. (Author) [pt

  4. Structural, photophysical, and theoretical studies of imidazole-based excited-state intramolecular proton transfer molecules

    Science.gov (United States)

    Somasundaram, Sivaraman; Kamaraj, Eswaran; Hwang, Su Jin; Park, Sanghyuk

    2018-02-01

    Imidazole-based excited state intramolecular proton transfer (ESIPT) blue fluorescent molecules, 2-(1-(4-chlorophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Cl) and 2-(1-(4-bromophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Br) were designed and synthesized by Debus-Radziszewski method through a one-pot multicomponent reaction in high yield. The synthesized compounds were fully characterized by 1H NMR, 13C NMR, FT-IR, FT-Raman, GC-Mass, and elemental analysis. The molecular structures in single crystal lattice were studied by X-ray crystallographic analysis. Because of the intramolecular hydrogen bonding, hydroxyphenyl group is planar to the central imidazole ring, while the other phenyl rings gave distorted conformations to the central heterocyclic ring. BHPI-Cl and BHPI-Br molecules showed intense ESIPT fluorescence at 480 nm, because the two twisted phenyl rings on 4- and 5-positions have reduced intermolecular interaction between adjacent molecules in each crystal through a head-to-tail packing manner. Quantum chemical calculations of energies were carried out by (TD-)DFT using B3LYP/6-31G(d, p) basis set to predict the electronic absorption spectra of the compounds, and they showed good agreement between the computational and the experimental values. The thermal analyses of the synthesized molecules were also carried out by TGA/DSC method.

  5. The estimation of the G-values for ionization and excitation of ten-electron molecules

    International Nuclear Information System (INIS)

    Okazaki, Kiyoshi; Sato, Shin; Ohno, Shin-ichi.

    1976-01-01

    The binary-encounter collision theory is applied to calculate the G-values for the ionization and excitation of methane, ammonia, and water irradiated by 100 keV electrons. Double collision of the incident electron in a molecule is also taken into account. On the assumption of the occurrence of certain reactions in the systems, the G-values for electrons, various radicals, and several final products were estimated. Some of the results are as follows: the G-values for electrons were 3.60 for methane, 3.56 for ammonia, and 3.00 for water. These values are in fair agreement with the experimental values: 3.6 for methane, 3.8 for ammonia, and 3.3 for water. The calculated G-value for hot hydrogen atoms was about 1.0 for all three compounds. The ratios of the G-value for excitation to that for electons are 1.1 for methane, 1.5 for ammonia, and 1.7 for water. An estimation was also made of the G-value for the emission of highly-excited hydrogen atoms using reported cross sections. The G-values are 0.1 for methane and ammonia, and 0.2 for water. (auth.)

  6. Transient spectral hole burning observed on the single-molecule level in terrylene-doped biphenyl

    International Nuclear Information System (INIS)

    Pärs, M.; Palm, V.; Kikas, J.

    2014-01-01

    We use the method of fluorescence correlation spectroscopy to analyze the single-molecule (SM) spectroscopy data earlier recorded for a special type of terrylene SM impurity center (referred as “spectrally confined unstable molecule”, SCM) in an incommensurate single crystal of biphenyl. The SCM's SM line seems to be chaotically jumping around within a broad “spectral envelope” and was first considered being subject to a peculiar spectral diffusion behavior. However, our correlation analysis reveals that all the features observed for SCM at 1.8 K are consistent with an assumption that this SM center participates in a process of reversible (transient) spectral hole burning (THB) earlier observed for terrylene-doped polycrystalline biphenyl. No observations of THB processes on SM level have been so far reported for this impurity system, partially due to a low concentration of relevant impurity centers. Another reason making searching for such centers experimentally challenging is an unusual SM line behavior: the photoinduced transition to a metastable “dark state” leads to the SM line saturational broadening, which is much stronger than the triplet broadening. Hence required prolonged observation is often prevented by an SM act of persistent spectral hole burning. - Highlights: • SCM—special type of terrylene single-molecule center in incommensurate biphenyl. • An unusually stable SCM was investigated during several hours at T=1.8 K. • SCM undergoes photoinduced transitions to an unknown metastable “dark state” (DS). • The long DS lifetime causes strong saturational broadening of SCM spectral line. • SCM participates in an earlier observed process of transient hole burning

  7. Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

    International Nuclear Information System (INIS)

    Ye, ChuanXiang; Zhao, Yi; Liang, WanZhen

    2015-01-01

    The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra with respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT

  8. Non-adiabatic Excited State Molecule Dynamics Modeling of Photochemistry and Photophysics of Materials

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Tammie Renee [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Tretiak, Sergei [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-01-06

    Understanding and controlling excited state dynamics lies at the heart of all our efforts to design photoactive materials with desired functionality. This tailor-design approach has become the standard for many technological applications (e.g., solar energy harvesting) including the design of organic conjugated electronic materials with applications in photovoltaic and light-emitting devices. Over the years, our team has developed efficient LANL-based codes to model the relevant photophysical processes following photoexcitation (spatial energy transfer, excitation localization/delocalization, and/or charge separation). The developed approach allows the non-radiative relaxation to be followed on up to ~10 ps timescales for large realistic molecules (hundreds of atoms in size) in the realistic solvent dielectric environment. The Collective Electronic Oscillator (CEO) code is used to compute electronic excited states, and the Non-adiabatic Excited State Molecular Dynamics (NA-ESMD) code is used to follow the non-adiabatic dynamics on multiple coupled Born-Oppenheimer potential energy surfaces. Our preliminary NA-ESMD simulations have revealed key photoinduced mechanisms controlling competing interactions and relaxation pathways in complex materials, including organic conjugated polymer materials, and have provided a detailed understanding of photochemical products and intermediates and the internal conversion process during the initiation of energetic materials. This project will be using LANL-based CEO and NA-ESMD codes to model nonradiative relaxation in organic and energetic materials. The NA-ESMD and CEO codes belong to a class of electronic structure/quantum chemistry codes that require large memory, “long-queue-few-core” distribution of resources in order to make useful progress. The NA-ESMD simulations are trivially parallelizable requiring ~300 processors for up to one week runtime to reach a meaningful restart point.

  9. Behavior of ro-vibrationally excited H2 molecules and H atoms in a plasma expansion

    International Nuclear Information System (INIS)

    Vankan, P.; Schram, D.C.; Engeln, R.

    2005-01-01

    The behavior in a supersonic plasma expansion of H atom and H2 molecules, both ground-state and ro-vibrationally excited, is studied using various laser spectroscopic techniques. The ground-state H2 molecules expand like a normal gas. The behavior of H atoms and H 2 rv molecules, on the other hand, is considerably influenced, and to some extend even determined, by their reactivity. The H atoms diffuse out of the expansion due to surface association at the walls of the vacuum vessel. Moreover, by reducing the surface area of the nozzle by a factor of two, the amount of H atoms leaving the source is increased by one order of magnitude, due to a decreased surface association of H atoms in the nozzle. The evolution of the ro-vibrational distributions along the expansion axis shows the relaxation of the molecular hydrogen from the high temperature in the up-stream region to the low ambient temperature in the down-stream region. Whereas the vibrational distribution resembles a Boltzmann distribution, the rotational distribution is a non-equilibrium one, in which the high rotational levels (J > 7) are much more populated than what is expected from the low rotational levels (J <5). We observed overpopulations of up to seven orders of magnitude. The production of the high rotational levels is very probably connected to the surface association in the nozzle

  10. History-dependent excitability as a single-cell substrate of transient memory for information discrimination.

    Directory of Open Access Journals (Sweden)

    Fabiano Baroni

    Full Text Available Neurons react differently to incoming stimuli depending upon their previous history of stimulation. This property can be considered as a single-cell substrate for transient memory, or context-dependent information processing: depending upon the current context that the neuron "sees" through the subset of the network impinging on it in the immediate past, the same synaptic event can evoke a postsynaptic spike or just a subthreshold depolarization. We propose a formal definition of History-Dependent Excitability (HDE as a measure of the propensity to firing in any moment in time, linking the subthreshold history-dependent dynamics with spike generation. This definition allows the quantitative assessment of the intrinsic memory for different single-neuron dynamics and input statistics. We illustrate the concept of HDE by considering two general dynamical mechanisms: the passive behavior of an Integrate and Fire (IF neuron, and the inductive behavior of a Generalized Integrate and Fire (GIF neuron with subthreshold damped oscillations. This framework allows us to characterize the sensitivity of different model neurons to the detailed temporal structure of incoming stimuli. While a neuron with intrinsic oscillations discriminates equally well between input trains with the same or different frequency, a passive neuron discriminates better between inputs with different frequencies. This suggests that passive neurons are better suited to rate-based computation, while neurons with subthreshold oscillations are advantageous in a temporal coding scheme. We also address the influence of intrinsic properties in single-cell processing as a function of input statistics, and show that intrinsic oscillations enhance discrimination sensitivity at high input rates. Finally, we discuss how the recognition of these cell-specific discrimination properties might further our understanding of neuronal network computations and their relationships to the distribution and

  11. Electronic excitation to low-lying states of GeF4 molecule by electron impact: A comparative study with CF4 and SiF4 molecules

    International Nuclear Information System (INIS)

    Ohtomi, S; Matsui, M; Mochizuki, Y; Suga, A; Kato, H; Hoshino, M; Tanaka, H; Duflot, D; Limão-Vieira, P

    2015-01-01

    We report on the measurements of the electron impact electronic excitation cross sections for XF 4 (X = C, Si and Ge) molecules at 100 eV, 5° scattering angle and 30 eV, 30° in the electron energy loss range 8.0 - 18 eV. For a target of GeF 4 molecule, the optically-forbidden behavior has been observed in the lower electron energy loss range. (paper)

  12. Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution

    Energy Technology Data Exchange (ETDEWEB)

    Imanbaew, D.; Nosenko, Y. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Kerner, C. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Chevalier, K.; Rupp, F. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Riehn, C., E-mail: riehn@chemie.uni-kl.de [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Thiel, W.R. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Diller, R. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany)

    2014-10-17

    Graphical abstract: - Highlights: • Ultrafast dynamics of new Ru(II) catalysts investigated in gas phase and solution. • Catalyst activation (HCl loss) achieved in ion trap by UV photoexcitation. • Electronic relaxation proceeds by IVR and IC followed by ground state dissociation. • No triplet formation in contrast to other Ru-polypyridine complexes. • Solvent prohibits catalyst activation in solution by fast vibrational cooling. - Abstract: We report studies on the excited state dynamics of new ruthenium(II) complexes [(η{sup 6}-cymene)RuCl(apypm)]PF{sub 6} (apypm=2-NR{sub 2}-4-(pyridine-2-yl)-pyrimidine, R=CH{sub 3} (1)/H (2)) which, in their active form [1{sup +}-HCl] and [2{sup +}-HCl], catalyze the transfer hydrogenation of arylalkyl ketones in the absence of a base. The investigations encompass femtosecond pump–probe transient mass spectrometry under isolated conditions and transient absorption spectroscopy in acetonitrile solution, both on the cations [(η{sup 6}-cymene)RuCl(apypm)]{sup +} (1{sup +}, 2{sup +}). Gas phase studies on mass selected ions were performed in an ESI ion trap mass spectrometer by transient photofragmentation, unambiguously proving the formation of the activated catalyst species [1{sup +}-HCl] or [2{sup +}-HCl] after photoexcitation being the only fragmentation channel. The primary excited state dynamics in the gas phase could be fitted to a biexponential decay, yielding time constants of <100 fs and 1–3 ps. Transient absorption spectroscopy performed in acetonitrile solution using femtosecond UV/Vis and IR probe laser pulses revealed additional deactivation processes on longer time scales (∼7–12 ps). However, the formation of the active catalyst species after photoexcitation could not be observed in solution. The results from both studies are compared to former CID investigations and DFT calculations concerning the activation mechanism.

  13. Analysis of Excitation and Ionization of Atoms and Molecules by Electron Impact

    CERN Document Server

    Chaudhry, Afzal

    2011-01-01

    Analysis of Excitation and Ionization of Atoms and Molecules by Electron Impact, by Afzal Chaudhry and Hans Kleinpoppen, describes in detail the measurements of the partial and total doubly differential cross sections for the multiple-ionization of rare gas atoms by electron impact. These measurements show, among other trends, the role of Auger transitions in the production of multiply ionized atoms in the region where the incident electron energy is sufficient to produce inner shell ionization. Other processes like Coster-Kronig transitions and shake off also contribute towards increasing the charge of the ions. As discussed in the book, an incident electron having energy of 6 keV, for example, in a collision with xenon atom can remove up to nine electrons! The measurements of doubly differential cross sections for the dissociative and non-dissociative ionization of hydrogen, sulfur dioxide and sulfur hexa fluoride molecular gases are also explored. The results of the measurements for the sulfur dioxide mole...

  14. Delta self-consistent field method to obtain potential energy surfaces of excited molecules on surfaces

    DEFF Research Database (Denmark)

    Gavnholt, Jeppe; Olsen, Thomas; Engelund, Mads

    2008-01-01

    is a density-functional method closely resembling standard density-functional theory (DFT), the only difference being that in Delta SCF one or more electrons are placed in higher lying Kohn-Sham orbitals instead of placing all electrons in the lowest possible orbitals as one does when calculating the ground......-state energy within standard DFT. We extend the Delta SCF method by allowing excited electrons to occupy orbitals which are linear combinations of Kohn-Sham orbitals. With this extra freedom it is possible to place charge locally on adsorbed molecules in the calculations, such that resonance energies can...... be estimated, which is not possible in traditional Delta SCF because of very delocalized Kohn-Sham orbitals. The method is applied to N2, CO, and NO adsorbed on different metallic surfaces and compared to ordinary Delta SCF without our modification, spatially constrained DFT, and inverse...

  15. Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

    Science.gov (United States)

    Marinov, Daniil; Guerra, Vasco; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine

    2013-10-01

    A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1-5 Torr and discharge currents ˜40-120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O_3^{*} , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O_3^{*} is strongly coupled with those of atomic oxygen and O2(a 1Δg) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established.

  16. Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

    International Nuclear Information System (INIS)

    Marinov, Daniil; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine; Guerra, Vasco

    2013-01-01

    A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1–5 Torr and discharge currents ∼40–120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O 3 * , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O 3 * is strongly coupled with those of atomic oxygen and O 2 (a 1 Δ g ) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established. (paper)

  17. Production of excited nitrogen atoms and ions by electron impact on nitrogen molecules

    International Nuclear Information System (INIS)

    Rall, D.L.A.; Anderson, L.W.; Lin, C.C.; Sharpton, F.A.

    1984-01-01

    Emission lines of the N atoms and N ions are produced by electron-beam dissociative excitation of N 2 molecules. The ns→3 /sub p/ (n=5 to 9), np→3s (n=3 to 7), nd→3 /sub p/ (n=4 to 8), nf→3d (n=4,5) transitions of N and the 3 /sub p/ →3s, 3d→3p, 4s→3p, 4p→3d, 4f→3d transitions of N + have been observed and optical emission cross sections at various incident electron energies have been measured. The energy dependence of the cross sections of the N emission lines is similar to that of the N + lines at high incident electron energies, but the low-energy behaviors are quite different. These features are explained by the mechanisms involved in the production of the excited N atoms and N + ions. Absolute optical emission cross sections for the N and N + lines are presented

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-14

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

  19. K-scrambling in a near-symmetric top molecule containing an excited noncoaxial internal rotor

    International Nuclear Information System (INIS)

    Ortigoso, Juan; Hougen, Jon T.

    2000-01-01

    Classical trajectories on rotational energy surfaces and coherent-state quantum projections have been used to study an asymmetric-top molecule containing a freely rotating internal symmetric top whose symmetry axis is not coincident with a principal axis of the molecule. Stationary points on the rotational energy surface, which strongly influence the trajectories, increase in number from two to four to six as J/n increases from zero to infinity (where J is the total and n is the free-internal-rotor angular momentum). For some J/n values trajectories can arise that sample a large fraction of K values (where K is the z-axis projection of J), corresponding in quantum wave functions to extensive K mixing in the symmetric-top basis set |J,K>. When such mixing cannot be made small for any choice of z axis, we call it K scrambling. For typical values of the torsion-rotation coupling parameter ρ, rotational eigenfunctions for a given J and torsional state turn out to be quite different from eigenfunctions for the same J in some other torsional state. Nonzero rotational overlap integrals are then distributed among many rotational functions for each (n,n ' ) pair, which may, in turn, contribute to internal rotation enhancement of intramolecular vibrational energy redistribution. We have also examined near-free-rotor levels of our test molecule acetaldehyde, which arise for excitation of ten or more quanta of methyl group torsion, and find that barrier effects do not change the qualitative picture obtained from the free-rotor treatment. (c) 2000 American Institute of Physics

  20. Extensive TD-DFT Benchmark: Singlet-Excited States of Organic Molecules.

    Science.gov (United States)

    Jacquemin, Denis; Wathelet, Valérie; Perpète, Eric A; Adamo, Carlo

    2009-09-08

    Extensive Time-Dependent Density Functional Theory (TD-DFT) calculations have been carried out in order to obtain a statistically meaningful analysis of the merits of a large number of functionals. To reach this goal, a very extended set of molecules (∼500 compounds, >700 excited states) covering a broad range of (bio)organic molecules and dyes have been investigated. Likewise, 29 functionals including LDA, GGA, meta-GGA, global hybrids, and long-range-corrected hybrids have been considered. Comparisons with both theoretical references and experimental measurements have been carried out. On average, the functionals providing the best match with reference data are, one the one hand, global hybrids containing between 22% and 25% of exact exchange (X3LYP, B98, PBE0, and mPW1PW91) and, on the other hand, a long-range-corrected hybrid with a less-rapidly increasing HF ratio, namely LC-ωPBE(20). Pure functionals tend to be less consistent, whereas functionals incorporating a larger fraction of exact exchange tend to underestimate significantly the transition energies. For most treated cases, the M05 and CAM-B3LYP schemes deliver fairly small deviations but do not outperform standard hybrids such as X3LYP or PBE0, at least within the vertical approximation. With the optimal functionals, one obtains mean absolute deviations smaller than 0.25 eV, though the errors significantly depend on the subset of molecules or states considered. As an illustration, PBE0 and LC-ωPBE(20) provide a mean absolute error of only 0.14 eV for the 228 states related to neutral organic dyes but are completely off target for cyanine-like derivatives. On the basis of comparisons with theoretical estimates, it also turned out that CC2 and TD-DFT errors are of the same order of magnitude, once the above-mentioned hybrids are selected.

  1. Comment on ’Single Pentacene Molecules Detected by Fluorescence Excitation in a P-Terphenyl Crystal’

    Science.gov (United States)

    1990-12-10

    8217 NO 11 TITLE (include Security Classification) Comment on "Single Pentacene Molecules Detected by Fluorescence Excitation in a p-Terphenyl Crystal" 12...8217 {Continue on reverse it necessary and identify by block numboer) Using h--,Ihly efficient Fluorescence excitation spectroscov of individual pentacene ...molecular impurities in p-terphenvl crystals, we have observed that some pentacene defects exhibit spcntaneous spectral jumps in their resonance frequency at

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  3. Fluorescence detection of single molecules using pulsed near-field optical excitation and time correlated photon counting

    International Nuclear Information System (INIS)

    Ambrose, W.P.; Goodwin, P.M.; Martin, J.C.; Keller, R.A.

    1994-01-01

    Pulsed excitation, time correlated single photon counting and time gated detection are used in near-field optical microscopy to enhance fluorescence images and measure the fluorescence lifetimes of single molecules of Rhodamine 6G on silica surfaces. Time gated detection is used to reject prompt scattered background and to improve the image signal to noise ratio. The excited state lifetime of a single Rhodamine 6G molecule is found to depend on the position of the near-field probe. We attribute the lifetime variations to spontaneous emission rate alterations by the fluorescence reflected from and quenching by the aluminum coated probe

  4. CN molecule vibrational spectra excitation in several LTE plasma sources conditions

    International Nuclear Information System (INIS)

    Iova, I.; Iova, Floriana; Ionita, I.; Bazavan, M.; Ilie, Gh.; Stanescu, G.

    2001-01-01

    Our interest in CN plasma study steams of the facilities to obtain the CN radicals in a free atmosphere electric discharge where the C of the coal electrodes can to combine in the enough high temperature plasma with the atmospheric nitrogen. Also of much interest is the very important phenomena in which the CN vibrational spectra can be implied and used as a diagnostic tool (plasma chemistry, astrophysics and so on). A peculiar importance presents the CN vibrational spectra in the transient plasmas. It is the reason why we have investigated here some internal processes of a continued and interrupted arc of various pulse lengths. To these purposes we present with enough accuracy the behaviour of the relative band head intensities of the sequences Δ v = +1 and Δ v = 0 belonging to the CN electronic transition (B 2 Σ - X 2 Σ), as a function of the pulse length (50 - 200 ms) as well as a function of the cathode to anode separation. These behaviours give us indications on the vibrational levels of the electronic state populations in several regions of the arc plasma as well on the efficiency of these levels excitation for several plasma pulse lengths. (authors)

  5. Assessment of oscillator strengths with multiconfigurational short-range density functional theory for electronic excitations in organic molecules

    DEFF Research Database (Denmark)

    Hedegård, Erik Donovan

    2017-01-01

    considered the large collection of organic molecules whose excited states were investigated with a range of electronic structure methods by Thiel et al. As a by-product of our calculations of oscillator strengths, we also obtain electronic excitation energies, which enable us to compare the performance......We have in a series of recent papers investigated electronic excited states with a hybrid between a complete active space self-consistent field (CASSCF) wave function and density functional theory (DFT). This method has been dubbed the CAS short-range DFT method (CAS–srDFT). The previous papers...

  6. Photoinduced dynamics of a cyanine dye: parallel pathways of non-radiative deactivation involving multiple excited-state twisted transients.

    Science.gov (United States)

    Upadhyayula, Srigokul; Nuñez, Vicente; Espinoza, Eli M; Larsen, Jillian M; Bao, Duoduo; Shi, Dewen; Mac, Jenny T; Anvari, Bahman; Vullev, Valentine I

    2015-04-01

    Cyanine dyes are broadly used for fluorescence imaging and other photonic applications. 3,3'-Diethylthiacyanine (THIA) is a cyanine dye composed of two identical aromatic heterocyclic moieties linked with a single methine, -CH 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 . The torsional degrees of freedom around the methine bonds provide routes for non-radiative decay, responsible for the inherently low fluorescence quantum yields. Using transient absorption spectroscopy, we determined that upon photoexcitation, the excited state relaxes along two parallel pathways producing three excited-state transients that undergo internal conversion to the ground state. The media viscosity impedes the molecular modes of ring rotation and preferentially affects one of the pathways of non-radiative decay, exerting a dominant effect on the emission

  7. Electronic excitation and deexcitation of atoms and molecules in nonequilibrium plasmas; Hiheiko plasma chu no denshi reiki ryushi hanno katei

    Energy Technology Data Exchange (ETDEWEB)

    Shimamori, H. [Fukui University of Technology, Fukui (Japan)

    1997-05-20

    Regarding excitation and deexcitation due to collision of electrons and deexcitation due to collision of baryons in nonequilibrium plasma, explanation is made about the general characteristics of the elementary processes involving their formation and disappearance and about the prediction of their sectional areas and velocity constants. As for the process of the formation of excited atoms and molecules by collision of electrons, it may be divided into the direct excitation in the ground state, excitation and light emission toward the resonance state, reexcitation and transformation of excited particles, recombination of electrons and positive atomic ions, and dissociation and recombination of electrons and positive molecular ions. As for the process of the disappearance of excited particles, there exist various courses it may follow, and it is quite complicated because it is dependent on the types of particles involved and the conditions the process proceeds under. Although the skeleton has been built of the theory of derivation of the sectional area of excitation due to collision of electrons and atoms/molecules, yet it is accurate enough only when applied to simple atomic/molecular systems, is far from satisfying in general, and is to be augmented by data from future experiments. 22 refs., 3 figs., 1 tab.

  8. Effect of vibrational excitation on the dynamics of ion-molecule reactions

    International Nuclear Information System (INIS)

    Anderson, S.L.

    1981-11-01

    A new experimental technique for the study of vibrational effects on ion-molecule reaction cross sections is described. Vibrational and collision energy dependent cross sections are presented for proton and H atom transfer, charge transfer and collision induced dissociation reactions in various isotopic H 2 + + H 2 systems. Charge and proton transfer cross sections are presented for the reactions of H 2 + and D 2 + with Ar, N 2 , CO, and O 2 . All the reactions are shown to be highly influenced by avoided crossings between the ground and first excited potential energy surfaces. Because of the nature of the crossings, vibrational motion of the systems can cause both adiabatic and non-adiabatic behavior of the system. This makes the vibrational dependences of the various cross sections a very sensitive probe of the dynamics of the collisions particularly, their behavior in the region of the crossings. Evidence is seen for charge transfer between reagents as they approach each other, transition to and in some cases reactions on excited potential energy surfaces, competition between different channels, and strong coupling of proton and charge transfer channels which occurs only for two of the systems studied (H 2 + + Ar, N 2 ). Oscillatory structure is observed in the collision energy dependence of the endoergic H 2 + (v = 0) + Ar charge transfer reaction for the first time, and a simple model which is commonly used for atom-atom charge transfer is used to fit the peaks. Finally a simple model is used to assess the importance of energy resonance and Franck-Condon effects on molecular charge transfer

  9. Quenching of excited uranyl ion during its photochemical reduction with triphenyl-phosphine : Part IV - effect of heterocyclic molecules

    International Nuclear Information System (INIS)

    Sidhu, M.S.; Bhatia, P.V.K.

    1994-01-01

    The presence of heterocyclic compounds triggers off a competition between photophysical and photochemical annihilation of excited uranyl ion during its photochemical reduction with triphenylphosphine. This competition is used to measure Stern-Volmer constant using UV visible spectrophotometer for quenching the uranyl ion luminescence with a number of heterocyclic molecules viz., pyridine, thiophene bipyridyl, tetrahydrofuran and piperidine. (author). 7 refs., 2 figs., 1 tab

  10. Short-term increases in transient receptor potential vanilloid-1 mediate stress-induced enhancement of neuronal excitation.

    Science.gov (United States)

    Weitlauf, Carl; Ward, Nicholas J; Lambert, Wendi S; Sidorova, Tatiana N; Ho, Karen W; Sappington, Rebecca M; Calkins, David J

    2014-11-12

    Progression of neurodegeneration in disease and injury is influenced by the response of individual neurons to stressful stimuli and whether this response includes mechanisms to counter declining function. Transient receptor potential (TRP) cation channels transduce a variety of disease-relevant stimuli and can mediate diverse stress-dependent changes in physiology, both presynaptic and postsynaptic. Recently, we demonstrated that knock-out or pharmacological inhibition of the TRP vanilloid-1 (TRPV1) capsaicin-sensitive subunit accelerates degeneration of retinal ganglion cell neurons and their axons with elevated ocular pressure, the critical stressor in the most common optic neuropathy, glaucoma. Here we probed the mechanism of the influence of TRPV1 on ganglion cell survival in mouse models of glaucoma. We found that induced elevations of ocular pressure increased TRPV1 in ganglion cells and its colocalization at excitatory synapses to their dendrites, whereas chronic elevation progressively increased ganglion cell Trpv1 mRNA. Enhanced TRPV1 expression in ganglion cells was transient and supported a reversal of the effect of TRPV1 on ganglion cells from hyperpolarizing to depolarizing, which was also transient. Short-term enhancement of TRPV1-mediated activity led to a delayed increase in axonal spontaneous excitation that was absent in ganglion cells from Trpv1(-/-) retina. In isolated ganglion cells, pharmacologically activated TRPV1 mobilized to discrete nodes along ganglion cell dendrites that corresponded to sites of elevated Ca(2+). These results suggest that TRPV1 may promote retinal ganglion cell survival through transient enhancement of local excitation and axonal activity in response to ocular stress. Copyright © 2014 the authors 0270-6474/14/3415369-13$15.00/0.

  11. Excitation of atoms and molecules in collisions with highly charged ions

    International Nuclear Information System (INIS)

    Watson, R.L.

    1993-01-01

    A study of the double ionization of He by high-energy N 7+ ions was extended up in energy to 40 MeV/amu. Coincidence time-of-flight studies of multicharged N 2 , O 2 , and CO molecular ions produced in collisions with 97-MeV Ar 14+ ions were completed. Analysis of the total kinetic energy distributions and comparison with the available data for CO 2+ and CO 3+ from synchrotron radiation experiments led to the conclusion that ionization by Ar-ion impact populates states having considerably higher excitation energies than those accessed by photoionization. The dissociation fractions for CO 1+ and CO 2+ molecular ions, and the branching ratios for the most prominent charge division channels of CO 2+ through CO 7+ were determined from time-of-flight singles and coincidence data. An experiment designed to investigate the orientation dependence of dissociative multielectron ionization of molecules by heavy ion impact was completed. Measurements of the cross sections for K-shell ionization of intermediate-Z elements by 30-MeV/amu H, N, Ne, and Ar ions were completed. The cross sections were determined for solid targets of Z = 13, 22, 26, 29, 32, 40, 42, 46, and 50 by recording the spectra of K x rays with a Si(Li) spectrometer

  12. Quantum electrodynamics with nonrelativistic sources. V. Electromagnetic field correlations and intermolecular interactions between molecules in either ground or excited states

    International Nuclear Information System (INIS)

    Power, E.A.; Thirunamachandran, T.

    1993-01-01

    Spatial correlations between electromagnetic fields arising from neutral sources with electric-dipole transition moments are calculated using nonrelativistic quantum electrodynamics in the multipolar formalism. Expressions for electric-electric, magnetic-magnetic, and electric-magnetic correlation functions at two points r and r' are given for a source molecule in either a ground or an excited state. In contrast to the electric-electric and magnetic-magnetic cases there are no electric-magnetic correlations for a ground-state molecule. For an excited molecule the downward transitions contribute additional terms which have modulating factors depending on (r-r')/λ. From these correlation functions electric and magnetic energy densities are found by setting r=r'. These energy densities are then used in a response formalism to calculate intermolecular energy shifts. In the case of two ground-state molecules this leads to the Casimir-Polder potential. However, for a pair of molecules, one or both excited, there are additional terms arising from downward transitions. An important feature of these energies is that they exhibit an R -2 dependence for large intermolecular separations R. This dependence is interpreted in terms of the Poynting vector, which itself can be obtained by setting r=r' in the electric-magnetic correlation function

  13. Three-dimensional finite element nonlinear dynamic analysis of pile groups for lateral transient and seismic excitations

    International Nuclear Information System (INIS)

    Maheshwari, B.K.; Truman, K.Z.; El Naggar, M.H.; Gould, P.L.

    2004-01-01

    The effects of material nonlinearity of soil and separation at the soil-pile interface on the dynamic behaviour of a single pile and pile groups are investigated. An advanced plasticity-based soil model, hierarchical single surface (HiSS), is incorporated in the finite element formulation. To simulate radiation effects, proper boundary conditions are used. The model and algorithm are verified with analytical results that are available for elastic and elastoplastic soil models. Analyses are performed for seismic excitation and for the load applied on the pile cap. For seismic analysis, both harmonic and transient excitations are considered. For loading on the pile cap, dynamic stiffness of the soil-pile system is derived and the effect of nonlinearity is investigated. The effects of spacing between piles are investigated, and it was found that the effect of soil nonlinearity on the seismic response is very much dependent on the frequency of excitation. For the loading on a pile cap, the nonlinearity increases the response for most of the frequencies of excitation while decreasing the dynamic stiffness of the soil-pile system. (author)

  14. A Simultaneous and Continuous Excitation Method for High-Speed Electrical Impedance Tomography with Reduced Transients and Noise Sensitivity

    Directory of Open Access Journals (Sweden)

    Antoine Dupré

    2018-03-01

    Full Text Available This paper presents a concept for soft field tomographic scan of all the projections of electromagnetic waves emanating from an array of electrodes. Instead of the sequential excitation of all pairs of electrodes in the list of all projections, the new method present here consists of a single and continuous excitation. This excitation signal is the linear combination of the excitation signals in the projection set at different AC frequencies. The response to a given projection is discriminated by selecting the corresponding AC frequency component in the signal spectra of the digitally demodulated signals. The main advantage of this method is the suppression of transients after each projection, which is particularly problematic in electrical impedance tomography due to contact impedance phenomena and skin effect. The second benefit over the sequential scan method is the increased number of samples for each measurement for reduced noise sensitivity with digital demodulation. The third benefit is the increased temporal resolution in high-speed applications. The main drawback is the increased number of signal sources required (one per electrode. This paper focuses on electrical impedance tomography, based on earlier work by the authors. An experimental proof-of-concept using a simple 4-electrodes electrical impedance tomographic system is presented using simulations and laboratory data. The method presented here may be extended to other modalities (ultrasonic, microwave, optical, etc..

  15. Calculation of 0-0 excitation energies of organic molecules by CIS(D) quantum chemical methods

    International Nuclear Information System (INIS)

    Grimme, Stefan; Izgorodina, Ekaterina I.

    2004-01-01

    The accuracy and reliability of the CIS(D) quantum chemical method and a spin-component scaled variant (SCS-CIS(D)) are tested for calculating 0-0 excitation energies of organic molecules. The ground and excited state geometries and the vibrational zero-point corrections are taken from (TD)DFT-B3LYP calculations. In total 32 valence excited states of different character are studied: π → π* states of polycyclic aromatic compounds/polyenes and n → π* states of carbonyl, thiocarbonyl and aza(azo)-aromatic compounds. This set is augmented by two systems of special interest, i.e., indole and the TICT state of dimethylaminbenzonitrile (DMABN). Both methods predict excitation energies that are on average higher than experiment by about 0.2 eV. The errors are found to be quite systematic (with a standard deviation of about 0.15 eV) and especially SCS-CIS(D) provides a more balanced treatment of π → π* vs. n → π* states. For the test suite of states, both methods clearly outperform the (TD)DFT-B3LYP approach. Opposed to previous conclusions about the performance of CIS(D), these methods can be recommended as reliable and efficient tools for computational studies of excited state problems in organic chemistry. In order to obtain conclusive results, however, the use of optimized excited state geometries and comparison with observables (0-0 excitation energies) are necessary

  16. Analytic description of highly excited vibrational-rotational states of diatomic molecules: II. Application to the hydrogen chloride molecule

    International Nuclear Information System (INIS)

    Burenin, A.V.; Ryabikin, M.Y.

    1995-01-01

    Processing of the precise experimental data on transition frequencies and energy levels in the ground electronic state of the H 35 Cl molecule was carried out on the basis of the asymptotically correct perturbation series analytically constructed to describe the discrete vibrational-rotational spectrum of a diatomic molecule. The perturbation series was shown to converge rapidly up to the dissociation energy E D , whereas the conventional Dunham series has a distinct limit of applicability equal to 0.39E D . 12 refs., 2 figs

  17. Sub-threshold excited Cl Kβ (K-V) x-ray fluorescence from CF3Cl molecule

    International Nuclear Information System (INIS)

    Perera, R.C.C.; Cowan, P.L.; Lindle, D.W.; LaVilla, R.E.

    1987-10-01

    With the availability of tunable synchrotron radiation sources, unoccupied molecular orbits (below vacuum level) can be selectively populated producing highly excited neutral molecules. X-ray fluorescence spectra from molecules were obtained with excitation below the ionization threshold and were observed to have significant intensity changes, absolute and relative energy position shifts and line width changes as compared to fluorescence spectra excited above the threshold. As an example, the Cl Kβ (K-V) emission spectra from CF 3 Cl vapor are presented. The energy shifts and intensity changes are explained in terms of perturbation effects due to the presence of an electron in an unoccupied molecular orbital. The narrow line widths obtained in the spectra excited below threshold are explained in terms of the ''effective'' hole production region in a core state limited by the broadening of the unoccupied level. The change in line widths as a function of below-threshold excitation energy is proposed as a novel technique to study the localized properties and reorganization effects of a hole in a core level. 10 refs., 4 figs., 1 tab

  18. Mechanism and models for collisional energy transfer in highly excited large polyatomic molecules

    International Nuclear Information System (INIS)

    Gilbert, R. G.

    1995-01-01

    Collisional energy transfer in highly excited molecules (say, 200-500 kJ mol -1 above the zero-point energy of reactant, or of product, for a recombination reaction) is reviewed. An understanding of this energy transfer is important in predicting and interpreting the pressure dependence of gas-phase rate coefficients for unimolecular and recombination reactions. For many years it was thought that this pressure dependence could be calculated from a single energy-transfer quantity, such as the average energy transferred per collision. However, the discovery of 'super collisions' (a small but significant fraction of collisions which transfer abnormally large amounts of energy) means that this simplistic approach needs some revision. The 'ordinary' (non-super) component of the distribution function for collisional energy transfer can be quantified either by empirical models (e.g., an exponential-down functional form) or by models with a physical basis, such as biased random walk (applicable to monatomic or diatomic collision partners) or ergodic (for polyatomic collision partners) treatments. The latter two models enable approximate expressions for the average energy transfer to be estimated from readily available molecular parameters. Rotational energy transfer, important for finding the pressure dependence for recombination reactions, can for these purposes usually be taken as transferring sufficient energy so that the explicit functional form is not required to predict the pressure dependence. The mechanism of 'ordinary' energy transfer seems to be dominated by low-frequency modes of the substrate, whereby there is sufficient time during a vibrational period for significant energy flow between the collision partners. Super collisions may involve sudden energy flow as an outer atom of the substrate is squashed between the substrate and the bath gas, and then is moved away from the interaction by large-amplitude motion such as a ring vibration or a rotation; improved

  19. Electron dynamics in the core-excited CS2 molecule revealed through resonant inelastic x-ray scattering spectroscopy

    International Nuclear Information System (INIS)

    Marchenko, T; Carniato, S; Journel, L; Guillemin, R; Kawerk, E; Simon, M; Žitnik, M; Kavčič, M; Bučar, K; Bohinc, R; Petric, M; Da Cruz, V Vaz; Gel'mukhanov, F

    2015-01-01

    We present an experimental and theoretical study of resonant inelastic x-ray scattering (RIXS) in the CS 2 molecule near the S 1s edge. We show that localization of the S 1s core-hole occurs in CS 2 during the RIXS process due to the orientational dephasing of interference between the waves scattering on the two sulfur atoms. Strong evolution of the RIXS profile with the excitation energy far below the first absorption resonance reflects the onset of electron dynamics triggered by a coherent excitation of multiple electronic states. (paper)

  20. Excitation of atoms and molecules in collisions with highly charged ions

    International Nuclear Information System (INIS)

    Watson, R.L.

    1992-01-01

    This report discusses research of multicharged nitrogen, oxygen and carbon monoxide molecular ions produced with collision with multicharged argon ions. Properties like ionization, dissociation, and excitation are investigated

  1. The effect of gold nanoparticles on exchange processes in collision complexes of triplet and singlet oxygen molecules with excited eosin molecules

    Science.gov (United States)

    Bryukhanov, V. V.; Minaev, B. M.; Tsibul'nikova, A. V.; Slezhkin, V. A.

    2015-07-01

    We have studied exchange processes in contact complexes of triplet eosin molecules with oxygen molecules in the triplet (3Σ{/g -}) and singlet (1Δ g ) states in thin polyvinylbutyral films in the presence of gold nanoparticles. Upon resonant excitation of surface plasmons in gold nanoparticles into the absorption band of eosin molecules-singlet oxygen sensitizers-we have obtained an increase in the intensity of the delayed fluorescence and an increase in the lifetime of the dye with simultaneous quenching of the luminescence of singlet oxygen. The kinetics of the delayed fluorescence of the dye as a result of singlet-triplet annihilation of triplet eosin molecules with singlet oxygen molecules has been investigated. To compare theoretical and experimental data, we have numerically simulated energy transfer processes. Rate constants of energy transfer and of singlet-triplet annihilation, as well as quenching constants of triplet states of the dye by molecular oxygen, have been calculated. Luminescence quantum yield 1Δ g of polyvinylbutyral has been estimated. We have analyzed quantum-chemically electronic mechanisms of singlet-triplet annihilation of oxygen and eosin.

  2. Overshoot mechanism in transient excitation of THz and Gunn oscillations in wide-bandgap semiconductors

    Science.gov (United States)

    Momox, Ernesto; Zakhleniuk, Nick; Balkan, Naci

    2012-11-01

    A detailed study of high-field transient and direct-current (DC) transport in GaN-based Gunn diode oscillators is carried out using the commercial simulator Sentaurus Device. Applicability of drift-diffusion (DD) and hydrodynamic (HD) models to high-speed, high-frequency devices is discussed in depth, and the results of the simulations from these models are compared. It is shown, for a highly homogeneous device based on a short (2 μm) supercritically doped (1017 cm-3) GaN specimen, that the DD model is unable to correctly take into account some essential physical effects which determine the operation mode of the device. At the same time, the HD model is ideally suited to solve such problems due to its ability to incorporate non-local effects. We show that the velocity overshoot near the device contacts and space charge injection and extraction play a crucial role in defining the operation mode of highly homogeneous short diodes in both the transient regime and the voltage-controlled oscillation regime. The transient conduction current responses are fundamentally different in the DD and HD models. The DD current simply repeats the velocity-field (v-F) characteristics, and the sample remains in a completely homogeneous state. In the HD model, the transient current pulse with a full width at half maximum of approximately 0.2 ps is increased about twofold due to the carrier injection (extraction) into (from) the active region and the velocity overshoot. The electron gas is characterized by highly inhomogeneous distributions of the carrier density, the electric field and the electron temperature. The simulation of the DC steady states of the diodes also shows very different results for the two models. The HD model shows the trapped stable anodic domain in the device, while the DD model completely retains all features of the v-F characteristics in a homogeneous gas. Simulation of the voltage-controlled oscillator shows that it operates in the accumulation layer mode

  3. Electron Dynamics in the Core-Excited CS 2 Molecule Revealed through Resonant Inelastic X-Ray Scattering Spectroscopy

    OpenAIRE

    Marchenko , T; Carniato , S; Journel , L; Guillemin , R; Kawerk , E; Žitnik , M; Kavčič , M; Bučar , K; Bohinc , R; Petric , M; Vaz Da Cruz , V; Gel 'mukhanov , F; Simon , Marielle

    2015-01-01

    International audience; We present an experimental and theoretical study of resonant inelastic x-ray scattering (RIXS) in the carbon disulphide CS 2 molecule near the sulfur K-absorption edge. We observe a strong evolution of the RIXS spectral profile with the excitation energy tuned below the lowest unoccupied molecular orbital (LUMO) absorption resonance. The reason for this is twofold. Reducing the photon energy in the vicinity of the LUMO absorption resonance leads to a relative suppressi...

  4. Routes to formation of highly excited neutral atoms in the break-up of strongly driven hydrogen molecule

    Science.gov (United States)

    Emmanouilidou, Agapi

    2012-06-01

    We present a theoretical quasiclassical treatment of the formation, during Coulomb explosion, of highly excited neutral H atoms for strongly-driven hydrogen molecule. This process, where after the laser field is turned off, one electron escapes to the continuum while the other occupies a Rydberg state, was recently reported in an experimental study in Phys. Rev. Lett 102, 113002 (2009). We find that two-electron effects are important in order to correctly account for all pathways leading to highly excited neutral hydrogen formation [1]. We identify two pathways where the electron that escapes to the continuum does so either very quickly or after remaining bound for a few periods of the laser field. These two pathways of highly excited neutral H formation have distinct traces in the probability distribution of the escaping electron momentum components. [4pt] [1] A. Emmanouilidou, C. Lazarou, A. Staudte and U. Eichmann, Phys. Rev. A (Rapid) 85 011402 (2012).

  5. Silicon as a virtual plasmonic material: Acquisition of its transient optical constants and the ultrafast surface plasmon-polariton excitation

    Energy Technology Data Exchange (ETDEWEB)

    Danilov, P. A.; Ionin, A. A.; Kudryashov, S. I., E-mail: sikudr@sci.lebedev.ru; Makarov, S. V.; Rudenko, A. A. [Lebedev Physical Institute (Russian Federation); Saltuganov, P. N. [Moscow Institute of Physics and Technology (State University) (Russian Federation); Seleznev, L. V.; Yurovskikh, V. I.; Zayarny, D. A. [Lebedev Physical Institute (Russian Federation); Apostolova, T. [Bulgarian Academy of Sciences, Institute for Nuclear Research and Nuclear Energetics (Bulgaria)

    2015-06-15

    Ultrafast intense photoexcitation of a silicon surface is complementarily studied experimentally and theoretically, with its prompt optical dielectric function obtained by means of time-resolved optical reflection microscopy and the underlying electron-hole plasma dynamics modeled numerically, using a quantum kinetic approach. The corresponding transient surface plasmon-polariton (SPP) dispersion curves of the photo-excited material were simulated as a function of the electron-hole plasma density, using the derived optical dielectric function model, and directly mapped at several laser photon energies, measuring spatial periods of the corresponding SPP-mediated surface relief nanogratings. The unusual spectral dynamics of the surface plasmon resonance, initially increasing with the increase in the electron-hole plasma density but damped at high interband absorption losses induced by the high-density electron-hole plasma through instantaneous bandgap renormalization, was envisioned through the multi-color mapping.

  6. Semiclassical study of the collision of a highly excited Rydberg atom with the molecules HF and HCl

    International Nuclear Information System (INIS)

    Kimura, M.; Lane, N.F.

    1990-01-01

    The semiclassical impact-parameter method is applied to the processes of state changing and energy transfer in the collision of a highly excited Rydberg atom (n≥20) with the polar molecules HF and HCl. The relative motion of the molecule and atomic nucleus is taken to be rectilinear; the electron-molecule and ion core-molecule interactions are represented by cutoff dipole forms. Cross sections for transitions involving quantum numbers n and l of the atom and rotational quantum number j of the molecule are obtained for a range of collision energies and initial atomic and molecular states. Comparisons are made with the results of earlier classical studies and with the quantum-mechanical impulse approximation. Collision rates are calculated and compared with experimental values for l mixing and n and j changing. The agreement between experiment and theory is shown to be satisfactory, within the uncertainties of both the measurements and the theory. Cases of agreement and disagreement between various theories are examined. One finding of the present work is that the quantum-mechanical impulse approximation appears to significantly overestimate the values of various state-changing cross sections when the internal energy defect is small. The validity of the impulse approximation for collisions of Rydberg atoms with polar molecules is discussed

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

    Energy Technology Data Exchange (ETDEWEB)

    Laursen, S.L.

    1990-01-01

    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.

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

    International Nuclear Information System (INIS)

    Laursen, S.L.

    1990-01-01

    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

  9. Remotely Exploring Deeper-Into-Matter by Non-Contact Detection of Audible Transients Excited by Laser Radiation

    Directory of Open Access Journals (Sweden)

    Javier Moros

    2017-12-01

    Full Text Available An acoustic spectroscopic approach to detect contents within different packaging, with substantially wider applicability than other currently available subsurface spectroscopies, is presented. A frequency-doubled Nd:YAG (neodymium-doped yttrium aluminum garnet pulsed laser (13 ns pulse length operated at 1 Hz was used to generate the sound field of a two-component system at a distance of 50 cm. The acoustic emission was captured using a unidirectional microphone and analyzed in the frequency domain. The focused laser pulse hitting the system, with intensity above that necessary to ablate the irradiated surface, transferred an impulsive force which led the structure to vibrate. Acoustic airborne transients were directly radiated by the vibrating elastic structure of the outer component that excited the surrounding air in contact with. However, under boundary conditions, sound field is modulated by the inner component that modified the dynamical integrity of the system. Thus, the resulting frequency spectra are useful indicators of the concealed content that influences the contributions originating from the wall of the container. High-quality acoustic spectra could be recorded from a gas (air, liquid (water, and solid (sand placed inside opaque chemical-resistant polypropylene and stainless steel sample containers. Discussion about effects of laser excitation energy and sampling position on the acoustic emission events is reported. Acoustic spectroscopy may complement the other subsurface alternative spectroscopies, severely limited by their inherent optical requirements for numerous detection scenarios.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  11. Carbon K-shell excitation in small molecules by high-resolution electron impact

    International Nuclear Information System (INIS)

    Tronc, M.; King, G.C.; Read, F.H.

    1979-01-01

    The excitation of 1s carbon electrons has been observed in C0, CH 4 , CF4, C0 2 , COS, C 2 H 2 and C 2 H 4 by means of the electron energy-loss technique with high resolution (70 meV in the 300 eV excitation energy range) and at an incident electron energy of 1.5 keV. The energies, widths and vibrational structures of excited states corresponding to the promotion of 1s carbon electrons to unoccupied valence and Rydberg orbitals have been obtained. The validity of the equivalent-core model, and the role of resonances caused by potential barriers, are discussed. (author)

  12. Metastable Molecules in the Ground and in Excited States, Theory Development, Implementation and Application

    National Research Council Canada - National Science Library

    Bartlett, Rodney J

    2006-01-01

    ... fingerprints for identification. We also make applications of interesting clusters, atmospheric systems, potential interstellar molecules, and to gas phase molecular reactions of the sort that can occur in flames.

  13. Effect of collision energy and vibrational excitation on endothermic ion-molecule reactions

    International Nuclear Information System (INIS)

    Turner, T.P.

    1984-07-01

    This thesis is divided into two major parts. In the first part an experimental study of proton and deuteron transfer in H 2 + + He and HD + + He has been carried out as a function of kinetic and vibrational energy. The data gives evidence that at lower kinetic energies, the spectator stripping mechanism indeed plays an important role when H 2 + or HD + is vibrationally excited. The second half of this thesis examines the relative efficiencies between the excitation of C-C stretching vibration and collision energy on the promotion of the H atom transfer reaction of C 2 H 2 + + H 2 → C 2 H 3 + + H

  14. Wobbling excitation of triaxial nuclear molecule 28Si – 28Si

    International Nuclear Information System (INIS)

    Uegaki, E; Abe, Y

    2013-01-01

    High-spin resonances observed in the 28 Si + 28 Si collisions are investigated with a molecular model. At high spins, a stable dinuclear configuration is found to be an equator-equator touching one. Since the E-E configuration is slightly triaxial, rotations of the total system induce mixing of K quantum numbers, called wobbling motion, which clearly explains the particle-γ angular correlations observed as well as the disalignments in a simple and natural way. Furthermore, predictions are given for the angular correlations of the wobbling excited states. The first excited state of wobbling shows strong alignments, which is quite different from the molecular ground state.

  15. Calculation of Ground State Rotational Populations for Kinetic Gas Homonuclear Diatomic Molecules including Electron-Impact Excitation and Wall Collisions

    International Nuclear Information System (INIS)

    Farley, David R.

    2010-01-01

    A model has been developed to calculate the ground-state rotational populations of homonuclear diatomic molecules in kinetic gases, including the effects of electron-impact excitation, wall collisions, and gas feed rate. The equations are exact within the accuracy of the cross sections used and of the assumed equilibrating effect of wall collisions. It is found that the inflow of feed gas and equilibrating wall collisions can significantly affect the rotational distribution in competition with non-equilibrating electron-impact effects. The resulting steady-state rotational distributions are generally Boltzmann for N (ge) 3, with a rotational temperature between the wall and feed gas temperatures. The N = 0,1,2 rotational level populations depend sensitively on the relative rates of electron-impact excitation versus wall collision and gas feed rates.

  16. Inner shell excitation in atoms and molecules by high resolution electron impact

    International Nuclear Information System (INIS)

    King, G.C.

    1986-01-01

    In this work an inner-shell spin-forbidden transition in N 2 and a parity-forbidden transition in Ar were studied. These transitions were observed by using incident electron energies as low as 1.15 times the excitation energy of the inner-shell states. (Auth.)

  17. Bottom-up excited state dynamics of two cinnamate-based sunscreen filter molecules.

    Science.gov (United States)

    Peperstraete, Yoann; Staniforth, Michael; Baker, Lewis A; Rodrigues, Natércia D N; Cole-Filipiak, Neil C; Quan, Wen-Dong; Stavros, Vasilios G

    2016-10-12

    Methyl-E-4-methoxycinnamate (E-MMC) is a model chromophore of the commonly used commercial sunscreen agent, 2-ethylhexyl-E-4-methoxycinnamate (E-EHMC). In an effort to garner a molecular-level understanding of the photoprotection mechanisms in operation with E-EHMC, we have used time-resolved pump-probe spectroscopy to explore E-MMC's and E-EHMC's excited state dynamics upon UV-B photoexcitation to the S 1 (1 1 ππ*) state in both the gas- and solution-phase. In the gas-phase, our studies suggest that the excited state dynamics are driven by non-radiative decay from the 1 1 ππ* to the S 3 (1 1 nπ*) state, followed by de-excitation from the 1 1 nπ* to the ground electronic state (S 0 ). Using both a non-polar-aprotic solvent, cyclohexane, and a polar-protic solvent, methanol, we investigated E-MMC and E-EHMC's photochemistry in a more realistic, 'closer-to-shelf' environment. A stark change to the excited state dynamics in the gas-phase is observed in the solution-phase suggesting that the dynamics are now driven by efficient E/Z isomerisation from the initially photoexcited 1 1 ππ* state to S 0 .

  18. Single photon excimer laser photodissociation of highly vibrationally excited polyatomic molecules

    International Nuclear Information System (INIS)

    Tiee, J.J.; Wampler, F.B.; Rice, W.W.

    1980-01-01

    The ir + uv photodissociation of SF 6 has been performed using CO 2 and ArF lasers. The two-color photolysis significantly enhances the photodissociation process over ArF irradiation alone and is found to preserve the initial isotopic specificity of the ir excitation process

  19. Do vibrationally excited OH molecules affect middle and upper atmospheric chemistry?

    Directory of Open Access Journals (Sweden)

    T. von Clarmann

    2010-10-01

    Full Text Available Except for a few reactions involving electronically excited molecular or atomic oxygen or nitrogen, atmospheric chemistry modelling usually assumes that the temperature dependence of reaction rates is characterized by Arrhenius' law involving kinetic temperatures. It is known, however, that in the upper atmosphere the vibrational temperatures may exceed the kinetic temperatures by several hundreds of Kelvins. This excess energy has an impact on the reaction rates. We have used upper atmospheric OH populations and reaction rate coefficients for OH(v=0...9+O3 and OH(v=0...9+O to estimate the effective (i.e. population weighted reaction rates for various atmospheric conditions. We have found that the effective rate coefficient for OH(v=0...9+O3 can be larger by a factor of up to 1470 than that involving OH in its vibrational ground state only. At altitudes where vibrationally excited states of OH are highly populated, the OH reaction is a minor sink of Ox and O3 compared to other reactions involving, e.g., atomic oxygen. Thus the impact of vibrationally excited OH on the ozone or Ox sink remains small. Among quiescent atmospheres under investigation, the largest while still small (less than 0.1% effect was found for the polar winter upper stratosphere and mesosphere. The contribution of the reaction of vibrationally excited OH with ozone to the OH sink is largest in the upper polar winter stratosphere (up to 4%, while its effect on the HO2 source is larger in the lower thermosphere (up to 1.5% for polar winter and 2.5% for midlatitude night conditions. For OH(v=0...9+O the effective rate coefficients are lower by up to 11% than those involving OH in its vibrational ground state. The effects on the odd oxygen sink are negative and can reach −3% (midlatitudinal nighttime lowermost thermosphere, i.e. neglecting vibrational excitation overestimates the odd

  20. Investigations of the potential functions of weakly bound diatomic molecules and laser-assisted excitive Penning ionization

    International Nuclear Information System (INIS)

    Goble, J.H. Jr.

    1982-05-01

    Three variations on the Dunham series expansion function of the potential of a diatomic molecule are compared. The differences among these expansions lie in the choice of the expansion variable, lambda. The functional form of these variables are lambda/sub s/ = l-r/sub e//r for the Simon-Parr-Finlan version, lambda/sub T/ - 1-(r/sub e//r)/sup p/ for that of Thakkar, and lambda/sub H/ = 1-exp(-rho(r/r/sub e/-1) for that of Huffaker. A wide selection of molecular systems are examined. It is found that, for potentials in excess of thirty kcal/mole, the Huffaker expansion provides the best description of the three, extrapolating at large internuclear separation to a value within 10% of the true dissociation energy. For potentials that result from the interaction of excited states, all series expansions show poor behavior away from the equilibrium internuclear separation of the molecule. The series representation of the potentials of weakly bound molecules are examined in more detail. The ground states of BeAr + , HeNe + , NaAr, and Ar 2 and the excited states of HeNe+, NaNe, and NaAr are best described by the Thakkar expansion. Finally, the observation of laser-assisted excitive Penning ionization in a flowing afterglow is reported. The reaction Ar( 3 P 2 ) + Ca + h nu → Ar + Ca + (5p 2 P/sub J/) + e - occurs when the photon energy, h nu, is approximately equal to the energy difference between the metastable argon and one of the fine structure levels of the ion's doublet. By monitoring the cascade fluorescence of the above reaction and comparing it to the flourescence from the field-free process Ar( 3 P 2 ) + Ca → Ar + Ca + (4p 2 P/sub J/) + e - a surprisingly large cross section of 6.7 x 10 3 A 2 is estimated

  1. Band-selective excited ultrahigh resolution PSYCHE-TOCSY: fast screening of organic molecules and complex mixtures.

    Science.gov (United States)

    Kakita, Veera Mohana Rao; Vemulapalli, Sahithya Phani Babu; Bharatam, Jagadeesh

    2016-04-01

    Precise assignments of (1) H atomic sites and establishment of their through-bond COSY or TOCSY connectivity are crucial for molecular structural characterization by using (1) H NMR spectroscopy. However, this exercise is often hampered by signal overlap, primarily because of (1) H-(1) H scalar coupling multiplets, even at typical high magnetic fields. The recent developments in homodecoupling strategies for effectively suppressing the coupling multiplets into nice singlets (pure-shift), particularly, Morris's advanced broadband pure-shift yielded by chirp excitation (PSYCHE) decoupling and ultrahigh resolution PSYCHE-TOCSY schemes, have shown new possibilities for unambiguous structural elucidation of complex organic molecules. The superior broadband PSYCHE-TOCSY exhibits enhanced performance over the earlier TOCSY methods, which however warrants prolonged experimental times due to the requirement of large number of dwell increments along the indirect dimension. Herein, we present fast and band-selective analog of the broadband PSYCHE-TOCSY, which is useful for analyzing complex organic molecules that exhibit characteristic yet crowded spectral regions. The simple pulse scheme relies on band-selective excitation (BSE) followed by PSYCHE homodecoupling in the indirect dimension. The BSE-PSYCHE-TOCSY has been exemplified for Estradiol and a complex carbohydrate mixture comprised of six constituents of closely comparable molecular weights. The experimental times are greatly reduced viz., ~20 fold for Estradiol and ~10 fold for carbohydrate mixture, with respect to the broadband PSYCHE-TOCSY. Furthermore, unlike the earlier homonuclear band-selective decoupling, the BSE-PSYCHE-decoupling provides fully decoupled pure-shift spectra for all the individual chemical sites within the excited band. The BSE-PSYCHE-TOCSY is expected to have significant potential for quick screening of complex organic molecules and mixtures at ultrahigh resolution. Copyright © 2015 John Wiley

  2. Quantum dynamics study on the binding of a positron to vibrationally excited states of hydrogen cyanide molecule

    Science.gov (United States)

    Takayanagi, Toshiyuki; Suzuki, Kento; Yoshida, Takahiko; Kita, Yukiumi; Tachikawa, Masanori

    2017-05-01

    We present computational results of vibrationally enhanced positron annihilation in the e+ + HCN/DCN collisions within a local complex potential model. Vibrationally elastic and inelastic cross sections and effective annihilation rates were calculated by solving a time-dependent complex-potential Schrödinger equation under the ab initio potential energy surface for the positron attached HCN molecule, [HCN; e+], with multi-component configuration interaction level (Kita and Tachikawa, 2014). We discuss the effect of vibrational excitation on the positron affinities from the obtained vibrational resonance features.

  3. Electron dynamics in the core-excited CS 2 molecule revealed through resonant inelastic x-ray scattering spectroscopy

    OpenAIRE

    Marchenko , T; Carniato , S; Journel , L; Guillemin , R; Kawerk , E; Žitnik , M; Kavčič , M; Bučar , K; Bohinc , R; Petric , M; da Cruz , V Vaz; Gel'mukhanov , F; Simon , Marielle

    2015-01-01

    International audience; We present an experimental and theoretical study of resonant inelastic x-ray scattering (RIXS) in the CS2 molecule near the S 1s edge. We show that localization of the S 1s core-hole occurs in CS2 during the RIXS process due to the orientational dephasing of interference between the waves scattering on the two sulfur atoms. Strong evolution of the RIXS profile with the excitation energy far below the first absorption resonance reflects the onset of electron dynamics tr...

  4. Rotational excitation of linear triatomic molecules: Ar, Kr + N2O, CO2

    International Nuclear Information System (INIS)

    Farrar, J.M.; Parson, J.M.; Lee, Y.T.

    1974-01-01

    Rotational excitation of N 2 O and CO 2 in collisions with Ar and Kr has been studied by crossing two supersonic molecular beams and detecting scattered products with a mass spectrometer. Measurement of the time of flight spectrum of the products as a function of laboratory scattering angle theta indicates that the inelasticity is concentrated in the forward direction in the center of mass system. Difference between CO 2 and N 2 O are discussed briefly

  5. Intramolecular Dynamics: A Study of Molecules at High Levels of Vibrational Excitation.

    Science.gov (United States)

    1988-05-27

    aareemlent stith the photoa.couxueC rexults.,I4 % obintied t r iii pfii ioaCOI it tic tveaxu retntsx." Si ne thle xhoxs xthat Iii the I ott fi nence...t 0 200 400 ns 6000 between pump and probe pulse for CH3 CHF2 at 660 Pa. Infrared excitation: 10.6 pim P(20) line, 0.5 ns pulse with average fluence

  6. Theoretical study of singlet oxygen molecule generation via an exciplex with valence-excited thiophene.

    Science.gov (United States)

    Sumita, Masato; Morihashi, Kenji

    2015-02-05

    Singlet-oxygen [O2((1)Δg)] generation by valence-excited thiophene (TPH) has been investigated using multireference Møller-Plesset second-order perturbation (MRMP2) theory of geometries optimized at the complete active space self-consistent field (CASSCF) theory level. Our results indicate that triplet TPH(1(3)B2) is produced via photoinduced singlet TPH(2(1)A1) because 2(1)A1 TPH shows a large spin-orbit coupling constant with the first triplet excited state (1(3)B2). The relaxed TPH in the 1(3)B2 state can form an exciplex with O2((3)Σg(-)) because this exciplex is energetically more stable than the relaxed TPH. The formation of the TPH(1(3)B2) exciplex with O2((3)Σg(-)) whose total spin multiplicity is triplet (T1 state) increases the likelihood of transition from the T1 state to the singlet ground or first excited singlet state. After the transition, O2((1)Δg) is emitted easily although the favorable product is that from a 2 + 4 cycloaddition reaction.

  7. The variational cellular method for quantum mechanical applications : calculations of the ground and excited states of F2 and Ne2 molecules

    International Nuclear Information System (INIS)

    Leite, J.R.; Fazzio, A.; Lima, M.A.P.; Dias, A.M.; Rosato, A.; Segre, E.R.A.

    1980-12-01

    A self-consistent calculation based on the Variational Cellular Method is performed on the F 2 and Ne 2 molecules. The potential curve for the group state and for excited states of these molecules are determined. Spectroscopic constants related to the potential curves are also obtained. (Author) [pt

  8. Excitation two-center interference and the orbital geometry in laser-induced nonsequential double ionization of diatomic molecules

    International Nuclear Information System (INIS)

    Shaaran, T.; Augstein, B. B.; Figueira de Morisson Faria, C.

    2011-01-01

    We address the influence of the molecular orbital geometry and of the molecular alignment with respect to the laser-field polarization on laser-induced nonsequential double ionization of diatomic molecules for different molecular species, namely N 2 and Li 2 . We focus on the recollision excitation with subsequent tunneling ionization (RESI) mechanism, in which the first electron, upon return, promotes the second electron to an excited state, from where it subsequently tunnels. We assume that both electrons are initially in the highest occupied molecular orbital (HOMO) and that the second electron is excited to the lowest unoccupied molecular orbital (LUMO). We show that the electron-momentum distributions exhibit interference maxima and minima due to the electron emission at spatially separated centers. We provide generalized analytical expressions for such maxima or minima, which take into account s-p mixing and the orbital geometry. The patterns caused by the two-center interference are sharpest for vanishing alignment angle and get washed out as this parameter increases. Apart from that, there exist features due to the geometry of the LUMO, which may be observed for a wide range of alignment angles. Such features manifest themselves as the suppression of probability density in specific momentum regions due to the shape of the LUMO wave function, or as an overall decrease in the RESI yield due to the presence of nodal planes.

  9. Electron Dynamics in the Core-Excited CS_{2} Molecule Revealed through Resonant Inelastic X-Ray Scattering Spectroscopy

    Directory of Open Access Journals (Sweden)

    T. Marchenko

    2015-08-01

    Full Text Available We present an experimental and theoretical study of resonant inelastic x-ray scattering (RIXS in the carbon disulphide CS_{2} molecule near the sulfur K-absorption edge. We observe a strong evolution of the RIXS spectral profile with the excitation energy tuned below the lowest unoccupied molecular orbital (LUMO absorption resonance. The reason for this is twofold. Reducing the photon energy in the vicinity of the LUMO absorption resonance leads to a relative suppression of the LUMO contribution with respect to the emission signal from the higher unoccupied molecular orbitals, which results in the modulation of the total RIXS profile. At even larger negative photon-energy detuning from the resonance, the excitation-energy dependence of the RIXS profile is dominated by the onset of electron dynamics triggered by a coherent excitation of multiple electronic states. Furthermore, our study demonstrates that in the hard x-ray regime, localization of the S 1s core hole occurs in CS_{2} during the RIXS process because of the orientational dephasing of interference between the waves scattering on the two sulfur atoms. Core-hole localization leads to violation of the symmetry selection rules for the electron transitions observed in the spectra.

  10. Contribution to simple and double photoionization studies in several molecules excited by synchrotron radiation

    International Nuclear Information System (INIS)

    Lablanquie, Pascal

    1984-01-01

    This work is divided into two parts. Photoelectron spectrometry has enabled us to study the simple photoionisation in inner and outer shell of the N 2 molecule. The limits of an independent particle model, and the importance of electronic interactions have been outlined; an analysis of the structures situated at a photon energy of 23 eV revealed the behavior of two kinds of autoionizing states; the shape resonances of the Σ g + states have been compared. We have then built a new experimental set-up to study double photoionisation. The case of the CS 2 molecule has been examined by mass spectrometry associated to a PIPICO (PhotoIon-PhotoIon Coincidence) technique. An approach of the spectroscopy of the CS 2 ++ ion has been proposed; two dissociation paths of the ion have been observed, their mechanisms are discussed. (author) [fr

  11. Satellite bands of the RbCs molecule in the range of highly excited states

    Energy Technology Data Exchange (ETDEWEB)

    Rakić, Mario; Beuc, Robert; Skenderović, Hrvoje, E-mail: hrvoje@ifs.hr [Institute of Physics, Bijenička cesta 46, Zagreb 10000 (Croatia); Bouloufa-Maafa, Nadia; Dulieu, Olivier; Vexiau, Romain [Laboratoire Aimé Cotton, CNRS, Université Paris-Sud, ENS Cachan, Université Paris-Saclay, Bât. 505, Campus d’Orsay, Orsay Cedex 91405 (France); Pichler, Goran [Physics Department, Kuwait University, PO Box 5969, Safat—13060 (Kuwait)

    2016-05-28

    We report on the observation of three RbCs satellite bands in the blue and green ranges of the visible spectrum. Absorption measurements are performed using all-sapphire cell filled with a mixture of Rb and Cs. We compare high resolution absorption spectrum of Rb-Cs vapor mixture with pure Rb and Cs vapor spectra from the literature. After detailed analysis, the new satellite bands of RbCs molecule at 418.3 nm, 468.3, and 527.5 nm are identified. The origin of these bands is discussed by direct comparison with difference potentials derived from quantum chemistry calculations of RbCs potential energy curves. These bands originate from the lower Rydberg states of the RbCs molecule. This study thus provides further insight into photoassociation of lower Rydberg molecular states, approximately between Cs(7s) + Rb(5s) and Cs(6s) + Rb(6p) asymptotes, in ultracold gases.

  12. Surface chemical reactions induced by molecules electronically-excited in the gas

    DEFF Research Database (Denmark)

    Petrunin, Victor V.

    2011-01-01

    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 kinetic energy may be used to overcome the chemical reaction barrier. While recombination chemical...... be readily produced. Products of chemical adsorption and/or chemical reactions induced within adsorbates are aggregated on the surface and observed by light scattering. We will demonstrate how pressure and spectral dependencies of the chemical outcomes, polarization of the light and interference of two laser...... beams inducing the reaction can be used to distinguish the new process we try to investigate from chemical reactions induced by photoexcitation within adsorbed molecules and/or gas phase photolysis....

  13. Bottom-up excited state dynamics of two cinnamate-based sunscreen filter molecules

    OpenAIRE

    Peperstraete, Yoann; Staniforth, Michael; Baker, Lewis A.; Rodrigues, Natércia D. N.; Cole-Filipiak, Neil C.; Quan, Wen-Dong; Stavros, Vasilios G.

    2016-01-01

    Methyl-E-4-methoxycinnamate (E-MMC) is a model chromophore of the commonly used commercial sunscreen agent, 2- ethylhexyl-E-4-methoxycinnamate (E-EHMC). In an effort to garner a molecular-level understanding of the photoprotection mechanisms in operation with E-EHMC, we have used time-resolved pump-probe spectroscopy to explore E-MMC’s and E-EHMC’s excited state dynamics upon UV-B photoexcitation to the S1 (11ππ*) state in both the gas- and solution-phase. In the gas-phase, our studies sugges...

  14. Excitation of chiral molecules and their hydrated by clusters by R2PI studies

    International Nuclear Information System (INIS)

    Satta, M.; Piccirillo, S.; Scuderia, D.; Paladini, A.; Della Vedova, L.; Filippi, A.; Speranza, M.; Giardini, A.

    2002-01-01

    Molecular clusters play a key role in the molecular scale explanation of macroscopic phenomena, being in between the isolated gas phase and the condensed phase. Thus, allowing to obtain information on intermolecular forces simply by studying the physicochemical properties of isolated clusters and to extend them macroscopic systems. A comprehensive study of the short-range forces operating in the molecular complexes between several chiral aromatic alcohols (M) and water (solv), through the application of mass resolved REMPI technique is reported. The experimental setup was composed by a supersonic molecular beam, two Nd-YAG pumped dye lasers and a time of flight mass spectrometer. The photoionization efficiency curves were obtained as follows: a) the first exciting laser (hv 1 ) was tuned on the S 1 0 transition of the species of interest; b) the laser intensity is lowered to about 1 % of the initial fluence to minimize the hv 1 absorption; c)a second laser (hv 2 ) is scanned through the cluster ionization and fragmentation threshold regions. The binding energy of the M-solv adduct was computed from the differences between its dissociative ionization threshold and the ionization threshold of bare M. The mass-resolved one colour R2PI excitation spectra of l-tetralol (THN R ), THN R -H 2 O, l i ndanol (I R ) and I R -H 2 O are given. (nevyjel)

  15. Excitation of atoms and molecules in collisions with highly charged ions

    International Nuclear Information System (INIS)

    Watson, R.L.

    1991-01-01

    Much of the work this year has been directed toward studies of charge exchange and ionization in single collisions of heavy ions with gaseous atoms and molecules. A study of the double ionization of He by high energy N 7+ ions, which began last year, was extended up in energy to 40 MeV/amu. These measurements verified the deviations from the predictions of theory observed in our previous work and indicated that the energy required to reach the limiting value of the ratio of double-to-single ionization cross sections may be as high as 70 MeV/amu

  16. Ab initio configuration interaction description of excitation energy transfer between closely packed molecules

    International Nuclear Information System (INIS)

    Fink, R.F.; Pfister, J.; Schneider, A.; Zhao, H.; Engels, B.

    2008-01-01

    We present new, generally applicable protocols for the computation of the coupling parameter, J, of excitation energy transfer with quantum chemical ab initio methods. The protocols allow to select the degree of approximation and computational demand such that they are applicable for realistic systems and still allow to control the quality of the approach. We demonstrate the capabilities of the different protocols using the CO dimer as a first example. Correlation effects are found to scale J by a factor of about 0.7 which is in good agreement to earlier results obtained for the ethene dimer. The various levels of the protocol allow to assess the influence of ionic configurations and the polarisation within the dimer. Further, the interplay between the Foerster and Dexter contribution to J is investigated. The computations also show error compensation within approximations that are widely used for extended systems as in particular the transition density cube method

  17. Ab initio configuration interaction description of excitation energy transfer between closely packed molecules

    Energy Technology Data Exchange (ETDEWEB)

    Fink, R.F. [University of Wuerzburg, Institute of Organic Chemistry, Am Hubland, D-97074 Wuerzburg (Germany)], E-mail: reinhold.fink@rub.de; Pfister, J.; Schneider, A.; Zhao, H.; Engels, B. [University of Wuerzburg, Institute of Organic Chemistry, Am Hubland, D-97074 Wuerzburg (Germany)

    2008-01-29

    We present new, generally applicable protocols for the computation of the coupling parameter, J, of excitation energy transfer with quantum chemical ab initio methods. The protocols allow to select the degree of approximation and computational demand such that they are applicable for realistic systems and still allow to control the quality of the approach. We demonstrate the capabilities of the different protocols using the CO dimer as a first example. Correlation effects are found to scale J by a factor of about 0.7 which is in good agreement to earlier results obtained for the ethene dimer. The various levels of the protocol allow to assess the influence of ionic configurations and the polarisation within the dimer. Further, the interplay between the Foerster and Dexter contribution to J is investigated. The computations also show error compensation within approximations that are widely used for extended systems as in particular the transition density cube method.

  18. Broadband transient absorption spectroscopy with 1- and 2-photon excitations: Relaxation paths and cross sections of a triphenylamine dye in solution

    Energy Technology Data Exchange (ETDEWEB)

    Moreno, J.; Dobryakov, A. L.; Hecht, S., E-mail: sh@chemie.hu-berlin.de, E-mail: skovale@chemie.hu-berlin.de; Kovalenko, S. A., E-mail: sh@chemie.hu-berlin.de, E-mail: skovale@chemie.hu-berlin.de [Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-St. 2, 12489 Berlin (Germany); Ioffe, I. N. [Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow (Russian Federation); Granovsky, A. A. [Firefly Project, 117593 Moscow (Russian Federation)

    2015-07-14

    1-photon (382 nm) and 2-photon (752 nm) excitations to the S{sub 1} state are applied to record and compare transient absorption spectra of a push-pull triphenylamine (TrP) dye in solution. After 1-photon excitation, ultrafast vibrational and structural molecular relaxations are detected on a 0.1 ps time scale in nonpolar hexane, while in polar acetonitrile, the spectral evolution is dominated by dipolar solvation. Upon 2-photon excitation, transient spectra in hexane reveal an unexpected growth of stimulated emission (SE) and excited-state absorption (ESA) bands. The behavior is explained by strong population transfer S{sub 1} → S{sub n} due to resonant absorption of a third pump photon. Subsequent S{sub n} → S{sub 1} internal conversion (with τ{sub 1} = 1 ps) prepares a very hot S{sub 1} state which cools down with τ{sub 2} = 13 ps. The pump pulse energy dependence proves the 2-photon origin of the bleach signal. At the same time, SE and ESA are strongly affected by higher-order pump absorptions that should be taken into account in nonlinear fluorescence applications. The 2-photon excitation cross sections σ{sup (2)} = 32 ⋅ 10{sup −50} cm{sup 4} s at 752 nm are evaluated from the bleach signal.

  19. Investigations of the potential functions of weakly bound diatomic molecules and laser-assisted excitive Penning ionization

    Energy Technology Data Exchange (ETDEWEB)

    Goble, J.H. Jr.

    1982-05-01

    Three variations on the Dunham series expansion function of the potential of a diatomic molecule are compared. The differences among these expansions lie in the choice of the expansion variable, lambda. The functional form of these variables are lambda/sub s/ = l-r/sub e//r for the Simon-Parr-Finlan version, lambda/sub T/ - 1-(r/sub e//r)/sup p/ for that of Thakkar, and lambda/sub H/ = 1-exp(-rho(r/r/sub e/-1) for that of Huffaker. A wide selection of molecular systems are examined. It is found that, for potentials in excess of thirty kcal/mole, the Huffaker expansion provides the best description of the three, extrapolating at large internuclear separation to a value within 10% of the true dissociation energy. For potentials that result from the interaction of excited states, all series expansions show poor behavior away from the equilibrium internuclear separation of the molecule. The series representation of the potentials of weakly bound molecules are examined in more detail. The ground states of BeAr/sup +/, HeNe/sup +/, NaAr, and Ar/sub 2/ and the excited states of HeNe+, NaNe, and NaAr are best described by the Thakkar expansion. Finally, the observation of laser-assisted excitive Penning ionization in a flowing afterglow is reported. The reaction Ar(/sup 3/P/sub 2/) + Ca + h nu ..-->.. Ar + Ca/sup +/(5p /sup 2/P/sub J/) + e/sup -/ occurs when the photon energy, h nu, is approximately equal to the energy difference between the metastable argon and one of the fine structure levels of the ion's doublet. By monitoring the cascade fluorescence of the above reaction and comparing it to the flourescence from the field-free process Ar(/sup 3/P/sub 2/) + Ca ..-->.. Ar + Ca/sup +/(4p /sup 2/P/sub J/) + e/sup -/ a surprisingly large cross section of 6.7 x 10/sup 3/ A/sup 2/ is estimated.

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

    International Nuclear Information System (INIS)

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

    2006-01-01

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

  1. Cross sections for electron-impact excitation of the H2 molecule using the MOB-SCI strategy

    International Nuclear Information System (INIS)

    Costa, Romarly F da; Paixao, Fernando J da; Lima, Marco A P

    2005-01-01

    In this paper, we report integral and differential cross sections for the electronic excitation of H 2 molecules by electron-impact. Our scattering amplitudes were calculated using the Schwinger multichannel method within the minimal orbital basis for single configuration interactions (MOB-SCI) level of approximation. Through the use of the present strategy we have investigated the coupling effects among ground state and first singlet and triplet states of the same spatial symmetry. The five-state (nine for degenerated states) close-coupling calculations joined the advantages of a well-described set of physical states of interest with a minimum associated pseudo-state space. The results obtained by means of the MOB-SCI technique show a significant improvement towards experimental data in comparison with previous two-channel close-coupling calculations

  2. Electron capture and excitation in collisions of O+(4S,2D,2P) with H2 molecules

    International Nuclear Information System (INIS)

    Pichl, Lukas; Li Yan; Liebermann, Heinz-Peter; Buenker, Robert J.; Kimura, Mineo

    2004-01-01

    Using an electronic-state close-coupling method, we treated the electron capture and excitation processes of O + ions both in ground state O + ( 4 S) and metastable states O +* ( 2 D) and O +* ( 2 P) in collisions with the H 2 molecule. In the ground-state projectile energy region considered (from 50 eV/amu to 10 keV/amu), the experimental data vary by orders of magnitude: our results smoothly connect to the data by Flesch and Ng [J. Chem. Phys. 94, 2372 (1991)] and Xu et al. [J. Phys. B 23, 1235 (1990)] at low energy and agree with Phaneuf et al. [Phys. Rev. A 17, 534 (1978)] in the high-energy region. The present values differ from Sieglaff et al. [Phys. Rev. A 59, 3538 (1999)] and Nutt et al. [J. Phys. B 12, L157 (1979)], especially in the energy region below 1 keV/amu. We provide the first calculated state-resolved cross sections of electron capture and target-projectile electronic excitations for the O + ( 4 S, 2 D, 2 P)-H 2 collision system

  3. Vibrational energy transfer in selectively excited diatomic molecules. [Relaxation rates, self-relaxation, upper limits

    Energy Technology Data Exchange (ETDEWEB)

    Dasch, C.J.

    1978-09-01

    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 295/sup 0/K 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 295/sup 0/K 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 ..delta..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.

  4. Extensive theoretical study on the excited states of the PCl+ molecule including spin-orbit coupling

    Science.gov (United States)

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

    2017-07-01

    The entire 23 Λ-S states of the PCl+ molecule have been studied by using the high-level relativistic MRCI+Q method with full-electron aug-cc-pCVQZ-DK basis set. The potential energy curves(PECs) and wavefunctions of the states have been calculated. From the PECs, the spectroscopic constants of the bound states are also determined, and the good agreements could be found with the experiments. The high density region of states exhibits many PECs' crossings, which lead to complicated interaction of the states. Here, the interactions arising from the dipolar interaction and spin-orbit coupling (SOC) effect have been discussed in detail. Under the influence of the SOC effect, the A2Π state is perturbed by the 14Σ- state. Considering the SOC effect, total 45 Ω states are generated from the original 23 Λ-S states. The transition properties are also predicted, including the transition dipole moments, Franck-Condon factors, and radiative lifetimes. The lifetimes of the transitions A2Π1/2-X2Π1/2 and A2Π3/2-X2Π3/2 are determined to be 478.9 ns and 487.0 ns(v'=0), respectively.

  5. Spectroscopic and electric properties of the LiCs molecule: a coupled cluster study including higher excitations

    Science.gov (United States)

    Sørensen, L. K.; Fleig, T.; Olsen, J.

    2009-08-01

    Aimed at obtaining complete and highly accurate potential energy surfaces for molecules containing heavy elements, we present a new general-order coupled cluster method which can be applied in the framework of the spin-free Dirac formalism. As an initial application we present a systematic study of electron correlation and relativistic effects on the spectroscopic and electric properties of the LiCs molecule in its electronic ground state. In particular, we closely investigate the importance of excitations higher than coupled cluster doubles, spin-free and spin-dependent relativistic effects and the correlation of outer-core electrons on the equilibrium bond length, the harmonic vibrational frequency, the dissociation energy, the dipole moment and the static electric dipole polarizability. We demonstrate that our new implementation allows for highly accurate calculations not only in the bonding region but also along the complete potential curve. The quality of our results is demonstrated by a vibrational analysis where an almost complete set of vibrational levels has been calculated accurately.

  6. Spectroscopic and electric properties of the LiCs molecule: a coupled cluster study including higher excitations

    International Nuclear Information System (INIS)

    Soerensen, L K; Fleig, T; Olsen, J

    2009-01-01

    Aimed at obtaining complete and highly accurate potential energy surfaces for molecules containing heavy elements, we present a new general-order coupled cluster method which can be applied in the framework of the spin-free Dirac formalism. As an initial application we present a systematic study of electron correlation and relativistic effects on the spectroscopic and electric properties of the LiCs molecule in its electronic ground state. In particular, we closely investigate the importance of excitations higher than coupled cluster doubles, spin-free and spin-dependent relativistic effects and the correlation of outer-core electrons on the equilibrium bond length, the harmonic vibrational frequency, the dissociation energy, the dipole moment and the static electric dipole polarizability. We demonstrate that our new implementation allows for highly accurate calculations not only in the bonding region but also along the complete potential curve. The quality of our results is demonstrated by a vibrational analysis where an almost complete set of vibrational levels has been calculated accurately.

  7. Optical oscillator strengths of the valence-shell excitations of atoms and molecules determined by the dipole ( γ,γ) method

    Science.gov (United States)

    Xu, Long-Quan; Liu, Ya-Wei; Xu, Xin; Ni, Dong-Dong; Yang, Ke; Zhu, Lin-Fan

    2017-07-01

    The dipole (γ,γ) method, which is the inelastic X-ray scattering operated at a negligibly small momentum transfer, has been developed to determine the absolute optical oscillator strengths of the valence-shell excitations of atoms and molecules. This new method is free from the line saturation effect, and its Bethe-Born conversion factor varies much more slowly with the excitation energy than that of the dipole (e, e) method. Thus the dipole (γ,γ) method provides a reliable approach to obtain the benchmark optical oscillator strengths of the valence-shell excitations for gaseous atoms and molecules. In this paper, we give a review of the dipole (γ,γ) method and some recent measurements of absolute optical oscillator strengths of gaseous atoms and molecules. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

  8. On the biphoton excitation of the fluorescence of the bacteriochlorophyll molecules of purple photosynthetic bacteria by powerful near IR femto-picosecond pulses

    Energy Technology Data Exchange (ETDEWEB)

    Borisov, A. Yu., E-mail: borissov@belozersky.msu.ru [Moscow State University, Belozersky Institute of Physicochemical Biology (Russian Federation)

    2011-11-15

    The authors of a number of experimental works detected nonresonance biphoton excitation of bacteriochlorophyll molecules, which represent the main pigment in the light-absorbing natural 'antenna' complexes of photosynthesizing purple bacteria, by femtosecond IR pulses (1250-1500 nm). They believe that IR quanta excite hypothetic forbidden levels of the pigments of these bacteria in the double frequency range 625-750 nm. We propose and ground an alternative triplet mechanism to describe this phenomenon. According to our hypothesis, the mechanism of biphoton excitation of molecules by IR quanta can manifest itself specifically, through high triplet levels of molecules in the high fields induced by femtosecond-picosecond laser pulses.

  9. Effects of excited state mixing on transient absorption spectra in dimers Application to photosynthetic light-harvesting complex II

    CERN Document Server

    Valkunas, L; Trinkunas, G; Müller, M G; Holzwarth, A R

    1999-01-01

    The excited state mixing effect is taken into account considering the difference spectra of dimers. Both the degenerate (homo) dimer as well as the nondegenerate (hetero) dimer are considered. Due to the higher excited state mixing with the two-exciton states in the homodimer, the excited state absorption (or the difference spectrum) can be strongly affected in comparison with the results obtained in the Heitler-London approximation. The difference spectrum of the heterodimer is influenced by two resonance effects (i) mixing of the ground state optical transitions of both monomers in the dimer and (ii) mixing of the excited state absorption of the excited monomer with the ground state optical transition in the nonexcited monomer. These effects have been tested by simulating the difference absorption spectra of the light-harvesting complex of photosystem II (LHC II) experimentally obtained with the 60 fs excitation pulses at zero delay times and various excitation wavelengths. The pairs of coupled chlorophylls...

  10. X-ray absorption spectroscopy of the chiral molecules fenchone, α-pinene, limonene and carvone in the C1s excitation region

    Energy Technology Data Exchange (ETDEWEB)

    Ozga, Christian, E-mail: ozga@physik.uni-kassel.de [Institute for Physics and CINSaT, University of Kassel, Heinrich-Plett Str. 40, 34132 Kassel (Germany); Jänkälä, Kari [Centre for Molecular Materials Research, University of Oulu, PO Box 3000, 90014 Oulu (Finland); Schmidt, Philipp; Hans, Andreas; Reiß, Philipp; Ehresmann, Arno; Knie, André [Institute for Physics and CINSaT, University of Kassel, Heinrich-Plett Str. 40, 34132 Kassel (Germany)

    2016-02-15

    Highlights: • Determination of the X-ray absorption spectra for two terpenoids and two terpenes. • Allocation of predominant or even site-selective excitation of stereocenters. • Fragment fluorescence spectra of the prototype molecules are identical. • Presented data can be used for future fluorescence circular dichroism experiments. - Abstract: Relative ionization cross sections and fluorescence intensities as functions of the exciting-photon energy were recorded for the chiral molecules carvone, α-pinene, limonene and fenchone after excitation by monochromatized synchrotron radiation with energies of the exciting-photons between 284 eV and 289 eV. At selected exciting-photon energies dispersed fragment fluorescence spectra in the wavelength range between 365 nm and 505 nm were obtained. Time dependent density functional theory (TD-DFT) computations were performed to analyze the experimentally observed resonance-structures. Comparison of the computed and recorded spectra demonstrates the possibility of a predominant or even specific excitation of one particular stereocenter site in a molecule with more than one stereocenter.

  11. Temperature dependence of the hydrated electron's excited-state relaxation. I. Simulation predictions of resonance Raman and pump-probe transient absorption spectra of cavity and non-cavity models

    Science.gov (United States)

    Zho, Chen-Chen; Farr, Erik P.; Glover, William J.; Schwartz, Benjamin J.

    2017-08-01

    We use one-electron non-adiabatic mixed quantum/classical simulations to explore the temperature dependence of both the ground-state structure and the excited-state relaxation dynamics of the hydrated electron. We compare the results for both the traditional cavity picture and a more recent non-cavity model of the hydrated electron and make definite predictions for distinguishing between the different possible structural models in future experiments. We find that the traditional cavity model shows no temperature-dependent change in structure at constant density, leading to a predicted resonance Raman spectrum that is essentially temperature-independent. In contrast, the non-cavity model predicts a blue-shift in the hydrated electron's resonance Raman O-H stretch with increasing temperature. The lack of a temperature-dependent ground-state structural change of the cavity model also leads to a prediction of little change with temperature of both the excited-state lifetime and hot ground-state cooling time of the hydrated electron following photoexcitation. This is in sharp contrast to the predictions of the non-cavity model, where both the excited-state lifetime and hot ground-state cooling time are expected to decrease significantly with increasing temperature. These simulation-based predictions should be directly testable by the results of future time-resolved photoelectron spectroscopy experiments. Finally, the temperature-dependent differences in predicted excited-state lifetime and hot ground-state cooling time of the two models also lead to different predicted pump-probe transient absorption spectroscopy of the hydrated electron as a function of temperature. We perform such experiments and describe them in Paper II [E. P. Farr et al., J. Chem. Phys. 147, 074504 (2017)], and find changes in the excited-state lifetime and hot ground-state cooling time with temperature that match well with the predictions of the non-cavity model. In particular, the experiments

  12. Molecular-dynamics study of the dynamical excitations in commensurate monolayer films of nitrogen molecules on graphite: A test of the corrugation in the nitrogen-graphite potential

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Bruch, Ludwig Walter

    1995-01-01

    The dynamical excitations in a commensurate monolayer solid of N2 molecules adsorbed on graphite have been studied using molecular-dynamics simulations. Velocity and rotational correlation functions as well as coherent intermediate scattering functions and dynamical structure factors have been ca...

  13. Control of population of excited nitrogen molecules by mixing hydrogen in low pressure discharge; Chisso jun`antei reiki bunshi mitsudo no quenching ni yoru seigyo no kento

    Energy Technology Data Exchange (ETDEWEB)

    Uematsu, K.; Yumoto, M.; Sakai, T. [Musashi Institute of Technology, Tokyo (Japan)

    1998-06-01

    The authors have studied on surface treatment of PTFE by a low pressure discharge. It is deduced that excited nitrogen molecules contribute to introduce polar components on the surface. To confirm the speculation, we tried to change population of metastable nitrogen N2 (A{sup 3}{Sigma}u{sup +}) by quenching precursor N2 (B{sup 3}{pi}g), with hydrogen molecule. The decrease of relaxation time which indicates a change of excited molecule and measured by emission spectroscopy using a time after glow method was obtained. As a result, the relaxation times of N2 (B{sup 3}{pi}g) and N2 (A{sup 3}{Sigma}u{sup +}) decreased to 55% and 20% respectively, when mixing ratio of hydrogen was 3%. It was also deduced that hydrogen atom may take a part in a quenching process of N2 (A{sup 3}{Sigma}u{sup +}). 14 refs., 11 figs., 1 tab.

  14. A “Swingable” straight-chain affinity molecule immobilized on a semi-conductor electrode for photo-excited current-based molecular sensing

    International Nuclear Information System (INIS)

    Takatsuji, Yoshiyuki; Wakabayashi, Ryo; Sakakura, Tatsuya; Haruyama, Tetsuya

    2015-01-01

    The molecular affinities of biomolecules have found applications in the areas of clinical diagnostics, drug discovery, as well as allied fields of study. An affinity sensor is a unique in situ assay tool, which is valuable and convenient in practical situations. In this study, we designed a photo-excitable molecular interface with an affinity domain and fabricated with a “swingable” straight-chain affinity molecule immobilized on a semi-conductor electrode (SCE). The straight-chain affinity molecule possessed a photo-excitable dye at one end and was bound to the SCE surface at the other by the EC tag method, which was developed previously. A straight-chain molecule is too long to transfer electrons from the photo-excited dye to the conduction band of the SCE. However, the straight-chain molecule was designed with a “swing” structure, which made the transfer of electrons possible. The central region of the chain molecule has an affinity to the activated estrogen receptor (ER). When the activated ER bound to the affinity region, the molecular lost its swingable function, the electron transfer from the photo-excited dye to the SCE was consequently suppressed. Based on the unique swingable molecular interface, the affinity sensor can be used to determine the in situ concentration of endocrine disrupter ESTROGEN (17β-estradiol) at concentrations ranging from 2 to 10 nM with very good reproducibility. The superior assay reproducibility is responsible for the success of the EC tag method, which is a quantitative method for immobilizing molecules on SCE.

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

    International Nuclear Information System (INIS)

    Smirnov, Yu.M.

    2006-01-01

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

  16. Dynamics of Activated Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Mullin, Amy S. [Univ. of Maryland, College Park, MD (United States)

    2016-11-16

    Experimental studies have been performed to investigate the collisional energy transfer processes of gas-phase molecules that contain large amounts of internal energy. Such molecules are prototypes for molecules under high temperature conditions relevant in combustion and information about their energy transfer mechanisms is needed for a detailed understanding and modeling of the chemistry. We use high resolution transient IR absorption spectroscopy to measure the full, nascent product distributions for collisions of small bath molecules that relax highly vibrationally excited pyrazine molecules with E=38000 cm-1 of vibrational energy. To perform these studies, we developed new instrumentation based on modern IR light sources to expand our experimental capabilities to investigate new molecules as collision partners. This final report describes our research in four areas: the characterization of a new transient absorption spectrometer and the results of state-resolved collision studies of pyrazine(E) with HCl, methane and ammonia. Through this research we have gained fundamental new insights into the microscopic details of relatively large complex molecules at high energy as they undergo quenching collisions and redistribute their energy.

  17. Charge-resonance excitations in symmetric molecules - Comparison of linear response DFT with CC3 for the excited states of a model dimer

    DEFF Research Database (Denmark)

    Kuhlman, Thomas Scheby; Mikkelsen, Kurt V.; Møller, Klaus Braagaard

    2009-01-01

    to a reference CC3 calculation revealing a better description of the excited states by CAM-B3LYP than that of B3LYP. The Λ parameter introduced by Peach et al. [M.J.G. Peach, P. Benfield, T. Helgaker, D.J. Tozer, J. Chem. Phys. 128 (2008) 044118] does not always reveal the problematic charge-resonance states...

  18. Coupled cluster calculations of mean excitation energies of the noble gas atoms He, Ne and Ar and of the H2 molecule

    DEFF Research Database (Denmark)

    Sauer, Stephan P. A.; Ul Haq, Inam; Sabin, John R.

    2014-01-01

    by about 1%. For the two-electron systems He and H2, our CCSD results (for a Lanczos chain length equal to the full excitation space), I0 = 42:28 eV (Helium) and I0 = 19:62 eV (H2), correspond to full conguration interaction results and are therefore the exact, non-relativistic theoretical values......Using an asymmetric-Lanczos-chain algorithm for the calculation of the coupled cluster linear response functions at the CCSD and CC2 levels of approximation, we have calculated the mean excitation energies of the noble gases He, Ne and Ar, and of the hydrogen molecule H2. Convergence with respect...... for the mean excitation energy of these two systems within the Bethe theory for the chosen basis set and, in the case of H2, at the experimental equilibrium geometry....

  19. Electronic excitation of molecules in solution calculated using the symmetry-adapted cluster–configuration interaction method in the polarizable continuum model

    International Nuclear Information System (INIS)

    Fukuda, Ryoichi; Ehara, Masahiro

    2015-01-01

    The effects from solvent environment are specific to the electronic states; therefore, a computational scheme for solvent effects consistent with the electronic states is necessary to discuss electronic excitation of molecules in solution. The PCM (polarizable continuum model) SAC (symmetry-adapted cluster) and SAC-CI (configuration interaction) methods are developed for such purposes. The PCM SAC-CI adopts the state-specific (SS) solvation scheme where solvent effects are self-consistently considered for every ground and excited states. For efficient computations of many excited states, we develop a perturbative approximation for the PCM SAC-CI method, which is called corrected linear response (cLR) scheme. Our test calculations show that the cLR PCM SAC-CI is a very good approximation of the SS PCM SAC-CI method for polar and nonpolar solvents

  20. MCSCF wave functions for excited states of polar molecules - Application to BeO. [Multi-Configuration Self-Consistent Field

    Science.gov (United States)

    Bauschlicher, C. W., Jr.; Yarkony, D. R.

    1980-01-01

    A previously reported multi-configuration self-consistent field (MCSCF) algorithm based on the generalized Brillouin theorem is extended in order to treat the excited states of polar molecules. In particular, the algorithm takes into account the proper treatment of nonorthogonality in the space of single excitations and invokes, when necessary, a constrained optimization procedure to prevent the variational collapse of excited states. In addition, a configuration selection scheme (suitable for use in conjunction with extended configuration interaction methods) is proposed for the MCSCF procedure. The algorithm is used to study the low-lying singlet states of BeO, a system which has not previously been studied using an MCSCF procedure. MCSCF wave functions are obtained for three 1 Sigma + and two 1 Pi states. The 1 Sigma + results are juxtaposed with comparable results for MgO in order to assess the generality of the description presented here.

  1. Torsion-inversion tunneling patterns in the CH-stretch vibrationally excited states of the G12 family of molecules including methylamine.

    Science.gov (United States)

    Dawadi, Mahesh B; Bhatta, Ram S; Perry, David S

    2013-12-19

    Two torsion-inversion tunneling models (models I and II) are reported for the CH-stretch vibrationally excited states in the G12 family of molecules. The torsion and inversion tunneling parameters, h(2v) and h(3v), respectively, are combined with low-order coupling terms involving the CH-stretch vibrations. Model I is a group theoretical treatment starting from the symmetric rotor methyl CH-stretch vibrations; model II is an internal coordinate model including the local-local CH-stretch coupling. Each model yields predicted torsion-inversion tunneling patterns of the four symmetry species, A, B, E1, and E2, in the CH-stretch excited states. Although the predicted tunneling patterns for the symmetric CH-stretch excited state are the same as for the ground state, inverted tunneling patterns are predicted for the asymmetric CH-stretches. The qualitative tunneling patterns predicted are independent of the model type and of the particular coupling terms considered. In model I, the magnitudes of the tunneling splittings in the two asymmetric CH-stretch excited states are equal to half of that in the ground state, but in model II, they differ when the tunneling rate is fast. The model predictions are compared across the series of molecules methanol, methylamine, 2-methylmalonaldehyde, and 5-methyltropolone and to the available experimental data.

  2. Formation of cold molecules through the photo-association of cold atoms of Cesium. Existence of long range forces between between cold excited atoms of Cesium

    International Nuclear Information System (INIS)

    Comparat, D.

    1999-09-01

    This thesis deals with the experimental study and the theoretical interpretation of the processes involved in photo-association and the formation of cold caesium molecules. It also presents a study of the dipolar forces between a pair of cold excited caesium atoms. We present here the first photo-association experiment on cold caesium atoms: two cold atoms absorb a photon to form an excited electronically excited molecules in a rotation-vibration level. The first production of cold molecules which was realised experimentally, after the spontaneous deexcitation of the photo-associated molecules, is described, stressing the role of the potential well of the molecular states O g - (6s+6p 3/2 ) or 1 u (6s+6p 3/2 ) of caesium. The detection of the formed caesium molecules is based on a two-photons resonant ionisation that creates Cs 2 + ions, afterwards selectively detected. Temperatures around 20-200 μK have been measured. The photo-associative spectroscopy is described on the theoretical point of view: a detailed theoretical study allows to calculate precisely the asymptotic parts of the potential curves. On the experimental point of view, we present the spectroscopy of the extern potential well of the caesium state O g - (6s+6p 3/2 ) and the construction of an effective potential curve of the RKR type. A unified theory of photo-association in weak field, considered as a collision assisted by laser, is developed. The cold atoms experiments allow to study and control the collision between two atoms whose mutual interaction is of the dipole-dipole type. Two different physical systems are studied: a sample of Rydberg atoms, and the photo-association process which is a laser-assisted collision. A modification of the motion of one pair of atoms makes it possible to control the bipolar forces and to choose the atoms relative speeds. (author)

  3. Stimulated Brillouin scattering phase-locking using a transient acoustic standing wave excited through an optical interference field

    International Nuclear Information System (INIS)

    Ondrej Slezak; Milan Kalal; Hon Jin Kong

    2010-01-01

    Complete text of publication follows. Analytical description of an experimentally verified scheme leading to a phase-locked stimulated Brillouin scattering (SBS), used in a laser beam combination systems, is presented. The essential condition for the phase-locking effect for SBS is the fixation of the starting position and time of the acoustic Brillouin wave. It is shown that the starting position fixation of this acoustic wave may have its origin in a transient acoustic standing wave initiated by an arising optical interference field produced by the back-seeding concave mirror. This interference field leads to a stationary density modulation of the medium. However, the way to the formation of this density modulation leads via the acoustic standing wave. An appropriate solution, in the form of the standing wave, was obtained from solving the acoustic wave-equation using the electrostriction as a driving force. As a consequence of the damping term included in this equation the acoustic standing wave becomes gradually attenuated and contrary to the undamped solution published earlier, thus constitutes a truly transient phenomenon. Using a mathematical formalism similar to that which is used for the SBS description in the case of a random phase, the coupled equations describing the phase-locked SBS were derived. Contrary to the case without the back-seeding mirror, where the wave chosen from the thermal noise background subsequently plays the role of a trigger of the stimulated process, in this case it is replaced by the transient standing wave produced as a consequence of the presence of an optical interference field arisen in the focal region of the back-seeding concave mirror.

  4. Measurement of g factors of excited states in radioactive beams by the transient field technique: 132Te

    International Nuclear Information System (INIS)

    Benczer-Koller, N.; Kumbartzki, G.; Gurdal, G; Gross, Carl J; Krieger, B; Hatarik, Robert; O'Malley, Patrick; Pain, S. D.; Segen, L.; Baktash, Cyrus; Bingham, C. R.; Danchev, M.; Grzywacz, R.; Mazzocchi, C.

    2008-01-01

    The g factor of the 2 1 + state in 52 132 Te, E(2 1 + ) = 0.9739 MeV, r = 2.6 ps, was measured by the transient field technique applied to a radioactive beam. The development of an experimental approach necessary for work in radioactive beam environments is described. The result g = 0.28(15) agrees with the previous measurement by the recoil-in-vacuum technique, but here the sign of the g factor is measured as well

  5. The g-factor of the first excited 4+ state in 20Ne from transient field precession measurement in gadolinium

    International Nuclear Information System (INIS)

    Tandon, P.N.; Speidel, K.H.; Mertens, V.; Trolenberg, W.; Kumbartzki, G.S.; Ayres de Campos, N.; Goldberg, M.B.; Gerber, J.; Toulemonde, M.

    1981-01-01

    The g-factor of the 4 + state in 20 Ne at 4.25 MeV has been obtained to be g = +0.08(20) from transient field precession measurements in Gd in agreement with the present authors' earlier reported value of g =- 0.10(19) (1980). The significant reduction in the value of the g- factor, g = -0.01(14), relative to that of the 2 + state (g = + 0.54(4))(1975) is in complete disagreement with theory. In addition the life time of the 4 + state has been measured to be tau = 95(13) fs. (author)

  6. Reaction-based small-molecule fluorescent probes for dynamic detection of ROS and transient redox changes in living cells and small animals.

    Science.gov (United States)

    Lü, Rui

    2017-09-01

    Dynamic detection of transient redox changes in living cells and animals has broad implications for human health and disease diagnosis, because intracellular redox homeostasis regulated by reactive oxygen species (ROS) plays important role in cell functions, normal physiological functions and some serious human diseases (e.g., cancer, Alzheimer's disease, diabetes, etc.) usually have close relationship with the intracellular redox status. Small-molecule ROS-responsive fluorescent probes can act as powerful tools for dynamic detection of ROS and redox changes in living cells and animals through fluorescence imaging techniques; and great advances have been achieved recently in the design and synthesis of small-molecule ROS-responsive fluorescent probes. This article highlights up-to-date achievements in designing and using the reaction-based small-molecule fluorescent probes (with high sensitivity and selectivity to ROS and redox cycles) in the dynamic detection of ROS and transient redox changes in living cells and animals through fluorescence imaging. Copyright © 2017. Published by Elsevier Ltd.

  7. PS II model based analysis of transient fluorescence yield measured on whole leaves of Arabidopsis thaliana after excitation with light flashes of different energies.

    Science.gov (United States)

    Belyaeva, N E; Schmitt, F-J; Paschenko, V Z; Riznichenko, G Yu; Rubin, A B; Renger, G

    2011-02-01

    Our recently presented PS II model (Belyaeva et al., 2008) was improved in order to permit a consistent simulation of Single Flash Induced Transient Fluorescence Yield (SFITFY) traces that were earlier measured by Steffen et al. (2005) on whole leaves of Arabidopsis (A.) thaliana at four different energies of the actinic flash. As the essential modification, the shape of the actinic flash was explicitly taken into account assuming that an exponentially decaying rate simulates the time dependent excitation of PS II by the 10 ns actinic flash. The maximum amplitude of this excitation exceeds that of the measuring light by 9 orders of magnitude. A very good fit of the SFITFY data was achieved in the time domain from 100 ns to 10s for all actinic flash energies (the maximum energy of 7.5 × 10¹⁶ photons/(cm²flash) is set to 100%, the relative energies of weaker actinic flashes were of ∼8%, 4%, ∼1%). Our model allows the calculation and visualization of the transient PS II redox state populations ranging from the dark adapted state, via excitation energy and electron transfer steps induced by pulse excitation, followed by final relaxation into the stationary state eventually attained under the measuring light. It turned out that the rate constants of electron transfer steps are invariant to intensity of the actinic laser flash. In marked contrast, an increase of the actinic flash energy by more than two orders of magnitude from 5.4×10¹⁴ photons/(cm²flash) to 7.5×10¹⁶ photons/(cm²flash), leads to an increase of the extent of fluorescence quenching due to carotenoid triplet (³Car) formation by a factor of 14 and of the recombination reaction between reduced primary pheophytin (Phe(-)) and P680(+) by a factor of 3 while the heat dissipation in the antenna complex remains virtually constant. The modified PS II model offers new opportunities to compare electron transfer and dissipative parameters for different species (e.g. for the green algae and the

  8. Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Ravi Kumar, Venkatraman; Ariese, Freek; Umapathy, Siva, E-mail: umapathy@ipc.iisc.ernet.in [Inorganic and Physical Chemistry Department, Indian Institute of Science, Bangalore 560012 (India)

    2016-03-21

    The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T{sub 1} and T{sub 2} states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S{sub 0} state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S{sub 0}, T{sub 1}, and T{sub 2} states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the nπ{sup ∗} triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents.

  9. Cross sections and oscillator strengths for electron-impact excitation of electronic states in polyatomic molecules. Application examples of the BEf- scaling model in optically-allowed transitions

    International Nuclear Information System (INIS)

    Kato, H.; Kawahara, H.; Hoshino, M.

    2009-12-01

    Integral cross sections for optically allowed electronic-state excitations by electron impact, are reviewed for polyatomic molecules by applying the Binary-Encounter-Bethe (BEB) scaling model. Following the context of the present review, the scaling model originally proposed by Yong-Ki Kim to determine electron-impact cross sections for ionization of atoms and molecules is also summarized briefly for its wide range of applications [Electron-Impact Cross Section Database, NIST, Y.-K. Kim]. The present report not only focuses on the need for the cross-section data, but also elucidates the verification of the scaling model in the general application for atoms and molecules. Since this report is for a data base, it is summarized for data base users by citing (copying) the descriptions in the original papers and the references within those papers in the style of a textbook. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-09

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

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

    International Nuclear Information System (INIS)

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

    1994-01-01

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

  12. [Excitation transfer between high-lying states in K2 in collisions with ground state K and H2 molecules].

    Science.gov (United States)

    Shen, Xiao-Yan; Liu, Jing; Dai, Kang; Shen, Yi-Fan

    2010-02-01

    Pure potassium vapor or K-H2 mixture was irradiated in a glass fluorescence cell with pulses of 710 nm radiation from an OPO laser, populating K2 (1lambda(g)) state by two-photon absorption. Cross sections for 1lambda(g)-3lambda(g) transfer in K2 were determined using methods of molecular fluorescence. During the experiments with pure K vapor, the cell temperature was varied between 553 and 603 K. The K number density was determined spectroscopically by the white-light absorption measurement in the blue wing of the self-broadened resonance D2 line. The resulting fluorescence included a direct component emitted in the decay of the optically excitation and a sensitized component arising from the collisionally populated state. The decay signal of time-resolved fluorescence from1lambda(g) -->1 1sigma(u)+ transition was monitored. It was seen that just after the laser pulse the fluorescence of the photoexcited level decreased exponentially. The effective lifetimes of the 1lambda(g) state can be resolved. The plot of reciprocal of effective lifetimes of the 1lambda(g) state against K densities yielded the slope that indicated the total cross section for deactivation and the intercept that provided the radiative lifetime of the state. The radiative lifetime (20 +/- 2) ns was obtained. The cross section for deactivation of the K2(1lambda(g)) molecules by collisions with K is (2.5 +/- 0.3) x 10(-14) cm2. The time-resolved intensities of the K23lambda(g) --> 1 3sigma(u)+ (484 nm) line were measured. The radiative lifetime (16.0 +/- 3.2) ns and the total cross section (2.5 +/- 0.6) x 10(-14) cm2 for deactivation of the K2 (3lambda(g)) state can also be determined through the analogous procedure. The time-integrated intensities of 1lambda(g) --> 1 1sigma(u)+ and 3lambda(g) --> 1 3sigma(u)+ transitions were measured. The cross section (1.1 +/- 0.3) x10(-14) cm2 was obtained for K2 (1lambda(g))+ K --> K2 (3lambda(g)) + K collisions. During the experiments with K-H2 mixture, the

  13. Application of the Real-Time Time-Dependent Density Functional Theory to Excited-State Dynamics of Molecules and 2D Materials

    Science.gov (United States)

    Miyamoto, Yoshiyuki; Rubio, Angel

    2018-04-01

    We review our recent developments in the ab initio simulation of excited-state dynamics within the framework of time-dependent density functional theory (TDDFT). Our targets range from molecules to 2D materials, although the methods are general and can be applied to any other finite and periodic systems. We discuss examples of excited-state dynamics obtained by real-time TDDFT coupled with molecular dynamics (MD) and the Ehrenfest approximation, including photoisomerization in molecules, photoenhancement of the weak interatomic attraction of noble gas atoms, photoenhancement of the weak interlayer interaction of 2D materials, pulse-laser-induced local bond breaking of adsorbed atoms on 2D sheets, modulation of UV light intensity by graphene nanoribbons at terahertz frequencies, and collision of high-speed ions with the 2D material to simulate the images taken by He ion microscopy. We illustrate how the real-time TDDFT approach is useful for predicting and understanding non-equilibrium dynamics in condensed matter. We also discuss recent developments that address the excited-state dynamics of systems out of equilibrium and future challenges in this fascinating field of research.

  14. Excitation energies and properties of open-shell singlet molecules applications to a new class of molecules for nonlinear optics and singlet fission

    CERN Document Server

    Nakano, Masayoshi

    2014-01-01

    This brief investigates the diradical character, which is one of the ground-state chemical indices for 'bond weakness' or 'electron correlation' and which allows researchers to explore the origins of the electron-correlation-driven physico-chemical phenomena concerned with electronic, optical and magnetic properties as well as to control them in the broad fields of physics and chemistry. It then provides the theoretical fundamentals of ground and excited electronic structures of symmetric and asymmetric open-shell molecular systems by using model molecular systems. Moreover, it presents the th

  15. Contribution to the determination of nuclear friction by studying the de-excitation of nuclei in the transient regime

    International Nuclear Information System (INIS)

    Hassani, S.

    1985-01-01

    An old idea of Kramers is to consider nuclear fission as a diffusion process in phase space corresponding to the collective variable of fission. The fission width is taken as an escape rate of the system over the barrier potential. The evolution of the distribution of this collective variable and its conjugate is governed by a Fokker-Planck equation. In a quasistationary treatment Kramers obtained a fission rate which differs from the result given by the transition state method by a friction dependent factor. The non quasistationary solution of the Fokker-Planck equation allows to obtain an escape rate that presents a transient regime: from zero it grows and reaches asymptotically the Kramers' value. This time-dependent fission width is included in a formalism that describes the deexcitation of the compound nucleus in order to calculate the neutron multiplicities in competition with fission. A sensitive friction-dependence of the multiplicities is obtained. Using this formalism and comparing the results with data of a recent experiment gives a good agreement; resolving the disagreement between data and the usual statistical model at high energy. A range of values of the friction coefficient is deduced [fr

  16. Transient, polarity-dependent dielectric response in a twisted nematic liquid crystal under very low frequency excitation.

    Science.gov (United States)

    Krishnamurthy, K S

    2015-09-01

    The electric Freedericksz transition is a second-order quadratic effect, which, in a planarly aligned nematic liquid crystal layer, manifests above a threshold field as a homogeneous symmetric distortion with maximum director-tilt in the midplane. We find that, upon excitation by a low frequency (wave field, the instability becomes spatially and temporally varying. This is demonstrated using calamitic liquid crystals, initially in the 90°-twisted planar configuration. The distortion occurs close to the negative electrode following each polarity switch and, for low-voltage amplitudes, decays completely in time. We use the elastically favorable geometry of Brochard-Leger walls to establish the location of maximum distortion. Thus, at successive polarity changes, the direction of extension of both annular and open walls switches between the alignment directions at the two substrates. For high voltages, this direction is largely along the midplane director, while remaining marginally oscillatory. These results are broadly understood by taking into account the time-varying and inhomogeneous field conditions that prevail soon after the polarity reverses. Polarity dependence of the instability is traced to the formation of intrinsic double layers that lead to an asymmetry in field distribution in the presence of an external bias. Momentary field elevation near the negative electrode following a voltage sign reversal leads to locally enhanced dielectric and gradient flexoelectric torques, which accounts for the surface-like phenomenon observed at low voltages. These spatiotemporal effects, also found earlier for other instabilities, are generic in nature.

  17. Theory of Transient Excited State Absorptions in Pentacene and Derivatives: Triplet-Triplet Biexciton versus Free Triplets.

    Science.gov (United States)

    Khan, Souratosh; Mazumdar, Sumit

    2017-12-07

    Recent experiments in several singlet-fission materials have found that the triplet-triplet biexciton either is the primary product of photoexcitation or has a much longer lifetime than believed until now. It thus becomes essential to determine the difference in the spectroscopic signatures of the bound triplet-triplet and free triplets to distinguish between them optically. We report calculations of excited state absorptions (ESAs) from the singlet and triplet excitons and from the triplet-triplet biexciton for a pentacene crystal with the herringbone structure and for nanocrystals of bis(triisopropylsilylethynyl) (TIPS)-pentacene. The triplet-triplet biexciton absorbs in both the visible and the near-infrared (NIR), while the monomer free triplet absorbs only in the visible. The intensity of the NIR absorption depends on the extent of intermolecular coupling, in agreement with observations in TIPS-pentacene nanocrystals. We predict additional weak ESA from the triplet-triplet but not from the triplet, at still lower energy.

  18. The MSINDO-sCIS and MSINDO-UCIS methods. Procedures for the calculation of properties of excited states in molecules and periodic systems by a semiempirical approach

    International Nuclear Information System (INIS)

    Gadaczek, Immanuel Patrick

    2013-01-01

    Theoretical background, parameterization and performance of the newly developed semiempirical configuration interaction singles (CIS) method MSINDO-sCIS (scaled configuration interaction singles) are presented. The CIS Hamiltonian is modified by scaling of the Coulomb and exchange integrals and a semiempirical correction of the diagonal elements. For a recently proposed benchmark set of 28 medium-sized organic molecules, vertical excitation energies for singlet and triplet states have been calculated and statistically evaluated. A full reparameterization of the MSINDO method for both ground and excited state properties was performed. The results of the reparameterized MSINDO-sCIS method are compared to the currently best semiempirical method for excited states, OM3-CISDTQ by Thiel et al., and to other standard methods, such as time-dependent density- functional theory. The mean absolute deviation with respect to the theoretical best estimates (TBEs) for MSINDO-sCIS is 0.44 eV, comparable to the OM3 method but significantly smaller than for Zerner's INDO/S. The computational effort is strongly reduced compared to OM3-CISDTQ and OM3-MRCISD, since only single excitations are taken into account. Higher excitations are implicitly included by parameterization and the empirical correction term. By application of the Davidson-Liu block diagonalization method high computational efficiency is achieved. Furthermore it is demonstrated, that the MSINDO-sCIS method correctly describes charge-transfer (CT) states, that represent a crucial problem for time-dependent density functional theory (TD-DFT) methods. Additionally this method is extended to open-shell systems by the UCIS (unrestricted CIS) approach. MSINDO allows the calculation of periodic systems via the cyclic cluster model (CCM) which is a direct-space approach and therefore can be in principle combined with all molecular quantum-chemical techniques. The sCIS/UCIS equations are solved for a cluster with periodic

  19. Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy.

    Science.gov (United States)

    Hayes, Dugan; Kohler, Lars; Hadt, Ryan G; Zhang, Xiaoyi; Liu, Cunming; Mulfort, Karen L; Chen, Lin X

    2018-01-28

    The kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(i) bis(phenanthroline)/ruthenium(ii) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(i)-Ru(ii) analogs of the homodinuclear Cu(i)-Cu(i) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These results suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.

  20. Excited states 2

    CERN Document Server

    Lim, Edward C

    2013-01-01

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

  1. Proton polarization in photo-excited aromatic molecule at room temperature enhanced by intense optical source and temperature control

    Energy Technology Data Exchange (ETDEWEB)

    Sakaguchi, S., E-mail: sakaguchi@phys.kyushu-u.ac.jp [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Uesaka, T. [RIKEN Nishina Center, Saitama 351-0198 (Japan); Kawahara, T. [Department of Physics, Toho University, Chiba 274-8510 (Japan); Ogawa, T. [RIKEN Advanced Science Institute, Saitama 351-0198 (Japan); Tang, L. [Center for Nuclear Study, University of Tokyo, Tokyo 113-0001 (Japan); Teranishi, T. [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Urata, Y.; Wada, S. [RIKEN Advanced Science Institute, Saitama 351-0198 (Japan); Wakui, T. [Cyclotron and Radioisotope Center (CYRIC), Tohoku University, Miyagi 980-8578 (Japan)

    2013-12-15

    Highlights: • Proton polarization in p-terphenyl at room-temperature is enhanced by a factor of 3. • Intense laser and temperature control are critically important for high polarization. • Optimization of time structure of laser pulse is effective for further improvement. -- Abstract: Proton polarization at room temperature, produced in a p-terphenyl crystal by using electron population difference in a photo-excited triplet state of pentacene, was enhanced by utilizing an intense laser with an average power of 1.5 W. It was shown that keeping the sample temperature below 300 K is critically important to prevent the rise of the spin–lattice relaxation rate caused by the laser heating. It is also reported that the magnitude of proton polarization strongly depends on the time structure of the laser pulse such as its width and the time interval between them.

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

    Science.gov (United States)

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

    2017-03-01

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

  3. Excited states

    CERN Document Server

    Lim, Edward C

    1974-01-01

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

  4. Core-excitation processes of O(1s) in CO, CO{sub 2} and OCS molecules by electron impact

    Energy Technology Data Exchange (ETDEWEB)

    Arretche, F; Mazon, K T; Falck, A S; Marin, A; Oliveira, H L; Pessoa, O A; Travessini, D; Michelin, S E; Fujimoto, M M; Lee, M T [Departamento de Fisica, UFSC, 88040-900 Florianopolis, SC (Brazil) and Departamento de Fisica, UFPR, 81531-990 Curitiba, PR (Brazil) and Departamento de Quimica, UFSCar, 13565-905, Sao Carlos, SP (Brazil)], E-mail: farretche@hotmail.com

    2008-05-15

    Distorted-wave approximation is applied to study electron-impact excitation of core electrons in CO{sub 2}, CO and OCS. Differential and integral cross sections for the transitions: X{sup 1}{sigma}{sup +}{sub g} {yields} {sup 1,3} {pi}{sub u}(1{sigma}{sub g} {yields} 2{pi}{sub u}) in CO{sub 2}, X{sup 1}{sigma}{sup +} {yields} {sup 1,3} {pi} (2{sigma} {yields} 4{pi}) in OCS, and X{sup 1}{sigma}{sup +} {yields} {sup 1,3} {pi} (1{sigma} {yields} 2{pi}) in CO are calculated and reported in the (550-1000)-eV incident energy range. Comparison is made among the calculated data for the three targets. The physical origins of the similarity and difference of these data are also discussed. In addition, the generalized oscillator strengths for singlet 1{sigma}{sub g} {yields} 2{pi}{sub u} and 1{sigma}{sub u} {yields} 2{pi}{sub u} transitions for CO{sub 2} are calculated at 1300 eV. The comparison of these results with the available data in the literature is encouraging.{sup 1}.

  5. Photoabsorption and S 2p photoionization of the SF6 molecule: resonances in the excitation energy range of 200-280 eV.

    Science.gov (United States)

    Stener, M; Bolognesi, P; Coreno, M; O'Keeffe, P; Feyer, V; Fronzoni, G; Decleva, P; Avaldi, L; Kivimäki, A

    2011-05-07

    Photoabsorption and S 2p photoionization of the SF(6) molecule have been studied experimentally and theoretically in the excitation energy range up to 100 eV above the S 2p ionization potentials. In addition to the well-known 2t(2g) and 4e(g) shape resonances, the spin-orbit-resolved S 2p photoionization cross sections display two weak resonances between 200 and 210 eV, a wide resonance around 217 eV, a Fano-type resonance around 240 eV, and a second wide resonance around 260 eV. Calculations based on time-dependent density functional theory allow us to assign the 217-eV and 260-eV features to the shape resonances in S 2p photoionization. The Fano resonance is caused by the interference between the direct S 2p photoionization channel and the resonant channel that results from the participator decay of the S 2s(-1)6t(1u) excited state. The weak resonances below 210-eV photon energy, not predicted by theory, are tentatively suggested to originate from the coupling between S 2p shake-up photoionization and S 2p single-hole photoionization. The experimental and calculated angular anisotropy parameters for S 2p photoionization are in good agreement.

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

    International Nuclear Information System (INIS)

    Grimes, R.M.

    1986-11-01

    To further understanding of gas phase collision dynamics involving electronically-excited molecules, a fully quantum mechanical study of He + H 2 (B 1 Σ/sub u/ + ) was undertaken. Iterative natural orbital configuration interaction (CI) calculations were performed to obtain the interaction potential between He and H 2 (B 1 Σ/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 + H 2 (E,F 1 Σ/sub g/ + ) and with He + H 2 (X 1 Σ/sub g/ + ) and cause a local maximum and a deep minimum in the He + H 2 (B 1 Σ/sub u/ + ) PES, respectively. The crossing with He + H 2 (X 1 Σ/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 H 2 (B 1 Σ/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

  7. Study of inner-shell excitation processes from N(1s) orbitals in N{sub 2}O molecules by electron impact

    Energy Technology Data Exchange (ETDEWEB)

    Michelin, S E [Departamento de Fisica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil); Arretche, F [Departamento de Fisica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil); Mazon, K T [Departamento de Fisica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil); Piacentini, J J [Departamento de Fisica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil); Marin, A [Departamento de Fisica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil); Oliveira, H L [Departamento de Fisica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil); Travessini, D [Departamento de Fisica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil); Lee, M-T [Departamento de Quimica, Universidade Federal de Sao Carlos, 13565-905 Sao Carlos, SP (Brazil); Iga, I [Departamento de Quimica, Universidade Federal de Sao Carlos, 13565-905 Sao Carlos, SP (Brazil); Fujimoto, M M [Departamento de Fisica, Universidade Federal do Parana, 81531-990 Curitiba, PR (Brazil)

    2007-11-28

    A combination of the iterative Schwinger variational method with the distorted-wave approximation is applied to study excitations of a core-level electron in a triatomic molecule by electron impact. More specifically, we report calculated differential and integral cross sections for the X{sup 1}{sigma}{sup +} {yields} {sup 1,3}{pi}(2{sigma} {yields} 3{pi}) and X{sup 1}{sigma}{sup +} {yields} {sup 1,3}{pi}(3{sigma} {yields} 3{pi}) transitions in N{sub 2}O in the 415-900 eV incident energy range. The RI(1:3) ratios, obtained via dividing the distorted-wave integral cross sections for transitions leading to the singlet core-excited states by those leading to triplet states, are also reported. The generalized oscillator-strength profiles for the singlet transitions have also been calculated at the incident energy of 3400 eV. The comparison of these quantities with the available theoretical and experimental data reported in the literature is encouraging.

  8. Study on excitation of vibrational levels of osmium tetroxide molecule by the continuous CO2 laser radiation

    International Nuclear Information System (INIS)

    Kompanets, O.N.; Letokhov, V.S.; Minogin, V.G.

    1975-01-01

    The mechanism of nonlinear infrared absorption in OsO 4 has been studied using a single-frequence continuous-wave CO 2 laser (10.6 μ). Measured are relationships between the OsO 4 absorption coefficient and the laser radiation intensity, the week beam transmission through a cell filled with OsO 4 and the frequency of the intensity modulation of the strong beam which saturates the absorption. It is indicated that the thermal mechanism prevails in OsO 4 bleaching under pressure (>=) 1mm Hg. A strong infrared fluorescence observed and studied at 5.3 and 10.6 μ in the molecular OsO 4 in the field of the high-power CO 2 laser has supplied another proof of the conclusion. The thermal diffusion rate and the coefficient of thermal conductivity for OsO 4 vapours have been determined. It has been revealed that the hot bands represent a significant part in thermal mechanism of the laser radiation absorption by the molecule

  9. Contribution to the theoretical study of collisions between highly excited atom and a neutral particle (atom or molecule)

    International Nuclear Information System (INIS)

    Prunele, Eugene de.

    1979-01-01

    The problem of the collision between an atom in the Rydberg state and a neutral atom (or molecule) is considerably simplified if it is considered as the collision of a B particle with a system of two linked particles A + and e - . If the interaction between these two particles is described by a potential and if the three-body interaction is approximated by a potential equal to the sum of the two-body interaction potentials, the problem is theoretically solvable exactly within the framework of quantum mechanics but, its explicit solution is very complicated, even for very simple potentials. Various types of approaches are then necessary. The choice of interaction potentials is already an approximation, for it is obviously not known how to describe exactly the interaction between the electron and atom B for example. The fact that the electron is, on average, very far from core A + has enabled an interaction potential to be simulated between B and e - when the latter is linked to A + , by utilizing the scattering data between free e - and B. (Fermi's pseudopotential). A second approach consists in utilizing the scattering data between free e - and B, without bringing in an interaction potential between e - and B. The first approach is more satisfactory from the theoretical point of view; the second and less ambitious one is more useful [fr

  10. Highly vibrationally excited O2 molecules in low-pressure inductively-coupled plasmas detected by high sensitivity ultra-broad-band optical absorption spectroscopy

    Science.gov (United States)

    Foucher, Mickaël; Marinov, Daniil; Carbone, Emile; Chabert, Pascal; Booth, Jean-Paul

    2015-08-01

    Inductively-coupled plasmas in pure O2 (at pressures of 5-80 mTorr and radiofrequency power up to 500 W) were studied by optical absorption spectroscopy over the spectral range 200-450 nm, showing the presence of highly vibrationally excited O2 molecules (up to vʺ = 18) by Schumann-Runge band absorption. Analysis of the relative band intensities indicates a vibrational temperature up to 10,000 K, but these hot molecules only represent a fraction of the total O2 density. By analysing the (11-0) band at higher spectral resolution the O2 rotational temperature was also determined, and was found to increase with both pressure and power, reaching 900 K at 80 mTorr 500 W. These measurements were achieved using a new high-sensitivity ultra-broad-band absorption spectroscopy setup, based on a laser-plasma light source, achromatic optics and an aberration-corrected spectrograph. This setup allows the measurement of weak broadband absorbances due to a baseline variability lower than 2   ×   10-5 across a spectral range of 250 nm.

  11. Comparative study of electron-impact C(1s) core-excitation processes in C{sub 2} and C{sub 2}N{sub 2} molecules

    Energy Technology Data Exchange (ETDEWEB)

    Michelin, S.E. [Departamento de Fisica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil)], E-mail: fsc1sem@fsc.ufsc.br; Mazon, K.T.; Arretche, F.; Tenfen, W.; Oliveira, H.L.; Falck, A.S.; Scopel, M.A.; Silva, L.S.S. da [Departamento de Fisica, Universidade Federal de Santa Catarina, 88040-900 Florianopolis, SC (Brazil); Fujimoto, M.M. [Departamento de Fisica, Universidade Federal do Parana, 81531-990 Curitiba, PR (Brazil); Iga, I.; Lee, M.-T. [Departamento de Quimica, Universidade Federal de Sao Carlos, 13565-905, Sao Carlos, SP (Brazil)

    2009-04-15

    Distorted-wave approximation (DWA) is applied to study core-orbital excitations in C{sub 2}and C{sub 2}N{sub 2} molecules by electron impact. More specifically, we report calculated integral cross sections (ICS) for the X{sup 1}{sigma}{sub g}{sup +}{yields}{sup 1,3}{pi}{sub u}(1s{sigma}{sub u}{yields}1p{pi}{sub g}) and X{sup 1}{sigma}{sub g}{sup +}{yields}{sup 1,3}{pi}{sub g}(1s{sigma}{sub g}{yields}1p{pi}{sub g}) transitions in the C{sub 2}, and X{sup 1}{sigma}{sub g}{sup +}{yields}{sup 1,3}{pi}{sub g}(2s{sigma}{sub g}{yields}2p{pi}{sub g}) and X{sup 1}{sigma}{sub g}{sup +}{yields}{sup 1,3}{pi}{sub u}(2s{sigma}{sub u}{yields}2p{pi}{sub g}) transitions in the C{sub 2}N{sub 2} molecules in the 300-800 eV incident energy range. The comparison of the calculated ICS of these targets with the corresponding data for C{sub 2}H{sub 2} presented. Comparison is also made for the theoretical RI(3:1) ratios of these targets which are calculated by dividing the ICS for triplet transitions by the corresponding results for singlet transitions. The similarities and differences of these results, particularly the presence of the shape resonances at near excitation thresholds, are discussed. The influence of the atomic (localized) and molecular (delocalized) characters of the core orbitals on the core-excitation processes is also investigated. In addition, generalized oscillator strengths for the singlet core-orbital transitions are calculated at incident energy of 1290 eV for C{sub 2} and C{sub 2}N{sub 2}. A comparison with the existing theoretical and experimental data for C{sub 2}H{sub 2} is also presented.

  12. Quantum analysis in the transition process to excited state of an oxygen molecule induced by electron collisions; Denshi shototsu ni tomonau sanso bunshi ni okeru reiki jotai sen`i no ryoshironteki kaiseki

    Energy Technology Data Exchange (ETDEWEB)

    Ishimaru, K. [Gifu National College of Technology, Gifu (Japan); Okazaki, K. [Tokyo Inst. of Technology, Tokyo (Japan)

    1996-06-25

    For understanding of fundamental chemical reactions under a highly non equilibrium condition which is quite often used in plasma processing, the relevant atomic and molecular processes must be clarified. In this study, an analysis of the transition process to the excited state of an oxygen molecule induced by electron collisions in the oxygen plasma has been carried out. First, the electron density distribution in an oxygen molecule has been calculated using the extended Huckel molecular orbital method. Then, the electron potential energy distribution in the transition process to the excited state has been estimated. The electron behavior has been calculated using the estimated unidimensional electron potential energy distribution and unsteady quantum mechanics. As a result, the transition process to the excited state of an oxygen molecule induced by electron collisions and its conditions have been clarified qualitatively. 9 refs., 9 figs.

  13. Spectroscopic calculation of the excited electronic states with spin orbit effect of the molecule NaCs

    International Nuclear Information System (INIS)

    Bleik, S.; Korek, M.; Allouche, A.R.

    2004-01-01

    Full text.The existence of new experimental data on the alkali dimers has stimulated theoretical approaches, necessary to provide predictions accurate enough to be useful for interpretation and evenly for guidance of experiments. With the aim of improving the accuracy of predictions we will perform a theoretical study of the electronic structure of the molecule NaCs using a method mainly in the way by which core-valence effects are taken into account. To investigate the electronic structure of NaCs we will use the package CIPSI (Configuration Interaction by Perturbation of a multiconfiguration wave function Selected Interactively) of the Laboratoire de Physique Quantique (Toulouse, France). The atoms Na and Cs will be treated through non-empirical effective one electron core potentials of Durand and Barthelat type. Molecular orbitals for NaCs will be derived from Self Consistent field Calculations (SCF) and full valence Configuration Interaction (IC) calculations. A core-core interaction more elaborated than the usual approximation 1/R will be taken into account as the sum of an exponential repulsive term plus a long range dispersion term approximated by the well known London formula. Potential energy calculations will be performed for different molecular states, for numerous values of the inter-nuclear distance R in a wide range. Spectroscopic constants have been derived for the bound states with regular shape. A ro vibrational study have been performed for the ground states with a calculation of the rotational and centrifugal distortion constants. A calculation for the transition dipole moment and matrix elements have been done for the bound states

  14. Formation of cold molecules through the photo-association of cold atoms of Cesium. Existence of long range forces between between cold excited atoms of Cesium; Formation de molecules froides par photoassociation d'atomes froids de cesium. Mise en evidence de forces a longue portee entre atomes froids excites de cesium

    Energy Technology Data Exchange (ETDEWEB)

    Comparat, D

    1999-09-01

    This thesis deals with the experimental study and the theoretical interpretation of the processes involved in photo-association and the formation of cold caesium molecules. It also presents a study of the dipolar forces between a pair of cold excited caesium atoms. We present here the first photo-association experiment on cold caesium atoms: two cold atoms absorb a photon to form an excited electronically excited molecules in a rotation-vibration level. The first production of cold molecules which was realised experimentally, after the spontaneous deexcitation of the photo-associated molecules, is described, stressing the role of the potential well of the molecular states O{sub g}{sup -}(6s+6p{sub 3/2}) or 1{sub u} (6s+6p{sub 3/2}) of caesium. The detection of the formed caesium molecules is based on a two-photons resonant ionisation that creates Cs{sub 2}{sup +} ions, afterwards selectively detected. Temperatures around 20-200 {mu}K have been measured. The photo-associative spectroscopy is described on the theoretical point of view: a detailed theoretical study allows to calculate precisely the asymptotic parts of the potential curves. On the experimental point of view, we present the spectroscopy of the extern potential well of the caesium state O{sub g}{sup -}(6s+6p{sub 3/2}) and the construction of an effective potential curve of the RKR type. A unified theory of photo-association in weak field, considered as a collision assisted by laser, is developed. The cold atoms experiments allow to study and control the collision between two atoms whose mutual interaction is of the dipole-dipole type. Two different physical systems are studied: a sample of Rydberg atoms, and the photo-association process which is a laser-assisted collision. A modification of the motion of one pair of atoms makes it possible to control the bipolar forces and to choose the atoms relative speeds. (author)

  15. Toll-Like Receptor and Accessory Molecule mRNA Expression in Humans and Mice as Well as in Murine Autoimmunity, Transient Inflammation, and Progressive Fibrosis

    Science.gov (United States)

    Ramaiah, Santhosh Kumar Vankayala; Günthner, Roman; Lech, Maciej; Anders, Hans-Joachim

    2013-01-01

    The cell type-, organ-, and species-specific expression of the Toll-like receptors (TLRs) are well described, but little is known about the respective expression profiles of their accessory molecules. We therefore determined the mRNA expression levels of LBP, MD2, CD36, CD14, granulin, HMGB1, LL37, GRP94, UNC93b1, TRIL, PRAT4A, AP3B1, AEP and the respective TLRs in human and mouse solid organs. Humans and mice displayed significant differences between their respective mRNA expression patterns of these factors. In addition, the expression profiles in transient tissue inflammation upon renal ischemia-reperfusion injury, in spleens and kidneys from mice with lupus-like systemic autoimmunity, and in progressive tissue fibrosis upon unilateral ureteral obstruction were studied. Several TLR co-factors were specifically regulated during the different phases of these disease entities, suggesting a functional involvement in the disease process. Thus, the organ- and species-specific expression patterns need to be considered in the design and interpretation of studies related to TLR-mediated innate immunity, which seems to be involved in the tissue injury phase, in the phase of tissue regeneration, and in progressive tissue remodelling. PMID:23803655

  16. Deconvolution of overlapping features in electron energy-loss spectra: the determination of absolute differential cross sections for electron-impact excitation of electronic states of molecules

    International Nuclear Information System (INIS)

    Campbell, L.; Brunger, M.J.; Teubner, O.J.P.; Mojarrabi, B.

    1996-06-01

    A set of three computer programs is reported which allow for the deconvolution of overlapping molecular electronic state structure in electron energy-loss spectra, even in highly perturbed systems. This procedure enables extraction of absolute differential cross sections for electron-impact excitation of electronic states of diatomic molecules from electron energy-loss spectra. The first code in the sequence uses the Rydberg-Klein-Rees procedure to generate potential energy curves from spectroscopic constants, while the second calculates Franck-Condon factors by numerical solution of the Schroedinger equation, given the potential energy curves. The third, given these Franck-Condon factors, the previously calculated relevant energies for the vibrational levels of the respective electronic states and the experimental energy-loss spectra, extracts the differential cross sections for each state. Each program can be run independently, or the three can run in sequence to determine these cross sections from the spectroscopic constants and the experimental energy-loss spectra. The application of these programs to the specific case of electron scattering from nitric oxide (NO) is demonstrated. 25 refs., 2 tabs., 2 figs

  17. Study of hyperfine transient field acting on the O16 excited nuclei (6.13 MeV, 3-) crossing iron and gadolinium magnetic foils

    International Nuclear Information System (INIS)

    Dekhissi, H.

    1985-07-01

    Precise measurements of transient magnetic field in iron and gadolinium have been obtained for oxygen ion at velocities from 2 to 8V o . At high recoil velocity, a transient field twice higher in gadolinium than in iron has been observed; this is contradictory with general predictions on transient field proportional growing with matrice polarization density. The degree of polarization can be deduced from transient field with measuring the ion fraction having an unpaired electron in K level. The resulting degree has been compared with theoretical estimations based on spin exchange, molecular orbital method, and polarized electron direct capture, as well as polarization mechanisms of 1s level of O 16 . Empiric forms aimed at the calibration of this field have been also tested [fr

  18. Transient Analysis of Dispersive Power-Ground Plate Pairs With Arbitrarily Shaped Antipads by the DGTD Method With Wave Port Excitation

    KAUST Repository

    Li, Ping; Jiang, Li Jun; Bagci, Hakan

    2016-01-01

    A discontinuous Galerkin time-domain (DGTD) method analyzing signal/power integrity on multilayered power-ground parallel plate pairs is proposed. The excitation is realized by introducing wave ports on the antipads where electric/magnetic current

  19. Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT).

    Science.gov (United States)

    Maurer, Reinhard J; Reuter, Karsten

    2013-07-07

    Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)] presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

  20. Laser induced transient absorptions of the excited triplet state of 9,10-anthraquinone-2-sulfonate. A further study by 248 nm laser photolysis

    International Nuclear Information System (INIS)

    Ma Jianhua; Lin Weizheng; Wang Wenfen; Yao Side; Lin Nianyun

    1999-01-01

    Transient absorption spectrum of triplet state of 9,10-anthraquinone-2-sulfonate (AQS) in aqueous solution has been investigated using 248 nm (KrF) laser photolysis. A whole transient absorption spectrum with absorption maxim at 380 nm and 580 nm has been assigned to triple AQS from detailed kinetic analysis of decay of 380 nm and 580 nm signals, which is the neat characteristic absorption of triplet AQS reported for the first time. In addition, the difference in feature of the spectrum of triplet AQS in H 2 O and that in CH 3 CN was eliminated by further study using 248 nm laser pulses

  1. Nonlinear characteristics of the rotating exciter system of power plant generators in case of electricity accidents; Transientes Verhalten des rotierenden Erregersystems von Kraftwerksgeneratoren bei elektrischen Stoerfaellen

    Energy Technology Data Exchange (ETDEWEB)

    Ataei, Nader

    2006-05-09

    Different types of exciter are used for voltage supply to the synchronous generators of power stations depending on the required power and design. The exciter system of the generator, which as a rule consists syncronous motors and commutators, is commonly modeled in conventional models by control units with nonlinear characteristics which do not give an accurate picture of the dynamic processes inside the exciter motor. It was not possible to assess the component loads of the exciter components and the physical characteristics within the exciter system. In this study, a brushless exciter for the grid-connected synchronous generator was investigated which consists of two synchronous motors as primary and secondary exciter and two commutator bridges. A dynamic simulation model was developed for calculating the interactions between the grid, generator and exciter unit in consideration of electromagnetic and galvanic coupling. For this, the normal control units were replaced by physical components of the exciter system, i.e. electric exciter motors and commutators. The study was carried out using an enhanced version of the Siemens NETOMAC software, which provided information on the loads on the exciter components in case of internal and external failures. In particular, loads in coils and commutators were calculated that could not be measured before. The findings enable more accurate dimensioning of the exciter unit making it more fail-safe, and the protective systems can be adjusted more accurately. One important result of the investigation was the identification of all dynamic processes going on between the exciter motors, commutators, generator and grid induced by external and internal failures. (orig.) [German] Zur Spannungsversorgung der Synchrongeneratoren in Kraftwerken werden je nach Leistungsanforderung und Baukonzept unterschiedliche Erregereinrichtungen verwendet. Das Erregersystem des Generators, das in der Regel aus Erregersynchronmaschinen und

  2. Optogalvanic transients in the 1s2,4→2p1,3 excitations of radio frequency neon plasma

    International Nuclear Information System (INIS)

    Yao, X.; Kumar, D.; McGlynn, S.P.

    1999-01-01

    The optogalvanic effects (OGE) induced by pulsed laser excitation of Ne 1s 2,4 →2p 1,3 transitions in a low power, ∼30 MHz radio frequency Ne discharge at ∼5 Torr are described. The polarity (sign) of the OGE signal is controlled by perturbations of the 1s j populations. The steady state 1s 4 population is ∼10 1 times larger than the 1s 2 population and the OGE signals for 1s 4 →2p 1,3 excitations are correspondingly stronger than those for 1s 2 →2p 1,3 excitations. The plasma temperature is found to be ∼1000 K. The excitations 1s 2,4 →2p 3 are more efficient at signal production than the 1s 2,4 →2p 1 excitations, which is contrary to prediction. The OGE signals are consequences of: (1) perturbation and reequilibration of the metastable 1s 3 and 1s 5 populations; (2) radiatively trapped 1s 2 → 1 S 0 photons; and (3) collisionally induced 1s 2 , 1s 4 ↔1s 3 , 1s 5 energy transfer. The OGE signal components, both the ionization and photoacoustic constituents, are temporally coincident only when the immediate causative agents are trapped photons. When otherwise produced, the photoacoustic part is delayed relative to the ionization component by the time required for the acoustic wave to travel from the locus of excitation to the sensitive region(s) of the plasma. copyright 1999 American Institute of Physics

  3. Unveiling the excited state energy transfer pathways in peridinin-chlorophyll a-protein by ultrafast multi-pulse transient absorption spectroscopy.

    Science.gov (United States)

    Redeckas, Kipras; Voiciuk, Vladislava; Zigmantas, Donatas; Hiller, Roger G; Vengris, Mikas

    2017-04-01

    Time-resolved multi-pulse methods were applied to investigate the excited state dynamics, the interstate couplings, and the excited state energy transfer pathways between the light-harvesting pigments in peridinin-chlorophyll a-protein (PCP). The utilized pump-dump-probe techniques are based on perturbation of the regular PCP energy transfer pathway. The PCP complexes were initially excited with an ultrashort pulse, resonant to the S 0 →S 2 transition of the carotenoid peridinin. A portion of the peridinin-based emissive intramolecular charge transfer (ICT) state was then depopulated by applying an ultrashort NIR pulse that perturbed the interaction between S 1 and ICT states and the energy flow from the carotenoids to the chlorophylls. The presented data indicate that the peridinin S 1 and ICT states are spectrally distinct and coexist in an excited state equilibrium in the PCP complex. Moreover, numeric analysis of the experimental data asserts ICT→Chl-a as the main energy transfer pathway in the photoexcited PCP systems. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. The Kinetics of Joined Action of Triplet-Triplet Annihilation and First-Order Decay of Molecules in T1 State in the Case of Nondominant First-Order Process: The Kinetic Model in the Case of Spatially Periodic Excitation

    Directory of Open Access Journals (Sweden)

    Paweł Borowicz

    2013-01-01

    Full Text Available In this paper the model developed for estimation of the diffusion coefficient of the molecules in the triplet state is presented. The model is based on the intuitive modification of the Smoluchowski equation for the time-dependent rate parameter. Since the sample is irradiated with the spatially periodic pattern nonexponential effects can be expected in the areas of the constructive interference of the exciting laser beams. This nonexponential effects introduce changes in the observed kinetics of the diffusion-controlled triplet-triplet annihilation. Due to irradiation with so-called long excitation pulse these non-exponential effects are very weak, so they can be described with introducing very simple correction to the kinetic model described in the first paper of this series. The values of diffusion coefficient of anthracene are used to calculate the annihilation radius from the data for spatially homogeneous excitation.

  5. Transient photocurrent in molecular junctions: singlet switching on and triplet blocking.

    Science.gov (United States)

    Petrov, E G; Leonov, V O; Snitsarev, V

    2013-05-14

    The kinetic approach adapted to describe charge transmission in molecular junctions, is used for the analysis of the photocurrent under conditions of moderate light intensity of the photochromic molecule. In the framework of the HOMO-LUMO model for the single electron molecular states, the analytic expressions describing the temporary behavior of the transient and steady state sequential (hopping) as well as direct (tunnel) current components have been derived. The conditions at which the current components achieve their maximal values are indicated. It is shown that if the rates of charge transmission in the unbiased molecular diode are much lower than the intramolecular singlet-singlet excitation/de-excitation rate, and the threefold degenerated triplet excited state of the molecule behaves like a trap blocking the charge transmission, a possibility of a large peak-like transient switch-on photocurrent arises.

  6. Intermolecular interaction of photoexcited Cu(/TMpy-P4) with water studied by transient resonance Raman and picosecond absorption spectroscopies

    NARCIS (Netherlands)

    Kruglik, S.; Kruglik, Sergei G.; Ermolenkov, Vladimir V.; Shvedko, Alexander G.; Orlovich, Valentine A.; Galievsky, Victor A.; Chirvony, Vladimir S.; Otto, Cornelis; Turpin, Pierre-Yves

    1997-01-01

    photoinduced complex between Cu(TMpy-P4) and water molecules, reversibly axially coordinated to the central metal, was observed in picosecond transient absorption and nanosecond resonance Raman experiments. This complex is rapidly created (τ1 = 15 ± 5 ps) in the excited triplet (π, π*) state of

  7. Imaging ultrafast excited state pathways in transition metal complexes by X-ray transient absorption and scattering using X-ray free electron laser source

    DEFF Research Database (Denmark)

    Chen, Lin X; Shelby, Megan L; Lestrange, Patrick J

    2016-01-01

    This report will describe our recent studies of transition metal complex structural dynamics on the fs and ps time scales using an X-ray free electron laser source, Linac Coherent Light Source (LCLS). Ultrafast XANES spectra at the Ni K-edge of nickel(ii) tetramesitylporphyrin (NiTMP) were measured...... on the low-energy shoulder of the edge, which is aided by the computation of X-ray transitions for postulated excited electronic states. The observed and computed inner shell to valence orbital transition energies demonstrate and quantify the influence of the electronic configuration on specific metal...

  8. The HIFI spectral survey of AFGL 2591 (CHESS). I. Highly excited linear rotor molecules in the high-mass protostellar envelope

    Science.gov (United States)

    van der Wiel, M. H. D.; Pagani, L.; van der Tak, F. F. S.; Kaźmierczak, M.; Ceccarelli, C.

    2013-05-01

    Context. Linear rotor molecules such as CO, HCO+ and HCN are important probes of star-forming gas. For these species, temperatures of ≲ 50 K are sufficient to produce emission lines that are observable from the ground at (sub)millimeter wavelengths. Molecular gas in the environment of massive protostellar objects, however, is known to reach temperatures of several hundred K. To probe this, space-based far-infrared observations are required. Aims: We aim to reveal the gas energetics in the circumstellar environment of the prototypical high-mass protostellar object AFGL 2591. Methods: Rotational spectral line signatures of CO species, HCO+, CS, HCN and HNC from a 490-1240 GHz survey with Herschel/HIFI, complemented by ground-based JCMT and IRAM 30 m spectra, cover transitions in the energy range (Eup/k) between 5 K and ~ 300 K. Selected frequency settings in the highest frequency HIFI bands (up to 1850 GHz) extend this range to 750 K for 12C16O. The resolved spectral line profiles are used to separate and study various kinematic components. Observed line intensities are compared with a numerical model that calculates excitation balance and radiative transfer based on spherical geometry. Results: The line profiles show two emission components, the widest and bluest of which is attributed to an approaching outflow and the other to the envelope. We find evidence for progressively more redshifted and wider line profiles from the envelope gas with increasing energy level. This trend is qualitatively explained by residual outflow contribution picked up in the systematically decreasing beam size. Integrated line intensities for each species decrease as Eup/k increases from ≲ 50 to ~700 K. The H2 density and temperature of the outflow gas are constrained to ~105-106 cm-3 and 60-200 K. In addition, we derive a temperature between 9 and 17 K and N(H2) ~ 3 × 1021 cm-2 for a known foreground cloud seen in absorption, and N(H2) ≲ 1019 cm-2 for a second foreground component

  9. Evidence for excited state intramolecular charge transfer reaction in donor-acceptor molecule 5-(4-dimethylamino-phenyl)-penta-2,4-dienoic acid methyl ester: Experimental and quantum chemical approach

    International Nuclear Information System (INIS)

    Kumar Paul, Bijan; Samanta, Anuva; Kar, Samiran; Guchhait, Nikhil

    2010-01-01

    Intramolecular charge transfer (ICT) reaction has been investigated in 5-(4-dimethylamino-phenyl)-penta-2,4-dienoic acid methyl ester (DPDAME) using spectroscopic techniques. The molecule DPDAME shows local emission in non-polar solvent and dual emission in polar solvents. Solvatochromic effects on the Stokes shifted emission band clearly demonstrate the charge transfer character of the excited state. Quantum chemical calculations have been performed at Hartree-Fock (HF) and density functional theoretical (DFT) levels to correlate the experimental findings. Potential energy curves (PECs) for the ICT reaction have been evaluated along the donor twist angle at DFT and time dependent density functional theory (TDDFT) levels for the ground and excited states, respectively, using B3LYP hybrid functional and 6-31G** basis set. The solvent effects on the spectral properties have been explored theoretically at the same level with time dependent density functional theory-polarized continuum model (TDDFT-PCM) and the theoretical results are found to well substantiate the solvent polarity dependent Stokes shifted emission of DPDAME. Huge enhancement of dipole moment (Δμ=16.42 D) of the molecule following photoexcitation dictates the highly polar character of the excited state. Although elucidation of PECs does not exactly predict the operation of ICT according to twisted intramolecular charge transfer (TICT) model in DPDAME, lowering of vertical transition energy as a function of the donor twist coordinate scripts the occurrence of red shifted emission as observed experimentally.

  10. Angle-resolving time-of-flight electron spectrometer for near-threshold precision measurements of differential cross sections of electron-impact excitation of atoms and molecules

    International Nuclear Information System (INIS)

    Lange, M.; Matsumoto, J.; Setiawan, A.; Panajotovic, R.; Harrison, J.; Lower, J. C. A.; Newman, D. S.; Mondal, S.; Buckman, S. J.

    2008-01-01

    This article presents a new type of low-energy crossed-beam electron spectrometer for measuring angular differential cross sections of electron-impact excitation of atomic and molecular targets. Designed for investigations at energies close to excitation thresholds, the spectrometer combines a pulsed electron beam with the time-of-flight technique to distinguish between scattering channels. A large-area, position-sensitive detector is used to offset the low average scattering rate resulting from the pulsing duty cycle, without sacrificing angular resolution. A total energy resolution better than 150 meV (full width at half maximum) at scattered energies of 0.5-3 eV is achieved by monochromating the electron beam prior to pulsing it. The results of a precision measurement of the differential cross section for electron-impact excitation of helium, at an energy of 22 eV, are used to assess the sensitivity and resolution of the spectrometer

  11. Excitation of transient lobe cell convection and auroral arc at the cusp poleward boundary during a transition of the interplanetary magnetic field from south to north

    Directory of Open Access Journals (Sweden)

    P. E. Sandholt

    2001-05-01

    Full Text Available We document the activation of transient polar arcs emanating from the cusp within a 15 min long intermediate phase during the transition from a standard two-cell convection pattern, representative of a strongly southward interplanetary magnetic field (IMF, to a "reverse" two-cell pattern, representative of strongly northward IMF conditions. During the 2–3 min lifetime of the arc, its base in the cusp, appearing as a bright spot, moved eastward toward noon by ~ 300 km. As the arc moved, it left in its "wake" enhanced cusp precipitation. The polar arc is a tracer of the activation of a lobe convection cell with clockwise vorticity, intruding into the previously established large-scale distorted two-cell pattern, due to an episode of localized lobe reconnection. The lobe cell gives rise to strong flow shear (converging electric field and an associated sheet of outflowing field-aligned current, which is manifested by the polar arc. The enhanced cusp precipitation represents, in our view, the ionospheric footprint of the lobe reconnection process.Key words. Magnetospheric physics (auroral phenomena; magnetopause, cusp, and boundary layers; plasma convection

  12. Evidence of excited state localization and static disorder in LH2 investigated by 2D-polarization single-molecule imaging at room temperature.

    Science.gov (United States)

    Tubasum, Sumera; Camacho, Rafael; Meyer, Matthias; Yadav, Dheerendra; Cogdell, Richard J; Pullerits, Tõnu; Scheblykin, Ivan G

    2013-12-07

    Two-dimensional polarization fluorescence imaging of single light harvesting complexes 2 (LH2) of Rps. acidophila was carried out to investigate the polarization properties of excitation and fluorescence emission simultaneously, at room temperature. In two separate experiments we excited LH2 with a spectrally narrow laser line matched to the absorption bands of the two chromophore rings, B800 and B850, thereby indirectly and directly triggering fluorescence of the B850 exciton state. A correlation analysis of the polarization modulation depths in excitation and emission for a large number of single complexes was performed. Our results show, in comparison to B800, that the B850 ring is a more isotropic absorber due to the excitonic nature of its excited states. At the same time, we observed a strong tendency for LH2 to emit with dipolar character, from which preferential localization of the emissive exciton, stable for minutes, is inferred. We argue that the observed effects can consistently be explained by static energetic disorder and/or deformation of the complex, with possible involvement of exciton self-trapping.

  13. Electronically excited C 2 from laser photodissociated C 60

    Science.gov (United States)

    Arepalli, S.; Scott, C. D.; Nikolaev, P.; Smalley, R. E.

    2000-03-01

    Spectral and transient emission measurements are made of radiation from products of laser excitation of buckminsterfullerene (C 60) vapor diluted in argon at 973 K. The principal radiation is from the Swan band system of C 2 and, at early times, also from a black-body continuum. Transient measurements indicate two characteristic periods of decay 2 and 50 μs long, with characteristic decay times of ˜0.3 and 5 μs, respectively. The first period is thought to be associated with decomposition and radiative cooling of C 60 molecules or nano-sized carbon particles and the second period continues with decomposition products of laser excited C 60, C 58, C 56, etc.

  14. Transient Analysis of Dispersive Power-Ground Plate Pairs With Arbitrarily Shaped Antipads by the DGTD Method With Wave Port Excitation

    KAUST Repository

    Li, Ping

    2016-09-09

    A discontinuous Galerkin time-domain (DGTD) method analyzing signal/power integrity on multilayered power-ground parallel plate pairs is proposed. The excitation is realized by introducing wave ports on the antipads where electric/magnetic current sources are represented in terms of the eigenmodes of the antipads. Since closed-forms solutions do not exist for the eigenmodes of the arbitrarily shaped antipads, they have to be calculated using numerical schemes. Spatial orthogonality of the eigenmodes permits determination of each mode\\'s temporal expansion coefficient by integrating the product of the electric field and the mode over the wave port. The temporal mode coefficients are then Fourier transformed to accurately calculate the S-parameters corresponding to different modes. Additionally, to generalize the DGTD to manipulate dispersive media, the auxiliary differential equation method is employed. This is done by introducing a time-dependent polarization volume current as an auxiliary unknown and the constitutive relation between this current and the electric field as an auxiliary equation. Consequently, computationally expensive temporal convolution is avoided. Various numerical examples, which demonstrate the applicability, robustness, and accuracy of the proposed method, are presented.

  15. Quenching reactions of electronically excited atoms

    International Nuclear Information System (INIS)

    Setser, D.W.

    2001-01-01

    The two-body, thermal quenching reactions of electronically excited atoms are reviewed using excited states of Ar, Kr, and Xe atoms as examples. State-specific interstate relaxation and excitation-transfer reactions with atomic colliders are discussed first. These results then are used to discuss quenching reactions of excited-state atoms with diatomic and polyatomic molecules, the latter have large cross sections, and the reactions can proceed by excitation transfer and by reactive quenching. Excited states of molecules are not considered; however, a table of quenching rate constants is given for six excited-state molecules in an appendix

  16. Excited states v.6

    CERN Document Server

    Lim, Edward C

    1982-01-01

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

  17. Formation of H- ions via vibrational excited molecules produced from recombinative wall desorption of H atoms in a low-pressure H/sub 2/ positive column

    NARCIS (Netherlands)

    Amorim, J.; Loureiro, J.; Schram, D.C.

    2001-01-01

    Recombinative wall desorption of hydrogen atoms in a low-pressure hydrogen positive column leading to formation of H/sub 2/ (X/sup 1/ Sigma /sub g//sup +/, v) molecules in optimum levels for H/sup -/ production by dissociative attachment is investigated. We employed a kinetic model that solves the

  18. Quantum dot molecules

    CERN Document Server

    Wu, Jiang

    2014-01-01

    This book reviews recent advances in the exciting and rapidly growing field of quantum dot molecules (QDMs). It offers state-of-the-art coverage of novel techniques and connects fundamental physical properties with device design.

  19. Inelastic Scattering of Identical Molecules within Framework of the Mixed Quantum/Classical Theory: Application to Rotational Excitations in H2 + H2.

    Science.gov (United States)

    Semenov, Alexander; Babikov, Dmitri

    2016-06-09

    Theoretical foundation is laid out for description of permutation symmetry in the inelastic scattering processes that involve collisions of two identical molecules, within the framework of the mixed quantum/classical theory (MQCT). In this approach, the rotational (and vibrational) states of two molecules are treated quantum-mechanically, whereas their translational motion (responsible for scattering) is treated classically. This theory is applied to H2 + H2 system, and the state-to-state transition cross sections are compared versus those obtained from the full-quantum calculations and experimental results from the literature. Good agreement is found in all cases. It is also found that results of MQCT, where the Coriolis coupling is included classically, are somewhat closer to exact full-quantum results than results of the other approximate quantum methods, where those coupling terms are neglected. These new developments allow applications of MQCT to a broad variety of molecular systems and processes.

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

    International Nuclear Information System (INIS)

    Clouvas, A.

    1985-12-01

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

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

    KAUST Repository

    Filatov, Mikhail A.

    2015-10-13

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

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

    KAUST Repository

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

    2015-01-01

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

  3. Toward a generalized computational workflow for exploiting transient pockets as new targets for small molecule stabilizers: Application to the homogentisate 1,2-dioxygenase mutants at the base of rare disease Alkaptonuria.

    Science.gov (United States)

    Bernini, Andrea; Galderisi, Silvia; Spiga, Ottavia; Bernardini, Giulia; Niccolai, Neri; Manetti, Fabrizio; Santucci, Annalisa

    2017-10-01

    Alkaptonuria (AKU) is an inborn error of metabolism where mutation of homogentisate 1,2-dioxygenase (HGD) gene leads to a deleterious or misfolded product with subsequent loss of enzymatic degradation of homogentisic acid (HGA) whose accumulation in tissues causes ochronosis and degeneration. There is no licensed therapy for AKU. Many missense mutations have been individuated as responsible for quaternary structure disruption of the native hexameric HGD. A new approach to the treatment of AKU is here proposed aiming to totally or partially rescue enzyme activity by targeting of HGD with pharmacological chaperones, i.e. small molecules helping structural stability. Co-factor pockets from oligomeric proteins have already been successfully exploited as targets for such a strategy, but no similar sites are present at HGD surface; hence, transient pockets are here proposed as a target for pharmacological chaperones. Transient pockets are detected along the molecular dynamics trajectory of the protein and filtered down to a set of suitable sites for structural stabilization by mean of biochemical and pharmacological criteria. The result is a computational workflow relevant to other inborn errors of metabolism requiring rescue of oligomeric, misfolded enzymes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. A transient absorption study of allophycocyanin

    Indian Academy of Sciences (India)

    Transient dynamics of allophycocyanin trimers and monomers are observed by using the pump-probe, transient absorption technique. The origin of spectral components of the transient absorption spectra is discussed in terms of both kinetics and spectroscopy. We find that the energy gap between the ground and excited ...

  5. Continuum emission of excited sodium dimer

    International Nuclear Information System (INIS)

    Pardo, A.; Poyato, J.M.L.; Alonso, J.I.; Rico, F.R.

    1980-01-01

    A study has been made of the behaviour of excited molecular sodium using high-power Ar + laser radiation. A continuum emission was observed in the red wavelength region. This emission was thought to be caused by the formation of excited triatomic molecules. Energy transfer was observed from excited molecules to atoms. (orig.)

  6. Application of R-matrix theory to resonant reactive electron-molecule scattering: Vibrational excitation and dissociative attachment of N2 and F2

    International Nuclear Information System (INIS)

    Wong, C.F.; Light, J.C.

    1984-01-01

    Based on the R-matrix approach of Schneider et al. [J. Phys. B 12, L 365 (1979)] to reactive electron-molecule scattering, a new propagative R-matrix method (PRMM) is presented which is more appropriate for polyatomic systems. The new method should be useful in other calculations where complicated integrals need to be propagated. We also introduce an effective R-matrix model (ERMM) in which the usual resonance parameters (potential and width) can be used as input in model R-matrix calculations. The PRMM and ERMM have been applied to the electron-N 2 system and the electron-F 2 system. The results agree very well with previous calculations for both vibrationally inelastic scattering and dissociative attachment when identical potentials and parameters are used

  7. Energy transfer upon collision of selectively excited CO{sub 2} molecules: State-to-state cross sections and probabilities for modeling of atmospheres and gaseous flows

    Energy Technology Data Exchange (ETDEWEB)

    Lombardi, A., E-mail: ebiu2005@gmail.com; Faginas-Lago, N.; Pacifici, L.; Grossi, G. [Dipartimento di Chimica, Università di Perugia, via Elce di Sotto 8, 06123 Perugia (Italy)

    2015-07-21

    Carbon dioxide molecules can store and release tens of kcal/mol upon collisions, and such an energy transfer strongly influences the energy disposal and the chemical processes in gases under the extreme conditions typical of plasmas and hypersonic flows. Moreover, the energy transfer involving CO{sub 2} characterizes the global dynamics of the Earth-atmosphere system and the energy balance of other planetary atmospheres. Contemporary developments in kinetic modeling of gaseous mixtures are connected to progress in the description of the energy transfer, and, in particular, the attempts to include non-equilibrium effects require to consider state-specific energy exchanges. A systematic study of the state-to-state vibrational energy transfer in CO{sub 2} + CO{sub 2} collisions is the focus of the present work, aided by a theoretical and computational tool based on quasiclassical trajectory simulations and an accurate full-dimension model of the intermolecular interactions. In this model, the accuracy of the description of the intermolecular forces (that determine the probability of energy transfer in molecular collisions) is enhanced by explicit account of the specific effects of the distortion of the CO{sub 2} structure due to vibrations. Results show that these effects are important for the energy transfer probabilities. Moreover, the role of rotational and vibrational degrees of freedom is found to be dominant in the energy exchange, while the average contribution of translations, under the temperature and energy conditions considered, is negligible. Remarkable is the fact that the intramolecular energy transfer only involves stretching and bending, unless one of the colliding molecules has an initial symmetric stretching quantum number greater than a threshold value estimated to be equal to 7.

  8. Energy transfer upon collision of selectively excited CO2 molecules: State-to-state cross sections and probabilities for modeling of atmospheres and gaseous flows.

    Science.gov (United States)

    Lombardi, A; Faginas-Lago, N; Pacifici, L; Grossi, G

    2015-07-21

    Carbon dioxide molecules can store and release tens of kcal/mol upon collisions, and such an energy transfer strongly influences the energy disposal and the chemical processes in gases under the extreme conditions typical of plasmas and hypersonic flows. Moreover, the energy transfer involving CO2 characterizes the global dynamics of the Earth-atmosphere system and the energy balance of other planetary atmospheres. Contemporary developments in kinetic modeling of gaseous mixtures are connected to progress in the description of the energy transfer, and, in particular, the attempts to include non-equilibrium effects require to consider state-specific energy exchanges. A systematic study of the state-to-state vibrational energy transfer in CO2 + CO2 collisions is the focus of the present work, aided by a theoretical and computational tool based on quasiclassical trajectory simulations and an accurate full-dimension model of the intermolecular interactions. In this model, the accuracy of the description of the intermolecular forces (that determine the probability of energy transfer in molecular collisions) is enhanced by explicit account of the specific effects of the distortion of the CO2 structure due to vibrations. Results show that these effects are important for the energy transfer probabilities. Moreover, the role of rotational and vibrational degrees of freedom is found to be dominant in the energy exchange, while the average contribution of translations, under the temperature and energy conditions considered, is negligible. Remarkable is the fact that the intramolecular energy transfer only involves stretching and bending, unless one of the colliding molecules has an initial symmetric stretching quantum number greater than a threshold value estimated to be equal to 7.

  9. Simple systematization of vibrational excitation cross-section calculations for resonant electron-molecule scattering in the boomerang and impulse models.

    Science.gov (United States)

    Sarma, Manabendra; Adhikari, S; Mishra, Manoj K

    2007-01-28

    Vibrational excitation (nu(f), where psi(nu(i))(R,t) approximately =e(-iH(A(2))-(R)t/h phi(nu(i))(R) with time evolution under the influence of the resonance anionic Hamiltonian H(A(2) (-))(A(2) (-)=N(2)(-)/H(2) (-)) implemented using Lanczos and fast Fourier transforms. The target (A(2)) vibrational eigenfunctions phi(nu(i))(R) and phi(nu(f))(R) are calculated using Fourier grid Hamiltonian method applied to potential energy (PE) curves of the neutral target. Application of this simple systematization to calculate vibrational structure in e-N(2) and e-H(2) scattering cross-sections provides mechanistic insights into features underlying presence/absence of structure in e-N(2) and e-H(2) scattering cross-sections. The results obtained with approximate PE curves are in reasonable agreement with experimental/calculated cross-section profiles, and cross correlation functions provide a simple demarcation between the boomerang and impulse models.

  10. Theoretical study of intermolecular energy transfer involving electronically excited molecules: He(/sup 1/S) + H/sub 2/(B /sup 1/. sigma. /sub u//sup +/). [Solution for coupled channel equations

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, R.M.

    1986-11-01

    To further understanding of gas phase collision dynamics involving electronically-excited molecules, a fully quantum mechanical study of He + H/sub 2/(B /sup 1/..sigma../sub u//sup +/) was undertaken. Iterative natural orbital configuration interaction (CI) calculations were performed to obtain the interaction potential between He and H/sub 2/(B /sup 1/..sigma../sub u//sup +/). 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 + H/sub 2/(E,F /sup 1/..sigma../sub g//sup +/) and with He + H/sub 2/(X /sup 1/..sigma../sub g//sup +/) and cause a local maximum and a deep minimum in the He + H/sub 2/(B /sup 1/..sigma../sub u//sup +/) PES, respectively. The crossing with He + H/sub 2/(X /sup 1/..sigma../sub g//sup +/) 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 H/sub 2/(B /sup 1/..sigma../sub u//sup +/) were computed for use in the multipole expansion, which is the analytic form of the long-range PES. 129 refs., 28 figs., 35 tabs.

  11. Ultrafast dynamics of ligand and substrate interaction in endothelial nitric oxide synthase under Soret excitation.

    Science.gov (United States)

    Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S

    2016-01-01

    Ultrafast transient absorption spectroscopy of endothelial NOS oxygenase domain (eNOS-oxy) was performed to study dynamics of ligand or substrate interaction under Soret band excitation. Photo-excitation dissociates imidazole ligand in 4ps. The eNOS-oxy without additive is partially bound with water molecule, thus its photoexcited dynamics also shows ligand dissociation in <800fs. Then it followed by vibrational cooling coupled with charge transfer in 4.8ps, and recombination of ligand to distal side of heme in 12ps. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Cryogenic exciter

    Science.gov (United States)

    Bray, James William [Niskayuna, NY; Garces, Luis Jose [Niskayuna, NY

    2012-03-13

    The disclosed technology is a cryogenic static exciter. The cryogenic static exciter is connected to a synchronous electric machine that has a field winding. The synchronous electric machine is cooled via a refrigerator or cryogen like liquid nitrogen. The static exciter is in communication with the field winding and is operating at ambient temperature. The static exciter receives cooling from a refrigerator or cryogen source, which may also service the synchronous machine, to selected areas of the static exciter and the cooling selectively reduces the operating temperature of the selected areas of the static exciter.

  13. Formation of Ultracold Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Cote, Robin [Univ. of Connecticut, Storrs, CT (United States)

    2016-01-28

    Advances in our ability to slow down and cool atoms and molecules to ultracold temperatures have paved the way to a revolution in basic research on molecules. Ultracold molecules are sensitive of very weak interactions, even when separated by large distances, which allow studies of the effect of those interactions on the behavior of molecules. In this program, we have explored ways to form ultracold molecules starting from pairs of atoms that have already reached the ultracold regime. We devised methods that enhance the efficiency of ultracold molecule production, for example by tuning external magnetic fields and using appropriate laser excitations. We also investigates the properties of those ultracold molecules, especially their de-excitation into stable molecules. We studied the possibility of creating new classes of ultra-long range molecules, named macrodimers, thousand times more extended than regular molecules. Again, such objects are possible because ultra low temperatures prevent their breakup by collision. Finally, we carried out calculations on how chemical reactions are affected and modified at ultracold temperatures. Normally, reactions become less effective as the temperature decreases, but at ultracold temperatures, they can become very effective. We studied this counter-intuitive behavior for benchmark chemical reactions involving molecular hydrogen.

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

    Science.gov (United States)

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

    2003-11-01

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

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

    International Nuclear Information System (INIS)

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

    2003-01-01

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

  16. Mean excitation energies for molecular ions

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, Phillip W.K.; Sauer, Stephan P.A. [Department of Chemistry, University of Copenhagen, Copenhagen (Denmark); Oddershede, Jens [Department of Physics, Chemistry, and Pharmacy, University of Southern Denmark, Odense (Denmark); Quantum Theory Project, Departments of Physics and Chemistry, University of Florida, Gainesville, FL (United States); Sabin, John R., E-mail: sabin@qtp.ufl.edu [Department of Physics, Chemistry, and Pharmacy, University of Southern Denmark, Odense (Denmark); Quantum Theory Project, Departments of Physics and Chemistry, University of Florida, Gainesville, FL (United States)

    2017-03-01

    The essential material constant that determines the bulk of the stopping power of high energy projectiles, the mean excitation energy, is calculated for a range of smaller molecular ions using the RPA method. It is demonstrated that the mean excitation energy of both molecules and atoms increase with ionic charge. However, while the mean excitation energies of atoms also increase with atomic number, the opposite is the case for mean excitation energies for molecules and molecular ions. The origin of these effects is explained by considering the spectral representation of the excited state contributing to the mean excitation energy.

  17. Coulomb excitation

    International Nuclear Information System (INIS)

    McGowan, F.K.; Stelson, P.H.

    1974-01-01

    The theory of Coulomb excitation and a brief review of pertinent treatments of the Coulomb excitation process that are useful for the analysis of experiments are given. Examples demonstrating the scope of nuclear structure information obtainable from gamma spectroscopy are presented. Direct Elambda excitation of 232 Th is discussed in terms of the one phonon octupole vibrational spectrum. B(MI) reduced transition probabilities resulting from Coulomb excitation of odd-A deformed nuclei with heavy ions are presented as a test of the rotational model. The use of gamma ray coincidence and particle-gamma coincidence as tools for investigating Coulomb excitation is discussed. (U.S.)

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

    Science.gov (United States)

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

    2007-11-14

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

  19. Transient analyzer

    International Nuclear Information System (INIS)

    Muir, M.D.

    1975-01-01

    The design and design philosophy of a high performance, extremely versatile transient analyzer is described. This sub-system was designed to be controlled through the data acquisition computer system which allows hands off operation. Thus it may be placed on the experiment side of the high voltage safety break between the experimental device and the control room. This analyzer provides control features which are extremely useful for data acquisition from PPPL diagnostics. These include dynamic sample rate changing, which may be intermixed with multiple post trigger operations with variable length blocks using normal, peak to peak or integrate modes. Included in the discussion are general remarks on the advantages of adding intelligence to transient analyzers, a detailed description of the characteristics of the PPPL transient analyzer, a description of the hardware, firmware, control language and operation of the PPPL transient analyzer, and general remarks on future trends in this type of instrumentation both at PPPL and in general

  20. Stationary and Transient Response Statistics

    DEFF Research Database (Denmark)

    Madsen, Peter Hauge; Krenk, Steen

    1982-01-01

    The covariance functions for the transient response of a linear MDOF-system due to stationary time limited excitation with an arbitrary frequency content are related directly to the covariance functions of the stationary response. For rational spectral density functions closed form expressions fo...

  1. Vibronic excitation in atom molecule collisions

    International Nuclear Information System (INIS)

    Kleyn, A.W.

    1980-01-01

    The molecular beam machine used for the experiments is described. Three setups are discussed: one to measure total cross sections for negative ion formation in Na, K, Cs + O 2 collisions (3-6000 eV); another to measure differential cross sections for neutral scattering and positive ion formation in K, Cs + O 2 and K + Br 2 collisions (20 - 150 eV); and a third to measure energy-loss spectra for neutral K scattered at a certain angle after a collision with O 2 or Br 2 (20 - 150 eV). (Auth.)

  2. Dissociative Electron Attachment to Rovibrationally Excited Molecules

    Science.gov (United States)

    1987-08-31

    autodetachment process [ 2 I + + e ]g -g the lowest contributing partial wave is an s-wave. Thus Wigner’s threshold law for the width of this state implies...118, 1153 (1960); L. Szasz and P. Mandal J. Phys. B 13, 1919 (1980); P. Mandal and S. and G. McGinn, J. Chem. Phys. 42, 2363 (1965). Guha, ibid. 13...threshold law , the width F(R) of the resonant ectr(- Ferg), (e,) state is taken to be of the form F(R)=ck (R), where k (R) FIG. 3. Cross sections for

  3. Exciter switch

    Science.gov (United States)

    Mcpeak, W. L.

    1975-01-01

    A new exciter switch assembly has been installed at the three DSN 64-m deep space stations. This assembly provides for switching Block III and Block IV exciters to either the high-power or 20-kW transmitters in either dual-carrier or single-carrier mode. In the dual-carrier mode, it provides for balancing the two drive signals from a single control panel located in the transmitter local control and remote control consoles. In addition to the improved switching capabilities, extensive monitoring of both the exciter switch assembly and Transmitter Subsystem is provided by the exciter switch monitor and display assemblies.

  4. Excited-state intramolecular proton transfer of 2-acetylindan-1,3-dione studied by ultrafast absorption and fluorescence spectroscopy

    Directory of Open Access Journals (Sweden)

    Pramod Kumar Verma

    2016-03-01

    Full Text Available We employ transient absorption from the deep-UV to the visible region and fluorescence upconversion to investigate the photoinduced excited-state intramolecular proton-transfer dynamics in a biologically relevant drug molecule, 2-acetylindan-1,3-dione. The molecule is a ß-diketone which in the electronic ground state exists as exocyclic enol with an intramolecular H-bond. Upon electronic excitation at 300 nm, the first excited state of the exocyclic enol is initially populated, followed by ultrafast proton transfer (≈160 fs to form the vibrationally hot endocyclic enol. Subsequently, solvent-induced vibrational relaxation takes place (≈10 ps followed by decay (≈390 ps to the corresponding ground state.

  5. Transient voltage oscillations in coils

    International Nuclear Information System (INIS)

    Chowdhuri, P.

    1985-01-01

    Magnet coils may be excited into internal voltage oscillations by transient voltages. Such oscillations may electrically stress the magnet's dielectric components to many times its normal stress. This may precipitate a dielectric failure, and the attendant prolonged loss of service and costly repair work. Therefore, it is important to know the natural frequencies of oscillations of a magnet during the design stage, and to determine whether the expected switching transient voltages can excite the magnet into high-voltage internal oscillations. The series capacitance of a winding significantly affects its natural frequencies. However, the series capacitance is difficult to calculate, because it may comprise complex capacitance network, consisting of intra- and inter-coil turn-to-turn capacitances of the coil sections. A method of calculating the series capacitance of a winding is proposed. This method is rigorous but simple to execute. The time-varying transient voltages along the winding are also calculated

  6. Quantum turnstile operation of single-molecule magnets

    International Nuclear Information System (INIS)

    Moldoveanu, V; Dinu, I V; Tanatar, B; Moca, C P

    2015-01-01

    The time-dependent transport through single-molecule magnets coupled to magnetic or non-magnetic electrodes is studied in the framework of the generalized master equation method. We investigate the transient regime induced by the periodic switching of the source and drain contacts. If the electrodes have opposite magnetizations the quantum turnstile operation allows the stepwise writing of intermediate excited states. In turn, the transient currents provide a way to read these states. Within our approach we take into account both the uniaxial and transverse anisotropy. The latter may induce additional quantum tunneling processes which affect the efficiency of the proposed read-and-write scheme. An equally weighted mixture of molecular spin states can be prepared if one of the electrodes is ferromagnetic. (paper)

  7. Transition state region in the A-Band photodissociation of allyl iodide—A femtosecond extreme ultraviolet transient absorption study

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacherjee, Aditi, E-mail: abhattacherjee@berkeley.edu, E-mail: andrewattar@berkeley.edu; Attar, Andrew R., E-mail: abhattacherjee@berkeley.edu, E-mail: andrewattar@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Leone, Stephen R., E-mail: srl@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States)

    2016-03-28

    Femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy based on a high-harmonic generation source is used to study the 266 nm induced A-band photodissociation dynamics of allyl iodide (CH{sub 2} =CHCH{sub 2}I). The photolysis of the C—I bond at this wavelength produces iodine atoms both in the ground ({sup 2}P{sub 3/2}, I) and spin-orbit excited ({sup 2}P{sub 1/2}, I*) states, with the latter as the predominant channel. Using XUV absorption at the iodine N{sub 4/5} edge (45–60 eV), the experiments constitute a direct probe of not only the long-lived atomic iodine reaction products but also the fleeting transition state region of the repulsive n{sub I}σ{sup ∗}{sub C—I} excited states. Specifically, three distinct features are identified in the XUV transient absorption spectrum at 45.3 eV, 47.4 eV, and 48.4 eV (denoted transients A, B, and C, respectively), which arise from the repulsive valence-excited nσ{sup ∗} states and project onto the high-lying core-excited states of the dissociating molecule via excitation of 4d(I) core electrons. Transients A and B originate from 4d(I) → n(I) core-to-valence transitions, whereas transient C is best assigned to a 4d(I) →σ{sup ∗}(C—I) transition. The measured differential absorbance of these new features along with the I/I* branching ratios known from the literature is used to suggest a more definitive assignment, albeit provisional, of the transients to specific dissociative states within the A-band manifold. The transients are found to peak around 55 fs–65 fs and decay completely by 145 fs–185 fs, demonstrating the ability of XUV spectroscopy to map the evolution of reactants into products in real time. The similarity in the energies of transients A and B with analogous features observed in methyl iodide [Attar et al. J. Phys. Chem. Lett. 6, 5072, (2015)] together with the new observation of transient C in the present work provides a more complete picture of the valence electronic

  8. Experimental studies of laser-generated translationally hot atoms and molecules

    International Nuclear Information System (INIS)

    Cousins, L.M.

    1989-01-01

    An important determinant of the outcome of a chemical interaction is the relative translational energy of the partners. This thesis focuses on the generation of translationally energetic atoms and molecules and the role of translational energy in chemical interactions. One set of studies examines the competitive pathways of reactions and energy transfer in hyperthermal collisions of fast H or D atoms with HF. The vibrational excitation of HF or DF is measured using a time- and wavelength-resolved infrared emission technique. The results suggest that different collision geometries can lead to markedly different mechanisms for vibrational excitation. Another set of experiments is performed with a goal to generate a repetitively pulsed source of molecules or atoms with translational energies in the 0.1-10 eV range. A pulsed UV laser is used to excite a molecular film, vaporizing a number of molecules near the surface of the film. The composition and velocity of these molecules are measured by their time-of-flight to a quadrupole mass spectrometer. Kinetic energies in the range of 0.1-10 eV are observed; the energies are continuously variable and the molecules can be repetitively and reproducibly generated. To establish the dynamics of the vaporization, the internal distributions of fast 0.1-0.7 eV NO molecules are measured using a laser multiphoton detection technique. These studies indicate that the translationally hot molecules are ejected rotationally cold, i.e. typically with only 3% of the energy in rotational excitation. The large disequilibrium between translation and rotation suggests that the vaporization occurs by a transient, nonequilibrium heating mechanism coupled with an adiabatic expansion. The result is additionally promising in light of the desire to produce fast beams of molecules with characterizable and narrow internal energy distributions

  9. Transient phenomena in electrical power systems

    CERN Document Server

    Venikov, V A; Higinbotham, W

    1964-01-01

    Electronics and Instrumentation, Volume 24: Transient Phenomena in Electrical Power Systems presents the methods for calculating the stability and the transient behavior of systems with forced excitation control. This book provides information pertinent to the analysis of transient phenomena in electro-mechanical systems.Organized into five chapters, this volume begins with an overview of the principal requirements in an excitation system. This text then explains the electromagnetic and electro-mechanical phenomena, taking into account the mutual action between the components of the system. Ot

  10. Coherent control of atoms and diatomic molecules with shaped ultrashort pulses; Manipulation coherente d'atomes et de molecules diatomiques avec des impulsions mises en forme

    Energy Technology Data Exchange (ETDEWEB)

    Degert, J

    2002-12-15

    This thesis deals with the theoretical and experimental study of coherent control of atomic and molecular systems with shaped pulses. At first, we present several experiments of control of coherent transients in rubidium. These transients appear when a two-level system is excited by a perturbative chirped pulse, and are characterized by oscillations in the excited state population. For a strong chirp, we show that a phase step in the spectrum modifies the phase of the oscillations. Then, by direct analogy with Fresnel zone lens, we conceive a chirped pulse with a highly modulated amplitude, allowing to suppress destructive contributions to the population transfer. In a second set of experiments, we focus on quantum path interferences in two-photon transitions excited by linearly chirped pulses. Owing to the broad bandwidth of ultrashort pulses, sequential and direct excitation paths contribute to the excited state population. Oscillations resulting from interferences between these two paths are observed in atomic sodium. Moreover, we show that they are observable whatever the sign of chirp. Theoretically, we study the control of the predissociation of a benchmark diatomic molecule: NaI. Predissociation leads to matter wave interferences in the fragments distribution. First, we show that a suitably chosen probe pulse allows the observation of theses interferences. Next, using a sequence of control pulse inducing electronic transition, we demonstrate the possibility to manipulate fragment energy distribution. (author)

  11. Electronic-excitation energy transfer in heterogeneous dye solutions under laser excitation

    International Nuclear Information System (INIS)

    Levshin, L.V.; Mukushev, B.T.; Saletskii, A.M.

    1995-01-01

    An experimental study has been made of electronic-excitation energy transfer (EEET) among dye molecules of different types for different exciting-fight wavelengths and temperatures. Upon selective laser excitation of the donor, the inhomogeneous broadening of molecular levels increases the probability of EEET from the donor to acceptor molecules. The efficiency of this process is directly proportional to the acceptor molecule concentration and is temperature dependent. The EEET is accompanied by the spectral migration of energy among donor molecules, which reduces the fluorescence quantum efficiency of the donor. Increasing the frequency of the exciting light decreases in the donor fluorescence quantum efficiency. An increase in the acceptor molecule concentration results in a decrease of the spectral migration of excitation in the donor molecule system. 5 refs., 5 figs

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-11-15

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

  13. Attosecond transient absorption spectroscopy of molecular hydrogen

    International Nuclear Information System (INIS)

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

    2015-01-01

    We extend attosecond transient absorption spectroscopy (ATAS) to the study of hydrogen molecules, demonstrating the potential of the technique to resolve – simultaneously and with state resolution – both the electronic and nuclear dynamics. (paper)

  14. Voiced Excitations

    National Research Council Canada - National Science Library

    Holzricher, John

    2004-01-01

    To more easily obtain a voiced excitation function for speech characterization, measurements of skin motion, tracheal tube, and vocal fold, motions were made and compared to EM sensor-glottal derived...

  15. Exciting Pools

    Science.gov (United States)

    Wright, Bradford L.

    1975-01-01

    Advocates the creation of swimming pool oscillations as part of a general investigation of mechanical oscillations. Presents the equations, procedure for deriving the slosh modes, and methods of period estimation for exciting swimming pool oscillations. (GS)

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

    Science.gov (United States)

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

    2006-01-01

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

  17. Multiphoton dissociation of polyatomic molecules

    International Nuclear Information System (INIS)

    Schulz, P.A.

    1979-10-01

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

  18. Coherent control of atoms and diatomic molecules with shaped ultrashort pulses

    International Nuclear Information System (INIS)

    Degert, J.

    2002-12-01

    This thesis deals with the theoretical and experimental study of coherent control of atomic and molecular systems with shaped pulses. At first, we present several experiments of control of coherent transients in rubidium. These transients appear when a two-level system is excited by a perturbative chirped pulse, and are characterized by oscillations in the excited state population. For a strong chirp, we show that a phase step in the spectrum modifies the phase of the oscillations. Then, by direct analogy with Fresnel zone lens, we conceive a chirped pulse with a highly modulated amplitude, allowing to suppress destructive contributions to the population transfer. In a second set of experiments, we focus on quantum path interferences in two-photon transitions excited by linearly chirped pulses. Owing to the broad bandwidth of ultrashort pulses, sequential and direct excitation paths contribute to the excited state population. Oscillations resulting from interferences between these two paths are observed in atomic sodium. Moreover, we show that they are observable whatever the sign of chirp. Theoretically, we study the control of the predissociation of a benchmark diatomic molecule: NaI. Predissociation leads to matter wave interferences in the fragments distribution. First, we show that a suitably chosen probe pulse allows the observation of theses interferences. Next, using a sequence of control pulse inducing electronic transition, we demonstrate the possibility to manipulate fragment energy distribution. (author)

  19. Superresolution microscopy with transient binding.

    Science.gov (United States)

    Molle, Julia; Raab, Mario; Holzmeister, Susanne; Schmitt-Monreal, Daniel; Grohmann, Dina; He, Zhike; Tinnefeld, Philip

    2016-06-01

    For single-molecule localization based superresolution, the concentration of fluorescent labels has to be thinned out. This is commonly achieved by photophysically or photochemically deactivating subsets of molecules. Alternatively, apparent switching of molecules can be achieved by transient binding of fluorescent labels. Here, a diffusing dye yields bright fluorescent spots when binding to the structure of interest. As the binding interaction is weak, the labeling is reversible and the dye ligand construct diffuses back into solution. This approach of achieving superresolution by transient binding (STB) is reviewed in this manuscript. Different realizations of STB are discussed and compared to other localization-based superresolution modalities. We propose the development of labeling strategies that will make STB a highly versatile tool for superresolution microscopy at highest resolution. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Excited fermions

    International Nuclear Information System (INIS)

    Boudjema, F.; Djouadi, A.; Kneur, J.L.

    1992-01-01

    The production of excited fermions with mass above 100 GeV is considered. f→Vf (1) decay widths are calculated where V=γ, Z or W. Excited fermion pair production in e + e - annihilation and in γγ collisions, and single production in e + e - annihilation, eγ and γγ collisions is also discussed. Cross sections are calculated for all these cases. The discovery potential of the NLC at 500 GeV is compared with that of other colliders. (K.A.) 15 refs., 5 figs., 2 tabs

  1. Vibrational excitation from heterogeneous catalysis

    International Nuclear Information System (INIS)

    Purvis, G.D. III; Redmon, M.J.; Woken, G. Jr.

    1979-01-01

    Classical trajectories have been used by numerous researchers to investigate the dynamics of exothermic chemical reactions (atom + diatom) with a view toward understanding what leads to vibrational excitation of the product molecule. Unlike these studies, the case where the reaction is catalyzed by a solid surface is considered. The trajectory studies indicate that there should be conditions under which considerable vibrational energy appears in the product molecules without being lost to the solid during the course of the reaction. 2 figures, 3 tables

  2. Experimental REMPI [Resonance Enhanced Multiphoton Ionization] studies of small molecules

    International Nuclear Information System (INIS)

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

    1986-01-01

    Resonance Enhanced Multiphoton Ionization (REMPI) utilizes tunable dye lasers to ionize an atom or molecule by first preparing an excited state by multiphoton absorption and then ionizing that state before it can decay. This process is highly selective with respect to both the initial and resonant intermediate states of the target, and it can be extremely sensitive. In addition, the products of the REMPI process can be detected as needed by analyzing the resulting electrons, ions, fluorescence, or by additional REMPI. This points to a number of exciting opportunities for both basic and applied science. On the applied side, REMPI has great potential as an ultrasensitive, highly selective detector for trace, reactive, or transient species. On the basic side, REMPI affords an unprecedented means of exploring excited state physics and chemistry at the quantum-state-specific level. We shall give an overview together with examples of current studies of excited molecular states to illustrate the principles of and prospects for REMPI. 27 refs., 3 figs

  3. Molecule nanoweaver

    Science.gov (United States)

    Gerald, II; Rex, E [Brookfield, IL; Klingler, Robert J [Glenview, IL; Rathke, Jerome W [Homer Glen, IL; Diaz, Rocio [Chicago, IL; Vukovic, Lela [Westchester, IL

    2009-03-10

    A method, apparatus, and system for constructing uniform macroscopic films with tailored geometric assemblies of molecules on the nanometer scale. The method, apparatus, and system include providing starting molecules of selected character, applying one or more force fields to the molecules to cause them to order and condense with NMR spectra and images being used to monitor progress in creating the desired geometrical assembly and functionality of molecules that comprise the films.

  4. Generation and decay dynamics of triplet excitons in Alq3 thin films under high-density excitation conditions.

    Science.gov (United States)

    Watanabe, Sadayuki; Furube, Akihiro; Katoh, Ryuzi

    2006-08-31

    We studied the generation and decay dynamics of triplet excitons in tris-(8-hydroxyquinoline) aluminum (Alq3) thin films by using transient absorption spectroscopy. Absorption spectra of both singlet and triplet excitons in the film were identified by comparison with transient absorption spectra of the ligand molecule (8-hydroxyquinoline) itself and the excited triplet state in solution previously reported. By measuring the excitation light intensity dependence of the absorption, we found that exciton annihilation dominated under high-density excitation conditions. Annihilation rate constants were estimated to be gammaSS = (6 +/- 3) x 10(-11) cm3 s(-1) for single excitons and gammaTT = (4 +/- 2) x 10(-13) cm3 s(-1) for triplet excitons. From detailed analysis of the light intensity dependence of the quantum yield of triplet excitons under high-density conditions, triplet excitons were mainly generated through fission from highly excited singlet states populated by singlet-singlet exciton annihilation. We estimated that 30% of the highly excited states underwent fission.

  5. Sub-Picosecond Injection of Electrons from Excited {Ru (2,2'-bipy-4,4'-dicarboxy)2(SCN)2} into TiO2 Using Transient Mid-Infrared Spectroscopy

    International Nuclear Information System (INIS)

    Nozik, A.J.; Ghosh, H.N.; Asbury, J.B.; Sprague, J.R.; Ellingson, R.J.; Ferrere, S.; Lian, T.

    1999-01-01

    We have used femtosecond pump-probe spectroscopy to time resolve the injection of electrons into nanocrystalline TiO2 film electrodes under ambient conditions following photoexcitation of the adsorbed dye, [Ru(4,4'-dicarboxy-2,2'-bipyridine)2(NCS)2] (N3). Pumping at one of the metal-to-ligand charge transfer adsorption peaks and probing the absorption of electrons injected into the TiO2 conduction band at 1.52 m and in the range of 4.1 to 7.0 m, we have directly observed the arrival of the injected electrons. Our measurements indicate an instrument-limited 50-fs upper limit on the electron injection time under ambient conditions in air. We have compared the infrared transient absorption for non-injecting (blank) systems consisting of N3 in ethanol and N3 adsorbed to films of nanocrystalline Al2O3 and ZrO2, and found no indication of electron injection at probe wavelengths in the mid-IR (4.1 to 7.0 m). At 1.52 m interferences exist in the observed transient adsorption signal for the blanks

  6. Excited baryons

    International Nuclear Information System (INIS)

    Mukhopadhyay, N.C.

    1986-01-01

    The status of the theory of the low-energy approach to hadron structure is reviewed briefly by surveying a few relevant models. A few examples of tests needed to sort out the predictions of different models pertaining to the quark-gluon structure of hadrons are discussed, and given the resulting physics objectives, a few experimental options for excited baryon research at CFBAF are suggested

  7. Excited baryons

    Energy Technology Data Exchange (ETDEWEB)

    Mukhopadhyay, N.C.

    1986-01-01

    The status of the theory of the low-energy approach to hadron structure is reviewed briefly by surveying a few relevant models. A few examples of tests needed to sort out the predictions of different models pertaining to the quark-gluon structure of hadrons are discussed, and given the resulting physics objectives, a few experimental options for excited baryon research at CFBAF are suggested. (LEW)

  8. Excited state dynamics & optical control of molecular motors

    Science.gov (United States)

    Wiley, Ted; Sension, Roseanne

    2014-03-01

    Chiral overcrowded alkenes are likely candidates for light driven rotary molecular motors. At their core, these molecular motors are based on the chromophore stilbene, undergoing ultrafast cis/trans photoisomerization about their central double bond. Unlike stilbene, the photochemistry of molecular motors proceeds in one direction only. This unidirectional rotation is a result of helicity in the molecule induced by steric hindrance. However, the steric hindrance which ensures unidirectional excited state rotation, has the unfortunate consequence of producing large ground state barriers which dramatically decrease the overall rate of rotation. These molecular scale ultrafast motors have only recently been studied by ultrafast spectroscopy. Our lab has studied the photochemistry and photophysics of a ``first generation'' molecular motor with UV-visible transient absorption spectroscopy. We hope to use optical pulse shaping to enhance the efficiency and turnover rate of these molecular motors.

  9. Transient Exciplex Formation Electron Transfer Mechanism

    OpenAIRE

    Michael G. Kuzmin; Irina V. Soboleva; Elena V. Dolotova

    2011-01-01

    Transient exciplex formation mechanism of excited-state electron transfer reactions is analyzed in terms of experimental data on thermodynamics and kinetics of exciplex formation and decay. Experimental profiles of free energy, enthalpy, and entropy for transient exciplex formation and decay are considered for several electron transfer reactions in various solvents. Strong electronic coupling in contact pairs of reactants causes substantial decrease of activation energy relative to that for c...

  10. High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

    Science.gov (United States)

    Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

    2016-04-18

    One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Nonlinear excitations in biomolecules

    International Nuclear Information System (INIS)

    Peyrard, M.

    1995-01-01

    The aim of the workshop entitled ''Nonlinear Excitations in Biomolecules'' is to attempt to bridge the gap between the physicists and biologists communities which is mainly due to language and cultural barriers. The progress of nonlinear science in the last few decades which have shown that the combination of nonlinearity, which characterize most biological phenomena, and cooperative effects in a system having a large number of degrees of freedom, can give rise to coherent excitations with remarkable properties. New concepts, such as solitons nd nonlinear energy localisation have become familiar to physicists and applied mathematicians. It is thus tempting to make an analogy between these coherent excitations and the exceptional stability of some biological processes, such as for instance DNA transcription, which require the coordination of many events in the ever changing environment of a cell. Physicists are now invoking nonlinear excitations to describe and explain many bio-molecular processes while biologists often doubt that the seemingly infinite variety of phenomena that they are attempting to classify can be reduced to such simple concepts. A large part of the meeting is devoted to tutorial lectures rather than to latest research results. The book provides a pedagogical introduction to the two topics forming the backbone of the meeting: the theory of nonlinear excitations and solitons, and their application in biology; and the structure and function of biomolecules, as well as energy and charge transport in biophysics. In order to emphasize the link between physics and biology, the volume is not divided along these two topics but according to biological subjects. Each chapter starts with a short introduction attempting to help the reader to find his way among the contributions and point out the connection between them. 23 lectures over the 32 presented have been selected and refers to quantum properties of macro-molecules. (J.S.)

  12. Mean excitation energies for molecular ions

    DEFF Research Database (Denmark)

    Jensen, Phillip W.K.; Sauer, Stephan P.A.; Oddershede, Jens

    2017-01-01

    The essential material constant that determines the bulk of the stopping power of high energy projectiles, the mean excitation energy, is calculated for a range of smaller molecular ions using the RPA method. It is demonstrated that the mean excitation energy of both molecules and atoms increase...

  13. Teaching lasers to control molecules

    International Nuclear Information System (INIS)

    Judson, R.S.; Rabitz, H.

    1992-01-01

    We simulate a method to teach a laser pulse sequences to excite specified molecular states. We use a learning procedure to direct the production of pulses based on ''fitness'' information provided by a laboratory measurement device. Over a series of pulses the algorithm learns an optimal sequence. The experimental apparatus, which consists of a laser, a sample of molecules and a measurement device, acts as an analog computer that solves Schroedinger's equation n/Iexactly, in real time. We simulate an apparatus that learns to excite specified rotational states in a diatomic molecule

  14. Transient pseudohypoaldosteronism

    Directory of Open Access Journals (Sweden)

    Stajić Nataša

    2011-01-01

    Full Text Available Introduction. Infants with urinary tract malformations (UTM presenting with urinary tract infection (UTI are prone to develop transient type 1 pseudohypoaldosteronism (THPA1. Objective. Report on patient series with characteristics of THPA1, UTM and/or UTI and suggestions for the diagnosis and therapy. Methods. Patients underwent blood and urine electrolyte and acid-base analysis, serum aldosterosterone levels and plasma rennin activity measuring; urinalysis, urinoculture and renal ultrasound were done and medical and/or surgical therapy was instituted. Results. Hyponatraemia (120.9±5.8 mmol/L, hyperkalaemia (6.9±0.9 mmol/L, metabolic acidosis (plasma bicarbonate, 11±1.4 mmol/L, and a rise in serum creatinine levels (145±101 μmol/L were associated with inappropriately high urinary sodium (51.3±17.5 mmol/L and low potassium (14.1±5.9 mmol/L excretion. Elevated plasma aldosterone concentrations (170.4±100.5 ng/dL and the very high levels of the plasma aldosterone to potassium ratio (25.2±15.6 together with diminished urinary K/Na values (0.31±0.19 indicated tubular resistance to aldosterone. After institution of appropriate medical and/or surgical therapy, serum electrolytes, creatinine, and acid-base balance were normalized. Imaging studies showed ureteropyelic or ureterovesical junction obstruction in 3 and 2 patients, respectively, posterior urethral valves in 3, and normal UT in 1 patient. According to our knowledge, this is the first report on THPA1 in the Serbian literature. Conclusion. Male infants with hyponatraemia, hyperkalaemia and metabolic acidosis have to have their urine examined and the renal ultrasound has to be done in order to avoid both, the underdiagnosis of THPA1 and the inappropriate medication.

  15. Excited-state molecular photoionization dynamics

    International Nuclear Information System (INIS)

    Pratt, S.T.

    1995-01-01

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

  16. Photoionization of atoms and molecules

    International Nuclear Information System (INIS)

    Samson, J.A.R.

    1976-01-01

    A literature review on the present state of knowledge in photoionization is presented. Various experimental techniques that have been developed to study photoionization, such as fluorescence and photoelectron spectroscopy, mass spectroscopy, are examined. Various atoms and molecules were chosen to illustrate these techniques, specifically helium and xenon atoms and hydrogen molecules. Specialized photoionization such as in positive and negative ions, excited states, and free radicals is also treated. Absorption cross sections and ionization potentials are also discussed

  17. Low pressure tritiation of molecules

    International Nuclear Information System (INIS)

    Moran, T.F.; Powers, J.C.; Lively, M.O.

    1980-01-01

    A method is described of tritiating sensitive biological molecules by depositing molecules of the substance to be tritiated on a supporting substrate in an evacuated vacuum chamber near, but not in the path of, an electron beam which traverses the chamber, admitting tritium gas into the chamber, and subjecting the tritium to the electron beam. Vibrationally excited tritium gas species are generated which collide and react with the substance thus incorporating tritium atoms into the substance. (U.K.)

  18. Molecule Matters

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 14; Issue 4. Molecule Matters – van der Waals Molecules - History and Some Perspectives on Intermolecular Forces. E Arunan. Feature Article Volume 14 Issue 4 April 2009 pp 346-356 ...

  19. Singlet versus Triplet Excited State Mediated Photoinduced Dehalogenation Reactions of Itraconazole in Acetonitrile and Aqueous Solutions.

    Science.gov (United States)

    Zhu, Ruixue; Li, Ming-de; Du, Lili; Phillips, David Lee

    2017-04-06

    Photoinduced dehalogenation of the antifungal drug itraconazole (ITR) in acetonitrile (ACN) and ACN/water mixed solutions was investigated using femtosecond and nanosecond time-resolved transient absorption (fs-TA and ns-TA, respectively) and nanosecond time-resolved resonance Raman spectroscopy (ns-TR 3 ) experiments. An excited resonance energy transfer is found to take place from the 4-phenyl-4,5-dihydro-3H-1,2,4-triazol-3-one part of the molecule to the 1,3-dichlorobenzene part of the molecule when ITR is excited by ultraviolet light. This photoexcitation is followed by a fast carbon-halogen bond cleavage that leads to the generation of radical intermediates via either triplet and/or singlet excited states. It is found that the singlet excited state-mediated carbon-halogen cleavage is the predominant dehalogenation process in ACN solvent, whereas a triplet state-mediated carbon-halogen cleavage prefers to occur in the ACN/water mixed solutions. The singlet-to-triplet energy gap is decreased in the ACN/water mixed solvents and this helps facilitate an intersystem crossing process, and thus, the carbon-halogen bond cleavage happens mostly through an excited triplet state in the aqueous solutions examined. The ns-TA and ns-TR 3 results also provide some evidence that radical intermediates are generated through a homolytic carbon-halogen bond cleavage via predominantly the singlet excited state pathway in ACN but via mainly the triplet state pathway in the aqueous solutions. In strong acidic solutions, protonation at the oxygen and/or nitrogen atoms of the 1,2,4-triazole-3-one group appears to hinder the dehalogenation reactions. This may offer the possibility that the phototoxicity of ITR due to the generation of aryl or halogen radicals can be reduced by protonation of certain moieties in suitably designed ITR halogen-containing derivatives.

  20. Energy storage and redistribution in molecules

    International Nuclear Information System (INIS)

    Hinze, J.

    1983-01-01

    This book presents information on the following topics: chemistry and spectroscopy of molecules at high levels of excitation; energy and phase randomization in large molecules as probed by laser spectroscopy; intramolecular processes in isolated polyatomic molecules; pulse-probe measurements in low-temperature, low-pressure SF 6 ; the photodissociation dynamics of H 2 S and CF 3 NO; photofragment spectroscopy of the NO 2 dissociation; preparation, laser spectroscopy and predissociation of alkali dimers in supersonic nozzle beams; excited states of small molecules - collisional quenching and photodissociation; quantum-state-resolved scattering of lithium hydride; and molecular negative ions

  1. A strong steric hindrance effect on ground state, excited state, and charge separated state properties of a CuI-diimine complex captured by X-ray transient absorption spectroscopy

    DEFF Research Database (Denmark)

    Huang, J.; Mara, M.W.; Stickrath, A.B.

    2014-01-01

    of phenanthroline. The structural dynamics of the photoinduced charge transfer process in the [CuI(dppS)2]+/TiO2 hybrid is also investigated, which suggests a more restricted environment for the complex upon binding to TiO2 NPs. Moreover, the Cu-N bond length of the oxidized state of [CuI(dppS)2]+ after electron...... dynamics and structures as well as those of the charge separated state resulting from the interfacial electron injection from the MLCT state to TiO2 nanoparticles (NPs). The OTA results show the absence of the sub-picosecond component previously assigned as the time constant for flattening, while the two...... injection to TiO2 NPs shortens by 0.05 Å compared to that in the ground state. The interpretation of these observed structural changes associated with excited and charge separated states will be discussed. These results not only set an example for applying XTA in capturing the intermediate structure...

  2. Exotic helium molecules

    International Nuclear Information System (INIS)

    Portier, M.

    2007-12-01

    We study the photo-association of an ultracold cloud of magnetically trapped helium atoms: pairs of colliding atoms interact with one or two laser fields to produce a purely long range 4 He 2 (2 3 S 1 -2 3 P 0 ) molecule, or a 4 He 2 (2 3 S 1 -2 3 S 1 ) long range molecule. Light shifts in one photon photo-association spectra are measured and studied as a function of the laser polarization and intensity, and the vibrational state of the excited molecule. They result from the light-induced coupling between the excited molecule, and bound and scattering states of the interaction between two metastable atoms. Their analysis leads to the determination of the scattering length a = (7.2 ± 0.6) ruling collisions between spin polarized atoms. The two photon photo-association spectra show evidence of the production of polarized, long-range 4 He 2 (2 3 S 1 -2 3 S 1 ) molecules. They are said to be exotic as they are made of two metastable atoms, each one carrying a enough energy to ionize the other. The corresponding lineshapes are calculated and decomposed in sums and products of Breit-Wigner and Fano profiles associated to one and two photon processes. The experimental spectra are fit, and an intrinsic lifetime τ = (1.4 ± 0.3) μs is deduced. It is checked whether this lifetime could be limited by spin-dipole induced Penning autoionization. This interpretation requires that there is a quasi-bound state close to the dissociation threshold in the singlet interaction potential between metastable helium atoms for the theory to match the experiment. (author)

  3. Laser spectroscopy and dynamics of transient species

    Energy Technology Data Exchange (ETDEWEB)

    Clouthier, D.J. [Univ. of Kentucky, Lexington (United States)

    1993-12-01

    The goal of this program is to study the vibrational and electronic spectra and excited state dynamics of a number of transient sulfur and oxygen species. A variety of supersonic jet techniques, as well as high resolution FT-IR and intracavity dye laser spectroscopy, have been applied to these studies.

  4. Magnetic field modification of ultracold molecule-molecule collisions

    International Nuclear Information System (INIS)

    Tscherbul, T V; Suleimanov, Yu V; Aquilanti, V; Krems, R V

    2009-01-01

    We present an accurate quantum mechanical study of molecule-molecule collisions in the presence of a magnetic field. The work focuses on the analysis of elastic scattering and spin relaxation in collisions of O 2 ( 3 Σ g - ) molecules at cold (∼0.1 K) and ultracold (∼10 -6 K) temperatures. Our calculations show that magnetic spin relaxation in molecule-molecule collisions is extremely efficient except at magnetic fields below 1 mT. The rate constant for spin relaxation at T=0.1 K and a magnetic field of 0.1 T is found to be as large as 6.1x10 -11 cm -3 s -1 . The magnetic field dependence of elastic and inelastic scattering cross sections at ultracold temperatures is dominated by a manifold of Feshbach resonances with the density of ∼100 resonances per Tesla for collisions of molecules in the absolute ground state. This suggests that the scattering length of ultracold molecules in the absolute ground state can be effectively tuned in a very wide range of magnetic fields. Our calculations demonstrate that the number and properties of the magnetic Feshbach resonances are dramatically different for molecules in the absolute ground and excited spin states. The density of Feshbach resonances for molecule-molecule scattering in the low-field-seeking Zeeman state is reduced by a factor of 10.

  5. Transient Exciplex Formation Electron Transfer Mechanism

    Directory of Open Access Journals (Sweden)

    Michael G. Kuzmin

    2011-01-01

    Full Text Available Transient exciplex formation mechanism of excited-state electron transfer reactions is analyzed in terms of experimental data on thermodynamics and kinetics of exciplex formation and decay. Experimental profiles of free energy, enthalpy, and entropy for transient exciplex formation and decay are considered for several electron transfer reactions in various solvents. Strong electronic coupling in contact pairs of reactants causes substantial decrease of activation energy relative to that for conventional long-range ET mechanism, especially for endergonic reactions, and provides the possibility for medium reorganization concatenated to gradual charge shift in contrast to conventional preliminary medium and reactants reorganization. Experimental criteria for transient exciplex formation (concatenated mechanism of excited-state electron transfer are considered. Available experimental data show that this mechanism dominates for endergonic ET reactions and provides a natural explanation for a lot of known paradoxes of ET reactions.

  6. Atkins' molecules

    CERN Document Server

    Atkins, Peters

    2003-01-01

    Originally published in 2003, this is the second edition of a title that was called 'the most beautiful chemistry book ever written'. In it, we see the molecules responsible for the experiences of our everyday life - including fabrics, drugs, plastics, explosives, detergents, fragrances, tastes, and sex. With engaging prose Peter Atkins gives a non-technical account of an incredible range of aspects of the world around us, showing unexpected connections, and giving an insight into how this amazing world can be understood in terms of the atoms and molecules from which it is built. The second edition includes dozens of extra molecules, graphical presentation, and an even more accessible and enthralling account of the molecules themselves.

  7. Interstellar Molecules

    Science.gov (United States)

    Solomon, Philip M.

    1973-01-01

    Radioastronomy reveals that clouds between the stars, once believed to consist of simple atoms, contain molecules as complex as seven atoms and may be the most massive objects in our Galaxy. (Author/DF)

  8. Excited-state dynamics of the medicinal pigment curcumin in a hydrogel.

    Science.gov (United States)

    Harada, Takaaki; Lincoln, Stephen F; Kee, Tak W

    2016-10-12

    Curcumin is a yellow polyphenol with multiple medicinal effects. These effects, however, are limited due to its poor aqueous stability and solubility. A hydrogel of 3% octadecyl randomly substituted polyacrylate (PAAC18) has been shown to provide high aqueous stability for curcumin under physiological conditions, offering a route for photodynamic therapy. In this study, the excited-state photophysics of curcumin in the PAAC18 hydrogel is investigated using a combination of femtosecond transient absorption and fluorescence upconversion spectroscopy. The transient absorption results reveal a multiexponential decay in the excited-state kinetics with fast (1 ps & 15 ps) and slow (110 ps & ≈5 ns) components. The fast decay component exhibits a deuterium isotope effect with D 2 O in the hydrogel, indicating that the 15 ps decay component is attributable to excited-state intramolecular hydrogen atom transfer of curcumin in the PAAC18 hydrogel. In addition, solvent reorganisation of excited-state curcumin is investigated using multiwavelength femtosecond fluorescence upconversion spectroscopy. The results show that the dominant solvation response (τ = 0.08 ps) is a fast inertial motion owing to the presence of bulk-like water in the vicinity of the hydrophobic octadecyl substituents of the PAAC18 hydrogel. The results also show an additional response with longer time constants of 1 and 6 ps, which is attributable to translational diffusion of confined water molecules in the three-dimensional, cross-linking network of the octadecyl substituents of PAAC18. Overall, we show that excited-state intramolecular hydrogen atom transfer and solvent reorganisation are major photophysical events for curcumin in the PAAC18 hydrogel.

  9. Vibrational excitation in a hydrogen volume source

    International Nuclear Information System (INIS)

    Eenshuistra, P.J.

    1989-01-01

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

  10. Current interruption transients calculation

    CERN Document Server

    Peelo, David F

    2014-01-01

    Provides an original, detailed and practical description of current interruption transients, origins, and the circuits involved, and how they can be calculated Current Interruption Transients Calculationis a comprehensive resource for the understanding, calculation and analysis of the transient recovery voltages (TRVs) and related re-ignition or re-striking transients associated with fault current interruption and the switching of inductive and capacitive load currents in circuits. This book provides an original, detailed and practical description of current interruption transients, origins,

  11. CINE: Comet INfrared Excitation

    Science.gov (United States)

    de Val-Borro, Miguel; Cordiner, Martin A.; Milam, Stefanie N.; Charnley, Steven B.

    2017-08-01

    CINE calculates infrared pumping efficiencies that can be applied to the most common molecules found in cometary comae such as water, hydrogen cyanide or methanol. One of the main mechanisms for molecular excitation in comets is the fluorescence by the solar radiation followed by radiative decay to the ground vibrational state. This command-line tool calculates the effective pumping rates for rotational levels in the ground vibrational state scaled by the heliocentric distance of the comet. Fluorescence coefficients are useful for modeling rotational emission lines observed in cometary spectra at sub-millimeter wavelengths. Combined with computational methods to solve the radiative transfer equations based, e.g., on the Monte Carlo algorithm, this model can retrieve production rates and rotational temperatures from the observed emission spectrum.

  12. Superexcited states of molecules

    International Nuclear Information System (INIS)

    Nakamura, Hiroki; Takagi, Hidekazu.

    1990-01-01

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

  13. Trajectory study of supercollision relaxation in highly vibrationally excited pyrazine and CO2.

    Science.gov (United States)

    Li, Ziman; Sansom, Rebecca; Bonella, Sara; Coker, David F; Mullin, Amy S

    2005-09-01

    Classical trajectory calculations were performed to simulate state-resolved energy transfer experiments of highly vibrationally excited pyrazine (E(vib) = 37,900 cm(-1)) and CO(2), which were conducted using a high-resolution transient infrared absorption spectrometer. The goal here is to use classical trajectories to simulate the supercollision energy transfer pathway wherein large amounts of energy are transferred in single collisions in order to compare with experimental results. In the trajectory calculations, Newton's laws of motion are used for the molecular motion, isolated molecules are treated as collections of harmonic oscillators, and intermolecular potentials are formed by pairwise Lennard-Jones potentials. The calculations qualitatively reproduce the observed energy partitioning in the scattered CO(2) molecules and show that the relative partitioning between bath rotation and translation is dependent on the moment of inertia of the bath molecule. The simulations show that the low-frequency modes of the vibrationally excited pyrazine contribute most to the strong collisions. The majority of collisions lead to small DeltaE values and primarily involve single encounters between the energy donor and acceptor. The large DeltaE exchanges result from both single impulsive encounters and chattering collisions that involve multiple encounters.

  14. Laser amplification in excited dielectrics

    DEFF Research Database (Denmark)

    Winkler, Thomas; Haahr-Lillevang, Lasse; Sarpe, Cristian

    2018-01-01

    Wide-bandgap dielectrics such as glasses or water are transparent at visible and infrared wavelengths. This changes when they are exposed to ultrashort and highly intense laser pulses. Different interaction mechanisms lead to the appearance of various transient nonlinear optical phenomena. Using...... these, the optical properties of dielectrics can be controlled from the transparent to the metal-like state. Here we expand this range by a yet unexplored mechanism in excited dielectrics: amplification. In a two-colour pump-probe experiment, we show that a 400nm femtosecond laser pulse is coherently...

  15. Adhesion molecules

    CERN Document Server

    Preedy, Victor R

    2016-01-01

    This book covers the structure and classification of adhesion molecules in relation to signaling pathways and gene expression. It discusses immunohistochemical localization, neutrophil migration, and junctional, functional, and inflammatory adhesion molecules in pathologies such as leukocyte decompression sickness and ischemia reperfusion injury. Highlighting the medical applications of current research, chapters cover diabetes, obesity, and metabolic syndrome; hypoxia; kidney disease; smoking, atrial fibrillation, and heart disease, the brain and dementia; and tumor proliferation. Finally, it looks at molecular imaging and bioinformatics, high-throughput technologies, and chemotherapy.

  16. Laser amplification in excited dielectrics

    Science.gov (United States)

    Winkler, Thomas; Haahr-Lillevang, Lasse; Sarpe, Cristian; Zielinski, Bastian; Götte, Nadine; Senftleben, Arne; Balling, Peter; Baumert, Thomas

    2018-01-01

    Wide-bandgap dielectrics such as glasses or water are transparent at visible and infrared wavelengths. This changes when they are exposed to ultrashort and highly intense laser pulses. Different interaction mechanisms lead to the appearance of various transient nonlinear optical phenomena. Using these, the optical properties of dielectrics can be controlled from the transparent to the metal-like state. Here we expand this range by a yet unexplored mechanism in excited dielectrics: amplification. In a two-colour pump-probe experiment, we show that a 400 nm femtosecond laser pulse is coherently amplified inside an excited sapphire sample on a scale of a few micrometres. Simulations strongly support the proposed two-photon stimulated emission process, which is temporally and spatially controllable. Consequently, we expect applications in all fields that demand strongly localized amplification.

  17. Multiple photon infrared processes in polyatomic molecules

    International Nuclear Information System (INIS)

    Harrison, R.G.; Butcher, S.R.

    1980-01-01

    This paper reviews current understanding of the process of multiple photon excitation and dissociation of polyatomic molecules, whereby in the presence of an intense infrared laser field a molecule may absorb upwards of 30 photons. The application of this process to new photochemistry and in particular laser isotope separation is also discussed. (author)

  18. Molecule Matters

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 16; Issue 12. Molecule Matters - Dinitrogen. A G Samuelson J Jabadurai. Volume 16 Issue 12 ... Author Affiliations. A G Samuelson1 J Jabadurai1. Department of Inroganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India.

  19. Molecule Matters

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 11; Issue 9. Molecule Matters - A Chromium Compound with a Quintuple Bond. K C Kumara Swamy. Feature Article Volume 11 Issue 9 September 2006 pp 72-75. Fulltext. Click here to view fulltext PDF. Permanent link:

  20. Adsorption properties of the molecule resveratrol on CNT(8,0-10) nanotube: Geometry optimization, molecular structure, spectroscopic (NMR, UV/Vis, excited state), FMO, MEP and HOMO-LUMO investigations

    Science.gov (United States)

    Sheikhi, Masoome; Shahab, Siyamak; Khaleghian, Mehrnoosh; Hajikolaee, Fatemeh Haji; Balakhanava, Iryna; Alnajjar, Radwan

    2018-05-01

    In the present work the adsorption properties of the molecule Resveratrol (RSV) (trans-3,5,4‧-Trihydroxystilbene) on CNT(8,0-10) nanotube was investigated by Density Functional Theory (DFT) in the gaseous phase for the first time. The non-bonded interaction effects of compounds RSV and CNT(8,0-10) nanotube on the electronic properties, chemical shift tensors and natural charge were determined and discussed. The electronic spectra of the RSV and the complex CNT(8,0-10)/RSV in the gaseous phase were calculated by Time Dependent Density Functional Theory (TD-DFT) for investigation of the maximum wavelength value of the RSV before and after the non-bonded interaction with the CNT(8,0-10) nanotube and molecular orbitals involved in the formation of absorption spectrum of the complex RSV at maximum wavelength.

  1. Fluorescence and picosecond induced absorption from the lowest singlet excited states of quercetin in solutions and polymer films

    Science.gov (United States)

    Bondarev, S. L.; Tikhomirov, S. A.; Buganov, O. V.; Knyukshto, V. N.; Raichenok, T. F.

    2017-03-01

    The spectroscopic and photophysical properties of the biologically important plant antioxidant quercetin in organic solvents, polymer films of polyvinyl alcohol, and a buffer solution at pH 7.0 are studied by stationary luminescence and femtosecond laser spectroscopy at room temperature and 77 K. The large magnitude of the dipole moment of the quercetin molecule in the excited Franck-Condon state μ e FC = 52.8 C m indicates the dipolar nature of quercetin in this excited state. The transient induced absorption spectra S 1→ S n in all solvents are characterized by a short-wave band at λ abs max = 460 nm with exponential decay times in the range of 10.0-20.0 ps. In the entire spectral range at times of >100 ps, no residual induced absorption was observed that could be attributed to the triplet-triplet transitions T 1 → T k in quercetin. In polar solvents, two-band fluorescence was also recorded at room temperature, which is due to the luminescence of the initial enol form of quercetin ( 415 nm) and its keto form with a transferred proton (550 nm). The short-wave band is absent in nonpolar 2-methyltetrahydrofuran (2-MTHF). The spectra of fluorescence and fluorescence excitation exhibit a low dependence on the wavelength of excitation and detection, which may be related to the solvation and conformational changes in the quercetin molecule. Decreasing the temperature of a glassy-like freezing quercetin solution in ethanol and 2-MTHF to 77 K leads to a strong increase in the intensity (by a factor of 100) of both bands. The energy circuits for the proton transfer process are proposed depending on the polarity of the medium. The main channel for the exchange of electronic excitation energy in the quercetin molecule at room temperature is the internal conversion S 1 ⇝ S 0, induced by the state with a proton transfer.

  2. Transient drainage summary report

    International Nuclear Information System (INIS)

    1996-09-01

    This report summarizes the history of transient drainage issues on the Uranium Mill Tailings Remedial Action (UMTRA) Project. It defines and describes the UMTRA Project disposal cell transient drainage process and chronicles UMTRA Project treatment of the transient drainage phenomenon. Section 4.0 includes a conceptual cross section of each UMTRA Project disposal site and summarizes design and construction information, the ground water protection strategy, and the potential for transient drainage

  3. PSH Transient Simulation Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Muljadi, Eduard [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2017-12-21

    PSH Transient Simulation Modeling presentation from the WPTO FY14 - FY16 Peer Review. Transient effects are an important consideration when designing a PSH system, yet numerical techniques for hydraulic transient analysis still need improvements for adjustable-speed (AS) reversible pump-turbine applications.

  4. Dynamics of anion-molecule reactions at low energy

    International Nuclear Information System (INIS)

    Mikosch, J.

    2007-11-01

    Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S N 2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S N 2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S N 2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S N 2 mechanism involving CH 3 -rotation. (orig.)

  5. Dynamics of anion-molecule reactions at low energy

    Energy Technology Data Exchange (ETDEWEB)

    Mikosch, J.

    2007-11-15

    Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S{sub N}2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S{sub N}2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S{sub N}2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S{sub N}2 mechanism involving CH{sub 3}-rotation. (orig.)

  6. Interstellar molecules and masers

    International Nuclear Information System (INIS)

    Nguyen-Q-Rieu; Guibert, J.

    1978-01-01

    The study of dense and dark clouds, in which hydrogen is mostly in molecular form, became possible since the discovery of interstellar molecules, emitting in the centimeter and millimeter wavelengths. The molecular lines are generally not in local thermal equilibrium (LTE). Their intensity can often be explained by invoking a population inversion mechanism. Maser emission lines due to OH, H 2 O and SiO molecules are among the most intense molecular lines. The H 2 CO molecule, detected in absorption in front of the cold cosmic background radiation of 2.7 K, illustrates the inverse phenomenon, the antimaser absorption. For a radio transition of frequency v, the inversion rate Δn (relative population difference between the upper and lower level) as well as the maser gain can be determined from the radio observations. In the case of the OH lines in the 2 PIsub(3/2), J=3/2 state, the inversion rates approximately 1 to 2% derived from the observations, are comparable with those obtained in the laboratory. The determination of the excitation mechanisms of the masers, through the statistical equilibrium and radiative transfer equations, implies the knowledge of collisional and radiative transition probabilities. A pumping model, which can satisfactorily explain the radio observations of some interstellar OH clouds, will be discussed [fr

  7. Emittance growth from transient coherent synchrotron radiation

    International Nuclear Information System (INIS)

    Bohn, C.L.; Li, R.; Bisognano, J.J.

    1996-01-01

    If the energies of individual particles in a bunch change as the bunch traverses a bending system, even if it is achromatic, betatron oscillations can be excited. Consequently, the transverse emittance of the bunch will grow as it moves downstream. Short bunches may be particularly susceptible to emission of coherent synchrotron radiation which can act back on the particles to change their energies and trajectories. Because a bend spans a well-defined length and angle, the bunch-excited wakefield and its effect back on the bunch are inherently transient. We outline a recently developed theory of this effect and apply it to example bending systems

  8. Femtosecond time-resolved photodissociation dynamics of methyl halide molecules on ultrathin gold films

    Directory of Open Access Journals (Sweden)

    Mihai E. Vaida

    2011-09-01

    Full Text Available The photodissociation of small organic molecules, namely methyl iodide, methyl bromide, and methyl chloride, adsorbed on a metal surface was investigated in real time by means of femtosecond-laser pump–probe mass spectrometry. A weakly interacting gold surface was employed as substrate because the intact adsorption of the methyl halide molecules was desired prior to photoexcitation. The gold surface was prepared as an ultrathin film on Mo(100. The molecular adsorption behavior was characterized by coverage dependent temperature programmed desorption spectroscopy. Submonolayer preparations were irradiated with UV light of 266 nm wavelength and the subsequently emerging methyl fragments were probed by photoionization and mass spectrometric detection. A strong dependence of the excitation mechanism and the light-induced dynamics on the type of molecule was observed. Possible photoexcitation mechanisms included direct photoexcitation to the dissociative A-band of the methyl halide molecules as well as the attachment of surface-emitted electrons with transient negative ion formation and subsequent molecular fragmentation. Both reaction pathways were energetically possible in the case of methyl iodide, yet, no methyl fragments were observed. As a likely explanation, the rapid quenching of the excited states prior to fragmentation is proposed. This quenching mechanism could be prevented by modification of the gold surface through pre-adsorption of iodine atoms. In contrast, the A-band of methyl bromide was not energetically directly accessible through 266 nm excitation. Nevertheless, the one-photon-induced dissociation was observed in the case of methyl bromide. This was interpreted as being due to a considerable energetic down-shift of the electronic A-band states of methyl bromide by about 1.5 eV through interaction with the gold substrate. Finally, for methyl chloride no photofragmentation could be detected at all.

  9. Excitation energy transfer in molecular complexes: transport processes, optical properties and effects of nearby placed metal nano-particles

    Science.gov (United States)

    May, Volkhard; Megow, Jörg; Zelinskyi, Iaroslav

    2012-04-01

    Excitation energy transfer (EET) in molecular systems is studied theoretically. Chromophore complexes are considered which are formed by a butanediamine dendrimer with four pheophorbide-a molecules. To achieve a description with an atomic resolution and to account for the effect of an ethanol solvent a mixed quantum classical methodology is utilized. Details of the EET and spectra of transient anisotropy showing signatures of EET are presented. A particular control of intermolecular EET is achieved by surface plasmons of nearby placed metal nanoparticles (MNP). To attain a quantum description of the molecule-MNP system a microscopic theory is introduced. As a particular application surface plasmon affected absorption spectra of molecular complexes placed in the proximity of a spherical MNP are discussed.

  10. Understanding Epileptiform After-Discharges as Rhythmic Oscillatory Transients.

    Science.gov (United States)

    Baier, Gerold; Taylor, Peter N; Wang, Yujiang

    2017-01-01

    Electro-cortical activity in patients with epilepsy may show abnormal rhythmic transients in response to stimulation. Even when using the same stimulation parameters in the same patient, wide variability in the duration of transient response has been reported. These transients have long been considered important for the mapping of the excitability levels in the epileptic brain but their dynamic mechanism is still not well understood. To investigate the occurrence of abnormal transients dynamically, we use a thalamo-cortical neural population model of epileptic spike-wave activity and study the interaction between slow and fast subsystems. In a reduced version of the thalamo-cortical model, slow wave oscillations arise from a fold of cycles (FoC) bifurcation. This marks the onset of a region of bistability between a high amplitude oscillatory rhythm and the background state. In vicinity of the bistability in parameter space, the model has excitable dynamics, showing prolonged rhythmic transients in response to suprathreshold pulse stimulation. We analyse the state space geometry of the bistable and excitable states, and find that the rhythmic transient arises when the impending FoC bifurcation deforms the state space and creates an area of locally reduced attraction to the fixed point. This area essentially allows trajectories to dwell there before escaping to the stable steady state, thus creating rhythmic transients. In the full thalamo-cortical model, we find a similar FoC bifurcation structure. Based on the analysis, we propose an explanation of why stimulation induced epileptiform activity may vary between trials, and predict how the variability could be related to ongoing oscillatory background activity. We compare our dynamic mechanism with other mechanisms (such as a slow parameter change) to generate excitable transients, and we discuss the proposed excitability mechanism in the context of stimulation responses in the epileptic cortex.

  11. Ultrafast transient absorption revisited: Phase-flips, spectral fingers, and other dynamical features

    Energy Technology Data Exchange (ETDEWEB)

    Cina, Jeffrey A., E-mail: cina@uoregon.edu; Kovac, Philip A. [Department of Chemistry and Biochemistry, and Oregon Center for Optical, Molecular, and Quantum Science, University of Oregon, Eugene, Oregon 97403 (United States); Jumper, Chanelle C. [Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6 (Canada); Dean, Jacob C.; Scholes, Gregory D., E-mail: gscholes@princeton.edu [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States)

    2016-05-07

    We rebuild the theory of ultrafast transient-absorption/transmission spectroscopy starting from the optical response of an individual molecule to incident femtosecond pump and probe pulses. The resulting description makes use of pulse propagators and free molecular evolution operators to arrive at compact expressions for the several contributions to a transient-absorption signal. In this alternative description, which is physically equivalent to the conventional response-function formalism, these signal contributions are conveniently expressed as quantum mechanical overlaps between nuclear wave packets that have undergone different sequences of pulse-driven optical transitions and time-evolution on different electronic potential-energy surfaces. Using this setup in application to a simple, multimode model of the light-harvesting chromophores of PC577, we develop wave-packet pictures of certain generic features of ultrafast transient-absorption signals related to the probed-frequency dependence of vibrational quantum beats. These include a Stokes-shifting node at the time-evolving peak emission frequency, antiphasing between vibrational oscillations on opposite sides (i.e., to the red or blue) of this node, and spectral fingering due to vibrational overtones and combinations. Our calculations make a vibrationally abrupt approximation for the incident pump and probe pulses, but properly account for temporal pulse overlap and signal turn-on, rather than neglecting pulse overlap or assuming delta-function excitations, as are sometimes done.

  12. Solvent-dependent excited-state hydrogen transfer and intersystem crossing in 2-(2′-hydroxyphenyl)-benzothiazole

    KAUST Repository

    Aly, Shawkat Mohammede

    2015-02-12

    The excited-state intramolecular hydrogen transfer (ESIHT) of 2-(2′-hydroxyphenyl) benzothiazole (HBT) has been investigated in a series of nonpolar, polar aprotic, and polar protic solvents. A variety of state-of-the-art experimental methods were employed, including femto- and nanosecond transient absorption and fluorescence upconversion spectroscopy with broadband capabilities. We show that the dynamics and mechanism of ESIHT of the singlet excited HBT are strongly solvent-dependent. In nonpolar solvents, the data demonstrate that HBT molecules adopt a closed form stabilized by O-H⋯N chelated hydrogen bonds with no twisting angle, and the photoinduced H transfer occurs within 120 fs, leading to the formation of a keto tautomer. In polar solvents, owing to dipole-dipole cross talk and hydrogen bonding interactions, the H transfer process is followed by ultrafast nonradiative deactivation channels, including ultrafast internal conversion (IC) and intersystem crossing (ISC). This is likely to be driven by the twisting motion around the C-C bond between the hydroxyphenyl and thiazole moieties, facilitating the IC back to the enol ground state or to the keto triplet state. In addition, our femtosecond time-resolved fluorescence experiments indicate, for the first time, that the lifetime of the enol form in ACN is approximately 280 fs. This observation indicates that the solvent plays a crucial role in breaking the H bond and deactivating the excited state of the HBT. Interestingly, the broadband transient absorption and fluorescence up-conversion data clearly demonstrate that the intermolecular proton transfer from the excited HBT to the DMSO solvent is about 190 fs, forming the HBT anion excited state.

  13. Solvent-dependent excited-state hydrogen transfer and intersystem crossing in 2-(2′-hydroxyphenyl)-benzothiazole

    KAUST Repository

    Aly, Shawkat Mohammede; Usman, Anwar; Alzayer, Maytham; Hamdi, Ghada A.; Alarousu, Erkki; Mohammed, Omar F.

    2015-01-01

    The excited-state intramolecular hydrogen transfer (ESIHT) of 2-(2′-hydroxyphenyl) benzothiazole (HBT) has been investigated in a series of nonpolar, polar aprotic, and polar protic solvents. A variety of state-of-the-art experimental methods were employed, including femto- and nanosecond transient absorption and fluorescence upconversion spectroscopy with broadband capabilities. We show that the dynamics and mechanism of ESIHT of the singlet excited HBT are strongly solvent-dependent. In nonpolar solvents, the data demonstrate that HBT molecules adopt a closed form stabilized by O-H⋯N chelated hydrogen bonds with no twisting angle, and the photoinduced H transfer occurs within 120 fs, leading to the formation of a keto tautomer. In polar solvents, owing to dipole-dipole cross talk and hydrogen bonding interactions, the H transfer process is followed by ultrafast nonradiative deactivation channels, including ultrafast internal conversion (IC) and intersystem crossing (ISC). This is likely to be driven by the twisting motion around the C-C bond between the hydroxyphenyl and thiazole moieties, facilitating the IC back to the enol ground state or to the keto triplet state. In addition, our femtosecond time-resolved fluorescence experiments indicate, for the first time, that the lifetime of the enol form in ACN is approximately 280 fs. This observation indicates that the solvent plays a crucial role in breaking the H bond and deactivating the excited state of the HBT. Interestingly, the broadband transient absorption and fluorescence up-conversion data clearly demonstrate that the intermolecular proton transfer from the excited HBT to the DMSO solvent is about 190 fs, forming the HBT anion excited state.

  14. Transient negative ions in benzene. Some N-heterocyclic and mono-substituted derivatives

    International Nuclear Information System (INIS)

    Nenner, Irene

    1975-01-01

    Electron transmission spectroscopy is used to study transient negative ions or shape resonances in various benzene derivatives. Because of the long lifetime of these ions (τ > 10 -14 S) the vibrational structure of their first two electronic states is observed superposed on the total electron cross section curves in the energy range 0-6 eV and the corresponding adiabatic electron affinities are determined. The comparison of the first electron affinity with the first ionization potential and the energy on the first excited state of each of the derivatives is used to characterize the 'donor' substituents on the benzene ring. As a complementary study, these derivatives are studied in the liquid phase using polarography (cyclic voltametry). The linear correlation established between polarographic potentials measured in dimethyl formamide and the electron affinities was used to deduce electron affinities for several molecules which are difficult to measure in the gas phase. (author) [fr

  15. Biexcitons in π-conjugated oligomers: Intensity-dependent femtosecond transient-absorption study

    Science.gov (United States)

    Klimov, V. I.; McBranch, D. W.; Barashkov, N.; Ferraris, J.

    1998-09-01

    We report femtosecond transient-absorption (TA) studies of a five-ring oligomer of poly(para-phenylene vinylene) prepared in two different forms: solid-state films and dilute solutions. At high pump fluences, in both types of samples, we observe generation of two-exciton states, which are detected by the evolution of TA spectra and dynamics with increasing pump intensity. In solutions, double excitation of molecules results in the formation of stable biexcitons with enhanced oscillator strength, leading to an increased efficiency of the radiative decay and a superlinear pump dependence of the stimulated emission. In solid-state samples, the two-exciton states are unstable and decay on the subpicosecond time scale due to ultrafast charge transfer, accompanied by generation of interchain excitons.

  16. Biexcitons in {pi}-conjugated oligomers: Intensity-dependent femtosecond transient-absorption study

    Energy Technology Data Exchange (ETDEWEB)

    Klimov, V.I.; McBranch, D.W. [Chemical Science and Technology Division, CST-6, Mail Stop J585, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Barashkov, N.; Ferraris, J. [Chemistry Department, University of Texas, Dallas, Texas 75083 (United States)

    1998-09-01

    We report femtosecond transient-absorption (TA) studies of a five-ring oligomer of poly({ital para}-phenylene vinylene) prepared in two different forms: solid-state films and dilute solutions. At high pump fluences, in both types of samples, we observe generation of two-exciton states, which are detected by the evolution of TA spectra and dynamics with increasing pump intensity. In solutions, double excitation of molecules results in the formation of stable biexcitons with enhanced oscillator strength, leading to an increased efficiency of the radiative decay and a superlinear pump dependence of the stimulated emission. In solid-state samples, the two-exciton states are unstable and decay on the subpicosecond time scale due to ultrafast charge transfer, accompanied by generation of interchain excitons. {copyright} {ital 1998} {ital The American Physical Society}

  17. TRANSIENT ELECTRONICS CATEGORIZATION

    Science.gov (United States)

    2017-08-24

    AFRL-RY-WP-TR-2017-0169 TRANSIENT ELECTRONICS CATEGORIZATION Dr. Burhan Bayraktaroglu Devices for Sensing Branch Aerospace Components & Subsystems...SUBTITLE TRANSIENT ELECTRONICS CATEGORIZATION 5a. CONTRACT NUMBER In-house 5b. GRANT NUMBER N/A 5c. PROGRAM ELEMENT NUMBER N/A 6. AUTHOR(S) Dr. Burhan...88ABW-2017-3747, Clearance Date 31 July 2017. Paper contains color. 14. ABSTRACT Transient electronics is an emerging technology area that lacks proper

  18. Ionization of highly excited atoms by atomic particle impact

    International Nuclear Information System (INIS)

    Smirnov, B.M.

    1976-01-01

    The ionization of a highly excited atom by a collision with an atom or molecule is considered. The theory of these processes is presented and compared with experimental data. Cross sections and ionization potential are discussed. 23 refs

  19. Molecule Matters van der Waals Molecules

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 14; Issue 12. Molecule Matters van der Waals Molecules - Noble Gas Clusters are London Molecules! E Arunan. Feature Article Volume 14 Issue 12 December 2009 pp 1210-1222 ...

  20. Molecule scattering from insulator and metal surfaces

    International Nuclear Information System (INIS)

    Moroz, Iryna; Ambaye, Hailemariam; Manson, J R

    2004-01-01

    Calculations are carried out and compared with data for the scattering of CH 4 molecules from a LiF(001) surface and for O 2 scattering from Al(111). The theory is a mixed classical-quantum formalism that includes energy and momentum transfers between the surface and projectile for translational and rotational motions as well as internal mode excitation of the projectile molecule. The translational and rotational degrees of freedom couple most strongly to multiphonon excitations of the surface and are treated with classical dynamics. Internal vibrational excitations of the molecules are treated with a semiclassical formalism with extension to arbitrary numbers of modes and arbitrary quantum numbers. Calculations show good agreement for the dependence on incident translational energy, incident beam angle and surface temperature when compared with data for energy-resolved intensity spectra and angular distributions

  1. Field-free orientation of molecules

    DEFF Research Database (Denmark)

    Machholm, Mette; Henriksen, Niels Engholm

    2001-01-01

    The excitation of angular motion, in particular, the creation of a wave packet in the angular degrees of freedom via short-pulse, off-resonant excitation with respect to rotational transitions, was examined. The key result was that field-free time-dependent orientation for a molecule like LiH can...... be generated after the turn-off of a state-of-the-art electromagnetic half-cycle pulse.......The excitation of angular motion, in particular, the creation of a wave packet in the angular degrees of freedom via short-pulse, off-resonant excitation with respect to rotational transitions, was examined. The key result was that field-free time-dependent orientation for a molecule like LiH can...

  2. Properties of excited xenon atoms in a plasma display panel

    International Nuclear Information System (INIS)

    Uhm, Han S.; Hong, Byoung H.; Oh, Phil Y.; Choi, Eun H.

    2009-01-01

    The luminance efficiency of a plasma display panel is directly related to the vacuum ultraviolet (VUV) light that is emitted from excited xenon (Xe) atoms and molecules. It is therefore necessary to investigate the properties of excited xenon atoms. This study presents experimental data associated with the behavior of excited xenon atoms in a PDP discharge cell and compares the data with the theoretical results obtained using an analytical model. The properties of excited xenon atoms in the discharge cells of a plasma display panel are investigated by measuring the excited atom density through the use of laser absorption spectroscopy. The density of the excited xenon atoms increases from zero, reaches its peak, and decreases with time in the discharge cells. The profile of the excited xenon atoms is also studied in terms of the xenon mole fraction. The typical density of the excited xenon atoms in the metastable state is on the order of 10 13 atoms per cubic cm.

  3. Fluorescence study of some xanthine dyes under stepped laser excitation

    International Nuclear Information System (INIS)

    Chirkova, L.V.; Ketsle, G.A.; Ermagambetov, K.T.

    1996-01-01

    Paper is devoted to definition of triplet state in molecules of xanthine dyes and study of intramolecular energy circulation. Stepped two-quanta excitation of dyes has been carried out with help of experimental unit. Intensive luminescence activated by excitation of triplet molecules of dyes within triplet-triplet band with wave length of 1060 nm was registered for eosin. Given luminescence spectrally coincides with fast fluorescence. 5 refs., 6 figs

  4. Ultrafast vibronic dynamics of dye molecules studied by the induced grating method

    International Nuclear Information System (INIS)

    Liu, C.H.; Troeger, P.; Laubereau, A.

    1985-08-01

    Previous work on transient polarization spectroscopy applying the induced grating technique concentrated on the time scale > 10 -11 s. Only one earlier study on a shorter time scale showed the occurrence of the so-called coherence peak without a detailed explanation for this phenomena. We report new theoretical and experimental data on a polarization effect that occurs in the nonlinear Rayleigh scattering of delayed probing pulses from induced population gratings. The periodic population changes are generated by two synchronized pumping pulses of the same frequency. Model calculations are presented, which carefully evaluate the orientational distribution and give quantitative information on the scattering signal for various polarization conditions. The scattering mechanism for the coherence peak is explained as a two step process with one photon absorption and emission process; it depends on the vibronic relaxation of the terminating level in the excited electronic state. Experimental results are reported for the vibrational and orientational relaxation times. For example values of tausub(v)=0.2+-0.2 ps and tausub(v)=0.8+-0.3 ps are measured respectively for Rhodamine 6G in ethanol and phenoxazone 9 in dioxane. Our three-beam transient grating technique under general polarization conditions can be used for the study of a variety of dynamic processes of molecules in the excited electronic or ground state. An important advantage compared to nonlinear absorption or induced dichroism techniques is that the scattering method avoids undesirable background signals. (author)

  5. Excited charmed mesons

    International Nuclear Information System (INIS)

    Butler, J.N.; Shukla, S.

    1995-05-01

    The experimental status of excited charmed mesons is reviewed and is compared to theoretical expectations. Six states have been observed and their properties are consistent with those predicted for excited charmed states with orbital angular momentum equal to one

  6. Portable vibration exciter

    Science.gov (United States)

    Beecher, L. C.; Williams, F. T.

    1970-01-01

    Gas-driven vibration exciter produces a sinusoidal excitation function controllable in frequency and in amplitude. It allows direct vibration testing of components under normal loads, removing the possibility of component damage due to high static pressure.

  7. Multi-frequency excitation

    KAUST Repository

    Younis, Mohammad I.

    2016-01-01

    Embodiments of multi-frequency excitation are described. In various embodiments, a natural frequency of a device may be determined. In turn, a first voltage amplitude and first fixed frequency of a first source of excitation can be selected

  8. Recent progress in electron scattering from atoms and molecules

    Energy Technology Data Exchange (ETDEWEB)

    Brunger, M. J. [Centre for Antimatter-Matter Studies, CAPS, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia and Institute of Mathematical Sciences, University of Malaya, Kuala Lumpur (Malaysia); Buckman, S. J. [Institute of Mathematical Sciences, University of Malaya, Kuala Lumpur, Malaysia and Centre for Antimatter-Matter Studies, AMPL, Australian National University, Canberra, ACT 0200 (Australia); Sullivan, J. P.; Palihawadana, P. [Centre for Antimatter-Matter Studies, AMPL, Australian National University, Canberra, ACT 0200 (Australia); Jones, D. B. [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia); Chiari, L.; Pettifer, Z. [Centre for Antimatter-Matter Studies, CAPS, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia); Silva, G. B. da [Centre for Antimatter-Matter Studies, CAPS, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia and Universidade Federal de Mato Grosso, Barra do Garças, Mato Grosso (Brazil); Lopes, M. C. A. [Centre for Antimatter-Matter Studies, CAPS, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia and Departamento de Fisica, Universidade Federal de Juiz de Fora, Juiz de Fora, MG (Brazil); Duque, H. V. [Departamento de Fisica, Universidade Federal de Juiz de Fora, Juiz de Fora, MG (Brazil); Masin, Z.; Gorfinkiel, J. D. [Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom); Garcia, G. [Instituto de Fisica Fundamental, CSIC, Madrid E-28006 (Spain); Hoshino, M.; Tanaka, H. [Department of Physics, Sophia University, Tokyo, 102-8554 (Japan); Limão-Vieira, P. [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)

    2014-03-05

    We present and discuss recent results, both experimental and theoretical (where possible), for electron impact excitation of the 3s[3/2 ]{sub 1} and 3s′[1/2 ]{sub 1} electronic states in neon, elastic electron scattering from the structurally similar molecules benzene, pyrazine, and 1,4-dioxane and excitation of the electronic states of the important bio-molecule analogue α-tetrahydrofurfuryl alcohol. While comparison between theoretical and experimental results suggests that benchmarked cross sections for electron scattering from atoms is feasible in the near-term, significant further theoretical development for electron-molecule collisions, particularly in respect to discrete excitation processes, is still required.

  9. Quantum Mechanical Study of Atoms and Molecules

    Science.gov (United States)

    Sahni, R. C.

    1961-01-01

    This paper, following a brief introduction, is divided into five parts. Part I outlines the theory of the molecular orbital method for the ground, ionized and excited states of molecules. Part II gives a brief summary of the interaction integrals and their tabulation. Part III outlines an automatic program designed for the computation of various states of molecules. Part IV gives examples of the study of ground, ionized and excited states of CO, BH and N2 where the program of automatic computation and molecular integrals have been utilized. Part V enlists some special problems of Molecular Quantum Mechanics are being tackled at New York University.

  10. Spectroscopic classification of transients

    DEFF Research Database (Denmark)

    Stritzinger, M. D.; Fraser, M.; Hummelmose, N. N.

    2017-01-01

    We report the spectroscopic classification of several transients based on observations taken with the Nordic Optical Telescope (NOT) equipped with ALFOSC, over the nights 23-25 August 2017.......We report the spectroscopic classification of several transients based on observations taken with the Nordic Optical Telescope (NOT) equipped with ALFOSC, over the nights 23-25 August 2017....

  11. SPIRITS: Uncovering Unusual Infrared Transients with Spitzer

    International Nuclear Information System (INIS)

    Kasliwal, Mansi M.; Jencson, Jacob E.; Tinyanont, Samaporn; Cao, Yi; Cook, David; Bally, John; Masci, Frank; Armus, Lee; Cody, Ann Marie; Bond, Howard E.; Contreras, Carlos; Dykhoff, Devin A.; Amodeo, Samuel; Carlon, Robert L.; Cass, Alexander C.; Corgan, David T.; Faella, Joseph; Boyer, Martha; Cantiello, Matteo; Fox, Ori D.

    2017-01-01

    We present an ongoing, five-year systematic search for extragalactic infrared transients, dubbed SPIRITS—SPitzer InfraRed Intensive Transients Survey. In the first year, using Spitzer /IRAC, we searched 190 nearby galaxies with cadence baselines of one month and six months. We discovered over 1958 variables and 43 transients. Here, we describe the survey design and highlight 14 unusual infrared transients with no optical counterparts to deep limits, which we refer to as SPRITEs (eSPecially Red Intermediate-luminosity Transient Events). SPRITEs are in the infrared luminosity gap between novae and supernovae, with [4.5] absolute magnitudes between −11 and −14 (Vega-mag) and [3.6]–[4.5] colors between 0.3 mag and 1.6 mag. The photometric evolution of SPRITEs is diverse, ranging from <0.1 mag yr −1 to >7 mag yr −1 . SPRITEs occur in star-forming galaxies. We present an in-depth study of one of them, SPIRITS 14ajc in Messier 83, which shows shock-excited molecular hydrogen emission. This shock may have been triggered by the dynamic decay of a non-hierarchical system of massive stars that led to either the formation of a binary or a protostellar merger.

  12. SPIRITS: Uncovering Unusual Infrared Transients with Spitzer

    Energy Technology Data Exchange (ETDEWEB)

    Kasliwal, Mansi M.; Jencson, Jacob E.; Tinyanont, Samaporn; Cao, Yi; Cook, David [Division of Physics, Mathematics and Astronomy, California Institute of Technology, Pasadena, CA 91125 (United States); Bally, John [Center for Astrophysics and Space Astronomy, University of Colorado, 389 UCB, Boulder, CO 80309 (United States); Masci, Frank; Armus, Lee [Infrared Processing and Analysis Center, California Institute of Technology, Pasadena, CA 91125 (United States); Cody, Ann Marie [NASA Ames Research Center, Moffett Field, CA 94035 (United States); Bond, Howard E. [Dept. of Astronomy and Astrophysics, Pennsylvania State University, University Park, PA 16802 (United States); Contreras, Carlos [Las Campanas Observatory, Carnegie Observatories, Casilla 601, La Serena (Chile); Dykhoff, Devin A.; Amodeo, Samuel; Carlon, Robert L.; Cass, Alexander C.; Corgan, David T.; Faella, Joseph [Minnesota Institute for Astrophysics, School of Physics and Astronomy, 116 Church Street, S. E., University of Minnesota, Minneapolis, MN 55455 (United States); Boyer, Martha [NASA Goddard Space Flight Center, MC 665, 8800 Greenbelt Road, Greenbelt, MD 20771 (United States); Cantiello, Matteo [Center for Computational Astrophysics, Flatiron Institute, 162 Fifth Avenue, New York, NY 10010 (United States); Fox, Ori D. [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States); and others

    2017-04-20

    We present an ongoing, five-year systematic search for extragalactic infrared transients, dubbed SPIRITS—SPitzer InfraRed Intensive Transients Survey. In the first year, using Spitzer /IRAC, we searched 190 nearby galaxies with cadence baselines of one month and six months. We discovered over 1958 variables and 43 transients. Here, we describe the survey design and highlight 14 unusual infrared transients with no optical counterparts to deep limits, which we refer to as SPRITEs (eSPecially Red Intermediate-luminosity Transient Events). SPRITEs are in the infrared luminosity gap between novae and supernovae, with [4.5] absolute magnitudes between −11 and −14 (Vega-mag) and [3.6]–[4.5] colors between 0.3 mag and 1.6 mag. The photometric evolution of SPRITEs is diverse, ranging from <0.1 mag yr{sup −1} to >7 mag yr{sup −1}. SPRITEs occur in star-forming galaxies. We present an in-depth study of one of them, SPIRITS 14ajc in Messier 83, which shows shock-excited molecular hydrogen emission. This shock may have been triggered by the dynamic decay of a non-hierarchical system of massive stars that led to either the formation of a binary or a protostellar merger.

  13. Dissociative Excitation of Thymine by Electron Impact

    Science.gov (United States)

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

    2014-05-01

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

  14. Millimeterwave spectroscopy of transient molecules produced in a ...

    Indian Academy of Sciences (India)

    produced inside the cell in a low pressure DC discharge of precursor gases. ... SO radical was also produced outside the cell by reactions of discharged oxygen .... have been reported by Dodd and Little [15] who have also calculated force.

  15. Intersystem crossing in complex molecules

    International Nuclear Information System (INIS)

    Pappalardo, R.G.

    1980-01-01

    The general question of singlet-triplet intersystem crossing is addressed in the context of large organic molecules, i.e., ''complex'' molecules capable of self-relaxation in the absence of collisions. Examples of spectral properties of such molecules in the vapor phase are discussed, relying on extensive Russian literature in this area. Formal expressions for the relaxation rate in the electronic excited states are derived on the basis of the formalism of collision theory, and are applied to the specific case of intersystem crossing. The derivation of the ''energy-gap'' law for triplet-singlet conversion in aromatic hydrocarbons is briefly outlined. The steep rise of internal conversion rates as a function of excess excitation energy, and its competition with the intersystem crossing process, are reviewed for the case of naphthalene vapor. A general expression for the spin-orbit interaction Hamiltonian in molecular systems is outlined. Experimental observations on singlet-triplet conversion rates and the factors that can drastically affect such rates are discussed, with emphasis on the ''in- ternal'' and ''external'' heavy-atom effects. Basic relations of ESR spectroscopy and magnetophotoselection are reviewed. Technological implications of the singlet-triplet crossing in complex molecules are discussed in the context of chelate lasers, dye lasers and luminescent displays. Effects related to singlet-triplet crossing, and generally to excited-state energy-transfer in biological systems, are exemplified by the role of aromatic amino-acids in the phosphorescence of proteins, by some recent studies of energy-transfer in models of biomembranes, and by the clustering of triplet-energy donor-acceptor pairs in micelles

  16. One-dimensional chain of quantum molecule motors as a mathematical physics model for muscle fibers

    International Nuclear Information System (INIS)

    Si Tie-Yan

    2015-01-01

    A quantum chain model of multiple molecule motors is proposed as a mathematical physics theory for the microscopic modeling of classical force-velocity relation and tension transients in muscle fibers. The proposed model was a quantum many-particle Hamiltonian to predict the force-velocity relation for the slow release of muscle fibers, which has not yet been empirically defined and was much more complicated than the hyperbolic relationships. Using the same Hamiltonian model, a mathematical force-velocity relationship was proposed to explain the tension observed when the muscle was stimulated with an alternative electric current. The discrepancy between input electric frequency and the muscle oscillation frequency could be explained physically by the Doppler effect in this quantum chain model. Further more, quantum physics phenomena were applied to explore the tension time course of cardiac muscle and insect flight muscle. Most of the experimental tension transient curves were found to correspond to the theoretical output of quantum two- and three-level models. Mathematical modeling electric stimulus as photons exciting a quantum three-level particle reproduced most of the tension transient curves of water bug Lethocerus maximus. (special topic)

  17. Elementary excitations in nuclei

    International Nuclear Information System (INIS)

    Lemmer, R.H.

    1987-01-01

    The role of elementary quasi-particle and quasi-hole excitations is reviewed in connection with the analysis of data involving high-lying nuclear states. This article includes discussions on: (i) single quasi-hole excitations in pick-up reactions, (ii) the formation of single quasi-hole and quasi-particle excitations (in different nuclei) during transfer reactions, followed by (iii) quasi-particle quasi-hole excitations in the same nucleus that are produced by photon absorption. Finally, the question of photon absorption in the vicinity of the elementary Δ resonance is discussed, where nucleonic as well as nuclear degrees of freedom can be excited

  18. Radiation produced by electrons incident on molecules

    International Nuclear Information System (INIS)

    Moehlman, G.R.

    1977-01-01

    The work described in this thesis deals with light intensity measurements of emission spectra (1850-9000 A) produced by a continuous or pulsed beam of monoenergetic electrons (0 - 2000 eV) incident on a variety of molecular gases like H 2 , D 2 , H 2 O, HCl, NH 3 and several hydrocarbons. The emission spectra are dominated by fluorescence from excited fragments produced via dissociative excitation, besides fluorescence from excited parent molecules themselves. The experimental results thus obtained are expressed in terms of emission cross sections and lifetimes

  19. Multi-frequency excitation

    KAUST Repository

    Younis, Mohammad I.

    2016-03-10

    Embodiments of multi-frequency excitation are described. In various embodiments, a natural frequency of a device may be determined. In turn, a first voltage amplitude and first fixed frequency of a first source of excitation can be selected for the device based on the natural frequency. Additionally, a second voltage amplitude of a second source of excitation can be selected for the device, and the first and second sources of excitation can be applied to the device. After applying the first and second sources of excitation, a frequency of the second source of excitation can be swept. Using the methods of multi- frequency excitation described herein, new operating frequencies, operating frequency ranges, resonance frequencies, resonance frequency ranges, and/or resonance responses can be achieved for devices and systems.

  20. Individual Magnetic Molecules on Ultrathin Insulating Surfaces

    Science.gov (United States)

    El Hallak, Fadi; Warner, Ben; Hirjibehedin, Cyrus

    2012-02-01

    Single molecule magnets have attracted ample interest because of their exciting magnetic and quantum properties. Recent studies have demonstrated that some of these molecules can be evaporated on surfaces without losing their magnetic properties [M. Mannini et al., Nature 468, 417, (2010)]. This remarkable progress enhances the chances of real world applications for these molecules. We present STM imaging and spectroscopy data on iron phthalocyanine molecules deposited on Cu(100) and on a Cu2N ultrathin insulating surface. These molecules have been shown to display a large magnetic anisotropy on another thin insulating surface, oxidized Cu(110) [N. Tsukahara et al., Phys. Rev. Lett. 102, 167203 (2009)]. By using a combination of elastic and inelastic electron tunnelling spectroscopy, we investigate the binding of the molecules to the surface and the impact that the surface has on their electronic and magnetic properties.

  1. Exotic helium molecules; Molecules exotiques d'helium

    Energy Technology Data Exchange (ETDEWEB)

    Portier, M

    2007-12-15

    We study the photo-association of an ultracold cloud of magnetically trapped helium atoms: pairs of colliding atoms interact with one or two laser fields to produce a purely long range {sup 4}He{sub 2}(2{sup 3}S{sub 1}-2{sup 3}P{sub 0}) molecule, or a {sup 4}He{sub 2}(2{sup 3}S{sub 1}-2{sup 3}S{sub 1}) long range molecule. Light shifts in one photon photo-association spectra are measured and studied as a function of the laser polarization and intensity, and the vibrational state of the excited molecule. They result from the light-induced coupling between the excited molecule, and bound and scattering states of the interaction between two metastable atoms. Their analysis leads to the determination of the scattering length a = (7.2 {+-} 0.6) ruling collisions between spin polarized atoms. The two photon photo-association spectra show evidence of the production of polarized, long-range {sup 4}He{sub 2}(2{sup 3}S{sub 1}-2{sup 3}S{sub 1}) molecules. They are said to be exotic as they are made of two metastable atoms, each one carrying a enough energy to ionize the other. The corresponding lineshapes are calculated and decomposed in sums and products of Breit-Wigner and Fano profiles associated to one and two photon processes. The experimental spectra are fit, and an intrinsic lifetime {tau} = (1.4 {+-} 0.3) {mu}s is deduced. It is checked whether this lifetime could be limited by spin-dipole induced Penning autoionization. This interpretation requires that there is a quasi-bound state close to the dissociation threshold in the singlet interaction potential between metastable helium atoms for the theory to match the experiment. (author)

  2. Exotic helium molecules; Molecules exotiques d'helium

    Energy Technology Data Exchange (ETDEWEB)

    Portier, M

    2007-12-15

    We study the photo-association of an ultracold cloud of magnetically trapped helium atoms: pairs of colliding atoms interact with one or two laser fields to produce a purely long range {sup 4}He{sub 2}(2{sup 3}S{sub 1}-2{sup 3}P{sub 0}) molecule, or a {sup 4}He{sub 2}(2{sup 3}S{sub 1}-2{sup 3}S{sub 1}) long range molecule. Light shifts in one photon photo-association spectra are measured and studied as a function of the laser polarization and intensity, and the vibrational state of the excited molecule. They result from the light-induced coupling between the excited molecule, and bound and scattering states of the interaction between two metastable atoms. Their analysis leads to the determination of the scattering length a = (7.2 {+-} 0.6) ruling collisions between spin polarized atoms. The two photon photo-association spectra show evidence of the production of polarized, long-range {sup 4}He{sub 2}(2{sup 3}S{sub 1}-2{sup 3}S{sub 1}) molecules. They are said to be exotic as they are made of two metastable atoms, each one carrying a enough energy to ionize the other. The corresponding lineshapes are calculated and decomposed in sums and products of Breit-Wigner and Fano profiles associated to one and two photon processes. The experimental spectra are fit, and an intrinsic lifetime {tau} = (1.4 {+-} 0.3) {mu}s is deduced. It is checked whether this lifetime could be limited by spin-dipole induced Penning autoionization. This interpretation requires that there is a quasi-bound state close to the dissociation threshold in the singlet interaction potential between metastable helium atoms for the theory to match the experiment. (author)

  3. Modeling pulsed excitation for gas-phase laser diagnostics

    International Nuclear Information System (INIS)

    Settersten, Thomas B.; Linne, Mark A.

    2002-01-01

    Excitation dynamics for pulsed optical excitation are described with the density-matrix equations and the rate equations for a two-level system. A critical comparison of the two descriptions is made with complete and consistent formalisms that are amenable to the modeling of applied laser-diagnostic techniques. General solutions, resulting from numerical integration of the differential equations describing the excitation process, are compared for collisional conditions that range from the completely coherent limit to the steady-state limit, for which the two formalisms are identical. This analysis demonstrates the failure of the rate equations to correctly describe the transient details of the excitation process outside the steady-state limit. However, reasonable estimates of the resultant population are obtained for nonsaturating (linear) excitation. This comparison provides the laser diagnostician with the means to evaluate the appropriate model for excitation through a simple picture of the breakdown of the rate-equation validity

  4. a simple a simple excitation control excitation control excitation

    African Journals Online (AJOL)

    eobe

    field voltages determined follow a simple quadratic relationship that offer a very simple control scheme, dependent on only the stator current. Keywords: saturated reactances, no-load field voltage, excitation control, synchronous generators. 1. Introduction. Introduction. Introduction. The commonest generator in use today is ...

  5. Communication: Rotational excitation of interstellar heavy water by hydrogen molecules.

    Science.gov (United States)

    Scribano, Yohann; Faure, Alexandre; Wiesenfeld, Laurent

    2010-12-21

    Cross sections and rate coefficients for low lying rotational transitions in D(2)O induced by para-H(2) collisions are presented for the first time. Calculations have been performed at the close-coupling level with the deuterated variant of the H(2)O-H(2) interaction potential of Valiron et al. [J. Chem. Phys. 129, 134306 (2008)]. Rate coefficients are presented for temperatures between 1 and 30 K and are compared to the corresponding rate coefficients for H(2)O. Significant differences caused by the isotopic substitution are observed and are attributed to both kinematics and intramolecular geometry effects. Astrophysical implications are briefly discussed in view of the very recent detection of D(2)O by the Herschel Space Observatory.

  6. Renormalization of Optical Excitations in Molecules near a Metal Surface

    DEFF Research Database (Denmark)

    García Lastra, Juan Maria; Thygesen, Kristian Sommer

    2011-01-01

    consequence we find that close to the metal surface the optical gap of benzene can exceed its quasiparticle gap. A classical image charge model for the screened Coulomb interaction can account for all these effects which, on the other hand, are completely missed by standard time-dependent density functional...

  7. Excitation energy transfer from dye molecules to doped graphene

    Indian Academy of Sciences (India)

    Recently, we have reported theoretical studies on the rate of energy transfer ... Dirac cone approximation and hence our conclusions are of qualitative nature. 2. .... make another change of variable to r given by r = ki q/2 to get. G1 (q) = Aq2.

  8. Summary of transient analysis

    International Nuclear Information System (INIS)

    Saha, P.

    1984-01-01

    This chapter reviews the papers on the pressurized water reactor (PWR) and boiling water reactor (BWR) transient analyses given at the American Nuclear Society Topical Meeting on Anticipated and Abnormal Plant Transients in Light Water Reactors. Most of the papers were based on the systems calculations performed using the TRAC-PWR, RELAP5 and RETRAN codes. The status of the nuclear industry in the code applications area is discussed. It is concluded that even though comprehensive computer codes are available for plant transient analysis, there is still a need to exercise engineering judgment, simpler tools and even hand calculations to supplement these codes

  9. The rotational excitation of HF by H

    Science.gov (United States)

    Desrousseaux, Benjamin; Lique, François

    2018-06-01

    The HF molecule is a key tracer of molecular hydrogen in diffuse interstellar medium (ISM). Accurate modelling of the HF abundance in such media requires one to model its excitation by both radiation and collisions. In diffuse ISM, the dominant collisional partners are atomic and molecular hydrogen. We report quantum time-independent calculations of collisional cross-sections and rate coefficients for the rotational excitation of HF by H. The reactive hydrogen exchange channels are taken into account in the scattering calculations. For the first time, HF-H rate coefficients are provided for temperature ranging from 10 to 500 K. The strongest collision-induced rotational HF transitions are those with Δj = 1, and the order of magnitude of the new HF-H rate coefficients is similar to that of the HF-H2 ones previously computed. As a first application, we simulate the excitation of HF by both H and H2 in typical diffuse ISM. We show that, depending on the rotational transition, hydrogen atoms increase or decrease the simulated excitation temperatures compared to collisional excitation only due to H2 molecules. Such results suggest that the new HF-H collisional data have to be used for properly modelling the abundance of HF in diffuse ISM.

  10. Site selective dissociation of ozone upon core excitation

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  11. Site selective dissociation of ozone upon core excitation

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-05-15

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

  12. PWR systems transient analysis

    International Nuclear Information System (INIS)

    Kennedy, M.F.; Peeler, G.B.; Abramson, P.B.

    1985-01-01

    Analysis of transients in pressurized water reactor (PWR) systems involves the assessment of the response of the total plant, including primary and secondary coolant systems, steam piping and turbine (possibly including the complete feedwater train), and various control and safety systems. Transient analysis is performed as part of the plant safety analysis to insure the adequacy of the reactor design and operating procedures and to verify the applicable plant emergency guidelines. Event sequences which must be examined are developed by considering possible failures or maloperations of plant components. These vary in severity (and calculational difficulty) from a series of normal operational transients, such as minor load changes, reactor trips, valve and pump malfunctions, up to the double-ended guillotine rupture of a primary reactor coolant system pipe known as a Large Break Loss of Coolant Accident (LBLOCA). The focus of this paper is the analysis of all those transients and accidents except loss of coolant accidents

  13. Transients: The regulator's view

    International Nuclear Information System (INIS)

    Sheron, B.W.; Speis, T.P.

    1984-01-01

    This chapter attempts to clarify the basis for the regulator's concerns for transient events. Transients are defined as both anticipated operational occurrences and postulated accidents. Recent operational experience, supplemented by improved probabilistic risk analysis methods, has demonstrated that non-LOCA transient events can be significant contributors to overall risk. Topics considered include lessons learned from events and issues, the regulations governing plant transients, multiple failures, different failure frequencies, operator errors, and public pressure. It is concluded that the formation of Owners Groups and Regulatory Response Groups within the owners groups are positive signs of the industry's concern for safety and responsible dealing with the issues affecting both the US NRC and the industry

  14. Electron-impact excitation of molecular ions

    International Nuclear Information System (INIS)

    Neufeld, D.A.; Dalgarno, A.

    1989-01-01

    A simple expression is derived that relates the rate coefficient for dipole-allowed electron-impact excitation of a molecular ion in the Coulomb-Born approximation to the Einstein A coefficient for the corresponding radiative decay. Results are given for several molecular ions of astrophysical interest. A general analytic expression is obtained for the equilibrium rotational level populations in the ground vibrational state of any molecular ion excited by collisions with electrons. The expression depends only upon the electron temperature, the electron density, and the rotational constant of the molecular ion. A similar expression is obtained for neutral polar molecules

  15. Transient multivariable sensor evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Vilim, Richard B.; Heifetz, Alexander

    2017-02-21

    A method and system for performing transient multivariable sensor evaluation. The method and system includes a computer system for identifying a model form, providing training measurement data, generating a basis vector, monitoring system data from sensor, loading the system data in a non-transient memory, performing an estimation to provide desired data and comparing the system data to the desired data and outputting an alarm for a defective sensor.

  16. Effect of Optical Excitation Energy on the Red Luminescence of Eu(3+) in GaN

    National Research Council Canada - National Science Library

    Peng, H. Y; Lee, C. W; Everitt, H. O; Lee, D. S; Steckl, A. J; Zavada, J. M

    2005-01-01

    ...)] transition from GaN:Eu. Time-resolved PL measurements revealed that for excitation at the GaN bound exciton energy, the decay transients are almost temperature insensitive between 86 K and 300 K, indicating an efficient...

  17. H2 molecules and the intercloud medium

    International Nuclear Information System (INIS)

    Hill, J.K.; Hollenbach, D.J.

    1976-01-01

    We discuss expected column of densities of H 2 in the intercloud medium and the possible use of molecules as indicators of intercloud physical conditions. We treat molecule formation by the H - process and on graphite grains and show that the Barlow-Silk hypothesis of a 1 eV semichemical hydrogen-graphite bond leads to a large enhancement of the intercloud molecule formation rate. Rotational excitation calculations are presented for both cloud and intercloud conditions which show, in agreement with Jura, that the presently observed optically thin H 2 absorption components are more likely to originate in cold clouds than in the intercloud medium

  18. Molecular Wring Resonances in Chain Molecules

    DEFF Research Database (Denmark)

    Bohr, Henrik; Brunak, Søren; Bohr, Jakob

    1997-01-01

    It is shown that the eigenfrequency of collective twist excitations in chain molecules can be in the megahertz and gigahertz range. Accordingly, resonance states can be obtained at specific frequencies, and phenomena that involve structural properties can take place. Chain molecules can alter the...... their conformation and their ability to function, and a breaking of the chain can result. It is suggested that this phenomenon forms the basis for effects caused by the interaction of microwaves and biomolecules, e.g. microwave assisted hydrolysis of chain molecules....

  19. On isospin excitation energy

    International Nuclear Information System (INIS)

    Li Wenfei; Zhang Fengshou; Chen Liewen

    2001-01-01

    Within the framework of Hartree-Fock theory using the extended Skyrme effective interaction, the isospin excitation energy as a function of relative neutron excess δ was investigated at different temperatures and densities. It was found that the isospin excitation energy decreased with the increment of temperature and/or the decrement of density. The authors pointed out that the decrement of isospin excitation energy was resulted from the weakening of quantum effect with increment of temperature and/or decrement of density. Meanwhile, the relationship between the isospin excitation energy and the symmetry energy was discussed and found that the symmetry energy was just a part of the isospin excitation energy. With increasing temperature and decreasing density, the contribution of the symmetry energy to the isospin excitation energy becomes more and more important. The isospin excitation energy as a function of relative neutron excess was also investigated using different potential parameters. The results shows that the isospin excitation energy is almost independent of the incompressibility and the effective mass, but strongly depends on the symmetry energy strength coefficient, which indicates that it is possible to extract the symmetry energy of the nuclear equation of state by investigating the isospin excitation energy in experiments

  20. Laser Control of Atoms and Molecules

    CERN Document Server

    Letkhov, V S

    2007-01-01

    This text treats laser light as a universal tool to control matter at the atomic and molecular level, one of the most exciting applications of lasers. Lasers can heat matter, cool atoms to ultra-low temperatures where they show quantum collective behaviour, and can act selectively on specific atoms and molecules for their detection and separation.

  1. Control of Single Molecule Fluorescence Dynamics by Stimulated Emission Depletion

    OpenAIRE

    Marsh, R. J.; Osborne, M. A.; Bain, A. J.

    2003-01-01

    The feasibility of manipulating the single molecule absorption-emission cycle using picosecond stimulated emission depletion (STED) is investigated using a stochastic computer simulation. In the simulation the molecule is subjected to repeated excitation and depletion events using time delayed pairs of excitation (PUMP) and depletion (DUMP) pulses derived from a high repetition rate pulsed laser system. The model is used to demonstrate that a significant and even substantial reduction in the ...

  2. Molecule Matters van der Waals Molecules

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 15; Issue 7. Molecule Matters van der Waals Molecules - Rg•••HF Complexes are Debye Molecules! E Arunan. Feature Article Volume 15 Issue 7 July 2010 pp 667-674. Fulltext. Click here to view fulltext PDF. Permanent link:

  3. Observation of correlated excitations in bimolecular collisions

    Science.gov (United States)

    Gao, Zhi; Karman, Tijs; Vogels, Sjoerd N.; Besemer, Matthieu; van der Avoird, Ad; Groenenboom, Gerrit C.; van de Meerakker, Sebastiaan Y. T.

    2018-02-01

    Although collisions between atoms and molecules are largely understood, collisions between two molecules have proven much harder to study. In both experiment and theory, our ability to determine quantum-state-resolved bimolecular cross-sections lags behind their atom-molecule counterparts by decades. For many bimolecular systems, even rules of thumb—much less intuitive understanding—of scattering cross sections are lacking. Here, we report the measurement of state-to-state differential cross sections on the collision of state-selected and velocity-controlled nitric oxide (NO) radicals and oxygen (O2) molecules. Using velocity map imaging of the scattered NO radicals, the full product-pair correlations of rotational excitation that occurs in both collision partners from individual encounters are revealed. The correlated cross sections show surprisingly good agreement with quantum scattering calculations using ab initio NO-O2 potential energy surfaces. The observations show that the well-known energy-gap law that governs atom-molecule collisions does not generally apply to bimolecular excitation processes, and reveal a propensity rule for the vector correlation of product angular momenta.

  4. Cross sections for collisions of subexcitation electrons with molecules

    International Nuclear Information System (INIS)

    Itikawa, Y.

    1983-01-01

    A short review is given on the present knowledge about the collision processes of subexcitation electrons (i.e., electrons whose energy is below the threshold of the first electronically excited state) with molecules. The processes considered are: vibrational and rotational excitations and elastic scattering. As an example, stopping cross sections for those processes (and electronic excitation and ionization, for comparison) are shown graphically for N 2 and H 2 O. 21 references, 2 figures

  5. Multiphoton processes in isolated atoms and molecules

    International Nuclear Information System (INIS)

    Sudbo, A.S.

    1979-11-01

    The theory of coherent excitation of a multilevel quantum mechanical system is developed. Damping of the system is taken into account by the use of a density matrix formalism. General properties of the wave function and/or the density matrix are discussed. The physical implications for the behavior of the system are described, together with possible applications of the formalism, including the infrared multiphoton excitation of molecules, and optical pumping in alkali atoms. Experimental results are presented on the infrared multiphoton dissociation of molecules, followed by a discussion of the general features of this process. The experimental results were obtained using a crossed laser and molecular beam method, and the emphasis is on determining the properties of the dissociating molecule and the dissociation products. The dissociation process is shown to be described very well by the standard statistical theory (RRKM theory) of unimolecular reactions, a brief presentation of which is also included

  6. Single molecule tracking

    Science.gov (United States)

    Shera, E. Brooks

    1988-01-01

    A detection system is provided for identifying individual particles or molecules having characteristic emission in a flow train of the particles in a flow cell. A position sensitive sensor is located adjacent the flow cell in a position effective to detect the emissions from the particles within the flow cell and to assign spatial and temporal coordinates for the detected emissions. A computer is then enabled to predict spatial and temporal coordinates for the particle in the flow train as a function of a first detected emission. Comparison hardware or software then compares subsequent detected spatial and temporal coordinates with the predicted spatial and temporal coordinates to determine whether subsequently detected emissions originate from a particle in the train of particles. In one embodiment, the particles include fluorescent dyes which are excited to fluoresce a spectrum characteristic of the particular particle. Photones are emitted adjacent at least one microchannel plate sensor to enable spatial and temporal coordinates to be assigned. The effect of comparing detected coordinates with predicted coordinates is to define a moving sample volume which effectively precludes the effects of background emissions.

  7. Effect of power frequency excitation character on ferroresonance in neutral-grounded system

    International Nuclear Information System (INIS)

    Hui Meng; Liu Chong-Xin

    2010-01-01

    In most earlier ferroresonance studies the traditional excitation characteristic of iron core, in which the traditional excitation characteristic contains harmonic voltages or currents, has been used as if it were made up of pure fundamental voltage or current. However, this is not always true. In comparison with traditional excitation characteristics, this paper introduces the power frequency excitation characteristic of the iron core, which contains no harmonics. The power frequency excitation characteristic of iron core has been obtained by Elector Magnetic Transient Program, resulting in discrete voltage and current pairs. Extensive simulations are carried out to analyse the effect of power frequency excitation characteristic on potential transformer ferroresonance. A detailed analysis of simulation results demonstrates that with power frequency excitation characteristic of iron core inclusion at certain excitation voltage the ferroresonance may happen, conversely it may not happen with traditional excitation characteristic inclusion. (general)

  8. Transient absorption spectroscopy in biology using the Super-ACO storage ring FEL and the synchrotron radiation combination

    International Nuclear Information System (INIS)

    Renault, Eric; Nahon, Laurent; Garzella, David; Nutarelli, Daniele; De Ninno, Giovanni; Hirsch, Matthias; Couprie, Marie Emmanuelle

    2001-01-01

    The Super-ACO storage ring FEL, covering the UV range down to 300 nm with a high average power (300 mW at 350 nm) together with a high stability and long lifetime, is a unique tool for the performance of users applications. We present here the first pump-probe two color experiments on biological species using a storage ring FEL coupled to the synchrotron radiation. The intense UV pulse of the Super-ACO FEL is used to prepare a high initial concentration of chromophores in their first singlet electronic excited state. The nearby bending magnet synchrotron radiation provides, on the other hand a pulsed, white light continuum (UV-IR), naturally synchronized with the FEL pulses and used to probe the photochemical subsequent events and the associated transient species. We have demonstrated the feasibility with a dye molecule (POPOP) observing a two-color effect, signature of excited state absorption and a temporal signature with Acridine. Applications on various chromophores of biological interest are carried out, such as the time-resolved absorption study of the first excited state of Acridine

  9. Transient flow combustion

    Science.gov (United States)

    Tacina, R. R.

    1984-01-01

    Non-steady combustion problems can result from engine sources such as accelerations, decelerations, nozzle adjustments, augmentor ignition, and air perturbations into and out of the compressor. Also non-steady combustion can be generated internally from combustion instability or self-induced oscillations. A premixed-prevaporized combustor would be particularly sensitive to flow transients because of its susceptability to flashback-autoignition and blowout. An experimental program, the Transient Flow Combustion Study is in progress to study the effects of air and fuel flow transients on a premixed-prevaporized combustor. Preliminary tests performed at an inlet air temperature of 600 K, a reference velocity of 30 m/s, and a pressure of 700 kPa. The airflow was reduced to 1/3 of its original value in a 40 ms ramp before flashback occurred. Ramping the airflow up has shown that blowout is more sensitive than flashback to flow transients. Blowout occurred with a 25 percent increase in airflow (at a constant fuel-air ratio) in a 20 ms ramp. Combustion resonance was found at some conditions and may be important in determining the effects of flow transients.

  10. Selective interaction between Xanthophylls and Chlorophylls in LHCII probed by femtosecond transient absoprtion spectroscopy

    NARCIS (Netherlands)

    Gradinaru, C.C.; Grondelle, van R.; Amerongen, van H.

    2003-01-01

    We have performed femtosecond transient absorption measurements on trimeric light-harvesting complex II from spinach. Either chlorophyll (Chl) a (675 nm) or Chl b (650 nm) was excited, and the spectral response was probed for wavelengths longer than 470 nm. Excitation of Chl b led to instantaneous

  11. A targeting drug-delivery model via interactions among cells and liposomes under ultrasonic excitation

    International Nuclear Information System (INIS)

    Xi Xiaoyu; Zhang Dong; Yang Fang; Gu Ning; Chen Di; Wu Junru; Luo Yi

    2008-01-01

    In our previous work, it was found that acoustic cavitation might play a role in improving the cell permeability to microparticles when liposomes were used in an in vitro experiment. The purpose of this project is to expand our study and to learn other possible mechanisms by which cells may interact with liposomes under ultrasound (US) excitation and become transiently permeable to microparticles. It is further hypothesized that two possible scenarios may be involved in in vitro experiments: (1) drug-carrying liposomes transiently overcome the cell membrane barrier and enter into a cell while the cell is still viable; (2) the liposomes incorporate with a cell at its membrane through a fusing process. To prove this hypothesis, liposomes of two different structures were synthesized: one has fluorescent molecules encapsulated into liposomes and the other has fluorescent markers incorporated into the shells of liposomes. Liposomes of each kind were mixed with human breast cancer cells (MCF7-cell line) in a suspension at 5 (liposomes) : 1 (cell) ratio and were then exposed to a focused 1 MHz ultrasound beam at its focal region for 40 s. The US signal contained 20 cycles per tone-burst at a pulse-repetition-frequency of 10 kHz; the spatial peak acoustic pressure amplitude was 0.25 MPa. It was found that the possible mechanisms might include the acoustic cavitation, the endocytosis and cell-fusion. Acoustic radiation force might make liposomes collide with cells effectively and facilitate the delivery process

  12. Dynamical analysis of highly excited molecular spectra

    Energy Technology Data Exchange (ETDEWEB)

    Kellman, M.E. [Univ. of Oregon, Eugene (United States)

    1993-12-01

    The goal of this program is new methods for analysis of spectra and dynamics of highly excited vibrational states of molecules. In these systems, strong mode coupling and anharmonicity give rise to complicated classical dynamics, and make the simple normal modes analysis unsatisfactory. New methods of spectral analysis, pattern recognition, and assignment are sought using techniques of nonlinear dynamics including bifurcation theory, phase space classification, and quantization of phase space structures. The emphasis is chaotic systems and systems with many degrees of freedom.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-07

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

  14. Molecular excitations: a new way to detect Dark Matter

    Energy Technology Data Exchange (ETDEWEB)

    Va' vra, J.

    2014-09-01

    We believe that the Dark Matter (DM) search should be expanded into the domain of detectors sensitive to molecular excitations, and so that we should create detectors which are more sensitive to collisions with very light WIMPs. In this paper we investigate in detail diatomic molecules, such as fused silica material with large OH-molecule content, and water molecules. Presently, we do not have suitable low-cost IR detectors to observe single photons, however some OH-molecular excitations extend to visible and UV wavelengths and can be measured by bialkali photocathodes. There are many other chemical substances with diatomic molecules, or more complex oil molecules, which could be also investigated. This idea invites searches in experiments having large target volumes of such materials coupled to a large array of single-photon detectors with bialkali or infrared-sensitive photocathodes.

  15. Transient hardened power FETs

    International Nuclear Information System (INIS)

    Dawes, W.R. Jr.; Fischer, T.A.; Huang, C.C.C.; Meyer, W.J.; Smith, C.S.; Blanchard, R.A.; Fortier, T.J.

    1986-01-01

    N-channel power FETs offer significant advantages in power conditioning circuits. Similiarily to all MOS technologies, power FET devices are vulnerable to ionizing radiation, and are particularily susceptible to burn-out in high dose rate irradiations (>1E10 rads(Si)/sec.), which precludes their use in many military environments. This paper will summarize the physical mechanisms responsible for burn-out, and discuss various fabrication techniques designed to improve the transient hardness of power FETs. Power FET devices were fabricated with several of these techniques, and data will be presented which demonstrates that transient hardness levels in excess of 1E12 rads(Si)/sec. are easily achievable

  16. Transients in the Vivitron

    International Nuclear Information System (INIS)

    Cooke, C.M.; Frick, G.; Roumie, M.

    1993-01-01

    Electrical measurements are presented for the construction of a model for the study of transients in the Vivitron. Observation of the transmission of electrical pulses in the porticos clearly shows transmission-line behaviour. Measurements of the vector impedance of the outer porticos show the same transmission-line properties, but also gives a description of the modification from a pure transmission line due to the circular electrodes. The results of this investigation should allow the construction of a computer model which predicts the evolution of the transients in the case of a spark in the Vivitron. (orig.)

  17. Excitation mechanism in the photoisomerization of a surface-bound azobenzene derivative: Role of the metallic substrate

    Science.gov (United States)

    Hagen, Sebastian; Kate, Peter; Leyssner, Felix; Nandi, Dhananjay; Wolf, Martin; Tegeder, Petra

    2008-10-01

    Two-photon photoemission spectroscopy is employed to elucidate the electronic structure and the excitation mechanism in the photoinduced isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). Our results demonstrate that the optical excitation and the mechanism of molecular switching at a metal surface is completely different compared to the corresponding process for the free molecule. In contrast to direct (intramolecular) excitation operative in the isomerization in the liquid phase, the conformational change in the surface-bound TBA is driven by a substrate-mediated charge transfer process. We find that photoexcitation above a threshold hν ≈2.2 eV leads to hole formation in the Au d-band followed by a hole transfer to the highest occupied molecular orbital of TBA. This transiently formed positive ion resonance subsequently results in a conformational change. The photon energy dependent photoisomerization cross section exhibit an unusual shape for a photochemical reaction of an adsorbate on a metal surface. It shows a thresholdlike behavior below hν ≈2.2 eV and above hν ≈4.4 eV. These thresholds correspond to the minimum energy required to create single or multiple hot holes in the Au d-bands, respectively. This study provides important new insights into the use of light to control the structure and function of molecular switches in direct contact with metal electrodes.

  18. Excitation mechanism in the photoisomerization of a surface-bound azobenzene derivative: Role of the metallic substrate

    International Nuclear Information System (INIS)

    Hagen, Sebastian; Kate, Peter; Leyssner, Felix; Nandi, Dhananjay; Wolf, Martin; Tegeder, Petra

    2008-01-01

    Two-photon photoemission spectroscopy is employed to elucidate the electronic structure and the excitation mechanism in the photoinduced isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). Our results demonstrate that the optical excitation and the mechanism of molecular switching at a metal surface is completely different compared to the corresponding process for the free molecule. In contrast to direct (intramolecular) excitation operative in the isomerization in the liquid phase, the conformational change in the surface-bound TBA is driven by a substrate-mediated charge transfer process. We find that photoexcitation above a threshold hν≅2.2 eV leads to hole formation in the Au d-band followed by a hole transfer to the highest occupied molecular orbital of TBA. This transiently formed positive ion resonance subsequently results in a conformational change. The photon energy dependent photoisomerization cross section exhibit an unusual shape for a photochemical reaction of an adsorbate on a metal surface. It shows a thresholdlike behavior below hν≅2.2 eV and above hν≅4.4 eV. These thresholds correspond to the minimum energy required to create single or multiple hot holes in the Au d-bands, respectively. This study provides important new insights into the use of light to control the structure and function of molecular switches in direct contact with metal electrodes.

  19. Effects of optical pumping in the photo-excitation of organic triplet states

    International Nuclear Information System (INIS)

    Lin, Tien-Sung; Yang, Tran-Chin; Sloop, David J.

    2013-01-01

    Highlights: • High electron spin polarization (ESP) was observed in pentacene triplets at room temperature. • The high ESP is transfer to the surrounding nuclear spin by optical pumping in zero-field (ZF). • The ZF transition frequencies and their line width depend on the laser pumping rate. • The spin–lattice relaxation times of the nuclear system are evaluated. - Abstract: Upon the application of laser and microwave pulses, non-zero magnetic moment of a photo-excited triplet state of organic molecules is generated in zero-field (ZF). The time evolution of the transient magnetic moments can be measured by free induction decay (FID) in ZF. The observed ZF spectra become broadened and ZF transition shifted to lower frequencies when the repetition rate of laser excitation is increased, which are attributed to the optical pumping of nuclear polarization (ONP) effect and the associated nuclear spin lattice relaxation processes. The observed ONP effect is discussed in terms of the local field effect and spin diffusion processes in optical pumping

  20. Effects of optical pumping in the photo-excitation of organic triplet states

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Tien-Sung, E-mail: lin@wustl.edu; Yang, Tran-Chin; Sloop, David J.

    2013-08-30

    Highlights: • High electron spin polarization (ESP) was observed in pentacene triplets at room temperature. • The high ESP is transfer to the surrounding nuclear spin by optical pumping in zero-field (ZF). • The ZF transition frequencies and their line width depend on the laser pumping rate. • The spin–lattice relaxation times of the nuclear system are evaluated. - Abstract: Upon the application of laser and microwave pulses, non-zero magnetic moment of a photo-excited triplet state of organic molecules is generated in zero-field (ZF). The time evolution of the transient magnetic moments can be measured by free induction decay (FID) in ZF. The observed ZF spectra become broadened and ZF transition shifted to lower frequencies when the repetition rate of laser excitation is increased, which are attributed to the optical pumping of nuclear polarization (ONP) effect and the associated nuclear spin lattice relaxation processes. The observed ONP effect is discussed in terms of the local field effect and spin diffusion processes in optical pumping.

  1. New excitation equipment for 220 MW generators in Kozloduy NPP

    International Nuclear Information System (INIS)

    Tomerlin, D.

    2001-01-01

    Rehabilitation on the excitation equipment for Generator 5, Reactor Unit 3, in Kozloduy NPP was completed in November 2000. ABB's Static Excitation System based on UNITROL 5000 technology has been chosen by the Bulgarian National Utility and Kozloduy NPP to substitute the original Russian excitation system equipment with electro-magnetic voltage regulators. The substitution is in a rehabilitation package of four excitation system equipment for Generator 5 and 6 of Reactor Unit 3 and Generator 7 and 8 of Reactor Unit 4 after a short overview of the original excitation system this paper describes the new Static Excitation System UNITROL 5000 including configuration with block diagram, its main features and merits such as modes of operation, limiter, special control functions and diagnostic facilities. Furthermore, new facilities, which are implemented in UNITROL 5000, such as dynamic current distribution among the thyristors working in parallel as well as the start-up from the residual magnetism are mentioned. Special functions including a so-called free-running mode of operation and automatic change over sequence from new excitation system to the stand-by excitation system, which is DC exciter machine, are described. Some records of the transient responses performed during the commissioning and a photograph of a manufactured system are provided. (author)

  2. Study on the adjustment capability of the excitation system located inside superconducting machine electromagnetic shield

    Science.gov (United States)

    Xia, D.; Xia, Z.

    2017-12-01

    The ability for the excitation system to adjust quickly plays a very important role in maintaining the normal operation of superconducting machines and power systems. However, the eddy currents in the electromagnetic shield of superconducting machines hinder the exciting magnetic field change and weaken the adjustment capability of the excitation system. To analyze this problem, a finite element calculation model for the transient electromagnetic field with moving parts is established. The effects of three different electromagnetic shields on the exciting magnetic field are analyzed using finite element method. The results show that the electromagnetic shield hinders the field changes significantly, the better its conductivity, the greater the effect on the superconducting machine excitation.

  3. Transient Heat Conduction

    DEFF Research Database (Denmark)

    Rode, Carsten

    1998-01-01

    Analytical theory of transient heat conduction.Fourier's law. General heat conducation equation. Thermal diffusivity. Biot and Fourier numbers. Lumped analysis and time constant. Semi-infinite body: fixed surface temperature, convective heat transfer at the surface, or constant surface heat flux...

  4. Transient cavitation in pipelines

    NARCIS (Netherlands)

    Kranenburg, C.

    1974-01-01

    The aim of the present study is to set up a one-dimensional mathematical model, which describes the transient flow in pipelines, taking into account the influence of cavitation and free gas. The flow will be conceived of as a three-phase flow of the liquid, its vapour and non-condensible gas. The

  5. Harmonic excitations in quasicrystals

    International Nuclear Information System (INIS)

    Luck, J.M.

    1986-03-01

    The harmonic excitations (phonons) of quasicrystals are studied in a simple one-dimensional model. The spectrum is a Cantor set, which exhibits selfsimilarity properties. The eigenstates are generically ''critical'', i.e. neither extended nor localized

  6. Radio frequency plasma excitation

    International Nuclear Information System (INIS)

    Burden, M.St.J.; Cross, K.B.

    1979-01-01

    An investigation into the use of rf sputtering for ion cleaning of insulating substrates before ion plating is reported. Initial experiments consisted of sputtering metals with rf power followed by the deposition of copper onto glass slides using rf plasma excitation and biasing supply. It was found that good quality films were obtained by rf ion plating onto plastics with excellent adhesion over a wide operating pressure range. A block schematic of the rf plasma excitation system is shown. (UK)

  7. High energy nuclear excitations

    International Nuclear Information System (INIS)

    Gogny, D.; Decharge, J.

    1983-09-01

    The main purpose of this talk is to see whether a simple description of the nuclear excitations permits one to characterize some of the high energy structures recently observed. The discussion is based on the linear response to different external fields calculated using the Random Phase Approximation. For those structure in heavy ion collisions at excitation energies above 50 MeV which cannot be explained with such a simple approach, we discuss a possible mechanism for this heavy ion scattering

  8. Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy† †Electronic supplementary information (ESI) available: Synthesis schemes, experimental methods, NMR spectra, X-ray crystallographic information, emission spectra, cyclic voltammetry, electronic structure calculations, data analysis and numerical methods, and other additional figures. CCDC 1561879. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04055e

    Science.gov (United States)

    Kohler, Lars; Hadt, Ryan G.; Zhang, Xiaoyi; Liu, Cunming

    2017-01-01

    The kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(i) bis(phenanthroline)/ruthenium(ii) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(i)–Ru(ii) analogs of the homodinuclear Cu(i)–Cu(i) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These results suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations. PMID:29629153

  9. Compressive Transient Imaging

    KAUST Repository

    Sun, Qilin

    2017-04-01

    High resolution transient/3D imaging technology is of high interest in both scientific research and commercial application. Nowadays, all of the transient imaging methods suffer from low resolution or time consuming mechanical scanning. We proposed a new method based on TCSPC and Compressive Sensing to achieve a high resolution transient imaging with a several seconds capturing process. Picosecond laser sends a serious of equal interval pulse while synchronized SPAD camera\\'s detecting gate window has a precise phase delay at each cycle. After capturing enough points, we are able to make up a whole signal. By inserting a DMD device into the system, we are able to modulate all the frames of data using binary random patterns to reconstruct a super resolution transient/3D image later. Because the low fill factor of SPAD sensor will make a compressive sensing scenario ill-conditioned, We designed and fabricated a diffractive microlens array. We proposed a new CS reconstruction algorithm which is able to denoise at the same time for the measurements suffering from Poisson noise. Instead of a single SPAD senor, we chose a SPAD array because it can drastically reduce the requirement for the number of measurements and its reconstruction time. Further more, it not easy to reconstruct a high resolution image with only one single sensor while for an array, it just needs to reconstruct small patches and a few measurements. In this thesis, we evaluated the reconstruction methods using both clean measurements and the version corrupted by Poisson noise. The results show how the integration over the layers influence the image quality and our algorithm works well while the measurements suffer from non-trival Poisson noise. It\\'s a breakthrough in the areas of both transient imaging and compressive sensing.

  10. Photoionization dynamics of excited molecular states

    International Nuclear Information System (INIS)

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

    1987-01-01

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

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

    Science.gov (United States)

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

    2014-06-23

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

  12. Vibrational Analysis of (SCN)2 and the Transient (SCN)2

    DEFF Research Database (Denmark)

    Jensen, N. H.; Wilbrandt, Robert Walter; Pagsberg, Palle Bjørn

    1979-01-01

    The vibrational spectra of thiocyanogen and the transient radical anion (SCN)2− are interpreted in detail through molecular orbital and normal coordinate calculations. The results support the assignment of (SCN)2− to the anion of thiocyanogen and indicate a substantial weakening of the S–S and C......≡N bonds in going from the parent molecule to its radical anion....

  13. Memory effects in single-molecule spectroscopy

    International Nuclear Information System (INIS)

    Schmitt, Daniel T.; Schulz, Michael; Reineker, Peter

    2007-01-01

    From the time series of LH2 optical single-molecule fluorescence excitation spectra of Rhodospirillum molischianum the memory function of the Mori-Zwanzig equation for the optical intensity is derived numerically. We show that the time dependence of the excited states is determined by at least three different non-Markovian stochastic processes with decay constants for the Mori-Zwanzig kernel on the order of 1-5min -1 . We suggest that this decay stems from the conformational motion of the protein scaffold of LH2

  14. Small molecule probes for cellular death machines.

    Science.gov (United States)

    Li, Ying; Qian, Lihui; Yuan, Junying

    2017-08-01

    The past decade has witnessed a significant expansion of our understanding about the regulated cell death mechanisms beyond apoptosis. The application of chemical biological approaches had played a major role in driving these exciting discoveries. The discovery and use of small molecule probes in cell death research has not only revealed significant insights into the regulatory mechanism of cell death but also provided new drug targets and lead drug candidates for developing therapeutics of human diseases with huge unmet need. Here, we provide an overview of small molecule modulators for necroptosis and ferroptosis, two non-apoptotic cell death mechanisms, and discuss the molecular pathways and relevant pathophysiological mechanisms revealed by the judicial applications of such small molecule probes. We suggest that the development and applications of small molecule probes for non-apoptotic cell death mechanisms provide an outstanding example showcasing the power of chemical biology in exploring novel biological mechanisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Ultrafast photo-induced nuclear relaxation of a conformationally disordered conjugated polymer probed with transient absorption and femtosecond stimulated Raman spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Wenjian; Donohoo-Vallett, Paul J.; Zhou, Jiawang; Bragg, Arthur E., E-mail: artbragg@jhu.edu [Department of Chemistry, Johns Hopkins University, 3400 N. Charles St., Baltimore, Maryland 21218 (United States)

    2014-07-28

    A combination of transient absorption (TAS) and femtosecond stimulated Raman (FSRS) spectroscopies were used to interrogate the photo-induced nuclear relaxation dynamics of poly(3-cyclohexyl,4-methylthiophene) (PCMT). The large difference in inter-ring dihedral angles of ground and excited-state PCMT make it an ideal candidate for studying large-amplitude vibrational relaxation associated with exciton trapping. Spectral shifting in the S{sub 1} TA spectra on sub-ps timescales (110 ± 20 and 800 ± 100 fs) is similar to spectroscopic signatures of excited-state relaxation observed with related photoexcited conjugated polymers and which have been attributed to exciton localization and a combination of resonant energy transfer and torsional relaxation, respectively. Measurements made with both techniques reveal fast PCMT S{sub 1} decay and triplet formation (τ{sub S1} = 25–32 ps), which is similar to the excited-state dynamics of short oligothiophenes and highly twisted polyconjugated molecules. On ultrafast timescales FSRS of S{sub 1} PCMT offers a new perspective on the nuclear dynamics that underlie localization of excitons in photoexcited conjugated polymers: Spectral dynamics in the C=C stretching region (1400–1600 cm{sup −1}) include a red-shift of the in-phase C=C stretching frequency, as well as a change in the relative intensity of in-phase and out-of-phase stretch intensities on a timescale of ∼100 fs. Both changes indicate an ultrafast vibrational distortion that increases the conjugation length in the region of the localized excitation and are consistent with exciton self-localization or trapping. Wavelength-dependent excited-state FSRS measurements further demonstrate that the C=C stretching frequency provides a useful spectroscopic handle for interrogating the degree of delocalization in excited conjugated polymers given the selectivity achieved via resonance enhancement.

  16. Breakdown of highly excited oxygen in a DC electric field

    International Nuclear Information System (INIS)

    Vagin, N.P.; Ionin, A.A.; Klimachev, Yu.M.; Sinitsin, D.V.; Yuryshev, N.N.; Deryugin, A.A.; Kochetov, I.V.; Napartovich, A.P.

    2000-01-01

    The breakdown of oxygen in a dc electric field is studied. A high concentration of oxygen molecules in the a 1 Δ g excited state is obtained in a purely chemical reactor. A decrease in the breakdown voltage at degrees of excitation exceeding 50% is observed. The theoretical decrement in the breakdown voltage obtained by solving the Boltzmann equation is in good agreement with the experimental data

  17. Electric moments in molecule interferometry

    International Nuclear Information System (INIS)

    Eibenberger, Sandra; Gerlich, Stefan; Arndt, Markus; Tuexen, Jens; Mayor, Marcel

    2011-01-01

    We investigate the influence of different electric moments on the shift and dephasing of molecules in a matter wave interferometer. Firstly, we provide a quantitative comparison of two molecules that are non-polar yet polarizable in their thermal ground state and that differ in their stiffness and response to thermal excitations. While C 25 H 20 is rather rigid, its larger derivative C 49 H 16 F 52 is additionally equipped with floppy side chains and vibrationally activated dipole moment variations. Secondly, we elucidate the role of a permanent electric dipole momentby contrasting the quantum interference pattern of a (nearly) non-polar and a polar porphyrin derivative. We find that a high molecular polarizability and even sizeable dipole moment fluctuations are still well compatible with high-contrast quantum interference fringes. The presence of permanent electric dipole moments, however, can lead to a dephasing and rapid degradation of the quantum fringe pattern already at moderate electric fields. This finding is of high relevance for coherence experiments with large organic molecules, which are generally equipped with strong electric moments.

  18. Spectroscopy and Chemistry of Cold Molecules

    Science.gov (United States)

    Momose, Takamasa

    2012-06-01

    Molecules at low temperatures are expected to behave quite differently from those at high temperatures because pronounced quantum effects emerge from thermal averages. Even at 10 K, a significant enhancement of reaction cross section is expected due to tunneling and resonance effects. Chemistry at this temperature is very important in order to understand chemical reactions in interstellar molecular clouds. At temperatures lower than 1 K, collisions and intermolecular interactions become qualitatively different from those at high temperatures because of the large thermal de Broglie wavelength of molecules. Collisions at these temperatures must be treated as the interference of molecular matter waves, but not as hard sphere collisions. A Bose-Einstein condensate is a significant state of matter as a result of coherent matter wave interaction. Especially, dense para-H_2 molecules are predicted to become a condensate even around 1 K. A convenient method to investigate molecules around 1 K is to dope molecules in cold matrices. Among various matrices, quantum hosts such as solid para-H_2 and superfluid He nano-droplets have been proven to be an excellent host for high-resolution spectroscopy. Rovibrational motion of molecules in these quantum hosts is well quantized on account of the weak interactions and the softness of quantum environment. The linewidths of infrared spectra of molecules in the quantum hosts are extremely narrow compared with those in other matrices. The sharp linewidths allow us to resolve fine spectral structures originated in subtle interactions between guest and host molecules. In this talk, I will describe how the splitting and lineshape of high-resolution spectra of molecules in quantum hosts give us new information on the static and dynamical interactions of molecules in quantum medium. The topics include dynamical response of superfluid environment upon rotational excitation, and possible superfluid phase of para-H_2 clusters. I will also

  19. Transient osteoporosis of hip

    Directory of Open Access Journals (Sweden)

    Mahesh M Choudhary

    2015-01-01

    Full Text Available We report a case of transient osteoporosis of the hip (TOH in a 50-year-old man including the clinical presentation, diagnostic studies, management, and clinical progress. TOH is a rare self-limiting condition that typically affects middle-aged men or, less frequently, women in the third trimester of pregnancy. Affected individuals present clinically with acute hip pain, limping gait, and limited ranges of hip motion. TOH may begin spontaneously or after a minor trauma. Radiographs are typically unremarkable but magnetic resonance (MR imaging studies yield findings consistent with bone marrow edema. TOH is referred to as regional migratory osteoporosis (RMO if it travels to other joints or the contralateral hip. TOH often resembles osteonecrosis but the two conditions must be differentiated due to different prognoses and management approaches. The term TOH is often used interchangeably and synonymously with transient bone marrow edema (TBME.

  20. Stability of Ignition Transients

    OpenAIRE

    V.E. Zarko

    1991-01-01

    The problem of ignition stability arises in the case of the action of intense external heat stimuli when, resulting from the cut-off of solid substance heating, momentary ignition is followed by extinction. Physical pattern of solid propellant ignition is considered and ignition criteria available in the literature are discussed. It is shown that the above mentioned problem amounts to transient burning at a given arbitrary temperature distribution in the condensed phase. A brief survey...

  1. Transient FDTD simulation validation

    OpenAIRE

    Jauregui Tellería, Ricardo; Riu Costa, Pere Joan; Silva Martínez, Fernando

    2010-01-01

    In computational electromagnetic simulations, most validation methods have been developed until now to be used in the frequency domain. However, the EMC analysis of the systems in the frequency domain many times is not enough to evaluate the immunity of current communication devices. Based on several studies, in this paper we propose an alternative method of validation of the transients in time domain allowing a rapid and objective quantification of the simulations results.

  2. Proposal for probing energy transfer pathway by single-molecule pump-dump experiment

    OpenAIRE

    Tao, Ming-Jie; Ai, Qing; Deng, Fu-Guo; Cheng, Yuan-Chung

    2016-01-01

    The structure of Fenna-Matthews-Olson (FMO) light-harvesting complex has long been recognized as containing seven bacteriochlorophyll (BChl) molecules. Recently, an additional BChl molecule was discovered in the crystal structure of the FMO complex, which may serve as a link between baseplate and the remaining seven molecules. Here, we investigate excitation energy transfer (EET) process by simulating single-molecule pump-dump experiment in the eight-molecules complex. We adopt the coherent m...

  3. MHD aspects of coronal transients

    International Nuclear Information System (INIS)

    Anzer, U.

    1979-10-01

    If one defines coronal transients as events which occur in the solar corona on rapid time scales (< approx. several hours) then one would have to include a large variety of solar phenomena: flares, sprays, erupting prominences, X-ray transients, white light transients, etc. Here we shall focus our attention on the latter two phenomena. (orig.) 891 WL/orig. 892 RDG

  4. Dynamics of the excited state intramolecular charge transfer

    International Nuclear Information System (INIS)

    Joo, T.; Kim, C.H.

    2006-01-01

    The 6-dodecanoyl-2-dimethylaminonaphtalene (laurdan), a derivative of 6-propanoyl- 2-dimethylaminonaphthalene (prodan), has been used as a fluorescent probe in cell imaging, especially in visualizing the lipid rafts by the generalized polarization (GP) images, where GP=(I 440 -I 490 )/(I 440 +I 490 ) with I being the fluorescence intensity. The fluorescence spectrum of laurdan is sensitive to its dipolar environment due to the intramolecular charge transfer (ICT) process in S 1 state, which results in a dual emission from the locally excited (LE) and the ICT states. The ICT process and the solvation of the ICT state are very sensitive to the dipolar nature of the environment. In this work, the ICT of laurdan in ethanol has been studied by femtosecond time resolved fluorescence (TRF), especially TRF spectra measurement without the conventional spectral reconstruction method. TRF probes the excited states exclusively, a unique advantage over the pump/probe transient absorption technique, although time resolution of the TRF is generally lower than transient absorption and the TRF spectra measurement was possible only though the spectral reconstruction. Over the years, critical advances in TRF technique have been made in our group to achieve <50 fs time resolution with direct full spectra measurement capability. Detailed ICT and the subsequent solvation processes can be visualized unambiguously from the TRF spectra. Fig. 1 shows the TRF spectra of laurdan in ethanol at several time delays. Surprisingly, two bands at 433 and 476 nm are clearly visible in the TRF spectra of laurdan even at T = 0 fs. As time increases, the band at 476 nm shifts to the red while its intensity increases. The band at 433 nm also shifts slightly to the red, but loses intensity as time increases. The intensity of the 476 nm band reaches maximum at around 5 ps, where it is roughly twice as intense as that at 0 fs, and stays constant until lifetime decay is noticeable. The spectra were fit by

  5. DARHT-II Injector Transients and the Ferrite Damper

    Energy Technology Data Exchange (ETDEWEB)

    Waldron, Will; Reginato, Lou; Chow, Ken; Houck, Tim; Henestroza, Enrique; Yu, Simon; Kang, Michael; Briggs, Richard

    2006-08-04

    This report summarizes the transient response of the DARHT-II Injector and the design of the ferrite damper. Initial commissioning of the injector revealed a rise time excited 7.8 MHz oscillation on the diode voltage and stalk current leading to a 7.8 MHz modulation of the beam current, position, and energy. Commissioning also revealed that the use of the crowbar to decrease the voltage fall time excited a spectrum of radio frequency modes which caused concern that there might be significant transient RF electric field stresses imposed on the high voltage column insulators. Based on the experience of damping the induction cell RF modes with ferrite, the concept of a ferrite damper was developed to address the crowbar-excited oscillations as well as the rise-time-excited 7.8 MHz oscillations. After the Project decided to discontinue the use of the crowbar, further development of the concept focused exclusively on damping the oscillations excited by the rise time. The design was completed and the ferrite damper was installed in the DARHT-II Injector in February 2006. The organization of this report is as follows. The suite of injector diagnostics are described in Section 2. The data and modeling of the injector transients excited on the rise-time and also by the crowbar are discussed in Section 3; the objective is a concise summary of the present state of understanding. The design of the ferrite damper, and the small scale circuit simulations used to evaluate the ferrite material options and select the key design parameters like the cross sectional area and the optimum gap width, are presented in Section 4. The details of the mechanical design and the installation of the ferrite damper are covered in Section 5. A brief summary of the performance of the ferrite damper following its installation in the injector is presented in Section 6.

  6. Selective laser photolysis of simple molecules

    International Nuclear Information System (INIS)

    Golnabi, Hossein.

    1984-01-01

    A two-photon technique is reported for the measurement of relative cross section for the photolysis of simple molecules into particular product channels. In this method two independently tunable dye lasers were used to sequentially dissociate molecules of Cs 2 and Cs-Kr for the wavelengths in the range 420 to 660 nm, and then to excite the resulting products to determine the relative cross sections for the photolysis of Cs 2 and Cs-kr into each of the lowest four of the energetically possible product states

  7. On the determination of the mean excitation energy of water

    DEFF Research Database (Denmark)

    Sabin, John R.; Oddershede, Jens; Sauer, Stephan P. A.

    2013-01-01

    Water is a ubiquitous substance in nature, and thus the mean excitation energy of water is an important quantity for understanding and prediction of the details of many fast ion/molecule collision processes such as those involved in external beam radiotherapy of tumors. There are several methods...... for determining numerical values for a mean excitation energy for water, both theoretical and experimental. Here the factors affecting the determination of the value of the mean excitation energy of water, especially from experiment, are discussed....

  8. Catalytic synthesis of ammonia using vibrationally excited nitrogen

    DEFF Research Database (Denmark)

    Henriksen, Niels Engholm; Billing, Gert D.; Hansen, Flemming Yssing

    1992-01-01

    In a previous study we have considered the catalytic synthesis of ammonia in the presence of vibrationally excited nitrogen. The distribution over vibrational states was assumed to be maintained during the reaction, and it was shown that the yield of ammonia increased considerably compared...... to that from conventional synthesis. In the present study the nitrogen molecules are only excited at the inlet of a plug flow reactor, and the importance of vibrational relaxation is investigated. We show that vibrational excitation can give an enhanced yield of ammonia also in the situation where vibrational...

  9. Energy redistribution in diatomic molecules on surfaces

    International Nuclear Information System (INIS)

    Asscher, M.; Somorjai, G.A.

    1984-04-01

    Translational and internal degrees of freedom of a scattered beam of NO molecules from a Pt(111) single crystal surface were measured as a function of scattering angle and crystal temperature in the range 450 to 1250K. None of the three degrees of freedom were found to fully accommodate to the crystal temperature, the translational degree being the most accommodated and the rotational degree of freedom the least. A precursor state model is suggested to account for the incomplete accommodation of translational and vibrational degrees of freedom as a function of crystal temperature and incident beam energy. The vibrational accommodation is further discussed in terms of a competition between desorption and vibrational excitation processes, thus providing valuable information on the interaction between vibrationally excited molecules and surfaces. Energy transfer into rotational degrees of freedom is qualitatively discussed

  10. Giant resonances on excited states

    International Nuclear Information System (INIS)

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

    1984-01-01

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

  11. A technique for the measurement of electron attachment to short-lived excited species

    International Nuclear Information System (INIS)

    Christophorou, L.G.; Pinnaduwage, L.A.; Bitouni, A.P.

    1990-01-01

    A technique is described for the measurement of electron attachment to short-lived (approx-lt 10 -9 s) excited species. Preliminary results are presented for photoenhanced electron attachment to short-lived electronically-excited states of triethylamine molecules produced by laser two-photon excitation. The attachment cross sections for these excited states are estimated to be >10 -11 cm 2 and are ∼10 7 larger compared to those for the unexcited (ground-state) molecules. 8 refs., 4 figs

  12. Off-resonant vibrational excitation: Orientational dependence and spatial control of photofragments

    DEFF Research Database (Denmark)

    Machholm, Mette; Henriksen, Niels Engholm

    2000-01-01

    Off-resonant and resonant vibrational excitation with short intense infrared (IR) laser pulses creates localized oscillating wave packets, but differs by the efficiency of the excitation and surprisingly by the orientational dependence. Orientational selectivity of the vibrational excitation...... of randomly oriented heteronuclear diatomic molecules can be obtained under simultaneous irradiation by a resonant and an off-resonant intense IR laser pulse: Molecules with one initial orientation will be vibrationally excited, while those with the opposite orientation will be at rest. The orientation-dependent...... distribution. (C) 2000 American Institute of Physics....

  13. Demystifying autofluorescence with excitation scanning hyperspectral imaging

    Science.gov (United States)

    Deal, Joshua; Harris, Bradley; Martin, Will; Lall, Malvika; Lopez, Carmen; Rider, Paul; Boudreaux, Carole; Rich, Thomas; Leavesley, Silas J.

    2018-02-01

    Autofluorescence has historically been considered a nuisance in medical imaging. Many endogenous fluorophores, specifically, collagen, elastin, NADH, and FAD, are found throughout the human body. Diagnostically, these signals can be prohibitive since they can outcompete signals introduced for diagnostic purposes. Recent advances in hyperspectral imaging have allowed the acquisition of significantly more data in a shorter time period by scanning the excitation spectra of fluorophores. The reduced acquisition time and increased signal-to-noise ratio allow for separation of significantly more fluorophores than previously possible. Here, we propose to utilize excitation-scanning of autofluorescence to examine tissues and diagnose pathologies. Spectra of autofluorescent molecules were obtained using a custom inverted microscope (TE-2000, Nikon Instruments) with a Xe arc lamp and thin film tunable filter array (VersaChrome, Semrock, Inc.) Scans utilized excitation wavelengths from 360 nm to 550 nm in 5 nm increments. The resultant spectra were used to examine hyperspectral image stacks from various collaborative studies, including an atherosclerotic rat model and a colon cancer study. Hyperspectral images were analyzed with ENVI and custom Matlab scripts including linear spectral unmixing (LSU) and principal component analysis (PCA). Initial results suggest the ability to separate the signals of endogenous fluorophores and measure the relative concentrations of fluorophores among healthy and diseased states of similar tissues. These results suggest pathology-specific changes to endogenous fluorophores can be detected using excitationscanning hyperspectral imaging. Future work will expand the library of pure molecules and will examine more defined disease states.

  14. Excitation of Nucleon Resonances

    International Nuclear Information System (INIS)

    Burkert, Volker D.

    2001-01-01

    I discuss developments in the area of nucleon resonance excitation, both necessary and feasible, that would put our understanding of nucleon structure in the regime of strong QCD on a qualitatively new level. They involve the collection of high quality data in various channels, a more rigorous approach in the search for ''missing'' resonances, an effort to compute some critical quantities in nucleon resonance excitations from first principles, i.e. QCD, and a proposal focused to obtain an understanding of a fundamental quantity in nucleon structure

  15. Room temperature excitation spectroscopy of single quantum dots

    Directory of Open Access Journals (Sweden)

    Christian Blum

    2011-08-01

    Full Text Available We report a single molecule detection scheme to investigate excitation spectra of single emitters at room temperature. We demonstrate the potential of single emitter photoluminescence excitation spectroscopy by recording excitation spectra of single CdSe nanocrystals over a wide spectral range of 100 nm. The spectra exhibit emission intermittency, characteristic of single emitters. We observe large variations in the spectra close to the band edge, which represent the individual heterogeneity of the observed quantum dots. We also find specific excitation wavelengths for which the single quantum dots analyzed show an increased propensity for a transition to a long-lived dark state. We expect that the additional capability of recording excitation spectra at room temperature from single emitters will enable insights into the photophysics of emitters that so far have remained inaccessible.

  16. Excitation dynamics and relaxation in a molecular heterodimer

    International Nuclear Information System (INIS)

    Balevičius, V.; Gelzinis, A.; Abramavicius, D.; Mančal, T.; Valkunas, L.

    2012-01-01

    Highlights: ► Dynamics of excitation within a heterogenous molecular dimer. ► Excited states can be swapped due to different reorganization energies of monomers. ► Conventional excitonic basis becomes renormalized due to interaction with the bath. ► Relaxation is independent of mutual positioning of monomeric excited states. -- Abstract: The exciton dynamics in a molecular heterodimer is studied as a function of differences in excitation and reorganization energies, asymmetry in transition dipole moments and excited state lifetimes. The heterodimer is composed of two molecules modeled as two-level systems coupled by the resonance interaction. The system-bath coupling is taken into account as a modulating factor of the molecular excitation energy gap, while the relaxation to the ground state is treated phenomenologically. Comparison of the description of the excitation dynamics modeled using either the Redfield equations (secular and full forms) or the Hierarchical quantum master equation (HQME) is demonstrated and discussed. Possible role of the dimer as an excitation quenching center in photosynthesis self-regulation is discussed. It is concluded that the system-bath interaction rather than the excitonic effect determines the excitation quenching ability of such a dimer.

  17. A vacuum-UV laser-induced fluorescence experiment for measurement of rotationally and vibrationally excited H2

    NARCIS (Netherlands)

    Vankan, P.J.W.; Heil, S.B.S.; Mazouffre, S.; Engeln, R.A.H.; Schram, D.C.; Döbele, H.F.

    2004-01-01

    An experimental setup is built to detect spatially resolved rovibrationally excited hydrogen molecules via laser-induced fluorescence. To excite the hydrogen molecules, laser radiation is produced in the vacuum UV part of the spectrum. The laser radiation is tunable between 120 nm and 230 nm and has

  18. Can Measured Synergy Excitations Accurately Construct Unmeasured Muscle Excitations?

    Science.gov (United States)

    Bianco, Nicholas A; Patten, Carolynn; Fregly, Benjamin J

    2018-01-01

    Accurate prediction of muscle and joint contact forces during human movement could improve treatment planning for disorders such as osteoarthritis, stroke, Parkinson's disease, and cerebral palsy. Recent studies suggest that muscle synergies, a low-dimensional representation of a large set of muscle electromyographic (EMG) signals (henceforth called "muscle excitations"), may reduce the redundancy of muscle excitation solutions predicted by optimization methods. This study explores the feasibility of using muscle synergy information extracted from eight muscle EMG signals (henceforth called "included" muscle excitations) to accurately construct muscle excitations from up to 16 additional EMG signals (henceforth called "excluded" muscle excitations). Using treadmill walking data collected at multiple speeds from two subjects (one healthy, one poststroke), we performed muscle synergy analysis on all possible subsets of eight included muscle excitations and evaluated how well the calculated time-varying synergy excitations could construct the remaining excluded muscle excitations (henceforth called "synergy extrapolation"). We found that some, but not all, eight-muscle subsets yielded synergy excitations that achieved >90% extrapolation variance accounted for (VAF). Using the top 10% of subsets, we developed muscle selection heuristics to identify included muscle combinations whose synergy excitations achieved high extrapolation accuracy. For 3, 4, and 5 synergies, these heuristics yielded extrapolation VAF values approximately 5% lower than corresponding reconstruction VAF values for each associated eight-muscle subset. These results suggest that synergy excitations obtained from experimentally measured muscle excitations can accurately construct unmeasured muscle excitations, which could help limit muscle excitations predicted by muscle force optimizations.

  19. Photoexcitation circular dichroism in chiral molecules

    Science.gov (United States)

    Beaulieu, S.; Comby, A.; Descamps, D.; Fabre, B.; Garcia, G. A.; Géneaux, R.; Harvey, A. G.; Légaré, F.; Mašín, Z.; Nahon, L.; Ordonez, A. F.; Petit, S.; Pons, B.; Mairesse, Y.; Smirnova, O.; Blanchet, V.

    2018-05-01

    Chiral effects appear in a wide variety of natural phenomena and are of fundamental importance in science, from particle physics to metamaterials. The standard technique of chiral discrimination—photoabsorption circular dichroism—relies on the magnetic properties of a chiral medium and yields an extremely weak chiral response. Here, we propose and demonstrate an orders of magnitude more sensitive type of circular dichroism in neutral molecules: photoexcitation circular dichroism. This technique does not rely on weak magnetic effects, but takes advantage of the coherent helical motion of bound electrons excited by ultrashort circularly polarized light. It results in an ultrafast chiral response and the efficient excitation of a macroscopic chiral density in an initially isotropic ensemble of randomly oriented chiral molecules. We probe this excitation using linearly polarized laser pulses, without the aid of further chiral interactions. Our time-resolved study of vibronic chiral dynamics opens a way to the efficient initiation, control and monitoring of chiral chemical change in neutral molecules at the level of electrons.

  20. Excitation of Stellar Pulsations

    DEFF Research Database (Denmark)

    Houdek, G.

    2012-01-01

    In this review I present an overview of our current understanding of the physical mechanisms that are responsible for the excitation of pulsations in stars with surface convection zones. These are typically cooler stars such as the δ Scuti stars, and stars supporting solar-like oscillations....

  1. Relativistic Coulomb excitation

    International Nuclear Information System (INIS)

    Winther, A.; Alder, K.

    1979-01-01

    Coulomb excitation of both target and projectile in relativistic heavy ion collisions is evaluated including the lowest order correction for the deviation from a straight line trajectory. Explicit results for differential and total cross sections are given in the form of tables and figures. (Auth.)

  2. Excited lepton search

    International Nuclear Information System (INIS)

    Behrend, H.J.; Buerger, J.; Criegee, L.; Fenner, H.; Field, J.H.; Franke, G.; Fuster, J.; Holler, Y.; Meyer, J.; Schroeder, V.; Sindt, H.; Timm, U.; Winter, G.G.; Zimmermann, W.; Bussey, P.J.; Campbell, A.J.; Dainton, J.B.; Hendry, D.; McCurrach, G.; Scarr, J.M.; Skillicorn, I.O.; Smith, K.M.; Blobel, V.; Poppe, M.; Spitzer, H.; Boer, W. de; Buschhorn, G.; Christiansen, W.; Grindhammer, G.; Gunderson, B.; Kiesling, C.; Kotthaus, R.; Kroha, H.; Lueers, D.; Oberlack, H.; Sack, B.; Schacht, P.; Shooshtari, G.; Wiedenmann, W.; Cordier, A.; Davier, M.; Fournier, D.; Gaillard, M.; Grivaz, J.F.; Haissinski, J.; Janot, P.; Journe, V.; Le Diberder, F.; Ros, E.; Spadafora, A.; Veillet, J.J.; Aleksan, R.; Cozzika, G.; Ducros, Y.; Jarry, P.; Lavagne, Y.; Ould Saada, F.; Pamela, J.; Pierre, F.; Zacek, J.; Alexander, G.; Bella, G.; Gnat, Y.; Grunhaus, J.

    1986-02-01

    Using the CELLO detector at PETRA we have searched for excited leptons by studying e + e - interactions which yield p + p - γγ, l + l - γ and γγ final states, where l = 3, μ or τ. We observe good agreement with QED and set new limits on e*, μ*, and τ* production. (orig.)

  3. Hardness and excitation energy

    Indian Academy of Sciences (India)

    It is shown that the first excitation energy can be given by the Kohn-Sham hardness (i.e. the energy difference of the ground-state lowest unoccupied and highest occupied levels) plus an extra term coming from the partial derivative of the ensemble exchange-correlation energy with respect to the weighting factor in the ...

  4. Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine)2(CN)2

    DEFF Research Database (Denmark)

    Kjær, Kasper Skov; Zhang, Wenkai; Alonso-Mori, Roberto

    2017-01-01

    We have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy)2(CN)2], where bpy=2,2′-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible...

  5. Hydride Molecules towards Nearby Galaxies

    Science.gov (United States)

    Monje, Raquel R.; La, Ngoc; Goldsmith, Paul

    2018-06-01

    Observations carried out by the Herschel Space Observatory revealed strong spectroscopic signatures from light hydride molecules within the Milky Way and nearby active galaxies. To better understand the chemical and physical conditions of the interstellar medium, we conducted the first comprehensive survey of hydrogen fluoride (HF) and water molecular lines observed through the SPIRE Fourier Transform Spectrometer. By collecting and analyzing the sub-millimeter spectra of over two hundred sources, we found that the HF J = 1 - 0 rotational transition which occurs at approximately 1232 GHz was detected in a total of 39 nearby galaxies both in absorption and emission. The analysis will determine the main excitation mechanism of HF in nearby galaxies and provide steady templates of the chemistry and physical conditions of the ISM to be used in the early universe, where observations of hydrides are more scarce.

  6. Magnetic transients in flares

    International Nuclear Information System (INIS)

    Zirin, H.; Tanaka, K.

    1981-01-01

    We present data on magnetic transients (mgtr's) observed in flares on 1980 July 1 and 5 with Big Bear videomagnetograph (VMG). The 1980 July 1 event was a white light flare in which a strong bipolar mgtr was observed, and a definite change in the sunspots occurred at the time of the flare. In the 1980 July 5 flare, a mgtr was observed in only one polarity, and, although no sunspot changes occurred simultaneous with the flare, major spot changes occurred in a period of hours

  7. Familial Transient Global Amnesia

    Directory of Open Access Journals (Sweden)

    R.Rhys Davies

    2012-12-01

    Full Text Available Following an episode of typical transient global amnesia (TGA, a female patient reported similar clinical attacks in 2 maternal aunts. Prior reports of familial TGA are few, and no previous account of affected relatives more distant than siblings or parents was discovered in a literature survey. The aetiology of familial TGA is unknown. A pathophysiological mechanism akin to that in migraine attacks, comorbidity reported in a number of the examples of familial TGA, is one possibility. The study of familial TGA cases might facilitate the understanding of TGA aetiology.

  8. Laser pulses for coherent xuv Raman excitation

    Science.gov (United States)

    Greenman, Loren; Koch, Christiane P.; Whaley, K. Birgitta

    2015-07-01

    We combine multichannel electronic structure theory with quantum optimal control to derive femtosecond-time-scale Raman pulse sequences that coherently populate a valence excited state. For a neon atom, Raman target populations of up to 13% are obtained. Superpositions of the ground and valence Raman states with a controllable relative phase are found to be reachable with up to 4.5% population and arbitrary phase control facilitated by the pump pulse carrier-envelope phase. Analysis of the optimized pulse structure reveals a sequential mechanism in which the valence excitation is reached via a fast (femtosecond) population transfer through an intermediate resonance state in the continuum rather than avoiding intermediate-state population with simultaneous or counterintuitive (stimulated Raman adiabatic passage) pulse sequences. Our results open a route to coupling valence excitations and core-hole excitations in molecules and aggregates that locally address specific atoms and represent an initial step towards realization of multidimensional spectroscopy in the xuv and x-ray regimes.

  9. Ultrafast transient-absorption of the solvated electron in water

    International Nuclear Information System (INIS)

    Kimura, Y.; Alfano, J.C.; Walhout, P.K.; Barbara, P.F.

    1994-01-01

    Ultrafast near infrared (NIR)-pump/variable wavelength probe transient-absorption spectroscopy has been performed on the aqueous solvated electron. The photodynamics of the solvated electron excited to its p-state are qualitatively similar to previous measurements of the dynamics of photoinjected electrons at high energy. This result confirms the previous interpretation of photoinjected electron dynamics as having a rate-limiting bottleneck at low energies presumably involving the p-state

  10. Ultrafast Degenerate Transient Lens Spectroscopy in Semiconductor Nanosctructures

    Directory of Open Access Journals (Sweden)

    Leontyev A.V.

    2015-01-01

    Full Text Available We report the non-resonant excitation and probing of the nonlinear refractive index change in bulk semiconductors and semiconductor quantum dots through degenerate transient lens spectroscopy. The signal oscillates at the center laser field frequency, and the envelope of the former in quantum dots is distinctly different from the one in bulk sample. We discuss the applicability of this technique for polarization state probing in semiconductor media with femtosecond temporal resolution.

  11. Numeric databases on the kinetics of transient species in solution

    International Nuclear Information System (INIS)

    Helman, W.P.; Hug, G.L.; Carmichael, Ian; Ross, A.B.

    1988-01-01

    A description is given of data compilations on the kinetics of transient species in solution. In particular information is available for the reactions of radicals in aqueous solution and for excited states such as singlet molecular oxygen and those of metal complexes in solution. Methods for compilation and use of the information in computer-readable form are also described. Emphasis is placed on making the database available for online searching. (author)

  12. Spin-lattice relaxation in phosphorescent triplet state molecules

    International Nuclear Information System (INIS)

    Verbeek, P.J.F.

    1979-01-01

    The present thesis contains the results of a study of spin-lattice relaxation (SLR) in the photo-excited triplet state of aromatic molecules, dissolved in a molecular host crystal. It appears that SLR in phosphorescent triplet state molecules often is related to the presence of so-called (pseudo) localized phonons in the molecular mixed crystals. These local phonons can be thought to correspond with vibrations (librations) of the guest molecule in the force field of the surrounding host molecules. Since the intermolecular forces are relatively weak, the frequencies corresponding with these vibrations are relatively low and usually are of the order of 10-30 cm -1 . (Auth.)

  13. Transient measurements with an ultrafast scanning tunneling microscope on semiconductor surfaces

    DEFF Research Database (Denmark)

    Keil, Ulrich Dieter Felix; Jensen, Jacob Riis; Hvam, Jørn Märcher

    1998-01-01

    We demonstrate: the use of an ultrafast scanning tunneling microscope on a semiconductor surface. Laser-induced transient signals with 1.8 ps rise time are detected, The investigated sample is a low-temperature grown GaAs layer plated on a sapphire substrate with a thin gold layer that serves as st...... bias contact, For comparison, the measurements are performed with the tip in contact to the sample as well as in tunneling above the surface, In contact and under bias, the transient signals are identified as a transient photocurrent, An additional signal is generated by a transient voltage induced...... by the nonuniform carrier density created by the absorption of the light (photo Dember effect). The transient depends in sign and in shape on the direction of optical excitation. This signal is the dominating transient in tunneling mode. The signals are explained by a capacitive coupling across the tunneling gap...

  14. Field-dependent molecular ionization and excitation energies: Implications for electrically insulating liquids

    Directory of Open Access Journals (Sweden)

    N. Davari

    2014-03-01

    Full Text Available The molecular ionization potential has a relatively strong electric-field dependence as compared to the excitation energies which has implications for electrical insulation since the excited states work as an energy sink emitting light in the UV/VIS region. At some threshold field, all the excited states of the molecule have vanished and the molecule is a two-state system with the ground state and the ionized state, which has been hypothesized as a possible origin of different streamer propagation modes. Constrained density-functional theory is used to calculate the field-dependent ionization potential of different types of molecules relevant for electrically insulating liquids. The low singlet-singlet excitation energies of each molecule have also been calculated using time-dependent density functional theory. It is shown that low-energy singlet-singlet excitation of the type n → π* (lone pair to unoccupied π* orbital has the ability to survive at higher fields. This type of excitation can for example be found in esters, diketones and many color dyes. For alkanes (as for example n-tridecane and cyclohexane on the other hand, all the excited states, in particular the σ → σ* excitations vanish in electric fields higher than 10 MV/cm. Further implications for the design of electrically insulating dielectric liquids based on the molecular ionization potential and excitation energies are discussed.

  15. Excitable particles in an optical torque wrench

    Science.gov (United States)

    Pedaci, Francesco; Huang, Zhuangxiong; van Oene, Maarten; Barland, Stephane; Dekker, Nynke H.

    2011-03-01

    The optical torque wrench is a laser trapping technique capable of applying and directly measuring torque on microscopic birefringent particles using spin momentum transfer, and has found application in the measurement of static torsional properties of biological molecules such as single DNAs. Motivated by the potential of the optical torque wrench to access the fast rotational dynamics of biological systems, a result of its all-optical manipulation and detection, we focus on the angular dynamics of the trapped birefringent particle, demonstrating its excitability in the vicinity of a critical point. This links the optical torque wrench to nonlinear dynamical systems such as neuronal and cardiovascular tissues, nonlinear optics and chemical reactions, all of which display an excitable binary (`all-or-none') response to input perturbations. On the basis of this dynamical feature, we devise and implement a conceptually new sensing technique capable of detecting single perturbation events with high signal-to-noise ratio and continuously adjustable sensitivity.

  16. Single molecule insights on conformational selection and induced fit mechanism

    DEFF Research Database (Denmark)

    Hatzakis, Nikos

    2014-01-01

    . To describe the molecular basis of this behavior, two main mechanisms have been advanced: 'induced fit' and 'conformational selection'. Our understanding of these models relies primarily on NMR, computational studies and kinetic measurements. These techniques report the average behavior of a large ensemble...... of unsynchronized molecules, often masking intrinsic dynamic behavior of proteins and biologically significant transient intermediates. Single molecule measurements are emerging as a powerful tool for characterizing protein function. They offer the direct observation and quantification of the activity, abundance...

  17. Measurand transient signal suppressor

    Science.gov (United States)

    Bozeman, Richard J., Jr. (Inventor)

    1994-01-01

    A transient signal suppressor for use in a controls system which is adapted to respond to a change in a physical parameter whenever it crosses a predetermined threshold value in a selected direction of increasing or decreasing values with respect to the threshold value and is sustained for a selected discrete time interval is presented. The suppressor includes a sensor transducer for sensing the physical parameter and generating an electrical input signal whenever the sensed physical parameter crosses the threshold level in the selected direction. A manually operated switch is provided for adapting the suppressor to produce an output drive signal whenever the physical parameter crosses the threshold value in the selected direction of increasing or decreasing values. A time delay circuit is selectively adjustable for suppressing the transducer input signal for a preselected one of a plurality of available discrete suppression time and producing an output signal only if the input signal is sustained for a time greater than the selected suppression time. An electronic gate is coupled to receive the transducer input signal and the timer output signal and produce an output drive signal for energizing a control relay whenever the transducer input is a non-transient signal which is sustained beyond the selected time interval.

  18. Transient regional osteoporosis

    Directory of Open Access Journals (Sweden)

    F. Trotta

    2011-09-01

    Full Text Available Transient osteoporosis of the hip and regional migratory osteoporosis are uncommon and probably underdiagnosed bone diseases characterized by pain and functional limitation mainly affecting weight-bearing joints of the lower limbs. These conditions are usually self-limiting and symptoms tend to abate within a few months without sequelae. Routine laboratory investigations are unremarkable. Middle aged men and women during the last months of pregnancy or in the immediate post-partum period are principally affected. Osteopenia with preservation of articular space and transitory edema of the bone marrow provided by magnetic resonance imaging are common to these two conditions, so they are also known by the term regional transitory osteoporosis. The appearance of bone marrow edema is not specific to regional transitory osteoporosis but can be observed in several diseases, i.e. trauma, reflex sympathetic dystrophy, avascular osteonecrosis, infections, tumors from which it must be differentiated. The etiology of this condition is unknown. Pathogenesis is still debated in particular the relationship with reflex sympathetic dystrophy, with which regional transitory osteoporosis is often identified. The purpose of the present review is to remark on the relationship between transient osteoporosis of the hip and regional migratory osteoporosis with particular attention to the bone marrow edema pattern and relative differential diagnosis.

  19. Using narrowband excitation to confirm that the S∗ state in carotenoids is not a vibrationally-excited ground state species

    Science.gov (United States)

    Jailaubekov, Askat E.; Song, Sang-Hun; Vengris, Mikas; Cogdell, Richard J.; Larsen, Delmar S.

    2010-02-01

    The hypothesis that S∗ is a vibrationally-excited ground-state population is tested and discarded for two carotenoid samples: β-carotene in solution and rhodopin glucoside embedded in the light harvesting 2 protein from Rhodopseudomonas acidophila. By demonstrating that the transient absorption signals measured in both systems that are induced by broadband (1000 cm -1) and narrowband (50 cm -1) excitation pulses are near identical and hence bandwidth independent, the impulsive stimulated Raman scattering mechanism proposed as the primary source for S∗ generation is discarded. To support this conclusion, previously published multi-pulse pump-dump-probe signals [17] are revisited to discard secondary mechanisms for S∗ formation.

  20. Single Molecule Spectroscopy on Photosynthetic Pigment-Protein Complexes

    CERN Document Server

    Jelezko, F; Schuler, S; Thews, E; Tietz, C; Wechsler, A; Wrachtrup, J

    2001-01-01

    Single molecule spectroscopy was applied to unravel the energy transfer pathway in photosynthetic pigment-protein complexes. Detailed analysis of excitation and fluorescence emission spectra has been made for peripheral plant antenna LHC II and Photosystem I from cyanobacterium Synechococcus elongatus. Optical transitions of individual pigments were resolved under nonselective excitation of antenna chlorophylls. High-resolution fluorescence spectroscopy of individual plant antenna LHC II indicates that at low temperatures, the excitation energy is localized on the red-most Chl a pool absorbing at 680 nm. More than one pigment molecule is responsible for the fluorescence emission of the LHC II trimer. The spectral lines of single Chl a molecules absorbing at 675 nm are broadened because of the Foerster energy transfer towards the red-most pigments. Low-temperature spectroscopy on single PS I trimers indicates that two subgroups of pigments, which are present in the red antenna pool, differ by the strength of t...

  1. Isotope separation by photodissociation of Van der Wall's molecules

    International Nuclear Information System (INIS)

    Lee, Y.T.

    1977-01-01

    A method of separating isotopes based on the dissociation of a Van der Waal's complex is described. A beam of molecules of a Van der Waal's complex containing, as one partner of the complex, a molecular species in which an element is present in a plurality of isotopes is subjected to radiation from a source tuned to a frequency which will selectively excite vibrational motion by a vibrational transition or through electronic transition of those complexed molecules of the molecular species which contain a desired isotope. Since the Van der Waal's binding energy is much smaller than the excitational energy of vibrational motion, the thus excited Van der Waal's complex dissociate into molecular components enriched in the desired isotope. The recoil velocity associated with vibrational to translational and rotational relaxation will send the separated molecules away from the beam whereupon the product enriched in the desired isotope can be separated from the constituents of the beam

  2. Sequential double excitations from linear-response time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Mosquera, Martín A.; Ratner, Mark A.; Schatz, George C., E-mail: g-schatz@northwestern.edu [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208 (United States); Chen, Lin X. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208 (United States); Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Ave., Lemont, Illinois 60439 (United States)

    2016-05-28

    Traditional UV/vis and X-ray spectroscopies focus mainly on the study of excitations starting exclusively from electronic ground states. However there are many experiments where transitions from excited states, both absorption and emission, are probed. In this work we develop a formalism based on linear-response time-dependent density functional theory to investigate spectroscopic properties of excited states. We apply our model to study the excited-state absorption of a diplatinum(II) complex under X-rays, and transient vis/UV absorption of pyrene and azobenzene.

  3. Transient absorption spectroscopy in biology using the Super-ACO storage ring FEL and the synchrotron radiation combination

    CERN Document Server

    Renault, E; De Ninno, G; Garzella, D; Hirsch, M; Nahon, L; Nutarelli, D

    2001-01-01

    The Super-ACO storage ring FEL, covering the UV range down to 300 nm with a high average power (300 mW at 350 nm) together with a high stability and long lifetime, is a unique tool for the performance of users applications. We present here the first pump-probe two color experiments on biological species using a storage ring FEL coupled to the synchrotron radiation. The intense UV pulse of the Super-ACO FEL is used to prepare a high initial concentration of chromophores in their first singlet electronic excited state. The nearby bending magnet synchrotron radiation provides, on the other hand a pulsed, white light continuum (UV-IR), naturally synchronized with the FEL pulses and used to probe the photochemical subsequent events and the associated transient species. We have demonstrated the feasibility with a dye molecule (POPOP) observing a two-color effect, signature of excited state absorption and a temporal signature with Acridine. Applications on various chromophores of biological interest are carried out,...

  4. Mechanism of calcium oxide excitation by atom hydrogen

    International Nuclear Information System (INIS)

    Kharlamov, V.F.

    1991-01-01

    Heterogeneous recombination of hydrogen atoms on the surface of calcium oxide proceeds according to the Langmuir-Hinshelwood mechanism with participation of atoms in two different states, belonging to adsorption centres of the same type. CaO excitation is broughty about by vibration-electron transitions during associative desorption of H 2 molecules

  5. On the nature of highly vibrationally excited states of thiophosgene

    Indian Academy of Sciences (India)

    Understanding the nature of the highly excited molecu- lar eigenstates is equivalent to deciphering the mecha- nism of intramolecular vibrational energy redistribution. (IVR) occurring in the molecule.1 However, the assign- ment of eigenstates is far from simple. The existence of and interplay of several strong anharmonic ...

  6. Fluorescent vibration-rotation excitation of cometary C2

    NARCIS (Netherlands)

    Gredel, R.; Dishoeck, van E.F.; Black, J.H.

    1989-01-01

    The statistical equilibrium equations that determine the population densities of the energy levels in cometary C2 molecules due to fluorescent excitation are examined in detail. The adopted model and molecular parameters are discussed, and a theoretical estimate is made of the two intercombination

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

    Science.gov (United States)

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

    2017-09-01

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

  8. Exotic nuclear excitations

    CERN Document Server

    Pancholi, S C

    2011-01-01

    By providing the reader with a foundational background in high spin nuclear structure physics and exploring exciting current discoveries in the field, this book presents new phenomena in a clear and compelling way. The quest for achieving the highest spin states has resulted in some remarkable successes which this monograph will address in comprehensive detail. The text covers an array of pertinent subject matter, including the rotational alignment and bandcrossings, magnetic rotation, triaxial strong deformation and wobbling motion and chirality in nuclei. Dr. Pancholi offers his readers a clearly-written and up-to-date treatment of the topics covered. The prerequisites for a proper appreciation are courses in nuclear physics and nuclear models and measurement techniques of observables like gamma-ray energies, intensities, multi-fold coincidences, angular correlations or distributions, linear polarization, internal conversion coefficients, short lifetime (pico-second range) of excited states etc. and instrum...

  9. Excited nuclei fragmentation

    International Nuclear Information System (INIS)

    Ngo, C.

    1986-11-01

    Experimental indications leading to the thought of a very excited nucleus fragmentation are resumed. Theoretical approaches are briefly described; they are used to explain the phenomenon in showing off they are based on a minimum information principle. This model is based on time dependent Thomas-Fermi calculation which allows the mean field effect description, and with a site-bound percolation model which allows the fluctuation description [fr

  10. Vibrational excitation of D2 by low energy electrons

    International Nuclear Information System (INIS)

    Buckman, S.J.; Phelps, A.V.

    1985-01-01

    Excitation coefficients for the production of vibrationally exicted D 2 by low energy electrons have been determined from measurements of the intensity of infrared emission from mixtures of D 2 and small concentrations of CO 2 or CO. The measurements were made using the electron drift tube technique and covered electric field to gas density ratios (E/n) from (5 to 80) x 10 -21 V m 2 , corresponding to mean electron energies between 0.45 and 4.5 eV. The CO 2 and CO concentrations were chosen to allow efficient excitation transfer from the D 2 to the carbon containing molecule, but to minimize direct excitation of the CO 2 or CO. The measured infrared intensities were normalized to predicted values for N 2 --CO 2 and N 2 --CO mixtures at E/n where the efficiency of vibrational excitation is known to be very close to 100%. The experimental excitation coefficients are in satisfactory agreement with predictions based on electron--D 2 cross sections at mean electron energies below 1 eV, but are about 50% too high at mean energies above about 2 eV. Application of the technique to H 2 did not yield useful vibrational excitation coefficients. The effective coefficients in H 2 --CO 2 mixtures were a factor of about 3 times the predicted values. For our H 2 --CO mixtures the excitation of CO via excitation transfer from H 2 is small compared to direct electron excitation of CO molecules. Published experiments and theories on electron--H 2 and electron--D 2 collisions are reviewed to obtain the cross sections used in the predictions

  11. The joy of transient chaos

    Energy Technology Data Exchange (ETDEWEB)

    Tél, Tamás [Institute for Theoretical Physics, Eötvös University, and MTA-ELTE Theoretical Physics Research Group, Pázmány P. s. 1/A, Budapest H-1117 (Hungary)

    2015-09-15

    We intend to show that transient chaos is a very appealing, but still not widely appreciated, subfield of nonlinear dynamics. Besides flashing its basic properties and giving a brief overview of the many applications, a few recent transient-chaos-related subjects are introduced in some detail. These include the dynamics of decision making, dispersion, and sedimentation of volcanic ash, doubly transient chaos of undriven autonomous mechanical systems, and a dynamical systems approach to energy absorption or explosion.

  12. Transient osteoporosis of the hip

    International Nuclear Information System (INIS)

    McWalter, Patricia; Hassan Ahmed

    2007-01-01

    Transient osteoporosis of the hip is an uncommon cause of hip pain, mostly affecting healthy middle-aged men and also women in the third trimester of pregnancy. We present a case of transient osteoporosis of the hip in a 33-year-old non-pregnant female patient. This case highlights the importance of considering a diagnosis of transient osteoporosis of the hip in patients who present with hip pain. (author)

  13. The ZTF Bright Transient Survey

    Science.gov (United States)

    Fremling, C.; Sharma, Y.; Kulkarni, S. R.; Miller, A. A.; Taggart, K.; Perley, D. A.; Gooba, A.

    2018-06-01

    As a supplement to the Zwicky Transient Facility (ZTF; ATel #11266) public alerts (ATel #11685) we plan to report (following ATel #11615) bright probable supernovae identified in the raw alert stream from the ZTF Northern Sky Survey ("Celestial Cinematography"; see Bellm & Kulkarni, 2017, Nature Astronomy 1, 71) to the Transient Name Server (https://wis-tns.weizmann.ac.il) on a daily basis; the ZTF Bright Transient Survey (BTS; see Kulkarni et al., 2018; arXiv:1710.04223).

  14. The joy of transient chaos.

    Science.gov (United States)

    Tél, Tamás

    2015-09-01

    We intend to show that transient chaos is a very appealing, but still not widely appreciated, subfield of nonlinear dynamics. Besides flashing its basic properties and giving a brief overview of the many applications, a few recent transient-chaos-related subjects are introduced in some detail. These include the dynamics of decision making, dispersion, and sedimentation of volcanic ash, doubly transient chaos of undriven autonomous mechanical systems, and a dynamical systems approach to energy absorption or explosion.

  15. Transient Infrared Emission Spectroscopy

    Science.gov (United States)

    Jones, Roger W.; McClelland, John F.

    1989-12-01

    Transient Infrared Emission Spectroscopy (TIRES) is a new technique that reduces the occurrence of self-absorption in optically thick solid samples so that analytically useful emission spectra may be observed. Conventional emission spectroscopy, in which the sample is held at an elevated, uniform temperature, is practical only for optically thin samples. In thick samples the emission from deep layers of the material is partially absorbed by overlying layers.1 This self-absorption results in emission spectra from most optically thick samples that closely resemble black-body spectra. The characteristic discrete emission bands are severely truncated and altered in shape. TIRES bypasses this difficulty by using a laser to heat only an optically thin surface layer. The increased temperature of the layer is transient since the layer will rapidly cool and thicken by thermal diffusion; hence the emission collection must be correlated with the laser heating. TIRES may be done with both pulsed and cw lasers.2,3 When a pulsed laser is used, the spectrometer sampling must be synchronized with the laser pulsing so that only emission during and immediately after each laser pulse is observed.3 If a cw laser is used, the sample must move rapidly through the beam. The hot, transient layer is then in the beam track on the sample at and immediately behind the beam position, so the spectrometer field of view must be limited to this region near the beam position.2 How much self-absorption the observed emission suffers depends on how thick the heated layer has grown by thermal diffusion when the spectrometer samples the emission. Use of a pulsed laser synchronized with the spectrometer sampling readily permits reduction of the time available for heat diffusion to about 100 acs .3 When a cw laser is used, the heat-diffusion time is controlled by how small the spectrometer field of view is and by how rapidly the sample moves past within this field. Both a very small field of view and a

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  17. Harmonically excited orbital variations

    International Nuclear Information System (INIS)

    Morgan, T.

    1985-01-01

    Rephrasing the equations of motion for orbital maneuvers in terms of Lagrangian generalized coordinates instead of Newtonian rectangular cartesian coordinates can make certain harmonic terms in the orbital angular momentum vector more readily apparent. In this formulation the equations of motion adopt the form of a damped harmonic oscillator when torques are applied to the orbit in a variationally prescribed manner. The frequencies of the oscillator equation are in some ways unexpected but can nonetheless be exploited through resonant forcing functions to achieve large secular variations in the orbital elements. Two cases are discussed using a circular orbit as the control case: (1) large changes in orbital inclination achieved by harmonic excitation rather than one impulsive velocity change, and (2) periodic and secular changes to the longitude of the ascending node using both stable and unstable excitation strategies. The implications of these equations are also discussed for both artificial satellites and natural satellites. For the former, two utilitarian orbits are suggested, each exploiting a form of harmonic excitation. 5 refs

  18. The status of molecules

    International Nuclear Information System (INIS)

    Barnes, T.; Oak Ridge National Lab., TN; Tennessee Univ., Knoxville, TN

    1994-06-01

    This report summarizes the experimental and theoretical status of hadronic molecules, which are weakly-bound states of two or more hadrons. We begin with a brief history of the subject and discuss a few good candidates, and then abstract some signatures for molecules which may be of interest in the classification of possible molecule states. Next we argue that a more general understanding of 2 → 2 hadron-hadron scattering amplitudes will be crucial for molecule searches, and discuss some of our recent work in this area. We conclude with a discussion of a few more recent molecule candidates (notably the f o (1710)) which are not well established as molecules but satisfy some of the expected signatures. (Author)

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

    Science.gov (United States)

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

    2013-11-01

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

  20. Low-lying excited states by constrained DFT

    Science.gov (United States)

    Ramos, Pablo; Pavanello, Michele

    2018-04-01

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