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Sample records for excited state structural

  1. Structure of excited states and properties of organic dyes

    NASA Astrophysics Data System (ADS)

    Klessinger, M.

    1992-03-01

    Optimized geometries and charge distributions for the ground state and the first allowed π,π* excited singlet state are reported for some polyenes, polyene aldehydes, merocyanines and cyanines, which may be considered as representatives of conjugated chain chromophores of organic dyes. The dependence of excited state properties on molecular structure is discussed in relation to spectroscopic properties of these systems.

  2. Computing electronic structures: A new multiconfiguration approach for excited states

    NASA Astrophysics Data System (ADS)

    Cancès, Éric; Galicher, Hervé; Lewin, Mathieu

    2006-02-01

    We present a new method for the computation of electronic excited states of molecular systems. This method is based upon a recent theoretical definition of multiconfiguration excited states [due to one of us, see M. Lewin, Solutions of the multiconfiguration equations in quantum chemistry, Arch. Rat. Mech. Anal. 171 (2004) 83-114]. Our algorithm, dedicated to the computation of the first excited state, always converges to a stationary state of the multiconfiguration model, which can be interpreted as an approximate excited state of the molecule. The definition of this approximate excited state is variational. An interesting feature is that it satisfies a non-linear Hylleraas-Undheim-MacDonald type principle: the energy of the approximate excited state is an upper bound to the true excited state energy of the N-body Hamiltonian. To compute the first excited state, one has to deform paths on a manifold, like this is usually done in the search for transition states between reactants and products on potential energy surfaces. We propose here a general method for the deformation of paths which could also be useful in other settings. We also compare our method to other approaches used in Quantum Chemistry and give some explanation of the unsatisfactory behaviours which are sometimes observed when using the latters. Numerical results for the special case of two-electron systems are provided: we compute the first singlet excited state potential energy surface of the H2 molecule.

  3. Computing electronic structures: A new multiconfiguration approach for excited states

    SciTech Connect

    Cances, Eric . E-mail: cances@cermics.enpc.fr; Galicher, Herve . E-mail: galicher@cermics.enpc.fr; Lewin, Mathieu . E-mail: lewin@cermic.enpc.fr

    2006-02-10

    We present a new method for the computation of electronic excited states of molecular systems. This method is based upon a recent theoretical definition of multiconfiguration excited states [due to one of us, see M. Lewin, Solutions of the multiconfiguration equations in quantum chemistry, Arch. Rat. Mech. Anal. 171 (2004) 83-114]. Our algorithm, dedicated to the computation of the first excited state, always converges to a stationary state of the multiconfiguration model, which can be interpreted as an approximate excited state of the molecule. The definition of this approximate excited state is variational. An interesting feature is that it satisfies a non-linear Hylleraas-Undheim-MacDonald type principle: the energy of the approximate excited state is an upper bound to the true excited state energy of the N-body Hamiltonian. To compute the first excited state, one has to deform paths on a manifold, like this is usually done in the search for transition states between reactants and products on potential energy surfaces. We propose here a general method for the deformation of paths which could also be useful in other settings. We also compare our method to other approaches used in Quantum Chemistry and give some explanation of the unsatisfactory behaviours which are sometimes observed when using the latter. Numerical results for the special case of two-electron systems are provided: we compute the first singlet excited state potential energy surface of the H {sub 2} molecule.

  4. Lifetimes and Structure of Excited States of 73AS

    NASA Astrophysics Data System (ADS)

    Bucurescu, D.; Căta-Danil, I.; Ivaşcu, M.; Mărginean, N.; Stroe, L.; Ur, C. A.; Dinu, N.

    The lifetimes of twelve low spin excited states in 73As, below 2 MeV excitation, have been measured with the DSA method in the 73Ge(p,nγ) reaction. The existing data (energy levels, electromagnetic moments, transition probabilities and branching ratios, one-nucleon transfer spectroscopic factors) are discussed in the frame of multi-shell interacting boson-fermion model calculations. A good agreement is obtained for a large number of levels.

  5. Lifetimes and structure of excited states of 115Sb

    NASA Astrophysics Data System (ADS)

    Lobach, Yu. N.; Bucurescu, D.

    1998-06-01

    Lifetimes of excited states of 115Sb were measured by the Doppler shift attenuation method in the (α,2nγ) reaction at Eα = 27.2 MeV. The experimental level scheme and the electromagnetic transition probabilities have been interpreted in terms of the interacting boson-fermion model. A reasonable agreement with the experiment was obtained for the positive-parity states. The experimental data also show the applicability of the cluster-vibrational model for the mixing of two 9/2+ states having different intrinsic configurations.

  6. Excitation Energy Transfer Dynamics and Excited-State Structure in Chlorosomes of Chlorobium phaeobacteroides

    PubMed Central

    Pšenčík, Jakub; Ma, Ying-Zhong; Arellano, Juan B.; Hála, Jan; Gillbro, Tomas

    2003-01-01

    The excited-state relaxation within bacteriochlorophyll (BChl) e and a in chlorosomes of Chlorobium phaeobacteroides has been studied by femtosecond transient absorption spectroscopy at room temperature. Singlet-singlet annihilation was observed to strongly influence both the isotropic and anisotropic decays. Pump intensities in the order of 1011 photons × pulse−1 × cm−2 were required to obtain annihilation-free conditions. The most important consequence of applied very low excitation doses is an observation of a subpicosecond process within the BChl e manifold (∼200–500 fs), manifesting itself as a rise in the red part of the Qy absorption band of the BChl e aggregates. The subsequent decay of the kinetics measured in the BChl e region and the corresponding rise in the baseplate BChl a is not single-exponential, and at least two components are necessary to fit the data, corresponding to several BChl e→BChl a transfer steps. Under annihilation-free conditions, the anisotropic kinetics show a generally slow decay within the BChl e band (10–20 ps) whereas it decays more rapidly in the BChl a region (∼1 ps). Analysis of the experimental data gives a detailed picture of the overall time evolution of the energy relaxation and energy transfer processes within the chlorosome. The results are interpreted within an exciton model based on the proposed structure. PMID:12547796

  7. Ground-state and excited-state structures of tungsten-benzylidyne complexes.

    PubMed

    Lovaasen, Benjamin M; Lockard, Jenny V; Cohen, Brian W; Yang, Shujiang; Zhang, Xiaoyi; Simpson, Cheslan K; Chen, Lin X; Hopkins, Michael D

    2012-05-21

    The molecular structure of the tungsten-benzylidyne complex trans-W(≡CPh)(dppe)(2)Cl (1; dppe = 1,2-bis(diphenylphosphino)ethane) in the singlet (d(xy))(2) ground state and luminescent triplet (d(xy))(1)(π*(WCPh))(1) excited state (1*) has been studied using X-ray transient absorption spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations. Molecular-orbital considerations suggest that the W-C and W-P bond lengths should increase in the excited state because of the reduction of the formal W-C bond order and decrease in W→P π-backbonding, respectively, between 1 and 1*. This latter conclusion is supported by comparisons among the W-P bond lengths obtained from the X-ray crystal structures of 1, (d(xy))(1)-configured 1(+), and (d(xy))(2) [W(CPh)(dppe)(2)(NCMe)](+) (2(+)). X-ray transient absorption spectroscopic measurements of the excited-state structure of 1* reveal that the W-C bond length is the same (within experimental error) as that determined by X-ray crystallography for the ground state 1, while the average W-P/W-Cl distance increases by 0.04 Å in the excited state. The small excited-state elongation of the W-C bond relative to the M-E distortions found for M(≡E)L(n) (E = O, N) compounds with analogous (d(xy))(1)(π*(ME))(1) excited states is due to the π conjugation within the WCPh unit, which lessens the local W-C π-antibonding character of the π*(WCPh) lowest unoccupied molecular orbital (LUMO). These conclusions are supported by DFT calculations on 1 and 1*. The similar core bond distances of 1, 1(+), and 1* indicates that the inner-sphere reorganization energy associated with ground- and excited-state electron-transfer reactions is small.

  8. Ground-state and excited-state structures of tungsten-benzylidyne complexes

    SciTech Connect

    Lovaasen, B. M.; Lockard, J. V.; Cohen, B. W.; Yang, S.; Zhang, X.; Simpson, C. K.; Chen, L. X.; Hopkins, M. D.

    2012-01-01

    The molecular structure of the tungsten-benzylidyne complex trans-W({triple_bond}CPh)(dppe){sub 2}Cl (1; dppe = 1,2-bis(diphenylphosphino)ethane) in the singlet (d{sub xy}){sup 2} ground state and luminescent triplet (d{sub xy}){sup 1}({pi}*(WCPh)){sup 1} excited state (1*) has been studied using X-ray transient absorption spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations. Molecular-orbital considerations suggest that the W-C and W-P bond lengths should increase in the excited state because of the reduction of the formal W-C bond order and decrease in W {yields} P {pi}-backbonding, respectively, between 1 and 1*. This latter conclusion is supported by comparisons among the W-P bond lengths obtained from the X-ray crystal structures of 1, (d{sub xy}){sup 1}-configured 1{sup +}, and (d{sub xy}){sup 2} [W(CPh)(dppe){sub 2}(NCMe)]{sup +} (2{sup +}). X-ray transient absorption spectroscopic measurements of the excited-state structure of 1* reveal that the W-C bond length is the same (within experimental error) as that determined by X-ray crystallography for the ground state 1, while the average W-P/W-Cl distance increases by 0.04 {angstrom} in the excited state. The small excited-state elongation of the W-C bond relative to the M-E distortions found for M({triple_bond}E)L{sub n} (E = O, N) compounds with analogous (d{sub xy}){sup 1}({pi}*(ME)){sup 1} excited states is due to the {pi} conjugation within the WCPh unit, which lessens the local W-C {pi}-antibonding character of the {pi}*(WCPh) lowest unoccupied molecular orbital (LUMO). These conclusions are supported by DFT calculations on 1 and 1*. The similar core bond distances of 1, 1{sup +}, and 1* indicates that the inner-sphere reorganization energy associated with ground- and excited-state electron-transfer reactions is small.

  9. Configuration interaction study of the ground and excited states of TiO2 ring structures

    NASA Astrophysics Data System (ADS)

    Tsuchiya, Takashi; Whitten, Jerry L.

    2011-03-01

    Theoretical studies of the ground and lowest excited singlet and triplet states of a series of titanium dioxide ring structures, (TiO2)2n, n = 3-9, are reported. Calculations are based on many-electron configuration theory, where energies of states and geometrical structures are determined by variational energy minimization. The lowest energy excited states correspond to excitations from oxygen 2p levels to unoccupied 3d orbitals on titanium. For each ring system, two types of excited state solutions are investigated: those that maintain periodic symmetry for individual orbitals and solutions that allow the symmetry to be broken. The latter solutions which correspond to localized states or excitons are found to be significantly lower in energy than the symmetric solutions. We compare the vertical excitation energy of these well-defined geometrical structures with size effects reported in experimental studies.

  10. The Structure of the Nucleon and it's Excited States

    SciTech Connect

    1995-02-20

    The past year has been an exciting and productive one for particle physics research at Abilene Christian University. The thrust of our experimental investigations is the study of the nucleon and its excited states. Laboratories where these investigations are presently being conducted are the AGS at Brookhaven, Fermilab and LAMPF. Some analysis of the data for experiments at the Petersburg Nuclear Physics Institute (Gatchina, Russia) is still in progress. Scheduling of activities at different laboratories inevitably leads to occasional conflicts. This likelihood is increased by the present budget uncertainties at the laboratories that make long-term scheduling difficult. For the most part, the investigators have been able to avoid such conflicts. Only one experiment received beam time in 1994 (E890 at the AGS). The situation for 1995-1996 also appears manageable at this point. E890 and another AGS experiment (E909) will run through May, 1995. El 178 at LAMPF is presently scheduled for August/September 1995. E866 at Fermilab is scheduled to start in Spring/Summer 1996. Undergraduate student involvement has been a key element in this research contract since its inception. Summer students participated at all of the above laboratories in 1994 and the same is planned in 1995. A transition to greater involvement by graduate students will provide cohesiveness to ACU involvement at a given laboratory and full-time on-site involvement in the longer running experiments at FNAL and BNL. Funds to support a full-time graduate student are requested this year. Finally, collaboration by Russian, Croatian and Bosnian scientists has proven to be mutually beneficial to these experimental programs and to the overall programs at the institutions involved. Past support has been augmented by other grants from government agencies and from the Research Council at Abilene Christian University. Additional funds are requested in this renewal to enable more programmatic support for these

  11. Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics.

    PubMed

    Neville, Simon P; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S

    2016-10-14

    We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L(2) method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

  12. Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

    NASA Astrophysics Data System (ADS)

    Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

    2016-10-01

    We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

  13. Triplet excited states of cyclic disulfides and related compounds: electronic structures, geometries, energies, and decay.

    PubMed

    Ginagunta, Saroja; Bucher, Götz

    2011-02-03

    We have performed a computational study on the properties of a series of heterocycles bearing two adjacent heteroatoms, focusing on the structures and electronic properties of their first excited triplet states. If the heteroatoms are both heavy chalcogens (S, Se, or Te) or isoelectronic species, then the lowest excited triplet state usually has (π*, σ*) character. The triplet energies are fairly low (30-50 kcal mol(-1)). The (π*, σ*) triplet states are characterized by a significantly lengthened bond between the two heteroatoms. Thus, in 1,2-dithiolane (1b), the S-S bond length is calculated to be 2.088 Å in the singlet ground state and 2.568 Å in the first triplet excited state. The spin density is predicted to be localized almost exclusively on the sulfur atoms. Replacing one heavy chalcogen atom by an oxygen atom or an NR group results in a significant destabilization of the (π*, σ*) triplet excited state, which then no longer is lower in energy than an open-chain biradical. The size of the heterocyclic ring also contributes to the stability of the (π*, σ*) triplet state, with five-membered rings being more favorable than six-membered rings. Benzoannulation, finally, usually lowers the energy of the (π*, σ*) triplet excited states. If one of the heteroatoms is an oxygen or nitrogen atom, however, the corresponding lowest triplet states are better described as σ,π-biradicals.

  14. Glycine in an electronically excited state: ab initio electronic structure and dynamical calculations.

    PubMed

    Muchová, Eva; Slavícek, Petr; Sobolewski, Andrzej L; Hobza, Pavel

    2007-06-21

    The goal of this study is to explore the photochemical processes following optical excitation of the glycine molecule into its two low-lying excited states. We employed electronic structure methods at various levels to map the PES of the ground state and the two low-lying excited states of glycine. It follows from our calculations that the photochemistry of glycine can be regarded as a combination of photochemical behavior of amines and carboxylic acid. The first channel (connected to the presence of amino group) results in ultrafast decay, while the channels characteristic for the carboxylic group occur on a longer time scale. Dynamical calculations provided the branching ratio for these channels. We also addressed the question whether conformationally dependent photochemistry can be observed for glycine. While electronic structure calculations favor this possibility, the ab initio multiple spawning (AIMS) calculations showed only minor relevance of the reaction path resulting in conformationally dependent dynamics.

  15. Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes.

    PubMed

    Lockard, Jenny V; Kabehie, Sanaz; Zink, Jeffrey I; Smolentsev, Grigory; Soldatov, Alexander; Chen, Lin X

    2010-11-18

    This study explores the influences of steric hindrance and excited state solvent ligation on the excited state dynamics of Cu(I) diimine complexes. Ultrafast excited state dynamics of Cu(I)bis(3,8-di(ethynyltrityl)-1,10-phenanthroline) [Cu(I)(detp)(2)](+) are measured using femtosecond transient absorption spectroscopy. The steady state electronic absorption spectra and measured lifetimes are compared to those of Cu(I)bis(1,10-phenanthroline), [Cu(I)(phen)(2)](+), and Cu(I)bis(2-9-dimethyl-1,10-phenanthroline), [Cu(I)(dmp)(2)](+), model complexes to determine the influence of different substitution patterns of the phenanthroline ligand on the structural dynamics associated with the metal to ligand charge transfer excited states. Similarities between the [Cu(I)(detp)(2)](+) and [Cu(I)(phen)(2)](+) excited state lifetimes were observed in both coordinating and noncoordinating solvents and attributed to the lack of steric hindrance from substitution at the 2- and 9-positions. The solution-phase X-ray absorption spectra of [Cu(I)(detp)(2)](+), [Cu(I)(phen)(2)](+), and [Cu(I)(dmp)(2)](+) are reported along with finite difference method calculations that are used to determine the degree of ground state dihedral angle distortion in solution and to account for the pre-edge features observed in the XANES region.

  16. Electronic and structural properties of low-lying excited states of vitamin B12.

    PubMed

    Lodowski, Piotr; Jaworska, Maria; Kornobis, Karina; Andruniów, Tadeusz; Kozlowski, Pawel M

    2011-11-17

    Time-dependent density functional theory (TD-DFT) has been applied to explore electronically excited states of vitamin B(12) (cyanocobalamin or CNCbl). To explain why the Co-C bond in CNCbl does not undergo photodissociation under conditions of simple photon excitation, electronically excited states have been computed along the Co-C(CN) stretched coordinate. It was found that the repulsive (3)(σ(Co-C) → σ*(Co-C)) triplet state drops in energy as the Co-C(CN) bond lengthens, but it does not become dissociative. Low-lying excited states were also computed as function of two axial bond lengths. Two energy minima have been located on the S(1)/CNCbl, as well as T(1)/CNCbl, surfaces. The full geometry optimization was carried out for each minimum and electronic properties associated with each optimized structure were analyzed in details. One minimum was described as excitation having mixed ππ*/MLCT (metal-to-ligand charge transfer) character, while the second as ligand-to-metal charge transfer (LMCT) transition. Neither of them, however, can be viewed as pure MLCT or LMCT transitions since additional excitation to or from σ-bonds (SB) of N-Co-C unit have also noticeable contributions. Inclusion of solvent altered the character of one of the excitations from ππ*/MLCT/SBLCT to ππ*/LMCT/LSBCT-type, and therefore, both of them gained significant contribution from LMCT/LSBCT transition. Finally, the nature of S(1) electronic state has been comparatively analyzed in CNCbl and MeCbl cobalamins.

  17. Ultrafast electron diffraction: Excited state structures and chemistries of aromatic carbonyls

    SciTech Connect

    Park, Sang Tae; Feenstra, Jonathan S.; Zewail, Ahmed H.

    2006-05-07

    The photophysics and photochemistry of molecules with complex electronic structures, such as aromatic carbonyls, involve dark structures of radiationless processes. With ultrafast electron diffraction (UED) of isolated molecular beams it is possible to determine these transient structures, and in this contribution we examine the nature of structural dynamics in two systems, benzaldehyde and acetophenone. Both molecules are seen to undergo a bifurcation upon excitation (S{sub 2}). Following femtosecond conversion to S{sub 1}, the bifurcation leads to the formation of molecular dissociation products, benzene and carbon monoxide for benzaldehyde, and benzoyl and methyl radicals for acetophenone, as well as intersystem crossing to the triplet state in both cases. The structure of the triplet state was determined to be 'quinoidlike' of {pi}{pi}* character with the excitation being localized in the phenyl ring. For the chemical channels, the product structures were also determined. The difference in photochemistry between the two species is discussed with respect to the change in large amplitude motion caused by the added methyl group in acetophenone. This discussion is also expanded to compare these results with the prototypical aliphatic carbonyl compounds, acetaldehyde and acetone. From these studies of structural dynamics, experimental and theoretical, we provide a landscape picture for, and the structures involved in, the radiationless pathways which determine the fate of molecules following excitation. For completeness, the UED methodology and the theoretical framework for structure determination are described in this full account of an earlier communication [J. S. Feenstra et al., J. Chem. Phys. 123, 221104 (2005)].

  18. Vibronic structure and coupling of higher excited electronic states in carotenoids

    NASA Astrophysics Data System (ADS)

    Krawczyk, Stanisław; Luchowski, Rafał

    2013-03-01

    Absorption spectra of all-trans carotenoids (lycopene, violaxanthin, ζ-carotene) at low temperature exhibit peculiar features in the UV range. The transition to the 11Ag+ state ('cis-band') weakens on cooling, indicating that it is induced by thermal deformations of the conjugated chain. The higher energy band has unique vibrational structure indicating the vibronic coupling of nBu with another electronic state. The electroabsorption spectra point to the electric field-induced mixing of the nBu state with the vibrational continuum of a lower-lying excited state (Fano effect). These observations widen the basis for elucidation of the vibronic coupling effects in the lower excited states.

  19. Infrared/ultraviolet quadruple resonance spectroscopy to investigate structures of electronically excited states

    SciTech Connect

    Weiler, M.; Bartl, K.; Gerhards, M.

    2012-03-21

    Molecular beam investigations in combination with IR/UV spectroscopy offer the possibility to obtain structural information on isolated molecules and clusters. One of the demanding tasks is the discrimination of different isomers, e.g., by the use of isomer specific UV excitations. If this discrimination fails due to overlaying UV spectra of different isomers, IR/IR methods offer another possibility. Here, we present a new IR/UV/IR/UV quadruple resonance technique to distinguish between different isomers especially in the electronically excited state. Due to the IR spectra, structural changes and photochemical pathways in excited states can be assigned and identified. The method is applied to the dihydrated cluster of 3-hydroxyflavone which has been investigated as photochemically relevant system and proton wire model in the S{sub 1} state. By applying the new IR/UV/IR/UV technique, we are able to show experimentally that both in the electronic ground (S{sub 0}) and the electronically excited state (S{sub 1}) two isomers have to be assigned.

  20. Effect of structure and size on the excited states dynamics of CaArn clusters

    NASA Astrophysics Data System (ADS)

    Plata, Jose J.; Heitz, Marie-Catherine; Spiegelman, Fernand

    2013-01-01

    The time-resolved photoelectron spectra, probing the non-adiabatic dynamics of CaAr n clusters excited by a pump pulse in the vicinity of the 4 s4 p 1P line of calcium, are simulated. The simulations involve Diatomics-In-Molecules modelling of the excited electronic structure, excited states dynamics with electronic transitions, and classical approximations to derive the time-resolved photoelectron spectra. The oscillations in the time-dependence of the spectra, associated with the relative motion of calcium with respect to the argon cluster, and the corresponding nonadiabatic relaxation processes are analysed according to cluster size ( n ≈ 55 and 147), structure (icosahedral versus cuboctahedral shape) and local environment (substitution versus surface deposition of calcium, surface type).

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    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.

  2. Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

    SciTech Connect

    Van Tassle, Aaron Justin

    2006-01-01

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

  3. Effect of structural modifications on the spectroscopic properties and dynamics of the excited states of peridinin

    PubMed Central

    Chatterjee, Nirmalya; Niedzwiedzki, Dariusz M.; Aoki, Kazuyoshi; Kajikawa, Takayuki; Katsumura, Shigeo; Hashimoto, Hideki; Frank, Harry A.

    2013-01-01

    The spectroscopic properties and dynamics of the lowest excited singlet states of peridinin and two derivatives have been studied by steady-state absorption and fast-transient optical spectroscopic techniques. One derivative denoted PerOlEs, possesses a double bond and a methyl ester group instead of the r-ylid-enebutenolide of peridinin. Another derivative denoted PerAcEs, is the biosynthetic precursor of peridinin and possesses a triple bond and a methyl ester group corresponding to the r-ylidenbutenolide function. Ultrafast time-resolved spectroscopic experiments in the visible and near-infrared regions were performed on the molecules and reveal the energies and regarding the structural features and interactions responsible for the unusual solvent-induced changes in the steady-state and transient absorption spectra and dynamics of dynamics of the excited electronic states. The data also provide information peridinin. PMID:19000898

  4. Electronic and structural elements that regulate the excited-state dynamics in purine nucleobase derivatives.

    PubMed

    Crespo-Hernández, Carlos E; Martínez-Fernández, Lara; Rauer, Clemens; Reichardt, Christian; Mai, Sebastian; Pollum, Marvin; Marquetand, Philipp; González, Leticia; Corral, Inés

    2015-04-08

    The excited-state dynamics of the purine free base and 9-methylpurine are investigated using experimental and theoretical methods. Femtosecond broadband transient absorption experiments reveal that excitation of these purine derivatives in aqueous solution at 266 nm results primarily in ultrafast conversion of the S2(ππ*) state to the vibrationally excited (1)nπ* state. Following vibrational and conformational relaxation, the (1)nπ* state acts as a doorway state in the efficient population of the triplet manifold with an intersystem crossing lifetime of hundreds of picoseconds. Experiments show an almost 2-fold increase in the intersystem crossing rate on going from polar aprotic to nonpolar solvents, suggesting that a solvent-dependent energy barrier must be surmounted to access the singlet-to-triplet crossing region. Ab initio static and surface-hopping dynamics simulations lend strong support to the proposed relaxation mechanism. Collectively, the experimental and computational results demonstrate that the accessibility of the nπ* states and the topology of the potential energy surfaces in the vicinity of conical intersections are key elements in controlling the excited-state dynamics of the purine derivatives. From a structural perspective, it is shown that the purine chromophore is not responsible for the ultrafast internal conversion in the adenine and guanine monomers. Instead, C6 functionalization plays an important role in regulating the rates of radiative and nonradiative relaxation. C6 functionalization inhibits access to the (1)nπ* state while simultaneously facilitating access to the (1)ππ*(La)/S0 conical intersection, such that population of the (1)nπ* state cannot compete with the relaxation pathways to the ground state involving ring puckering at the C2 position.

  5. Electronic and Structural Elements That Regulate the Excited-State Dynamics in Purine Nucleobase Derivatives

    PubMed Central

    2015-01-01

    The excited-state dynamics of the purine free base and 9-methylpurine are investigated using experimental and theoretical methods. Femtosecond broadband transient absorption experiments reveal that excitation of these purine derivatives in aqueous solution at 266 nm results primarily in ultrafast conversion of the S2(ππ*) state to the vibrationally excited 1nπ* state. Following vibrational and conformational relaxation, the 1nπ* state acts as a doorway state in the efficient population of the triplet manifold with an intersystem crossing lifetime of hundreds of picoseconds. Experiments show an almost 2-fold increase in the intersystem crossing rate on going from polar aprotic to nonpolar solvents, suggesting that a solvent-dependent energy barrier must be surmounted to access the singlet-to-triplet crossing region. Ab initio static and surface-hopping dynamics simulations lend strong support to the proposed relaxation mechanism. Collectively, the experimental and computational results demonstrate that the accessibility of the nπ* states and the topology of the potential energy surfaces in the vicinity of conical intersections are key elements in controlling the excited-state dynamics of the purine derivatives. From a structural perspective, it is shown that the purine chromophore is not responsible for the ultrafast internal conversion in the adenine and guanine monomers. Instead, C6 functionalization plays an important role in regulating the rates of radiative and nonradiative relaxation. C6 functionalization inhibits access to the 1nπ* state while simultaneously facilitating access to the 1ππ*(La)/S0 conical intersection, such that population of the 1nπ* state cannot compete with the relaxation pathways to the ground state involving ring puckering at the C2 position. PMID:25763596

  6. Strong steric hindrance effect on excited state structural dynamics of Cu(I) diimine complexes.

    PubMed

    Gothard, Nosheen A; Mara, Michael W; Huang, Jier; Szarko, Jodi M; Rolczynski, Brian; Lockard, Jenny V; Chen, Lin X

    2012-03-08

    The metal-to-ligand-charge-transfer (MLCT) excited state of Cu(I) diimine complexes is known to undergo structural reorganization, transforming from a pseudotetrahedral D(2d) symmetry in the ground state to a flattened D(2) symmetry in the MLCT state, which allows ligation with a solvent molecule, forming an exciplex intermediate. Therefore, the structural factors that influence the coordination geometry change and the solvent accessibility to the copper center in the MLCT state could be used to control the excited state properties. In this study, we investigated an extreme case of the steric hindrance caused by attaching bulky tert-butyl groups in bis(2,9-di-tert-butyl-1,10-phenanthroline)copper(I), [Cu(I)(dtbp)(2)](+). The two bulky tert-butyl groups on the dtbp ligand lock the MLCT state into the pseudotetrahedral coordination geometry and completely block the solvent access to the copper center in the MLCT state of [Cu(I)(dtbp)(2)](+). Using ultrafast transient absorption spectroscopy and time-resolved emission spectroscopy, we investigated the MLCT state property changes due to the steric hindrance and demonstrated that [Cu(I)(dtbp)(2)](+) exhibited a long-lived emission but no subpicosecond component that was previously assigned as the flattening of the pseudotetrahedral coordination geometry. This suggests the retention of its pseudotetrahedral D(2d) symmetry and the blockage of the solvent accessibility. We made a comparison between the excited state dynamics of [Cu(I)(dtbp)(2)](+) with its mono-tert-butyl counterpart, bis(2-tert-butyl-1,10-phenanthroline)copper(I) [Cu(I)(tbp)(2)](+). The subpicosecond component assigned to the flattening of the D(2d) coordination geometry in the MLCT excited state was again present in the latter because the absence of a tert-butyl on the phenanthroline allows flattening to the pseudotetrahedral coordination geometry. Unlike the [Cu(I)(dtbp)(2)](+), [Cu(I)(tbp)(2)](+) exhibited no detectable emission at room temperature in

  7. Ab initio, DFT, and spectroscopic studies of excited-state structure and dynamics of 9-ethylfluorene

    NASA Astrophysics Data System (ADS)

    Boo, Bong Hyun; Lee, Jae Kwang; Lim, Edward C.

    2008-12-01

    Fluorescence excitation and resonant two-photon ionization spectra were measured for 9-ethylfluorene ( EFR) molecule cooled in pulsed supersonic expansion of He in the range of 286.5 ˜ 300 nm. The structures and energies of the global and local minima and the transition states separating them are evaluated with the B3LYP/6-31G(d) and MP2/cc-pVTZ methods. It is found that the vertical excitation energies of fluorene and the EFR conformers can be reliably predicted by the time-dependent DFT method within 8.72%. The vibrational bands above the electronic origin are assigned on the basis of the RCIS/6-31G(d) calculation. Ethyl (or ethene) elimination from the excited neutral and/or ionic molecule is presumed to occur as an activation process along the adiabatic potential energy surface.

  8. Fluorescence excitation and ultraviolet absorption spectra and theoretical calculations for benzocyclobutane: Vibrations and structure of its excited S1(π,π*) electronic state

    PubMed Central

    Shin, Hee Won; Ocola, Esther J.; Kim, Sunghwan; Laane, Jaan

    2014-01-01

    The fluorescence excitation spectra of jet-cooled benzocyclobutane have been recorded and together with its ultraviolet absorption spectra have been used to assign the vibrational frequencies for this molecule in its S1(π,π*) electronic excited state. Theoretical calculations at the CASSCF(6,6)/aug-cc-pVTZ level of theory were carried out to compute the structure of the molecule in its excited state. The calculated structure was compared to that of the molecule in its electronic ground state as well as to the structures of related molecules in their S0 and S1(π,π*) electronic states. In each case the decreased π bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S0 and S1(π,π*) states were remarkably harmonic in contrast to the other bicyclic molecules. The decreases in the frequencies of the out-of-plane skeletal modes reflect the increased floppiness of these bicyclic molecules in their S1(π,π*) excited state. PMID:25669377

  9. Electronic structures and population dynamics of excited states of xanthione and its derivatives

    NASA Astrophysics Data System (ADS)

    Fedunov, Roman G.; Rogozina, Marina V.; Khokhlova, Svetlana S.; Ivanov, Anatoly I.; Tikhomirov, Sergei A.; Bondarev, Stanislav L.; Raichenok, Tamara F.; Buganov, Oleg V.; Olkhovik, Vyacheslav K.; Vasilevskii, Dmitrii A.

    2017-09-01

    A new compound, 1,3-dimethoxy xanthione (DXT), has been synthesized and its absorption (stationary and transient) and luminescence spectra have been measured in n-hexane and compared with xanthione (XT) spectra. The pronounced broadening of xanthione vibronic absorption band related to the electronic transition to the second singlet excited state has been observed. Distinctions between the spectra of xanthione and its methoxy derivatives are discussed. Quantum chemical calculations of these compounds in the ground and excited electronic states have been accomplished to clarify the nature of electronic spectra changes due to modification of xanthione by methoxy groups. Appearance of a new absorption band of DXT caused by symmetry changes has been discussed. Calculations of the second excited state structure of xanthione and its methoxy derivatives confirm noticeable charge transfer (about 0.1 of the charge of an electron) from the methoxy group to thiocarbonyl group. Fitting of the transient spectra of XT and DXT has been fulfilled and the time constants of internal conversion S2 →S1 and intersystem crossing S1 →T1 have been determined. A considerable difference between the time constants of internal conversion S2 →S1 in XT and DXT is uncovered.

  10. Excited-state dynamics of oxazole: A combined electronic structure calculations and dynamic simulations study

    NASA Astrophysics Data System (ADS)

    Cao, Jun; Xie, Zhi-Zhong; Yu, Xiaodong

    2016-08-01

    In the present work, the combined electronic structure calculations and surface hopping simulations have been performed to investigate the excited-state decay of the parent oxazole in the gas phase. Our calculations show that the S2 state decay of oxazole is an ultrafast process characterized by the ring-opening and ring-closure of the five-membered oxazole ring, in which the triplet contribution is minor. The ring-opening involves the Osbnd C bond cleavage affording the nitrile ylide and airine intermediates, while the ring-closure gives rise to a bicyclic species through a 2sbnd 5 bond formation. The azirine and bicyclic intermediates in the S0 state are very likely involved in the phototranspositions of oxazoles. This is different from the previous mechanism in which these intermediates in the T1 state have been proposed for these phototranspositions.

  11. Synthesis, crystal structure and DFT studies of a dual fluorescent ketamine: Structural changes in the ground and excited states

    NASA Astrophysics Data System (ADS)

    Latha, V.; Balakrishnan, C.; Neelakantan, M. A.

    2015-07-01

    A fluorescent probe 2Z,2‧Z-3,3‧-(4,4‧-methylenebis(4,1-phenylene) bis(azanediyl))bis (1,3-diphenylprop-2-en-1-one) (L) was synthesized and characterized by IR, 1H NMR, ESI-mass, UV-visible and fluorescence spectral techniques. The single crystal analysis illustrates the existence of L in ketamine form. The crystal structure is stabilized by intramolecular and intermolecular hydrogen bonding. The thermal stability of L was studied by TG analysis. The fluorescence spectrum of L shows dual emission, and is due to excited state intramolecular proton transfer (ESIPT) process. This is supported by the high Stokes shift value. Electronic structure calculations of L in the ground and excited state have been carried out using DFT and TD-DFT at B3LYP/6-31G (d,p) level, respectively. The vibrational spectrum was computed at this level and compared with experimental values. Major orbital contributions for the electronic transitions were assigned with the help of TD-DFT. The changes in the Mulliken charge, bond lengths and bond angles between the ground and excited states of the tautomers demonstrate that twisted intramolecular charge transfer (TICT) process occurs along with ESIPT in the excited state.

  12. Structural relaxation in the singlet excited state of star-shaped oligofluorenes having a truxene or isotruxene as a core.

    PubMed

    Fujitsuka, Mamoru; Cho, Dae Won; Huang, Hsin-Hau; Yang, Jye-Shane; Majima, Tetsuro

    2011-11-24

    Oligofluorenes attract wide attention due to their excellent fluorescent properties. For the detailed understanding of the excited state properties, ultrafast processes have to be clarified. Here, we have investigated the structural relaxation in the singlet excited state of star-shaped oligofluorenes with a truxene or isotruxene core, to which oligofluorenes (n = 1-4) were attached. The transient absorption peak showed red-shift with time upon excitation. The fluorescence decay profiles in the picosecond domain showed the fast component in addition to the component corresponding to the singlet excited state lifetime. These ultrafast phenomena can be attributed to the structural relaxation, i.e., planarization, in the singlet excited state. The planarization process was supported by the theoretical calculation based on the time-dependent density functional theory. Furthermore, dependence of two-photon absorption cross section on the core of the star-shaped oligofluorene has been elucidated. © 2011 American Chemical Society

  13. Decomposing the Excited State Dynamics of Carotenoids in Light Harvesting Complexes and Dissecting Pulse Structures from Optimal Control Experiments

    NASA Astrophysics Data System (ADS)

    Papagiannakis, Emmanouil; van Stokkum, Ivo H. M.; van Grondelle, Rienk; Vengris, Mikas; Valkunas, Leonas; Cogdell, Richard J.; Larsen, Delmar S.

    Dispersed transient absorption and multi-pump spectroscopies were used to illustrate how the interplay between excited-state dynamics, saturation, and annihilation phenomena in the LH2 protein from Rhodopseudomonas acidophila generates structured pulses in optimal control experiments.

  14. Excited-state energies and fine structure of highly charged lithiumlike ions

    NASA Astrophysics Data System (ADS)

    Li, Jin-ying; Ding, Da-jun; Wang, Zhi-wen

    2013-10-01

    The full-core-plus-correlation method (FCPC) is extended to calculate the energies and fine structures of 1s2nd and 1s2nf (n≤5) states for the lithiumlike systems with high nuclear charge from Z = 41 to 50. In calculating energy, the higher-order relativistic contribution is estimated under a hydrogenic approximation. The nonrelativistic energies and wave functions are calculated by the Rayleigh-Ritz method. The mass polarization and the relativistic corrections including the kinetic energy correction, the Darwin term, the electron-electron contact term, and the orbit-orbit interaction are calculated perturbatively as the first-order correction. The quantum-electrodynamics contributions to the energy and to the fine-structure splitting are estimated by using the effective nuclear charge formula. The excited energies, the fine structures, and other relevant term energies are given and compared with the data available in the literature.

  15. Vertical and adiabatic excitations in anthracene from quantum Monte Carlo: Constrained energy minimization for structural and electronic excited-state properties in the JAGP ansatz

    SciTech Connect

    Dupuy, Nicolas; Bouaouli, Samira; Mauri, Francesco Casula, Michele; Sorella, Sandro

    2015-06-07

    We study the ionization energy, electron affinity, and the π → π{sup ∗} ({sup 1}L{sub a}) excitation energy of the anthracene molecule, by means of variational quantum Monte Carlo (QMC) methods based on a Jastrow correlated antisymmetrized geminal power (JAGP) wave function, developed on molecular orbitals (MOs). The MO-based JAGP ansatz allows one to rigorously treat electron transitions, such as the HOMO → LUMO one, which underlies the {sup 1}L{sub a} excited state. We present a QMC optimization scheme able to preserve the rank of the antisymmetrized geminal power matrix, thanks to a constrained minimization with projectors built upon symmetry selected MOs. We show that this approach leads to stable energy minimization and geometry relaxation of both ground and excited states, performed consistently within the correlated QMC framework. Geometry optimization of excited states is needed to make a reliable and direct comparison with experimental adiabatic excitation energies. This is particularly important in π-conjugated and polycyclic aromatic hydrocarbons, where there is a strong interplay between low-lying energy excitations and structural modifications, playing a functional role in many photochemical processes. Anthracene is an ideal benchmark to test these effects. Its geometry relaxation energies upon electron excitation are of up to 0.3 eV in the neutral {sup 1}L{sub a} excited state, while they are of the order of 0.1 eV in electron addition and removal processes. Significant modifications of the ground state bond length alternation are revealed in the QMC excited state geometry optimizations. Our QMC study yields benchmark results for both geometries and energies, with values below chemical accuracy if compared to experiments, once zero point energy effects are taken into account.

  16. Vertical and adiabatic excitations in anthracene from quantum Monte Carlo: Constrained energy minimization for structural and electronic excited-state properties in the JAGP ansatz.

    PubMed

    Dupuy, Nicolas; Bouaouli, Samira; Mauri, Francesco; Sorella, Sandro; Casula, Michele

    2015-06-07

    We study the ionization energy, electron affinity, and the π → π(∗) ((1)La) excitation energy of the anthracene molecule, by means of variational quantum Monte Carlo (QMC) methods based on a Jastrow correlated antisymmetrized geminal power (JAGP) wave function, developed on molecular orbitals (MOs). The MO-based JAGP ansatz allows one to rigorously treat electron transitions, such as the HOMO → LUMO one, which underlies the (1)La excited state. We present a QMC optimization scheme able to preserve the rank of the antisymmetrized geminal power matrix, thanks to a constrained minimization with projectors built upon symmetry selected MOs. We show that this approach leads to stable energy minimization and geometry relaxation of both ground and excited states, performed consistently within the correlated QMC framework. Geometry optimization of excited states is needed to make a reliable and direct comparison with experimental adiabatic excitation energies. This is particularly important in π-conjugated and polycyclic aromatic hydrocarbons, where there is a strong interplay between low-lying energy excitations and structural modifications, playing a functional role in many photochemical processes. Anthracene is an ideal benchmark to test these effects. Its geometry relaxation energies upon electron excitation are of up to 0.3 eV in the neutral (1)La excited state, while they are of the order of 0.1 eV in electron addition and removal processes. Significant modifications of the ground state bond length alternation are revealed in the QMC excited state geometry optimizations. Our QMC study yields benchmark results for both geometries and energies, with values below chemical accuracy if compared to experiments, once zero point energy effects are taken into account.

  17. Ground- and excited-state structural orientation of 2-(2`-hydroxyphenyl)benzazoles in cyclodextrins

    SciTech Connect

    Roberts, E.L.; Dey, J.; Warner, I.M.

    1996-12-12

    The effects of {alpha}-, {beta}-, {gamma}-, and 2,6-di-O-methyl-{beta}-cyclodextrins (CDs) on the ground- and excited-state properties of 2-(2`-hydroxyphenyl)benzoxazole, 2-(2`-hydroxyphenyl)benzothiazole, and 2-(2`-hydroxyphenyl)benzimidazole in aqueous media are investigated. Steady-state fluorescence measurements are used to characterize the interaction of CDs with these azoles. Absorbance measurements indicate increased solubility of the azoles in aqueous solutions of CDs. Measurements of acidity constants (pK{sub a}) and data from induced circular dichroism indicate increased ground- and excited-state acidities of the phenolic protons of the molecules in the presence of CDs and axial orientation of the molecules within the CD cavity, respectively. The data further suggest a planar structure for HBO and a twisted confirmation for both HBT and HBI. The association constants of the inclusion complexes have also been estimated. These studies are further supplemented by comparative spectroscopic studies of 2-(2`-methoxyphenyl)benzothiazole in aqueous solutions of CDs. On the basis of the spectral data acquired, it is believed that the HBA molecules exist as zwitterionic tautomers in the presence of CDs. 35 refs., 6 figs., 2 tabs.

  18. Structural Optimization by Quantum Monte Carlo: Investigating the Low-Lying Excited States of Ethylene.

    PubMed

    Barborini, Matteo; Sorella, Sandro; Guidoni, Leonardo

    2012-04-10

    We present full structural optimizations of the ground state and of the low lying triplet state of the ethylene molecule by means of Quantum Monte Carlo methods. Using the efficient structural optimization method based on renormalization techniques and on adjoint differentiation algorithms recently proposed [Sorella, S.; Capriotti, L. J. Chem. Phys.2010, 133, 234111], we present the variational convergence of both wave function parameters and atomic positions. All of the calculations were done using an accurate and compact wave function based on Pauling's resonating valence bond representation: the Jastrow Antisymmetrized Geminal Power (JAGP). All structural and wave function parameters are optimized, including coefficients and exponents of the Gaussian primitives of the AGP and the Jastrow atomic orbitals. Bond lengths and bond angles are calculated with a statistical error of about 0.1% and are in good agreement with the available experimental data. The Variational and Diffusion Monte Carlo calculations estimate vertical and adiabatic excitation energies in the ranges 4.623(10)-4.688(5) eV and 3.001(5)-3.091(5) eV, respectively. The adiabatic gap, which is in line with other correlated quantum chemistry methods, is slightly higher than the value estimated by recent photodissociation experiments. Our results demonstrate how Quantum Monte Carlo calculations have become a promising and computationally affordable tool for the structural optimization of correlated molecular systems.

  19. Luminescent copper(I) halide and pseudohalide phenanthroline complexes revisited: simple structures, complicated excited state behavior.

    PubMed

    Nitsch, Jörn; Kleeberg, Christian; Fröhlich, Roland; Steffen, Andreas

    2015-04-21

    We have synthesized a series of luminescent trigonal [CuX(dtbphen)] (X = I (), Br (), Cl (), CN (), dtbphen = 2,9-di-tert-butylphenanthroline) and tetrahedral [Cu2(μ-I)2(L)2] (L = phenanthroline (), 2,9-dimethylphenanthroline ()) copper diimine complexes. Bearing in mind the chemical simplicity of this class of long-known Cu(i) phenanthroline compounds, it is surprising that they exhibit non-trivial photophysical properties, which have not been fully recognized. They display broad XMLCT absorption between ca. 450-600 nm, and the broad emission between ca. 550-850 nm in the solid state occurring with lifetimes on the μs timescale indicates phosphorescence, although the energetic overlap between excitation and emission suggests thermally activated delayed fluorescence (TADF) from S1. In line with the latter assumption, low temperature measurements of in the solid state show an energetic separation of emission and excitation. However, a counter-intuitive decrease of emission intensity and simultaneous increase of the emission lifetime at low temperatures are observed for , which indicates two triplet states also being involved. Our DFT and TD-DFT calculations show that emission from the lowest excited triplet state T1 is of (3)LMXCT nature, separated by only ca. 0.16 eV from S1. Low temperature photophysical measurements at 77 K in a glassy matrix of in 2-Me-THF and of in the solid state are in agreement with the theoretical results, revealing in addition that π-interactions in the solid state also greatly influence the photophysical properties, making a clear conclusion towards TADF ambiguous. This study suggests that other related simple and long-known Cu(i) systems may exhibit a similar, more complex excited state behavior than previously appreciated, involving several emitting states and important intermolecular interactions.

  20. Hetero-ring-expansion design for purine analogs: A theoretical study on the structural, electronic, and excited-state properties

    NASA Astrophysics Data System (ADS)

    Zhang, Laibin; Zhou, Liuzhu; Tian, Jianxiang; Li, Xiaoming

    2014-03-01

    A series of hetero-ring-expanded purine analogs are designed and their structural, electronic and excited-state properties are investigated by DFT calculations. The results indicate that the designed analogs can form stable base pairs with natural counterparts. Compared with natural ones, these size-expanded analogs and corresponding base pairs have smaller ionization potentials and HOMO-LUMO gaps. Furthermore, the A-analogs have ionization potentials even lower than natural G. Finally, the electronic absorption spectra are calculated and the nature of the low-lying excited states is discussed. These observations imply their promising applications as molecular wires and new DNA motifs.

  1. Structure of the photochemical reaction path populated via promotion of CF(2)I(2) into its first excited state.

    PubMed

    El-Khoury, Patrick Z; Tarnovsky, Alexander N; Schapiro, Igor; Ryazantsev, Mikhail N; Olivucci, Massimo

    2009-10-08

    The photochemical reaction path following the promotion of CF(2)I(2) into its lowest-lying excited electronic singlet state has been modeled using ab initio multiconfigurational quantum chemical calculations. It is found that a conical intersection drives the electronically excited CF(2)I(2)* species either to the CF(2)I + I radical pair or back to the starting CF(2)I(2) structure. The structures of the computed relaxation pathways explain the photoproduct selectivity previously observed in the gas phase. Furthermore, the results provide the basis for explaining the condensed-phase photochemistry of CF(2)I(2).

  2. Vibrational structure of the S 2 (1B u) excited state of diphenyloctatetraene observed by femtosecond stimulated Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Kukura, Philipp; McCamant, David W.; Davis, Paul H.; Mathies, Richard A.

    2003-11-01

    Femtosecond time-resolved stimulated Raman spectroscopy (FSRS) is used to study the vibrational structure and dynamics of the S 2 state of diphenyloctatetraene. Strong vibrational features at 1184, 1259 and 1578 cm -1 whose linewidths are determined by the S 2 electronic lifetime are observed at early times after photoexcitation at 397 nm. Kinetic analysis of the integrated Raman intensities as well as the transient absorption reveals an exponential decay of the S 2 state on the order of 100 fs. These results demonstrate the ability of FSRS to study the vibrational structure of excited state and chemical reaction dynamics on the femtosecond timescale.

  3. Excited states in 129I

    NASA Astrophysics Data System (ADS)

    Deleanu, D.; Balabanski, D. L.; Venkova, Ts.; Bucurescu, D.; Mărginean, N.; Ganioǧlu, E.; Căta-Danil, Gh.; Atanasova, L.; Căta-Danil, I.; Detistov, P.; Filipescu, D.; Ghiţă, D.; Glodariu, T.; Ivaşcu, M.; Mărginean, R.; Mihai, C.; Negret, A.; Pascu, S.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N. V.

    2013-01-01

    Excited states in 129I were populated with the 124Sn(7Li,2n) reaction at 23 MeV. In-beam measurements of γ-ray coincidences were performed with an array of eight HPGe detectors and five LaBr3(Ce) scintillation detectors. Based on the γγ coincidence data, a positive parity band structure built on the 7/2+ ground state was established and the πg7/2 configuration at oblate deformation was assigned to it. The results are compared to interacting Boson-Fermion model (IBFM) and total Routhian surface (TRS) calculations.

  4. Equilibrium structure and anharmonic potential function of phosgene: Microwave spectra of vibrationally excited states

    NASA Astrophysics Data System (ADS)

    Yamamoto, Satoshi; Nakata, Munetaka; Sugie, Masaaki; Takeo, Harutoshi; Matsumura, Chi; Kuchitsu, Kozo

    1984-06-01

    The vibrational satellites in the microwave spectra of 35Cl 2CO were measured and analyzed for the ν2, ν3, 2 ν3, ν4, ν5, ν6, and ν2 + ν3 states. The rotational constants for the ν5 state were first estimated by an analysis of anharmonic potential constants derived from the available rotational constants for the other excited states and other isotopic species and the electron diffraction intensity, and used for the assignment of its weak satellites. The Coriolis resonance between ν2 and ν4 was analyzed, and the difference in their wavenumbers, ν˜4 - ν˜2 = 9.553(3) cm-1, was obtained. The sign of the perturbation (positive) was determined using the infrared band envelope.

  5. Influence of ligand substitution on excited state structural dynamics in Cu(I) bis-phenanthroline complexes.

    SciTech Connect

    Lockard, J. V.; Kabehie, S.; Zink, J. I.; Smolentsev, G.; Soldatov, A.; Chen, L. X.

    2010-01-01

    This study explores the influences of steric hindrance and excited state solvent ligation on the excited state dynamics of Cu{sup I} diimine complexes. Ultrafast excited state dynamics of Cu(I)bis(3,8-di(ethynyltrityl)-1,10-phenanthroline) [Cu{sup I}(detp){sub 2}]{sup +} are measured using femtosecond transient absorption spectroscopy. The steady state electronic absorption spectra and measured lifetimes are compared to those of Cu(I)bis(1,10-phenanthroline), [Cu{sup I}(phen){sub 2}]{sup +}, and Cu(I)bis(2-9-dimethyl-1,10-phenanthroline), [Cu{sup I}(dmp){sub 2}]{sup +}, model complexes to determine the influence of different substitution patterns of the phenanthroline ligand on the structural dynamics associated with the metal to ligand charge transfer excited states. Similarities between the [Cu{sup I}(detp){sub 2}]{sup +} and [Cu{sup I}(phen){sub 2}]{sup +} excited state lifetimes were observed in both coordinating and noncoordinating solvents and attributed to the lack of steric hindrance from substitution at the 2- and 9-positions. The solution-phase X-ray absorption spectra of [Cu{sup I}(detp){sub 2}]{sup +}, [Cu{sup I}(phen){sub 2}]{sup +}, and [Cu{sup I}(dmp){sub 2}]{sup +} are reported along with finite difference method calculations that are used to determine the degree of ground state dihedral angle distortion in solution and to account for the pre-edge features observed in the XANES region.

  6. Structure and spectroscopy of ground and excited states of LiYb.

    PubMed

    Zhang, P; Sadeghpour, H R; Dalgarno, A

    2010-07-28

    Multireference configuration interaction and coupled cluster calculations have been carried out to determine the potential energy curves for the ground and low-lying excited states of the LiYb molecule. The scalar relativistic effects have been included by means of the Douglas-Kroll Hamiltonian and effective core potential and the spin-orbit couplings have been evaluated by the full microscopic Breit-Pauli operator. The LiYb permanent dipole moment, static dipole polarizability, and Franck-Condon factors have been determined. Perturbations of the vibrational spectrum due to nonadiabatic interactions are discussed.

  7. Structure of Low-Lying Excited States of Guanine in DNA and Solution: Combined Molecular Mechanics and High-Level Coupled Cluster Studies

    DOE PAGES

    Kowalski, Karol; Valiev, Marat

    2007-01-01

    High-level ab-initio equation-of-motion coupled-cluster methods with singles, doubles, and noniterative triples are used, in conjunction with the combined quantum mechanical molecular mechanics approach, to investigate the structure of low-lying excited states of the guanine base in DNA and solvated environments. Our results indicate that while the excitation energy of the first excited state is barely changed compared to its gas-phase counterpart, the excitation energy of the second excited state is blue-shifted by 0.24 eV.

  8. Energy, fine structure, hyperfine structure, and radiative transition rates of the high-lying multi-excited states for B-like neon

    NASA Astrophysics Data System (ADS)

    Zhang, Chun Mei; Chen, Chao; Sun, Yan; Gou, Bing Cong; Shao, Bin

    2015-04-01

    The Rayleigh-Ritz variational method with multiconfiguration interaction wave functions is used to obtain the energies of high-lying multi-excited quartet states 1 s 22 s2 pnl and 1 s 22 p 2 nl 4Pe,o ( n ≥ 2) in B-like neon, including the mass polarization and relativistic corrections. The fine structure and hyperfine structure of the excited quartet states for this system are investigated. Configuration structures of the high-lying multi-excited series are further identified by relativistic corrections and fine structure splittings. The transition rates and wavelengths are also calculated. Calculated wavelengths include the quantum electrodynamic effects. The results are compared with other theoretical and experimental data in the literature.

  9. Optically excited states in positronium

    NASA Technical Reports Server (NTRS)

    Howell, R. H.; Ziock, Klaus P.; Magnotta, F.; Dermer, Charles D.; Failor, R. A.; Jones, K. M.

    1990-01-01

    Optical excitation are reported of the 1 3S-2 3P transition in positronium, and a second excitation from n=2 to higher n states. The experiment used light from two pulsed dye lasers. Changes in the positronium annihilation rate during and after the laser pulse were used to deduce the excited state populations. The n=2 level was found to be saturable and excitable to a substantial fraction of n=2 positronium to higher levels. Preliminary spectroscopic measurements were performed on n=14 and n=15 positronium.

  10. Excitation Methods for Bridge Structures

    SciTech Connect

    Farrar, C.R.; Duffy, T.A.; Cornwell, P.J.; Doebling, S.W.

    1999-02-08

    This paper summarizes the various methods that have been used to excited bridge structures during dynamic testing. The excitation methods fall into the general categories of ambient excitation methods and measured-input excitation methods. During ambient excitation the input to the bridge is not directly measured. In contrast, as the category label implies, measured-input excitations are usually applied at a single location where the force input to the structure can be monitored. Issues associated with using these various types of measurements are discussed along with a general description of the various excitation methods.

  11. Structure, initial excited-state relaxation, and energy storage of rhodopsin resolved at the multiconfigurational perturbation theory level.

    PubMed

    Andruniów, Tadeusz; Ferré, Nicolas; Olivucci, Massimo

    2004-12-28

    We demonstrate that a "brute force" quantum chemical calculation based on an ab initio multiconfigurational second order perturbation theory approach implemented in a quantum mechanics/molecular mechanics strategy can be applied to the investigation of the excited state of the visual pigment rhodopsin (Rh) with a computational error <5 kcal.mol(-1). As a consequence, the simulation of the absorption and fluorescence of Rh and its retinal chromophore in solution allows for a nearly quantitative analysis of the factors determining the properties of the protein environment. More specifically, we demonstrate that the Rh environment is more similar to the "gas phase" than to the solution environment and that the so-called "opsin shift" originates from the inability of the solvent to effectively "shield" the chromophore from its counterion. The same strategy is used to investigate three transient structures involved in the photoisomerization of Rh under the assumption that the protein cavity does not change shape during the reaction. Accordingly, the analysis of the initially relaxed excited-state structure, the conical intersection driving the excited-state decay, and the primary isolable bathorhodopsin intermediate supports a mechanism where the photoisomerization coordinate involves a "motion" reminiscent of the so-called bicycle-pedal reaction coordinate. Most importantly, it is shown that the mechanism of the approximately 30 kcal.mol(-1) photon energy storage observed for Rh is not consistent with a model based exclusively on the change of the electrostatic interaction of the chromophore with the protein/counterion environment.

  12. Excited States of Non-Isolated Chromophores

    NASA Astrophysics Data System (ADS)

    Matsika, S.; Kozak, C.; Kistler, K.

    2009-06-01

    The photophysical and photochemical behavior of nucleobases is very important because of their biological role as the building blocks in DNA and RNA. Great progress has been made in understanding the excited-state properties of single bases. In order to understand the photophysical properties of nucleobases in complex environments we have investigated their excited states (a) in aqueous solutions and (b) as π-stacked dimers in DNA. The solvatochromic shifts of the excited states of pyrimidine nucleobases in aqueous solution have been investigated using a combined QM/MM procedure where the quantum mechanical solute is described using high level multireference configuration interaction methods while molecular dynamics simulations are used to obtain the structure of the solvent around the solute in an average way. The excited states of π-stacked nucleobases have also been investigated using various ab initio methods. The effect of the environment on the excited states and conical intersections is investigated.

  13. Electronic structure and excited state properties of iron carbene photosensitizers - A combined X-ray absorption and quantum chemical investigation

    NASA Astrophysics Data System (ADS)

    Ericson, Fredric; Honarfar, Alireza; Prakash, Om; Tatsuno, Hideyuki; Fredin, Lisa A.; Handrup, Karsten; Chabera, Pavel; Gordivska, Olga; Kjær, Kasper S.; Liu, Yizhu; Schnadt, Joachim; Wärnmark, Kenneth; Sundström, Villy; Persson, Petter; Uhlig, Jens

    2017-09-01

    The electronic structure and excited state properties of a series of iron carbene photosensitizers are elucidated through a combination of X-ray absorption measurements and density functional theory calculations. The X-ray absorption spectra are discussed with regard to the unusual bonding environment in these carbene complexes, highlighting the difference between ferrous and ferric carbene complexes. The valence electronic structure of the core excited FeIII - 3d5 complex is predicted by calculating the properties of a CoIII - 3d6 carbene complex using the Z+1 approximation. Insight is gained into the potential of sigma-donating ligands as strategy to tune properties for light harvesting applications.

  14. Magnetic structures and excitations in CePd2(Al,Ga)2 series: Development of the "vibron" states

    NASA Astrophysics Data System (ADS)

    Klicpera, M.; Boehm, M.; Doležal, P.; Mutka, H.; Koza, M. M.; Rols, S.; Adroja, D. T.; Puente Orench, I.; Rodríguez-Carvajal, J.; Javorský, P.

    2017-02-01

    CePd2Al2 -xGax compounds crystallizing in the tetragonal CaBe2Ge2 -type structure (space group P 4 /n m m ) and undergoing a structural phase transition to an orthorhombic structure (C m m e ) at low temperatures were studied by means of neutron scattering. The amplitude-modulated magnetic structure of CePd2Al2 is described by an incommensurate propagation vector k ⃗=(δx,1/2 +δy,0 ) with δx=0.06 and δy=0.04 . The magnetic moments order antiferromagnetically within the a b planes stacked along the c axis and are arranged along the direction close to the orthorhombic a axis with a maximum value of 1.5(1) μB/Ce3 +. CePd2Ga2 reveals a magnetic structure composed of two components: the first is described by the propagation vector k1⃗=(1/2 ,1/2 ,0 ) , and the second one propagates with k2⃗=(0 ,1/2 ,0 ) . The magnetic moments of both components are aligned along the same direction—the orthorhombic [100] direction—and their total amplitude varies depending on the mutual phase of magnetic moment components on each Ce site. The propagation vectors k1⃗ and k2⃗ describe also the magnetic structure of substituted CePd2Al2 -xGax compounds, except the one with x =0.1 .CePd2Al1.9Ga0.1 with magnetic structure described by k ⃗ and k1⃗ stays on the border between pure CePd2Al2 and the rest of the series. Determined magnetic structures are compared with other Ce 112 compounds. Inelastic neutron scattering experiments disclosed three nondispersive magnetic excitations in the paramagnetic state of CePd2Al2 , while only two crystal field (CF) excitations are expected from the splitting of ground state J =5/2 of the Ce3 + ion in a tetragonal/orthorhombic point symmetry. Three magnetic excitations at 1.4, 7.8, and 15.9 meV are observed in the tetragonal phase of CePd2Al2 . A structural phase transition to an orthorhombic structure shifts the first excitation up to 3.7 meV, while the other two excitations remain at almost the same energy. The presence of an additional

  15. Excited-state structure, vibrations, and nonradiative relaxation of jet-cooled 5-fluorocytosine.

    PubMed

    Lobsiger, Simon; Trachsel, Maria A; Den, Takuya; Leutwyler, Samuel

    2014-03-20

    The S0 → S1 vibronic spectrum and S1 state nonradiative relaxation of jet-cooled keto-amino 5-fluorocytosine (5FCyt) are investigated by two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm(–1) resolution. The 0(0)(0) rotational band contour is polarized in-plane, implying that the electronic transition is (1)ππ*. The electronic transition dipole moment orientation and the changes of rotational constants agree closely with the SCS-CC2 calculated values for the (1)ππ* (S1) transition of 5FCyt. The spectral region from 0 to 300 cm(–1) is dominated by overtone and combination bands of the out-of-plane ν1′ (boat), ν2′ (butterfly), and ν3′ (HN–C6H twist) vibrations, implying that the pyrimidinone frame is distorted out-of-plane by the (1)ππ* excitation, in agreement with SCS-CC2 calculations. The number of vibronic bands rises strongly around +350 cm(–1); this is attributed to the (1)ππ* state barrier to planarity that corresponds to the central maximum of the double-minimum out-of-plane vibrational potentials along the ν1′, ν2′, and ν3′ coordinates, which gives rise to a high density of vibronic excitations. At +1200 cm(–1), rapid nonradiative relaxation (k(nr) ≥ 10(12) s(–1)) sets in, which we interpret as the height of the (1)ππ* state barrier in front of the lowest S1/S0 conical intersection. This barrier in 5FCyt is 3 times higher than that in cytosine. The lifetimes of the ν′ = 0, 2ν1′, 2ν2′, 2ν1′ + 2ν2′, 4ν2′, and 2ν1′ + 4ν2′ levels are determined from Lorentzian widths fitted to the rotational band contours and are τ ≥ 75 ps for ν′ = 0, decreasing to τ ≥ 55 ps at the 2ν1′ + 4ν2′ level at +234 cm(–1). These gas-phase lifetimes are twice those of S1 state cytosine and 10–100 times those of the other canonical nucleobases in the gas phase. On the other hand, the 5FCyt gas-phase lifetime is close to the 73 ps lifetime in room-temperature solvents. This lack of

  16. The excited-state structure, vibrations, lifetimes, and nonradiative dynamics of jet-cooled 1-methylcytosine

    NASA Astrophysics Data System (ADS)

    Trachsel, Maria A.; Wiedmer, Timo; Blaser, Susan; Frey, Hans-Martin; Li, Quansong; Ruiz-Barragan, Sergi; Blancafort, Lluís; Leutwyler, Samuel

    2016-10-01

    We have investigated the S0 → S1 UV vibronic spectrum and time-resolved S1 state dynamics of jet-cooled amino-keto 1-methylcytosine (1MCyt) using two-color resonant two-photon ionization, UV/UV holeburning and depletion spectroscopies, as well as nanosecond and picosecond time-resolved pump/delayed ionization measurements. The experimental study is complemented with spin-component-scaled second-order coupled-cluster and multistate complete active space second order perturbation ab initio calculations. Above the weak electronic origin of 1MCyt at 31 852 cm-1 about 20 intense vibronic bands are observed. These are interpreted as methyl group torsional transitions coupled to out-of-plane ring vibrations, in agreement with the methyl group rotation and out-of-plane distortions upon 1ππ∗ excitation predicted by the calculations. The methyl torsion and ν1 ' (butterfly) vibrations are strongly coupled, in the S1 state. The S0 → S1 vibronic spectrum breaks off at a vibrational excess energy Eexc ˜ 500 cm-1, indicating that a barrier in front of the ethylene-type S1⇝S0 conical intersection is exceeded, which is calculated to lie at Eexc = 366 cm-1. The S1⇝S0 internal conversion rate constant increases from kIC = 2 ṡ 109 s-1 near the S1(v = 0) level to 1 ṡ 1011 s-1 at Eexc = 516 cm-1. The 1ππ∗ state of 1MCyt also relaxes into the lower-lying triplet T1 (3ππ∗) state by intersystem crossing (ISC); the calculated spin-orbit coupling (SOC) value is 2.4 cm-1. The ISC rate constant is 10-100 times lower than kIC; it increases from kISC = 2 ṡ 108 s-1 near S1(v = 0) to kISC = 2 ṡ 109 s-1 at Eexc = 516 cm-1. The T1 state energy is determined from the onset of the time-delayed photoionization efficiency curve as 25 600 ± 500 cm-1. The T2 (3nπ∗) state lies >1500 cm-1 above S1(v = 0), so S1⇝T2 ISC cannot occur, despite the large SOC parameter of 10.6 cm-1. An upper limit to the adiabatic ionization energy of 1MCyt is determined as 8.41 ± 0.02 e

  17. The excited-state structure, vibrations, lifetimes, and nonradiative dynamics of jet-cooled 1-methylcytosine.

    PubMed

    Trachsel, Maria A; Wiedmer, Timo; Blaser, Susan; Frey, Hans-Martin; Li, Quansong; Ruiz-Barragan, Sergi; Blancafort, Lluís; Leutwyler, Samuel

    2016-10-07

    We have investigated the S0 → S1 UV vibronic spectrum and time-resolved S1 state dynamics of jet-cooled amino-keto 1-methylcytosine (1MCyt) using two-color resonant two-photon ionization, UV/UV holeburning and depletion spectroscopies, as well as nanosecond and picosecond time-resolved pump/delayed ionization measurements. The experimental study is complemented with spin-component-scaled second-order coupled-cluster and multistate complete active space second order perturbation ab initio calculations. Above the weak electronic origin of 1MCyt at 31 852 cm(-1) about 20 intense vibronic bands are observed. These are interpreted as methyl group torsional transitions coupled to out-of-plane ring vibrations, in agreement with the methyl group rotation and out-of-plane distortions upon (1)ππ(∗) excitation predicted by the calculations. The methyl torsion and ν1(') (butterfly) vibrations are strongly coupled, in the S1 state. The S0 → S1 vibronic spectrum breaks off at a vibrational excess energy Eexc ∼ 500 cm(-1), indicating that a barrier in front of the ethylene-type S1⇝S0 conical intersection is exceeded, which is calculated to lie at Eexc = 366 cm(-1). The S1⇝S0 internal conversion rate constant increases from kIC = 2 ⋅ 10(9) s(-1) near the S1(v = 0) level to 1 ⋅ 10(11) s(-1) at Eexc = 516 cm(-1). The (1)ππ(∗) state of 1MCyt also relaxes into the lower-lying triplet T1 ((3)ππ(∗)) state by intersystem crossing (ISC); the calculated spin-orbit coupling (SOC) value is 2.4 cm(-1). The ISC rate constant is 10-100 times lower than kIC; it increases from kISC = 2 ⋅ 10(8) s(-1) near S1(v = 0) to kISC = 2 ⋅ 10(9) s(-1) at Eexc = 516 cm(-1). The T1 state energy is determined from the onset of the time-delayed photoionization efficiency curve as 25 600 ± 500 cm(-1). The T2 ((3)nπ(∗)) state lies >1500 cm(-1) above S1(v = 0), so S1⇝T2 ISC cannot occur, despite the large SOC parameter of 10.6 cm(-1). An upper limit to the adiabatic

  18. Observation of structural relaxation during exciton self-trapping via excited-state resonant impulsive stimulated Raman spectroscopy

    SciTech Connect

    Mance, J. G.; Felver, J. J.; Dexheimer, S. L.

    2015-02-28

    We detect the change in vibrational frequency associated with the transition from a delocalized to a localized electronic state using femtosecond vibrational wavepacket techniques. The experiments are carried out in the mixed-valence linear chain material [Pt(en){sub 2}][Pt(en){sub 2}Cl{sub 2}]⋅(ClO{sub 4}){sub 4} (en = ethylenediamine, C{sub 2}H{sub 8}N{sub 2}), a quasi-one-dimensional system with strong electron-phonon coupling. Vibrational spectroscopy of the equilibrated self-trapped exciton is carried out using a multiple pulse excitation technique: an initial pump pulse creates a population of delocalized excitons that self-trap and equilibrate, and a time-delayed second pump pulse tuned to the red-shifted absorption band of the self-trapped exciton impulsively excites vibrational wavepacket oscillations at the characteristic vibrational frequencies of the equilibrated self-trapped exciton state by the resonant impulsive stimulated Raman mechanism, acting on the excited state. The measurements yield oscillations at a frequency of 160 cm{sup −1} corresponding to a Raman-active mode of the equilibrated self-trapped exciton with Pt-Cl stretching character. The 160 cm{sup −1} frequency is shifted from the previously observed wavepacket frequency of 185 cm{sup −1} associated with the initially generated exciton and from the 312 cm{sup −1} Raman-active symmetric stretching mode of the ground electronic state. We relate the frequency shifts to the changes in charge distribution and local structure that create the potential that stabilizes the self-trapped state.

  19. Structure, initial excited-state relaxation, and energy storage of rhodopsin resolved at the multiconfigurational perturbation theory level

    PubMed Central

    Andruniów, Tadeusz; Ferré, Nicolas; Olivucci, Massimo

    2004-01-01

    We demonstrate that a “brute force” quantum chemical calculation based on an ab initio multiconfigurational second order perturbation theory approach implemented in a quantum mechanics/molecular mechanics strategy can be applied to the investigation of the excited state of the visual pigment rhodopsin (Rh) with a computational error <5 kcal·mol-1. As a consequence, the simulation of the absorption and fluorescence of Rh and its retinal chromophore in solution allows for a nearly quantitative analysis of the factors determining the properties of the protein environment. More specifically, we demonstrate that the Rh environment is more similar to the “gas phase” than to the solution environment and that the so-called “opsin shift” originates from the inability of the solvent to effectively “shield” the chromophore from its counterion. The same strategy is used to investigate three transient structures involved in the photoisomerization of Rh under the assumption that the protein cavity does not change shape during the reaction. Accordingly, the analysis of the initially relaxed excited-state structure, the conical intersection driving the excited-state decay, and the primary isolable bathorhodopsin intermediate supports a mechanism where the photoisomerization coordinate involves a “motion” reminiscent of the so-called bicycle-pedal reaction coordinate. Most importantly, it is shown that the mechanism of the ∼30 kcal·mol-1 photon energy storage observed for Rh is not consistent with a model based exclusively on the change of the electrostatic interaction of the chromophore with the protein/counterion environment. PMID:15604139

  20. Excited-State Structure of Oligothiophene Dendrimers: Computational and Experimental Study

    DTIC Science & Technology

    2010-01-01

    supramolecular calculations of the systems with strong covalent bonding and high geometrical disorder. Approximations to the excitation energies are often done...Badaeva et al. (73) Kobko, N.; Masunov, A.; Tretiak, S. Chem. Phys. Lett. 2004, 392, 444–451. (74) Bartholomew , G. P.; Rumi, M.; Pond, S. J. K.; Perry, J

  1. The spectroscopy of singlets and triplets excites electronic states, spatial and electronic structure of hydrocarbons and quantum classifications in chemmotology

    NASA Astrophysics Data System (ADS)

    Obukhov, A. E.

    2016-12-01

    In this work we demonstrate the physical foundations of the spectroscopy of the grounds states: E- and X-ray, (RR) Raman scattering the NMR 1H and 13C and IR-, EPR- absorption and the singlets and triplets electronic excited states in the multinuclear hydrocarbons in chemmotology. The parameters of UV-absorption, RR-Raman scattering of light, the fluorescence and the phosphorescence and day-lasers at the pumping laser and lamp, OLEDs and OTETs- are measurements. The spectral-energy properties are briefly studied. The quantum-chemical LCAO-MO SCF expanded-CI PPP/S and INDO/S methods in the electronic and spatial structure hidrocarbons are considered.

  2. Density functional investigation of the electronic structure and charge transfer excited states of a multichromophoric antenna

    NASA Astrophysics Data System (ADS)

    Basurto, Luis; Zope, Rajendra R.; Baruah, Tunna

    2016-05-01

    We report an electronic structure study of a multichromophoric molecular complex containing two of each borondipyrromethane dye, Zn-tetraphenyl-porphyrin, bisphenyl anthracene and a fullerene. The snowflake shaped molecule behaves like an antenna capturing photon at different frequencies and transferring the photon energy to the porphyrin where electron transfer occurs from the porphyrin to the fullerene. The study is performed within density functional formalism using large polarized Guassian basis sets (12,478 basis functions in total). The energies of the HOMO and LUMO states in the complex, as adjudged by the ionization potential and the electron affinity values, show significant differences with respect to their values in participating subunits in isolation. These differences are also larger than the variations of the ionization potential and electron affinity values observed in non-bonded C60-ZnTPP complexes in co-facial arrangement or end-on orientations. An understanding of the origin of these differences is obtained by a systematic study of the effect of structural strain, the presence of ligands, the effect of orbital delocalization on the ionization energy and the electron affinity. Finally, a few lowest charge transfer energies involving electronic transitions from the porphyrin component to the fullerene subunit of the complex are predicted.

  3. Infrared, Raman, and ultraviolet absorption spectra and theoretical calculations and structure of 2,6-difluoropyridine in its ground and excited electronic states.

    PubMed

    Sheu, Hong-Li; Kim, Sunghwan; Laane, Jaan

    2013-12-19

    The infrared and Raman spectra of 2,6-difluoropyridine (26DFPy) along with ab initio and DFT computations have been used to assign the vibrations of the molecule in its S0 electronic ground state and to calculate its structure. The ultraviolet absorption spectrum showed the electronic transition to the S1(π,π*) state to be at 37,820.2 cm(-1). With the aid of ab initio computations the vibrational frequencies for this excited state were also determined. TD-B3LYP and CASSCF computations for the excited states were carried out to calculate the structures for the S1(π,π*) and S2(n,π*) excited states. The CASSCF results predict that the S1(π,π*) state is planar and that the S2(n,π*) state has a barrier to planarity of 256 cm(-1). The TD-B3LYP computations predict a barrier of 124 cm(-1) for the S1(π,π*) state, but the experimental results support the planar structure. Hypothetical models for the ring-puckering potential energy function were calculated for both electronic excited states to show the predicted quantum states. The changes in the vibrational frequencies in the two excited states reflect the weaker π bonding within the pyridine ring.

  4. Infrared, Raman, and Ultraviolet Absorption Spectra and Theoretical Calculations and Structure of 2,6-Difluoropyridine in its Ground and Excited Electronic States

    PubMed Central

    Sheu, Hong-Li; Kim, Sunghwan; Laane, Jaan

    2014-01-01

    The infrared and Raman spectra of 2,6-difluoropyridine (26DFPy) along with ab initio and DFT computations have been used to assign the vibrations of the molecule in its S0 electronic ground state and to calculate its structure. The ultraviolet absorption spectrum showed the electronic transition to the S1(π,π*) state to be at 37,820.2 cm−1. With the aid of ab initio computations the vibrational frequencies for this excited state were also determined. TD-B3LYP and CASSCF computations for the excited states were carried out to calculate the structures for the S1(π,π*) and S2(n,π*) excited states. The CASSCF results predict that the S1(π,π*) state is planar and the S2(n,π*) state has a barrier to planarity of 256 cm−1. The TD-B3LYP computations predict a barrier of 124 cm−1 for the S1(π,π*) states, but the experimental results support the planar structure. Hypothetical models for the ring-puckering potential energy function were calculated for both electronic excited states to show the predicted quantum states. The changes in the vibrational frequencies in the two excited states reflect the weaker π bonding within the pyridine ring. PMID:24070189

  5. Ultrafast Structural Rearrangements in the MLCT Excited State for Copper(I) bis-Phenanthrolines in Solution

    SciTech Connect

    Shaw, G B; Grant, C D; Shirota, H; Castner Jr., E W; Meyer, G J; Chen, L X

    2006-10-05

    Ultrafast excited state structural dynamics of [Cu{sup I}(dmp){sub 2}]{sup +} (dmp = 2,9-dimethyl-1,10-phenanthroline) have been studied to identify structural origins of transient spectroscopic changes during the photoinduced metal-to-ligand-charge-transfer (MLCT) transition that induces an electronic configuration change from Cu(I) (3d{sup 10}) to Cu(II) (3d{sup 9}). This study has important connections with the flattening of the Franck-Condon state tetrahedral geometry and the ligation of Cu(II)* with the solvent observed in the thermally equilibrated MLCT state by our previous laser-initiated time-resolved x-ray absorption spectroscopy (LITR-XAS) results. To better understand the structural photodynamics of Cu(I) complexes, we have studied both [Cu{sup I}(dmp){sub 2}]{sup +} and [Cu{sup I}(dpp){sub 2}]{sup +} (dpp = 2,9-diphenyl-1,10-phenanthroline) in solvents with different dielectric constants, viscosities and thermal diffusivities by transient absorption spectroscopy. The observed spectral dynamics suggest that a solvent-independent inner-sphere relaxation process is occurring despite the large amplitude motions due to the flattening of the tetrahedral coordinated geometry. The singlet fluorescence dynamics of photoexcited [Cu{sup I}(dmp){sub 2}]{sup +} were measured in the coordinating solvent acetonitrile, using the fluorescence upconversion method at different emission wavelengths. At the bluest emission wavelengths, a prompt fluorescence lifetime of 66 fs is attributed to the excited state deactivation processes due to the internal conversion and intersystem crossing at the Franck-Condon state geometry. The differentiation between the prompt fluorescence lifetime with the tetrahedral Franck-Condon geometry and that with the flattened tetrahedral geometry uncovers an unexpected ultrafast flattening process in the MLCT state of [Cu{sup I}(dmp){sub 2}]{sup +}. These results provide guidance for future x-ray structural studies on ultrafast time scale, as

  6. Excited-state molecular structures captured by X-ray transient absorption spectroscopy: a decade and beyond.

    PubMed

    Chen, Lin X; Zhang, Xiaoyi; Lockard, Jenny V; Stickrath, Andrew B; Attenkofer, Klaus; Jennings, Guy; Liu, Di-Jia

    2010-03-01

    Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes have been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled.

  7. Excited-state molecular structures captured by x-ray transient absorption spectroscopy : a decade and beyond.

    SciTech Connect

    Chen, L. X.; Zhang, X.; Lockard, J. V.; Stickrath, A. B.; Attenkofer, K.; Jennings, G.; Liu, D.-J.; Northwestern Univ.

    2010-03-02

    Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes have been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled.

  8. Sub-structures formed in the excited state are responsible for tryptophan residues fluorescence in β-lactoglobulin.

    PubMed

    Albani, Jihad-Rene

    2011-07-01

    Origin of tryptophan residues fluorescence in β-lactoglobulin is analyzed. Fluorescence lifetimes and spectra of β-lactoglobulin solution are measured at pH going from 2 to 12 and in 6 M guanidine. Tryptophan residues emit with three lifetimes at all conditions. Two lifetimes (0.4-0.5 ns and 2-4 ns) are in the same range of those measured for tryptophan free in solution. Lifetimes in the denatured states are lower than those measured in the native state. Pre-exponential values are modified with the protein structure. Data are identical to those already obtained for other proteins. Fluorescence lifetimes characterize internal states of the tryptophan residues (Tryptophan sub-structures) independently of the tryptophan environments, the third lifetime results from the interaction that is occurring between the Trp residues and its environment. Pre-exponential values characterize substructures populations. In conclusion, tryptophan mission occurs from substates generated in the excited state. This is in good agreement with the theory we described in recent works.

  9. Structural dynamics of phenylisothiocyanate in the light-absorbing excited states: resonance Raman and complete active space self-consistent field calculation study.

    PubMed

    Ouyang, Bing; Xue, Jia-Dan; Zheng, Xuming; Fang, Wei-Hai

    2014-05-21

    The excited state structural dynamics of phenyl isothiocyanate (PITC) after excitation to the light absorbing S2(A'), S6(A'), and S7(A') excited states were studied by using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The UV absorption bands of PITC were assigned. The vibrational assignments were done on the basis of the Fourier transform (FT)-Raman and FT-infrared measurements, the density-functional theory computations, and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohexane, acetonitrile, and methanol solvents were, respectively, obtained at 299.1, 282.4, 266.0, 252.7, 228.7, 217.8, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PITC. The results indicated that the structural dynamics in the S2(A'), S6(A'), and S7(A') excited states were very different. The conical intersection point CI(S2/S1) were predicted to play important role in the low-lying excited state decay dynamics. Two major decay channels were predicted for PITC upon excitation to the S2(A') state: the radiative S(2,min) → S0 transition and the nonradiative S2 → S1 internal conversion via CI(S2/S1). The differences in the decay dynamics between methyl isothiocyanate and PITC in the first light absorbing excited state were discussed. The role of the intersystem crossing point ISC(S1/T1) in the excited state decay dynamics of PITC is evaluated.

  10. Structural dynamics of phenylisothiocyanate in the light-absorbing excited states: Resonance Raman and complete active space self-consistent field calculation study

    SciTech Connect

    Ouyang, Bing Xue, Jia-Dan Zheng, Xuming E-mail: zxm@zstu.edu.cn; Fang, Wei-Hai E-mail: fangwh@dnu.edu.cn

    2014-05-21

    The excited state structural dynamics of phenyl isothiocyanate (PITC) after excitation to the light absorbing S{sub 2}(A′), S{sub 6}(A′), and S{sub 7}(A′) excited states were studied by using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The UV absorption bands of PITC were assigned. The vibrational assignments were done on the basis of the Fourier transform (FT)-Raman and FT-infrared measurements, the density-functional theory computations, and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohexane, acetonitrile, and methanol solvents were, respectively, obtained at 299.1, 282.4, 266.0, 252.7, 228.7, 217.8, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PITC. The results indicated that the structural dynamics in the S{sub 2}(A′), S{sub 6}(A′), and S{sub 7}(A′) excited states were very different. The conical intersection point CI(S{sub 2}/S{sub 1}) were predicted to play important role in the low-lying excited state decay dynamics. Two major decay channels were predicted for PITC upon excitation to the S{sub 2}(A′) state: the radiative S{sub 2,min} → S{sub 0} transition and the nonradiative S{sub 2} → S{sub 1} internal conversion via CI(S{sub 2}/S{sub 1}). The differences in the decay dynamics between methyl isothiocyanate and PITC in the first light absorbing excited state were discussed. The role of the intersystem crossing point ISC(S{sub 1}/T{sub 1}) in the excited state decay dynamics of PITC is evaluated.

  11. LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Two-photon-excited luminescence of biologically active solid-state structures

    NASA Astrophysics Data System (ADS)

    Gorelik, V. S.; Kozulin, E. A.

    1994-05-01

    A study was made of the characteristics of two-photon-excited luminescence of a number of pharmaceutical and biologically active solid-state materials: aspirin, sulfadimethoxine, Streptocid (sulfanilamide), pig insulin, and lysozyme. This luminescence was excited by pulse-periodic laser radiation. The characteristics of the luminescence spectra were compared with the familiar spectra of two-photon-excited luminescence of L-tryptophan. The results were used to determine the characteristics of molecular excitons in the investigated organic crystals and to estimate the concentration of tryptophan in solid-state proteins.

  12. Targeting individual excited states in DMRG.

    NASA Astrophysics Data System (ADS)

    Dorando, Jonathan; Hachmann, Johannes; Kin-Lic Chan, Garnet

    2007-03-01

    The low-lying excited states of π-conjugated molecules are important for the development of novel devices such as lasers, light-emitting diodes, photovoltaic cells, and field-effect transistors [1,2]. The ab-intio Density Matrix Renormalization Group (DMRG) provides a powerful way to explore the electronic structure of quasi-one-dimensional systems such as conjugated organic oligomers. However, DMRG is limited to targeting only low-lying excited states through state-averaged DMRG (SDMRG). There are several drawbacks; state-averaging degrades the accuracy of the excited states and is limited to at most a few of the low-lying states [3]. In this study, we present a new method for targeting higher individual excited states. Due to progress in the field of numerical analysis presented by Van Der Horst and others [4], we are able to target individual excited states of the Hamiltonian. This is accomplished by modifying the Jacobi-Davidson algorithm via a ``Harmonic Ritz'' procedure. We will present studies of oligoacenes and polyenes that compare the accuracy of SDMRG and Harmonic Davidson DMRG. [1] Burroughes, et al. , Nature 347, 539 (1990). [2] Shirota, J. Mater. Chem. 10, 1, (2000). [3] Ramasesha, Pati, Krishnamurthy, Shuai, Bredas, Phys. Rev. B. 54, 7598, (1997). [4] Bai, Demmel, Dongarra, Ruhe, Van Der Horst, Templates for the Solution of Algebraic Eigenvalue Problems, SIAM, 2000.

  13. Dynamics of excited molecular states

    NASA Astrophysics Data System (ADS)

    Meyer, Hans-Dieter

    2005-01-01

    The photo-excitation or photo-ionization of a polyatomic molecule is typically accompanied by a strong excitation of the vibrational modes. In particular when a conical intersection of the electronic potential energy surfaces involved lies within or close to the Frank-Condon zone, the nuclear motion becomes very complicated, often chaotic, and the spectra become irregular and dense. An accurate simulation of the dynamics of such excited molecules requires firstly that the multi-dimensional and multi-state potential energy surface - or a reliable model thereof - can be determined. Secondly, the multi-dimensional quantum dynamics have to be solved. This is a very difficult task, because of the high dimensionality of the problem (6 to 30 degrees of freedom, say). The multi-configuration time-dependent Hartree (MCTDH) method has proven to be very useful for the study of such problems. In fact, an accurate treatment of the quantal dynamics of molecules like the allene cation (C3 H+4, 15D), the butatriene cation (C4 H+4, 18D), or the pyrazine molecule (C4N2H4, 24D) in their full dimensionality, is - up to date - only possible with MCTDH. (The acronym n D denotes the dimensionality.) The construction of the vibronic model Hamiltonian and the MCTDH method will be briefly discussed. After this, the excited state dynamics of the butatriene and pyrazine molecules will be discussed.

  14. Initial excited-state structural dynamics of 6-substituted uracil derivatives: femtosecond angle and bond lengthening dynamics in pyrimidine nucleobase photochemistry.

    PubMed

    Teimoory, Faranak; Loppnow, Glen R

    2014-12-26

    Substituents on the pyrimidine ring of nucleobases appear to play a major role in determining their initial excited-state structural dynamics and resulting photochemistry. To better understand the determinants of nucleobase initial excited-state structural dynamics, we have measured the absorption and resonance Raman excitation profiles of 6-deuterouracil (6-d-U) and 6-methyluracil (6-MeU). Simulation of the resonance Raman excitation profiles and absorption spectrum with a self-consistent, time-dependent formalism shows the effect of the deuterium and methyl group on the photochemically active internal coordinates, i.e. C5C6 stretch and C5X and C6X bends. The methyl group on either the C5 or C6 position of uracil equally increases the excited-state reorganization energies along the C5C6 stretch. However, a lower reorganization energy of the C5X + C6X bends in 6-MeU than uracil and 5-MeU shows that C6 methyl substituents reduce the bending reorganization energy. In addition, deuterium substitution at either C5 or C6 has a much smaller effect on the initial excited-state structural dynamics than methyl substitution, consistent with a mass effect. These results will be discussed in light of the resulting photochemistry of pyrimidine nucleobases.

  15. Coulomb excitation of states in 232Th

    NASA Astrophysics Data System (ADS)

    McGowan, F. K.; Milner, W. T.

    1993-09-01

    Twenty-five states in 232Th have been observed with 18 MeV 4He ions on a thick target. Eleven 2 + states between 774 and 1554 keV and three 3 - states are populated by direct E2 and E3, respectively. The remaining states are either weakly excited by multiple Coulomb excitation and/or populated by the decay of the directly excited states. Spin assignments are based on γ-ray angular distributions. Reduced transition probabilities have been deduced from the γ-ray yields. The B(E2) values for excitation of the 2 + states range from 0.024 to 3.5 W.u. (222 W.u. for the first 2 + state). For the 3 - states, the B(E3,0 → 3 -) values are 1.7, 11, and 24 W.u. A possible two-phonon state at 1554 keV, which is nearly harmonic, decays to four members of the one-phonon states, to the ground-state band, and to the K = 0 - octupole band. The B(E2) value for excitation of this state is 0.66 ± 0.05 W.u. and the B(E1) values for decay of this state are (2 and 6)×10 -4 W.u. The B(E2) values between two- and one-phonon vibrational states range between 16 and 53 W.u. which are an order of magnitude larger than the B(E2) values between the one- and zero-phonon states. This disagrees with our present understanding of collectivity in nuclei if this 2 + state is considered to be a collective two-phonon excitation. The 2 + states at 1477 and 1387 keV, which are also nearly harmonic, are possible candidates with two-phonon structure. The agreement between the experimental results and the microscopic calculations by Neergård and Vogel of the B(E3,0 → 3) for the 3 - members of the one-phonon octupole quadruplet is satisfactory when the Coriolis coupling between the states with K and K ± 1 is included. The B(E1) branching ratios for transitions from the 3 - and 1 - states to the ground-state band have large deviations from the Alaga-rule predictions. These deviations can be understood by the strong Coriolis coupling between the states of the octupole quadruplet in deformed nuclei.

  16. Tuning excited state isomerization dynamics through ground state structural changes in analogous ruthenium and osmium sulfoxide complexes.

    PubMed

    Garg, Komal; Engle, James T; Ziegler, Christopher J; Rack, Jeffrey J

    2013-08-26

    The complexes [Ru(bpy)2(pyESO)](PF6)2 and [Os(bpy)2(pyESO)](PF6)2, in which bpy is 2,2'-bipyridine and pyESO is 2-((isopropylsulfinyl)ethyl)pyridine, were prepared and studied by (1)H NMR, UV-visible and ultrafast transient absorption spectroscopy, as well as by electrochemical methods. Crystals suitable for X-ray structural analysis were grown for [Ru(bpy)2(pyESO)](PF6)2. Cyclic voltammograms of both complexes provide evidence for S→O and O→S isomerization as these voltammograms are described by an ECEC (electrochemical-chemical electrochemical-chemical) mechanism in which isomerization follows Ru(2+) oxidation and Ru(3+) reduction. The S- and O-bonded Ru(3+/2+) couples appear at 1.30 and 0.76 V versus Ag/AgCl in propylene carbonate. For [Os(bpy)2(pyESO)](PF6)2, these couples appear at 0.97 and 0.32 V versus Ag/AgCl in acetonitrile, respectively. Charge-transfer excitation of [Ru(bpy)2(pyESO)](PF6)2 results in a significant change in the absorption spectrum. The S-bonded isomer of [Ru(bpy)2(pyESO)](2+) features a lowest energy absorption maximum at 390 nm and the O-bonded isomer absorbs at 480 nm. The quantum yield of isomerization in [Ru(bpy)2(pyESO)](2+) was found to be 0.58 in propylene carbonate and 0.86 in dichloroethane solution. Femtosecond transient absorption spectroscopic measurements were collected for both complexes, revealing time constants of isomerizations of 81 ps (propylene carbonate) and 47 ps (dichloroethane) in [Ru(bpy)2(pyESO)](2+). These data and a model for the isomerizing complex are presented. A striking conclusion from this analysis is that expansion of the chelate ring by a single methylene leads to an increase in the isomerization time constant by nearly two orders of magnitude.

  17. Early time excited-state structural evolution of pyranine in methanol revealed by femtosecond stimulated Raman spectroscopy.

    PubMed

    Wang, Yanli; Liu, Weimin; Tang, Longteng; Oscar, Breland; Han, Fangyuan; Fang, Chong

    2013-07-25

    To understand chemical reactivity of molecules in condensed phase in real time, a structural dynamics technique capable of monitoring molecular conformational motions on their intrinsic time scales, typically on femtoseconds to picoseconds, is needed. We have studied a strong photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS, pK(a)* ≈ 0) in pure methanol and observed that excited-state proton transfer (ESPT) is absent, in sharp contrast with our previous work on HPTS in aqueous solutions wherein ESPT prevails following photoexcitation. Two transient vibrational marker bands at ~1477 (1454) and 1532 (1528) cm(-1) appear in CH3OH (CD3OD), respectively, rising within the instrument response time of ~140 fs and decaying with 390-470 (490-1400) fs and ~200 ps time constants in CH3OH (CD3OD). We attribute the mode onset to small-scale coherent proton motion along the pre-existing H-bonding chain between HPTS and methanol, and the two decay stages to the low-frequency skeletal motion-modulated Franck-Condon relaxation within ~1 ps and subsequent rotational diffusion of H-bonding partners in solution before fluorescence. The early time kinetic isotope effect (KIE) of ~3 upon methanol deuteration argues active proton motions particularly within the first few picoseconds when coherent skeletal motions are underdamped. Pronounced quantum beats are observed for high-frequency modes consisting of strong phenolic COH rocking (1532 cm(-1)) or H-out-of-plane wagging motions (952 cm(-1)) due to anharmonic coupling to coherent low-frequency modes impulsively excited at ca. 96, 120, and 168 cm(-1). The vivid illustration of atomic motions of HPTS in varying H-bonding geometry with neighboring methanol molecules unravels the multidimensional energy relaxation pathways immediately following photoexcitation, and provides compelling evidence that, in lieu of ESPT, the photoacidity of HPTS promptly activates characteristic low-frequency skeletal motions to search phase

  18. Electronic excited states as a probe of surface adsorbate structure and dynamics in liquid xenon

    SciTech Connect

    Peterson, Eric Scott

    1992-08-01

    A combination of second harmonic generation (SHG) and a simple dipole-dipole interaction model is presented as a new technique for determining adsorbate geometries on surfaces. The polarization dependence of SHG is used to define possible geometries of the adsorbate about the surface normal. Absorption band shifts using geometry constraints imposed by SHG data are derived for a dimer constructed from two arbitrarily placed monomers on the surface using the dipole-dipole interaction potential. These formulae can be used to determine the orientation of the two monomers relative to each other. A simplified version of this formalism is used to interpret absorption band shifts for rhodamine B adsorbed on fused silica. A brief history of the exciton is given with particular detail to Xe. Data are presented for transient absorption at RT in liquid xenon on the picosecond time scale. These are observations of both tunneling through the barrier that separates the free and trapped exciton states and the subsequent trapping of the exciton. In high densities both of these processes are found to occur within 2 to 6 picoseconds in agreement with theories of Kmiecik and Schreiber and of Martin. A threshold density is observed that separates relaxation via single binary collisions and relaxation that proceeds via Martin`s resonant energy transfer hopping mechanism.

  19. Electronic excited states as a probe of surface adsorbate structure and dynamics in liquid xenon

    SciTech Connect

    Peterson, E.S.

    1992-08-01

    A combination of second harmonic generation (SHG) and a simple dipole-dipole interaction model is presented as a new technique for determining adsorbate geometries on surfaces. The polarization dependence of SHG is used to define possible geometries of the adsorbate about the surface normal. Absorption band shifts using geometry constraints imposed by SHG data are derived for a dimer constructed from two arbitrarily placed monomers on the surface using the dipole-dipole interaction potential. These formulae can be used to determine the orientation of the two monomers relative to each other. A simplified version of this formalism is used to interpret absorption band shifts for rhodamine B adsorbed on fused silica. A brief history of the exciton is given with particular detail to Xe. Data are presented for transient absorption at RT in liquid xenon on the picosecond time scale. These are observations of both tunneling through the barrier that separates the free and trapped exciton states and the subsequent trapping of the exciton. In high densities both of these processes are found to occur within 2 to 6 picoseconds in agreement with theories of Kmiecik and Schreiber and of Martin. A threshold density is observed that separates relaxation via single binary collisions and relaxation that proceeds via Martin's resonant energy transfer hopping mechanism.

  20. Excited state structures and decay dynamics of 1,3-dimethyluracils in solutions: resonance Raman and quantum mechanical calculation study.

    PubMed

    Li, Ming-Juan; Liu, Ming-Xia; Zhao, Yan-Ying; Pei, Ke-Mei; Wang, Hui-Gang; Zheng, Xuming; Fang, Wei Hai

    2013-10-03

    The resonance Raman spectroscopic study of the excited state structural dynamics of 1,3-dimethyluracil (DMU), 5-bromo-1,3-dimethyluracil (5BrDMU), uracil, and thymine in water and acetonitrile were reported. Density functional theory calculations were carried out to help elucidate the ultraviolet electronic transitions associated with the A-, and B-band absorptions and the vibrational assignments of the resonance Raman spectra. The effect of the methylation at N1, N3 and C5 sites of pyrimidine ring on the structural dynamics of uracils in different solvents were explored on the basis of the resonance Raman intensity patterns. The relative resonance Raman intensities of DMU and 5BrDMU are computed at the B3LYP-TD level. Huge discrepancies between the experimental resonance Raman intensities and the B3LYP-TD predicted ones were observed. The underlying mechanism was briefly discussed. The decay channel through the S1((1)nπ*)/S2((1)ππ*) conical intersection and the S1((1)nπ*)/T1((3)ππ*) intersystem crossing were revealed by using the CASSCF(8,7)/6-31G(d) level of theory calculations.

  1. Excited state molecular structure determination in disordered media using laser pump/x-ray probe time-domain x-ray absorption spectroscopy.

    SciTech Connect

    Chen, L. X.; Chemistry

    2003-01-01

    Advances in X-ray technologies provide opportunities for solving structures of photoexcited state molecules with short lifetimes. Using X-ray pulses from a modern synchrotron source, the structure of a metal-to-ligand-charge-transfer (MLCT) excited state of CuI(dmp)2+ (dmp 1/4 2,9-dimethyl-1,10-phenanthroline) was investigated by laser pump/X-ray probe X-ray absorption fine structure (LPXP-XAFS) in fluid solution at room temperature on a nanosecond time scale. The experimental requirements for such pump-probe XAFS are described in terms of technical challenges: (1) conversion of optimal excited state population, (2) synchronization of the pump laser pulse and probe Xray pulse, and (3) timing of the detection. Using a laser pump pulse for the photoexcitation, a photoluminescent MLCT excited state of CuI(dmp)2(BArF), (dmp 1/4 2,9-dimethyl-1,10-phenanthroline), BArF 1/4 tetrakis(3,5-bis(trifluoromethylphenyl)borate) with a lifetime of 98{+-}5 ns was created. Probing the structure of this state at its optimal concentration using an X-ray pulse cluster with a total duration of 14.2 ns revealed that (1) a Cu{sup II} center was generated via a whole charge transfer; (2) the copper in the MLCT state bound an additional ligand to form a penta-coordinate complex with a likely trigonal bipyramidal geometry; and (3) the average Cu-N bond length increases in the MLCT excited state by 0.07 . In contrast to previously reported literature, the photoluminescence of this pentacoordinate MLCT state was not quenched upon ligation with the fifth ligand. On the basis of experimental results, we propose that the absorptive and emissive states have distinct geometries. The results represent X-ray characterization of a molecular excited state in fluid solution on a nanosecond time scale.

  2. Structure Determination and Excited State Proton Transfer Reaction of 1-NAPHTHOL-AMMONIA Clusters in the S_{1} State Studied by Uv-Ir Mid-Ir Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yoshikawa, Shunpei; Miyazaki, Mitsuhiko; Martin, Weiler; Ishikawa, Haruki; Fujii, Masaaki

    2013-06-01

    1-naphthol ammonia clusters have been studied long time as a benchmark system of the excited state proton transfer (ESPT) reactions. Understanding the ESPT reaction in this system has still not been fully established. To detect the cluster size dependence of the S_{1} state properties, many researcher extensively investigated such as emission spectra, lifetime, solvents (ammonia) evaporation pattern. Curiously, cluster structure that is fundamental to discuss the reaction has not been determined for the system. Thus we applied an IR spectroscopy to the S_{1} states of the system to determine the cluster structure and to discuss the minimum size inducing the ionic dissociation of the O-H bond in the S_{1} state. IR spectra were recorded not only the O-H and N-H stretching region (3 {μ}m) but also the skeletal vibrational region (5.5-10 {μ}m). Though O-H and N-H stretching vibrations do not provide useful structural information due to the broadness, the skeletal vibrations hold the sharpness even in the S_{1} states. Changes in the skeletal vibrations due to the ammonia solvation, e.g. C-O stretching and C-O-H bending, will be discussed based on a comparison with theoretical calculations. O. Cheshnovsky and S. Leutwylar, J. Chem. Phys. 1, 4127 (1988). S. K. Kim et al., Chem. Phys. lett. 228, 369 (1994). C. Dedonder-Lardeux et al., Phys. Chem, Chem, Phys. 3, 4316 (2001).

  3. Molecular Level Understanding of Interfaces and Excited State Electronic Structure in Organic Solar Cells Using Soft X-ray Techniques

    NASA Astrophysics Data System (ADS)

    Gliboff, Matthew

    between structure and performance in active layer polymers for organic electronics is not yet well understood. To gain insight into the effect of the excited state electronic structure on device performance, we examine two similar donor-acceptor polymers: PCPDTBT and PCDTBT, which produce devices with internal quantum efficiency (IQE) of 70% and 100% respectively. We use time-dependent density functional theory (TD-DFT) in combination with near edge x-ray absorption fine structure (NEXAFS) and resonant Auger spectroscopy to predict the electronic structure of the lowest unoccupied molecular orbital (LUMO). The resonant Auger results are found to be independent of film morphology and likely dominated by monomer structure. We show that the degree of LUMO localization onto the benzothiadiazole acceptor group in each polymer is similar, indicating that that the differences in IQE between these two polymers are driven by larger-scale morphology and not explained by the electronic structure of the excited state.

  4. Infrared spectra and molecular structure of excited electronic metastable states of the nitroprusside anion, [Fe(CN) 5NO] 2-

    NASA Astrophysics Data System (ADS)

    Güida, J. A.; Aymonino, P. J.; Piro, O. E.; Castellano, E. E.

    1993-04-01

    Na 2[Fe(CN) 5NO].2H 2O (SNP) and Ba[Fe(CN) 5NO].3H 2O (BNP) irradiated at low temperature with light in the green—blue region exhibit two new sets of infrared (IR) bands. These can be assigned to two, long-lived, electronically excited metastable states of the [Fe(CN) 5NO] 2- (NP) ion. Upon heating, these states depopulate following decay processes with different onset temperatures. We considerably extend here previous polarized IR data on irradiated SNP (100) plates to include the other basal planes. All IR-active CN, NO and FeN stretching modes and FENO bending modes of NP in both metastable states exhibit frequency down shifts This points to a softening of the corresponding bonds upon excitation. Relative frequency shift values observed for modes associated with the FeNO group are about one order of magnitude larger than the corresponding values for CN stretching modes. This supports the conclusion that the metastable states are reached through an electronic transition involving mainly the metal( nd)-NO bonding. We employ dichroic measurements in SNP to estimate the orientation in the lattice of the transition dipole moment vector corresponding to the NO mode of NP in both metastable states. Results show that the FeNO group is not appreciably bent upon excitation of NP to either of these states.

  5. Theoretical studies of electronically excited states

    SciTech Connect

    Besley, Nicholas A.

    2014-10-06

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

  6. Constrained Variational Response to Fock-Space Multi-Reference Coupled-Cluster Theory: Formulation for Excited-State Electronic Structure Calculations and Some Pilot Applications

    NASA Astrophysics Data System (ADS)

    Manohar, Prashant Uday; Pal, Sourav

    2007-11-01

    Fock-space (FS) multi-reference (MR) coupled-cluster (CC) method has emerged as compact tool to account for electronic structure of open-shell systems and molecules in low-lying excited states. Development of linear response (LR) has been one of the challenging problems in FSMRCC due to multiple-root nature of effective Hamiltonian. The recently developed constrained variational approach (CVA) has opened up a promising tool for efficient evaluation of analytic response properties. In this article, we present formulation of the method for excited state calculations. We discuss the decoupling of equations as a result of spin-adaptation and present some preliminary results for analytical dipole moments and polarizabilities of some molecules in low-lying triplet excited states.

  7. Single determinant calculations of excited state polarizabilities

    NASA Astrophysics Data System (ADS)

    Jonsson, Dan; Norman, Patrick; Ågren, Hans

    1997-12-01

    We apply response theory to simulate excited state polarizabilities emphasizing the possibility to do so by means of optimization of a ground state single determinant only. The excited state polarizabilities are given by the double residues of the cubic response functions. A set of molecules with varying ground state configurations and properties have been considered: water, ozone, formaldehyde, ethylene, butadiene, cyclobutadiene, pyridine, pyrazine and s-tetrazine. The results have been compared to excited state experiments where available and with linear response calculations of the multi-determinant optimized excited state. It is shown that calculations of excited state polarizabilities based on a ground state optimized single determinant work well for most of the cases investigated. This contention is exemplified by the fact the gas phase value from an electrochromism experiment for the polarizability of the 1 1B2 excited state of formaldehyde is better reproduced by ground state cubic response theory than by the corresponding separate state linear response function calculation, and by that the calculations call for an experimental reinvestigation of the excited state polarizabilities of s-tetrazine. A few prerequisites are given: The excited state should be isolated in energy, the ordering of the main contributing states should be reproduced, and the geometric conformation of the excited state in question should not be very different from the ground state geometry. The computational and formal advantages of the approach are discussed.

  8. Resource Paper: Molecular Excited State Relaxation Processes.

    ERIC Educational Resources Information Center

    Rhodes, William

    1979-01-01

    Develops the concept of oscillatory v dissipative limits as it applies to electronic excited state processes in molecular systems. Main emphasis is placed on the radiative and nonradiative dynamics of the excited state of a molecule prepared by interaction with light or some other excitation source. (BT)

  9. Electronic Structure and Excited-State Dynamics of an Arduengo-Type Carbene and its Imidazolone Oxidation Product.

    PubMed

    Schmitt, Hans-Christian; Flock, Marco; Welz, Eileen; Engels, Bernd; Schneider, Heidi; Radius, Udo; Fischer, Ingo

    2017-03-02

    We describe an investigation of the excited-state dynamics of isolated 1,3-di-tert-butyl-imidazoline-2-ylidene (tBu2 Im, C11 H20 N2 , m/z=180), an Arduengo-type carbene, by time- and frequency-resolved photoionization using a picosecond laser system. The energies of several singlet and triplet excited states were calculated by time-dependent density functional theory (TD-DFT). The S1 state of the carbene deactivates on a 100 ps time scale possibly by intersystem crossing. In the experiments we observed an additional signal at m/z=196, that was assigned to the oxidation product 1,3-di-tert-butyl-imidazolone, tBu2 ImO. It shows a well-resolved resonance-enhanced multiphoton ionization (REMPI) spectrum with an origin located at 36951 cm(-1) . Several low-lying vibrational bands could be assigned, with a lifetime that depends strongly on the excitation energy. At the origin the lifetime is longer than 3 ns, but drops to 49 ps at higher excess energies. To confirm formation of the imidazolone we also performed experiments on benzimidazolone (BzImO) for comparison. Apart from a redshift for BzImO the spectra of the two compounds are very similar. The TD-DFT values display a very good agreement with the experimental data.

  10. Structural and photophysical studies on gallium(III) 8-hydroxyquinoline-5-sulfonates. Does excited state decay involve ligand photolabilisation?

    PubMed

    Ramos, M Luísa; de Sousa, Andreia R E; Justino, Licínia L G; Fonseca, Sofia M; Geraldes, Carlos F G C; Burrows, Hugh D

    2013-03-14

    Multinuclear ((1)H, (13)C and (71)Ga) magnetic resonance spectroscopy (1D and 2D), DFT calculations and luminescence techniques have been used to study 8-hydroxyquinoline-5-sulfonate (8-HQS) and its complexes with Ga(III) in aqueous solutions. The study combines the high sensitivity of luminescence techniques and the selectivity of multinuclear NMR spectroscopy with the structural details accessible through DFT calculations, and aims to obtain a complete understanding of the complexation between the Ga(3+) ion and 8-HQS, and how this influences the luminescence behaviour. A full speciation study has been performed on this system and three complexes detected, with (metal : ligand) 1 : 1, 1 : 2 and 1 : 3 stoichiometries, the results being consistent with those previously found for the system Al(III)-8-HQS. Complexation in these systems is relevant to their potential biomedical, sensing and optoelectronic applications. On binding to Ga(III), a marked increase is seen in the intensity of the 8-HQS fluorescence band, which is accompanied by changes in the absorption spectra. These support the use of 8-HQS as a sensitive fluorescent sensor to detect Ga(3+) metal ions in surface waters, biological fluids, etc., and its metal complexes as an emitting or charge transport layer in light emitting devices. However, the fluorescence quantum yield of the Ga(III)-8-HQS 1 : 3 complex is about 35% of that of the corresponding system with Al(III). Although this may be due in part to a heavy atom effect favouring S(1)→ T(1) intersystem crossing with Ga(3+), this does not agree with transient absorption measurements on the triplet state yield, which is lower with the Ga(III) system than with Al(III). Instead, it is suggested that photolabilisation of ligand exchange plays a major role in nonradiative decay of the excited state and that this is more efficient with the Ga(3+) complex. Based on these results, suggestions are made of ways of enhancing fluorescence

  11. Multimode optical fibers: steady state mode exciter.

    PubMed

    Ikeda, M; Sugimura, A; Ikegami, T

    1976-09-01

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

  12. Magnetic moments, E3 transitions and the structure of high-spin core excited states in 211Rn

    NASA Astrophysics Data System (ADS)

    Poletti, A. R.; Dracoulis, G. D.; Byrne, A. P.; Stuchbery, A. E.; Poletti, S. J.; Gerl, J.; Lewis, P. M.

    1985-05-01

    The results of g-factor measurements of high-spin states in 211Rn are: Ex = 8856 + Δ' keV (Jπ = 63/2-), g = 0.626(7); 6101 + Δ' KeV (49/2+), 0.766(8); 5347 + Δ' KeV (43/2-), 0.74(2); 3927 + Δ KeV (35/2+), 1.017(12); 1578 + Δ KeV (17/2-), 0.912(9). These results together with measured E3 transition strengths and shell model calculations are used to assign configurations to the core excited states in 211Rn. Mixed configurations are required to explain the g-factors and enhanced E3 strengths simultaneously.

  13. A genetic algorithm based determination of the ground and excited (1Lb) state structure and the orientation of the transition dipole moment of benzimidazole.

    PubMed

    Schmitt, Michael; Krügler, Daniel; Böhm, Marcel; Ratzer, Christian; Bednarska, Violetta; Kalkman, Ivo; Meerts, W Leo

    2006-01-14

    The structure of benzimidazole has been determined in the electronic ground and excited states using rotationally resolved electronic spectroscopy. The rovibronic spectra of four isotopomers and subsequently the structure of benzimidazole have been automatically assigned and fitted using a genetic algorithm based fitting strategy. The lifetimes of the deuterated isotopomers have been shown to depend on the position of deuteration. The angle of the transition dipole moment with the inertial a-axis could be determined to be -30 degrees. Structures and transition dipole moment orientation have been calculated at various levels of theory and were compared to the experimental results.

  14. Excited States of {sup 11}Be

    SciTech Connect

    Cappuzzello, F.; Cunsolo, A.; Fortier, S.; Foti, A.; Laurent, H.; Lenske, H.; Maison, J.M.; Melita, A.L.; Nociforo, C.; Rosier, L.; Stephan, C.; Tassan-Got, L.; Winfield, J.S.; Wolter, H.H.

    2000-12-31

    The {sup 11}B({sup 7}Li,{sup 7}Be){sup 11}Be reaction at 57 MeV incident energy was used to explore the {sup 11}Be excitation energy spectrum at forward angles. Angular distributions were extracted for the transitions to the ground and to the states of {sup 11}Be at excitation energies of E*=0.32, 1.78, 2.69, 3.41, 3.89, 3.96, 6.05 MeV combined with the ground and the first excited state of {sup 7}Be. Also the SDR [1][2] oscillation mode was observed at E*=9.5 MeV and FWHM{approx}9 MeV and a new peak at E*=6.05 MeV and FWHM{approx}0.3 MeV was observed. QRPA calculations in the G-matrix representation are in progress in order to describe the continuum structure of {sup 11}Be. DWBA calculations have been started to evaluate transferred angular momenta both in the one step and in the two steps dynamical framework.

  15. Dilute Excited States in Light Nuclei

    NASA Astrophysics Data System (ADS)

    Demyanova, A. S.; Ogloblin, A. A.; Danilov, A. N.; Goncharov, S. A.; Belyaeva, T. L.; Trzaska, W. H.

    2015-11-01

    A review of measurements of the radii of 11B, 12C and 13C nuclei in some excited states, whose structure recently attracted a lot of attention, is presented. The differential cross-sections of the inelastic α-scattering were measured. The radii values were extracted from the date using the Modified Diffraction Model (MDM). The evidence that the famous Hoyle state (0+, 7.65 MeV) in 12C has the enhanced dimensions and is the head of a new rotational band (besides the known band based on the 12C ground state) was obtained. The radius of the second 2+ member state (E* = 9.8 or 9.6 MeV) was seen to be similar to that of the Hoyle state (~3.0 fm). A 4+ state was identified at E* = 13.75 MeV. The radii of the 8.86 MeV, 1/2- state in 13C and 8.56 MeV, 3/2- state in 11B are found to be close to that of the Hoyle state and these states can be considered as analogues of the latter. Comparison of the data with the predictions of some theoretical models, e.g., alpha condensation, has been made. The obtained results show that one may speak only about rudimentary manifestation of the condensate effects.

  16. Excited-to-excited-state scattering using weak measurements

    NASA Astrophysics Data System (ADS)

    U, Satya Sainadh; Narayanan, Andal

    2015-11-01

    Weak measurements are a subset of measurement processes in quantum mechanics wherein the system, which is being measured, interacts very weakly with the measuring apparatus. Measurement values of observables undergoing a weak interaction and their amplification are concepts that have sharpened our understanding of interaction processes in quantum mechanics. Recent experiments show that naturally occurring processes such as resonance fluorescence from excited states of an atom can exhibit weak value amplification effect. In this paper we theoretically analyze the process of elastic resonance fluorescence from a V -type three-level atomic system, using the well-known Weiskopff-Wigner (WW) theory of spontaneous emission. Within this theory we show that a weak interaction regime can be identified and for suitable choices of initial and final excited states the mean scattering time between these states show an amplification effect during interaction with the vacuum bath modes of the electromagnetic field. We thus show that a system-bath interaction can show weak value amplification. Using our theory we reproduce the published experimental results carried out in such a system. More importantly, our theory can calculate scattering time scales in elastic resonance scattering between multiple excited states of a single atom or between common excited state configurations of interacting multiatom systems.

  17. Ultrafast dynamics of hydrophilic carbonyl carotenoids - Relation between structure and excited-state properties in polar solvents

    NASA Astrophysics Data System (ADS)

    Chábera, Pavel; Fuciman, Marcel; Razi Naqvi, K.; Polívka, Tomáš

    2010-07-01

    We present a study of excited-state dynamics of water-soluble carbonyl carotenoids, crocin, norbixin, and astalysine in solvents with different polarity. While no polarity effects were observed in 2-propanol and methanol, polarity-induced lifetime shortening has been detected in water. For crocin and astalysine the S 1 lifetime decreases from 135 ps to 61 ps (crocin), and from 4 ps to 2.2 ps (astalysine) when going from methanol to water. The S 1 lifetime of norbixin is within the 15-18 ps range in all solvents, an effect attributed to its carboxylic group, which isolates the carbonyl group from the rest of conjugation. No spectral bands attributable to the intramolecular charge transfer (ICT) state have been found in any transient absorption spectra. The ICT-S n transition is made forbidden, we suggest, by the symmetric location of the conjugated carbonyl groups. In astalysine, we have found a clear signature of the S∗ state with a lifetime of 7 ps (methanol) and 6.1 ps (water).

  18. Excited states of a significantly ruffled porphyrin: computational study on structure-induced rapid decay mechanism via intersystem crossing.

    PubMed

    Bai, Fu-Quan; Nakatani, Naoki; Nakayama, Akira; Hasegawa, Jun-ya

    2014-06-12

    The compound meso-tetra-tert-butylporphyrin (H2T(t-Bu)P) is a significantly ruffled porphyrin and known as a good quencher. Compared with planar porphyrins, H2T(t-Bu)P showed bathochromic shift and rapid radiationless decay of the (1)(π, π*) excited state. Density functional theory, approximated coupled-cluster theory, and complete active space self-consistent field method level calculations were performed for the potential energy surface (PES) of the low-lying singlet and triplet states of H2T(t-Bu)P. The origin of the bathochromic shift in the absorption and fluorescence spectra was attributed to both steric distortions of the ring and electronic effects of the substituents. The nonradiative deactivation process of H2T(t-Bu)P via intersystem crossing (ISC) is proposed as (S1 → T2 → T1 → S0). Along a nonplanar distortion angle, the PESs of the S1 and T2 states are very close to each other, which suggests that many channels exist for ISC. For the T1 → S0 transition, minimum energy ISC points were located, and spin-orbit coupling (SOC) was evaluated. The present results indicate that the ISC can also occur at the T1/S0 intersection, in addition to the vibrational SOC promoted by specific normal modes.

  19. Vertical electric field induced suppression of fine structure splitting of excited state excitons in a single GaAs/AlGaAs island quantum dots

    SciTech Connect

    Ghali, Mohsen; Ohno, Yuzo; Ohno, Hideo

    2015-09-21

    We report experimentally on fine structure splitting (FSS) of various excitonic transitions in single GaAs island quantum dots, formed by a monolayer thickness fluctuation in the narrow GaAs/AlGaAs quantum well, and embedded in an n-i-Schottky diode device. By applying a forward vertical electric field (F) between the top metallic contact and the sample substrate, we observed an in-plane polarization rotation of both the ground and the excited state excitons with increasing the electric field. The polarization rotations were accompanied with a strong decrease in the FSS of the ground as well as the excited state excitons with the field, until the FSS vanished as F approached 30 kV/cm.

  20. Effects of electronic and nuclear interactions on the excited-state properties and structural dynamics of copper(I) diimine complexes.

    PubMed

    Mara, Michael W; Jackson, Nicholas E; Huang, Jier; Stickrath, Andrew B; Zhang, Xiaoyi; Gothard, Nosheen A; Ratner, Mark A; Chen, Lin X

    2013-02-14

    The effects of structural constraints on the metal-to-ligand charge transfer (MLCT) excited state structural dynamics of cuprous bis-2,9-diphenyl-phenanthroline ([Cu(I)(dpp)(2)](+)) in both coordinating acetonitrile and noncoordinating toluene were studied using X-ray transient absorption (XTA) spectroscopy and density functional theory (DFT) calculations. The phenyl groups attached to the phenanthroline ligands not only effectively shield the Cu(I) center from solvent molecules, but also force a flattened tetrahedral coordination geometry of the Cu(I) center. Consequently, the MLCT state lifetime in [Cu(I)(dpp)(2)](+) is solvent-independent, unlike the previously studied 2,9-methyl substituted bis-phenanthroline Cu(I) complex. The MLCT state of [Cu(I)(dpp)(2)](+) still undergoes a "pseudo Jahn-Teller distortion," with the angle between the two phenanthroline ligand planes decreased further by 7°. The XTA results indicate that, in the MLCT excited state of [Cu(I)(dpp)(2)](+), the phenyls at the 2, 9 positions of the phenanthroline rotate, breaking the π-π interaction with the phenanthroline ligands without ever rotating in-plane with the phenanthroline ligands. Hence, the transferred electron density from the Cu(I) center is localized on the phenanthroline moiety with no charge density present on the phenyl rings. The insight about the effect of the structural constraints on the MLCT state properties will guide the design of Cu(I) diimine complexes with suitable excited-state properties to function as earth-abundant dye sensitizers for solar electricity generation.

  1. Local pair natural orbitals for excited states

    NASA Astrophysics Data System (ADS)

    Helmich, Benjamin; Hättig, Christof

    2011-12-01

    We explore how in response calculations for excitation energies with wavefunction based (e.g., coupled cluster) methods the number of double excitation amplitudes can be reduced by means of truncated pair natural orbital (PNO) expansions and localized occupied orbitals. Using the CIS(D) approximation as a test model, we find that the number of double excitation amplitudes can be reduced dramatically with minor impact on the accuracy if the excited state wavefunction is expanded in state-specific PNOs generated from an approximate first-order guess wavefunction. As for ground states, the PNO truncation error can also for excitation energies be controlled by a single threshold related to generalized natural occupation numbers. The best performance is found with occupied orbitals which are localized by the Pipek-Mezey localization. For a large test set of excited states we find with this localization that already a PNO threshold of 10-8-10-7, corresponding to an average of only 40-80 PNOs per pair, is sufficient to keep the PNO truncation error for vertical excitation energies below 0.01 eV. This is a significantly more rapid convergence with the number doubles amplitudes than in domain-based local response approaches. We demonstrate that the number of significant excited state PNOs scales asymptotically linearly with the system size in the worst case of completely delocalized excitations and sub-linearly whenever the chromophore does not increase with the system size. Moreover, we observe that the flexibility of state-specific PNOs to adapt to the character of an excitation allows for an almost unbiased treatment of local, delocalized and charge transfer excited states.

  2. Local pair natural orbitals for excited states.

    PubMed

    Helmich, Benjamin; Hättig, Christof

    2011-12-07

    We explore how in response calculations for excitation energies with wavefunction based (e.g., coupled cluster) methods the number of double excitation amplitudes can be reduced by means of truncated pair natural orbital (PNO) expansions and localized occupied orbitals. Using the CIS(D) approximation as a test model, we find that the number of double excitation amplitudes can be reduced dramatically with minor impact on the accuracy if the excited state wavefunction is expanded in state-specific PNOs generated from an approximate first-order guess wavefunction. As for ground states, the PNO truncation error can also for excitation energies be controlled by a single threshold related to generalized natural occupation numbers. The best performance is found with occupied orbitals which are localized by the Pipek-Mezey localization. For a large test set of excited states we find with this localization that already a PNO threshold of 10(-8)-10(-7), corresponding to an average of only 40-80 PNOs per pair, is sufficient to keep the PNO truncation error for vertical excitation energies below 0.01 eV. This is a significantly more rapid convergence with the number doubles amplitudes than in domain-based local response approaches. We demonstrate that the number of significant excited state PNOs scales asymptotically linearly with the system size in the worst case of completely delocalized excitations and sub-linearly whenever the chromophore does not increase with the system size. Moreover, we observe that the flexibility of state-specific PNOs to adapt to the character of an excitation allows for an almost unbiased treatment of local, delocalized and charge transfer excited states.

  3. Excited-State Deactivation of Branched Phthalocyanine Compounds.

    PubMed

    Zhu, Huaning; Li, Yang; Chen, Jun; Zhou, Meng; Niu, Yingli; Zhang, Xinxing; Guo, Qianjin; Wang, Shuangqing; Yang, Guoqiang; Xia, Andong

    2015-12-21

    The excited-state relaxation dynamics and chromophore interactions in two phthalocyanine compounds (bis- and trisphthalocyanines) are studied by using steady-state and femtosecond transient absorption spectral measurements, where the excited-state energy-transfer mechanism is explored. By exciting phthalocyanine compounds to their second electronically excited states and probing the subsequent relaxation dynamics, a multitude of deactivation pathways are identified. The transient absorption spectra show the relaxation pathway from the exciton state to excimer state and then back to the ground state in bisphthalocyanine (bis-Pc). In trisphthalocyanine (tris-Pc), the monomeric and dimeric subunits are excited and the excitation energy transfers from the monomeric vibrationally hot S1 state to the exciton state of a pre-associated dimer, with subsequent relaxation to the ground state through the excimer state. The theoretical calculations and steady-state spectra also show a face-to-face conformation in bis-Pc, whereas in tris-Pc, two of the three phthalocyanine branches form a pre-associated face-to-face dimeric conformation with the third one acting as a monomeric unit; this is consistent with the results of the transient absorption experiments from the perspective of molecular structure. The detailed structure-property relationships in phthalocyanine compounds is useful for exploring the function of molecular aggregates in energy migration of natural photosynthesis systems.

  4. Excitation of a composite structure by collisions

    SciTech Connect

    Newby, N.D. Jr.

    1984-08-01

    A simple model is employed to study the excitation of a composite structure by collisions. The composite structure is a diatomic ''molecule'' composed of two equal point masses joined by a Hooke's law spring of constant, k/sub 1/. This structure, in an unexcited state, makes a one-dimensional head-on collision with a fixed wall. The interaction with the wall is mediated by a second Hooke's law spring of constant, k/sub 2/. After rebounding from the wall the diatom may be in an excited state. The excitation energy is calculated as a function of the hardness of the wall. An eigenvalue problem is solved which yields an infinite number of ..beta..'s (..beta.. = k/sub 1//k/sub 2/) which leave the diatom unexcited. The phenomenon of ''double hitting'' : when a soft structure strikes a hard wall: is discussed. The maximum energy transfer into the internal mode is 23%. An air-track experiment is suggested to check the theoretical predictions.

  5. The molecular structure and a Renner-Teller analysis of the ground and first excited electronic states of the jet-cooled CS2+ molecular ion

    NASA Astrophysics Data System (ADS)

    He, Sheng-Gui; Clouthier, Dennis J.

    2006-02-01

    The ÃΠu2-X˜Πg2 electronic band system of the jet-cooled CS2+ ion has been studied by laser-induced fluorescence and wavelength-resolved emission techniques. The ions were produced in a pulsed electric discharge jet using a precursor mixture of carbon disulfide vapor in high-pressure argon. Rotational analysis of the high-resolution spectrum of the Π3/22 component of the 000 band gave linear-molecule molecular structures of r0″=1.5554(10)Å and r0'=1.6172(12)Å. Renner-Teller analyses of the vibronic structure in the spectra showed that the ground-state spin-orbit splitting (A =-447.0cm-1) is much larger than that of the excited state (A=-177.5cm-1), but that the Renner-Teller parameters are of similar magnitude and that a strong ν1-2ν2 Fermi resonance occurs in both states. Previous analyses of the vibronic structure in the ground and excited states of the ion from pulsed field-ionization-photoelectron data are shown to be substantially correct.

  6. Hydrogen Bonds in Excited State Proton Transfer

    NASA Astrophysics Data System (ADS)

    Horke, D. A.; Watts, H. M.; Smith, A. D.; Jager, E.; Springate, E.; Alexander, O.; Cacho, C.; Chapman, R. T.; Minns, R. S.

    2016-10-01

    Hydrogen bonding interactions between biological chromophores and their surrounding protein and solvent environment significantly affect the photochemical pathways of the chromophore and its biological function. A common first step in the dynamics of these systems is excited state proton transfer between the noncovalently bound molecules, which stabilizes the system against dissociation and principally alters relaxation pathways. Despite such fundamental importance, studying excited state proton transfer across a hydrogen bond has proven difficult, leaving uncertainties about the mechanism. Through time-resolved photoelectron imaging measurements, we demonstrate how the addition of a single hydrogen bond and the opening of an excited state proton transfer channel dramatically changes the outcome of a photochemical reaction, from rapid dissociation in the isolated chromophore to efficient stabilization and ground state recovery in the hydrogen bonded case, and uncover the mechanism of excited state proton transfer at a hydrogen bond, which follows sequential hydrogen and charge transfer processes.

  7. Quantitative excited state spectroscopy of a single InGaAs quantum dot molecule through multi-million-atom electronic structure calculations.

    PubMed

    Usman, Muhammad; Tan, Yui-Hong Matthias; Ryu, Hoon; Ahmed, Shaikh S; Krenner, Hubert J; Boykin, Timothy B; Klimeck, Gerhard

    2011-08-05

    Atomistic electronic structure calculations are performed to study the coherent inter-dot couplings of the electronic states in a single InGaAs quantum dot molecule. The experimentally observed excitonic spectrum by Krenner et al (2005) Phys. Rev. Lett. 94 057402 is quantitatively reproduced, and the correct energy states are identified based on a previously validated atomistic tight binding model. The extended devices are represented explicitly in space with 15-million-atom structures. An excited state spectroscopy technique is applied where the externally applied electric field is swept to probe the ladder of the electronic energy levels (electron or hole) of one quantum dot through anti-crossings with the energy levels of the other quantum dot in a two-quantum-dot molecule. This technique can be used to estimate the spatial electron-hole spacing inside the quantum dot molecule as well as to reverse engineer quantum dot geometry parameters such as the quantum dot separation. Crystal-deformation-induced piezoelectric effects have been discussed in the literature as minor perturbations lifting degeneracies of the electron excited (P and D) states, thus affecting polarization alignment of wavefunction lobes for III-V heterostructures such as single InAs/GaAs quantum dots. In contrast, this work demonstrates the crucial importance of piezoelectricity to resolve the symmetries and energies of the excited states through matching the experimentally measured spectrum in an InGaAs quantum dot molecule under the influence of an electric field. Both linear and quadratic piezoelectric effects are studied for the first time for a quantum dot molecule and demonstrated to be indeed important. The net piezoelectric contribution is found to be critical in determining the correct energy spectrum, which is in contrast to recent studies reporting vanishing net piezoelectric contributions.

  8. Characterizing RNA Excited States using NMR Relaxation Dispersion

    PubMed Central

    Xue, Yi; Kellogg, Dawn; Kimsey, Isaac J; Sathyamoorthy, Bharathwaj; Stein, Zachary W; McBrairty, Mitchell; Al-Hashimi, Hashim M.

    2016-01-01

    Changes in RNA secondary structure play fundamental roles in the cellular functions of a growing number of non-coding RNAs. This chapter describes NMR-based approaches for characterizing microsecond-to-millisecond changes in RNA secondary structure that are directed toward short-lived and low-populated species often referred to as “excited states”. Compared to larger-scale changes in RNA secondary structure, transitions towards excited states do not require assistance from chaperones, are often orders of magnitude faster, and are localized to a small number of nearby base pairs in and around non-canonical motifs. Here we describe a procedure for characterizing RNA excited states using off-resonance R1ρ NMR relaxation dispersion utilizing low-to-high spin-lock fields (25–3000 Hz). R1ρ NMR relaxation dispersion experiments are used to measure carbon and nitrogen chemical shifts in base and sugar moieties of the excited state. The chemical shift data is then interpreted with the aid of secondary structure prediction to infer potential excited states that feature alternative secondary structures. Candidate structures are then tested by using mutations, single-atom substitutions, or by changing physiochemical conditions, such as pH and temperature, to either stabilize or destabilize the candidate excited state. The resulting chemical shifts of the mutants or under different physiochemical conditions are then compared to those of the ground and excited state. Application is illustrated with a focus on the transactivation response element (TAR) from the human immune deficiency virus type 1 (HIV-1), which exists in dynamic equilibrium with at least two distinct excited states. PMID:26068737

  9. S1←S0 vibronic spectra and structure of cyclopropanecarboxaldehyde molecule in the S1 lowest excited singlet electronic state

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    The S1←S0 vibronic spectra of gas-phase absorption at room temperature and fluorescence excitation of jet-cooled cyclopropanecarboxaldehyde (CPCA, c-C3H5CHO)were obtained and analyzed. In addition, the quantum chemical calculation (CASPT2/cc-pVTZ)was carried out for CPCA in the ground (S0) and lowest excited singlet (S1) electronic states. As a result, it was proved that the S1←S0 electronic excitation of the CPCA conformers (syn and anti) causes (after geometrical relaxation) significant structural changes, namely, the carbonyl fragments become non-planar and the cyclopropyl groups rotate around the central C-C bond. As a consequence, the potential energy surface of CPCA in the S1 state has six minima, 1ab, 2ab, and 3ab, corresponding to three pairs of mirror symmetry conformers: a and b. It was shown that vibronic bands of experimental spectra can be assigned to the 2(S1)←syn(S0) electronic transition with the origin at 30,481 cm-1. A number of fundamental vibrational frequencies for the 2 conformer of CPCA were assigned. In addition, several inversional energy levels for the 2 conformer were found and the 2a↔2b potential function of inversion was determined. The experimental barrier to inversion and the equilibrium angle between the CH bond and the CCO plane were calculated as 570 cm-1 and 28°, respectively.

  10. Multi-Hazard Risk Assessment of Structures Subjected to Seismic Excitation and Blast for the Limit State of Collapse

    SciTech Connect

    Asprone, D.; Jalayer, F.; Prota, A.; Manfredi, G.

    2008-07-08

    Multi-hazard approach represents a convenient way to address structural reliability of a critical infrastructure. Objective of the present paper is to present a multi-hazard methodology for evaluation of the risk associated with the limit state of collapse for a reinforced concrete (RC) structure subject to both seismic and blast threats. Blast fragility can be defined as the probability of progressive collapse given a blast event has taken place and its evaluation is here suggested via a Monte Carlo procedure, generating different possible blast configurations. For each blast scenario, the consequent damages occurring to the investigated structure are identified and an updating of the structure is then performed. The structural stability under gravity loading is then verified by employing a kinematic plastic limit analysis. The conditional probability of collapse or the blast fragility is then calculated as the mean value of the collapse indicator variable over the number of cases generated by the simulation procedure. Therefore, the seismic fragility is also determined via classical methods described elsewhere and the total risk of collapse is evaluated as the sum of blast and seismic contributions.

  11. Direct observation of photoinduced bent nitrosyl excited-state complexes

    SciTech Connect

    Sawyer, Karma R.; Steele, Ryan P.; Glascoe, Elizabeth A.; Cahoon, James F.; Schlegel, Jacob P.; Head-Gordon, Martin; Harris, Charles B.

    2008-06-28

    Ground state structures with side-on nitrosyl ({eta}{sup 2}-NO) and isonitrosyl (ON) ligands have been observed in a variety of transition-metal complexes. In contrast, excited state structures with bent-NO ligands have been proposed for years but never directly observed. Here we use picosecond time-resolved infrared spectroscopy and density functional theory (DFT) modeling to study the photochemistry of Co(CO){sub 3}(NO), a model transition-metal-NO compound. Surprisingly, we have observed no evidence for ON and {eta}{sup 2}-NO structural isomers, but have observed two bent-NO complexes. DFT modeling of the ground and excited state potentials indicates that the bent-NO complexes correspond to triplet excited states. Photolysis of Co(CO){sub 3}(NO) with a 400-nm pump pulse leads to population of a manifold of excited states which decay to form an excited state triplet bent-NO complex within 1 ps. This structure relaxes to the ground triplet state in ca. 350 ps to form a second bent-NO structure.

  12. Charmonium excited state spectrum in lattice QCD

    SciTech Connect

    Jozef Dudek; Robert Edwards; Nilmani Mathur; David Richards

    2008-02-01

    Working with a large basis of covariant derivative-based meson interpolating fields we demonstrate the feasibility of reliably extracting multiple excited states using a variational method. The study is performed on quenched anisotropic lattices with clover quarks at the charm mass. We demonstrate how a knowledge of the continuum limit of a lattice interpolating field can give additional spin-assignment information, even at a single lattice spacing, via the overlap factors of interpolating field and state. Excited state masses are systematically high with respect to quark potential model predictions and, where they exist, experimental states. We conclude that this is most likely a result of the quenched approximation.

  13. Excited State Dynamics of DNA and RNA bases

    NASA Astrophysics Data System (ADS)

    Hudock, Hanneli; Levine, Benjamin; Martinez, Todd

    2007-03-01

    Recent ultrafast spectroscopic experiments have reported excited state lifetimes for DNA and RNA bases and assigned these lifetimes to various electronic states. We have used theoretical and simulation methods to describe the excited state dynamics of these bases in an effort to provide a mechanistic explanation for the observed lifetimes. Our simulations are based on ab initio molecular dynamics, where the electronic and nuclear Schrodinger equations are solved simultaneously. The results are further verified by comparison to high-level ab initio electronic structure methods, including dynamic electron correlation effects through multireference perturbation theory, at important points along the dynamical pathways. Our results provide an explanation of the photochemical mechanism leading to nonradiative decay of the electronic excited states and some suggestions as to the origin of the different lifetimes. Comparisons between pyrimidines illustrate how chemical differences impact excited state dynamics and may play a role in explaining the propensity for dimer formation in thymine.

  14. Spiroconjugated intramolecular charge-transfer emission in non-typical spiroconjugated molecules: the effect of molecular structure upon the excited-state configuration.

    PubMed

    Zhu, Linna; Zhong, Cheng; Liu, Cui; Liu, Zhongyin; Qin, Jingui; Yang, Chuluo

    2013-04-02

    A set of terfluorenes and terfluorene-like molecules with different pendant substitutions or side groups were designed and synthesized, their photophysical properties and the excited-state geometries were studied. Dual fluorescence emissions were observed in compounds with rigid pendant groups bearing electron-donating N atoms. According to our earlier studies, in this set of terfluorenes, the blue emission is from the local π-π* transition, while the long-wavelength emission is attributed to a spiroconjugation-like through-space charge-transfer process. Herein, we probe further into how the molecular structures (referring to the side groups, the type of linkage between central fluorene and the 2,2'-azanediyldiethanol units, and-most importantly-the amount of pendant groups), as well as the excited-state geometries, affect the charge-transfer process of these terfluorenes or terfluorene-like compounds. 9-(9,9,9'',9''-tetrahexyl-9H,9'H,9''H-[2,2':7',2''-terfluoren]-9'-yl)-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinolone (TFPJH), with only one julolidine pendant group, was particularly synthesized, which exhibits complete "perpendicular" conformation between julolidine and the central fluorene unit in the excited state, thus typical spiroconjugation could be achieved. Notably, its photophysical behaviors resemble those of TFPJ with two pendant julolidines. This study proves that spiroconjugation does happen in these terfluorene derivatives, although their structures are not in line with the typical orthogonal π fragments. The spiroconjugation charge-transfer emission closely relates to the electron-donating N atoms on the pendant groups, and to the rigid connection between the central fluorene and the N atoms, whereas the amount of pendant groups and the nature of the side chromophores have little effect. These findings may shed light on the understanding of the through-space charge-transfer properties and the emission color tuning of fluorene derivatives.

  15. Excited-state imaging of cold atoms

    NASA Astrophysics Data System (ADS)

    Sheludko, David V.; Bell, Simon C.; Vredenbregt, Edgar J. D.; Scholten, Robert E.

    2007-09-01

    We have investigated state-selective diffraction contrast imaging (DCI) of cold 85Rb atoms in the first excited (52P3/2) state. Excited-state DCI requires knowledge of the complex refractive index of the atom cloud, which was calculated numerically using a semi-classical model. The Autler-Townes splitting predicted by the model was verified experimentally, showing excellent agreement. 780 nm lasers were used to cool and excite atoms within a magneto-optical trap, and the atoms were then illuminated by a 776 nm imaging laser. Several excited-state imaging techniques, including blue cascade fluorescence, on-resonance absorption, and DCI have been demonstrated. Initial results show that improved signal-to-noise ratio (SNR) will be required to accurately determine the excited state fraction. We have demonstrated magnetic field gradient compression of the cold atom cloud, and expect that further progress on compression and additional cooling will achieve sufficient diffraction contrast for quantitative state-selective imaging.

  16. Electron excitation from ground state to first excited state: Bohmian mechanics method

    NASA Astrophysics Data System (ADS)

    Yang, Song; Shuang, Zhao; Fu-Ming, Guo; Yu-Jun, Yang; Su-Yu, Li

    2016-03-01

    The excitation process of electrons from the ground state to the first excited state via the resonant laser pulse is investigated by the Bohmian mechanics method. It is found that the Bohmian particles far away from the nucleus are easier to be excited and are excited firstly, while the Bohmian particles in the ground state is subject to a strong quantum force at a certain moment, being excited to the first excited state instantaneously. A detailed analysis for one of the trajectories is made, and finally we present the space and energy distribution of 2000 Bohmian particles at several typical instants and analyze their dynamical process at these moments. Project supported by the Doctoral Research Start-up Funding of Northeast Dianli University, China (Grant No. BSJXM-201332), the National Natural Science Foundation of China (Grant Nos. 11547114, 11534004, 11474129, 11274141, 11447192, and 11304116), and the Graduate Innovation Fund of Jilin University, China (Grant No. 2015091).

  17. Coulomb excitation of states in 238U

    NASA Astrophysics Data System (ADS)

    McGowan, F. K.; Milner, W. T.

    1994-05-01

    Twenty-two states in 238U have been observed with 18 MeV 4He ions on a thick target. Eight 2 + states between 966 and 1782 keV and three 3 - states are populated by direct E2 and E3, respectively. The remaining states are either weakly excited by multiple Coulomb excitation and /or populated by the γ-ray decay of the directly excited states. Spin assignments are based on γ-ray angular distributions. Reduced transition probabilities have been deduced from the γ-ray yields. The B(E2) values for excitation of the 2 + states range from 0.10 to 3.0 W.u. (281 W.u. for the first 2 + state). For the 3 states, the B(E3, 0 → 3 -) values are 7.1, 7.8, and 24.2 W.u. Several of the 2 + states have decay branches to the one-phonon states with B(E2) values between 27 and 56 W.u. which are an order of magnitude larger than the B(E2) values between the one- and zero-phonon states. This disagrees with our present understanding of collectivity in nuclei if these 2 + states are considered to be collective two-phonon excitations. However, the excitation energies of these 2 + states with respect to the one-phonon states are only 1.3 to 1.6. The B(E1) values for 17 transitions between the positive- and negative-parity states range between 10 -3 and 10 -7 W.u. The B(E1) branching ratios for many of these transitions have large deviations from the Alaga-rule predictions. These deviations can be understood by the strong Coriolis coupling between the states of the one-phonon octupole quadruplet in deformed nuclei. The general features of the experimental results for the B(E3) values are reproduced by the microscopic calculations of Neergård and Vogel when the Coriolis coupling between the states of the octupole quadruplet is included.

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

    PubMed

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

    2015-04-15

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

  19. Two-Photon Excitation of Conjugated Molecules in Solution: Spectroscopy and Excited-State Dynamics

    NASA Astrophysics Data System (ADS)

    Elles, Christopher G.; Houk, Amanda L.; de Wergifosse, Marc; Krylov, Anna

    2017-06-01

    We examine the two-photon absorption (2PA) spectroscopy and ultrafast excited-state dynamics of several conjugated molecules in solution. By controlling the relative wavelength and polarization of the two photons, the 2PA measurements provide a more sensitive means of probing the electronic structure of a molecule compared with traditional linear absorption spectra. We compare experimental spectra of trans-stilbene, cis-stilbene, and phenanthrene in solution with the calculated spectra of the isolated molecules using EOM-EE-CCSD. The calculated spectra show good agreement with the low-energy region of the experimental spectra (below 6 eV) after suppressing transitions with strong Rydberg character and accounting for solvent and method-dependent shifts of the valence transitions. We also monitor the excited state dynamics following two-photon excitation to high-lying valence states of trans-stilbene up to 6.5 eV. The initially excited states rapidly relax to the lowest singlet excited state and then follow the same reaction path as observed following direct one-photon excitation to the lowest absorption band at 4.0 eV.

  20. Excited state electronic structures and photochemistry of heterocyclic annulated perylene (HAP) materials tuned by heteroatoms: S, Se, N, O, C, Si, and B.

    PubMed

    Zhao, Guang-Jiu; Han, Ke-Li

    2009-04-23

    Time-dependent density functional theory (TDDFT) method was performed to investigate the excited state electronic structures and photochemistry of a variety of heterocyclic annulated perylene (HAP) materials. The calculated electronic structures and photochemical properties of the newly synthesized S-, Se-, and N-heterocyclic annulated perylenes were in good agreement with the experimental results. Moreover, the O-, C-, Si-, and B-heterocyclic annulated perylenes were also theoretically designed and investigated by using the same computational methods in this work. As a result, we found that the electronic structures and photochemical properties of S-, Se-, N-, O-, and C-heterocyclic annulated perylenes are similar to each other. The energy levels of the LUMO orbital for the S-, Se-, N-, O-, and C-heterocyclic annulated perylenes become higher than those of unsubstituted perylene. At the same time, the energy gaps between LUMO and HOMO for these heterocyclic annulated perylenes are also increased in comparison with those of unsubstituted perylene. Hence, both absorption and fluorescence spectra of S-, Se-, N-, O-, and C-heterocyclic annulated perylenes are correspondingly blue-shifted relative to those of unsubstituted perylene. In addition, two bonds formed by heteroatoms with perylene are lengthened in the electronic excited state of S-, Se-, N-, O-, and C-heterocyclic annulated perylenes. On the contrary, these bonds formed by heteroatoms with perylene are shortened in the electronic excited state of Si- and B-heterocyclic annulated perylenes. Furthermore, energy levels of the LUMO orbital for Si- and B-heterocyclic annulated perylenes become significantly lowered in comparison with that of unsubstituted perylene. At the same time, energy gaps between LUMO and HOMO for Si- and B-heterocyclic annulated perylenes become decreased relative to those of unsubstituted perylene. Thus, both absorption and fluorescence spectra of Si- and B-heterocyclic annulated

  1. Computing correct truncated excited state wavefunctions

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  2. X-ray Diffraction Analysis of Geometry Changes upon Excitation: The Ground-State and Metastable-State Structures of K(2)[Ru(NO(2))(4)(OH)(NO)].

    PubMed

    Fomitchev, Dmitry V.; Coppens, Philip

    1996-11-20

    The structure of the laser-light-induced metastable state MS(1) of the [Ru(NO(2))(4)(OH)(NO)](2)(-) anion in K(2)[Ru(NO(2))(4)(OH)(NO)] was determined by X-ray analysis at 50 K of a crystal with a 16% excited-state population. Results of an independent determination of the ground-state structure were used in the analysis. The most pronounced geometrical change upon excitation was an increase of the Ru-(NO) distance by 0.097(11) Å, significantly larger than the change of the corresponding distance in sodium nitroprusside (Pressprich, M. R.; White, M. A.; Vekhter, Y.; Coppens, P. J. Am. Chem. Soc. 1994, 116, 5233-5238). A decrease in the angleRu-(N-O) angle from 174.0(2) to 169(1) degrees was observed. The diffraction results provide evidence that the photoinduced state MS(1) of the transition metal nitrosyl complexes is a linkage isomer in which the NO group is attached to the metal atom through the oxygen, instead of through the nitrogen atom, rather than an electronic excited state as reported previously.

  3. The electronic structure of VO in its ground and electronically excited states: A combined matrix isolation and quantum chemical (MRCI) study

    NASA Astrophysics Data System (ADS)

    Hübner, Olaf; Hornung, Julius; Himmel, Hans-Jörg

    2015-07-01

    The electronic ground and excited states of the vanadium monoxide (VO) molecule were studied in detail. Electronic absorption spectra for the molecule isolated in Ne matrices complement the previous gas-phase spectra. A thorough quantum chemical (multi-reference configuration interaction) study essentially confirms the assignment and characterization of the electronic excitations observed for VO in the gas-phase and in Ne matrices and allows the clarification of open issues. It provides a complete overview over the electronically excited states up to about 3 eV of this archetypical compound.

  4. The electronic structure of VO in its ground and electronically excited states: A combined matrix isolation and quantum chemical (MRCI) study

    SciTech Connect

    Hübner, Olaf; Hornung, Julius; Himmel, Hans-Jörg

    2015-07-14

    The electronic ground and excited states of the vanadium monoxide (VO) molecule were studied in detail. Electronic absorption spectra for the molecule isolated in Ne matrices complement the previous gas-phase spectra. A thorough quantum chemical (multi-reference configuration interaction) study essentially confirms the assignment and characterization of the electronic excitations observed for VO in the gas-phase and in Ne matrices and allows the clarification of open issues. It provides a complete overview over the electronically excited states up to about 3 eV of this archetypical compound.

  5. Long-lived excited states in metal clusters.

    PubMed

    Koop, Alexander; Gantefoer, Gerd; Kim, Young Dok

    2017-08-16

    Bare metal clusters have properties that make them interesting for applications in photochemistry and photovoltaics. Long-lived excited states are a prerequisite for such applications, because in them the energy of the photon can be stored. Clusters have a low density of states and long-lived excited states should therefore occur frequently. However, in fact, such states are a rarity, as indicated by time-resolved photoelectron data of mass-selected cluster anions. And there is another puzzling observation: only clusters with narrow peaks in their photoelectron spectra exhibit long-lived excited states. Both findings can be explained if internal conversion, i.e. the conversion of electronic excitation energy into vibrational excitations, is the major relaxation mechanism in clusters. It becomes more likely, if a change of the electronic configuration results in a large geometry change, which is probably the case for most clusters. Only clusters with a weak coupling between geometric and electronic structure may have long-lived excited states and narrow peaks.

  6. Excited State Dynamics in Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Miyamoto, Yoshiyuki

    2004-03-01

    Carbon nanotube, one of the most promising materials for nano-technology, still suffers from its imperfection in crystalline structure that will make performance of nanotube behind theoretical limit. From the first-principles simulations, I propose efficient methods to overcome the imperfection. I show that photo-induced ion dynamics can (1) identify defects in nanotubes, (2) stabilize defected nanotubes, and (3) purify contaminated nanotubes. All of these methods can be alternative to conventional heat treatments and will be important techniques for realizing nanotube-devices. Ion dynamics under electronic excitation has been simulated with use of the computer code FPSEID (First-Principles Simulation tool for Electron Ion Dynamics) [1], which combines the time-dependent density functional method [2] to classical molecular dynamics. This very challenging approach is time-consuming but can automatically treat the level alternation of differently occupied states, and can observe initiation of non-adiabatic decay of excitation. The time-dependent Kohn-Sham equation has been solved by using the Suzuki-Trotter split operator method [3], which is a numerically stable method being suitable for plane wave basis, non-local pseudopotentials, and parallel computing. This work has been done in collaboration with Prof. Angel Rubio, Prof. David Tomanek, Dr. Savas Berber and Mina Yoon. Most of present calculations have been done by using the SX5 Vector-Parallel system in the NEC Fuchu-plant, and the Earth Simulator in Yokohama Japan. [1] O. Sugino and Y. Miyamoto, Phys. Rev. B59, 2579 (1999); ibid, B66 089901(E) (2001) [2] E. Runge and E. K. U. Gross, Phys. Rev. Lett. 52, 997 (1984). [3] M. Suzuki, J. Phys. Soc. Jpn. 61, L3015 (1992).

  7. Multisite constrained model of trans-4-(N,N-dimethylamino)-4'-nitrostilbene for structural elucidation of radiative and nonradiative excited states.

    PubMed

    Lin, Cheng-Kai; Wang, Yu-Fu; Cheng, Yuan-Chung; Yang, Jye-Shane

    2013-04-18

    A constrained model compound of trans-4-(N,N-dimethylamino)-4'-nitrostilbene (DNS), namely, compound DNS-B3 that is limited to torsions about the phenyl-nitro C-N bond and the central C═C bond, was prepared to investigate the structural nature of the radiative and nonradiative states of electronically excited DNS. The great similarities in solvent-dependent electronic spectra, fluorescence decay times, and quantum yields for fluorescence (Φf) and trans → cis photoisomerization (Φtc) between DNS and DNS-B3 indicate that the fluorescence is from a planar charge-transfer state and torsion of the nitro group is sufficient to account for the nonradiative decay of DNS. This conclusion is supported by TDDFT calculations on DNS-B3 in dichloromethane. The structure at the conical intersection for internal conversion is associated with not only a twisting but also a pyramidalization of the nitro group. The mechanism of the NO2 torsion is discussed in terms of the effects of solvent polarity, the substituents, and the volume demand. The differences and analogies of the NO2- vs amino-twisted intramolecular charge-transfer (TICT) state of trans-aminostilbenes are also discussed.

  8. Investigating nuclear shell structure in the vicinity of 78Ni: Low-lying excited states in the neutron-rich isotopes Zn,8280

    NASA Astrophysics Data System (ADS)

    Shiga, Y.; Yoneda, K.; Steppenbeck, D.; Aoi, N.; Doornenbal, P.; Lee, J.; Liu, H.; Matsushita, M.; Takeuchi, S.; Wang, H.; Baba, H.; Bednarczyk, P.; Dombradi, Zs.; Fulop, Zs.; Go, S.; Hashimoto, T.; Honma, M.; Ideguchi, E.; Ieki, K.; Kobayashi, K.; Kondo, Y.; Minakata, R.; Motobayashi, T.; Nishimura, D.; Otsuka, T.; Otsu, H.; Sakurai, H.; Shimizu, N.; Sohler, D.; Sun, Y.; Tamii, A.; Tanaka, R.; Tian, Z.; Tsunoda, Y.; Vajta, Zs.; Yamamoto, T.; Yang, X.; Yang, Z.; Ye, Y.; Yokoyama, R.; Zenihiro, J.

    2016-02-01

    The low-lying level structures of nuclei in the vicinity of 78Ni were investigated using in-beam γ -ray spectroscopy to clarify the nature of the nuclear magic numbers Z =28 and N =50 in systems close to the neutron drip line. Nucleon knockout reactions were employed to populate excited states in 80Zn and 82Zn. A candidate for the 41+ level in 80Zn was identified at 1979(30) keV, and the lifetime of this state was estimated to be 136-67+92 ps from a line-shape analysis. Moreover, the energy of the 21+ state in 82Zn is reported to lie at 621(11) keV. The large drop in the 21+ energy at 82Zn indicates the presence of a significant peak in the E (21+) systematics at N =50 . Furthermore, the E (41+) /E (21+) and B (E 2 ;41+→21+) /B (E 2 ;21+→0g.s . +) ratios in 80Zn were deduced to be 1.32 (3 ) and 1 .12-60+80 , respectively. These results imply that 80Zn can be described in terms of two-proton configurations with a 78Ni core and are consistent with a robust N =50 magic number along the Zn isotopic chain. These observations, therefore, indicate a persistent N =50 shell closure in nuclei far from the line of β stability, which in turn suggests a doubly magic structure for 78Ni.

  9. Paramagnetic excited vortex states in superconductors

    NASA Astrophysics Data System (ADS)

    Gomes, Rodolpho Ribeiro; Doria, Mauro M.; Romaguera, Antonio R. de C.

    2016-06-01

    We consider excited vortex states, which are vortex states left inside a superconductor once the external applied magnetic field is switched off and whose energy is lower than of the normal state. We show that this state is paramagnetic and develop here a general method to obtain its Gibbs free energy through conformal mapping. The solution for any number of vortices in any cross-section geometry can be read off from the Schwarz-Christoffel mapping. The method is based on the first-order equations used by Abrikosov to discover vortices.

  10. Excited triplet state spectroscopy in the infrared

    NASA Astrophysics Data System (ADS)

    Baiardo, Joseph; Mukherjee, Ranajit; Vala, Martin

    1982-03-01

    A new method for the investigation of the infrared spectra of metastable excitedelectronic states is presented. With a Fourier Transform infrared spectrometer as the probe and a CW Xe lamp source as the pump, the infrared spectrum of the lowest triplet state of triphenylene isolated in a N 2 matrix at 15K has been examined. CH out-of-plane wagging modes are prominent and shifted from their ground state frequencies. It is expected that when fully developed this method will provide important information on excited state force constants and potential energy surfaces.

  11. On the Electronically Excited States of Uracil

    SciTech Connect

    Epifanovsky, Evgeny; Kowalski, Karol; Fan, Peng-Dong; Valiev, Marat; Matsika, Spiridoula; Krylov, Anna

    2008-10-09

    Vertical excitation energies in uracil in the gas phase and in water solution are investigated by the equation-of-motion coupled-cluster and multi-reference configuration interaction methods. Basis set effects are found to be important for converged results. The analysis of electronic wave functions reveals that the lowest singlet states are predominantly of a singly excited character and are therefore well described by single-reference equation-of-motion methods augmented by a perturbative triples correction to account for dynamical correlation. Our best estimates for the vertical excitation energies for the lowest singlet n and are 5.0±0.1 eV and 5.3±0.1 eV, respectively. The solvent effects for these states are estimated to be +0.5 eV and ±0.1 eV, respectively. We attribute the difference between the computed vertical excitations and the maximum of the experimental absorption to strong vibronic interaction between the lowest A00 and A0 states leading to intensity borrowing by the forbidden transition.

  12. STIRAP on helium: Excitation to Rydberg states

    NASA Astrophysics Data System (ADS)

    Yuan, Deqian

    Research in optically induced transitions between dierent atomic levels has a long history. For transitions between states driven by a coherent optical eld, the theoretical eciency could be ideally high as 100% but there could be many factors preventing this. In the three state helium atom excitation process, i.e. 23S→33P→nL , the stimulated emission from intermediate state makes it hard to achieve ecient population transfer to the nal state through an intuitive excitation order. One technique to achieve a higher eciency is Stimulated Raman Adiabatic Passage (STIRAP) which is being studied and under research in our lab. Unlike traditional three level excitation processes, STIRAP actually uses a counter intuitive pulsed laser beams timing arrangement. The excitation objects are metastable helium atoms traveling in a vacuum system with a longitudinal velocity of ~ 1070 m/s. We are using a 389 nm UV laser to connect the 23S and the 33P state and a frequency tunable ~790 nm IR laser to connect the 33P state and the dierent Rydberg states. A third 1083 nm wavelength laser beam drives the 23S → 23P transition to transversely separate the residual metastable atoms and the Rydberg atoms for eciency measurements. The data is taken by a stainless steel detector in the vacuum system. As the Rydberg atoms will get ionized by blackbody radiation under room temperature, we can utilize this for their detection. An ion detector sitting on the eld plate is capable to collect the ion signals of the Rydberg atoms for detection. So far the whole system has not been ready for data collection and measurement, so here we are using data and results from previous theses for discussions. The highest transition frequency that has ever been achieved in our lab is around 70% after corrections.

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

    PubMed

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

    2002-03-20

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

  14. Accelerating slow excited state proton transfer

    PubMed Central

    Stewart, David J.; Concepcion, Javier J.; Brennaman, M. Kyle; Binstead, Robert A.; Meyer, Thomas J.

    2013-01-01

    Visible light excitation of the ligand-bridged assembly [(bpy)2RuaII(L)RubII(bpy)(OH2)4+] (bpy is 2,2′-bipyridine; L is the bridging ligand, 4-phen-tpy) results in emission from the lowest energy, bridge-based metal-to-ligand charge transfer excited state (L−•)RubIII-OH2 with an excited-state lifetime of 13 ± 1 ns. Near–diffusion-controlled quenching of the emission occurs with added HPO42− and partial quenching by added acetate anion (OAc−) in buffered solutions with pH control. A Stern–Volmer analysis of quenching by OAc− gave a quenching rate constant of kq = 4.1 × 108 M−1⋅s−1 and an estimated pKa* value of ∼5 ± 1 for the [(bpy)2RuaII(L•−)RubIII(bpy)(OH2)4+]* excited state. Following proton loss and rapid excited-state decay to give [(bpy)2RuaII(L)RubII(bpy)(OH)3+] in a H2PO4−/HPO42− buffer, back proton transfer occurs from H2PO4− to give [(bpy)2RuaII(L)Rub(bpy)(OH2)4+] with kPT,2 = 4.4 × 108 M−1⋅s−1. From the intercept of a plot of kobs vs. [H2PO4−], k = 2.1 × 106 s−1 for reprotonation by water providing a dramatic illustration of kinetically limiting, slow proton transfer for acids and bases with pKa values intermediate between pKa(H3O+) = −1.74 and pKa(H2O) = 15.7. PMID:23277551

  15. Two-neutron decay of excited states of 11Li

    NASA Astrophysics Data System (ADS)

    Smith, Jenna; MoNA Collaboration

    2013-10-01

    One prominent example of a Borromean nucleus is the two-neutron halo nucleus, 11Li. All excited states of this nucleus are unbound to two-neutron decay. Many theories propose that the two valence neutrons exhibit dineutron behavior in the ground state, but it is unclear what effect such a structure would have on the decay of the excited states. We have recently completed an experiment designed to study the decay of one of these excited states. Unbound 11Li was populated via a two-proton knockout from 13B. The two emitted neutrons were detected with the Modular Neutron Array (MoNA) and the Large-area multi-Institutional Scintillator Array (LISA) in coincidence with the daughter fragment, 9Li. Preliminary results will be discussed.

  16. Peculiarities of excited state structure and photoluminescence in Bi(3+)-doped Lu(3)Al(5)O(12) single-crystalline films.

    PubMed

    Babin, V; Gorbenko, V; Krasnikov, A; Makhov, A; Nikl, M; Polak, K; Zazubovich, S; Zorenko, Yu

    2009-10-14

    Single-crystalline films of Lu(3)Al(5)O(12):Bi, prepared by the liquid phase epitaxy method from the melt-solution based on Bi(2)O(3) flux, have been studied at 4.2-400 K by time-resolved luminescence spectroscopy methods. Their emission spectra consist of two types of bands with strongly different characteristics. The ultraviolet emission band consists of two components, arising from the electronic transitions which correspond to the [Formula: see text] and [Formula: see text] transitions in a free Bi(3+) ion. At low temperatures, mainly the lower-energy component of this emission is observed, having the decay time∼10(-3) s at T<100 K and arising from the metastable (3)P(0) level. At T>100 K, the higher-energy emission component appears, arising from the thermally populated emitting (3)P(1) level. The visible emission spectrum consists of two dominant strongly overlapped broad bands with large Stokes shifts. At 4.2 K, their decay times are ∼10(-5) s and decrease with increasing temperature. Both of the visible emission bands are assumed to have an exciton origin. The lower-energy band is ascribed to an exciton, localized near a single Bi(3+) ion. The higher-energy band shows a stronger intensity dependence on the Bi(3+) content and is assumed to arise from an exciton localized near a dimer Bi(3+) center. The origin and structure of the corresponding excited states is considered and the processes, taking place in the excited states, are discussed.

  17. Photoionization of aligned molecular excited states

    NASA Astrophysics Data System (ADS)

    Appling, J. R.; White, M. G.; Kessler, W. J.; Fernandez, R.; Poliakoff, E. D.

    1988-02-01

    Photoelectron angular distributions of several excited states of NO have been measured in an effort to better elucidate the role of alignment in resonant multiphoton excitation processes of molecules. In contrast to previous molecular REMPI measurements on NO, (2+1) angular distributions taken for low rotational levels of the E 2Σ+ (4sσ) Rydberg state of NO exhibit complex angular behavior which is characteristic of strong spatial alignment of the optically prepared levels. Photoelectron angular distributions were also found to be strongly branch and J dependent with the lowest rotational levels of the R21+S11 branch exhibiting the full anisotropy expected for an overall three-photon process. Fluorescence anisotropies extracted from complementary two-photon fluorescence angular distribution measurements reveal small, but nonzero alignment in all rotational levels with J>1/2, in contrast to the photoelectron results. Additional photoelectron angular distributions taken for (1+1) REMPI via the A 2Σ+ (3sσ), v=0 state exhibit near ``cos2θ'' distributions characteristic of photoionization of unaligned target states. The observed photoelectron data are qualitatively interpreted on the basis of the angular momentum constraints of the excitation-induced alignment and photoionization dynamics which determine the observable moments in the angular distribution.

  18. Excited-state distortions of cyclometalated Ir(III) complexes determined from the vibronic structure in luminescence spectra.

    PubMed

    Wang, Xianghuai; Li, Jian; Thompson, Mark E; Zink, Jeffrey I

    2007-05-03

    The luminescence spectra of [(tpy)(2)Ir(CN-t-Bu)2](CF(3)SO(3)) in methylcyclohexane glass and frozen n-nonane at 15 K reveal well-resolved vibronic fine structure. The vibronic peaks are assigned by comparison with the vibrational frequencies obtained from Raman and IR spectra and those obtained using DFT electronic structure calculations. The magnitudes of the distortions along the normal coordinates are calculated by fitting the emission spectra using the time-dependent theory of spectroscopy. Broadening effects and the MIME frequency observed at room temperature are interpreted. The most highly distorted normal modes involve atomic motions on the tpy ligand, consistent with the metal to ligand/ligand centered assignment of the electronic transition.

  19. Intermediate Excited States in Rhodopsin Photochemistry

    NASA Astrophysics Data System (ADS)

    Rothberg, L. J.; Yan, M.; Jedju, T. M.; Callender, R. H.; Chao, H.; Alfano, R. R.

    1996-03-01

    Recent work by Wang et.al. footnote Q. Wang et.al., Science 266, 422 (1994) reports rapid coherent photoisomerization in rhodopsin. The bathorhodopsin photoproduct appears in 200 fs and exhibits torsional oscillations which remain synchronized with the initial photoexcitation. We report transient absorption experiments which suggest that the fraction of excited rhodopsin molecules which does not isomerize in this fashion (approximately 1/3) remains in an electronically excited state, probably the twisted state described by Birge and Hubbard,footnote R. R. Birge and L. M. Hubbard, J. Am. Chem. Soc. 102, 2195 (1980) for ~ 3 ps and then reforms rhodopsin. This picture explains the long bleaching recovery time for rhodopsin and the controversial spectral dynamics which are observed in the red.

  20. Structure and excited state relaxation dynamics in nanoscale self-assembled arrays: multiporphyrin complexes, porphyrin-quantum dot composites

    NASA Astrophysics Data System (ADS)

    Zenkevich, E. I.; von Borczyskowski, C.

    2005-06-01

    Self-assembled nanoscale arrays of controllable geometry and composition (up to 8 tetrapyrroles) have been formed via non-covalent binding interactions of the meso-phenyl bridged Zn-octaethylporphyrin chemical dimers or trimers with di- /tetrapyridyl substituted porphyrin extra-ligands. In these complexes using steady-state and time-resolved (ps fluorescence and fs pump-probe) measurements pathways and efficiencies of the energy transfer photoinduced charge separation as well as exchange d-π effects have been studied in solutions of variable polarity at 77-293 K. The same principles of aggregation via the key-hole scheme "Zn-pyridyl" have been used also for the surface passivation of pyridylsubstituted tetrapyrroles on the coreshell semiconductor CdSe/ZnS quantum dots (QD) showing quantum confinement effects. Picosecond time-resolved and steady-state data reveal that CdSe/ZnS QD emission is multiexponential and the efficiency of its quenching by attached porphyrins (due to energy transfer and photoinduced charge separation) depends strongly on the number of anchoring groups their arrangement in the porphyrin molecule as well as on QD size and number of ZnS monolayers. The analysis of spectroscopic and kinetic findings reveals that on average only ~l/5 porphyrin molecules are assembled on the QD and a limited number of "vacancies" accessible for porphyrin attachment is available on the QD surface.

  1. Ethyne-bridged (porphinato)zinc(II)-(porphinato)iron(III) complexes: phenomenological dependence of excited-state dynamics upon (porphinato)iron electronic structure.

    PubMed

    Duncan, Timothy V; Wu, Sophia P; Therien, Michael J

    2006-08-16

    We report the synthesis, spectroscopy, potentiometric properties, and excited-state dynamical studies of 5-[(10,20-di-((4-ethyl ester)methylene-oxy)phenyl)porphinato]zinc(II)-[5'-[(10',20'- di-((4-ethyl ester)methylene-oxy)phenyl)porphinato]iron(III)-chloride]ethyne (PZn-PFe-Cl), along with a series of related supermolecules ([PZn-PFe-(L)1,2]+ species) that possess a range of metal axial ligation environments (L = pyridine, 4-cyanopyridine, 2,4,6-trimethylpyridine (collidine), and 2,6-dimethylpyridine (2,6-lutidine)). Relevant monomeric [(porphinato)iron-(ligand)1,2]+ ([PFe(L)1,2]+) benchmarks have also been synthesized and fully characterized. Ultrafast pump-probe transient absorption spectroscopic experiments that interrogate the initially prepared electronically excited states of [PFe(L)1,2]+ species bearing nonhindered axial ligands demonstrated subpicosecond-to-picosecond relaxation dynamics to the ground electronic state. Comparative pump-probe transient absorption experiments that interrogate the initially prepared excited states of PZn-PFe-Cl, [PZn-PFe-(py)2]+, [PZn-PFe-(4-CN-py)2]+, [PZn-PFe-(collidine)]+, and [PZn-PFe-(2,6-lutidine)]+ demonstrate that the spectra of all these species are dominated by a broad, intense NIR S1 --> Sn transient absorption manifold. While PZn-PFe-Cl, [PZn-PFe-(py)2]+, and [PZn-PFe-(4-CN-py)2]+ evince subpicosecond and picosecond time-scale relaxation of their respective initially prepared electronically excited states to the ground state, the excited-state dynamics observed for [PZn-PFe-(2,6-lutidine)]+ and [PZn-PFe-(collidine)]+ show fast relaxation to a [PZn+-PFe(II)] charge-separated state having a lifetime of nearly 1 ns. Potentiometric data indicate that while DeltaGCS for [PZn-PFe-(L)1,2]+ species is strongly influenced by the PFe+ ligation state [ligand (DeltaGCS): 4-cyanopyridine (-0.79 eV) < pyridine (-1.04 eV) < collidine (-1.35 eV) < chloride (-1.40 eV); solvent = CH2Cl2], the pump-probe transient absorption

  2. Exploration of Excited State Deactivation Pathways of Adenine Monohydrates.

    PubMed

    Chaiwongwattana, Sermsiri; Sapunar, Marin; Ponzi, Aurora; Decleva, Piero; Došlić, Nađa

    2015-10-29

    Binding of a single water molecule has a dramatic effect on the excited state lifetime of adenine. Here we report a joint nonadiabatic dynamics and reaction paths study aimed at understanding the sub-100 fs lifetime of adenine in the monohydrates. Our nonadiabatic dynamics simulations, performed using the ADC(2) electronic structure method, show a shortening of the excited state lifetime in the monohydrates with respect to bare adenine. However, the computed lifetimes were found to be significantly longer that the observed one. By comparing the reaction pathways of several excited state deactivation processes in adenine and adenine monohydrates, we show that electron-driven proton transfer from water to nitrogen atom N3 of the adenine ring may be the process responsible for the observed ultrafast decay. The inaccessibility of the electron-driven proton transfer pathway to trajectory-based nonadiabatic dynamics simulation is discussed.

  3. Stretched-State Excitations with the

    NASA Astrophysics Data System (ADS)

    Garcia, Luis Alberto Casimiro

    Neutron time-of-fight spectra were obtained for the ^{14}C(p,n) ^{14}N, ^{18 }O(p,n)^{18}F, and ^{30}Si(p,n) ^{30}P reactions at 135 MeV with the beam-swinger system at the Indiana University Cyclotron Facility. Excitation-energy spectra and the differential cross sections for the observed excitations in these reactions were extracted over the momentum transfer range from 0 to 2.7 fm^{-1}. The primary goal of this work was to obtain the strengths and distributions for the "stretched" states. The identification of these states was based on comparisons of the theoretical differential cross sections, performed in a DWIA formalism, with the experimental cross sections. Isospin assignments were based primarily on comparisons of the measured (p,n) and (e,e^') spectroscopic strengths. Candidate (pid_ {5/2},nu{rm p}_sp {3/2}{-1}), J^ pi = 4 ^- T = 0, 1 and 2, 1 hbaromega states, were identified at E_{x} = 8.5, 13.8, 19.5, and 26.7 MeV in the ^{14}C(p,n) ^{14}N reaction, and the corresponding isovector strengths were extracted. The observed 4^--state excitation energies and the strengths are in good agreement with the analog T = 1 and 2, 4^--states observed in the (e,e^') reaction. Large -basis shell-model calculations were found to predict reasonably well the excitation energies; however, these calculations overpredict the strength by a factor of 2, for the T = 1 and 2 components. In the ^{18}O(p,n) ^{18}F reaction at 135 MeV, (pi d_{5/2},nu {rm d}_sp{5/2}{-1 }) 5^+ T = 0 0hbaromega strength was observed, concentrated in a single state, at E_{x} = 1.1 MeV, with 75% of the extreme-single-particle-model (ESPM) strength, in good agreement with a shell-model calculation. No 6^- 1hbaromega strength was observed in this reaction. Candidate (pi {rm d}_{5/2},nu p _sp{3/2}{-1}) J ^pi = 4^- T = 0, 1 and 2, 1hbaromega states, were identified at E_{x} = 3.9, 9.4, 10.2, 11.4, 12.0, 14.4, 15.3, 17.3, 18.0, 19.7, 21.4, and 23.4 MeV. The observed 4^- T = 2 state excitation energies and

  4. Excited state baryon spectroscopy from lattice QCD

    DOE PAGES

    Robert G. Edwards; Dudek, Jozef J.; Richards, David G.; ...

    2011-10-31

    Here, we present a calculation of the Nucleon and Delta excited state spectrum on dynamical anisotropic clover lattices. A method for operator construction is introduced that allows for the reliable identification of the continuum spins of baryon states, overcoming the reduced symmetry of the cubic lattice. Using this method, we are able to determine a spectrum of single-particle states for spins up to and including $J = 7/2$, of both parities, the first time this has been achieved in a lattice calculation. We find a spectrum of states identifiable as admixtures of $SU(6) Ⓧ O(3)$ representations and a counting ofmore » levels that is consistent with the non-relativistic $qqq$ constituent quark model. This dense spectrum is incompatible with quark-diquark model solutions to the "missing resonance problem" and shows no signs of parity doubling of states.« less

  5. Excited state baryon spectroscopy from lattice QCD

    SciTech Connect

    Robert G. Edwards; Dudek, Jozef J.; Richards, David G.; Wallace, Stephen J.

    2011-10-31

    Here, we present a calculation of the Nucleon and Delta excited state spectrum on dynamical anisotropic clover lattices. A method for operator construction is introduced that allows for the reliable identification of the continuum spins of baryon states, overcoming the reduced symmetry of the cubic lattice. Using this method, we are able to determine a spectrum of single-particle states for spins up to and including $J = 7/2$, of both parities, the first time this has been achieved in a lattice calculation. We find a spectrum of states identifiable as admixtures of $SU(6) Ⓧ O(3)$ representations and a counting of levels that is consistent with the non-relativistic $qqq$ constituent quark model. This dense spectrum is incompatible with quark-diquark model solutions to the "missing resonance problem" and shows no signs of parity doubling of states.

  6. Low-Lying ππ* States of Heteroaromatic Molecules: A Challenge for Excited State Methods.

    PubMed

    Prlj, Antonio; Sandoval-Salinas, María Eugenia; Casanova, David; Jacquemin, Denis; Corminboeuf, Clémence

    2016-06-14

    The description of low-lying ππ* states of linear acenes by standard electronic structure methods is known to be challenging. Here, we broaden the framework of this problem by considering a set of fused heteroaromatic rings and demonstrate that standard electronic structure methods do not provide a balanced description of the two (typically) lowest singlet state (La and Lb) excitations. While the Lb state is highly sensitive to correlation effects, La suffers from the same drawbacks as charge transfer excitations. We show that the comparison between CIS/CIS(D) can serve as a diagnostic for detecting the two problematic excited states. Standard TD-DFT and even its spin-flip variant lead to inaccurate excitation energies and interstate gaps, with only a double hybrid functional performing somewhat better. The complication inherent to a balanced description of these states is so important that even CC2 and ADC(2) do not necessarily match the ADC(3) reference.

  7. Radiative and Excited State Charmonium Physics

    SciTech Connect

    Jozef Dudek

    2007-07-30

    Renewed interest in the spectroscopy of charmonium has arisen from recent unexpected observations at $e^+e^-$ colliders. Here we report on a series of works from the previous two years examining the radiative physics of charmonium states as well as the mass spectrum of states of higher spin and internal excitation. Using new techniques applied to Domain-Wall and Clover quark actions on quenched isotropic and anisotropic lattices, radiative transitions and two-photon decays are considered for the first time. Comparisons are made with experimental results and with model approaches. Forthcoming application to the light-quark sector of relevance to experiments like Jefferson Lab's GlueX is discussed.

  8. Role of conformation and electronic structure in the chemistry of ground and excited state o-pyrazolylphenylnitrenes.

    PubMed

    Carra, Claudio; Bally, Thomas; Albini, Angelo

    2005-04-20

    The chemistry of 2-(1-pyrazolyl)- (2a) and 2-[1-(3,5-dimethylpyrazolyl]phenylnitrene (2b) has been studied in EtOH solution at room temperature, in EtOH glasses at 90 K, and in Ar matrices at 12 K. These nitrenes were chosen as suitable models for clarifying the mechanism of intramolecular reactions because attack at the pyrazole ring can occur according to different modes and the asymmetry of the substituent gives rise to different conformations. Detailed DFT and CASSCF/CASPT2 studies on the conformation and decay paths of both spin states of the nitrenes have been carried out. Ring expansion to dehydroazepines (via benzoazirines) is calculated to be competitive in both nitrenes, but in the dimethyl derivative, 2b, attack onto the N lone pair (which is made more nucleophilic by the methyl groups) is favored. The higher barriers (by 4-8 kcal/mol) in singlet 2a cause 60-70% of this nitrene to decay by intersystem crossing to the triplet. Thus, the seemingly straightforward formation of benzo-fused heterocycles through intramolecular attack of the pyrazoline N lone pair by the singlet phenylnitrene can only overcome ring expansion and intermolecular reactions under favorable circumstances. The comparatively persistent triplet nitrenes are characterized in matrices, and the yields of photocyclization products (mainly pyrazolo[1,5-a]benzimidazole (7) from 2a and 5,6-dihydropyrazolo[1,5-a]quinoxaline (8) from 2b) are shown to depend on the preferred conformation of the starting azide and nitrene.

  9. Ensemble density functional theory method correctly describes bond dissociation, excited state electron transfer, and double excitations

    SciTech Connect

    Filatov, Michael; Huix-Rotllant, Miquel; Burghardt, Irene

    2015-05-14

    State-averaged (SA) variants of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, SA-REKS and state-interaction (SI)-SA-REKS, implement ensemble density functional theory for variationally obtaining excitation energies of molecular systems. In this work, the currently existing version of the SA-REKS method, which included only one excited state into the ensemble averaging, is extended by adding more excited states to the averaged energy functional. A general strategy for extension of the REKS-type methods to larger ensembles of ground and excited states is outlined and implemented in extended versions of the SA-REKS and SI-SA-REKS methods. The newly developed methods are tested in the calculation of several excited states of ground-state multi-reference systems, such as dissociating hydrogen molecule, and excited states of donor–acceptor molecular systems. For hydrogen molecule, the new method correctly reproduces the distance dependence of the lowest excited state energies and describes an avoided crossing between the doubly excited and singly excited states. For bithiophene–perylenediimide stacked complex, the SI-SA-REKS method correctly describes crossing between the locally excited state and the charge transfer excited state and yields vertical excitation energies in good agreement with the ab initio wavefunction methods.

  10. Electronic structure, transport properties, and excited states in CoTiSb, CoZrSb, and CoHfSb half-Heusler compounds

    NASA Astrophysics Data System (ADS)

    Janotti, Anderson; Gui, Zhigang; Kawasaki, Jason; Palmstrom, Chris; Himmetoglu, Burak

    CoTiSb is a member of a large family of half-Heusler compounds with 18 valence electrons. CoTiSb is semiconductor material with a band gap a little over 1 eV, and it has been considered promising for thermoelectric applications. It can be grown on conventional III-V semiconductors, and could potentially be integrated in III-V devices. Here we present results of first-principles calculations of electronic structure, transport properties, and excited states in CoTiSb, as well as CoZrSb and CoHfSb. Electronic structures are studied using density functional theory within the local density approximation, hybrid functional and quasiparticle GW methods. Both room-temperature Seebeck coefficient and carrier mobility are calculated from first-principles. We also determine the band alignments to III-V semiconductors, and all the results are presented and discussed in the light of available experimental data. This work was supported by the DOE.

  11. Excited state structural events of a dual-emission fluorescent protein biosensor for Ca²⁺ imaging studied by femtosecond stimulated Raman spectroscopy.

    PubMed

    Wang, Yanli; Tang, Longteng; Liu, Weimin; Zhao, Yongxin; Oscar, Breland G; Campbell, Robert E; Fang, Chong

    2015-02-12

    Fluorescent proteins (FPs) are luminescent biomolecules that emit characteristic hues upon irradiation. A group of calmodulin (CaM)-green FP (GFP) chimeras have been previously engineered to enable the optical detection of calcium ions (Ca(2+)). We investigate one of these genetically encoded Ca(2+) biosensors for optical imaging (GECOs), GEM-GECO1, which fluoresces green without Ca(2+) but blue with Ca(2+), using femtosecond stimulated Raman spectroscopy (FSRS). The time-resolved FSRS data (<800 cm(-1)) reveal that initial structural evolution following 400 nm photoexcitation involves small-scale coherent proton motions on both ends of the chromophore two-ring system with a <250 fs time constant. Upon Ca(2+) binding, the chromophore adopts a more twisted conformation in the protein pocket with increased hydrophobicity, which inhibits excited-state proton transfer (ESPT) by effectively trapping the protonated chromophore in S1. Both the chromophore photoacidity and local environment form the ultrafast structural dynamics basis for the dual-emission properties of GEM-GECO1. Its photochemical transformations along multidimensional reaction coordinates are evinced by distinct stages of FSRS spectral evolution, particularly related to the ∼460 and 504 cm(-1) modes. The direct observation of lower frequency modes provides crucial information about the nuclear motions preceding ESPT, which enriches our understanding of photochemistry and enables the rational design of new biosensors.

  12. Excited state electron affinity calculations for aluminum

    NASA Astrophysics Data System (ADS)

    Hussein, Adnan Yousif

    2017-08-01

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

  13. Molecular and vibrational structure of tetroxo d0 metal complexes in their excited states. a study based on time-dependent density functional calculations and Franck-Condon theory.

    PubMed

    Jose, Linta; Seth, Michael; Ziegler, Tom

    2012-02-23

    We have applied time dependent density functional theory to study excited state structures of the tetroxo d(0) transition metal complexes MnO(4)(-), TcO(4)(-), RuO(4), and OsO(4). The excited state geometry optimization was based on a newly implemented scheme [Seth et al. Theor. Chem. Acc. 2011, 129, 331]. The first excited state has a C(3v) geometry for all investigated complexes and is due to a "charge transfer" transition from the oxygen based HOMO to the metal based LUMO. The second excited state can uniformly be characterized by "charge transfer" from the oxygen HOMO-1 to the metal LUMO with a D(2d) geometry for TcO(4)(-), RuO(4), and OsO(4) and two C(2v) geometries for MnO(4)(-). It is finally found that the third excited state of MnO(4)(-) representing the HOMO to metal based LUMO+1 orbital transition has a D(2d) geometry. On the basis of the calculated excited state structures and vibrational modes, the Franck-Condon method was used to simulate the vibronic structure of the absorption spectra for the tetroxo d(0) transition metal complexes. The Franck-Condon scheme seems to reproduce the salient features of the experimental spectra as well as the simulated vibronic structure for MnO(4)(-) generated from an alternative scheme [Neugebauer J. J. Phys. Chem. A 2005, 109, 1168] that does not apply the Franck-Condon approximation.

  14. Polymethine and squarylium molecules with large excited-state absorption

    NASA Astrophysics Data System (ADS)

    Lim, Jin Hong; Przhonska, Olga V.; Khodja, Salah; Yang, Sidney; Ross, T. S.; Hagan, David J.; Van Stryland, Eric W.; Bondar, Mikhail V.; Slominsky, Yuriy L.

    1999-07-01

    We study nonlinear absorption in a series of ten polymethine dyes and two squarylium dyes using Z-scan, pump-probe and optical limiting experiments. Both picosecond and nanosecond characterization were performed at 532 nm, while picosecond measurements were performed using an optical parametric oscillator (OPO) from 440 to 650 nm. The photophysical parameters of these dyes including cross sections and excited-state lifetimes are presented both in solution in ethanol and in an elastopolymeric material, polyurethane acrylate (PUA). We determine that the dominant nonlinearity in all these dyes is large excited-state absorption (ESA), i.e. reverse saturable absorption. For several of the dyes we measure a relatively large ground-state absorption cross section, σ01, which effectively populates an excited state that possesses an extremely large ESA cross section, σ12. The ratios of σ12/ σ01 are the largest we know of, up to 200 at 532 nm, and lead to very low thresholds for optical limiting. However, the lifetimes of the excited state are of the order of 1 ns in ethanol, which is increased to up to 3 ns in PUA. This lifetime is less than optimum for sensor protection applications for Q-switched inputs, and intersystem crossing times for these molecules are extremely long, so that triplet states are not populated. These parameters show a significant improvement over those of the first set of this class of dyes studied and indicate that further improvement of the photophysical parameters may be possible. From these measurements, correlations between molecular structure and nonlinear properties are made. We propose a five-level, all-singlet state model, which includes reorientation processes in the first excited state. This includes a trans- cis conformational change that leads to the formation of a new state with a new molecular configuration which is also absorbing but can undergo a light-induced degradation at high inputs.

  15. Electronically excited states of sodium-water clusters

    NASA Astrophysics Data System (ADS)

    Schulz, Claus Peter; Bobbert, Christiana; Shimosato, Taku; Daigoku, Kota; Miura, Nobuaki; Hashimoto, Kenro

    2003-12-01

    The lowest electronically excited state of small Na(H2O)n clusters has been investigated experimentally and theoretically. The excitation energy as determined by the depletion spectroscopy method drops from 16 950 cm-1 for the sodium atom down to 9670 cm-1 when only three water molecules are attached to the Na atom. For larger clusters the absorption band shifts back towards higher energies and reaches 10 880 cm-1 for n=12. The experimental data are compared to quantum-chemical calculations at the Møeller-Plesset second-order perturbation and multireference single and double excitation configuration interaction levels. We found that the observed size dependence of the transition energy is well reproduced by the interior structure where the sodium atom is surrounded by water molecules. The analysis of the radial charge distribution of the unpaired electron in these interior structures gives a new insight into the formation of the "solvated" electron.

  16. Semiclassical quantization of highly excited scar states

    NASA Astrophysics Data System (ADS)

    Vergini, Eduardo G.

    2017-04-01

    The semiclassical quantization of Hamiltonian systems with classically chaotic dynamics is restricted to low excited states, close to the ground state, because the number of required periodic orbits grows exponentially with energy. Nevertheless, here we demonstrate that it is possible to find eigenenergies of highly excited states scarred by a short periodic orbit. Specifically, by using 18146 homoclinic orbits (HO)s of the shortest periodic orbit of the hyperbola billiard, we find eigenenergies of the strongest scars over a range which includes 630 even eigenfunctions. The analysis of data reveals that the used semiclassical formula presents two regimes. First, when all HOs with excursion time smaller than the Heisenberg time t H are included, the error is around 3.3% of the mean level spacing. Second, in the energy region defined by \\tilde{t}/ tH > 0.13 , where \\tilde{t} is the maximum excursion time included in the calculation, the error is around 15% of the mean level spacing.

  17. Ultrafast Structural Dynamics of Tertiary Amines upon Electronic Excitation

    NASA Astrophysics Data System (ADS)

    Cheng, Xinxin; Minitti, Michael P.; Deb, Sanghamitra; Zhang, Yao; Budarz, James; Weber, Peter M.

    2011-06-01

    The structural response of several tertiary amines to electronic excitation has been investigated using Rydberg Fingerprint Spectroscopy. The 3p Rydberg states are reached by excitation with a 5.93 eV photon while 3s states are populated by electronic relaxation from 3p state. We observe binding energy shifts on ultrafast time scales in all peaks that reflect the structural change of the molecular ion cores. The shifts are in the range of 15 meV to 30 meV, within time scales of less than 500 fs, depending on the specific molecular systems and the nature of the electronic state. In cases where the p states are spectrally separate, the trends of the energy shifts are different for the p_z and p_x_y Rydberg states whereas the p_z and s states are similar. This suggests that the response of the Rydberg states to structural displacements depends on the symmetry. Very fast binding energy shifts, observed on sub-picosecond time scales, are attributed to the structural adjustment from a pyramidal to a planar structure upon Rydberg excitation. The quantitative values of the binding energy shifts can also be affected by laser chirp, which we model using simulations.

  18. Atomic Resolution Mapping of the Excited-State Electronic Structure of Cu2O with Time-Resolved X-Ray Absorption Spectroscopy

    SciTech Connect

    Hillyard, Patrick B.; Kuchibhatla, Satyanarayana V N T; Glover, T. E.; Hertlein, M. P.; Huse, N.; Nachimuthu, Ponnusamy; Saraf, Laxmikant V.; Thevuthasan, Suntharampillai; Gaffney, Kelly J.

    2009-09-29

    We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the O K-edge and the Cu L3-edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that that the conduction band and valence band edges have very similar Cu 3d and O 2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the Cu L3- and O K-edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process.

  19. Atomic resolution mapping of the excited-state electronic structure of Cu2O with time-resolved x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Hillyard, P. W.; Kuchibhatla, S. V. N. T.; Glover, T. E.; Hertlein, M. P.; Huse, N.; Nachimuthu, P.; Saraf, L. V.; Thevuthasan, S.; Gaffney, K. J.

    2009-09-01

    We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the OK edge and the CuL3 edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that the conduction-band and valence-band edges have very similar Cu3d and O2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the CuL3 - and OK -edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process.

  20. Atomic resolution mapping of the excited-state electronic structure of Cu2O with time-resolved x-ray absorption spectroscopy

    SciTech Connect

    Hillyard, P. W.; Kuchibhatla, S. V. N. T.; Glover, T. E.; Hertlein, M. P.; Huse, Nils; Nachimuthu, P.; Saraf, L. V.; Thevuthasan, S.; Gaffney, K. J.

    2010-05-02

    We have used time-resolved soft x-ray spectroscopy to investigate the electronic structure of optically excited cuprous oxide at the O K-edge and the Cu L3-edge. The 400 nm optical excitation shifts the Cu and O absorptions to lower energy, but does not change the integrated x-ray absorption significantly for either edge. The constant integrated x-ray absorption cross-section indicates that the conduction-band and valence-band edges have very similar Cu 3d and O 2p orbital contributions. The 2.1 eV optical band gap of Cu2O significantly exceeds the one eV shift in the Cu L3- and O K-edges absorption edges induced by optical excitation, demonstrating the importance of core-hole excitonic effects and valence electron screening in the x-ray absorption process.

  1. Multiparticle configurations of excited states in 155Lu

    NASA Astrophysics Data System (ADS)

    Carroll, R. J.; Hadinia, B.; Qi, C.; Joss, D. T.; Page, R. D.; Uusitalo, J.; Andgren, K.; Cederwall, B.; Darby, I. G.; Eeckhaudt, S.; Grahn, T.; Gray-Jones, C.; Greenlees, P. T.; Jones, P. M.; Julin, R.; Juutinen, S.; Leino, M.; Leppänen, A.-P.; Nyman, M.; Pakarinen, J.; Rahkila, P.; Sandzelius, M.; Sarén, J.; Scholey, C.; Seweryniak, D.; Simpson, J.

    2016-12-01

    Excited states in the neutron-deficient N =84 nuclide 155Lu have been populated by using the 102Pd(58Ni,α p ) reaction. The 155Lu nuclei were separated by using the gas-filled recoil ion transport unit (RITU) separator and implanted into the Si detectors of the gamma recoil electron alpha tagging (GREAT) spectrometer. Prompt γ -ray emissions measured at the target position using the JUROGAM Ge detector array were assigned to 155Lu through correlations with α decays measured in GREAT. Structures feeding the (11 /2-) and (25 /2-)α -decaying states have been revised and extended. Shell-model calculations have been performed and are found to reproduce the excitation energies of several of the low-lying states observed to within an average of 71 keV. In particular, the seniority inversion of the 25 /2- and 27 /2- states is reproduced.

  2. Excitation of a slow wave structure

    SciTech Connect

    Zhang Peng; Lau, Y. Y.; Hoff, Brad; French, D. M.; Luginsland, J. W.

    2012-12-15

    The Green's function on a slow wave structure is constructed. The Green's function includes all radial modes, and for each radial mode, all space harmonics. We compare the analytic solution of the frequency response on the slow wave structure with that obtained from a particle-in-cell code. Favorable comparison is obtained when the first few lower order modes are resonantly excited. This gives some confidence in the prediction of converting a pulse train into radiation using a slow wave structure.

  3. Excited-State Electronic Structure with Configuration Interaction Singles and Tamm-Dancoff Time-Dependent Density Functional Theory on Graphical Processing Units.

    PubMed

    Isborn, Christine M; Luehr, Nathan; Ufimtsev, Ivan S; Martínez, Todd J

    2011-06-14

    Excited-state calculations are implemented in a development version of the GPU-based TeraChem software package using the configuration interaction singles (CIS) and adiabatic linear response Tamm-Dancoff time-dependent density functional theory (TDA-TDDFT) methods. The speedup of the CIS and TDDFT methods using GPU-based electron repulsion integrals and density functional quadrature integration allows full ab initio excited-state calculations on molecules of unprecedented size. CIS/6-31G and TD-BLYP/6-31G benchmark timings are presented for a range of systems, including four generations of oligothiophene dendrimers, photoactive yellow protein (PYP), and the PYP chromophore solvated with 900 quantum mechanical water molecules. The effects of double and single precision integration are discussed, and mixed precision GPU integration is shown to give extremely good numerical accuracy for both CIS and TDDFT excitation energies (excitation energies within 0.0005 eV of extended double precision CPU results).

  4. Lifetimes of Bound Excited States of Si^-

    NASA Astrophysics Data System (ADS)

    O'Malley, Steven M.; Beck, Donald R.

    2003-05-01

    The bound excited states of Si^- lie 6955 cm-1 (^2D_3/2), 6969 cm-1 (M. Scheer et al, Phys. Rev. Lett. 80), 2562 (1998). (^2D_5/2), and 10 977 cm-1 (A. Kasden et al, J. Chem. Phys. 62), 541 (1975). (^2P_1/2) above the ^4S_3/2 ground state. Transitions from each of the bottom three levels to the ^2P_1/2 level are LS allowed (both E2 and M1) and thus relatively uncomplicated calculations, resulting in a lifetime for the ^2P_1/2 level of ˜25 s. The ^4S/^2D/^2P mixing is critical for the ^4S arrow ^2D LS forbidden transitions, and LS purity is greater than 99.5% for such a light (nonrelativistic) system. At the Dirac-Fock level we find the most important factor in the ^4S_3/2 arrow ^2D_3/2 transition is the amount of ^4S mixing in the ^2D_3/2 level. With no such ^4S component in the ^2D_5/2 level, its lifetime is over 100 000 s. Important correlation configurations which act to lower the ^2D_3/2 lifetime include the valence excitations 3p arrow p and 3p^2 arrow p^2 and the core-valence 3s,3p and 2p,3p pair excitations. Our current ^2D_3/2 lifetime in an ongoing series of calculations is ˜200 s.

  5. The polaron: Ground state, excited states, and far from equilibrium

    SciTech Connect

    Trugman, S.A.; Bonca, J. |

    1998-12-01

    The authors describe a variational approach for solving the Holstein polaron model with dynamical quantum phonons on an infinite lattice. The method is simple, fast, extremely accurate, and gives ground and excited state energies and wavefunctions at any momentum k. The method can also be used to calculate coherent quantum dynamics for inelastic tunneling and for strongly driven polarons far from equilibrium.

  6. Excited state quenching via "unsuccessful" chemical reactions.

    PubMed

    Sinicropi, Adalgisa; Nau, Werner M; Olivucci, Massimo

    2002-08-01

    We discuss the results of recent photochemical reaction path computations on 1n,pi* azoalkanes interacting with a single quencher molecule. We provide computational and experimental evidence that there are two basic mechanisms for the true quenching of 1n,pi* states both based on unsuccessful chemical reactions. The first mechanism is based upon an unsuccessful hydrogen atom transfer and may occur through two different (direct and stepwise) routes. The second mechanism is based on an unsuccessful charge transfer reaction that occurs exclusively in a direct fashion. We show that the efficiency of the two quenching mechanisms is substantially due to the existence of two different types of conical intersections between the excited and ground state potential energy surfaces of the reacting bimolecular system.

  7. Self-Scattering for Dark Matter with an Excited State

    NASA Astrophysics Data System (ADS)

    Schutz, Katelin; Slatyer, Tracy

    2015-01-01

    Self-interacting dark matter scenarios have recently attracted much attention as a possible means to alleviate the tension between N-body simulations and observations of the dark matter distribution on galactic and sub-galactic scales. The presence of internal structure for the dark matter --- for example, a nearly-degenerate state in the spectrum that could decay, or be collisionally excited or de-excited --- has also been proposed as a possible means to address these discrepancies. Such internal structure can be a source of interesting signatures in direct and indirect dark matter searches, for example providing a novel explanation for the 3.5 keV line recently observed in galaxies and galaxy clusters. We analyze a simple model of dark matter self-scattering including a nearly-degenerate excited state, and develop an accurate analytic approximation for the elastic and inelastic s-wave cross sections, which is valid outside the perturbative regime provided the particle velocity is sufficiently low (this condition is also required for the s-wave to dominate over higher partial waves). We anticipate our results will be useful in incorporating inelastic self-scattering into N-body simulations, in order to study the quantitative impact of nearly-degenerate states in the dark matter spectrum on galactic structure and dynamics, and in computing the indirect signatures of multi-state dark matter.

  8. A treatment of excited states in nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Gupta, Sanjib Shankar

    2002-10-01

    Many isotopes of importance to nucleosynthesis have metastable states whose decay to the ground state is strongly inhibited by a high angular momentum difference. Traditionally, excited states of a nucleus have been treated by assuming attainment of thermal equilibrium; a Hauser-Feshbach calculation is then performed on the whole nucleus to determine nuclear reaction rates. A description of the nucleus when it is not in equilibrium, and a method for computing reaction rates that does not presume thermalization are presented in this work. In nucleosynthesis calculations, we may characterize the internal electromagnetic transitions of a nucleus as a Markov process. This allows us to decompose the interaction of radiation with nucleons into effective interactions between ensembles. Rather than consider a single isotope, we construct the canonical ensembles which are the true nuclear species of interest. We are then in a position to specify nonequilibrium occupations of the ensembles by discretizing the Nuclear Level Density function. The generality of the stochastic process identified at the outset now permits the description of nucleosynthesis as Markov flows in networks of suitably populated ensembles. This allows us to use as many excited states as we wish in nucleosyn thesis while tracking their nonequilibrium evolution as substochastic processes. A website utilizing these principles is discussed in some detail. It accesses the theoretical NLD database from the Brussels Intitute of Astrophysics to supplement adopted experimental data from the ENSDF database (maintained by Brookhaven National Laboratories). The composite is processed by a CGI (Common Gateway Interface) application to dynamically obtain plots and tables of rates on a specified temperature grid. Beta-decay rates are discussed for an isotope important to nuclear astrophysics ( 180TA) as a test-bed for the techniques implemented.

  9. Theory of elementary excitations in quasiperiodic structures

    NASA Astrophysics Data System (ADS)

    Albuquerque, E. L.; Cottam, M. G.

    2003-03-01

    The aim of this work is to present a comprehensive and up-to-date review of the main physical properties (such as energy profiles, localization, scale laws, multifractal analysis, transmission spectra, transmission fingerprints, electronic structures, magnetization curves and thermodynamic properties) of the elementary excitations that can propagate in multilayered structures with constituents arranged in a quasiperiodic fashion. These excitations include plasmon-polaritons, spin waves, light waves and electrons, among others. A complex fractal or multifractal profile of the energy spectra is the common feature among these excitations. The quasiperiodic property is formed by the incommensurate arrangement of periodic unit cells and can be of the type referred to as deterministic (or controlled) disorder. The resulting excitations are characterized by the nature of their Fourier spectrum, which can be dense pure point (as for the Fibonacci sequence) or singular continuous (as for the Thue-Morse and double-period sequences). These sequences are described in terms of a series of generations that obey particular recursion relations, and they can be considered as intermediate systems between a periodic crystal and the random amorphous solids, thus defining a novel description of disorder. A discussion is also included of some spectroscopic techniques used to probe the excitations, emphasizing Raman and Brillouin light scattering.

  10. Theoretical study on the excited-state intramolecular proton transfer in the aromatic schiff base salicylidene methylamine: an electronic structure and quantum dynamical approach.

    PubMed

    Ortiz-Sanchez, Juan Manuel; Gelabert, Ricard; Moreno, Miquel; Lluch, José M

    2006-04-13

    The proton-transfer dynamics in the aromatic Schiff base salicylidene methylamine has been theoretically analyzed in the ground and first singlet (pi,pi) excited electronic states by density functional theory calculations and quantum wave-packet dynamics. The potential energies obtained through electronic calculations that use the time-dependent density functional theory formalism, which predict a barrierless excited-state intramolecular proton transfer, are fitted to a reduced three-dimensional potential energy surface. The time evolution in this surface is solved by means of the multiconfiguration time-dependent Hartree algorithm applied to solve the time-dependent Schrödinger equation. It is shown that the excited-state proton transfer occurs within 11 fs for hydrogen and 25 fs for deuterium, so that a large kinetic isotope effect is predicted. These results are compared to those of the only previous theoretical work published on this system [Zgierski, M. Z.; Grabowska, A. J. Chem. Phys. 2000, 113, 7845], reporting a configuration interaction singles barrier of 1.6 kcal mol(-1) and time reactions of 30 and 115 fs for the hydrogen and deuterium transfers, respectively, evaluated with the semiclassical instanton approach.

  11. How much double excitation character do the lowest excited states of linear polyenes have?

    NASA Astrophysics Data System (ADS)

    Starcke, Jan Hendrik; Wormit, Michael; Schirmer, Jochen; Dreuw, Andreas

    2006-10-01

    Doubly excited states play important roles in the low-energy region of the optical spectra of polyenes and their investigation has been subject of theoretical and experimental studies for more than 30 years now and still is in the focus of ongoing research. In this work, we address the question why doubly excited states play a role in the low-energy region of the optical spectrum of molecular systems at all, since from a naive point of view one would expect their excitation energy approximately twice as large as the one of the corresponding single excitation. Furthermore, we show that extended-ADC(2) is well suited for the balanced calculation of the low-lying excited 21Ag-, 11Bu- and 11Bu+ states of long all- trans polyenes, which are known to possess substantial double excitation character. A careful re-investigation of the performance of TDDFT calculations for these states reveals that the previously reported good performance for the 21Ag- state relies heavily on fortuitous cancellation of errors. Finally, the title question is answered such that for short polyenes the lowest excited 21Ag- and 11Bu- states can clearly be classified as doubly excited, whereas the 11Ag- ground state is essentially represented by the (ground-state) HF determinant. For longer polyenes, in addition to increasing double excitation contributions in the 21Ag- and 11Bu- states, the ground state itself aquires substantial double excitation character (45% in C 22H 24), so that the transition from the ground state to these excited states should not be addressed as the excitation of two electrons relative to the 11Ag- ground state.

  12. Synthesis, structural, and photophysical studies of π-fused acenaphtho[1,2-d]imidazole-based excited-state intramolecular proton transfer molecules

    NASA Astrophysics Data System (ADS)

    Somasundaram, Sivaraman; Kamaraj, Eswaran; Hwang, Su Jin; Jung, Sooyoung; Choi, Moon Gun; Park, Sanghyuk

    2017-06-01

    Orange-red fluorescent molecules are promising materials for use in a new generation of displays, light sources, and chemosensors because conventional red-emitters have lower fluorescence quantum efficiencies. In this work, a set of orange-emitting fused imidazole series 2-(7-(4-fluorophenyl)-7H-acenaphtho[1,2-d]imidazol-8-yl)phenol (AHPI-F), 2-(7-(4-chlorophenyl)-7H-acenaphtho[1,2-d]imidazol-8-yl)phenol (AHPI-Cl), and 2-(7-(4-bromophenyl)-7H-acenaphtho[1,2-d]imidazol-8-yl)phenol (AHPI-Br) have been synthesized via multicomponent reaction method with high yield. Synthesized molecules were fully characterized by 1H NMR, 13C NMR, GC-Mass, UV-vis. absorption, PL, and TGA-DSC. The compounds AHPI-F, AHPI-Cl, AHPI-Br showed large Stokes' shifted emission due to excited-state intramolecular proton transfer (ESIPT) process, and they effectively formed large single crystals. The crystal structure of each compound was identified by X-ray crystallographic analysis. To elucidate the photophysical properties of the molecule, theoretical calculation were performed by density functional theory (DFT) with B3LYP 6-31G(d,p) basis sets using the identified molecular conformations from X-ray analysis. Calculated electronic properties including HOMO-LUMO levels were compared with the experimental results. As a result of ESIPT process, extended conjugation length through acenaphto[1,2-d]imidazole, and charge transfer characteristics by the introduction of halogen atoms, all of the materials showed orange ESIPT emission with no spatial overlap between absorption (λmax,abs = 325 nm) and emission (λmax,ems = 578 nm).

  13. Photodissociation of FONO: an excited state nonadiabatic dynamics study.

    PubMed

    Hilal, Allaa R; Hilal, Rifaat

    2017-03-01

    The photo dissociation of nitrosyl fluorite, FONO, a potential source of atmospheric fluorine, underlies its active role in ozone depletion and other activities in the troposphere. In the present work, the electronic structure of FONO is revisited at high level of ab initio and density functional theory (DFT) theoretical levels. Several different post SCF methods were used to compute excited states, vertical excitation energies and intensities, namely configuration interaction with single excitations (CIS), equation of motion coupled cluster with single and double excitations (EOM-CCSD), and symmetry adopted cluster configuration interaction (SAC-CI) methods. The potential energy functions along two internal coordinates, namely the F-ONO bond and the FONO dihedral angle, have been computed on the ground state relaxed potential energy surface (PES) for the ground, 5A' and 5A″ excited states using the EOM-CCSD method. In the gas phase, the decay of the excited states of FONO was examined closely by calculating the UV photoabsorption cross-section spectrum and by nonadiabatic dynamics simulations. Nonadiabatic dynamics were simulated by sampling 300 trajectories in two spectral windows at 3.0 ± 0.25 and 4.5 ± 0.25 eV using the surface hopping method. Two different photodissociation reaction pathways with two main products, including multifragmentation (FO+NO) and atomic elimination (F) mechanisms were identified. For the cis-isomer, the main photochemical channel is F+NO2, representing 67% of all processes. For the trans-isomer, however, the main dissociation pathway is (FO+NO). Graphical Abstract Photodisscociation of nitrosyl fluorite (FONO) seems to underlie its active role in ozone depletion and other activities in the troposphere. The present research revisits the electronic structure of FONO at high level of ab initio and DFT theoretical levels. Cis-trans isomerization and dissociation in the ground and low lying excited states were examined

  14. Excited State Quantum-Classical Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Krstic, Predrag

    2005-05-01

    The development of a new theoretical, algorithmic, and computational framework is reported describing the corresponding excited state many-body dynamics by applying multiphysics described by classical equations of motion for nuclei and Hartree-Fock/Multi-Configuration Hartree-Fock and multiresolution techniques for solving the quantum part of the problem (i.e. the motion of the electrons). We primarily have in mind reactive and electron-transition dynamics which involves molecular clusters, containing hundreds of atoms, perturbed by a slow ionic/atomic/molecular projectile, with possible applications in plasma-surface interactions, cluster physics, chemistry and biotechnology. The validation of the developed technique is performed at three-body systems. Application to the transition dynamics in small carbon clusters and hydrocarbons perturbed by slow carbon ions resolves some long-standing issues in the ion-surface interactions in fusion tokamaks.

  15. Excited-state one-neutron halo nuclei within a parallel momentum distribution analysis

    NASA Astrophysics Data System (ADS)

    Shubhchintak

    2017-08-01

    Using a fully quantum mechanical post-form finite-range distorted-wave Born approximation theory of Coulomb breakup, I study the parallel momentum distribution of the core in the Coulomb breakup of suggested excited-state one-neutron halo nuclei considered in their different bound excited states. Narrow momentum distributions obtained in the present calculations for some cases indicate the possibilities of the excited-state halo structure in the nuclei under consideration and therefore favor the previous predictions.

  16. Electronically excited rubidium atom in helium clusters and films. II. Second excited state and absorption spectrum.

    PubMed

    Leino, Markku; Viel, Alexandra; Zillich, Robert E

    2011-01-14

    Following our work on the study of helium droplets and film doped with one electronically excited rubidium atom Rb(∗) ((2)P) [M. Leino, A. Viel, and R. E. Zillich, J. Chem. Phys. 129, 184308 (2008)], we focus in this paper on the second excited state. We present theoretical studies of such droplets and films using quantum Monte Carlo approaches. Diffusion and path integral Monte Carlo algorithms combined with a diatomics-in-molecule scheme to model the nonpair additive potential energy surface are used to investigate the energetics and the structure of Rb(∗)He(n) clusters. Helium films as a model for the limit of large clusters are also considered. As in our work on the first electronic excited state, our present calculations find stable Rb(∗)He(n) clusters. The structures obtained are however different with a He-Rb(∗)-He exciplex core to which more helium atoms are weakly attached, preferentially on one end of the core exciplex. The electronic absorption spectrum is also presented for increasing cluster sizes as well as for the film.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    In this work, we report a comparative study of computed excitation energies, oscillator strengths, and excited-state energy gradients of (S)-nicotine, chosen as a test case, using multireference methods, coupled cluster singles and doubles, and methods based on time-dependent density functional theory. This system was chosen because its apparent simplicity hides a complex electronic structure, as several different types of valence excitations are possible, including n-π*, π-π*, 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.

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

    SciTech Connect

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

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

    PubMed

    Mondal, Sayan; Puranik, Mrinalini

    2016-05-18

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

  20. Ultra-Fast Excited State Dynamics in Green Fluorescent Protein: Multiple States and Proton Transfer

    NASA Astrophysics Data System (ADS)

    Chattoraj, Mita; King, Brett A.; Bublitz, Gerold U.; Boxer, Steven G.

    1996-08-01

    The green fluorescent protein (GFP) of the jellyfish Aequorea Victoria has attracted widespread interest since the discovery that its chromophore is generated by the autocatalytic, posttranslational cyclization and oxidation of a hexapeptide unit. This permits fusion of the DNA sequence of GFP with that of any protein whose expression or transport can then be readily monitored by sensitive fluorescence methods without the need to add exogenous fluorescent dyes. The excited state dynamics of GFP were studied following photo-excitation of each of its two strong absorption bands in the visible using fluorescence upconversion spectroscopy (about 100 fs time resolution). It is shown that excitation of the higher energy feature leads very rapidly to a form of the lower energy species, and that the excited state interconversion rate can be markedly slowed by replacing exchangeable protons with deuterons. This observation and others lead to a model in which the two visible absorption bands correspond to GFP in two ground-state conformations. These conformations can be slowly interconverted in the ground state, but the process is much faster in the excited state. The observed isotope effect suggests that the initial excited state process involves a proton transfer reaction that is followed by additional structural changes. These observations may help to rationalize and motivate mutations that alter the absorption properties and improve the photo stability of GFP.

  1. Excited-State Proton Transfer in Indigo.

    PubMed

    Pina, J; Sarmento, Daniela; Accoto, Marco; Gentili, Pier Luigi; Vaccaro, Luigi; Galvão, Adelino; Seixas de Melo, J Sérgio

    2017-03-16

    Excited-state proton transfer (ESPT) in Indigo and its monohexyl-substituted derivative (Ind and NHxInd, respectively) in solution was investigated experimentally as a function of solvent viscosity, polarity, and temperature, and theoretically by time-dependent density functional theory (TDDFT) calculations. Although a single emission band is observed, the fluorescence decays (collected at different wavelengths along the emission band using time-correlated single photon counting (TCSPC)) are biexponential, with two identical decay times but different pre-exponential factors, which is consistent with the existence of excited-state keto and enol species. The femtosecond (fs)-transient absorption data show that two similar decay components are present, in addition to a shorter (<3 ps) component associated with vibrational relaxation. From TDDFT calculations it was shown that with both Ind and NHxInd, the reaction proceeds through a single ESPT mechanism driven by an Arrhenius-type activation through a saddle point, which is enhanced by tunneling through the barrier. From the temperature dependence of the steady-state and time-resolved fluorescence data, the activation energy for the process was found to be ∼11 kJ mol(-1) for Ind and ∼5 kJ mol(-1) for NHxInd, in close agreement with the values calculated by TDDFT: 12.3 kJ mol(-1) (Ind) and 3.1 kJ mol(-1) (NHxInd). From time-resolved data, the rate constants for the ESPT process in dimethyl sulfoxide were found to be 9.24 × 10(10) s(-1) (Ind) and 7.12 × 10(10) s(-1) (NHxInd). The proximity between the two values suggests that the proton transfer mechanism in indigo is very similar to that found in NHxInd, where a single proton is involved. In addition, with NHxInd, the TDDFT calculations, together with the viscosity dependence of the fast component, and differences in the activation energy values between the steady-state and time-resolved data indicate that an additional nonradiative process is involved, which

  2. Excited states of the 150Pm odd-odd nucleus

    NASA Astrophysics Data System (ADS)

    Bucurescu, D.; Drăgulescu, E.; Pascu, S.; Wirth, H.-F.; Filipescu, D.; Căta-Danil, G.; Căta-Danil, I.; Deleanu, D.; Eppinger, K.; Faestermann, T.; Ghiţă, D. G.; Glodariu, T.; Hertenberger, R.; Ivaşcu, M.; Krücken, R.; Mărginean, N.; Mărginean, R.; Mihai, C.; Negret, A.; Sava, T.; Stroe, L.; Wimmer, K.; Zamfir, N. V.

    2012-01-01

    The knowledge of excited states in the odd-odd 150Pm, completely unknown until recently, is important both for understanding double β decay of 150Nd and for nuclear structure studies in mass regions with a quantum phase transition. A large number of excited states have been determined for the first time in this nucleus by measuring spectra of the 152Sm(d,α) direct reaction at 25 MeV with the Munich Q3D spectrograph and by γ-ray spectroscopy with the (p,nγ) reaction at 7.1 MeV at the Bucharest tandem accelerator. Some of these levels correspond to peaks recently observed with the (3He,t) reaction at 140 MeV/u.

  3. Highly excited Rydberg states of pyrazine and their autoionization

    SciTech Connect

    Goto, A.; Fujii, M.; Ito, M.

    1987-04-23

    The two-color MPI spectra of jet-cooled pyrazine obtained via various vibrational levels in the S/sub 1/(n,..pi..*) state have been observed. A regularity was found in that the Rydberg series lying above the adiabatic ionization potential appear upon excitation of the S/sub 1/ vibronic level containing the nontotally symmetric vibration but they are apparently absent upon excitation of the S/sub 1/ vibronic level containing the totally symmetric vibration. The regularity is similar to that found by Hager et al. for aniline and can be explained as due to the interaction between a discrete level and an isoenergetic ionization continuum. The appearance or apparent absence of the Rydberg series results from the absorption cross section of the interacting ionization continuum in the transition from the S/sub 1/ vibronic level. The electronic structures of the Rydberg state and ion and the vibrational potentials of the ion are discussed.

  4. Excited State Properties of Hybrid Perovskites.

    PubMed

    Saba, Michele; Quochi, Francesco; Mura, Andrea; Bongiovanni, Giovanni

    2016-01-19

    Metal halide perovskites have come to the attention of the scientific community for the progress achieved in solar light conversion. Energy sustainability is one of the priorities of our society, and materials advancements resulting in low-cost but efficient solar cells and large-area lighting devices represent a major goal for applied research. From a basic point of view, perovskites are an exotic class of hybrid materials combining some merits of organic and inorganic semiconductors: large optical absorption, large mobilities, and tunable band gap together with the possibility to be processed in solution. When a novel class of promising semiconductors comes into the limelight, lively discussions ensue on the photophysics of band-edge excitations, because just the states close to the band edge are entailed in energy/charge transport and light emission. This was the case several decades ago for III-V semiconductors, it has been up to 10 years ago for organics, and it is currently the case for perovskites. Our aim in this Account is to rationalize the body of experimental evidence on perovskite photophysics in a coherent theoretical framework, borrowing from the knowledge acquired over the years in materials optoelectronics. A crucial question is whether photon absorption leads to a population of unbound, conductive free charges or instead excitons, neutral and insulating bound states created by Coulomb interaction just below the energy of the band gap. We first focus on the experimental estimates of the exciton binding energy (Eb): at room temperature, Eb is comparable to the thermal energy kBT in MAPbI3 and increases up to values 2-3kBT in wide band gap MAPbBr3 and MAPbCl3. Statistical considerations predict that these values, even though comparable to or larger than thermal energy, let free carriers prevail over bound excitons for all levels of excitation densities relevant for devices. The analysis of photophysics evidence confirms that all hybrid halide

  5. Lifetimes of the 7D excited states of francium

    NASA Astrophysics Data System (ADS)

    Grossman, J. S.; Fliller, R. P., III; Orozco, L. A.; Pearson, M. R.; Sprouse, G. D.

    2000-06-01

    We report our measurement of the lifetimes of the 7D_3/2 and 7D_5/2 levels of francium, using time-correlated single-photon counting techniques. We collect francium atoms in a magneto-optical trap (MOT) in the target room of the superconducting LINAC at Stony Brook. We use two-photon resonant excitation to reach either of the 7D levels. The trapping Ti:Sapph laser operating at 718 nm on the D2 line provides the first photon of the excitation. A second Ti:Sapph probe laser at 969 nm or 961 nm excites the second step to the 7D_3/2 or 7D_5/2 level, respectively. We chop the probe laser and monitor the fluorescent decay to the ground state via the 7P levels using a photomultiplier tube (PMT). The PMT photon-detection pulses are sent to a time to amplitude converter (TAC), and a histogram of the data gives the exponential decay of the fluorescence. Measurements of state lifetimes provide an important check of ab initio calculations of the structure of this simple, heavy atom. In this regard, the d states provide a stringent test that goes beyond the well understood s and p states. Work supported by the NSF.

  6. Characterizing excited conformational states of RNA by NMR spectroscopy

    PubMed Central

    Zhao, Bo; Zhang, Qi

    2016-01-01

    Conformational dynamics is a hallmark of diverse non-coding RNA functions. During these functional processes, RNA molecules almost ubiquitously undergo conformational transitions that are tuned to meet distinct structural and kinetic requirements for proper function. A complete mechanistic understanding of RNA function requires comprehensive structural and dynamic knowledge of these complex transitions, which often involve alternative higher-energy conformational states that pose a major challenge for high-resolution structural study by conventional methods. In this review, we describe recent progress in RNA NMR that has started to unveil detailed structural, thermodynamic and kinetic insights into some of these excited conformational states of RNA and their functional roles in biology. PMID:25765780

  7. Self-scattering for Dark Matter with an excited state

    SciTech Connect

    Schutz, Katelin; Slatyer, Tracy R. E-mail: tslatyer@mit.edu

    2015-01-01

    Self-interacting dark matter scenarios have recently attracted much attention, as a possible means to alleviate the tension between N-body simulations and observations of the dark matter distribution on galactic and sub-galactic scales. The presence of internal structure for the dark matter—for example, a nearly-degenerate state in the spectrum that could decay, or be collisionally excited or de-excited—has also been proposed as a possible means to address these discrepancies. Such internal structure can be a source of interesting signatures in direct and indirect dark matter searches, for example providing a novel explanation for the 3.5 keV line recently observed in galaxies and galaxy clusters. We analyze a simple model of dark matter self-scattering including a nearly-degenerate excited state, and develop an accurate analytic approximation for the elastic and inelastic s-wave cross sections, which is valid outside the perturbative regime provided the particle velocity is sufficiently low (this condition is also required for the s-wave to dominate over higher partial waves). We anticipate our results will be useful in incorporating inelastic self-scattering into N-body simulations, in order to study the quantitative impact of nearly-degenerate states in the dark matter spectrum on galactic structure and dynamics, and in computing the indirect signatures of multi-state dark matter.

  8. Vibronic coupling in the excited-states of carotenoids

    SciTech Connect

    Miki, Takeshi; Buckup, Tiago; Krause, Marie S.; Southall, June; Cogdell, Richard J.; Motzkus, Marcus

    2016-01-01

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

  9. Excited-State Effective Masses in Lattice QCD

    SciTech Connect

    George Fleming, Saul Cohen, Huey-Wen Lin

    2009-10-01

    We apply black-box methods, i.e. where the performance of the method does not depend upon initial guesses, to extract excited-state energies from Euclidean-time hadron correlation functions. In particular, we extend the widely used effective-mass method to incorporate multiple correlation functions and produce effective mass estimates for multiple excited states. In general, these excited-state effective masses will be determined by finding the roots of some polynomial. We demonstrate the method using sample lattice data to determine excited-state energies of the nucleon and compare the results to other energy-level finding techniques.

  10. Excited-State Effective Masses in Lattice QCD

    SciTech Connect

    Fleming, George; Cohen, Saul; Lin, Huey-Wen

    2009-01-01

    We apply black-box methods, i.e. where the performance of the method does not depend upon initial guesses, to extract excited-state energies from Euclidean-time hadron correlation functions. In particular, we extend the widely used effective-mass method to incorporate multiple correlation functions and produce effective mass estimates for multiple excited states. In general, these excited-state effective masses will be determined by finding the roots of some polynomial. We demonstrate the method using sample lattice data to determine excited-state energies of the nucleon and compare the results to other energy-level finding techniques.

  11. Excited State Biexcitons in Atomically Thin MoSe2.

    PubMed

    Pei, Jiajie; Yang, Jiong; Wang, Xibin; Wang, Fan; Mokkapati, Sudha; Lü, Tieyu; Zheng, Jin-Cheng; Qin, Qinghua; Neshev, Dragomir; Tan, Hark Hoe; Jagadish, Chennupati; Lu, Yuerui

    2017-07-25

    The tightly bound biexcitons found in atomically thin semiconductors have very promising applications for optoelectronic and quantum devices. However, there is a discrepancy between theory and experiment regarding the fundamental structure of these biexcitons. Therefore, the exploration of a biexciton formation mechanism by further experiments is of great importance. Here, we successfully triggered the emission of biexcitons in atomically thin MoSe2, via the engineering of three critical parameters: dielectric screening, density of trions, and excitation power. The observed binding energy and formation dynamics of these biexcitons strongly support the model that the biexciton consists of a charge attached to a trion (excited state biexciton) instead of four spatially symmetric particles (ground state biexciton). More importantly, we found that the excited state biexcitons not only can exist at cryogenic temperatures but also can be triggered at room temperature in a freestanding bilayer MoSe2. The demonstrated capability of biexciton engineering in atomically thin MoSe2 provides a route for exploring fundamental many-body interactions and enabling device applications, such as bright entangled photon sources operating at room temperature.

  12. Lattice QCD sprectrum of excited states of the nucleon

    NASA Astrophysics Data System (ADS)

    Wallace, Stephen

    2012-03-01

    Lattice QCD results are presented for the spectrum of excited states of the nucleon. Matrices of correlation functions are calculated using lattice operators that incorporate up to two covariant derivatives in combinations that transform according to SU(2) symmetry restricted to the lattice. Although the lattice has cubic symmetry, identification of continuum SU(2) spins is straightforward using such operators. Overlaps of the operators with the lattice QCD states obtained by diagonalizing matrices of correlation functions provide the link of continuum spins to lattice states. Spins up to 7/2 are identified clearly. Evidence for an approximate realization of rotational symmetry in the spectrum is presented, which helps to explain why the continuum spins can be identified. In lattice simulations with pion mass equal to 392 MeV, the low-lying excited states of lattice QCD are found to have the same spin quantum numbers as the states of SU(6)xO(3) symmetry. The lattice QCD spectra are inconsistent with either a quark-diquark model or parity doubling of states. They suggest that the Roper resonance may have a complex structure consisting of contributions from L=0, 1 and 2.

  13. Quantum entanglement of locally excited states in Maxwell theory

    NASA Astrophysics Data System (ADS)

    Nozaki, Masahiro; Watamura, Naoki

    2016-12-01

    In 4 dimensional Maxwell gauge theory, we study the changes of (Rényi) entanglement entropy which are defined by subtracting the entropy for the ground state from the one for the locally excited states, generated by acting with gauge invariant local operators on the state. The changes for the operators which we consider in this paper reflect the electric-magnetic duality. The late-time value of changes can be interpreted in terms of electromagnetic quasi-particles. When the operator constructed of both electric and magnetic fields acts on the ground state, it shows that the operator acts on the late-time structure of quantum entanglement differently from free scalar fields.

  14. Excited electronic states and spectroscopy of unsymmetrically substituted polyenes

    NASA Astrophysics Data System (ADS)

    Itoh, Takao

    2013-09-01

    α-Methyl-ω-phenylpolyenes, Me-(CH=CH)N-Ph, (MPPNs) with N = 2, 3, and 4 were synthesized. Fluorescence, absorption, and excitation spectra of MPPNs have been measured under different conditions along with those of β-methylstyrene. It is shown that there is a forbidden singlet (π, π*) excited state located at energies below the absorbing state for MPPNs with N = 3 and 4. Excitation energies of these polyenes are determined as a function of N. Quantitative analysis of the temperature dependence of the relative intensity of the fluorescence spectrum and its solvent shift behavior extract estimates of the various physical parameters that characterize excitation energies and excited-state dynamical behavior of MPPN with N = 3. The singlet excited states of the MPPNs were compared with those of the α,ω-diphenylpolyenes and α,ω-dimethylpolyenes.

  15. Excited electronic states and spectroscopy of unsymmetrically substituted polyenes.

    PubMed

    Itoh, Takao

    2013-09-07

    α-Methyl-ω-phenylpolyenes, Me-(CH=CH)N-Ph, (MPPNs) with N = 2, 3, and 4 were synthesized. Fluorescence, absorption, and excitation spectra of MPPNs have been measured under different conditions along with those of β-methylstyrene. It is shown that there is a forbidden singlet (π, π∗) excited state located at energies below the absorbing state for MPPNs with N = 3 and 4. Excitation energies of these polyenes are determined as a function of N. Quantitative analysis of the temperature dependence of the relative intensity of the fluorescence spectrum and its solvent shift behavior extract estimates of the various physical parameters that characterize excitation energies and excited-state dynamical behavior of MPPN with N = 3. The singlet excited states of the MPPNs were compared with those of the α,ω-diphenylpolyenes and α,ω-dimethylpolyenes.

  16. An exploration of electronic structure and nuclear dynamics in tropolone: II. The A~ 1B2 (π*π) excited state

    NASA Astrophysics Data System (ADS)

    Burns, Lori A.; Murdock, Daniel; Vaccaro, Patrick H.

    2009-04-01

    The first excited singlet state of tropolone (à B12) and the attendant π∗←π electronic transition have been examined computationally by applying several quantum chemical treatments built upon the aug-cc-pVDZ basis set, including time-dependent density functional theory (TDDFT/B3LYP), configuration interaction singles with perturbative corrections [CIS and CIS(D)], and equation-of-motion coupled-cluster schemes [EOM-CCSD and CR-EOMCCSD(T)]. As in the case of the X˜ A11 ground state [L. A. Burns, D. Murdock, and P. H. Vaccaro, J. Chem. Phys. 124, 204307 (2006)], geometry optimization procedures and harmonic force-field calculations predict the electronically excited potential surface to support a global minimum-energy configuration of rigorously planar (Cs) symmetry. Minimal Hartree-Fock (HF/CIS) and density-functional (DFT/TDDFT) approaches yield inconsistent results for the X˜ A11 and à B12 manifolds; however, coupled-cluster (CCSD/EOM-CCSD) methods give fully relaxed proton-transfer barrier heights of ΔEptX˜=3296.1 cm-1 and ΔEptÃ=1270.6 cm-1 that are in accordance with the experimentally observed increase in vibrationless tunneling splitting upon electronic excitation. Detailed analyses show that this reduction in ΔEpt stems from a variety of complementary factors, most notably an overall contraction of the proton-transfer reaction site (whereby the equilibrium O⋯O donor-acceptor distance decreases from 2.53 to 2.46 Å) and a concomitant shortening of the intramolecular hydrogen bond. Further refinement of à B12 energies through single-point perturbative triples corrections [CR-EOMCCSD(T)] leads to 1316.1 cm-1 as the best current estimate for ΔEptÃ. Direct comparison of the lowest-lying out-of-plane torsional mode [ν39(a2)] for X˜ A11 and à B12 tropolone reveals that its disparate nature (cf. ν39X˜=101.2 cm-1 and ν39Ã=42.0 cm-1) mediates vibrational-averaging effects which can account for inertial defects extracted by rotationally

  17. Infrared spectroscopy of excited states and transients in photochemistry

    NASA Astrophysics Data System (ADS)

    Schaffner, Kurt; Grevels, Friedrich-Wilhelm

    Flash photolysis with time-resolved IR detection is used in investigations of the primary photoreactions of chromium, molybdenum, tungsten, manganese, iron, and osmium carbonyl complexes, and of the ensuing transformations of transient products in room temperature solution. The method bridges the gap to spectral data obtained at low temperatures. It provides information which has previously been inaccessible, such as detailed structural information, and kinetic data in cases where the UV-visible absorptions of the species of interest overlap. Finally, excited-state IR spectroscopy has now become feasible for many organic compounds with the most recent instrumental set-up which reaches a time resolution of ≥ 50 ns.

  18. Direct excitation of microwave-spin dressed states using a laser-excited resonance Raman interaction

    NASA Astrophysics Data System (ADS)

    Shahriar, M. S.; Hemmer, P. R.

    1990-10-01

    We have used a laser-induced resonance Raman transition between the ground-state hyperfine sublevels in a sodium atomic beam to excite individual dressed states of the microwave-spin hyperfine transition. In addition, we have used the microwave interaction to excite the Raman trapped state. Extension of this technique to mm waves or to the far infrared may lead to applications such as mm-wave-beam steering and holographic image conversion.

  19. Experimental Investigation of Excited-State Lifetimes in Atomic Ytterbium

    SciTech Connect

    Bowers, C.J.; Budker, D.; Commins, E.D.; DeMille, D.; Freedman, S.J.; Nguyen, A.-T.; Shang, S.-Q.; Zolotorev, M.; /SLAC

    2011-11-15

    Lifetimes of 21 excited states in atomic Yb were measured using time-resolved fluorescence detection following pulsed laser excitation. The lifetime of the 4f{sup 14}5d6s {sup 3}D{sub 1} state, which is of particular importance for a proposed study of parity nonconservation in atoms, was measured to be 380(30) ns.

  20. Role of Excited States In High-order Harmonic Generation

    NASA Astrophysics Data System (ADS)

    Beaulieu, S.; Camp, S.; Descamps, D.; Comby, A.; Wanie, V.; Petit, S.; Légaré, F.; Schafer, K. J.; Gaarde, M. B.; Catoire, F.; Mairesse, Y.

    2016-11-01

    We investigate the role of excited states in high-order harmonic generation by studying the spectral, spatial, and temporal characteristics of the radiation produced near the ionization threshold of argon by few-cycle laser pulses. We show that the population of excited states can lead either to direct extreme ultraviolet emission through free induction decay or to the generation of high-order harmonics through ionization from these states and recombination to the ground state. By using the attosecond lighthouse technique, we demonstrate that the high-harmonic emission from excited states is temporally delayed by a few femtoseconds compared to the usual harmonics, leading to a strong nonadiabatic spectral redshift.

  1. Role of Excited States In High-order Harmonic Generation.

    PubMed

    Beaulieu, S; Camp, S; Descamps, D; Comby, A; Wanie, V; Petit, S; Légaré, F; Schafer, K J; Gaarde, M B; Catoire, F; Mairesse, Y

    2016-11-11

    We investigate the role of excited states in high-order harmonic generation by studying the spectral, spatial, and temporal characteristics of the radiation produced near the ionization threshold of argon by few-cycle laser pulses. We show that the population of excited states can lead either to direct extreme ultraviolet emission through free induction decay or to the generation of high-order harmonics through ionization from these states and recombination to the ground state. By using the attosecond lighthouse technique, we demonstrate that the high-harmonic emission from excited states is temporally delayed by a few femtoseconds compared to the usual harmonics, leading to a strong nonadiabatic spectral redshift.

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

    NASA Astrophysics Data System (ADS)

    Nelson, Tammie; Naumov, Artem; Fernandez-Alberti, Sebastian; Tretiak, Sergei

    2016-12-01

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

  3. Charge-displacement analysis for excited states

    SciTech Connect

    Ronca, Enrico Tarantelli, Francesco; Pastore, Mariachiara Belpassi, Leonardo; De Angelis, Filippo; Angeli, Celestino; Cimiraglia, Renzo

    2014-02-07

    We extend the Charge-Displacement (CD) analysis, already successfully employed to describe the nature of intermolecular interactions [L. Belpassi et al., J. Am. Chem. Soc. 132, 13046 (2010)] and various types of controversial chemical bonds [L. Belpassi et al., J. Am. Chem. Soc. 130, 1048 (2008); N. Salvi et al., Chem. Eur. J. 16, 7231 (2010)], to study the charge fluxes accompanying electron excitations, and in particular the all-important charge-transfer (CT) phenomena. We demonstrate the usefulness of the new approach through applications to exemplary excitations in a series of molecules, encompassing various typical situations from valence, to Rydberg, to CT excitations. The CD functions defined along various spatial directions provide a detailed and insightful quantitative picture of the electron displacements taking place.

  4. Charge-displacement analysis for excited states

    NASA Astrophysics Data System (ADS)

    Ronca, Enrico; Pastore, Mariachiara; Belpassi, Leonardo; De Angelis, Filippo; Angeli, Celestino; Cimiraglia, Renzo; Tarantelli, Francesco

    2014-02-01

    We extend the Charge-Displacement (CD) analysis, already successfully employed to describe the nature of intermolecular interactions [L. Belpassi et al., J. Am. Chem. Soc. 132, 13046 (2010)] and various types of controversial chemical bonds [L. Belpassi et al., J. Am. Chem. Soc. 130, 1048 (2008); N. Salvi et al., Chem. Eur. J. 16, 7231 (2010)], to study the charge fluxes accompanying electron excitations, and in particular the all-important charge-transfer (CT) phenomena. We demonstrate the usefulness of the new approach through applications to exemplary excitations in a series of molecules, encompassing various typical situations from valence, to Rydberg, to CT excitations. The CD functions defined along various spatial directions provide a detailed and insightful quantitative picture of the electron displacements taking place.

  5. Structural responses to arbitrarily coherent stationary random excitations

    NASA Astrophysics Data System (ADS)

    Lin, Jia-Hao; Zhang, Wen-Shou; Li, Jian-Jun

    1994-03-01

    The pseudo-excitation or fast CQC method for a single excitation problem is extended to deal with general MIMO (multi-input, multi-output) problems in which the excitations can be fully or partially coherent, i.e. the excitation PSD matrices are more general Hermitian matrices. This extension makes the analyses of structural responses to general stationary multipoint excitations computationally more efficient and convenient.

  6. Excited baryon structure using exclusive reactions with CLAS12

    NASA Astrophysics Data System (ADS)

    Carman, Daniel S.

    2016-05-01

    Studying excited nucleon structure through exclusive electroproduction reactions is an important avenue for exploring the nature of the non-perturbative strong interaction. Electrocouplings for N* states in the mass range below 1.8 GeV have been determined from analyses of CLAS πN, ηN, and ππN data. This work made it clear that consistency of independent analyses of exclusive channels with different couplings and non-resonant backgrounds but the same N* electro-excitation amplitudes, is essential to have confidence in the extracted results. In terms of hadronic coupling, many high-lying N* states preferentially decay through the ππN channel instead of πN. Data from the KY channels will therefore be critical to provide an independent analysis with which to compare the extracted electrocouplings for the high-lying N* states against those determined from the πN and ππN channels. A program to study excited N* decays to non-strange and strange exclusive final states using CLAS12 will measure differential cross sections to be used as input to extract the γvNN* transition form factors for the most prominent N* states in the range of invariant energy W up 3 GeV in the virtually unexplored domain of momentum transfers Q2 up to 12 GeV2.

  7. Optimal control of peridinin excited-state dynamics

    NASA Astrophysics Data System (ADS)

    Dietzek, Benjamin; Chábera, Pavel; Hanf, Robert; Tschierlei, Stefanie; Popp, Jürgen; Pascher, Torbjörn; Yartsev, Arkady; Polívka, Tomáš

    2010-07-01

    Optimal control is applied to study the excited-state relaxation of the carbonyl-carotenoid peridinin in solution. Phase-shaping of the excitation pulses is employed to influence the photoinduced reaction dynamics of peridinin. The outcome of various control experiments using different experimentally imposed fitness parameters is discussed. Furthermore, the effects of pump-wavelength and different solvents on the control efficiency are presented. The data show that excited-state population within either the S 1 or the ICT state can be reduced significantly by applying optimal control, while the efficiency of control decreases upon excitation into the low-energy side of the absorption band. However, we are unable to alter the ratio of S 1 and ICT population or increase the population of either state compared to excitation with a transform-limited pulse. We compare the results to various control mechanisms and argue that characteristic low-wavenumber modes are relevant for the photochemistry of peridinin.

  8. Theoretical Study of Tautomerization Reactions for the Ground and First Excited Electronic States of Adenine

    NASA Technical Reports Server (NTRS)

    Salter, Latasha M.; Chaban, Galina M.; Kwak, Dochan (Technical Monitor)

    2002-01-01

    Geometrical structures and energetic properties for different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest singlet excited state potential energy surfaces are studied. Four tautomeric forms are considered, and their energetic order is found to be different on the ground and the excited state potential energy surfaces. Minimum energy reaction paths are obtained for hydrogen atom transfer (tautomerization) reactions in the ground and the lowest excited electronic states. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic states, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. This tautomerization process should become possible in the presence of water or other polar solvent molecules and should play an important role in the photochemistry of adenine.

  9. Role of ribose in the initial excited state structural dynamics of thymidine in water solution: a resonance Raman and density functional theory investigation.

    PubMed

    Zhu, Xin-Ming; Wang, Hui-gang; Zheng, Xuming; Phillips, David Lee

    2008-12-11

    Resonance Raman spectra were obtained for thymidine and thymine with excitation wavelengths in resonance with the approximately 260 nm band absorption spectrum. The spectra indicate that the Franck-Condon (FC) region photodissociation dynamics of thymidine have multidimensional character with motion predominantly along the nominal C5=C6 stretch + C6-H bend nu17 (delta = 0.75, lambda = 468 cm(-1)), the nominal thymine ring stretch + C6-H bend + N1-C1, stretch nu29 (delta = 0.73, lambda = 363 cm(-1)), the nominal thymine ring stretch + C5-CH3/ N1-C1, stretch nu37 (delta = 0.69, lambda = 292 cm(-1)), and accompanied by the moderate and minor changes in the nu40, nu20 and nu23, nu55, nu60, nu61, nu63 modes. A preliminary resonance Raman intensity analysis was done, and these results for thymidine and thymine were compared to each other. The roles of ribose in the FC structure dynamics of thymidine were explored and the results were used to correlate to its lifetime constants tau1 and tau2 for two nonradiative decay channels. Spi/Sn conical intersection versus a distorted structure of Spi,min in the FC region was briefly discussed.

  10. Analysis of the excited-state absorption spectral bandshape of oligofluorenes

    NASA Astrophysics Data System (ADS)

    Hayes, Sophia C.; Silva, Carlos

    2010-06-01

    We present ultrafast transient absorption spectra of two oligofluorene derivatives in dilute solution. These spectra display a photoinduced absorption band with clear vibronic structure, which we analyze rigorously using a time-dependent formalism of absorption to extract the principal excited-state vibrational normal-mode frequencies that couple to the electronic transition, the configurational displacement of the higher-lying excited state, and the reorganization energies. We can model the excited-state absorption spectrum using two totally symmetric vibrational modes with frequencies 450 (dimer) or 400 cm-1 (trimer), and 1666 cm-1. The reorganization energy of the ground-state absorption is rather insensitive to the oligomer length at 230 meV. However, that of the excited-state absorption evolves from 58 to 166 meV between the oligofluorene dimer and trimer. Based on previous theoretical work [A. Shukla et al., Phys. Rev. B 67, 245203 (2003)], we assign the absorption spectra to a transition from the 1Bu excited state to a higher-lying mAg state, and find that the energy of the excited-state transition with respect to the ground-state transition energy is in excellent agreement with the theoretical predictions for both oligomers studied here. These results and analysis permit profound understanding of the nature of excited-state absorption in π-conjugated polymers, which are the subject of general interest as organic semiconductors in the solid state.

  11. New results on the excited states in ^32Mg

    NASA Astrophysics Data System (ADS)

    McGauley, A. J.; Mach, H.; Fraile, L. M.; Tengblad, O.; Boutami, R.; Jouliet, C.; Plociennik, W.; Yordanov, D. Z.; Stanoiu, M.

    2008-10-01

    ^32Mg is located at the center of a region known as the ``island of inversion,'' a region in which the classic picture of stable shell structure was shattered when the energy of the 2^+ state in ^32Mg was found to be only 885 keV, much lower than expected for a nucleus with a closed neutron shell. The collapse of the N=20 shell closure has been extensively studied, yet very little information exists on the excited states in ^32Mg, which is the critical nucleus. We have studied the levels in ^32Mg populated from the beta-decay of ^32Na at the ISOLDE facility at CERN. We have established a new level scheme which includes 9 excited states and 18 transitions based on the gamma-gamma coincidences. The statistics exceeded by about 2 orders of magnitude statistics collected in previous measurements of ^32Mg [1]. We do not confirm two levels previously proposed, while two new levels and five new transitions are included in the level scheme. [1] G. Klotz et al., Phys. Rev. C47, 2502 (1993), C.M. Mattoon et al., Phys. Rev. C75, 017302 (2007), and V. Tripathi et al., Phys. Rev C77, 034310 (2008).

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

    PubMed

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

    2010-05-21

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

  13. Excited State Mass Spectra of Ω0 c Baryon

    NASA Astrophysics Data System (ADS)

    Shah, Z.; Thakkar, K.; Rai, A. K.; Vinodkumar, P. C.

    2016-10-01

    We have calculated the radial and orbital excited states of singly charmed baryon Oc using the Hypercentral Constituent Quark Model (hCQM). The confinement potential is assumed as coulomb plus power potential (CPP V ). The ground state and excited state masses are determined with and with out first order correction to the potential. Furthermore, we plot graph between Mass(M) → Potential Index(v). Our calculated results are in good agreement with experimental and other theoretical predictions.

  14. Jet-resolved vibronic structure in the higher excited states of N2O - Ultraviolet three-photon absorption spectroscopy from 80,000 to 90,000/cm

    NASA Technical Reports Server (NTRS)

    Patsilinakou, E.; Wiedmann, R. T.; Fotakis, C.; Grant, E. R.

    1989-01-01

    Ionization-detected UV multiphoton absorption spectroscopy of the excited states of N2O is presented, showing Rydberg structure within 20,000/cm of the first ionization threshold. Despite evidence for strong Rydberg-continuum coupling in the form of broadened bands and Fano line-shapes, the Rydberg structure persists, with atomic-like quantum defects and vibration structure well-matched with that of the ion. In the most clearly resolved spectrum, corresponding to the 3p(delta)1Pi state, Renner-Teller and Herzberg-Teller coupling of electronic and vibrational angular momentum are revealed. It is suggested that these mixings are properties of the N2O(+)Pi ion core.

  15. Probing vibrationally mediated ultrafast excited-state reaction dynamics with multireference (CASPT2) trajectories.

    PubMed

    El-Khoury, Patrick Z; Joseph, Saju; Schapiro, Igor; Gozem, Samer; Olivucci, Massimo; Tarnovsky, Alexander N

    2013-11-07

    Excited-state trajectories computed at the complete active space second-order perturbation theory (CASPT2) reveal how vibrational excitation controls the molecular approach to the intersection space that drives the photodissociation of a prototypical halogenated methyl radical, namely CF2I. Translating the Franck-Condon structure along the ground-state CASPT2 vibrational modes in this system followed by propagating the displaced structures in the first excited doublet state simulates specific vibrational excitations and vibrationally mediated dynamics, respectively. Three distinct situations are encountered: the trajectories (i) converge to an energetically flat segment of the intersection space, (ii) locate a segment of the intersection space, and (iii) access a region where the intersection space degeneracy is lifted to form a ridge of avoided crossings. The computational protocol documented herein can be used as a tool to design control strategies based on selective excitation of vibrational modes, including adaptive feedback schemes using coherent light sources.

  16. Population shuffling between ground and high energy excited states.

    PubMed

    Sabo, T Michael; Trent, John O; Lee, Donghan

    2015-11-01

    Stochastic processes powered by thermal energy lead to protein motions traversing time-scales from picoseconds to seconds. Fundamental to protein functionality is the utilization of these dynamics for tasks such as catalysis, folding, and allostery. A hierarchy of motion is hypothesized to connect and synergize fast and slow dynamics toward performing these essential activities. Population shuffling predicts a "top-down" temporal hierarchy, where slow time-scale conformational interconversion leads to a shuffling of the free energy landscape for fast time-scale events. Until now, population shuffling was only applied to interconverting ground states. Here, we extend the framework of population shuffling to be applicable for a system interconverting between low energy ground and high energy excited states, such as the SH3 domain mutants G48M and A39V/N53P/V55L from the Fyn tyrosine kinase, providing another tool for accessing the structural dynamics of high energy excited states. Our results indicate that the higher energy gauche - rotameric state for the leucine χ2 dihedral angle contributes significantly to the distribution of rotameric states in both the major and minor forms of the SH3 domain. These findings are corroborated with unrestrained molecular dynamics (MD) simulations on both the major and minor states of the SH3 domain demonstrating high correlations between experimental and back-calculated leucine χ2 rotameric populations. Taken together, we demonstrate how fast time-scale rotameric side-chain population distributions can be extracted from slow time-scale conformational exchange data further extending the scope and the applicability of the population shuffling model.

  17. Population shuffling between ground and high energy excited states

    PubMed Central

    Sabo, T Michael; Trent, John O; Lee, Donghan

    2015-01-01

    Stochastic processes powered by thermal energy lead to protein motions traversing time-scales from picoseconds to seconds. Fundamental to protein functionality is the utilization of these dynamics for tasks such as catalysis, folding, and allostery. A hierarchy of motion is hypothesized to connect and synergize fast and slow dynamics toward performing these essential activities. Population shuffling predicts a “top-down” temporal hierarchy, where slow time-scale conformational interconversion leads to a shuffling of the free energy landscape for fast time-scale events. Until now, population shuffling was only applied to interconverting ground states. Here, we extend the framework of population shuffling to be applicable for a system interconverting between low energy ground and high energy excited states, such as the SH3 domain mutants G48M and A39V/N53P/V55L from the Fyn tyrosine kinase, providing another tool for accessing the structural dynamics of high energy excited states. Our results indicate that the higher energy gauche− rotameric state for the leucine χ2 dihedral angle contributes significantly to the distribution of rotameric states in both the major and minor forms of the SH3 domain. These findings are corroborated with unrestrained molecular dynamics (MD) simulations on both the major and minor states of the SH3 domain demonstrating high correlations between experimental and back-calculated leucine χ2 rotameric populations. Taken together, we demonstrate how fast time-scale rotameric side-chain population distributions can be extracted from slow time-scale conformational exchange data further extending the scope and the applicability of the population shuffling model. PMID:26316263

  18. Neutron decay widths of excited states of {sup 11}Be

    SciTech Connect

    Haigh, P. J.; Freer, M.; Ashwood, N. I.; Bloxham, T.; Curtis, N.; McEwan, P.; Bohlen, H. G.; Dorsch, T.; Kokalova, Tz.; Schulz, Ch.; Wheldon, C.

    2009-01-15

    The two-neutron transfer reaction {sup 9}Be({sup 16}O, {sup 14}O){sup 11}Be[{sup 10}Be +n] has been used to measure the branching ratios for the neutron decay of excited states of {sup 11}Be. The {sup 14}O ejectile was detected by a Q3D spectrometer at forward angles. The energies and angles of the {sup 10}Be fragments of the decaying {sup 11}Be* recoil were measured in coincidence with the {sup 14}O ejectile using a double-sided silicon strip detector array at backward angles. This enabled a kinematic reconstruction of the reaction to be performed. Theoretical decay branch ratios were calculated using barrier penetrability factors and were compared to the measured ratios to provide information on the relative reduced widths of the states. The decay widths have been used to link states in {sup 11}Be with a common structure and structurally to states in the daughter nucleus {sup 10}Be. The 3/2{sup -} 8.82-MeV state was identified as a candidate for a molecular band head.

  19. Cyclopropyl Group: An Excited-State Aromaticity Indicator?

    PubMed

    Ayub, Rabia; Papadakis, Raffaello; Jorner, Kjell; Zietz, Burkhard; Ottosson, Henrik

    2017-07-06

    The cyclopropyl (cPr) group, which is a well-known probe for detecting radical character at atoms to which it is connected, is tested as an indicator for aromaticity in the first ππ* triplet and singlet excited states (T1 and S1 ). Baird's rule says that the π-electron counts for aromaticity and antiaromaticity in the T1 and S1 states are opposite to Hückel's rule in the ground state (S0 ). Our hypothesis is that the cPr group, as a result of Baird's rule, will remain closed when attached to an excited-state aromatic ring, enabling it to be used as an indicator to distinguish excited-state aromatic rings from excited-state antiaromatic and nonaromatic rings. Quantum chemical calculations and photoreactivity experiments support our hypothesis; calculated aromaticity indices reveal that openings of cPr substituents on [4n]annulenes ruin the excited-state aromaticity in energetically unfavorable processes. Yet, polycyclic compounds influenced by excited-state aromaticity (e.g., biphenylene), as well as 4nπ-electron heterocycles with two or more heteroatoms represent limitations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Excited-State Dynamics in Folic Acid and 6-CARBOXYPTERIN upon Uva Excitation

    NASA Astrophysics Data System (ADS)

    Huang, Huijuan; Vogt, R. Aaron; Crespo-Hernandez, Carlos E.

    2013-06-01

    The excited-state dynamics of folic acid (FA) and 6-carboxypterin (6CP) are poorly understood and work is needed to uncover the relaxation pathways that ultimately lead to their oxidative damage of DNA. In our approach, broad-band transient absorption spectroscopy was used to monitor the evolution of the excited states in FA and 6CP in basic aqueous solution upon excitation at 350 nm. In addition, quantum-chemical calculations were performed to assist in the interpretation of the experimental results and in the postulation of kinetic mechanisms. The combined experimental and computational results support a kinetic model where excitation of FA results in ultrafast charge separation (τ = 0.6 ps), which decays back to the ground state primarily by charge recombination with a lifetime of 2.2 ps. A small fraction of the charge transfer state undergoes intersystem crossing to populate the lowest-energy triplet state with a lifetime of 200 ps. On the other hand, a large fraction of the initially excited singlet state in 6CP decays by fluorescence emission with a lifetime of 100 ps, while intersystem crossing to the triplet state occurs with a lifetime of 4.4 ns. The potential implications of these results to the oxidative damage of DNA by FA and 6CP will be discussed. Funding from the National Science Foundation is gratefully acknowledged (CHE-1255084).

  1. Search for dilute excited states in 16O

    NASA Astrophysics Data System (ADS)

    Ogloblin, A. A.; Danilov, A. N.; Demyanova, A. S.; Goncharov, S. A.; Belyaeva, T. L.

    2016-11-01

    The root mean square radii of 16O in the short-lived 0+ excited states were experimentally deduced for the first time from the analyses of α +16O diffraction scattering. Differential cross sections of the elastic and inelastic α +16O and 16O+16O scattering in the incident energy range from a few MeV/nucleon up to 100 MeV/nucleon were analyzed by the modified diffraction model. No significant radius enhancement in any state in comparison with the ground state was observed. This concerns, in particular, the 15.1-MeV 06+ state of 16O, located in the vicinity of the four-α -particle complete dissociation threshold, for which we did not confirm the "gigantic" size predicted by the α -particle condensation model. This result does not support the idea that 16O in the 06+ state has a dilute structure and can be considered as an analog of the famous 7.65-MeV 02+ Hoyle state of 12C.

  2. Excited-State Decay Paths in Tetraphenylethene Derivatives

    PubMed Central

    2017-01-01

    The photophysical properties of tetraphenylethene (TPE) compounds may differ widely depending on the substitution pattern, for example, with regard to the fluorescence quantum yield ϕf and the propensity to exhibit aggregation-induced emission (AIE). We report combined electronic structure calculations and nonadiabatic dynamics simulations to study the excited-state decay mechanisms of two TPE derivatives with four methyl substituents, either in the meta position (TPE-4mM, ϕf = 0.1%) or in the ortho position (TPE-4oM, ϕf = 64.3%). In both cases, two excited-state decay pathways may be relevant, namely, photoisomerization around the central ethylenic double bond and photocyclization involving two adjacent phenyl rings. In TPE-4mM, the barrierless S1 cyclization is favored; it is responsible for the ultralow fluorescence quantum yield observed experimentally. In TPE-4oM, both the S1 photocyclization and photoisomerization paths are blocked by non-negligible barriers, and fluorescence is thus feasible. Nonadiabatic dynamics simulations with more than 1000 surface hopping trajectories show ultrafast cyclization upon photoexcitation of TPE-4mM, whereas TPE-4oM remains unreactive during the 1 ps simulations. We discuss the chances for spectroscopic detection of the postulated cyclic photoproduct of TPE-4mM and the relevance of our findings for the AIE process. PMID:28318255

  3. Excited-State Decay Paths in Tetraphenylethene Derivatives.

    PubMed

    Gao, Yuan-Jun; Chang, Xue-Ping; Liu, Xiang-Yang; Li, Quan-Song; Cui, Ganglong; Thiel, Walter

    2017-04-06

    The photophysical properties of tetraphenylethene (TPE) compounds may differ widely depending on the substitution pattern, for example, with regard to the fluorescence quantum yield ϕf and the propensity to exhibit aggregation-induced emission (AIE). We report combined electronic structure calculations and nonadiabatic dynamics simulations to study the excited-state decay mechanisms of two TPE derivatives with four methyl substituents, either in the meta position (TPE-4mM, ϕf = 0.1%) or in the ortho position (TPE-4oM, ϕf = 64.3%). In both cases, two excited-state decay pathways may be relevant, namely, photoisomerization around the central ethylenic double bond and photocyclization involving two adjacent phenyl rings. In TPE-4mM, the barrierless S1 cyclization is favored; it is responsible for the ultralow fluorescence quantum yield observed experimentally. In TPE-4oM, both the S1 photocyclization and photoisomerization paths are blocked by non-negligible barriers, and fluorescence is thus feasible. Nonadiabatic dynamics simulations with more than 1000 surface hopping trajectories show ultrafast cyclization upon photoexcitation of TPE-4mM, whereas TPE-4oM remains unreactive during the 1 ps simulations. We discuss the chances for spectroscopic detection of the postulated cyclic photoproduct of TPE-4mM and the relevance of our findings for the AIE process.

  4. Ultrafast excited state relaxation in long-chain polyenes

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

  5. The examination of berberine excited state by laser flash photolysis

    NASA Astrophysics Data System (ADS)

    Cheng, Lingli; Wang, Mei; Zhao, Ping; Zhu, Hui; Zhu, Rongrong; Sun, Xiaoyu; Yao, Side; Wang, Shilong

    2009-07-01

    The property of the excited triplet state of berberine (BBR) was investigated by using time-resolved laser flash photolysis of 355 nm in acetonitrile. The transient absorption spectra of the excited triplet BBR were obtained in acetonitrile, which have an absorption maximum at 420 nm. And the ratio of excitation to ionization of BBR in acetonitrile solvent was calculated. The self-decay and self-quenching rate constants, and the absorption coefficient of 3BBR* were investigated and the excited state quantum yield was determined. Furthermore utilizing the benzophenone (BEN) as a triplet sensitizer, and the β-carotene (Car) as an excited energy transfer acceptor, the assignment of 3BBR* was further confirmed and the related energy transfer rate constants were also determined.

  6. Peroxyacetyl radical: Electronic excitation energies, fundamental vibrational frequencies, and symmetry breaking in the first excited state

    SciTech Connect

    Copan, Andreas V.; Wiens, Avery E.; Nowara, Ewa M.; Schaefer, Henry F.; Agarwal, Jay

    2015-02-07

    Peroxyacetyl radical [CH{sub 3}C(O)O{sub 2}] is among the most abundant peroxy radicals in the atmosphere and is involved in OH-radical recycling along with peroxyacetyl nitrate formation. Herein, the ground (X{sup ~}) and first (A{sup ~}) excited state surfaces of cis and trans peroxyacetyl radical are characterized using high-level ab initio methods. Geometries, anharmonic vibrational frequencies, and adiabatic excitation energies extrapolated to the complete basis-set limit are reported from computations with coupled-cluster theory. Excitation of the trans conformer is found to induce a symmetry-breaking conformational change due to second-order Jahn-Teller interactions with higher-lying excited states. Additional benchmark computations are provided to aid future theoretical work on peroxy radicals.

  7. Elementary Excitations and Dynamic Structure of Quantum Fluids

    NASA Astrophysics Data System (ADS)

    Saarela, M.

    The equations of motion method for studying excitations and dynamic structure of quantum fluids is reviewed in this series of lectures. The method is based on the least action principle where one minimizes the action integral of the dynamic system. As a result one gets the continuity equations, which connect the density fluctuations and currents to an external driving force. The external force is assumed to infinitesimal and the response of the system to that is linear. The real poles of the linear response function determine the elementary excitation modes and the imaginary part of the self energy defines the continuum limit and gives the finite lifetime of the decaying modes. Our dynamic wave function contains time-dependent one- and two-particle correlation functions, which includes couplings between three modes. Thus one mode can split into two modes if energy and momentum are conserved. We begin with the Feenberg's β-derivative formulation of the optimized ground state and then derive general equations of motion for the dynamic system from the least action principle. We show how the simplest one-body approximation leads to the Feynman theory of excitations. By including the fluctuating two-body correlation function within the uniform limit one recovers the correlated basic function approximation. The fully consistent theory gives a good account of the elementary excitations and we show results on current patterns in the maxon-roton regions and on the precursor of the liquid-solid phase transition. Finally we apply the method to the excitations of the impurity and derive the hydrodynamic effective mass of the 3He impurity in 4He and the 3He dynamic structure function.

  8. Mode specific excited state dynamics study of bis(phenylethynyl)benzene from ultrafast Raman loss spectroscopy

    NASA Astrophysics Data System (ADS)

    Roy, Khokan; Kayal, Surajit; Ariese, Freek; Beeby, Andrew; Umapathy, Siva

    2017-02-01

    Femtosecond transient absorption (fs-TA) and Ultrafast Raman Loss Spectroscopy (URLS) have been applied to reveal the excited state dynamics of bis(phenylethynyl)benzene (BPEB), a model system for one-dimensional molecular wires that have numerous applications in opto-electronics. It is known from the literature that in the ground state BPEB has a low torsional barrier, resulting in a mixed population of rotamers in solution at room temperature. For the excited state this torsional barrier had been calculated to be much higher. Our femtosecond TA measurements show a multi-exponential behaviour, related to the complex structural dynamics in the excited electronic state. Time-resolved, excited state URLS studies in different solvents reveal mode-dependent kinetics and picosecond vibrational relaxation dynamics of high frequency vibrations. After excitation, a gradual increase in intensity is observed for all Raman bands, which reflects the structural reorganization of Franck-Condon excited, non-planar rotamers to a planar conformation. It is argued that this excited state planarization is also responsible for its high fluorescence quantum yield. The time dependent peak positions of high frequency vibrations provide additional information: a rapid, sub-picosecond decrease in peak frequency, followed by a slower increase, indicates the extent of conjugation during different phases of excited state relaxation. The CC triple (-C≡C-) bond responds somewhat faster to structural reorganization than the CC double (>C=C<) bonds. This study deepens our understanding of the excited state of BPEB and analogous linear pi-conjugated systems and may thus contribute to the advancement of polymeric "molecular wires."

  9. Mode specific excited state dynamics study of bis(phenylethynyl)benzene from ultrafast Raman loss spectroscopy.

    PubMed

    Roy, Khokan; Kayal, Surajit; Ariese, Freek; Beeby, Andrew; Umapathy, Siva

    2017-02-14

    Femtosecond transient absorption (fs-TA) and Ultrafast Raman Loss Spectroscopy (URLS) have been applied to reveal the excited state dynamics of bis(phenylethynyl)benzene (BPEB), a model system for one-dimensional molecular wires that have numerous applications in opto-electronics. It is known from the literature that in the ground state BPEB has a low torsional barrier, resulting in a mixed population of rotamers in solution at room temperature. For the excited state this torsional barrier had been calculated to be much higher. Our femtosecond TA measurements show a multi-exponential behaviour, related to the complex structural dynamics in the excited electronic state. Time-resolved, excited state URLS studies in different solvents reveal mode-dependent kinetics and picosecond vibrational relaxation dynamics of high frequency vibrations. After excitation, a gradual increase in intensity is observed for all Raman bands, which reflects the structural reorganization of Franck-Condon excited, non-planar rotamers to a planar conformation. It is argued that this excited state planarization is also responsible for its high fluorescence quantum yield. The time dependent peak positions of high frequency vibrations provide additional information: a rapid, sub-picosecond decrease in peak frequency, followed by a slower increase, indicates the extent of conjugation during different phases of excited state relaxation. The CC triple (-C≡C-) bond responds somewhat faster to structural reorganization than the CC double (>C=C<) bonds. This study deepens our understanding of the excited state of BPEB and analogous linear pi-conjugated systems and may thus contribute to the advancement of polymeric "molecular wires."

  10. Investigation into chromophore excited-state coupling in allophycocyanin

    NASA Astrophysics Data System (ADS)

    Zheng, Xiguang; Zhao, Fuli; Wang, He Z.; Gao, Zhaolan; Yu, Zhenxin; Zhu, Jinchang; Xia, Andong; Jiang, Lijin

    1994-08-01

    Both theoretical and experimental studies are presented on chromophore excited-state coupling in linker-free allophycocyanin (APC), one of the antenna phycobiliproteins in algal photosynthesis. A three-site-coupling model has been introduced to describe the exciton interaction mechanism amoung the excited (beta) chromophore in APC, and the exciton energy splitting is estimated. Picosecond polarized fluorescence experiments both on monomeric and trimeric APC isolated from alga Spirulina platensis have been performed. The experimental results show that APC monomer and trimer exhibit remarkedly different spectropic characteristics, and satisfy the suggestion of strong excited- state coupling among chromophores in APC.

  11. Photoacoustic imaging of the excited state lifetime of fluorophores

    NASA Astrophysics Data System (ADS)

    Märk, Julia; Schmitt, Franz-Josef; Laufer, Jan

    2016-05-01

    Photoacoustic (PA) imaging using pump-probe excitation has been shown to allow the detection and visualization of fluorescent contrast agents. The technique relies upon inducing stimulated emission using pump and probe pulses at excitation wavelengths that correspond to the absorption and fluorescence spectra. By changing the time delay between the pulses, the excited state lifetime of the fluorophore is modulated to vary the amount of thermalized energy, and hence PA signal amplitude, to provide fluorophore-specific PA contrast. In this study, this approach was extended to the detection of differences in the excited state lifetime of fluorophores. PA waveforms were measured in solutions of a near-infrared fluorophore using simultaneous and time-delayed pump-probe excitation. The lifetime of the fluorophore solutions was varied by using different solvents and quencher concentrations. By calculating difference signals and by plotting their amplitude as a function of pump-probe time delay, a correlation with the excited state lifetime of the fluorophore was observed. The results agreed with the output of a forward model of the PA signal generation in fluorophores. The application of this method to tomographic PA imaging of differences in the excited state lifetime was demonstrated in tissue phantom experiments.

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

    SciTech Connect

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

    2008-07-15

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

  13. A photo-induced excited state structure of a hetero-bimetallic ionic pair complex, Nd(DMA)[subscript 4](H[subscript 2]O)[subscript 4]Fe(CN)[subscript 6]·3H[subscript 2]O, analyzed by single crystal X-ray diffraction

    SciTech Connect

    Svendsen, Helle; Overgaard, Jacob; Chen, Yu-Sheng; Iversen, Bo B.

    2012-02-07

    The excited state crystal structure of the ionic complex Nd(DMA){sub 4}(H{sub 2}O){sub 4}-Fe(CN){sub 6} {center_dot} 3H{sub 2}O (DMA = dimethylacetamide) has been determined at 15 K upon UV illumination by single crystal X-ray diffraction. Significant structural changes are observed around the Fe site in the excited state. These changes are similar to those observed for a related molecular compound exhibiting photomagnetic properties.

  14. Study of excited nucleons and their structure

    SciTech Connect

    Burkert, Volker D.

    2014-01-01

    Recent advances in the study of excited nucleons are discussed. Much of the progress has been achieved due to the availability of high precision meson production data in the photoproduction and electroproduction sectors, the development of multi-channel partial wave analysis techniques, and advances in Lattice QCD with predictions of the full excitation spectrum.

  15. Benzonitrile: Electron affinity, excited states, and anion solvation.

    PubMed

    Dixon, Andrew R; Khuseynov, Dmitry; Sanov, Andrei

    2015-10-07

    We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X̃(1)A1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, ã(3)A1, is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet Ã(1)A1, is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

  16. Targeting excited states in all-trans polyenes with electron-pair states.

    PubMed

    Boguslawski, Katharina

    2016-12-21

    Wavefunctions restricted to electron pair states are promising models for strongly correlated systems. Specifically, the pair Coupled Cluster Doubles (pCCD) ansatz allows us to accurately describe bond dissociation processes and heavy-element containing compounds with multiple quasi-degenerate single-particle states. Here, we extend the pCCD method to model excited states using the equation of motion (EOM) formalism. As the cluster operator of pCCD is restricted to electron-pair excitations, EOM-pCCD allows us to target excited electron-pair states only. To model singly excited states within EOM-pCCD, we modify the configuration interaction ansatz of EOM-pCCD to contain also single excitations. Our proposed model represents a simple and cost-effective alternative to conventional EOM-CC methods to study singly excited electronic states. The performance of the excited state models is assessed against the lowest-lying excited states of the uranyl cation and the two lowest-lying excited states of all-trans polyenes. Our numerical results suggest that EOM-pCCD including single excitations is a good starting point to target singly excited states.

  17. Targeting excited states in all-trans polyenes with electron-pair states

    NASA Astrophysics Data System (ADS)

    Boguslawski, Katharina

    2016-12-01

    Wavefunctions restricted to electron pair states are promising models for strongly correlated systems. Specifically, the pair Coupled Cluster Doubles (pCCD) ansatz allows us to accurately describe bond dissociation processes and heavy-element containing compounds with multiple quasi-degenerate single-particle states. Here, we extend the pCCD method to model excited states using the equation of motion (EOM) formalism. As the cluster operator of pCCD is restricted to electron-pair excitations, EOM-pCCD allows us to target excited electron-pair states only. To model singly excited states within EOM-pCCD, we modify the configuration interaction ansatz of EOM-pCCD to contain also single excitations. Our proposed model represents a simple and cost-effective alternative to conventional EOM-CC methods to study singly excited electronic states. The performance of the excited state models is assessed against the lowest-lying excited states of the uranyl cation and the two lowest-lying excited states of all-trans polyenes. Our numerical results suggest that EOM-pCCD including single excitations is a good starting point to target singly excited states.

  18. Microsolvation Effects on the Excited-State Dynamics of Protonated Tryptophan

    NASA Astrophysics Data System (ADS)

    Guglielmi, Matteo; Mercier, Sebastien; Boyarkin, Oleg; Kamariotis, Anthi; Tavernelli, Ivano; Cascella, Michele; Roethlisberger, Ursula; Rizzo, Thomas

    2008-03-01

    To better understand the complex photophysics of the amino acid tryptophan, which is widely used as a probe of protein structure and dynamics, we have measured electronic spectra of protonated, gas-phase tryptophan solvated with a controlled number of water molecules and cooled to ˜10 K. We observe that, even at this temperature, the bare molecule exhibits a broad electronic spectrum, implying ultrafast, nonradiative decay of the excited state. Surprisingly, the addition of two water molecules sufficiently lengthens the excited-state lifetime that we obtain a fully vibrationally resolved electronic spectrum. Quantum chemical calculations at the RI-CC2/aug-cc-pVDZ level, together with TDDFT/pw based first-principles MD simulations of the excited-state dynamics, clearly demonstrate how interactions with water destabilize the photodissociative states and increase the excited-state lifetime.

  19. Resonance-Enhanced Excited-State Raman Spectroscopy of Conjugated Thiophene Derivatives: Combining Experiment with Theory

    NASA Astrophysics Data System (ADS)

    Barclay, Matthew S.; Quincy, Timothy J.; Caricato, Marco; Elles, Christopher G.

    2017-06-01

    Resonance-enhanced Femtosecond Stimulated Raman Spectroscopy (FSRS) is an ultrafast experimental method that allows for the study of excited-state structural behaviors, as well as the characterization of higher electronically excited states accessible through the resonant conditions of the observed vibrations. However, interpretation of the experiment is difficult without an accurate vibrational assignment of the resonance-enhanced spectra. We therefore utilize simulations of off-resonant excited-state Raman spectra, in which we employ a numerical derivative of the analytical excited-state polarizabilities along the normal mode displacements, in order to identify and interpret the resonance-enhanced vibrations observed in experiment. We present results for a benchmark series of conjugated organic thiophene derivatives, wherein we have computed the off-resonant excited-state Raman spectra for each molecule and matched it with its resonance-enhanced experimental spectrum. This comparison allows us to successfully identify the vibrational displacements of the observed FSRS bands, as well as validate the accuracy of the theoretical results through an experimental benchmark. The agreement between the experimental and computed results demonstrates that we are able to predict qualitatively accurate excited-state Raman spectra for these conjugated thiophenes, allowing for a more thorough interpretation of excited-state Raman signals at relatively low computational cost.

  20. An Ab Initio Exciton Model Including Charge-Transfer Excited States

    DOE PAGES

    Li, Xin; Parrish, Robert M.; Liu, Fang; ...

    2017-06-15

    Here, the Frenkel exciton model is a useful tool for theoretical studies of multichromophore systems. We recently showed that the exciton model could be used to coarse-grain electronic structure in multichromophoric systems, focusing on singly excited exciton states. However, our previous implementation excluded charge-transfer excited states, which can play an important role in light-harvesting systems and near-infrared optoelectronic materials. Recent studies have also emphasized the significance of charge-transfer in singlet fission, which mediates the coupling between the locally excited states and the multiexcitonic states. In this work, we report on an ab initio exciton model that incorporates charge-transfer excited statesmore » and demonstrate that the model provides correct charge-transfer excitation energies and asymptotic behavior. Comparison with TDDFT and EOM-CC2 calculations shows that our exciton model is robust with respect to system size, screening parameter, and different density functionals. Inclusion of charge-transfer excited states makes the exciton model more useful for studies of singly excited states and provides a starting point for future construction of a model that also includes double-exciton states.« less

  1. Excited states and reduced transition probabilities in 168Os

    NASA Astrophysics Data System (ADS)

    Grahn, T.; Stolze, S.; Joss, D. T.; Page, R. D.; Sayǧı, B.; O'Donnell, D.; Akmali, M.; Andgren, K.; Bianco, L.; Cullen, D. M.; Dewald, A.; Greenlees, P. T.; Heyde, K.; Iwasaki, H.; Jakobsson, U.; Jones, P.; Judson, D. S.; Julin, R.; Juutinen, S.; Ketelhut, S.; Leino, M.; Lumley, N.; Mason, P. J. R.; Möller, O.; Nomura, K.; Nyman, M.; Petts, A.; Peura, P.; Pietralla, N.; Pissulla, Th.; Rahkila, P.; Sapple, P. J.; Sarén, J.; Scholey, C.; Simpson, J.; Sorri, J.; Stevenson, P. D.; Uusitalo, J.; Watkins, H. V.; Wood, J. L.

    2016-10-01

    The level scheme of the neutron-deficient nuclide 168Os has been extended and mean lifetimes of excited states have been measured by the recoil distance Doppler-shift method using the JUROGAM γ -ray spectrometer in conjunction with the IKP Köln plunger device. The 168Osγ rays were measured in delayed coincidence with recoiling fusion-evaporation residues detected at the focal plane of the RITU gas-filled separator. The ratio of reduced transition probabilities B (E 2 ;41+→21+) /B (E 2 ;21+→01+) is measured to be 0.34(18), which is very unusual for collective band structures and cannot be reproduced by interacting boson model (IBM-2) calculations based on the SkM* energy-density functional.

  2. Chimera states and excitation waves in networks with complex topologies

    NASA Astrophysics Data System (ADS)

    Schöll, Eckehard

    2016-06-01

    Chimera patterns, which consist of coexisting spatial domains of coherent (synchronized) and incoherent (desyn- chronized) dynamics are studied in networks of FitzHugh-Nagumo systems with complex topologies. To test the robustness of chimera patterns with respect to changes in the structure of the network, we study the following network topologies: Regular ring topology with R nearest neigbors coupled to each side, small-world topology with additional long-range random links, and a hierarchical geometry in the connectivity matrix. We find that chimera states are generally robust with respect to these perturbations, but qualitative changes of the chimera patterns in form of nested coherent and incoherent regions can be induced by a hierarchical topology. The suppression of propagating excitation waves by a small-world topology is also reviewed.

  3. Masses of Ground- and Excited-State Hadrons

    NASA Astrophysics Data System (ADS)

    Roberts, Hannes L. L.; Chang, Lei; Cloët, Ian C.; Roberts, Craig D.

    2011-07-01

    We present the first Dyson-Schwinger equation calculation of the light hadron spectrum that simultaneously correlates the masses of meson and baryon ground- and excited-states within a single framework. At the core of our analysis is a symmetry-preserving treatment of a vector-vector contact interaction. In comparison with relevant quantities the root-mean-square-relative-error/degree-of freedom is 13%. Notable amongst our results is agreement between the computed baryon masses and the bare masses employed in modern dynamical coupled-channels models of pion-nucleon reactions. Our analysis provides insight into numerous aspects of baryon structure; e.g., relationships between the nucleon and Δ masses and those of the dressed-quark and diquark correlations they contain.

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

    SciTech Connect

    Guevara, Z. E. Torres, D. A.

    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.

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

    NASA Astrophysics Data System (ADS)

    Guevara, Z. E.; Torres, D. A.

    2016-07-01

    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 106Cd to study excited states of 110Sn and the beam nuclei itself will be presented.

  6. Size and shape dependent photoluminescence and excited state decay rates of diamondoids.

    PubMed

    Richter, Robert; Wolter, David; Zimmermann, Tobias; Landt, Lasse; Knecht, Andre; Heidrich, Christoph; Merli, Andrea; Dopfer, Otto; Reiss, Philipp; Ehresmann, Arno; Petersen, Jens; Dahl, Jeremy E; Carlson, Robert M K; Bostedt, Christoph; Möller, Thomas; Mitric, Roland; Rander, Torbjörn

    2014-02-21

    We present photoluminescence spectra and excited state decay rates of a series of diamondoids, which represent molecular structural analogues to hydrogen-passivated bulk diamond. Specific isomers of the five smallest diamondoids (adamantane-pentamantane) have been brought into the gas phase and irradiated with synchrotron radiation. All investigated compounds show intrinsic photoluminescence in the ultraviolet spectral region. The emission spectra exhibit pronounced vibrational fine structure which is analyzed using quantum chemical calculations. We show that the geometrical relaxation of the first excited state of adamantane, exhibiting Rydberg character, leads to the loss of Td symmetry. The luminescence of adamantane is attributed to a transition from the delocalized first excited state into different vibrational modes of the electronic ground state. Similar geometrical changes of the excited state structure have also been identified in the other investigated diamondoids. The excited state decay rates show a clear dependence on the size of the diamondoid, but are independent of the particle geometry, further indicating a loss of particle symmetry upon electronic excitation.

  7. The excited state antiaromatic benzene ring: a molecular Mr Hyde?

    PubMed

    Papadakis, Raffaello; Ottosson, Henrik

    2015-09-21

    The antiaromatic character of benzene in its first ππ* excited triplet state (T1) was deduced more than four decades ago by Baird using perturbation molecular orbital (PMO) theory [J. Am. Chem. Soc. 1972, 94, 4941], and since then it has been confirmed through a range of high-level quantum chemical calculations. With focus on benzene we now first review theoretical and computational studies that examine and confirm Baird's rule on reversal in the electron count for aromaticity and antiaromaticity of annulenes in their lowest triplet states as compared to Hückel's rule for the ground state (S0). We also note that the rule according to quantum chemical calculations can be extended to the lowest singlet excited state (S1) of benzene. Importantly, Baird, as well as Aihara [Bull. Chem. Soc. Jpn. 1978, 51, 1788], early put forth that the destabilization and excited state antiaromaticity of the benzene ring should be reflected in its photochemical reactivity, yet, today these conclusions are often overlooked. Thus, in the second part of the article we review photochemical reactions of a series of benzene derivatives that to various extents should stem from the excited state antiaromatic character of the benzene ring. We argue that benzene can be viewed as a molecular "Dr Jekyll and Mr Hyde" with its largely unknown excited state antiaromaticity representing its "Mr Hyde" character. The recognition of the "Jekyll and Hyde" split personality feature of the benzene ring can likely be useful in a range of different areas.

  8. Controlling chimera states: The influence of excitable units

    NASA Astrophysics Data System (ADS)

    Isele, Thomas; Hizanidis, Johanne; Provata, Astero; Hövel, Philipp

    2016-02-01

    We explore the influence of a block of excitable units on the existence and behavior of chimera states in a nonlocally coupled ring-network of FitzHugh-Nagumo elements. The FitzHugh-Nagumo system, a paradigmatic model in many fields from neuroscience to chemical pattern formation and nonlinear electronics, exhibits oscillatory or excitable behavior depending on the values of its parameters. Until now, chimera states have been studied in networks of coupled oscillatory FitzHugh-Nagumo elements. In the present work, we find that introducing a block of excitable units into the network may lead to several interesting effects. It allows for controlling the position of a chimera state as well as for generating a chimera state directly from the synchronous state.

  9. Excited state correlations of the finite Heisenberg chain

    NASA Astrophysics Data System (ADS)

    Pozsgay, Balázs

    2017-02-01

    We consider short range correlations in excited states of the finite XXZ and XXX Heisenberg spin chains. We conjecture that the known results for the factorized ground state correlations can be applied to the excited states too, if the so-called physical part of the construction is changed appropriately. For the ground state we derive simple algebraic expressions for the physical part; the formulas only use the ground state Bethe roots as an input. We conjecture that the same formulas can be applied to the excited states as well, if the exact Bethe roots of the excited states are used instead. In the XXZ chain the results are expected to be valid for all states (except certain singular cases where regularization is needed), whereas in the XXX case they only apply to singlet states or group invariant operators. Our conjectures are tested against numerical data from exact diagonalization and coordinate Bethe Ansatz calculations, and perfect agreement is found in all cases. In the XXX case we also derive a new result for the nearest-neighbour correlator < σ 1zσ 2z> , which is valid for non-singlet states as well. Our results build a bridge between the known theory of factorized correlations, and the recently conjectured TBA-like description for the building blocks of the construction.

  10. Aqueous reactions of triplet excited states with allylic compounds

    NASA Astrophysics Data System (ADS)

    Kaur, R.; Anastasio, C.; Hudson, B. M.; Tantillo, D. J.

    2016-12-01

    Triplet excited states of dissolved organic matter react with several classes of aromatic organics such as phenols, anilines, sulfonamide antibiotics and phenylurea herbicides. Aqueous triplets appear to be among the most important oxidants for atmospheric phenols in regions with biomass burning, with phenol lifetimes on the order of a few hours to a day. However, little is known of the reactions of triplets with other classes of organic compounds. Recent work from our group shows that triplets react rapidly with several biogenic volatile organic compounds (BVOCs), such as methyl jasmonate, cis-3-hexenyl acetate, and cis-3-hexen-1-ol. However, there are only a few rate constants for aqueous reactions between alkenes such as these and triplet excited states. For our work, we refer to these and similar alkenes which have hydrogen(s) attached to a carbon adjacent to the double bond, as allylic compounds. To better assess the importance of triplets as aqueous oxidants, we measured second-order rate constants (kAC+3BP*) for a number of allylic compounds (ACs) with the triplet state of benzophenone; then established a quantitative structure-activity relationship (QSAR) between kAC+3BP* and computed oxidation potential of the ACs (R2 =0.65). Using the QSAR, we estimated the rate constants for triplets with some allylic isoprene and limonene oxidation products that have high Henry's law constants (KH>103 M atm-1). Hydroxylated limonene products and the delta-isomers of isoprene hydroxyhydroperoxides (δ4ISOPOOH) and hydroxynitrates (δ4ISONO2) were faster with predicted kAC+3BP* values ranging between (0.5-3.5) x 109 M-1-s-1 whereas the beta-isomers of ISOPOOH and ISONO2 were slower (kAC+3BP* < 0.5 x 109 M-1s-1). We scaled the predicted kAC+3BP* to represent less reactive atmospheric triplets that have been measured in fog drops, and compared to gas and aqueous hydroxyl radical and ozone, triplets in fog could account for up to 20 % of the measured loss of these compounds

  11. Dynamics of Excited States for Fluorescent Emitters with Hybridized Local and Charge-Transfer Excited State in Solid Phase: A QM/MM Study.

    PubMed

    Fan, Jianzhong; Cai, Lei; Lin, Lili; Wang, Chuan-Kui

    2016-12-01

    The highly efficient organic light-emitting diodes (OLEDS) based on fluorescent emitters with hybridized local and charge-transfer (HLCT) excited state have attracted great attention recently. The excited-state dynamics of the fluorescent molecule with consideration of molecular interaction are studied using the hybrid quantum mechanics/molecular mechanics method. The results show that, in solid state, the internal conversion rate (KIC) between the first singlet excited state (S1) and the ground state (S0) is smaller than the fluorescent rate (Kr), while in gas phase KIC is much larger than Kr. By analyzing the Huang-Rhys (HR) factor and reorganization energy (λ), we find that these two parameters in solid state are much smaller than those in gas phase due to the suppression of the vibration modes in low-frequency regions (<200 cm(-1)) related with dihedral angles between donor and acceptor groups. This is further demonstrated by the geometrical analysis that variation of the dihedral angle between geometries of S1 and S0 is smaller in solid state than that in gas phase. Moreover, combining the dynamics of the excited states and the adiabatic energy structures calculated in solid state, we illustrate the suggested "hot-exciton" mechanism of the HLCT emitters in OLEDs. Our work presents a rational explanation for the experimental results and demonstrates the importance of molecular interaction for theoretical simulation of the working principle of OLEDs.

  12. Excited-State OH Masers and Supernova Remnants

    NASA Astrophysics Data System (ADS)

    Pihlström, Ylva M.; Fish, Vincent L.; Sjouwerman, Loránt O.; Zschaechner, Laura K.; Lockett, Philip B.; Elitzur, Moshe

    2008-03-01

    The collisionally pumped, ground-state 1720 MHz maser line of OH is widely recognized as a tracer for shocked regions and observed in star-forming regions and supernova remnants. Whereas some lines of excited states of OH have been detected and studied in star-forming regions, the subject of excited-state OH in supernova remnants—where high collision rates are to be expected—is only recently being addressed. Modeling of collisional excitation of OH demonstrates that 1720, 4765, and 6049 MHz masers can occur under similar conditions in regions of shocked gas. In particular, the 6049 and 4765 MHz masers become more significant at increased OH column densities where the 1720 MHz masers begin to be quenched. In supernova remnants, the detection of excited-state OH line maser emission could therefore serve as a probe of regions of higher column densities. Using the Very Large Array, we searched for excited-state OH in the 4.7, 7.8, 8.2, and 23.8 GHz lines in four well-studied supernova remnants with strong 1720 MHz maser emission (Sgr A East, W28, W44 and IC 443). No detections were made, at typical detection limits of around 10 mJy beam-1. The search for the 6 GHz lines were done using Effelsberg since the VLA receivers did not cover those frequencies, and are reported on in an accompanying letter (Fish and coworkers). We also cross-correlated the positions of known supernova remnants with the positions of 1612 MHz maser emission obtained from blind surveys. No probable associations were found, perhaps except in the Sgr A East region. The lack of detections of excited-state OH indicates that the OH column densities suffice for 1720 MHz inversion but not for inversion of excited-state transitions, consistent with the expected results for C-type shocks.

  13. Nature of ground and electronic excited states of higher acenes

    PubMed Central

    Yang, Yang; Yang, Weitao

    2016-01-01

    Higher acenes have drawn much attention as promising organic semiconductors with versatile electronic properties. However, the nature of their ground state and electronic excited states is still not fully clear. Their unusual chemical reactivity and instability are the main obstacles for experimental studies, and the potentially prominent diradical character, which might require a multireference description in such large systems, hinders theoretical investigations. Here, we provide a detailed answer with the particle–particle random-phase approximation calculation. The 1Ag ground states of acenes up to decacene are on the closed-shell side of the diradical continuum, whereas the ground state of undecacene and dodecacene tilts more to the open-shell side with a growing polyradical character. The ground state of all acenes has covalent nature with respect to both short and long axes. The lowest triplet state 3B2u is always above the singlet ground state even though the energy gap could be vanishingly small in the polyacene limit. The bright singlet excited state 1B2u is a zwitterionic state to the short axis. The excited 1Ag state gradually switches from a double-excitation state to another zwitterionic state to the short axis, but always keeps its covalent nature to the long axis. An energy crossing between the 1B2u and excited 1Ag states happens between hexacene and heptacene. Further energetic consideration suggests that higher acenes are likely to undergo singlet fission with a low photovoltaic efficiency; however, the efficiency might be improved if a singlet fission into multiple triplets could be achieved. PMID:27528690

  14. Nature of ground and electronic excited states of higher acenes.

    PubMed

    Yang, Yang; Davidson, Ernest R; Yang, Weitao

    2016-08-30

    Higher acenes have drawn much attention as promising organic semiconductors with versatile electronic properties. However, the nature of their ground state and electronic excited states is still not fully clear. Their unusual chemical reactivity and instability are the main obstacles for experimental studies, and the potentially prominent diradical character, which might require a multireference description in such large systems, hinders theoretical investigations. Here, we provide a detailed answer with the particle-particle random-phase approximation calculation. The (1)Ag ground states of acenes up to decacene are on the closed-shell side of the diradical continuum, whereas the ground state of undecacene and dodecacene tilts more to the open-shell side with a growing polyradical character. The ground state of all acenes has covalent nature with respect to both short and long axes. The lowest triplet state (3)B2u is always above the singlet ground state even though the energy gap could be vanishingly small in the polyacene limit. The bright singlet excited state (1)B2u is a zwitterionic state to the short axis. The excited (1)Ag state gradually switches from a double-excitation state to another zwitterionic state to the short axis, but always keeps its covalent nature to the long axis. An energy crossing between the (1)B2u and excited (1)Ag states happens between hexacene and heptacene. Further energetic consideration suggests that higher acenes are likely to undergo singlet fission with a low photovoltaic efficiency; however, the efficiency might be improved if a singlet fission into multiple triplets could be achieved.

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

    SciTech Connect

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

    2014-04-28

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

  16. Observation of Excited State Spin Ordering under Pulsed Magnetic Field

    NASA Astrophysics Data System (ADS)

    Amaya, Kiichi; Karaki, Yoshitomo; Yamada, Norikatsu; Haseda, Taiichiro

    1981-10-01

    Spin ordering among excited levels in NaNi Acac3\\cdotbenzene is observed in the course of pulsed adiabatic magnetization with sweep rate of 105 T/sec. For initial temperatures below 1 K, dM/dt signals give the characteristic double peaks around the field of 2.11 T where the excited singlet and the upper state of the ground doublet crosses.

  17. Ultrafast excited-state intramolecular proton transfer of aloesaponarin I.

    PubMed

    Nagaoka, Shin-ichi; Uno, Hidemitsu; Huppert, Dan

    2013-04-25

    Time-resolved emission of aloesaponarin I was studied with the fluorescence up-conversion and time-correlated single-photon-counting techniques. The rates of the excited-state intramolecular proton transfer, of the solvent and molecular rearrangements, and of the decay from the excited proton-transferred species were determined and interpreted in the light of time-dependent density functional calculations. These results were discussed in conjunction with UV protection and singlet-oxygen quenching activity of aloe.

  18. Excitation energies of superdeformed states in the Pb isotopes

    SciTech Connect

    Wilson, A. N.; Byrne, A. P.; Dracoulis, G. D.; Davidson, P. M.; Lane, G. J.; Huebel, H.; Rossbach, D.; Schonwasser, G.; Korichi, A.; Hannachi, F.; Lopez-Martens, A.; Clark, R. M.; Fallon, P.; Macchiavelli, A. O.; Ward, D.

    2006-04-26

    Measurements of the excitation energies of superdeformed states via the observation of single-step linking transitions have now been made in three even-A Pb nuclei, with a quasicontinuum analysis providing a limit in a fourth, odd-A case. These results allow us to take the first steps towards establishing systematic trends in excitation energies and binding energies in the second minimum in Pb isotopes.

  19. Excited states of Ne isoelectronic ions: SAC-CI study

    NASA Astrophysics Data System (ADS)

    Das, A. K.; Ehara, M.; Nakatsuji, H.

    2001-01-01

    Excited states of the s, p, and d symmetries up to principal quantum number n = 4 are studied for the first eight members of Ne isoelectronic sequence (Ne to Cl7+) by the SAC-CI (symmetry-adapted-cluster configuration-interaction) method. The valence STO basis sets of Clementi et al. and the optimized excited STO are used by the STO-6G expansion method. The calculated transition energies agree well with the experimental values wherever available.

  20. Dynamics and spectroscopy of CH₂OO excited electronic states.

    PubMed

    Kalinowski, Jaroslaw; Foreman, Elizabeth S; Kapnas, Kara M; Murray, Craig; Räsänen, Markku; Gerber, R Benny

    2016-04-28

    The excited states of the Criegee intermediate CH2OO are studied in molecular dynamics simulations using directly potentials from multi-reference perturbation theory (MR-PT2). The photoexcitation of the species is simulated, and trajectories are propagated in time on the excited state. Some of the photoexcitation events lead to direct fragmentation of the molecule, but other trajectories describe at least several vibrations in the excited state, that may terminate by relaxation to the ground electronic state. Limits on the role of non-adiabatic contributions to the process are estimated by two different simulations, one that forces surface-hopping at potential crossings, and another that ignores surface hopping altogether. The effect of non-adiabatic transitions is found to be small. Spectroscopic implications and consequences for the interpretation of experimental results are discussed.

  1. Ab Initio Excited State Properties and Dynamics of a Prototype σ-Bridged-Donor-Acceptor Molecule

    NASA Astrophysics Data System (ADS)

    Tapavicza, Enrico; Tavernelli, Ivano; Rothlisberger, Ursula

    2009-08-01

    The photophysical and dynamical properties of the donor-(σ-bridge)-acceptor molecule N-phenylpiperindone-malondinitrile are investigated by second-order approximate coupled cluster (CC2) and time-dependent density functional theory (TDDFT). The study is based on optimized equilibrium geometries for ground and excited states as well as on ab initio molecular dynamics simulations. While CC2 and DFT both predict ground state geometries that are consistent with the crystal structure, equilibrium geometries for the fluorescent charge transfer (CT) state are qualitatively different between CC2 and TDDFT. CC2 reproduces the experimental results for vertical excitations (within 0.3 eV) and provides an orbital assignment of the experimental absorption bands that is supported by experiments. Using CC2, a good agreement is also found for fluorescence energies (within 0.1-0.6 eV). At contrast, CT absorption and fluorescence energies are strongly underestimated by TDDFT using the semi-local functional PBE but improved agreement is found for the hybrid functional PBE0. However, for both functionals, TDDFT fails to predict an equilibrium geometry of the intradonor excited state because of mixing between this state and an artificially low-lying CT state during the optimization. This is an example where the well documented CT failure of TDDFT affects properties of other locally excited states. The minimum of the intradonor locally excited state was therefore only located by the CC2 method. The internal conversion (IC) process from a locally excited donor state to the CT state is simulated by excited state ab initio molecular dynamics based on CC2 and where nonadiabatic transitions are described using the Landau-Zener approximation. We find the IC process to occur a few tens of femtoseconds after excitation. The simulation provides a detailed description of the atomic rearrangements in electron donor and acceptor that drive the interconversion process.

  2. The Chemical Production of Excited State Moleculea.

    DTIC Science & Technology

    2014-09-26

    reverse side It necessary and identify by block number) dioxetanes chemilumuniscence amino peroxides ’jto Most of e search deals with the effect of...n, state (vs carbonyl formation and attempts to trap the proposed 1,4-dioxybiradica intermediate from thermolysis of dioxetanes. Some amino peroxides ...ring peroxide in order to distinguish between concerted vs stepwise decomposition routes. This study was pertinent to the mechanism of dioxetane (a

  3. A TDDFT study on the excited-state intramolecular proton transfer (ESIPT): excited-state equilibrium induced by electron density swing.

    PubMed

    Zhang, Mingzhen; Yang, Dapeng; Ren, Baiping; Wang, Dandan

    2013-07-01

    One important issue of current interest is the excited-state equilibrium for some ESITP dyes. However, so far, the information about the driving forces for excited-state equilibrium is very limited. In this work, the time-dependent density functional theory (TDDFT) method was employed to investigate the nature of the excited-state intramolecular proton transfer (ESIPT). The geometric structures, vibrational frequencies, frontier molecular orbitals (MOs) and the potential-energy curves for 1-hydroxy-11H-benzo[b]fluoren-11-one (HHBF) in the ground and the first singlet excited state were calculated. Analysis of the results shows that the intramolecular hydrogen bond of HHBF is strengthened from E to E*. Moreover, it is found that electron density swing between the proton acceptor and donor provides the driving forces for the forward and backward ESIPT, enabling the excited-state equilibrium to be established. Furthermore, we proposed that the photoexcitation and the interchange of position for electron-donating and electron-withdrawing groups are the main reasons for the electron density swing. The potential-energy curves suggest that the forward ESIPT and backward ESIPT may happen on the similar timescale, which is faster than the fluorescence decay of both E* and K* forms.

  4. Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States

    DOE PAGES

    Bühler, Christine C.; Minitti, Michael P.; Deb, Sanghamitra; ...

    2011-01-01

    The ultrafast dynamics of 1,3-cyclohexadiene has been investigated via structurally sensitive Rydberg electron binding energies and shown to differ upon excitation to the 1B state and the 3p Rydberg state. Excitation of the molecule with 4.63 eV photons into the ultrashort-lived 1B state yields the well-known ring opening to 1,3,5-hexatriene, while a 5.99 eV photon lifts the molecule directly into the 3p-Rydberg state. Excitation to 3p does not induce ring opening. In both experiments, time-dependent shifts of the Rydberg electron binding energy reflect the structural dynamics of the molecular core. Structural distortions associated with 3p-excitation cause a dynamical shift in the -more » and -binding energies by 10 and 26 meV/ps, respectively, whereas after excitation into 1B, more severe structural transformations along the ring-opening coordinate produce shifts at a rate of 40 to 60 meV/ps. The experiment validates photoionization-photoelectron spectroscopy via Rydberg states as a powerful technique to observe structural dynamics of polyatomic molecules.« less

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

    NASA Astrophysics Data System (ADS)

    Ramon, John Glenn Santos

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

  6. Electronic structure, excited states, and photoelectron spectra of uranium, thorium, and zirconium bis(Ketimido) complexes (C5R5)2M[-NCPh2]2 (M = Th, U, Zr; R = H, CH3).

    PubMed

    Clark, Aurora E; Martin, Richard L; Hay, P Jeffrey; Green, Jennifer C; Jantunen, Kimberly C; Kiplinger, Jaqueline L

    2005-06-23

    Organometallic actinide bis(ketimide) complexes (C5Me5)2An[-N=C(Ph)(R)]2 (where R = Ph, Me, and CH2Ph) of thorium(IV) and uranium(IV) have recently been synthesized that exhibit chemical, structural, and spectroscopic (UV-Visible, resonance-enhanced Raman) evidence for unusual actinide-ligand bonding. [Da Re et al., J. Am. Chem. Soc., 2005, 127, 682; Jantunen et al., Organometallics, 2004, 23, 4682; Morris et al., Organometallics, 2004, 23, 5142.] Similar evidence has been observed for the group 4 analogue (C5H5)2Zr[-N=CPh2]2. [Da Re et al., J. Am. Chem. Soc., 2005, 127, 682.] These compounds have important implications for the development of new heavy-element systems that possess novel electronic and magnetic properties. Here, we have investigated M-ketimido bonding (M = Th, U, Zr), as well as the spectroscopic properties of the highly colored bis-ketimido complexes, using density functional theory (DFT). Photoelectron spectroscopy (PES) has been used to experimentally elucidate the ground-state electronic structure of the thorium and uranium systems. Careful examination of the ground-state electronic structure, as well as a detailed modeling of the photoelectron spectra, reveals similar bonding interactions between the thorium and uranium compounds. Using time-dependent DFT (TDDFT), we have assigned the bands in the previously reported UV-Visible spectra for (C5Me5)2Th[-N=CPh2]2, (C5Me5)2U[-N=CPh2]2, and (C5H5)2Zr[-N=CPh2]2. The low-energy transitions are attributed to ligand-localized N p --> C=N pi excitations. These excited states may be either localized on a single ketimido unit or may be of the ligand-ligand charge-transfer type. Higher-energy transitions are cyclopentadienyl pi --> CN pi or cyclopentadienyl pi --> phenyl pi in character. The lowest-energy excitation in the (C5Me5)2U[-N=Ph2]2 compound is attributed to f-f and metal-ligand charge-transfer transitions that are not available in the thorium and zirconium analogues. Geometry optimization and

  7. Excited-state mixed-valence distortions in a diisopropyl diphenyl hydrazine cation.

    PubMed

    Lockard, Jenny V; Zink, Jeffrey I; Luo, Yun; Weaver, Michael N; Konradsson, Asgeir E; Fowble, Joseph W; Nelsen, Stephen F

    2006-12-27

    Excited-state mixed valence (ESMV) occurs in the 1,2-diphenyl-1,2-diisopropyl hydrazine radical cation, a molecule in which the ground state has a symmetrical charge distribution localized primarily on the hydrazine, but the phenyl to hydrazine charge-transfer excited state has two interchangeably equivalent phenyl groups that have different formal oxidation states. Electronic absorption and resonance Raman spectra are presented. The neighboring orbital model is employed to interpret the absorption spectrum and coupling. Resonance Raman spectroscopy is used to determine the excited-state distortions. The frequencies of the enhanced modes from the resonance Raman spectra are used together with the time-dependent theory of spectroscopy to fit the two observed absorption bands that have resolved vibronic structure. The origins of the vibronic structure and relationships with the neighboring orbital model are discussed.

  8. Lifetime of the Excited State In Vivo

    PubMed Central

    Mar, T.; Govindjee; Singhal, G. S.; Merkelo, H.

    1972-01-01

    Using a mode-locked laser (λ, 632.8 nm), fluorescence decay of chlorophyll (Chl) a in the green alga Chlorella pyrenoidosa, the red alga Porphyridium cruentum, and the blue-green alga Anacystis nidulans was measured by the phase-shift method under conditions when photosynthesis was not operative (3-(3,4-dichlorophenyl)-1,1-dimethylurea [DCMU] poisoning, or cooling to 77°K). In the presence of 10-5 M DCMU, the lifetime of Chl a fluorescence (τ) at room temperature is about 1.7 nsec in Chlorella, 1.0 nsec in Porphyridium, and 0.7 nsec in Anacystis. At 77°K, τ is 1.4 nsec (for fluorescence at about 685 nm, F-685) and 2.3 nsec (for F-730) in Chlorella, 0.9 nsec (F-685) and 1.2 nsec (F-730) in Porphyridium, and 0.8 nsec (F-685 and F-730) in Anacystis. From the above measurement, and the assumption that τ0 (the intrinsic fluorescence lifetime) for Chl a in all three algae is 15.2 nsec, we have calculated the rate constants of radiationless transition (that includes energy transfer to weakly fluorescent system I) processes competing with fluorescence at room temperature to be about 5 × 108 sec-1 in Chlorella, 9 × 108 sec-1 in Porphyridium, and 13 × 108 sec-1 in Anacystis. At 77°K, this rate constant for Chl a that fluoresces at 685 nm remains, in the first approximation, the same as at room temperature. From the τ data, the rate constant for the trapping of excitation energy is calculated to be about 1.2 × 109 sec-1 for Chlorella, 2 × 109 sec-1 for Porphyridium, and 2 × 109 sec-1 for Anacystis. The efficiency of trapping is calculated to be about 66% (Chlorella), 68% (Porphyridium), and 60% (Anacystis). (It is recognized that variations in the above values are to be expected if algae grown under different conditions are used for experimentation.) The maximum quantum yield of Chl a fluorescence for system II (λ, 632.8 nm), calculated from τ measurements, is about 10% in Chlorella, 6-7% in Porhyridium, and 5% in Anacystis under conditions when photosynthesis

  9. Excited State Chemistry of Halogen Azides.

    DTIC Science & Technology

    1982-08-01

    a. CONTRACT OR GRANT "UMSERas A.T. Pritt, Jr. F49620-79-C-0053 S. PERF004IIN ORGANIZATION NAME AND ADDRESS 10. PROGRAM EL EMEN T. PROJECT. T ASK...intensities of transitions to the Q = 0+ and a = 1± states in NBr do not agree with calculations based on values of rotational and spin-rotational...and in our own laboratory.12 As is the case for other covalently bound azides, however, it is probable that the strongest absorptions in these

  10. Excited state of protonated benzene and toluene

    SciTech Connect

    Esteves-López, Natalia; Dedonder-Lardeux, Claude; Jouvet, Christophe

    2015-08-21

    We present photo-fragmentation electronic spectra of the simplest protonated aromatic molecules, protonated benzene and toluene, recorded under medium resolution conditions and compared with the photo-fragmentation spectrum of protonated pyridine. Despite the resolution and cold temperature achieved in the experiment, the electronic spectra of protonated benzene and toluene are structure-less, thus intrinsically broadened. This is in agreement with the large geometrical changes and the fast dynamic toward internal conversion predicted by ab initio calculations for protonated benzene [Rode et al., J. Phys. Chem. A 113, 5865–5873 (2009)].

  11. SW Sextantis in an excited, low state

    NASA Astrophysics Data System (ADS)

    Groot, P. J.; Rutten, R. G. M.; van Paradijs, J.

    2001-03-01

    We present low-resolution spectrophotometric optical observations of the eclipsing nova-like cataclysmic variable SW Sex, the prototype of the SW Sex stars. We observed the system when it was in an unusual low state. The spectrum is characterized by the presence of strong Heii and Civ emission lines as well as the normal single peaked Balmer emission lines. The radial temperature profile of the disk follows the expected T~ R-3/4 only in the outer parts and flattens off inside 0.5 times the white dwarf Roche lobe radius. The single peaked emission lines originate in a region above the plane of the disk, at the position of the hot spot.

  12. Excited-state dynamics of astaxanthin aggregates

    NASA Astrophysics Data System (ADS)

    Fuciman, Marcel; Durchan, Milan; Šlouf, Václav; Keşan, Gürkan; Polívka, Tomáš

    2013-05-01

    Astaxanthin forms three types of aggregates in hydrated dimethyl sulfoxide (DMSO). In DMSO/water ratio of 1:1, a red-shifted J-aggregate with maximum at 570 nm is generated, while a ratio of 1:9 produces blue-shifted H-aggregates with peaks at 386 nm (H1) and 460 nm (H2). Monomeric astaxanthin in DMSO has an S1 lifetime of 5.3 ps, but a long-lived (33 ps) S∗ signal was also identified. Aggregation changes the S1 lifetimes to 17 ps (H1), 30 ps (H2), and 14 ps (J). Triplet state of astaxanthin, most likely generated via singlet homofission, was observed in H1 and H2 aggregates.

  13. Excited state entanglement in homogeneous fermionic chains

    NASA Astrophysics Data System (ADS)

    Ares, F.; Esteve, J. G.; Falceto, F.; Sánchez-Burillo, E.

    2014-06-01

    We study the Rényi entanglement entropy of an interval in a periodic fermionic chain for a general eigenstate of a free, translational invariant Hamiltonian. In order to analytically compute the entropy we use two technical tools. The first is used to logarithmically reduce the complexity of the problem and the second to compute the Rényi entropy of the chosen subsystem. We introduce new strategies to perform the computations, derive new expressions for the entropy of these general states and show the perfect agreement of the analytical computations and the numerical outcome. Finally we discuss the physical interpretation of our results and generalize them to compute the entanglement entropy for a fragment of a fermionic ladder.

  14. Quenching of excited triplet states by dissolved natural organic matter.

    PubMed

    Wenk, Jannis; Eustis, Soren N; McNeill, Kristopher; Canonica, Silvio

    2013-11-19

    Excited triplet states of aromatic ketones and quinones are used as proxies to assess the reactivity of excited triplet states of the dissolved organic matter ((3)DOM*) in natural waters. (3)DOM* are crucial transients in environmental photochemistry responsible for contaminant transformation, production of reactive oxygen species, and potentially photobleaching of DOM. In recent photochemical studies aimed at clarifying the role of DOM as an inhibitor of triplet-induced oxidations of organic contaminants, aromatic ketones have been used in the presence of DOM, and the question of a possible interaction between their excited triplet states and DOM has emerged. To clarify this issue, time-resolved laser spectroscopy was applied to measure the excited triplet state quenching of four different model triplet photosensitizers induced by a suite of DOM from various aquatic and terrestrial sources. While no quenching for the anionic triplet sensitizers 4-carboxybenzophenone (CBBP) and 9,10-anthraquinone-2,6-disulfonic acid (2,6-AQDS) was detected, second-order quenching rate constants with DOM for the triplets of 2-acetonaphthone (2AN) and 3-methoxyacetophenone (3MAP) in the range of 1.30-3.85 × 10(7) L mol(C)(-1) s(-1) were determined. On the basis of the average molecular weight of DOM molecules, the quenching for these uncharged excited triplet molecules is nearly diffusion-controlled, but significant quenching (>10%) in aerated water is not expected to occur below DOM concentrations of 22-72 mg(C) L(-1).

  15. Two-Mode Excited Entangled Coherent State: Nonclassicality and Entanglement

    NASA Astrophysics Data System (ADS)

    Zhang, Hao-Liang; Wu, Jia-Ni; Liu, Cun-Jin; Hu, Yin-Quan; Hu, Li-Yun

    2017-03-01

    Two-mode excited entangled coherent states (TME-ECSs) are introduced by operating repeatedly the photon-excited operator on the ECSs. It is shown that the normalization constant is related to the product of two Laguerre polynomials. The influence of the operation on nonclassical behaviour of the ECSs is investigated in terms of cross-correlation function, anti-bunching effect and the negativity of Wigner function, which show that nonclassical properties can be enhanced. In addition, inseparability properties of the TME-ECSs are discussed by using Bell inequality and concurrence. It is found that the degree of quantum entanglement of even ECSs increases with the increase of the total excited photon number, and the violation of Bell inequality can be present for both even and odd case only when the total excited photon numbers are even and odd, respectively.

  16. State-Selective Excitation of Quantum Systems via Geometrical Optimization.

    PubMed

    Chang, Bo Y; Shin, Seokmin; Sola, Ignacio R

    2015-09-08

    We lay out the foundations of a general method of quantum control via geometrical optimization. We apply the method to state-selective population transfer using ultrashort transform-limited pulses between manifolds of levels that may represent, e.g., state-selective transitions in molecules. Assuming that certain states can be prepared, we develop three implementations: (i) preoptimization, which implies engineering the initial state within the ground manifold or electronic state before the pulse is applied; (ii) postoptimization, which implies engineering the final state within the excited manifold or target electronic state, after the pulse; and (iii) double-time optimization, which uses both types of time-ordered manipulations. We apply the schemes to two important dynamical problems: To prepare arbitrary vibrational superposition states on the target electronic state and to select weakly coupled vibrational states. Whereas full population inversion between the electronic states only requires control at initial time in all of the ground vibrational levels, only very specific superposition states can be prepared with high fidelity by either pre- or postoptimization mechanisms. Full state-selective population inversion requires manipulating the vibrational coherences in the ground electronic state before the optical pulse is applied and in the excited electronic state afterward, but not during all times.

  17. Accurate Excited State Geometries within Reduced Subspace TDDFT/TDA.

    PubMed

    Robinson, David

    2014-12-09

    A method for the calculation of TDDFT/TDA excited state geometries within a reduced subspace of Kohn-Sham orbitals has been implemented and tested. Accurate geometries are found for all of the fluorophore-like molecules tested, with at most all valence occupied orbitals and half of the virtual orbitals included but for some molecules even fewer orbitals. Efficiency gains of between 15 and 30% are found for essentially the same level of accuracy as a standard TDDFT/TDA excited state geometry optimization calculation.

  18. First-principles Calculation of Excited State Spectra in QCD

    SciTech Connect

    Jozef Dudek,Robert Edwards,Michael Peardon,David Richards,Christopher Thomas

    2011-05-01

    Recent progress at understanding the excited state spectra of mesons and baryons is described. I begin by outlining the application of the variational method to compute the spectrum of QCD, and then present results for the excited meson spectrum, with continuum quantum numbers of the states clearly delineated. I emphasise the need to extend the calculation to encompass multi-hadron contributions, and describe a recent calculation of the I=2 pion-pion energy-dependent phase shifts as a precursor to the study of channels with resonant behavior. I conclude with recent results for the low lying baryon spectrum, and the prospects for future calculations.

  19. 2{sup +} excitation of the {sup 12}C Hoyle state

    SciTech Connect

    Freer, M.; Fujita, H.; Carter, J.; Usman, I.; Buthelezi, Z.; Foertsch, S. V.; Neveling, R.; Perez, S. M.; Smit, F. D.; Fearick, R. W.; Papka, P.; Swartz, J. A.

    2009-10-15

    A high-energy-resolution magnetic spectrometer has been used to measure the {sup 12}C excitation energy spectrum to search for the 2{sup +} excitation of the 7.65 MeV, 0{sup +} Hoyle state. By measuring in the diffractive minimum of the angular distribution for the broad 0{sup +} background, evidence is found for a possible 2{sup +} state at 9.6(1) MeV with a width of 600(100) keV. The implications for the {sup 8}Be+{sup 4}He reaction rate in stellar environments are discussed.

  20. First-order derivative couplings between excited states from adiabatic TDDFT response theory

    SciTech Connect

    Ou, Qi; Subotnik, Joseph E.; Bellchambers, Gregory D.; Furche, Filipp

    2015-02-14

    We present a complete derivation of derivative couplings between excited states in the framework of adiabatic time-dependent density functional response theory. Explicit working equations are given and the resulting derivative couplings are compared with derivative couplings from a pseudo-wavefunction ansatz. For degenerate excited states, i.e., close to a conical intersection (CI), the two approaches are identical apart from an antisymmetric overlap term. However, if the difference between two excitation energies equals another excitation energy, the couplings from response theory exhibit an unphysical divergence. This spurious behavior is a result of the adiabatic or static kernel approximation of time-dependent density functional theory leading to an incorrect analytical structure of the quadratic response function. Numerical examples for couplings close to a CI and for well-separated electronic states are given.

  1. First-order derivative couplings between excited states from adiabatic TDDFT response theory.

    PubMed

    Ou, Qi; Bellchambers, Gregory D; Furche, Filipp; Subotnik, Joseph E

    2015-02-14

    We present a complete derivation of derivative couplings between excited states in the framework of adiabatic time-dependent density functional response theory. Explicit working equations are given and the resulting derivative couplings are compared with derivative couplings from a pseudo-wavefunction ansatz. For degenerate excited states, i.e., close to a conical intersection (CI), the two approaches are identical apart from an antisymmetric overlap term. However, if the difference between two excitation energies equals another excitation energy, the couplings from response theory exhibit an unphysical divergence. This spurious behavior is a result of the adiabatic or static kernel approximation of time-dependent density functional theory leading to an incorrect analytical structure of the quadratic response function. Numerical examples for couplings close to a CI and for well-separated electronic states are given.

  2. Formation of metastable excited states during sputtering of transition metals

    SciTech Connect

    Wucher, A.; Sroubek, Z.

    1997-01-01

    We propose a simple model which treats the formation of metastable excited neutral atoms during sputtering of a transition metal as a two step process. First, the energy deposited into the electronic system of the solid by electronic energy losses of all moving particles in the collision cascade is considered to lead to a locally altered equilibrium electronic state of the solid. It is found that this step is dominated by collective interaction with the conduction band electrons rather than by electron promotion in binary atom-atom collisions. Second, sputtered excited atoms are assumed to be formed by resonant neutralization of excited ions (reflecting the altered equilibrium state) while crossing the surface. It is shown that this model explains the total as well as the velocity dependent excitation probability observed in recent experiments on sputtered neutral silver atoms, which cannot be understood in terms of existing theories describing the formation of excited states in sputtering. {copyright} {ital 1996} {ital The American Physical Society}

  3. Two-color excited-state absorption imaging of melanins

    NASA Astrophysics Data System (ADS)

    Fu, Dan; Ye, Tong; Matthews, Thomas E.; Yurtsever, Gunay; Hong, Lian; Simon, John D.; Warren, Warren S.

    2007-02-01

    We have demonstrated a new method for imaging melanin with two-color excited state absorption microscopy. If one of two synchronized mode-locked pulse trains at different colors is intensity modulated, the modulation transfers to the other pulse train when nonlinear absorption takes place in the medium. We can easily measure 10 -6 absorption changes caused by either instantaneous two-photon absorption or relatively long lived excited state absorption with a RF lock-in amplifier. Eumelanin and pheomelanin exhibit similar excited state dynamics. However, their difference in excited state absorption and ground state absorption leads to change in the phase of the transient absorption signal. Scanning microscopic imaging is performed with B16 cells, melanoma tissue to demonstrate the 3D high resolution imaging capability. Different melanosome samples are also imaged to illustrate the differences between eumelanin and pheomelanin signals. These differences could enable us to image their respective distribution in tissue samples and provide us with valuable information in diagnosing malignant transformation of melanocytes.

  4. The excited spin-triplet state of a charged exciton in quantum dots

    NASA Astrophysics Data System (ADS)

    Molas, M. R.; Nicolet, A. A. L.; Piętka, B.; Babiński, A.; Potemski, M.

    2016-09-01

    We report on spectroscopic studies of resonances related to ladder of states of a charged exciton in single GaAlAs/AlAs quantum dot structures. Polarization-resolved photoluminescence, photoluminescence excitation and photon-correlation measurements were performed at low (T  =  4.2 K) temperature also in magnetic field applied in Faraday configuration. The investigated resonances are assigned to three different configurations of a positively charged exciton. Together with a singlet ground state and a conventional triplet state (involving an electron from the ground state electronic s-shell), an excited triplet state, which involved an electron from the excited electronic p-shell was identified in single dots. The appearance of an emission line related to the latter complex is due to a partially suppressed electron relaxation in the investigated dots. An analysis of this emission line allows us to scrupulously determine properties of the excited triplet state and compare them with those of the conventional triplet state. Both triplets exhibit similar patterns of anisotropic fine structure and Zeeman splitting, however their amplitudes significantly differ for those two states. Presented results emphasize the role of the symmetry of the electronic state on the properties of the triplet states of two holes  +  electron excitonic complex.

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

    NASA Astrophysics Data System (ADS)

    Closser, Kristina Danielle

    This thesis presents new developments in excited state electronic structure theory. Contrasted with the ground state, the electronically excited states of atoms and molecules often are unstable and have short lifetimes, exhibit a greater diversity of character and are generally less well understood. The very unusual excited states of helium clusters motivated much of this work. These clusters consist of large numbers of atoms (experimentally 103--109 atoms) and bands of nearly degenerate excited states. For an isolated atom the lowest energy excitation energies are from 1s → 2s and 1s → 2 p transitions, and in clusters describing the lowest energy band minimally requires four states per atom. In the ground state the clusters are weakly bound by van der Waals interactions, however in the excited state they can form well-defined covalent bonds. The computational cost of quantum chemical calculations rapidly becomes prohibitive as the size of the systems increase. Standard excited-state methods such as configuration interaction singles (CIS) and time-dependent density functional theory (TD-DFT) can be used with ≈100 atoms, and are optimized to treat only a few states. Thus, one of our primary aims is to develop a method which can treat these large systems with large numbers of nearly degenerate excited states. Additionally, excited states are generally formed far from their equilibrium structures. Vertical excitations from the ground state induce dynamics in the excited states. Thus, another focus of this work is to explore the results of these forces and the fate of the excited states. Very little was known about helium cluster excited states when this work began, thus we first investigated the excitations in small helium clusters consisting of 7 or 25 atoms using CIS. The character of these excited states was determined using attachment/detachment density analysis and we found that in the n = 2 manifold the excitations could generally be interpreted as

  6. Internal conversion from excited electronic states of 229Th ions

    NASA Astrophysics Data System (ADS)

    Bilous, Pavlo V.; Kazakov, Georgy A.; Moore, Iain D.; Schumm, Thorsten; Pálffy, Adriana

    2017-03-01

    The process of internal conversion from excited electronic states is investigated theoretically for the case of the vacuum-ultraviolet nuclear transition of 229Th. Due to the very low transition energy, the 229Th nucleus offers the unique possibility to open the otherwise forbidden internal conversion nuclear decay channel for thorium ions via optical laser excitation of the electronic shell. We show that this feature can be exploited to investigate the isomeric state properties via observation of internal conversion from excited electronic configurations of +Th and Th+2 ions. A possible experimental realization of the proposed scenario at the nuclear laser spectroscopy facility IGISOL in Jyväskylä, Finland, is discussed.

  7. Excited state tautomerization of 7-azaindole catalyzed by pyrazole

    NASA Astrophysics Data System (ADS)

    Karmakar, Shreetama; Mukherjee, Moitrayee; Chakraborty, Tapas

    2013-03-01

    Pyrazole, a five member cyclic azole, is reported here as an efficient catalyst for excited state tautomeric conversion of 7-azaindole. In hydrocarbon solution the two compounds efficiently form a doubly hydrogen-bonded 1:1 cyclic complex whose association constant value is found comparable with 7-azaindole dimerization constant, and according to B3LYP/6-311G++∗∗ calculation the binding energies of the complex and dimer are nearly same. In the excited state (S1), the TDDFT calculation predicts tautomer of the complex to be 13.4 kcal/mol more stable than normal form. Fluorescence spectra reveal that upon UV excitation the complex emits exclusively from the tautomeric form.

  8. 7/3 fractional quantum Hall effect: topology, trion excitations and edge states

    NASA Astrophysics Data System (ADS)

    Balram, Ajit C.; Wu, Ying-Hai; Sreejith, G. J.; Wójs, Arkadiusz; Jain, J. K.

    2013-03-01

    Exact diagonalization studies on finite systems show that the quasihole and quasiparticle excitations in the 7/3 fractional quantum Hall (FQH) state are qualitatively distinct from those of the 1/3 state, suggesting the possibility of different topological origins for the two states. We perform composite-fermion diagonalization on larger systems and also evaluate the entanglement spectrum, which shows that in spite of these strong finite size deviations, the 7/3 and 1/3 FQH states have the same topological structure in the thermodynamic limit. Nonetheless, there are substantial non-topological differences between the two, arising from the stronger residual interaction between composite fermions at 7/3. In particular, we show that the lowest energy charged excitations of the 7/3 state are complex trions of composite fermions, which have a much larger size than the charged excitations at 1/3. We discuss many observable consequences of our results.

  9. Double excitations and state-to-state transition dipoles in π-π∗ excited singlet states of linear polyenes: Time-dependent density-functional theory versus multiconfigurational methods

    NASA Astrophysics Data System (ADS)

    Mikhailov, Ivan A.; Tafur, Sergio; Masunov, Artëm E.

    2008-01-01

    The effect of static and dynamic electron correlation on the nature of excited states and state-to-state transition dipole moments is studied with a multideterminant wave function approach on the example of all-trans linear polyenes ( C4H6 , C6H8 , and C8H10 ). Symmetry-forbidden singlet nAg states were found to separate into three groups: purely single, mostly single, and mostly double excitations. The excited-state absorption spectrum is dominated by two bright transitions: 1Bu-2Ag and 1Bu-mAg , where mAg is the state, corresponding to two-electron excitation from the highest occupied to lowest unoccupied molecular orbital. The richness of the excited-state absorption spectra and strong mixing of the doubly excited determinants into lower- nAg states, reported previously at the complete active space self-consistent field level of theory, were found to be an artifact of the smaller active space, limited to π orbitals. When dynamic σ-π correlation is taken into account, single- and double-excited states become relatively well separated at least at the equilibrium geometry of the ground state. This electronic structure is closely reproduced within time-dependent density-functional theory (TD DFT), where double excitations appear in a second-order coupled electronic oscillator formalism and do not mix with the single excitations obtained within the linear response. An extension of TD DFT is proposed, where the Tamm-Dancoff approximation (TDA) is invoked after the linear response equations are solved (a posteriori TDA). The numerical performance of this extension is validated against multideterminant-wave-function and quadratic-response TD DFT results. It is recommended for use with a sum-over-states approach to predict the nonlinear optical properties of conjugated molecules.

  10. Direct Lifetime Measurements of the Excited States in 72Ni

    NASA Astrophysics Data System (ADS)

    Kolos, K.; Miller, D.; Grzywacz, R.; Iwasaki, H.; Al-Shudifat, M.; Bazin, D.; Bingham, C. R.; Braunroth, T.; Cerizza, G.; Gade, A.; Lemasson, A.; Liddick, S. N.; Madurga, M.; Morse, C.; Portillo, M.; Rajabali, M. M.; Recchia, F.; Riedinger, L. L.; Voss, P.; Walters, W. B.; Weisshaar, D.; Whitmore, K.; Wimmer, K.; Tostevin, J. A.

    2016-03-01

    The lifetimes of the first excited 2+ and 4+ states in 72>Ni were measured at the National Superconducting Cyclotron Laboratory with the recoil-distance Doppler-shift method, a model-independent probe to obtain the reduced transition probability. Excited states in 72Ni were populated by the one-proton knockout reaction of an intermediate energy 73Cu beam. γ -ray-recoil coincidences were detected with the γ -ray tracking array GRETINA and the S800 spectrograph. Our results provide evidence of enhanced transition probability B (E 2 ;2+→0+) as compared to 68Ni, but do not confirm the trend of large B (E 2 ) values reported in the neighboring isotope 70Ni obtained from Coulomb excitation measurement. The results are compared to shell model calculations. The lifetime obtained for the excited 41+ state is consistent with models showing decay of a seniority ν =4 , 4+ state, which is consistent with the disappearance of the 8+ isomer in 72Ni.

  11. Tuning ground states and excitations in complex electronic materials

    SciTech Connect

    Bishop, A.R.

    1996-09-01

    Modern electronic materials are characterized by a great variety of broken-symmetry ground states and excitations. Their control requires understanding and tuning underlying driving forces of spin-charge-lattice coupling, critical to macroscopic properties and applications. We report representative model calculations which demonstrate some of the richness of the phenomena and the challenges for successful microscopic modeling.

  12. Suppression of excited-state absorption in laser crystals

    NASA Astrophysics Data System (ADS)

    Kuznetsova, Elena; Kolesov, Roman; Kocharovskaya, Olga

    2004-10-01

    Currently, a lot of experimental effort in solid-state optics is devoted to searching for laser materials suitable for tunable lasing, primarily in UV and VUV spectral regions. Researchers mainly focus on optical crystals doped with either transition metal or rare-earth ions. The latter ones doped into wide bandgap dielectric crystals have spectrally broad vibronic emission bands associated with 4fn-15d â" 4fn interconfigurational transitions, whose energies lie mostly in UV and VUV regions of the spectrum. The transitions are electric-dipole-allowed, therefore have large absorption and emission cross-sections, and are promising for efficient tunable laser action. However, in almost all promising crystals laser action in UV and VUV is hindered or completely prohibited due to excited-state absorption (ESA), i.e. absorption from metastable laser levels to higher-energy states, which occurs at emission or/and pump wavelengths. A method of suppression of losses due to excited-state absorption (ESA) in laser crystals is proposed, based on a well-known phenomenon of electromagnetically induced transparency (EIT). Absorption from a populated excited electronic state can be reduced under the action of an additional driving coherent field, resonantly coupling the terminal state of ESA to some intermediate discrete state.

  13. The dispersed fluorescence spectrum of NaAr - Ground and excited state potential curves

    NASA Technical Reports Server (NTRS)

    Tellinghuisen, J.; Ragone, A.; Kim, M. S.; Auerbach, D. J.; Smalley, R. E.; Wharton, L.; Levy, D. H.

    1979-01-01

    Potential curves for the ground state and the first excited state of NaAr were determined. The van der Waals molecule NaAr was prepared by supersonic free jet expansion of a mixture of sodium, argon, and helium. The electronic transition from the ground state to the first excited state A2pi was excited by a tunable dye laser and the resulting fluorescence was studied. The dispersed fluorescence spectra show discrete and diffuse features, corresponding to transitions from excited vibrational levels of the A state to bound and unbound levels of the x state. The characteristic reflection structure in the bound-free spectra permits an unambiguous assignment of the vibrational numbering in the A state, and this assignment together with previously measured spectroscopic constants are used to calculate the potential curve of the A state. The discrete structure in the fluorescence spectra is used to determine the potential curve of the x state in the well region, and the repulsive part of the X curve is then deduced through trial-and-error simulation of the bound-free spectra.

  14. Coherent motion of excited state cyclic ketones: The have and the have-nots

    NASA Astrophysics Data System (ADS)

    Larsen, M. A. B.; Stephansen, A. B.; Sølling, T. I.

    2017-09-01

    The internal conversion processes of four cyclic ketones; cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone and cyclohexanone are investigated by Velocity Map Imaging (VMI) photoelectron spectroscopy. A 201 nm pump accesses the second excited state (n,3s) and the ultrafast dynamics is mapped by subsequent ionization with a 350 nm probe. Three of the four investigated molecular systems show an oscillatory time-dependence in the peak position of the 3s photoelectron band, while the last one simply decays exponentially. We find that the most plausible reason for the absence of the oscillation is due to high structural similarity between the excited state and the ionic state along the active coordinate.

  15. Excited-state quantum phase transition in the Rabi model

    NASA Astrophysics Data System (ADS)

    Puebla, Ricardo; Hwang, Myung-Joong; Plenio, Martin B.

    2016-08-01

    The Rabi model, a two-level atom coupled to a harmonic oscillator, can undergo a second-order quantum phase transition (QPT) [M.-J. Hwang et al., Phys. Rev. Lett. 115, 180404 (2015), 10.1103/PhysRevLett.115.180404]. Here we show that the Rabi QPT accompanies critical behavior in the higher-energy excited states, i.e., the excited-state QPT (ESQPT). We derive analytic expressions for the semiclassical density of states, which show a logarithmic divergence at a critical energy eigenvalue in the broken symmetry (superradiant) phase. Moreover, we find that the logarithmic singularities in the density of states lead to singularities in the relevant observables in the system such as photon number and atomic polarization. We corroborate our analytical semiclassical prediction of the ESQPT in the Rabi model with its numerically exact quantum mechanical solution.

  16. Variational state specific solvent models for excited states from time dependent self-consistent field methods

    NASA Astrophysics Data System (ADS)

    Bjorgaard, Josiah; Velizhanin, Kirill; Tretiak, Sergei

    2015-03-01

    The effect of a dielectric environment on a molecule can be profound, causing changes in nuclear configuration and electronic structure. Quantum chemical simulation of a solute-solvent system can be prohibitively expensive due to the large number of degrees of freedom attributed to the solvent. To remedy this, the solvent can be treated as a dielectric cavity. Mutual polarization of the solute and solvent must be considered for accurate treatment of an optically excited state (ES) with a state-specific solvent model (SSM). In vacuum, time dependent self-consistent field (TD-SCF) methods (e,g, TD-HF, TD-DFT) give variational excitation energies. With the well known Z-vector equation, a variational ES energy is used to explore the ES potential energy surface (PES) with analytical gradients. Modification of the standard TD-SCF eigensystem to accommodate a SSM creates a nonlinear TD-SCF equation with non-variational excitation energies. This prevents analytical gradients from being formulated so that the ES PES cannot be explored. Here, we show how a variational formulation of existing SSMs can be derived from a Lagrangian formalism and give numerical results for the variability of calculated quantities. Model dynamics using SSMs are showcased.

  17. Direct excitation of butterfly states in Rydberg molecules

    NASA Astrophysics Data System (ADS)

    Lippe, Carsten; Niederpruem, Thomas; Thomas, Oliver; Eichert, Tanita; Ott, Herwig

    2016-05-01

    Since their first theoretical prediction Rydberg molecules have become an increasing field of research. These exotic states originate from the binding of a ground state atom in the electronic wave function of a highly-excited Rydberg atom mediated by a Fermi contact type interaction. A special class of long-range molecular states, the butterfly states, were first proposed by Greene et al.. These states arise from a shape resonance in the p-wave scattering channel of a ground state atom and a Rydberg electron and are characterized by an electron wavefunction whose density distribution resembles the shape of a butterfly. We report on the direct observation of deeply bound butterfly states of Rydberg molecules of 87 Rb. The butterfly states are studied by high resolution spectroscopy of UV-excited Rydberg molecules. We find states bound up to - 50 GHz from the 25 P1/2 , F = 1 state, corresponding to binding lengths of 50a0 to 500a0 and with permanent electric dipole moments of up to 500 Debye. This distinguishes the observed butterfly states from the previously observed long range Rydberg molecules in rubidium.

  18. Ultrafast excited state dynamics of fucoxanthin: excitation energy dependent intramolecular charge transfer dynamics.

    PubMed

    Kosumi, Daisuke; Kusumoto, Toshiyuki; Fujii, Ritsuko; Sugisaki, Mitsuru; Iinuma, Yoshiro; Oka, Naohiro; Takaesu, Yuki; Taira, Tomonori; Iha, Masahiko; Frank, Harry A; Hashimoto, Hideki

    2011-06-14

    Carotenoids containing a carbonyl group in conjugation with their polyene backbone are naturally-occurring pigments in marine organisms and are essential to the photosynthetic light-harvesting function in aquatic algae. These carotenoids exhibit spectral characteristics attributed to an intramolecular charge transfer (ICT) state that arise in polar solvents due to the presence of the carbonyl group. Here, we report the spectroscopic properties of the carbonyl carotenoid fucoxanthin in polar (methanol) and nonpolar (cyclohexane) solvents studied by steady-state absorption and femtosecond pump-probe measurements. Transient absorption associated with the optically forbidden S(1) (2(1)A) state and/or the ICT state were observed following one-photon excitation to the optically allowed S(2) (1(1)B) state in methanol. The transient absorption measurements carried out in methanol showed that the ratio of the ICT-to-S(1) state formation increased with decreasing excitation energy. We also showed that the ICT character was clearly visible in the steady-state absorption in methanol based on a Franck-Condon analysis. The results suggest that two spectroscopic forms of fucoxanthin, blue and red, exist in the polar environment. This journal is © the Owner Societies 2011

  19. Excited States of the Diatomic Molecule CrHe

    NASA Astrophysics Data System (ADS)

    Pototschnig, Johann V.; Ratschek, Martin; Hauser, Andreas W.; Ernst, Wolfgang E.

    2013-06-01

    Chromium (Cr) atoms embedded in superfluid helium nanodroplets (He_N) have been investigated by laser induced fluorescence, beam depletion and resonant two-photon ionization spectroscopy in current experiments at our institute. Cr is found to reside inside the He_N in the a^7S ground state. Two electronically excited states, z^7P and y^7P, are involved in a photoinduced ejection process which allowed us to study Fano resonances in the photoionisation spectra The need for a better understanding of the experimental observations triggered a theoretical approach towards the computation of electronically excited states via high-level methods of computational chemistry. Two well-established, wave function-based methods, CASSCF and MRCI, are combined to calculate the potential energy curves for the three states involved. The character of the two excited states z^7P and y^7P turns out to be significantly different. Theory predicts the ejection of the Cr atom in the case of an y^7P excitation as was observed experimentally. The quasi-inert helium environment is expected to weaken spin selection rules, allowing a coupling between different spin states especially during the ejection process. We therefore extend our theoretical analysis to the lowest state in the triplet- and quintet- manifold. Most of these alternative states show very weak bonding of only a few wn. A. Kautsch, M. Hasewend, M. Koch and W. E. Ernst, Phys. Rev. A 86, 033428 (2012). A. Kautsch, M. Koch and W. E. Ernst, J. Phys. Chem. A, accepted, doi:10.1021/jp312336m}.

  20. Doubly Excited Resonance States of Helium Atom: Complex Entropies

    NASA Astrophysics Data System (ADS)

    Kuroś, Arkadiusz; Kościk, Przemysław; Saha, Jayanta K.

    2016-12-01

    We provide a diagonal form of a reduced density matrix of S-symmetry resonance states of two electron systems determined under the framework of the complex scaling method. We have employed the variational Hylleraas type wavefunction to estimate the complex entropies in doubly excited resonance states of helium atom. Our results are in good agreement with the corresponding ones determined under the framework of the stabilization method (Lin and Ho in Few-Body Syst 56:157, 2015).

  1. Ground and Excited State Spectra of a Quantum Dot

    NASA Astrophysics Data System (ADS)

    Stewart, D. R.; Sprinzak, D.; Patel, S. R.; Marcus, C. M.; Duruoz, C. I.; Harris, J. S.

    1998-03-01

    We present linear and nonlinear magnetoconductance measurements of the ground and excited state spectra for successive electron occupancy in a gate defined lateral quantum dot. Previous measurementsfootnote D.R. Stewart, D. Sprinzak, C.M. Marcus, C.I. Duruoz and J.S. Harris Jr., Science 278, (1997). showed a direct correlation between the mth excited state of the N-electron system and the ground state of the (N+m)-electron system for m up to 4, consistent to a large degree with a single-particle picture. Here we report quantitative deviations of the excited state spectra from the spectrum of ground state magnetoconductances, attributed to many-body interactions in the finite system of N ~200 electrons. We also describe the behaviour of anticrossings in the ground state magnetoconductances. We acknowledge the support of JSEP (DAAH04-94-G-0058), ARO (DAAH04-95-1-0331), ONR-YIP (N00014-94-1-0622) and the NSF-PECASE program. D.S. acknowledges the support of MINERVA grant.

  2. On the excited-state multi-dimensionality in cyanines

    NASA Astrophysics Data System (ADS)

    Dietzek, Benjamin; Brüggemann, Ben; Persson, Petter; Yartsev, Arkady

    2008-03-01

    Vibrational coherences in a photoexcited cyanine dye are preserved for the time-scale of diffusive torsional motion to the bottom of the excited-state potential. The coherently excited modes are virtually unaffected by solvent friction and thus distinct from the bond-twisting motion, which is strongly coupled to the surrounding solvent. We correlate the modes apparent in the resonance Raman and the four-wave mixing signal of 1,1'-diethyl-2,2'-cyanine with the understanding of optimal control of isomerization. In turn, the experimental results illustrate that optimal control might be used to obtain vibrational information complementary to conventional spectroscopic data.

  3. Observation of Excited Quadrupole-Bound States in Cold Anions

    NASA Astrophysics Data System (ADS)

    Zhu, Guo-Zhu; Liu, Yuan; Wang, Lai-Sheng

    2017-07-01

    We report the first observation of an excited quadrupole-bound state (QBS) in an anion. High-resolution photoelectron imaging of cryogenically cooled 4-cyanophenoxide (4 CP- ) anions yields an electron detachment threshold of 24 927 cm-1 . The photodetachment spectrum reveals a resonant transition 20 cm-1 below the detachment threshold, which is attributed to an excited QBS of 4 CP- because neutral 4CP has a large quadrupole moment with a negligible dipole moment. The QBS is confirmed by observation of seventeen above-threshold resonances due to autodetachment from vibrational levels of the QBS.

  4. The Single-Determinant Approximation with a Local Potential for Excited States

    SciTech Connect

    Glushkov, V.N.

    2005-11-15

    The specific features of the calculations of the electronic structure in the approximation of a local exchange potential that is identical for all the electrons involved are considered. An optimized effective potential method is proposed for calculating the energies of excited electronic states of the same symmetry. A single-particle Schroedinger equation is derived for an excited state whose orbitals are described by a single-determinant wave function orthogonal to the ground state. The equations determining the local potential for excited states are obtained within the variational approach. The solution to these equations is analyzed in the framework of the parameterized representation of the effective potential. The efficiency of the proposed method is demonstrated by calculating the energies of three excited states of the same symmetry for a HeH molecule. The difference between the results obtained by the Hartree-Fock method and the method proposed in this paper is equal, on average, to 0.05%. A comparison with the results obtained from precise calculations based on the configuration interaction method shows that the accuracy in determining the energy of the excited states by the optimized effective potential method is comparable to the accuracy in calculating the energy of the ground state.

  5. On the nature of excited states of photosynthetic reaction centers: An ultrafast infrared study

    SciTech Connect

    Haran, G.; Wynne, K.; Reid, G.D.

    1995-12-31

    Bacterial photosynthetic reaction centers (RC) contain eight chromophores forming a well-defined supramolecular structure within a protein framework. Theoretical studies suggest that the excited states of these chromophores are delocalized and contain important contributions from charge-transfer and resonance states. There is no clear-cut experimental evidence pertaining to the degree of localization of excited states. We have used ultrafast near and mid-infrared spectroscopic methods to investigate the character of some of the excited states. Exciting the 800 nm, absorption band, we followed the fate of the excitation energy using either the stimulated emission of the special pair at 920 nm or a transient absorption at 1.2 {mu}m. For a completely localized system, Forster theory-based calculations are expected to accurately predict the kinetics of energy transfer. It was found, however, that calculated rates arc much faster than measured rates. This corroborates a delocalized picture, with internal conversion rather than energy transfer between states. We have also measured the transient absorption spectrum of the RC in the infrared spectral region, detecting several new low-lying electronic states. Assignments for these states, and implications for the localization problem will be discussed.

  6. Highly Excited States of cs Atoms on Helium Nanodroplets

    NASA Astrophysics Data System (ADS)

    Lackner, F.; Theisen, M.; Koch, M.; Ernst, W. E.

    2011-06-01

    Cs atoms on the surface of helium nanodroplets have been excited to high lying nS (n = 8-11), nP (n = 8-11), and nD (n = 6-10) levels. A two-step excitation scheme via the 62P1/2(2Π1/2) state using two cw lasers was applied. This intermediate state has the advantage that a large fraction of the excited Cs atoms does not desorb from the helium nanodroplets. An absorption spectrum was recorded by detecting laser induced fluorescence light from the 62P3/2→62S1/2 transition. The pseudo-diatomic model for helium nanodroplets doped with single alkali-metal atoms holds for the observed spectrum. An investigation of spectral trends shows that the n'2P(Π)←62P1/2(2Π1/2) and n'2D(Δ)←62P1/2(2Π1/2) (n' > 9) transitions are lower in energy than the corresponding free-atom transitions. This indicates that the Cs*--HeN potential becomes attractive for these highly excited states. Our results suggest a possibility of generating an artificial super-atom with a positive ion core inside a helium nanodroplet and the electron outside, which will be subject to future experiments. M. Theisen, F. Lackner, F. Ancilotto, C. Callegari, and W.E. Ernst, Eur. Phys. J. D 61, 403-408 (2011)

  7. Potential-energy surfaces of local excited states from subsystem- and selective Kohn-Sham-TDDFT

    NASA Astrophysics Data System (ADS)

    Kovyrshin, Arseny; Neugebauer, Johannes

    2011-11-01

    Calculating excited-state potential-energy surfaces for systems with a large number of close-lying excited states requires the identification of the relevant electronic transitions for several geometric structures. Time-dependent density functional theory (TDDFT) is very efficient in such calculations, but the assignment of local excited states of the active molecule can be difficult. We compare the results of the frozen-density embedding (FDE) method with those of standard Kohn-Sham density-functional theory (KS-DFT) and simpler QM/MM-type methods. The FDE results are found to be more accurate for the geometry dependence of excitation energies than classical models. We also discuss how selective iterative diagonalization schemes can be exploited to directly target specific excitations for different structures. Problems due to strongly interacting orbital transitions and possible solutions are discussed. Finally, we apply FDE and the selective KS-TDDFT to investigate the potential energy surface of a high-lying π → π∗ excitation in a pyridine molecule approaching a silver cluster.

  8. Controlling the dissociation dynamics of acetophenone radical cation through excitation of ground and excited state wavepackets

    NASA Astrophysics Data System (ADS)

    Moore Tibbetts, Katharine; Tarazkar, Maryam; Bohinski, Timothy; Romanov, Dmitri A.; Matsika, Spiridoula; Levis, Robert J.

    2015-08-01

    Time-resolved measurements of the acetophenone radical cation prepared via adiabatic ionization with strong field 1270 nm excitation reveal coupled wavepacket dynamics that depend on the intensity of the 790 nm probe pulse. At probe intensities below 7× {10}11 W cm-2, out of phase oscillations between the parent molecular ion and the benzoyl fragment ion are shown to arise from a one-photon excitation from the ground D0 ionic surface to the D1 and/or D2 excited surfaces by the probe pulse. At higher probe intensities, a second set of wavepacket dynamics are observed that couple the benzoyl ion to the phenyl, butadienyl, and acylium fragment ions. Equation of motion coupled cluster calculations of the ten lowest lying ionic surfaces and the dipole couplings between the ground ionic surface D0 and the nine excited states enable elucidation of the dissociation pathways and deduction of potential dissociation mechanisms. The results can lead to improved control schemes for selective dissociation of the acetophenone radical cation.

  9. Vibrations of acrylonitrile in N 1s excited states

    NASA Astrophysics Data System (ADS)

    Ilakovac, V.; Carniato, S.; Gallet, J.-J.; Kukk, E.; Horvatić, D.; Ilakovac, A.

    2008-01-01

    The N 1s near edge x-ray absorption fine structure spectra of acrylonitrile gas are accurately reproduced by a complete ab initio multidimensional vibrational analysis. The role of π∗ -orbital localization and hybridization on vibrations accompanying core excitation is discussed. Transition to the π⊥∗(C=C-C≡N) delocalized orbital excites mostly stretching vibrations of the whole spinal column of the molecule. Promoting a core electron to the localized π∥∗(C≡N) produces C≡N stretching vibration combined with two strong bending modes of the C-C≡N end of the molecule, related to the change of carbon hybridization.

  10. Theory of electronic states and excitations in PPV

    NASA Astrophysics Data System (ADS)

    Brazovskii, S.; Kirova, N.; Bishop, A. R.

    1998-01-01

    We present a consistent theoretical picture for optical properties of phenyl based polymers, especially for the PPV family. The model is based upon an analytical solution for the band structure of PPV oligomers, while invoking the dominant Coulomb corrections for electron-hole interactions. The adjustable parameters are only the common shift for the bands centers of gravity and a dielectric susceptibility at small distances. Our picture gives a clear understanding for the origin of all possible transitions in linear and nonlinear optics. We describe both tightly bound localized excitons and excitons of intermediate range (i.e. of both the Frenkel and Wannier-Mott types). The quantitative description of excitons is obtained from the long range Coulomb interactions, We emphasize where the ring torsion plays a role in the overall energy minimization of the excited state. This article provides theory details for the joint article [S. Brazovskii, N. Kirova, A.R. Bishop, V. Klimov, D. McBranch, N.N. Barashkov, J.P. Ferraris, Opt. Mater. 9 (1998) 472], where a complete picture was outlined.

  11. Excited state dipole moments of 4-(dimethylamino)benzaldehyde

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Kukliński, B.; Bojarski, P.

    2007-11-01

    The effect of various polar solvents on the location of absorption and dual fluorescence (short wavelength emission, SE, and long wavelength emission, LE) of 4-(dimethylamino)benzaldehyde (DMABA) at room temperature was investigated. It was found that the fluorescence intensities ratio LE/SE is constant for concentrations ranging from 10 -5 M to 10 -1 M, which evidences that the LE-band is not of excimer origin. Based on the batochromic shift of electronic spectra of DMABA and Bilot-Kawski theory the values of excited state dipole moments in SE: μeSE=7.6D and the Onsager radius a = 4.3 Å were found using the known from literature value of ground state dipole moment μg = 5.6 D. For the emitting twisted intramolecular charge transfer (TICT) excited state the value of μeLE=12D was found.

  12. Basicity of coumarin derivatives in the ground and excited states

    SciTech Connect

    Ponomarev, O.A.; Mitina, V.G.; Vasina, E.R.; Yarmolenko, S.N.

    1985-07-01

    The acid-base properties of coumarin luminophores are widely used for widening the optical spectrum generated by lasers. The aim of this work was a quantitative study of the proton-acceptor capacity of a series of substituted coumarins at the H-complex formation stage and during protonation, and also to evaluate the basicity of these compounds in the first excited singlet state. The compounds chosen were the 4- and 7-substituted coumarins, most widely used in laser technology. In the ground state the sensitivity of the carbonyl group to the effect of a substituent was twice as great in position 4 as in position 7; for the excited state the effect was reversed.

  13. Optical nanoscopy with excited state saturation at liquid helium temperatures

    NASA Astrophysics Data System (ADS)

    Yang, B.; Trebbia, J.-B.; Baby, R.; Tamarat, Ph.; Lounis, B.

    2015-10-01

    Optical resolution of solid-state single quantum emitters at the nanometre scale is a challenging step towards the control of delocalized states formed by strongly and coherently interacting emitters. We have developed a simple super-resolution optical microscopy method operating at cryogenic temperatures, which is based on optical saturation of the excited state of single fluorescent molecules with a doughnut-shaped beam. Sub-10 nm resolution is achieved with extremely low excitation intensities, a million times lower than those used in room-temperature stimulated emission depletion microscopy. Compared with super-localization approaches, our technique offers a unique opportunity to super-resolve single molecules with overlapping optical resonance frequencies and paves the way to the study of coherent interactions between single emitters and to the manipulation of their degree of entanglement.

  14. Clustered chimera states in systems of type-I excitability

    NASA Astrophysics Data System (ADS)

    Vüllings, Andrea; Hizanidis, Johanne; Omelchenko, Iryna; Hövel, Philipp

    2014-12-01

    The chimera state is a fascinating phenomenon of coexisting synchronized and desynchronized behaviour that was discovered in networks of nonlocally coupled identical phase oscillators over ten years ago. Since then, chimeras have been found in numerous theoretical and experimental studies and more recently in models of neuronal dynamics as well. In this work, we consider a generic model for a saddle-node bifurcation on a limit cycle representative of neural excitability type I. We obtain chimera states with multiple coherent regions (clustered chimeras/multi-chimeras) depending on the distance from the excitability threshold, the range of nonlocal coupling and the coupling strength. A detailed stability diagram for these chimera states and other interesting coexisting patterns (like traveling waves) is presented.

  15. Relativistic calculations of excited states of molecular iodine

    NASA Astrophysics Data System (ADS)

    Teichteil, C.; Pelissier, M.

    1994-02-01

    An ab initio relativistic atomic pseudopotential method is used for the calculation of the 23 valence excited states of the I 2 molecule which dissociate into the 2Pj+ 2Pj' ( J, J' = 3/2, 1/2) atomic states. The vertical transition energies are in very good agreement with experimental results, and the deficiency of the dissociation energy is discussed. The potential energy curves are given without and with spin-orbit coupling, and a semi-empirical improvement is proposed. In this way, we obtain for the first time very reliable potential energy curves for these excited states. The quality of these curves is tested by a careful comparison with all the available experimental data.

  16. The Exotic Excited State Behavior of 3-PHENYL-2-PROPYNENITRILE

    NASA Astrophysics Data System (ADS)

    Jawad, Khadija M.; Viquez Rojas, Claudia I.; Slipchenko, Lyudmila V.; Zwier, Timothy S.

    2017-06-01

    3-phenyl-2-propynenitrile (Ph-C≡C-C≡N) is of interest to the study of Titan's atmosphere as it is a likely product of the photochemical reaction between two known species in that environment: benzene and cyanoacetylene. The gas phase jet-cooled resonant two-photon ionization, laser induced fluorescence, and preliminary dispersed fluorescence spectra were previously reported without firm assignments due to the scarcity of totally symmetric vibrations and the prevalence of strong bands of b2 and b1 symmetry vibrations. These had called into question the identity and geometry of the excited state(s) involved in the transitions. We will here present the completed set of dispersed fluorescence data along with an analysis of the potential energy surfaces and vibronic coupling characteristic of the close-lying excited states in this intriguing molecule.

  17. Characterising a configuration interaction excited state using natural transition geminals

    NASA Astrophysics Data System (ADS)

    Coe, J. P.; Paterson, M. J.

    2014-03-01

    We introduce natural transition geminals as a means to qualitatively understand a transition where double excitations are important. The first two A1 singlet states of the CH cation are used as an initial example. We calculate these states with configuration interaction singles and state-averaged Monte Carlo configuration interaction (SA-MCCI). For each method, we compare the important natural transition geminals with the dominant natural transition orbitals. We then compare SA-MCCI and full configuration interaction with regards to the natural transition geminals using the beryllium atom. We compare using the natural transition geminals with analysing the important configurations in the CI expansion to give the dominant transition for the beryllium atom and the carbon dimer. Finally, we calculate the natural transition geminals for two electronic excitations of formamide.

  18. Ultrafast excited-state dynamics of RNA and DNA C tracts

    PubMed Central

    Cohen, Boiko; Larson, Matthew H.; Kohler, Bern

    2008-01-01

    The excited-state dynamics of the RNA homopolymer of cytosine and of the 18-mer (dC)18 were studied by steady-state and time-resolved absorption and emission spectroscopy. At pH 6.8, excitation of poly(rC) by a femtosecond UV pump pulse produces excited states that decay up to one order of magnitude more slowly than the excited states formed in the mononucleotide cytidine 5’-monophosphate under the same conditions. Even slower relaxation is observed for the hemiprotonated, self-associated form of poly(rC), which is stable at acidic pH. Transient absorption and time-resolved fluorescence signals for (dC)18 at pH 6.8 are similar to ones observed for poly(rC) near pH 4, indicating that hemiprotonated structures are found in DNA C tracts at neutral pH. In both systems, there is evidence for two kinds of emitting states with lifetimes of ~100 ps and slightly more than 1 ns. The former states are responsible for the bulk of emission from the hemiprotonated structures. Evidence suggests that slow electronic relaxation in these self-complexes is the result of vertical base stacking. The similar signals from RNA and DNA C tracts suggest a common base-stacked structure, which may be identical with that of i-motif DNA. PMID:18574520

  19. Excited state dynamics of the astaxanthin radical cation

    NASA Astrophysics Data System (ADS)

    Amarie, Sergiu; Förster, Ute; Gildenhoff, Nina; Dreuw, Andreas; Wachtveitl, Josef

    2010-07-01

    Femtosecond transient absorption spectroscopy in the visible and NIR and ultrafast fluorescence spectroscopy were used to examine the excited state dynamics of astaxanthin and its radical cation. For neutral astaxanthin, two kinetic components corresponding to time constants of 130 fs (decay of the S 2 excited state) and 5.2 ps (nonradiative decay of the S 1 excited state) were sufficient to describe the data. The dynamics of the radical cation proved to be more complex. The main absorption band was shifted to 880 nm (D 0 → D 3 transition), showing a weak additional band at 1320 nm (D 0 → D 1 transition). We found, that D 3 decays to the lower-lying D 2 within 100 fs, followed by a decay to D 1 with a time constant of 0.9 ps. The D 1 state itself exhibited a dual behavior, the majority of the population is transferred to the ground state in 4.9 ps, while a small population decays on a longer timescale of 40 ps. Both transitions from D 1 were found to be fluorescent.

  20. Controlling excited-state contamination in nucleon matrix elements

    SciTech Connect

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

    2016-06-08

    We present a detailed analysis of methods to reduce statistical errors and excited-state contamination in the calculation of matrix elements of quark bilinear operators in nucleon states. All the calculations were done on a 2+1-flavor ensemble with lattices of size 323 × 64 generated using the rational hybrid Monte Carlo algorithm at a = 0.081 fm and with Mπ = 312 MeV. The statistical precision of the data is improved using the all-mode-averaging method. We compare two methods for reducing excited-state contamination: a variational analysis and a 2-state fit to data at multiple values of the source-sink separation tsep. We show that both methods can be tuned to significantly reduce excited-state contamination and discuss their relative advantages and cost effectiveness. As a result, a detailed analysis of the size of source smearing used in the calculation of quark propagators and the range of values of tsep needed to demonstrate convergence of the isovector charges of the nucleon to the tsep → ∞ estimates is presented.

  1. Controlling excited-state contamination in nucleon matrix elements

    DOE PAGES

    Yoon, Boram; Gupta, Rajan; Bhattacharya, Tanmoy; ...

    2016-06-08

    We present a detailed analysis of methods to reduce statistical errors and excited-state contamination in the calculation of matrix elements of quark bilinear operators in nucleon states. All the calculations were done on a 2+1-flavor ensemble with lattices of size 323 × 64 generated using the rational hybrid Monte Carlo algorithm at a = 0.081 fm and with Mπ = 312 MeV. The statistical precision of the data is improved using the all-mode-averaging method. We compare two methods for reducing excited-state contamination: a variational analysis and a 2-state fit to data at multiple values of the source-sink separation tsep. Wemore » show that both methods can be tuned to significantly reduce excited-state contamination and discuss their relative advantages and cost effectiveness. As a result, a detailed analysis of the size of source smearing used in the calculation of quark propagators and the range of values of tsep needed to demonstrate convergence of the isovector charges of the nucleon to the tsep → ∞ estimates is presented.« less

  2. Controlling excited-state contamination in nucleon matrix elements

    SciTech Connect

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

    2016-06-08

    We present a detailed analysis of methods to reduce statistical errors and excited-state contamination in the calculation of matrix elements of quark bilinear operators in nucleon states. All the calculations were done on a 2+1-flavor ensemble with lattices of size 323 × 64 generated using the rational hybrid Monte Carlo algorithm at a = 0.081 fm and with Mπ = 312 MeV. The statistical precision of the data is improved using the all-mode-averaging method. We compare two methods for reducing excited-state contamination: a variational analysis and a 2-state fit to data at multiple values of the source-sink separation tsep. We show that both methods can be tuned to significantly reduce excited-state contamination and discuss their relative advantages and cost effectiveness. As a result, a detailed analysis of the size of source smearing used in the calculation of quark propagators and the range of values of tsep needed to demonstrate convergence of the isovector charges of the nucleon to the tsep → ∞ estimates is presented.

  3. Controlling excited-state contamination in nucleon matrix elements

    SciTech Connect

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

    2016-06-01

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

  4. Embedding potentials for excited states of embedded species

    SciTech Connect

    Wesolowski, Tomasz A.

    2014-05-14

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

  5. Embedding potentials for excited states of embedded species.

    PubMed

    Wesolowski, Tomasz A

    2014-05-14

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

  6. Excitation and suppression of chimera states by multiplexing.

    PubMed

    Maksimenko, Vladimir A; Makarov, Vladimir V; Bera, Bidesh K; Ghosh, Dibakar; Dana, Syamal Kumar; Goremyko, Mikhail V; Frolov, Nikita S; Koronovskii, Alexey A; Hramov, Alexander E

    2016-11-01

    We study excitation and suppression of chimera states in an ensemble of nonlocally coupled oscillators arranged in a framework of multiplex network. We consider the homogeneous network (all identical oscillators) with different parametric cases and interlayer heterogeneity by introducing parameter mismatch between the layers. We show the feasibility to suppress chimera states in the multiplex network via moderate interlayer interaction between a layer exhibiting chimera state and other layers which are in a coherent or incoherent state. On the contrary, for larger interlayer coupling, we observe the emergence of identical chimera states in both layers which we call an interlayer chimera state. We map the spatiotemporal behavior in a wide range of parameters, varying interlayer coupling strength and phase lag in two and three multiplexing layers. We also prove the emergence of interlayer chimera states in a multiplex network via evaluation of a continuous model. Furthermore, we consider the two-layered network of Hindmarsh-Rose neurons and reveal that in such a system multiplex interaction between layers is capable of exciting not only the synchronous interlayer chimera state but also nonidentical chimera patterns.

  7. Excitation on the Coherent States of Pseudoharmonic Oscillator

    NASA Astrophysics Data System (ADS)

    Popov, Dusan; Pop, Nicolina; Sajfert, Vjekoslav

    2009-05-01

    In the last decades, much attention has been paid to the excitation on coherent states, especially for coherent states of the harmonic oscillator ([1] and references therein). But an interesting anharmonic oscillator with many potential applications is also the pseudoharmonic oscillator (PHO). So, in the present paper we have defined the excitation on the Klauder-Perelomov coherent states (E-KP-CSs) for the PHO. These states are obtained by repeatedly operating the raising operator K+ on a usual Klauder-Perelomov coherent state (KP-CS) of the PHO [2]. We have verified that really, the E-KP-CSs fulfill all the properties of the coherent states, as stated by Klauder [3]. We have examined the nonclassical properties of the E-KP-CSs, by using the density matrix formalism and examining the dependence of the Mandel parameter Qz,k;m(|z|2) on the |z|2 and on the m. It seems that these states can be used in optical communication field and in the physics of quantum information, as signal beams, due to the fact that in these fields the nonclassicality plays an important role.

  8. Excitation on the Coherent States of Pseudoharmonic Oscillator

    SciTech Connect

    Popov, Dusan; Pop, Nicolina; Sajfert, Vjekoslav

    2009-05-22

    In the last decades, much attention has been paid to the excitation on coherent states, especially for coherent states of the harmonic oscillator ([1] and references therein). But an interesting anharmonic oscillator with many potential applications is also the pseudoharmonic oscillator (PHO). So, in the present paper we have defined the excitation on the Klauder-Perelomov coherent states (E-KP-CSs) for the PHO. These states are obtained by repeatedly operating the raising operator K{sub +} on a usual Klauder-Perelomov coherent state (KP-CS) of the PHO [2]. We have verified that really, the E-KP-CSs fulfill all the properties of the coherent states, as stated by Klauder [3]. We have examined the nonclassical properties of the E-KP-CSs, by using the density matrix formalism and examining the dependence of the Mandel parameter Q{sub z,k;m}(|z|{sup 2}) on the |z|{sup 2} and on the m. It seems that these states can be used in optical communication field and in the physics of quantum information, as signal beams, due to the fact that in these fields the nonclassicality plays an important role.

  9. Excitation and suppression of chimera states by multiplexing

    NASA Astrophysics Data System (ADS)

    Maksimenko, Vladimir A.; Makarov, Vladimir V.; Bera, Bidesh K.; Ghosh, Dibakar; Dana, Syamal Kumar; Goremyko, Mikhail V.; Frolov, Nikita S.; Koronovskii, Alexey A.; Hramov, Alexander E.

    2016-11-01

    We study excitation and suppression of chimera states in an ensemble of nonlocally coupled oscillators arranged in a framework of multiplex network. We consider the homogeneous network (all identical oscillators) with different parametric cases and interlayer heterogeneity by introducing parameter mismatch between the layers. We show the feasibility to suppress chimera states in the multiplex network via moderate interlayer interaction between a layer exhibiting chimera state and other layers which are in a coherent or incoherent state. On the contrary, for larger interlayer coupling, we observe the emergence of identical chimera states in both layers which we call an interlayer chimera state. We map the spatiotemporal behavior in a wide range of parameters, varying interlayer coupling strength and phase lag in two and three multiplexing layers. We also prove the emergence of interlayer chimera states in a multiplex network via evaluation of a continuous model. Furthermore, we consider the two-layered network of Hindmarsh-Rose neurons and reveal that in such a system multiplex interaction between layers is capable of exciting not only the synchronous interlayer chimera state but also nonidentical chimera patterns.

  10. Quantum correlations in excited coherent W-type state

    NASA Astrophysics Data System (ADS)

    Sathiyabama, R.; Ahmed, A. B. M.; Mohammed, S. Naina

    2017-06-01

    The tripartite W-state plays an important role in the quantum information science, due to its non vanishing bipartite correlations even after partially tracing one of the modes. The continuous variable extension of the W state is constructed using Glauber coherent states and excited using bosonic creation operators. The bipartite entanglement is measured through concurrence and tangle is also evaluated. The non classicality introduced in the three modes is measured in terms of quadrature squeezing and higher order squeezing. The influence of photon addition process on the entanglement and squeezing is derived, and from the result it is evident that the photon addition enhances the operational aspects of quantum correlation.

  11. Structural control and health monitoring of building structures with unknown ground excitations: Experimental investigation

    NASA Astrophysics Data System (ADS)

    He, Jia; Xu, You-Lin; Zhan, Sheng; Huang, Qin

    2017-03-01

    When health monitoring system and vibration control system both are required for a building structure, it will be beneficial and cost-effective to integrate these two systems together for creating a smart building structure. Recently, on the basis of extended Kalman filter (EKF), a time-domain integrated approach was proposed for the identification of structural parameters of the controlled buildings with unknown ground excitations. The identified physical parameters and structural state vectors were then utilized to determine the control force for vibration suppression. In this paper, the possibility of establishing such a smart building structure with the function of simultaneous damage detection and vibration suppression was explored experimentally. A five-story shear building structure equipped with three magneto-rheological (MR) dampers was built. Four additional columns were added to the building model, and several damage scenarios were then simulated by symmetrically cutting off these columns in certain stories. Two sets of earthquakes, i.e. Kobe earthquake and Northridge earthquake, were considered as seismic input and assumed to be unknown during the tests. The structural parameters and the unknown ground excitations were identified during the tests by using the proposed identification method with the measured control forces. Based on the identified structural parameters and system states, a switching control law was employed to adjust the current applied to the MR dampers for the purpose of vibration attenuation. The experimental results show that the presented approach is capable of satisfactorily identifying structural damages and unknown excitations on one hand and significantly mitigating the structural vibration on the other hand.

  12. Can Excited State Electronic Coherence Be Tuned via Molecular Structural Modification? A First-Principles Quantum Electronic Dynamics Study of Pyrazolate-Bridged Pt(II) Dimers.

    PubMed

    Lingerfelt, David B; Lestrange, Patrick J; Radler, Joseph J; Brown-Xu, Samantha E; Kim, Pyosang; Castellano, Felix N; Chen, Lin X; Li, Xiaosong

    2017-03-09

    Materials and molecular systems exhibiting long-lived electronic coherence can facilitate coherent transport, opening the door to efficient charge and energy transport beyond traditional methods. Recently, signatures of a possible coherent, recurrent electronic motion were identified in femtosecond pump-probe spectroscopy experiments on a binuclear platinum complex, where a persistent periodic beating in the transient absorption signal's anisotropy was observed. In this study, we investigate the excitonic dynamics that underlie the suspected electronic coherence for a series of binuclear platinum complexes exhibiting a range of interplatinum distances. Results suggest that the long-lived coherence can only result when competitive electronic couplings are in balance. At longer Pt-Pt distances, the electronic couplings between the two halves of the binuclear system weaken, and exciton localization and recombination is favored on short time scales. For short Pt-Pt distances, electronic couplings between the states in the coherent superposition are stronger than the coupling with other excitonic states, leading to long-lived coherence.

  13. Direct lifetime measurements of the excited states in Ni72

    DOE PAGES

    Kolos, K.; Miller, D.; Grzywacz, R.; ...

    2016-03-22

    The lifetimes of the first excited 2+ and 4+ states in 72Ni were measured at the National Superconducting Cyclotron Laboratory with the recoil-distance Doppler-shift method, a model-independent probe to obtain the reduced transition probability. Excited states in 72Ni were populated by the one-proton knockout reaction of an intermediate energy 73Cu beam. γ-ray-recoil coincidences were detected with the γ-ray tracking array GRETINA and the S800 spectrograph. Our results provide evidence of enhanced transition probability B(E2;2+ → 0+) as compared to 68Ni, but do not confirm the trend of large B(E2) values reported in the neighboring isotope 70Ni obtained from Coulomb excitationmore » measurement. The results are compared to shell model calculations. Here, the lifetime obtained for the excited 4+1 state is consistent with models showing decay of a seniority ν = 4, 4+ state, which is consistent with the disappearance of the 8+ isomer in 72Ni.« less

  14. Signature of nonadiabatic coupling in excited-state vibrational modes.

    PubMed

    Soler, Miguel A; Nelson, Tammie; Roitberg, Adrian E; Tretiak, Sergei; Fernandez-Alberti, Sebastian

    2014-11-13

    Using analytical excited-state gradients, vibrational normal modes have been calculated at the minimum of the electronic excited-state potential energy surfaces for a set of extended conjugated molecules with different coupling between them. Molecular model systems composed of units of polyphenylene ethynylene (PPE), polyphenylenevinylene (PPV), and naphthacene/pentacene (NP) have been considered. In all cases except the NP model, the influence of the nonadiabatic coupling on the excited-state equilibrium normal modes is revealed as a unique highest frequency adiabatic vibrational mode that overlaps with the coupling vector. This feature is removed by using a locally diabatic representation in which the effect of NA interaction is removed. Comparison of the original adiabatic modes with a set of vibrational modes computed in the locally diabatic representation demonstrates that the effect of nonadiabaticity is confined to only a few modes. This suggests that the nonadiabatic character of a molecular system may be detected spectroscopically by identifying these unique state-specific high frequency vibrational modes.

  15. Controlling autoionization in strontium two-electron-excited states

    NASA Astrophysics Data System (ADS)

    Fields, Robert; Zhang, Xinyue; Dunning, F. Barry; Yoshida, Shuhei; Burgdörfer, Joachim

    2016-05-01

    One challenge in engineering long-lived two-electron-excited states, i.e., so-called planetary atoms, is autoionization. Autoionization, however, can be suppressed if the outermost electron is placed in a high- n, n ~ 300 - 600 , high- L state because such states have only a very small overlap with the inner electron, even when this is also excited to a state of relatively high n and hence of relatively long lifetime. Here the L-dependence of the autoionization rate for high- n strontium Rydberg atoms is examined during excitation of the core ion 5 s 2S1 / 2 - 5 p 2P3 / 2 transition. Measurements in which the angular momentum of the Rydberg electron is controlled using a pulsed electric field show that the autoionization rate decreases rapidly with increasing L and becomes very small for values larger than ~ 20 . The data are analyzed with the aid of calculations undertaken using complex scaling. Research supported by the NSF and Robert A. Welch Foundation.

  16. Towards experimental determination of conical intersection properties: a twin state based comparison with bound excited states.

    PubMed

    Zilberg, Shmuel; Haas, Yehuda

    2011-07-07

    The energy and approximate structure of certain S(0)/S(1) conical intersections (CI) are shown computationally to be deducible from those of two bound states: the first triplet (T(1)), which is iso-energetic with the CI, and the second excited singlet state (S(2)). This is demonstrated for acepentalene (I) and its perfluoro derivative (II) using the twin state concept for three states systems and based on the fact that the triplet T(1) is almost degenerate with the CI. The stable S(2) (C(3v) configuration) state exhibits unusual exaltation of Jahn-Teller active degenerate mode-ν(JT) = 2058 cm(-1) (∼500 cm(-1) higher than analogous e-mode of the symmetric (C(3v)) T(1) and the dianion I(-2) or any C-C vibration of the Jahn-Teller distorted (C(s)) ground state minimum). The acepentalene molecule, whose rigid structure and possibility to attain the relatively high symmetry C(3v) configuration, is a particularly suitable candidate for this purpose.

  17. Resolving sugar puckers in RNA excited states exposes slow modes of repuckering dynamics.

    PubMed

    Clay, Mary C; Ganser, Laura R; Merriman, Dawn K; Al-Hashimi, Hashim M

    2017-08-21

    Recent studies have shown that RNAs exist in dynamic equilibrium with short-lived low-abundance 'excited states' that form by reshuffling base pairs in and around non-canonical motifs. These conformational states are proposed to be rich in non-canonical motifs and to play roles in the folding and regulatory functions of non-coding RNAs but their structure proves difficult to characterize given their transient nature. Here, we describe an approach for determining sugar pucker conformation in RNA excited states through nuclear magnetic resonance measurements of C1΄ and C4΄ rotating frame spin relaxation (R1ρ) in uniformly 13C/15N labeled RNA samples. Application to HIV-1 TAR exposed slow modes of sugar repuckering dynamics at the μs and ms timescale accompanying transitions between non-helical (C2΄-endo) to helical (C3΄-endo) conformations during formation of two distinct excited states. In contrast, we did not obtain any evidence for slow sugar repuckering dynamics for nucleotides in a variety of structural contexts that do not undergo non-helical to helical transitions. Our results outline a route for significantly improving the conformational characterization of RNA excited states and suggest that slow modes of repuckering dynamics gated by transient changes in secondary structure are quite common in RNA. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

  18. Excitation and Evolution of Structure in Galaxies

    NASA Technical Reports Server (NTRS)

    Weinberg, Martin D.

    1996-01-01

    Even casual examination shows that most disk galaxies are not truly symmetric but exhibit a variety of morphological peculiarities of which spiral arms and bars are the most pronounced. After decades of effort, we now know that these features may be driven by environmental disturbance acting directly on the disk, in addition to self-excitation of a local disturbance (e.g. by swing amplification). However, all disks are embedded within halos and therefore are not dynamically independent. Are halos susceptible to such disturbances as well? If so, can the affect disks and on what time scales? y Until recently, conventional wisdom was that halos acted to stabilize disks but otherwise remained relatively inert. The argument behind this assumption is as follows. Halos, spheroids and bulges are supported against their own gravity by the random motion of their stars, a so-called "hot" distribution. On all but the largest scales, they look like a nearly homogeneous thermal bath of stars. Because all self-sustaining patterns or waves in a homogeneous universe of stars with a Maxwellian velocity distribution are predicted to damp quickly (e.g. Ikeuchi et al. 1974), one expects that any pattern will be strongly damped in halos and spheroids as well. However, recent work suggests that halos do respond to tidal encounters by companions or cluster members and are susceptible to induction of long-lived modes.

  19. The electronic excited states of green fluorescent protein chromophore models

    NASA Astrophysics Data System (ADS)

    Olsen, Seth Carlton

    We explore the properties of quantum chemical approximations to the excited states of model chromophores of the green fluorescent protein of A. victoria. We calculate several low-lying states by several methods of quantum chemical calculation, including state-averaged complete active space SCF (CASSCF) methods, time dependent density functional theory (TDDFT), equation-of motion coupled cluster (EOM-CCSD) and multireference perturbation theory (MRPT). Amongst the low-lying states we identify the optically bright pipi* state of the molecules and examine its properties. We demonstrate that the state is dominated by a single configuration function. We calculate zero-time approximations to the resonance Raman spectrum of GFP chromophore models, and assign published spectra based upon these.

  20. Influence of Temperature and Magnetic Field on the First Excited State of a Quantum Pseudodot

    NASA Astrophysics Data System (ADS)

    Cai, Chun-Yu; Zhao, Cui-Lan; Xiao, Jing-Lin

    2017-02-01

    Investigations on the properties of excited states of complex quantum systems can not only reveal the internal structure and properties of the system but also verify the accuracy of quantum theory. In the case of strong electron-longitudinal optical phonon coupling in a quantum pseudodot with an external magnetic field, the first excited state and transition frequency can be obtained by using the Pekar variational method and quantum statistics theory. Numerical calculations for CsI crystal show that (1) they are increasing functions of the magnetic field, and (2) they will first decrease and then increase as the temperature is increased from a low value.

  1. Excited State Processes in Transition Metal Complexes, Redox Splitting in Soluble Polymers

    SciTech Connect

    Meyer, T.J.; Papanikolas, J.M.

    2002-08-08

    The photochemical and photophysical properties of polypyridyl complexes of Ru, Os, and Re have been investigated by transient absorption, emission, resonance raman and infrared spectroscopies. The latter technique has been especially useful in defining the acceptor ligand in metal-to-ligand charge transfer (MLCT) excited states and probing the details of excited state electronic and molecular structure. Derivatives of these complexes have been attached to soluble polystyrene polymers. In the resulting metal complex polymer composites it has been possible to demonstrate long range energy transfer and the existence of an antenna effect and create a mimic for the active site in the photosynthetic membrane.

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

    SciTech Connect

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

    1981-12-16

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

  3. Excited state proton transfer in the Cinchona alkaloid cupreidine.

    PubMed

    Qian, Junhong; Brouwer, Albert M

    2010-10-21

    Photophysical properties of the organocatalyst cupreidine (CPD) and its chromophoric building block 6-hydroxyquinoline (6HQ) in protic and nonprotic polar solvents (methanol and acetonitrile) were investigated by means of UV-vis absorption, and steady state and time resolved fluorescence spectroscopy. The effects of the catalytically relevant interactions with electrophilic and hydrogen bonding agents (p-toluene sulfonic acid and water) on their spectral characteristics were studied. In neutral CPD in acetonitrile, quenching of fluorescence occurs due to electron transfer from the quinuclidine nitrogen to the excited quinoline chromophore. Protonation suppresses this process, while complexation with water leads to enhanced excited state proton transfer from the 6'-OH group to the quinuclidine nitrogen, and emission occurs from the anionic form of the chromophore. The weakly emitting zwitterionic form of the hydroxyquinoline chromophore is readily formed in methanol, but not in acetonitrile.

  4. Theoretical Studies of Excited State Dynamics in Semiconductor Materials

    NASA Astrophysics Data System (ADS)

    Liu, Jin

    The motivation of this research work is to investigate excited state dynamics of semiconductor systems using quantum computational techniques. The detailed ultrafast photoinduced processes, such as charge recombination, charge relaxation, energy/charge transfer, etc., sometimes cannot be fully addressed by spectroscopy experiments. The nonadiabatic molecular dynamics (NAMD), on the other hand, provides critical insights into the complex processes. In this thesis, we apply the NAMD simulation method to various semiconductor systems, ranging from bulk crystals, nanoparticles to clusters, to study the electronic and optical properties of semiconductors. The first chapter outlines important concepts in excited states dynamics and semiconductor disciplinary. The second chapter explains the theoretical methodology related to the research work, including approximations, computational methods and simulation details, etc. Starting from chapter three to chapter six, we present a comprehensive study focusing on silicon clusters, cadmium selenide quantum dots, cycloparaphenylenes and perovskites. Potential applications include solar harvesting, photoluminescence, energy transfer, etc.

  5. Excited-state absorption measurements of Tm3+-doped crystals

    NASA Astrophysics Data System (ADS)

    Szela, J. W.; Mackenzie, J. I.

    2012-06-01

    High resolution, absolute excited-state absorption (ESA) spectra, at room temperature, from the long-lived 3F4 energy level of several crystals doped with trivalent thulium (Tm3+) ions have been measured employing high-brightness narrowband (FWHM <30 nm) light emitting diodes (LEDs) as a probe wavelength. The aim of this investigation was to determine the strength of ESA channels at wavelengths addressable by commercially available semiconductor laser diodes operating around 630-680 nm. The favourable lifetime of the 3F4 manifold and negligible ground-state absorption (GSA) for the red-wavelength second-step excitation, ensures a direct and efficient route for a dual-wavelength pumping scheme of the thulium ion, which will enable blue-green laser emission from its 1G4 upper-laser level.

  6. Accesses to electronic structures and the excited states of blue luminescent copper(I) complexes containing N-heterocyclic carbene ligands: a DFT/TDDFT exploitation.

    PubMed

    Li, Qiang; Zhao, Feng; Xu, Shengxian; Xia, Hongying; Wang, Jinglan; Wang, Yibo

    2014-09-01

    The ground electronic states and photophysical properties of three designed Cu(I) complexes [Cu(ImNHC)(POP)](+) (1), [Cu(methyl-ImNHC)(POP)](+) (2), and [Cu(BenzImNHC)(POP)](+) (3); where [ImNHC = 3-methyl-1-(pyridin-2-yl)-1H-imidazol-2-ylidene; methyl-ImNHC = 3-methyl-1-(pyridin-2-ylmethyl)-1H-imidazol-2-ylidene; BenzImNHC = 3-methyl-1-(pyridin-2-yl)-1H-benzimidazol-2-ylidene], have been investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The results reveal that the presence of the methylene spacer in the NHC ligands has a more direct effect on the distribution of frontier molecular orbitals while the elongation of π conjugation provided by the fused imidazole in the NHC ligands has a negligible effect. The UV-vis absorption spectra of all the complexes are well produced by TD-DFT calculations based on the charge transfer amount calculations and the corresponding band assignments are discussed. Importantly, the triplet energy calculations demonstrated that complex 2 would be a highly efficient blue emitter with the deep-blue of 440 nm.

  7. The effect of dimerization on the excited state behavior of methylated xanthine derivatives: a computational study.

    PubMed

    Nachtigallová, Dana; Aquino, Adelia J A; Horn, Shawn; Lischka, Hans

    2013-08-01

    The behavior of monomers and dimers of methylated xanthine derivatives in their excited states is investigated by means of the ADC(2), CASSCF, and CASPT2 methods. The results of the calculations of stationary points in the ground and excited states, minima on the S0/S1 crossing seams and the relaxation pathways are used to provide the interpretation of experimental observations of the monomer xanthine derivatives. The effect of dimerization on the excited state properties is studied for various relative orientations of the monomers in the dimer complexes in comparison with the relevant monomer species. A significant stabilization in the excited state minima of dimers is observed. These can act as trapping sites. Various types of conical intersections, with both localized and delocalized characters of wavefunctions, have been found, mainly energetically above the lowest bright excited state in the FC region. In addition, structures with the bonds formed between the two monomers were also found on the crossing seams. The possibility of ultrafast relaxation via these conical intersections is discussed.

  8. DNA Excited-State Dynamics: From Single Bases to the Double Helix

    NASA Astrophysics Data System (ADS)

    Middleton, Chris T.; de La Harpe, Kimberly; Su, Charlene; Law, Yu Kay; Crespo-Hernández, Carlos E.; Kohler, Bern

    2009-05-01

    Ultraviolet light is strongly absorbed by DNA, producing excited electronic states that sometimes initiate damaging photochemical reactions. Fully mapping the reactive and nonreactive decay pathways available to excited electronic states in DNA is a decades-old quest. Progress toward this goal has accelerated rapidly in recent years, in large measure because of ultrafast laser experiments. Here we review recent discoveries and controversies concerning the nature and dynamics of excited states in DNA model systems in solution. Nonradiative decay by single, solvated nucleotides occurs primarily on the subpicosecond timescale. Surprisingly, excess electronic energy relaxes one or two orders of magnitude more slowly in DNA oligo- and polynucleotides. Highly efficient nonradiative decay pathways guarantee that most excited states do not lead to deleterious reactions but instead relax back to the electronic ground state. Understanding how the spatial organization of the bases controls the relaxation of excess electronic energy in the double helix and in alternative structures is currently one of the most exciting challenges in the field.

  9. Excited State Absorption Measurements In Some Scintillator Dye Solutions

    NASA Astrophysics Data System (ADS)

    Dharamsi, A., N.; Jong, Shawpin; Hassam, A. B.

    1986-11-01

    Time-resolved excited state triplet-triplet absorption spectra were measured for solutions of 2,5 diphenyloxazole (PPO) and 2,1 napthyl, 5 phenyloxazole (aNPO) in several solvents. Concentration quenching effects due to excimer formation in nonaromatic solvents were observed. A numerical analysis of the experimental results yielded the rate constants for intersystem crossing, triplet quenching by 02, triplet self quenching and the formation of excimers.

  10. Temperature dependence of the excited state absorption of alexandrite

    SciTech Connect

    Shand, M.L.; Jenssen, H.P.

    1983-03-01

    The temperature dependence from 28 to 290/sup 0/C of the excited-state absorption cross section sigma /SUB 2a/ (E) in the gain wavelength region of alexandrite has been determined from the temperature dependence of the single pass gain (SPG) and of the fluorescence. sigma /SUB 2a/ (E) and the emission cross section increase with temperature at approximately the same rate.

  11. Precision Excited State Lifetime Measurements for Atomic Parity Violation and Atomic Clocks

    NASA Astrophysics Data System (ADS)

    Sell, Jerry; Patterson, Brian; Gearba, Alina; Snell, Jeremy; Knize, Randy

    2016-05-01

    Measurements of excited state atomic lifetimes provide a valuable test of atomic theory, allowing comparisons between experimental and theoretical transition dipole matrix elements. Such tests are important in Rb and Cs, where atomic parity violating experiments have been performed or proposed, and where atomic structure calculations are required to properly interpret the parity violating effect. In optical lattice clocks, precision lifetime measurements can aid in reducing the uncertainty of frequency shifts due to the surrounding blackbody radiation field. We will present our technique for precisely measuring excited state lifetimes which employs mode-locked ultrafast lasers interacting with two counter-propagating atomic beams. This method allows the timing in the experiment to be based on the inherent timing stability of mode-locked lasers, while counter-propagating atomic beams provides cancellation of systematic errors due to atomic motion to first order. Our current progress measuring Rb excited state lifetimes will be presented along with future planned measurements in Yb.

  12. Isolating excited states of the nucleon in lattice QCD

    SciTech Connect

    Mahbub, M. S.; Cais, Alan O.; Kamleh, Waseem; Lasscock, B. G.; Leinweber, Derek B.; Williams, Anthony G.

    2009-09-01

    We discuss a robust projection method for the extraction of excited-state masses of the nucleon from a matrix of correlation functions. To illustrate the algorithm in practice, we present results for the positive parity excited states of the nucleon in quenched QCD. Using eigenvectors obtained via the variational method, we construct an eigenstate-projected correlation function amenable to standard analysis techniques. The method displays its utility when comparing results from the fit of the projected correlation function with those obtained from the eigenvalues of the variational method. Standard nucleon interpolators are considered, with 2x2 and 3x3 correlation matrix analyses presented using various combinations of source-smeared, sink-smeared, and smeared-smeared correlation functions. Using these new robust methods, we observe a systematic dependency of the extracted nucleon excited-state masses on source- and sink-smearing levels. To the best of our knowledge, this is the first clear indication that a correlation matrix of standard nucleon interpolators is insufficient to isolate the eigenstates of QCD.

  13. The structure of triply excited, negative-ion resonances in the autoionizing region of helium

    NASA Astrophysics Data System (ADS)

    Trantham, K. W.; Jacka, M.; Rau, A. R. P.; Buckman, S. J.

    1999-02-01

    The formation and decay of the two lowest-lying, triply excited 0953-4075/32/3/021/img7 resonances in the autoionizing region of the helium spectrum (57-60 eV) have been studied by measuring electron-impact excitation functions for the n = 2 singly excited states of helium as a function of electron scattering angle. These results offer unambiguous confirmation of the classification of these states as 0953-4075/32/3/021/img8 and 0953-4075/32/3/021/img9, respectively. Furthermore, the observation of the relative strengths of the decay of these features into the various final states enables some speculation as to the structure of the three excited electrons.

  14. Locally-excited (LE) versus charge-transfer (CT) excited state competition in a series of para-substituted neutral green fluorescent protein (GFP) chromophore models.

    PubMed

    Olsen, Seth

    2015-02-12

    In this paper, I provide a characterization of the low-energy electronic structure of a series of para-substituted neutral green fluorescent protein (GFP) chromophore models using a theoretical approach that blends linear free energy relationships (LFERs) with state-averaged complete-active-space self-consistent field (SA-CASSCF) theory. The substituents are chosen to sample the Hammett σ(p) scale from R = F to NH2, and a model of the neutral GFP chromophore structure (R = OH) is included. I analyze the electronic structure for different members of the series in a common complete-active-space valence-bond (CASVB) representation, exploiting an isolobal analogy between active-space orbitals for different members of the series. I find that the electronic structure of the lowest adiabatic excited state is a strong mixture of weakly coupled states with charge-transfer (CT) or locally excited (LE) character and that the dominant character changes as the series is traversed. Chromophores with strongly electron-donating substituents have a CT-like excited state such as expected for a push-pull polyene or asymmetric cyanine. Chromophores with weakly electron-donating (or electron-withdrawing) substituents have an LE-like excited state with an ionic biradicaloid structure localized to the ground-state bridge π bond.

  15. Note: Excited State Studies of Ozone using State-Specific Multireference Coupled Cluster Methods

    SciTech Connect

    Bhaskaran-Nair, Kiran; Kowalski, Karol

    2012-12-07

    Vertical excitation energies obtained with state-specific multi-reference coupled cluster (MRCC) methods are reported for the ozone molecule. Using state-specific MRCC non-iterative methods with singles, doubles, and non-iterative triples (MRCCSD(T)) we obtain 4.40 eV for the challenging doubly excited 21A1 state when using a reliable model space. This estimate is in good agreement with experiment (4.5 eV). We also compare our MRCC results with the excitation energies obtained with high-order equation-of-motion coupled cluster methods

  16. Quantal density-functional theory of excited states: The state arbitrariness of the model noninteracting system

    SciTech Connect

    Slamet, Marlina; Singh, Ranbir; Sahni, Viraht; Massa, Lou

    2003-10-01

    The quantal density-functional theory (Q-DFT) of nondegenerate excited-states maps the pure state of the Schroedinger equation to one of noninteracting fermions such that the equivalent excited state density, energy, and ionization potential are obtained. The state of the model S system is arbitrary in that it may be in a ground or excited state. The potential energy of the model fermions differs as a function of this state. The contribution of correlations due to the Pauli exclusion principle and Coulomb repulsion to the potential and total energy of these fermions is independent of the state of the S system. The differences are solely a consequence of correlation-kinetic effects. Irrespective of the state of the S system, the highest occupied eigenvalue of the model fermions is the negative of the ionization potential. In this paper we demonstrate the state arbitrariness of the model system by application of Q-DFT to the first excited singlet state of the exactly solvable Hookean atom. We construct two model S systems: one in a singlet ground state (1s{sup 2}), and the other in a singlet first excited state (1s2s). In each case, the density and energy determined are equivalent to those of the excited state of the atom, with the highest occupied eigenvalues being the negative of the ionization potential. From these results we determine the corresponding Kohn-Sham density-functional theory (KS-DFT) 'exchange-correlation' potential energy for the two S systems. Further, based on the results of the model calculations, suggestions for the KS-DFT of excited states are made.

  17. An incompressible state of a photo-excited electron gas

    PubMed Central

    Chepelianskii, Alexei D.; Watanabe, Masamitsu; Nasyedkin, Kostyantyn; Kono, Kimitoshi; Konstantinov, Denis

    2015-01-01

    Two-dimensional electrons in a magnetic field can form new states of matter characterized by topological properties and strong electronic correlations as displayed in the integer and fractional quantum Hall states. In these states, the electron liquid displays several spectacular characteristics, which manifest themselves in transport experiments with the quantization of the Hall resistance and a vanishing longitudinal conductivity or in thermodynamic equilibrium when the electron fluid becomes incompressible. Several experiments have reported that dissipationless transport can be achieved even at weak, non-quantizing magnetic fields when the electrons absorb photons at specific energies related to their cyclotron frequency. Here we perform compressibility measurements on electrons on liquid helium demonstrating the formation of an incompressible electronic state under these resonant excitation conditions. This new state provides a striking example of irradiation-induced self-organization in a quantum system. PMID:26007282

  18. Excited State Dynamics of Protonated Phenylalanine and Tyrosine: Photo-Induced Reactions Following Electronic Excitation.

    PubMed

    Féraud, Géraldine; Broquier, Michel; Dedonder, Claude; Jouvet, Christophe; Grégoire, Gilles; Soorkia, Satchin

    2015-06-11

    The electronic spectroscopy and the electronic excited state properties of cold protonated phenylalanine and protonated tyrosine have been revisited on a large spectral domain and interpreted by comparison with ab initio calculations. The protonated species are stored in a cryogenically cooled Paul trap, maintained at ∼10 K, and the parent and all the photofragment ions are mass-analyzed in a time-of-flight mass spectrometer, which allows detecting the ionic species with an improved mass resolution compared to what is routinely achieved with a quadrupole mass spectrometer. These new results emphasize the competition around the band origin between two proton transfer reactions from the ammonium group toward either the aromatic chromophore or the carboxylic acid group. These reactions are initiated by the coupling of the locally excited ππ* state with higher charge transfer states, the positions and coupling of which depend on the conformation of the protonated molecules. Each of these reaction processes gives rise to specific fragmentation channels that supports the conformer selectivity observed in the photofragmentation spectra of protonated tyrosine and phenylalanine.

  19. Hedgehog Excitations and their Superconducting Cores in the Antiferromagnetic State of SO(5) Materials

    NASA Astrophysics Data System (ADS)

    Goldbart, Paul M.

    1998-03-01

    Zhang's SO(5) approach to the physics of high-temperature superconducting materials(S.-C. Zhang, Science 275), 1089 (1997). contains the possibility that the antiferromagnetic state should support novel excitations that resemble antiferromagnetic hedgehogs at large distances but are predominantly superconducting inside a core region(P. M. Goldbart, Antiferromagnetic hedgehogs with superconducting cores); cond- mat/9711088 (UIUC Preprint P-97-10-030-iii).. Neither singular nor topologically stable, in contrast with their hedgehog cousins in pure antiferromagnetism, these excitations are what hedgehogs become when antiferromagnetic order is permitted to `` escape'' toward superconductivity---a central element in Zhang's approach. We describe the structure of antiferromagnetic hedgehog excitations with superconducting cores within the context of Zhang's approach to high-temperature superconducting materials, and touch upon a number of the experimental implications that these excitations engender.

  20. Optical spectroscopy and excited state dynamics of CaMoO4:Pr3+

    NASA Astrophysics Data System (ADS)

    Cavalli, Enrico; Angiuli, Fabio; Boutinaud, Philippe; Mahiou, Rachid

    2012-01-01

    The luminescence properties of CaMoO4:Pr3+ have been investigated in different experimental conditions in order to obtain information on the excitation and de-excitation pathways of this system. The structure of the emission spectrum depends on different factors: excitation conditions, doping level, temperature, etc. In addition, measurements carried out on single crystals and on micro- or nano-crystalline powders obtained by solid state reaction and sol-gel method have revealed that the morphology of the sample, and then the concentration of the lattice defects, strongly influences the excitation mechanism. These effects have been analysed in the light of available models and a general scheme accounting for the experimental observations has been proposed.

  1. Rotational Spectra in 29 Vibrationally Excited States of Interstellar Aminoacetonitrile

    NASA Astrophysics Data System (ADS)

    Kolesniková, L.; Alonso, E. R.; Mata, S.; Alonso, J. L.

    2017-04-01

    We report a detailed spectroscopic investigation of the interstellar aminoacetonitrile, a possible precursor molecule of glycine. Using a combination of Stark and frequency-modulation microwave and millimeter wave spectroscopies, we observed and analyzed the room-temperature rotational spectra of 29 excited states with energies up to 1000 cm‑1. We also observed the 13C isotopologues in the ground vibrational state in natural abundance (1.1%). The extensive data set of more than 2000 new rotational transitions will support further identifications of aminoacetonitrile in the interstellar medium.

  2. Leptonic partial widths of the excited {psi} states

    SciTech Connect

    Mo, X. H.; Yuan, C. Z.; Wang, P.

    2010-10-01

    The resonance parameters of the excited {psi}-family resonances, namely, the {psi}(4040), {psi}(4160), and {psi}(4415), were determined by fitting the R values measured by experiments. It is found that the previously reported leptonic partial widths of these states were merely one possible solution among a four-fold ambiguity. By fitting the most precise experimental data on the R values measured by the BES collaboration, this work presents all four sets of solutions. These results may affect the interpretation of the charmonium and charmonium-like states above 4 GeV/c{sup 2}.

  3. Generalized variational principle for excited states using nodes of trial functions.

    PubMed

    Bressanini, Dario; Reynolds, Peter J

    2011-10-01

    The familiar variational principle provides an upper bound to the ground-state energy of a given Hamiltonian. This allows one to optimize a trial wave function by minimizing the expectation value of the energy. This approach is also trivially generalized to excited states, so that given a trial wave function of a certain symmetry, one can compute an upper bound to the lowest-energy level of that symmetry. In order to generalize further and build an upper bound of an arbitrary excited state of the desired symmetry, a linear combination of basis functions is generally used to generate an orthogonal set of trial functions, all bounding their respective states. However, sometimes a compact wave-function form is sought, and a basis-set expansion is not desirable or possible. Here we present an alternative generalization of the variational principle to excited states that does not require explicit orthogonalization to lower-energy states. It is valid for one-dimensional systems and, with additional information, to at least some n-dimensional systems. This generalized variational principle exploits information about the nodal structure of the trial wave function, giving an upper bound to the exact energy without the need to build a linear combination of basis functions. To illustrate the theorem we apply it to a nontrivial example: the 1s2s (1)S excited state of the helium atom.

  4. Excited states from quantum Monte Carlo in the basis of Slater determinants

    SciTech Connect

    Humeniuk, Alexander; Mitrić, Roland

    2014-11-21

    Building on the full configuration interaction quantum Monte Carlo (FCIQMC) algorithm introduced recently by Booth et al. [J. Chem. Phys. 131, 054106 (2009)] to compute the ground state of correlated many-electron systems, an extension to the computation of excited states (exFCIQMC) is presented. The Hilbert space is divided into a large part consisting of pure Slater determinants and a much smaller orthogonal part (the size of which is controlled by a cut-off threshold), from which the lowest eigenstates can be removed efficiently. In this way, the quantum Monte Carlo algorithm is restricted to the orthogonal complement of the lower excited states and projects out the next highest excited state. Starting from the ground state, higher excited states can be found one after the other. The Schrödinger equation in imaginary time is solved by the same population dynamics as in the ground state algorithm with modified probabilities and matrix elements, for which working formulae are provided. As a proof of principle, the method is applied to lithium hydride in the 3-21G basis set and to the helium dimer in the aug-cc-pVDZ basis set. It is shown to give the correct electronic structure for all bond lengths. Much more testing will be required before the applicability of this method to electron correlation problems of interesting size can be assessed.

  5. Generalized variational principle for excited states using nodes of trial functions

    SciTech Connect

    Bressanini, Dario; Reynolds, Peter J.

    2011-10-15

    The familiar variational principle provides an upper bound to the ground-state energy of a given Hamiltonian. This allows one to optimize a trial wave function by minimizing the expectation value of the energy. This approach is also trivially generalized to excited states, so that given a trial wave function of a certain symmetry, one can compute an upper bound to the lowest-energy level of that symmetry. In order to generalize further and build an upper bound of an arbitrary excited state of the desired symmetry, a linear combination of basis functions is generally used to generate an orthogonal set of trial functions, all bounding their respective states. However, sometimes a compact wave-function form is sought, and a basis-set expansion is not desirable or possible. Here we present an alternative generalization of the variational principle to excited states that does not require explicit orthogonalization to lower-energy states. It is valid for one-dimensional systems and, with additional information, to at least some n-dimensional systems. This generalized variational principle exploits information about the nodal structure of the trial wave function, giving an upper bound to the exact energy without the need to build a linear combination of basis functions. To illustrate the theorem we apply it to a nontrivial example: the 1s2s {sup 1} S excited state of the helium atom.

  6. Ground and Excited States Of OH(-)(H2O)n Clusters.

    PubMed

    Zanuttini, David; Gervais, Benoit

    2015-07-23

    We present an ab initio study of OH(-)(H2O)n (n = 1-7) clusters in their lowest three singlet and two triplet electronic states, calculated with the RASPT2 method. Minimum energy structures were obtained by geometry optimization for both (a) the 1(1)Σ(+) ground state and (b) the 1(3)Π excited state. From these structures, vertical detachment energies (VDEs), transition energies, and atomic charges were calculated. (a) We found that ground-state geometries present the hydroxide at the surface, accepting three and four H bonds from water. The excess charge is strongly stabilized by water up to a VDE of 6.7 eV for n = 7. Bound singlet excited states for ground-state geometries exist for n ≥ 3, and their VDE increases up to 1 eV for n = 7. (b) The 1(3)Π state equilibrium geometries completely differ from the ground-state geometries. They are characterized by the hydroxide acting as a single H bond donor to a water molecule, which then donates a H-bond to two others, forming a "tree" pattern. All minimum energy structures present this "tree" pattern and a constant total number of 2n - 2 H bonds, or equivalently 3 dangling hydrogens. The excess charge stabilizes from n = 2 and goes mainly at the surface, on the dangling hydrogens of water. An almost neutral OH radical is then formed. Resulting structural resemblances with the neutral system make the VDEs of the first excited states weakly geometry dependent but size sensitive because of additive polarization effects. In contrast, the 1(1)Σ(+) state at the 1(3)Π geometries is strongly sensitive to structural patterns. We bring out existing correlations between these patterns and the corresponding 1(1)Σ(+) state energy increase, which leads to couplings with excited states and possibly to an inversion of the state energy order. From these assessments, we propose a scenario for recombination of aqueous hydroxide following excitation in a charge-transfer-to-solvent state.

  7. Excited-state PAW Potentials: Modelling Hot-Dense Plasmas From First Principles

    NASA Astrophysics Data System (ADS)

    Hollebon, Patrick; Vinko, Sam; Ciricosta, Orlando; Wark, Justin

    2015-11-01

    Finite temperature density functional theory has proven to be a successful means of modelling warm and hot dense plasma systems, including the calculation of transport properties, equation of state and ionization potential depression. Such methods take into account the non-negligible influence of quantum mechanics on the electronic structure of these strongly coupled systems. We apply excited state frozen core potentials to model general core-hole states in high density plasma, allowing for the calculation of the electronic structure of a range of ionic configurations. The advantages of using excited-state potentials are explored and we investigate their application towards various response function calculations, with the results shown to be in good agreement with all-electron calculations at finite-temperatures.

  8. Electronic spectroscopy and excited state dynamics of the Al-N 2 complex

    NASA Astrophysics Data System (ADS)

    Yang, Xin; Gerasimov, Irina; Dagdigian, Paul J.

    1998-12-01

    The weakly bound Al⋯N 2 complex was prepared in a pulsed supersonic beam and studied with laser fluorescence excitation spectroscopy. Transitions to bound vibrational levels in electronic states correlating with the Al(5s, 4d)+N 2 asymptotes have been observed. Resonance fluorescence from the excited levels could not be detected. These excited levels decay nonradiatively, and the excitation spectrum was obtained by monitoring emission from the lower Al atomic levels. The band systems were dominated by progressions in the excited state Al-N stretch vibrational mode. Vibrational assignments were made through analysis of nitrogen isotope shifts. The rotational contours were obscured by Lorentzian line broadening from the nonradiative decay. However, for excitation to the Al(5s)⋯N 2 state the rotational structure of bands with small linewidths was consistent with a 2Σ+- 2Π electronic transition of a linear molecule, in accord with the previously calculated linear structure of the ground state [G. Chaban, M.S. Gordon, J. Chem. Phys. 107 (1997) 2160]. The excited state binding energies were estimated to be 1218±10 cm -1 for the Al(5s)⋯N 2 state [ 2Σ+ symmetry] and 2705±165 cm -1 for the Al(4d)⋯N 2 state of 2Δ symmetry. From the threshold for formation of Al(5s) from the nonradiative decay of Al(4d)⋯N 2, an upper bound to the ground state dissociation energy D0″≤354±2 cm -1 was obtained. For comparison with high-resolution scans over Al⋯N 2 bands, we have also recorded and analyzed similar scans over several bands of the AlAr H 2Σ+-X 2Π1/2 transition, which correlates with the Al 5s←3p atomic transition. Excited-state rotational constants were derived and employed to obtain Be'=0.1128±0.0020 cm -1, and hence Re'=3.05±0.03 Å. A weak predissociation, leading to formation of Al(3d), was observed for AlAr( H 2Σ+).

  9. Excited states in 146Sm and 147Sm

    NASA Astrophysics Data System (ADS)

    Kownacki, J.; Sujkowski, Z.; Hammarén, E.; Liukkonen, E.; Piiparinen, M.; Lindblad, Th.; Ryde, H.; Paar, V.

    1980-03-01

    The 144, 146Nd(α, χn) and 146,148Nd( 3He, χn) reactions with Eα = 20-43 MeV and E3He , = 19-27 MeV are used to investigate excited states in the isotopes 146Sm and 147Sm. The experiments involve measurements of singles γ-ray spectra and conversion electron spectra, γ-ray angular distributions and three-parameter ( Eγ- Eγ-time) coincidences. From these experiments information is obtained for states with spin up to I = 13 +and I = {27}/{2}-, respectively. These states are interpreted within the framework of the cluster-vibration model (CVM) as well as the shell model. In the latter approach, the energies of several well established states, in both isotopes, are calculated using empirical singleparticle energies, empirical two-particle interaction matrix elements and angular momentum algebra. The average deviation between the calculated and the experimental energies is less than 100 keV. The CVM calculations involve the coupling of a three-particle neutron cluster to the quadrupole vibration of the core. For 147Sm, these calculations reproduce the observed sequence of states based on the I π = {7}/{2}- ground state, as well as the sequence of states based on the I π = {13}/{2}+ excited state. The CVM calculations also reproduce the ground band in 146Sm, while for the negative parity states based on the cluster (f {7}/{2}i {13}/{2}) 3 --10 - an additional shift in energy is expected due to the mixing with octupole phonons.

  10. Dynamic insight into protein structure utilizing red edge excitation shift.

    PubMed

    Chattopadhyay, Amitabha; Haldar, Sourav

    2014-01-21

    Proteins are considered the workhorses in the cellular machinery. They are often organized in a highly ordered conformation in the crowded cellular environment. These conformations display characteristic dynamics over a range of time scales. An emerging consensus is that protein function is critically dependent on its dynamics. The subtle interplay between structure and dynamics is a hallmark of protein organization and is essential for its function. Depending on the environmental context, proteins can adopt a range of conformations such as native, molten globule, unfolded (denatured), and misfolded states. Although protein crystallography is a well established technique, it is not always possible to characterize various protein conformations by X-ray crystallography due to transient nature of these states. Even in cases where structural characterization is possible, the information obtained lacks dynamic component, which is needed to understand protein function. In this overall scenario, approaches that reveal information on protein dynamics are much appreciated. Dynamics of confined water has interesting implications in protein folding. Interfacial hydration combines the motion of water molecules with the slow moving protein molecules. The red edge excitation shift (REES) approach becomes relevant in this context. REES is defined as the shift in the wavelength of maximum fluorescence emission toward higher wavelengths, caused by a shift in the excitation wavelength toward the red edge of absorption spectrum. REES arises due to slow rates (relative to fluorescence lifetime) of solvent relaxation (reorientation) around an excited state fluorophore in organized assemblies such as proteins. Consequently, REES depends on the environment-induced motional restriction imposed on the solvent molecules in the immediate vicinity of the fluorophore. In the case of a protein, the confined water in the protein creates a dipolar field that acts as the solvent for a fluorophore

  11. Excitation of guided waves in layered structures with negative refraction.

    PubMed

    Shadrivov, Ilya; Ziolkowski, Richard; Zharov, Alexander; Kivshar, Yuri

    2005-01-24

    We study the electromagnetic beam reflection from layered structures that include the so-called double-negative metamaterials, also called left-handed metamaterials. We predict that such structures can demonstrate a giant lateral Goos-Hänchen shift of the scattered beam accompanied by a splitting of the reflected and transmitted beams due to the resonant excitation of surface waves at the interfaces between the conventional and double-negative materials as well as due to the excitation of leaky modes in the layered structures. The beam shift can be either positive or negative, depending on the type of the guided waves excited by the incoming beam. We also perform finite-difference time-domain simulations and confirm the major effects predicted analytically.

  12. Excited-State Properties of Molecular Solids from First Principles.

    PubMed

    Kronik, Leeor; Neaton, Jeffrey B

    2016-05-27

    Molecular solids have attracted attention recently in the context of organic (opto)electronics. These materials exhibit unique charge carrier generation and transport phenomena that are distinct from those of conventional semiconductors. Understanding these phenomena is fundamental to optoelectronics and requires a detailed description of the excited-state properties of molecular solids. Recent advances in many-body perturbation theory (MBPT) and density functional theory (DFT) have made such description possible and have revealed many surprising electronic and optical properties of molecular crystals. Here, we review this progress. We summarize the salient aspects of MBPT and DFT as well as various properties that can be described by these methods. These properties include the fundamental gap and its renormalization, hybridization and band dispersion, singlet and triplet excitations, optical spectra, and excitonic properties. For each, we present concrete examples, a comparison to experiments, and a critical discussion.

  13. Electronic Ground and Excited State Spectral Diffusion of a Photocatalyst

    NASA Astrophysics Data System (ADS)

    Kiefer, Laura M.; King, John T.; Kubarych, Kevin J.

    2014-06-01

    Re(bpy)(CO)_3Cl is a well studied CO_2 reduction catalyst, known for its ability as both a photosensitizer and a catalyst with a high quantum yield and product selectivity. The catalysis reaction is initiated by a 400 nm excitation, followed by an intersystem crossing (ISC) and re-equilibration in the lowest triplet state. We utilize the quasi-equilibrium nature of this long-lived triplet metal-to-ligand charge-transfer (3MLCT) state to completely characterize the solvent dynamics using the technique of transient two-dimensional infrared (t-2DIR) spectroscopy to extract observables such as the frequency-frequency correlation function (FFCF), an equilibrium function. The electronic ground state solvent dynamics are characterized using equilibrium two-dimensional infrared spectroscopy (2D IR). Our technique allows us to independently observe the solvent dynamics of different electronic states and compare them. In this study, three carbonyl stretching modes were utilized to probe both the intramolecular and solvent environments in each electronic state. In the electronic ground state, the totally symmetric mode exhibits pure homogeneous broadening and a lack of spectral dynamics, while the two other modes have similar FFCF decay times of ˜ 1.5 ps. In the 3MLCT, however, all three modes experience similar spectral dynamics and have a FFCF decay time of ˜ 4.5 ps, three times slower than in the electronic ground state. Our technique allows us to directly observe the differences in spectral dynamics of the ground and excited electronic states and allows us to attribute the differences to specific origins such as solvent-solute coupling and molecular flexibility.

  14. Output power of a quantum dot laser: Effects of excited states

    SciTech Connect

    Wu, Yuchang; Jiang, Li Asryan, Levon V.

    2015-11-14

    A theory of operating characteristics of quantum dot (QD) lasers is discussed in the presence of excited states in QDs. We consider three possible situations for lasing: (i) ground-state lasing only; (ii) ground-state lasing at first and then the onset of also excited-state lasing with increasing injection current; (iii) excited-state lasing only. The following characteristics are studied: occupancies of the ground-state and excited-state in QDs, free carrier density in the optical confinement layer, threshold currents for ground- and excited-state lasing, densities of photons emitted via ground- and excited-state stimulated transitions, output power, internal and external differential quantum efficiencies. Under the conditions of ground-state lasing only, the output power saturates with injection current. Under the conditions of both ground- and excited-state lasing, the output power of ground-state lasing remains pinned above the excited-state lasing threshold while the power of excited-state lasing increases. There is a kink in the light-current curve at the excited-state lasing threshold. The case of excited-state lasing only is qualitatively similar to that for single-state QDs—the role of ground-state transitions is simply reduced to increasing the threshold current.

  15. Phosphorescence, ODMR and ODNQR investigation of the distorted lowest excited triplet state of sym-tetrachloropyrazine

    NASA Astrophysics Data System (ADS)

    von Borczyskowski, C.

    The lowest excited triplet state of sym-tetrachloropyrazine has been investigated at 1·5 K in single crystals of sym-tetramethylbenzene (TMB) and symtetrachlorobenzene (TCB). By analysis of the chlorine and nitrogen hyperfine interaction a 3ππ* state with B2u symmetry has been identified which is contrary to the B1u symmetry of TCB. The large difference between chlorine quadrupole resonance transitions in the singlet ground and excited triplet state of 2·75 MHz (TCB) and 3·3 MHz (TMB) suggests an out-of-plane position of chlorine nuclei in the triplet state. Analysis of the vibronic structure of the phosphorescence reveals that vibronic coupling to an energetically close lying 3nπ* state is, in comparison with other pyrazines, greatly reduced.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  17. Self-energy correction to the hyperfine splitting for excited states

    SciTech Connect

    Wundt, B. J.; Jentschura, U. D.

    2011-05-15

    The self-energy corrections to the hyperfine splitting is evaluated for higher excited states in hydrogenlike ions using an expansion in the binding parameter Z{alpha}, where Z is the nuclear-charge number and {alpha} is the fine-structure constant. We present analytic results for D, F, and G states, and for a number of highly excited Rydberg states, with principal quantum numbers in the range 13{<=}n{<=}16, and orbital angular momenta l=n-2 and l=n-1. A closed-form analytic expression is derived for the contribution of high-energy photons, valid for any state with l{>=}2 and arbitrary n, l, and total angular momentum j. The low-energy contributions are written in the form of generalized Bethe logarithms and evaluated for selected states.

  18. Multiple-state interfacial electron injection competes with excited state relaxation and de-excitation to determine external quantum efficiencies of organic dye-sensitized solar cells.

    PubMed

    Zhang, Min; Yang, Lin; Yan, Cancan; Ma, Wentao; Wang, Peng

    2014-10-14

    A comprehensive description of the complicated dynamics of excited state evolution and charge transfer at the photochemical interface in dye-sensitized solar cells is crucial to understand the mechanism of converting solar photons to clean electricity, providing an informative basis for the future development of advanced organic materials. By selecting two triarylamine-based organic donor-acceptor dyes characteristic of the respective benzoic acid and cyanoacrylic acid anchors, in this paper we reveal stepwise excited state relaxations and multiple-state electron injections at a realistic titania/dye/electrolyte interface based upon ultrafast spectroscopic measurements and theoretical simulations. Density functional theory (DFT) and time-dependent DFT calculations show that the optically generated "hot" excited state of the dye molecules can undergo a significant conformational relaxation via multistage torsional motions, and thereby transform into an equilibrium quinonoid structure characteristic of a more planar conjugated backbone. A set of kinetic parameters derived from the target analysis of femtosecond transient absorption spectra have been utilized to estimate the electron injection yield, which is in good accord with the maximum of external quantum efficiencies.

  19. Application of spectroscopy and super-resolution microscopy: Excited state

    SciTech Connect

    Bhattacharjee, Ujjal

    2016-02-19

    Photophysics of inorganic materials and organic molecules in complex systems have been extensively studied with absorption and emission spectroscopy.1-4 Steady-state and time-resolved fluorescence studies are commonly carried out to characterize excited-state properties of fluorophores. Although steady-state fluorescence measurements are widely used for analytical applications, time-resolved fluorescence measurements provide more detailed information about excited-state properties and the environment in the vicinity of the fluorophore. Many photophysical processes, such as photoinduced electron transfer (PET), rotational reorientation, solvent relaxation, and energy transfer, occur on a nanosecond (10-9 s) timescale, thus affecting the lifetime of the fluorophores. Moreover, time-resolved microscopy methods, such as lifetimeimaging, combine the benefits of the microscopic measurement and information-rich, timeresolved data. Thus, time-resolved fluorescence spectroscopy combined with microscopy can be used to quantify these processes and to obtain a deeper understanding of the chemical surroundings of the fluorophore in a small area under investigation. This thesis discusses various photophysical and super-resolution microscopic studies of organic and inorganic materials, which have been outlined below.

  20. Excited electronic states of thiophene: high resolution photoabsorption Fourier transform spectroscopy and ab initio calculations.

    PubMed

    Holland, D M P; Trofimov, A B; Seddon, E A; Gromov, E V; Korona, T; de Oliveira, N; Archer, L E; Joyeux, D; Nahon, L

    2014-10-21

    The recently introduced synchrotron radiation-based Fourier transform spectroscopy has been employed to study the excited electronic states of thiophene. A highly resolved photoabsorption spectrum has been measured between ∼5 and 12.5 eV, providing a wealth of new data. High-level ab initio computations have been performed using the second-order algebraic-diagrammatic construction (ADC(2)) polarization propagator approach, and the equation-of-motion coupled-cluster (EOM-CC) method at the CCSD and CC3 levels, to guide the assignment of the spectrum. The adiabatic energy corrections have been evaluated, thereby extending the theoretical study beyond the vertical excitation picture and leading to a significantly improved understanding of the spectrum. The low-lying π→π* and π→σ* transitions result in prominent broad absorption bands. Two strong Rydberg series converging onto the X(~)(2)A2 state limit have been assigned to the 1a2→npb1(1)B2 and the 1a2→nda2(1)A1 transitions. A second, and much weaker, d-type series has been assigned to the 1a2→ndb1(1)B2 transitions. Excitation into some of the Rydberg states belonging to the two strong series gives rise to vibrational structure, most of which has been interpreted in terms of excitations of the totally symmetric ν4 and ν8 modes. One Rydberg series, assigned to the 3b1→nsa1(1)B1 transitions, has been identified converging onto the Ã(2)B1 state limit, and at higher energies Rydberg states converging onto the B(~)(2)A1 state limit could be identified. The present spectra reveal highly irregular vibrational structure in certain low energy absorption bands, and thus provide a new source of information for the rapidly developing studies of excited state non-adiabatic dynamics and photochemistry.

  1. Optimal Filtering Methods to Structural Damage Estimation under Ground Excitation

    PubMed Central

    Hsieh, Chien-Shu; Liaw, Der-Cherng; Lin, Tzu-Hsuan

    2013-01-01

    This paper considers the problem of shear building damage estimation subject to earthquake ground excitation using the Kalman filtering approach. The structural damage is assumed to take the form of reduced elemental stiffness. Two damage estimation algorithms are proposed: one is the multiple model approach via the optimal two-stage Kalman estimator (OTSKE), and the other is the robust two-stage Kalman filter (RTSKF), an unbiased minimum-variance filtering approach to determine the locations and extents of the damage stiffness. A numerical example of a six-storey shear plane frame structure subject to base excitation is used to illustrate the usefulness of the proposed results. PMID:24453869

  2. Excitation of Helium to Rydberg States Using STIRAP

    NASA Astrophysics Data System (ADS)

    Lu, Xiaoxu

    2011-12-01

    Driving atoms from an initial to a final state of the same parity via an intermediate state of opposite parity is most efficiently done using STIRAP, because it does not populate the intermediate state. For optical transitions this requires appropriate pulses of light in the counter-intuitive order - first coupling the intermediate and final states. We populate Rydberg states of helium (n = 12 ˜ 30) in a beam of average velocity 1070 m/s by having the atoms cross two laser beams in a tunable dc electric field. The "red" light near lambda = 790 ~ 830 nm connects the 33P states to the Rydberg states and the "blue" beam of lambda = 389 nm connects the metastable 2 3S state atoms emitted by our source to the 33 P states. By varying the relative position of these beams we can vary both the order and the overlap encountered by the atoms. We vary either the dc electric field and fix the " red " laser frequency or vary the "red" laser frequency and fix the dc electric field to sweep across Stark states of the Rydberg manifolds. Several mm downstream of the interaction region we apply the very strong bichromatic force on the 23S → 2 3P transition at lambda = 1083 nm. It deflects the remaining 23S atoms out of the beam and the ratio of this signal measured with STIRAP beam on and off provides an absolute measure of the fraction of the atoms remaining in the 23 S state. Simple three-level models of STIRAP all predict 100% excitation probability, but our raw measurements are typically around half of this, and vary with both n and l of the Rydberg states selected for excitation by the laser frequency and electric field tuning on our Stark maps. For states with high enough Rabi frequency, after correction for the decay back to the metastable state before the deflection, the highest efficiencies are around 70%. An ion detector readily detects the presence of Rydberg atoms. We believe that the observed signals are produced by black-body ionization at a very low rate, but

  3. An effect of charged and excited states on the decomposition of FOX-7

    NASA Astrophysics Data System (ADS)

    Kimmel, Anna; Sushko, Peter; Shluger, Alexander; Kuklja, Maija

    2007-06-01

    Various decomposition mechanisms in 1,1-diamino-2,2-dinitroethylene (FOX-7) in both gas and solid phases have been investigated by means of density functional theory calculations using an embedded cluster model. We found that the molecular excitations and charge trapping have a dramatic effect on the decomposition process by facilitating some mechanisms of dissociation and precluding the others; the excited states not only reduce the energetic reaction barriers but also change the type of the dominating chemistry from endothermic to exothermic. We found that the decomposition of FOX-7 in the gas phase is defined by two competing low- energy mechanisms, the C-NO2 scission and C-NO2 to CONO isomerisation. Decomposition in solid state of FOX-7 is much more complex and is controlled by cooperative behavior, which involves the excitation processes and structural inhomogeneities in crystalline lattice.

  4. Describing excited state relaxation and localization in TiO2 nanoparticles using TD-DFT

    DOE PAGES

    Berardo, Enrico; Hu, Han -Shi; van Dam, Hubertus J. J.; ...

    2014-02-26

    We have investigated the description of excited state relaxation in naked and hydrated TiO2 nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials; B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to be themore » inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree-Fock Like Exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT-problems for certain particles. We hypothesize that the spurious stabilization of CT-states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries than those obtained using TD-CAM-B3LYP or TD-BHLYP. In conclusion, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in naked and hydrated TiO2 nanoparticles is predicted to be associated with a large Stokes’ shift.« less

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Coherent Structures in a Supersonic Jet Excited by Plasma Actuators

    NASA Astrophysics Data System (ADS)

    Gaitonde, Datta; Samimy, Mo

    2010-11-01

    Simulations are used in conjunction with experimental measurements to understand the coherent structures generated by excitation of a Mach 1.3 jet by eight localized arc filament plasma actuators uniformly distributed just upstream of the nozzle exit. Several modes are excited, including the axisymmetric (m=0), helical (m=1-3), and mixed modes (m=±1, ±2) modes. The Strouhal number for all cases is fixed at 0.3, which corresponds to the most amplified frequency. The simulations reproduce the distinct coherent structures measured in the experiment for each azimuthal mode. Detailed analysis of instantaneous, time- and phase-averaged quantities highlights a complex coherent structure generation, evolution and dissipation process. A key feature observed is the initiation of hairpin-like structures with tips/heads in the outer region of the jet shear layer and legs extending forward and slightly inclined in the direction of the jet axis, where the velocity is higher. The subsequent interactions of these structures yield different composite structures in the downstream region. For example, for m=0, adjacent hairpin structures merge to yield axisymmetric rings, with the legs connecting successive structures in the form of ribs in the braid region; and with m=1 and 2 mode excitation, distinct helical and double-helical structures are observed, respectively, with the hairpins forming substructures in the coils.

  7. Ramsey interferometry for resonant Auger decay through core-excited states

    NASA Astrophysics Data System (ADS)

    Chatterjee, Souvik; Nakajima, Takashi

    2016-08-01

    We theoretically investigate the electron dynamics in Ne atoms involving core-excited states through the Ramsey scheme with a pair of time-delayed x-ray pulses. Irradiation of Ne atoms by the ˜1 femtosecond x-ray pulse simultaneously populates two core-excited states, and an identical but time-delayed x-ray pulse probes the dynamics of the core-excited electron wave packet which is subject to the resonant Auger decay. The energy-integrated total Auger electron yield and energy-resolved Auger electron spectra in the time domain show periodic structures due to the temporal evolution of the wave packet, from which we can obtain the counterpart in the frequency domain through the Fourier transformation. The Auger electron energy spectra in the time as well as frequency domains show the interference patterns between the two Auger electron wave packets released into the continuum from the superposition of two core-excited states at different times. These spectra are important to clarify the individual contribution of the different Auger decay channels upon core excitation by the x-ray pulse.

  8. Excited-state intramolecular proton-transfer (ESIPT)-inspired solid state emitters.

    PubMed

    Padalkar, Vikas S; Seki, Shu

    2016-01-07

    Solid state emitters based on excited state intramolecular proton transfer (ESIPT) have been attracting considerable interest since the past few years in the field of optoelectronic devices because of their desirable unique photophysical properties. The photophysical properties of the solid state ESIPT fluorophores determine their possible applicability in functional materials. Less fluorescence quantum efficiencies and short fluorescence lifetime in the solid state are the shortcomings of the existing ESIPT solid state emitters. Designing of ESIPT chromophores with high fluorescence quantum efficiencies and a long fluorescence lifetime in the solid state is a challenging issue because of the unclear mechanism of the solid state emitters in the excited state. Reported design strategies, detailed photophysical properties, and their applications will help in assisting researchers to overcome existing challenges in designing novel solid state ESIPT fluorophores for promising applications. This review highlights recently developed solid state ESIPT emitters with focus on molecular design strategies and their photophysical properties, reported in the last five years.

  9. Ground and Flight Test Structural Excitation Using Piezoelectric Actuators

    NASA Technical Reports Server (NTRS)

    Voracek, David F.; Reaves, Mercedes C.; Horta, Lucas G.; Potter, Starr; Richwine, David (Technical Monitor)

    2002-01-01

    A flight flutter experiment at the National Aeronautics and Space Administration (NASA) Dryden Flight Research Center, Edwards, California, used an 18-inch half-span composite model called the Aerostructures Test Wing (ATW). The ATW was mounted on a centerline flight test fixture on the NASA F-15B and used distributed piezoelectric strain actuators for in-flight structural excitation. The main focus of this paper is to investigate the performance of the piezoelectric actuators and test their ability to excite the first-bending and first-torsion modes of the ATW on the ground and in-flight. On the ground, wing response resulting from piezoelectric and impact excitation was recorded and compared. The comparison shows less than a 1-percent difference in modal frequency and a 3-percent increase in damping. A comparison of in-flight response resulting from piezoelectric excitation and atmospheric turbulence shows that the piezoelectric excitation consistently created an increased response in the wing throughout the flight envelope tested. The data also showed that to obtain a good correlation between the piezoelectric input and the wing accelerometer response, the input had to be nearly 3.5 times greater than the turbulence excitation on the wing.

  10. Re and Br X-ray absorption near-edge structure study of the ground and excited states of [ReBr(CO)3(bpy)] interpreted by DFT and TD-DFT calculations.

    PubMed

    Záliš, Stanislav; Milne, Chris J; El Nahhas, Amal; Blanco-Rodríguez, Ana María; van der Veen, Renske M; Vlček, Antonín

    2013-05-20

    X-ray absorption spectra of fac-[ReBr(CO)3(bpy)] near the Re L3- and Br K-edges were measured in a steady-state mode as well as time-resolved at 630 ps after 355 nm laser pulse excitation. Relativistic spin-orbit time-dependent density functional theory (TD-DFT) calculations account well for the shape of the near-edge absorption (the ″white line″) of the ground-state Re spectrum, assigning the lowest-lying transitions as core-to-ligand metal-to-ligand charge transfer from Re 2p(3/2) into predominantly π*(bpy) molecular orbitals (MOs) containing small 5d contributions, followed in energy by transitions into π* Re(CO)3 and delocalized σ*/π* MOs. Transitions gain their intensities from Re 5d and 6s participation in the target orbitals. The 5d character is distributed over many unoccupied MOs; the 5d contribution to any single empty MO does not exceed 29%. The Br K-edge spectrum is dominated by the ionization edge and multiple scattering features, the pre-edge electronic transitions being very weak. Time-resolved spectra measured upon formation of the lowest electronic excited state show changes characteristic of simultaneous Re and Br electronic depopulation: shifts of the Re and Br edges and the Re white line to higher energies and emergence of new intense pre-edge features that are attributed by TD-DFT to transitions from Re 2p(3/2) and Br 1s orbitals into a vacancy in the HOMO-1 created by electronic excitation. Experimental spectra together with quantum chemical calculations provide a direct evidence for a ReBr(CO)3 → bpy delocalized charge transfer character of the lowest excited state. Steady-state as well as time-resolved Re L3 spectra of [ReCl(CO)3(bpy)] and [Re(Etpy)(CO)3(bpy)](+) are very similar to those of the Br complex, in agreement with similar (TD) DFT calculated transition energies as well as delocalized excited-state spin densities and charge changes upon excitation.

  11. Excited state mass spectra of doubly heavy Ξ baryons

    NASA Astrophysics Data System (ADS)

    Shah, Zalak; Rai, Ajay Kumar

    2017-02-01

    In this paper, the mass spectra are obtained for doubly heavy Ξ baryons, namely, Ξ _{cc}+, Ξ _{cc}^{++}, Ξ _{bb}-, Ξ _{bb}0, Ξ _{bc}0 and Ξ _{bc}+. These baryons consist of two heavy quarks ( cc, bb, and bc) with a light ( d or u) quark. The ground, radial, and orbital states are calculated in the framework of the hypercentral constituent quark model with Coulomb plus linear potential. Our results are also compared with other predictions, thus, the average possible range of excited states masses of these Ξ baryons can be determined. The study of the Regge trajectories is performed in ( n, M2) and ( J, M2) planes and their slopes and intercepts are also determined. Lastly, the ground state magnetic moments of these doubly heavy baryons are also calculated.

  12. TBA and TCSA with boundaries and excited states

    NASA Astrophysics Data System (ADS)

    Dorey, Patrick; Pocklington, A. J.; Tateo, Roberto; Watts, Gérard

    1998-08-01

    We study the spectrum of the scaling Lee-Yang model on a finite interval from two points of view: via a generalisation of the truncated conformal space approach to systems with boundaries, and via the boundary thermodynamic Bethe ansatz. This allows reflection factors to be matched with specific boundary conditions, and leads us to propose a new (and non-minimal) family of reflection factors to describe the one relevant boundary perturbation in the model. The equations proposed previously for the ground state on an interval must be revised in certain regimes, and we find the necessary modifications by analytic continuation. We also propose new equations to describe excited states, and check all equations against boundary truncated conformal space data. Access to the finite-size spectrum enables us to observe boundary flows when the bulk remains massless, and the formation of boundary bound states when the bulk is massive.

  13. Excited-state proton transfer of firefly dehydroluciferin.

    PubMed

    Presiado, Itay; Erez, Yuval; Simkovitch, Ron; Shomer, Shay; Gepshtein, Rinat; Pinto da Silva, Luís; Esteves da Silva, Joaquim C G; Huppert, Dan

    2012-11-08

    Steady-state and time-resolved emission techniques were used to study the protolytic processes in the excited state of dehydroluciferin, a nonbioluminescent product of the firefly enzyme luciferase. We found that the ESPT rate coefficient is only 1.1 × 10(10) s(-1), whereas those of d-luciferin and oxyluciferin are 3.7 × 10(10) and 2.1 × 10(10) s(-1), respectively. We measured the ESPT rate in water-methanol mixtures, and we found that the rate decreases nonlinearly as the methanol content in the mixture increases. The deprotonated form of dehydroluciferin has a bimodal decay with short- and long-time decay components, as was previously found for both D-luciferin and oxyluciferin. In weakly acidic aqueous solutions, the deprotonated form's emission is efficiently quenched. We attribute this observation to the ground-state protonation of the thiazole nitrogen, whose pK(a) value is ~3.

  14. Radiative Decays of Low-Lying Excited-State Hyperons

    SciTech Connect

    Taylor, Simon

    2000-05-01

    The quark wave-functions of the lower-lying excited-state hyperons Lambda(1405), Sigma(1385), and Lambda(1520) are not well understood. For example, the Lambda(1405) may not be a regular three-quark state but a $\\bar{K}$N molecule. Several competing models have been proposed, but none have been convincingly eliminated. Measuring radiative decays provides a means of discriminating between the models. The radiative branching of ratios are predicted to be small (~1%), but the radiative widths vary by factors of 2-10 from model to model. The existing experimental data is sparse and inconsistent; moreover, the radiative decay of the Sigma(1385) has never been observed before (except for one event). These lower-lying excited state hypersons were produced in a tagged photon-beam experiment in the CLAS detector at TJNAF in the reaction gamma p → K+ Y* for photon energies from threshold to 2.4 GeV. The radiative branching ration for the Sigma0(1385) relative to the Sigma0(1385) → Lambda pi0 channel was measured to be 0.021 ± 0.008$+0.004\\atop{-0.007}$, corresponding to a partial width of 640 ± 270$+130\\atop{-220}$ keV.

  15. Nonlinear absorption properties and excited state dynamics of ferrocene.

    PubMed

    Scuppa, Stefano; Orian, Laura; Dini, Danilo; Santi, Saverio; Meneghetti, Moreno

    2009-08-20

    We report on the first observation of reverse saturable absorption by ferrocene (Fc) in toluene using nanosecond pulses at 532 nm. Pump and probe experiments in the visible spectral region show the existence of an excited triplet state with an intersystem crossing quantum yield S1 --> T1 of 0.085 and a molar extinction coefficient epsilon(Fc)(T) of 5650 L mol(-1) cm(-1) at 700 nm. The full understanding of the nonlinear optical behavior of Fc cannot be obtained, however, with a model that includes only the one-photon absorption from T1, but it is mandatory to consider also a simultaneous two-photon absorption from an excited singlet state of Fc (two-photon absorption cross section: 2.4 x 10(-41) cm4 s ph(-1) mol(-1)). The optical spectrum of the ground and triplet state of Fc are calculated within a TD-DFT approach considering several functionals (PBE, BLYP, LDA, OPBE) for the optimization of molecular geometry.

  16. Carbon nanorings with inserted acenes: Breaking symmetry in excited state dynamics

    DOE PAGES

    Franklin-Mergarejo, R.; Alvarez, D. Ondarse; Tretiak, S.; ...

    2016-08-10

    Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation tomore » the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Lastly, our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications.« less

  17. Carbon nanorings with inserted acenes: Breaking symmetry in excited state dynamics

    SciTech Connect

    Franklin-Mergarejo, R.; Fernandez-Alberti, S.

    2016-08-10

    Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation to the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Lastly, our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications.

  18. Elucidation of the relationships between H-bonding patterns and excited state dynamics in cyclovalone.

    PubMed

    Lamperti, Marco; Maspero, Angelo; Tønnesen, Hanne H; Bondani, Maria; Nardo, Luca

    2014-08-28

    Cyclovalone is a synthetic curcumin derivative in which the keto-enolic system is replaced by a cyclohexanone ring. This modification of the chemical structure might in principle result in an excited state that is more stable than that of curcumin, which in turn should produce an enhanced phototoxicity. Indeed, although curcumin exhibits photosensitized antibacterial activity, this compound is characterized by very fast excited-state dynamics which limit its efficacy as a photosensitizer. In previous works we showed that the main non-radiative decay pathway of keto-enolic curcuminoids is through excited-state transfer of the enolic proton to the keto-oxygen. Another effective deactivation pathway involves an intermolecular charge transfer mechanism occurring at the phenyl rings, made possible by intramolecular H-bonding between the methoxy and the hydroxyl substituent. In this paper we present UV-Vis and IR absorption spectra data with the aim of elucidating the intramolecular charge distribution of this compound and its solvation patterns in different environments, with particular focus on solute-solvent H-bonding features. Moreover, we discuss steady state and time-resolved fluorescence data that aim at characterizing the excited-state dynamics of cyclovalone, and we compare its decay photophysics to that of curcumin. Finally, because during the characterization procedures we found evidence of very fast photodegradation of cyclovalone, its photostability in four organic solvents was studied by HPLC and the corresponding relative degradation rates were calculated.

  19. Carbon nanorings with inserted acenes: breaking symmetry in excited state dynamics

    NASA Astrophysics Data System (ADS)

    Franklin-Mergarejo, R.; Alvarez, D. Ondarse; Tretiak, S.; Fernandez-Alberti, S.

    2016-08-01

    Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation to the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications.

  20. Carbon nanorings with inserted acenes: breaking symmetry in excited state dynamics

    PubMed Central

    Franklin-Mergarejo, R.; Alvarez, D. Ondarse; Tretiak, S.; Fernandez-Alberti, S.

    2016-01-01

    Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation to the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications. PMID:27507429

  1. Excited State Effects in Nucleon Matrix Element Calculations

    SciTech Connect

    Constantia Alexandrou, Martha Constantinou, Simon Dinter, Vincent Drach, Karl Jansen, Theodoros Leontiou, Dru B Renner

    2011-12-01

    We perform a high-statistics precision calculation of nucleon matrix elements using an open sink method allowing us to explore a wide range of sink-source time separations. In this way the influence of excited states of nucleon matrix elements can be studied. As particular examples we present results for the nucleon axial charge g{sub A} and for the first moment of the isovector unpolarized parton distribution x{sub u-d}. In addition, we report on preliminary results using the generalized eigenvalue method for nucleon matrix elements. All calculations are performed using N{sub f} = 2+1+1 maximally twisted mass Wilson fermions.

  2. Triaxiality near the 110Ru ground state from Coulomb excitation

    NASA Astrophysics Data System (ADS)

    Doherty, D. T.; Allmond, J. M.; Janssens, R. V. F.; Korten, W.; Zhu, S.; Zielińska, M.; Radford, D. C.; Ayangeakaa, A. D.; Bucher, B.; Batchelder, J. C.; Beausang, C. W.; Campbell, C.; Carpenter, M. P.; Cline, D.; Crawford, H. L.; David, H. M.; Delaroche, J. P.; Dickerson, C.; Fallon, P.; Galindo-Uribarri, A.; Kondev, F. G.; Harker, J. L.; Hayes, A. B.; Hendricks, M.; Humby, P.; Girod, M.; Gross, C. J.; Klintefjord, M.; Kolos, K.; Lane, G. J.; Lauritsen, T.; Libert, J.; Macchiavelli, A. O.; Napiorkowski, P. J.; Padilla-Rodal, E.; Pardo, R. C.; Reviol, W.; Sarantites, D. G.; Savard, G.; Seweryniak, D.; Srebrny, J.; Varner, R.; Vondrasek, R.; Wiens, A.; Wilson, E.; Wood, J. L.; Wu, C. Y.

    2017-03-01

    A multi-step Coulomb excitation measurement with the GRETINA and CHICO2 detector arrays was carried out with a 430-MeV beam of the neutron-rich 110Ru (t1/2 = 12 s) isotope produced at the CARIBU facility. This represents the first successful measurement following the post-acceleration of an unstable isotope of a refractory element. The reduced transition probabilities obtained for levels near the ground state provide strong evidence for a triaxial shape; a conclusion confirmed by comparisons with the results of beyond-mean-field and triaxial rotor model calculations.

  3. Theoretical study on the excited states of HCN

    NASA Astrophysics Data System (ADS)

    Nayak, Malaya K.; Chaudhuri, Rajat K.; Krishnamachari, S. N. L. G.

    2005-05-01

    In the flash-photolysis of oxazole, iso-oxazole, and thiozole a transient band system was observed in the region 2500-3050 Å. This band system was attributed to a meta-stable form of HCN, i.e., either HNC or triplet HCN. Theoretical investigations have been carried out on the ground and excited states of HCN to characterize this and other experimentally observed transitions. The predicted geometries are compared with the experiment and earlier theoretical calculations. The present calculations show that the band system in the region 2500-3050 Å corresponds to the transition 43-A'←13-A' of HCN.

  4. Triaxiality near the 110Ru ground state from Coulomb excitation

    DOE PAGES

    Doherty, D. T.; Allmond, James M.; Janssens, R. V. F.; ...

    2017-01-20

    A multi-step Coulomb excitation measurement with the GRETINA and CHICO2 detector arrays was carried out with a 430-MeV beam of the neutron-rich 110Ru (t1/2 = 12 s) isotope produced at the CARIBU facility. This represents the first successful measurement following the post-acceleration of an unstable isotope of a refractory element. The reduced transition probabilities obtained for levels near the ground state provide strong evidence for a triaxial shape; a conclusion confirmed by comparisons with the results of beyond-mean-field and triaxial rotor model calculations.

  5. Ground- and excited-state impurity bands in quantum wells

    NASA Astrophysics Data System (ADS)

    Ghazali, A.; Gold, A.; Serre, J.

    1989-02-01

    The density of states and the spectral density of electrons in quantum wells with charged impurities are calculated with use of a multiple-scattering method. The impurity-density-dependent broadening and the gradual merging of the ground (1s) and excited (2p+/-,2s) impurity levels into impurity bands are investigated. At low density the shapes of the 1s, 2p+/-, and 2s spectral densities are found to be in excellent agreement with the analytical results obtained for the ideal two-dimensional Coulomb problem.

  6. Photosensitized Thymine Dimerization via Delocalized Triplet Excited States.

    PubMed

    Miro, Paula; Lhiaubet-Vallet, Virginie; Marin, M Luisa; Miranda, Miguel A

    2015-11-16

    A new mechanism of photosensitized formation of thymine (Thy) dimers is proposed, which involves generation of a delocalized triplet excited state as the key step. This is supported by chemical evidence obtained by combining one benzophenone and two Thy units with different degrees of freedom, whereby the photoreactivity is switched from a clean Paternò-Büchi reaction to a fully chemo-, regio-, and stereoselective [2+2] cycloaddition. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. State-to-state kinetics and transport properties of electronically excited N and O atoms

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    A theoretical model of transport properties in electronically excited atomic gases in the state-to-state approach is developed. Different models for the collision diameters of atoms in excited states are discussed, and it is shown that the Slater-like models can be applied for the state-resolved transport coefficient calculations. The influence of collision diameters of N and O atoms with electronic degrees of freedom on the transport properties is evaluated. Different distributions on the electronic energy are considered for the calculation of transport coefficients. For the Boltzmann-like distributions at temperatures greater than 15000 K, an important effect of electronic excitation on the thermal conductivity and viscosity coefficients is found; the coefficients decrease significantly when many electronic states are taken into account. It is shown that under hypersonic reentry conditions the impact of collision diameters on the transport properties is not really important since the populations of high levels behind the shock waves are low.

  8. The excited spin state of Comet 2P/Encke

    NASA Astrophysics Data System (ADS)

    Belton, Michael J. S.; Samarasinha, Nalin H.; Fernández, Yan R.; Meech, Karen J.

    2005-05-01

    Ways to rationalize the different periods (e.g., 15.08 h, Luu and Jewitt, 1990, Icarus 86, 69-81; 11.01 h, Fernández et al., 2004, Icarus, in this issue; Lowry et al., 2003, Lunar Planet. Sci. XXXIV, Abstract 2056) seen in near aphelion R-band light curves of Comet 2P/Encke are explored. We show that the comet is usually active at aphelion and it's observed light curves contain signal from both the nucleus and an unresolved coma. The coma contribution to the observed brightness is generally found to dominate with the nucleus providing from 28 to 87% of the total brightness. The amplitude of the observed variations cannot be explained by the nucleus alone and are due to coma activity. We show that some seven periodicities exist in the observed light curves at various times and that this is likely the result of an active nucleus spinning in an excited spin state. The changing periodicities are probably due to changes in the relative strengths of the active areas. We work out possible excited states based on experience with model light curves and by using an analogy to light curve observations of Comet 1P/Halley for which the spin state has been separately determined from spacecraft observations. There is a possibility of a fully relaxed principal axis spin state (0.538 d -1; P=44.6 h) but, because it provides a poorer fit to the observed periodicities than the best fit excited state together with the absence of a peak near 1.08 d -1 ( 2f) in the frequency spectrum of the Fernández et al. (2000, Icarus 147, 145-160) thermal IR lightcurve, we consider it unlikely. Both SAM and LAM excited states are allowed by the underlying periodicities and additional information is needed to choose between these. Our choice of a low excitation SAM state, i.e., one in which the instantaneous spin axis nutates around the total angular momentum vector in a motion that is characterized by limited angular oscillations around the long axis, is based on Sekanina's (1988, Astron J. 95

  9. Jet spectroscopy and excited state dynamics of benzyl and substituted benzyl radicals

    NASA Astrophysics Data System (ADS)

    Fukushima, Masaru; Obi, Kinichi

    1990-12-01

    Benzyl and its p-fluoro and p-methyl derivatives are produced by the ArF laser (193 nm) photolysis of their chlorides in the supersonic free jet. The spectroscopy and excited state dynamics of these radicals are studied by the laser induced fluorescence (LIF) method under the collision free condition. The assignments of vibronic bands are carried out from the LIF excitation and dispersed spectra and the vibrational energies of the D1 state are determined. The excitation spectrum of p-fluorobenzyl shows quite similar vibrational structure to that of p-fluorotoluene up to about 1000 cm-1 from the 000 band, which indicates that D2 of p-fluorobenzyl lies about 1000 cm-1 above D1 and no vibronic coupling exists lower than this energy. On the other hand, benzyl and p-methylbenzyl show very complicated and irregular vibronic structures in excitation spectra, which are not similar to those of toluene and p-xylene. This complication is explained by the D1-D2 vibronic coupling caused by low lying D2 states in these radicals. Time profiles of the emission intensity of p-fluorobenzyl and p-methylbenzyl show single exponential decay and their lifetimes do not indicate significant dependence on vibronic levels. On the other hand, benzyl shows dual exponential decay, which is interpreted by intermediate coupling case behavior.

  10. Tuning ground states of bis(triarylamine) dications: from a closed-shell singlet to a diradicaloid with an excited triplet state.

    PubMed

    Su, Yuanting; Wang, Xingyong; Zheng, Xin; Zhang, Zaichao; Song, You; Sui, Yunxia; Li, Yizhi; Wang, Xinping

    2014-03-10

    Three bis(triarylamine) dications were isolated by using weakly coordinating anions. Their electronic structures in the ground state were investigated by various experiments in conjunction with theoretical calculations. The ground-state electronic structures of these species were tunable by substituent effects, with two of them as closed-shell singlets and one of them as an open-shell singlet in the solid state. The excited state of the latter is thermally accessible, indicated by EPR and SQUID measurements. The work provides a new and stable diradicaloid structure motif with an excited triplet sate.

  11. Experimental and computational exploration of ground and excited state properties of highly strained ruthenium terpyridine complexes.

    PubMed

    Vallett, Paul J; Damrauer, Niels H

    2013-08-01

    Dissociative electron transfer reactions are prevalent in one-electron reduced aryl halides; however, calculations applied to charge-transfer excited states of metal complexes suggest that this reaction would be strongly endergonic unless attention is paid to specific structural details. In this current study, we explore the effect of introducing intramolecular strain into a series of halogenated ruthenium(II) polypyridyls. Parent [Ru(tpy)2](2+) (1) (tpy = 2,2':6',2″-terpyridine) is compared with two complexes, [Ru(6,6″-Br2-tpy)(tpy)](2+) (2) and [Ru(6,6″-Br2-tpy)2](2+) (3) (6,6″-Br2-tpy = 6,6″-dibromo-tpy) that incorporate interligand van der Waals strain derived from the large halogen substituents. DFT calculations and the crystal structure of 3 show how this strain distorts the geometry of 3 as compared to 1. Time-dependent DFT calculations are used to explain the effect of this strain on electronic absorption spectra where, in particular, a transition observed in 3 is attenuated in 2 and absent in 1 and heralds interligand charge transfer mediated by the halogen substituent. Ultrafast transient absorption spectroscopy reveals coherent vibrational dynamics particularly in 3 but also in 2 that is interpreted as reflecting heavy-atom motion. Surprisingly, in spite of the additional strain, the excited-state lifetime of 3 is observed to be approximately a factor of 6 longer than 2. Constrained-DFT calculations show that while the excited behavior of 2 is similar to 1, the strain-induced geometric distortions in 3 cause a nesting of excited state triplet surfaces resulting in a longer excited state lifetime. This may afford the additional time needed to engage in photochemistry, and kinetic evidence is observed for the breaking of a C-Br bond in 3 and formation of a contact ion pair state.

  12. Excited state absorption spectra and intersystem crossing kinetics in diazanaphthalenes

    NASA Astrophysics Data System (ADS)

    Scott, Gary W.; Talley, Larry D.; Anderson, Robert W.

    1980-05-01

    Picosecond time-resolved, excited state absorption spectra in the visible following excitation at 355 nm are discussed for room temperature solutions of four diazanaphthalenes (DN)—quinoxaline (1,4-DN), quinazoline (1,3-DN), cinnoline (1,2-DN), and phthalazine (2,3-DN). Kinetics of singlet state decay are obtained by monitoring the decay of Sn←S1 bands. The intersystem crossing rate constant (kisc) is found to vary as kisc(1,4-DN)≳kisc(1,3-DN)≳kisc(1,2-DN). The kisc in phthalazine could not be determined from the weak, visible Sn←S1 absorption. Assuming rapid singlet vibrational relaxation and only minor effects due to energy gap variations, these experimental results agree with statistical limit predictions for the relative nonradiative rate. Calculations of the spin-orbit coupling matrix element βel= , using INDO wave functions, give the ordering βel(1,4-DN)≳βel(2,3-DN)≳βel(1,3-DN) ≳βel(1,2-DN).

  13. Probing the Locality of Excited States with Linear Algebra.

    PubMed

    Etienne, Thibaud

    2015-04-14

    This article reports a novel theoretical approach related to the analysis of molecular excited states. The strategy introduced here involves gathering two pieces of physical information, coming from Hilbert and direct space operations, into a general, unique quantum mechanical descriptor of electronic transitions' locality. Moreover, the projection of Hilbert and direct space-derived indices in an Argand plane delivers a straightforward way to visually probe the ability of a dye to undergo a long- or short-range charge-transfer. This information can be applied, for instance, to the analysis of the electronic response of families of dyes to light absorption by unveiling the trend of a given push-pull chromophore to increase the electronic cloud polarization magnitude of its main transition with respect to the size extension of its conjugated spacer. We finally demonstrate that all the quantities reported in this article can be reliably approximated by a linear algebraic derivation, based on the contraction of detachment/attachment density matrices from canonical to atomic space. This alternative derivation has the remarkable advantage of a very low computational cost with respect to the previously used numerical integrations, making fast and accurate characterization of large molecular systems' excited states easily affordable.

  14. The Microwave Spectroscopy of Aminoacetonitrile in the Vibrational Excited State

    NASA Astrophysics Data System (ADS)

    Fujita, Chiho; Ozeki, Hiroyuki; Kobayashi, Kaori

    2015-06-01

    Aminoacetonitrile (NH_2CH_2CN) is a potential precursor of the simplest amino acid, glycine and was detected toward SgrB2(N). It is expected that the strongest transitions will be found in the terahertz region so that we have extended measurements up to 1.3 THz. This study gave an accurate prediction of aminoacetonitrile up to 2 THz which is useful for astronomically search. This molecule has a few low-lying vibrational excited states and the pure rotational transitions in these vibrational excited states are expected to found. We found a series of transitions with intensity of about 30%. Eighty-eight spectral lines including both a-type and b-type transitions were recorded in the frequency region of 400 - 450 GHz, and centrifugal distortion constants up to the sextic term were determined. Perturbation was recognized. We will report the current status of the analysis. A. Belloche, K. M. Menten, C. Comito, H. S. P. Müller, P. Schilke, J. Ott, S. Thorwirth, and C. Hieret, 2008, Astronom. & Astrophys. 482, 179 (2008). Y. Motoki, Y. Tsunoda, H. Ozeki, and K. Kobayashi, Astrophys. J. Suppl. Ser. 209, 23 (2013). B. Bak, E. L. Hansen, F. M. Nicolaisen, and O. F. Nielsen, Can. J. Phys. 53, 2183 (1975).

  15. The Astrophysical Weeds: Rotational Transitions in Excited Vibrational States

    NASA Astrophysics Data System (ADS)

    Alonso, José L.; Kolesniková, Lucie; Alonso, Elena R.; Mata, Santiago

    2017-06-01

    The number of unidentified lines in the millimeter and submillimeter wave surveys of the interstellar medium has grown rapidly. The major contributions are due to rotational transitions in excited vibrational states of a relatively few molecules that are called the astrophysical weeds. necessary data to deal with spectral lines from astrophysical weeds species can be obtained from detailed laboratory rotational measurements in the microwave and millimeter wave region. A general procedure is being used at Valladolid combining different time and/or frequency domain spectroscopic tools of varying importance for providing the precise set of spectroscopic constants that could be used to search for this species in the ISM. This is illustrated in the present contribution through its application to several significant examples. Fortman, S. M., Medvedev, I. R., Neese, C.F., & De Lucia, F.C. 2010, ApJ,725, 1682 Rotational Spectra in 29 Vibrationally Excited States of Interstellar Aminoacetonitrile, L. Kolesniková, E. R. Alonso, S. Mata, and J. L. Alonso, The Astrophysical Journal Supplement Series 2017, (in press).

  16. Excited state mass spectra of singly charmed baryons

    NASA Astrophysics Data System (ADS)

    Shah, Zalak; Thakkar, Kaushal; Kumar Rai, Ajay; Vinodkumar, P. C.

    2016-10-01

    Mass spectra of excited states of the singly charmed baryons are calculated using the hypercentral description of the three-body system. The baryons consist of a charm quark and light quarks ( u, d and s) are studied in the framework of QCD motivated constituent quark model. The form of the confinement potential is hyper-Coloumb plus power potential with potential index ν, varying from 0.5 to 2.0. The first-order correction to the confinement potential is also incorporated in this approach. The radial as well as orbital excited state masses of Σc^{++}, Σc+, Σc0, Ξc+, Ξc0, Λc+, Ωc0 baryons, are reported in this paper. We have incorporated spin-spin, spin-orbit and tensor interactions perturbatively in the present study. The semi-electronic decay of Ωc and Ξc are also calculated using the spectroscopic parameters of these baryons. The computed results are compared with other theoretical predictions as well as with the available experimental observations. We also construct the Regge trajectory in (nr, M2) and (J, M2) planes for these baryons.

  17. Repetitive impact response of a beam structure subjected to harmonic base excitation

    NASA Astrophysics Data System (ADS)

    Ervin, Elizabeth K.; Wickert, J. A.

    2007-10-01

    This paper investigates the forced response dynamics of a clamped-clamped beam to which a rigid body is attached, and in the presence of periodic or non-periodic impacts between the body and a comparatively compliant base structure. The assembly is subjected to base excitation at specified frequency and acceleration, and the potentially complex responses that occur are examined analytically. The two sets of natural frequencies and vibration modes of the beam-rigid body structure (in its in-contact state, and in its not-in-contact state), are used to treat the forced response problem through a series of algebraic mappings among those states. A modal analysis based on extended operators for the (continuous) beam and (discrete) rigid body establishes a piecewise linear state-to-state mapping for transition between the in-contact and not-in-contact conditions. The contact force, impulse, and displacement each exhibit complex response characteristics as a function of the excitation frequency. Periodic responses occurring at the excitation frequency, period-doubling bifurcations, grazing impacts, sub-harmonic regions, fractional harmonic resonances, and apparently chaotic responses each occur at various combinations of damping, excitation frequency, and contact stiffness. The results of parameter studies in structural asymmetry and the eccentricity of the contact point's location are discussed.

  18. Donor-Acceptor Conjugated Linear Polyenes: A Study of Excited State Intramolecular Charge Transfer, Photoisomerization and Fluorescence Probe Properties.

    PubMed

    Hota, Prasanta Kumar; Singh, Anil Kumar

    2014-07-27

    Numerous studies of donor-acceptor conjugated linear polyenes have been carried out with the goal to understand the exact nature of the excited state electronic structure and dynamics. In this article we discuss our endeavours with regard to the excited state intramolecular charge transfer, photoisomerization and fluorescence probe properties of various donor-acceptor substituted compounds of diphenylpolyene [Ar(CH = CH) n Ar] series and ethenylindoles.

  19. New measurements of the lifetimes of excited states of {sup 55}Mn below 2.7 MeV

    SciTech Connect

    Caggiano, J. A.; Warren, G. A.; Hasty, R. D.; Korbly, S. E.; Park, W. H.

    2009-09-15

    The lifetimes of the excited states of {sup 55}Mn between 1.5 and 2.7 MeV were measured using nuclear resonance fluorescence. The absolute lifetimes of the excited levels were determined from simultaneous measurements of manganese and aluminum. In this approach, the precisely known aluminum state serves as a means to normalize the results. Our findings differ from the evaluated level lifetimes in the Evaluated Nuclear Structure Data File (ENSDF), but agree with earlier nuclear resonance fluorescence measurements.

  20. Excited state dynamics of thulium ions in yttrium aluminum garnets

    NASA Technical Reports Server (NTRS)

    Armagan, G.; Buoncristiani, A. M.; Dibartolo, B.

    1991-01-01

    The processes that take place in the excited states of a trivalent Thulium (Tm) ion in an Yttrium Aluminum Garnet (YAG) crystal, being relevant to the use of this system for laser applications, have been the object of several studies. We have reexamined this system focusing our attention on the dynamics of Tm following its excitation in the H-3(sub 4) level. Under these conditions the system relaxes through a cross-relaxation process. H-3(sub 4) yields F-3(sub 4), H-3(sub 6) yields F-3(sub 4), whose rate depends upon both the concentration of the Tm ion and the temperature of the crystal. The excitation spectrum obtained by monitoring the 1.8 micron emission of Tm (due to the F-3(sub 4) yields H-3(sub 6) transition) indicates an increase in the contribution to this emission from the H-3(sub 4) level relative to the H-3(sub 5) level as the Tm concentration increases; this shows the increased role played by the H-3(sub 4) level in pumping the infrared emission. Correspondingly, the duration of the luminescence originating in the H-3(sub 4) level is shortened as the concentration of Tm increases. The concentration quenching of this lifetime can be fit to a model which assumes that the cross-relaxation is due to a dipole-dipole interaction; from this fit, the intrinsic Tm lifetime in the absence of cross relaxation can be derived. We have used this lifetime to calculate the rate of the cross-relaxation process. We have evaluated this rate as a function of the temperature and found it to be fastest at 77 K. We have also calculated the microscopic interaction parameters for the cross-relaxation process by using two independent experimental features: (1) the time evolution of the emission from the H-3(sub 4) level; and (2) the spectral overlap between the H-3(sub 4) yields F-3(sub 4) emission and the H-3(sub 6) yields F-3(sub 4) absorption. We have also considered the migration of excitation among the Tm ions in the F-3(sub 4) level and calculated the relevant

  1. Trapped electronic states in YAG crystal excited by femtosecond radiation

    NASA Astrophysics Data System (ADS)

    Zavedeev, E. V.; Kononenko, V. V.; Konov, V. I.

    2017-07-01

    The excitation of an electronic subsystem of an yttrium aluminum garnet by 800 nm femtosecond radiation was studied theoretically and experimentally. The spatio-temporal dynamics of the refractive index ( n) inside the beam waist was explored by means of the pump-probe interferometric technique with a submicron resolution. The observed increase in n indicated the formation of bound electronic states relaxed for {˜}150 ps. We showed that the experimental data agreed with the computational simulation based on the numerical solution of the nonlinear Schrödinger equation only if these transient states were considered to arise from a direct light-induced process but not from the decay of radiatively generated free-electron-hole pairs.

  2. Initial excited-state dynamics of an N-alkylated indanylidene-pyrroline (NAIP) rhodopsin analog.

    PubMed

    Schapiro, Igor; Fusi, Stefania; Olivucci, Massimo; Andruniów, Tadeusz; Sasidharanpillai, Swaroop; Loppnow, Glen R

    2014-10-23

    N-Alkylated indanylidene-pyrroline-based molecular switches mimic different aspects of the light-induced retinal chromophore isomerization in rhodopsin: the vertebrate dim-light visual pigment. In particular, they display a similar ultrashort excited-state lifetime, subpicosecond photoproduct appearance time, and photoproduct vibrational coherence. To better understand the early light-induced dynamics of such systems, we measured and modeled the resonance Raman spectra of the Z-isomer of the N-methyl-4-(5'-methoxy-2',2'-dimethyl-indan-1'-ylidene)-5-methyl-2,3-dihydro-2H-pyrrolium (NAIP) switch in methanol solution. It is shown that the data, complemented with a <70 fs excited-state trajectory computation, demonstrate initial excited-state structural dynamics dominated by double-bond expansion and single-bond contraction stretches. This mode subsequently couples with the five-membered ring inversion and double-bond torsion. These results are discussed in the context of the mechanism of the excited-state photoisomerization of NAIP switches in solution and the 11-cis retinal in rhodopsin.

  3. Ab initio study on an excited-state intramolecular proton-transfer reaction in ionic liquid.

    PubMed

    Hayaki, Seigo; Kimura, Yoshifumi; Sato, Hirofumi

    2013-06-06

    An excited-state intramolecular proton transfer (ESIPT) reaction of 4'-N,N-dimethylamino-3-hydroxyflavone in room temperature ionic liquid is theoretically investigated using RISM-SCF-SEDD, which is a hybrid method of molecular liquid theory and ab initio molecular orbital theory. The photo-excitation and proton-transfer processes are computed by considering the solvent fluctuation. The calculated absorption and emission energy are in good agreement with the experiments. The changes in the dipole moment indicate that the drastic solvation relaxation is accompanied by the excitation and an ESIPT process, which is consistent with the remarkable dynamic Stokes shift observed in the experiments. We calculated the nonequilibrium free-energy contour as a function of the proton coordinate and the solvation coordinate. We conclude that although immediately after the excitation the barrier height of the ESIPT process is relatively small, the barrier becomes larger as the solvation relaxation to the excited normal state proceeds. The solvation relaxation process is also investigated on the basis of microscopic solvation structure obtained by RISM calculations.

  4. Universal crossover from ground-state to excited-state quantum criticality

    NASA Astrophysics Data System (ADS)

    Kang, Byungmin; Potter, Andrew C.; Vasseur, Romain

    2017-01-01

    We study the nonequilibrium properties of a nonergodic random quantum chain in which highly excited eigenstates exhibit critical properties usually associated with quantum critical ground states. The ground state and excited states of this system belong to different universality classes, characterized by infinite-randomness quantum critical behavior. Using strong-disorder renormalization group techniques, we show that the crossover between the zero and finite energy density regimes is universal. We analytically derive a flow equation describing the unitary dynamics of this isolated system at finite energy density from which we obtain universal scaling functions along the crossover.

  5. Excited state properties of the astaxanthin radical cation: A quantum chemical study

    NASA Astrophysics Data System (ADS)

    Dreuw, Andreas; Starcke, Jan Hendrik; Wachtveitl, Josef

    2010-07-01

    Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT rad + ) are investigated. While the optically allowed excited D 1 and D 3 states are typical ππ∗ excited states, the D 2 and D 4 states are nπ∗ states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed ππ∗ states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.

  6. Open-shell nuclei and excited states from multireference normal-ordered Hamiltonians

    NASA Astrophysics Data System (ADS)

    Gebrerufael, Eskendr; Calci, Angelo; Roth, Robert

    2016-03-01

    We discuss the approximate inclusion of three-nucleon (3 N ) interactions into ab initio nuclear structure calculations using a multireference formulation of normal ordering and Wick's theorem. Following the successful application of single-reference normal ordering for the study of ground states of closed-shell nuclei, e.g., in coupled-cluster theory, multireference normal ordering opens a path to open-shell nuclei and excited states. Based on different multideterminantal reference states we benchmark the truncation of the normal-ordered Hamiltonian at the two-body level in no-core shell-model calculations for p -shell nuclei, including 6Li,12C, and 10B. We find that this multireference normal-ordered two-body approximation is able to capture the effects of the 3 N interaction with sufficient accuracy, both for ground-state and excitation energies, at the computational cost of a two-body Hamiltonian. It is robust with respect to the choice of reference states and has a multitude of applications in ab initio nuclear structure calculations of open-shell nuclei and their excitations as well as in nuclear reaction studies.

  7. Ultrafast electronic relaxation of excited state vitamin B 12 in the gas phase

    NASA Astrophysics Data System (ADS)

    Shafizadeh, Niloufar; Poisson, Lionel; Soep, Benoıˆt

    2008-06-01

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

  8. Conformation excited-state of o-phenylenes by DFT method

    NASA Astrophysics Data System (ADS)

    Muraoka, Azusa; Yamashita, Koichi

    2014-03-01

    Conjugated polymers such as polyaromatic molecules with the π/ π stacking interaction have recently attracted much interest in the production and the development of the solar cell materials. Polyphenylene nanostructures are now well established in the fundamental class of conjugated polymers. This class can be divided into para, meta and orthophenylenes. In previously, we have found that the ground-state structures of tetrameric orthophenylenes (4-OP) have helical tightly packed n-phenylenes with π/ π stacking interactions. In this study, in order to investigate electronic energy transfer in orthophenylenes, we determine the excited-state structures and UV-visible absorption spectra in 4-OP using the density functional theory method.

  9. Theory of Highly Excited Molecular States : Some Recent Developments

    NASA Astrophysics Data System (ADS)

    Jungen, Christian

    2000-06-01

    Throughout his career Gerhard Herzberg had an interest in Rydberg states. This began with his observation of the Balmer series of hydrogen during his thesis work and led to the discovery of `Rydberg molecules' late in his career (i.e. molecules, such as H_3, which are unstable in their ground state but possess stable Rydberg states). While initially GH focussed mainly on the structural properties of Rydberg states, he later also studied their internal dynamics (uncoupling phenomena) and radiationless decay (preionization and predissociation). All of these phenomena play a crucial role in modern-day experiments where ultra-high spectral resolution resolves the hyperfine structure in high Rydberg states, while time-resolved experiments lead to the observation of Rydberg wave packets. Both these aspects, hyperfine effects and wavepacket motion in Rydberg states, will be discussed from a theoretical point of view.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  11. Dynamics of ground and excited state vibrational relaxation and energy transfer in transition metal carbonyls.

    PubMed

    Delor, Milan; Sazanovich, Igor V; Towrie, Michael; Spall, Steven J; Keane, Theo; Blake, Alexander J; Wilson, Claire; Meijer, Anthony J H M; Weinstein, Julia A

    2014-10-09

    Nonlinear vibrational spectroscopy provides insights into the dynamics of vibrational energy transfer in and between molecules, a crucial phenomenon in condensed phase physics, chemistry, and biology. Here we use frequency-domain 2-dimensional infrared (2DIR) spectroscopy to investigate the vibrational relaxation (VR) and vibrational energy transfer (VET) rates in different solvents in both the electronic ground and excited states of Re(Cl)(CO)3(4,4'-diethylester-2,2'-bipyridine), a prototypical transition metal carbonyl complex. The strong C≡O and ester C═O stretch infrared reporters, located on opposite sides of the molecule, were monitored in the 1600-2100 cm(-1) spectral region. VR in the lowest charge transfer triplet excited state ((3)CT) is found to be up to eight times faster than in the ground state. In the ground state, intramolecular anharmonic coupling may be solvent-assisted through solvent-induced frequency and charge fluctuations, and as such VR rates are solvent-dependent. In contrast, VR rates in the solvated (3)CT state are surprisingly solvent-insensitive, which suggests that predominantly intramolecular effects are responsible for the rapid vibrational deactivation. The increased VR rates in the excited state are discussed in terms of intramolecular electrostatic interactions helping overcome structural and thermodynamic barriers for this process in the vicinity of the central heavy atom, a feature which may be of significance to nonequilibrium photoinduced processes observed in transition metal complexes in general.

  12. Status in calculating electronic excited states in transition metal oxides from first principles.

    PubMed

    Bendavid, Leah Isseroff; Carter, Emily Ann

    2014-01-01

    Characterization of excitations in transition metal oxides is a crucial step in the development of these materials for photonic and optoelectronic applications. However, many transition metal oxides are considered to be strongly correlated materials, and their complex electronic structure is challenging to model with many established quantum mechanical techniques. We review state-of-the-art first-principles methods to calculate charged and neutral excited states in extended materials, and discuss their application to transition metal oxides. We briefly discuss developments in density functional theory (DFT) to calculate fundamental band gaps, and introduce time-dependent DFT, which can model neutral excitations. Charged excitations can be described within the framework of many-body perturbation theory based on Green's functions techniques, which predominantly employs the GW approximation to the self-energy to facilitate a feasible solution to the quasiparticle equations. We review the various implementations of the GW approximation and evaluate each approach in its calculation of fundamental band gaps of many transition metal oxides. We also briefly review the related Bethe-Salpeter equation (BSE), which introduces an electron-hole interaction between GW-derived quasiparticles to describe accurately neutral excitations. Embedded correlated wavefunction theory is another framework used to model localized neutral or charged excitations in extended materials. Here, the electronic structure of a small cluster is modeled within correlated wavefunction theory, while its coupling to its environment is represented by an embedding potential. We review a number of techniques to represent this background potential, including electrostatic representations and electron density-based methods, and evaluate their application to transition metal oxides.

  13. Excited state lifetime measurements of ytterbium in indium phosphide

    NASA Astrophysics Data System (ADS)

    Desrocher, David

    1989-12-01

    The AFIT Time Resolved Photoluminescence (TRPL) lab was disassembled, relocated and rebuilt with improvements to layout and performance. Excited state lifetime measurements of ytterbium implanted in indium phosphide were conducted using the new lab. Effects of sample temperature, rapid thermal annealing (RTA) time and RTA temperature on the lifetimes of the 1.002 microns Yb3+ line were examined. Lifetime measurements of Er, Pr and Tm in GaAs were also attempted. Ytterbium concentrations were 3 x 10(exp 13) ions/sq cm, implanted at an ion energy of 1 MeV in semi-insulating InP substrate. Sample temperatures ranged from 4.2 to 90K. Annealing times ranged from 1 to 25 seconds on samples annealed at 850 C. Annealing temperatures ranged from 400 to 850 C, with RTA times of 15 seconds. The excitation source was a nitrogen-pumped dye laser with primary wavelength at 580 nm. A germanium photodiode detector was selected to eliminate the long time constant associated with available S1 power supplies and to enable detection at the near infrared wavelengths of the other rare earths. Data acquisition was accomplished with a boxcar averager and a microcomputer equipped with acquisition hardware and software. Thermal quenching was clearly observed in lifetimes at increasing sample temperatures, most dramatically at above 50 C. The results would be very helpful in device fabrication/operation considerations, and some of the sample preparation parameters may be equally applicable for other RE doped III-V semiconductors.

  14. UV-excited transient raman spectra and the co stretching frequencies of the lowest excited triplet state of benzophenone

    NASA Astrophysics Data System (ADS)

    Tahara, Tahei; Hamaguchi, Hiro-o.; Tasumi, Mitsuo

    1988-11-01

    Transient resonance Raman spectra of T 1 benzophenone (BP) and its carbonyl- 18O-substituted analogue were measured with 355 nm excitation which is in resonance with a triplet-triplet (T n←T 1) transition in the ultraviolet. The intensity of the CO stretch band was greatly enhanced under this resonance condition. Reliable values of the T 1 CO stretching frequency were obtained including the solvent shifts. It is concluded that the solvent dependence of the photochemical reactivity of BP is not primarily due to the solvent-induced structural changes in the T 1 state. The character of the two different T-T transitions (T n←T 1 and T n←T 1) is discussed in relation to the observed Raman spectral changes with different resonance conditions.

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

    SciTech Connect

    Blom, Alex Jason

    2009-01-01

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

  16. Relationship between the excited state relaxation paths of rhodopsin and isorhodopsin.

    PubMed

    Strambi, Angela; Coto, Pedro B; Frutos, Luis Manuel; Ferré, Nicolas; Olivucci, Massimo

    2008-03-19

    The pigment Isorhodopsin, an analogue of the visual pigment Rhodopsin, is investigated via quantum-mechanics/molecular-mechanics computations based on an ab initio multiconfigurational quantum chemical treatment. The limited <5 kcal mol(-1) error found for the spectral parameters allows for a nearly quantitative analysis of the excited-state structure and reactivity of its 9-cis-retinal chromophore. We demonstrate that, similar to Rhodopsin, Isorhodopsin features a shallow photoisomerization path. However, the structure of the reaction coordinate appears to be reversed. In fact, while the coordinate still corresponds to an asynchronous crankshaft motion, the dominant isomerization component involves a counterclockwise, rather than clockwise, twisting of the 9-cis bond. Similarly, the minor component involves a clockwise, rather than counterclockwise, twisting of the 11-trans bond. Ultimately, these results indicate that Rhodopsin and Isorhodopsin relax along a common excited-state potential energy valley starting from opposite ends. The fact that the central and lowest energy region of such valley runs along a segment of the intersection space between the ground and excited states of the protein explains why the pigments decay at distinctive conical intersection structures.

  17. Disentangling structural information from core-level excitation spectra

    NASA Astrophysics Data System (ADS)

    Niskanen, Johannes; Sahle, Christoph J.; Gilmore, Keith; Uhlig, Frank; Smiatek, Jens; Föhlisch, Alexander

    2017-07-01

    Core-level spectra of liquids can be difficult to interpret due to the presence of a range of local environments. We present computational methods for investigating core-level spectra based on the idea that both local structural parameters and the x-ray spectra behave as functions of the local atomic configuration around the absorbing site. We identify correlations between structural parameters and spectral intensities in defined regions of interest, using the oxygen K-edge excitation spectrum of liquid water as a test case. Our results show that this kind of analysis can find the main structure-spectral relationships of ice, liquid water, and supercritical water.

  18. Excitation energies of a water-bridged twisted retinal structure in the bacteriorhodopsin proton pump: a theoretical investigation.

    PubMed

    Wolter, Tino; Welke, Kai; Phatak, Prasad; Bondar, Ana-Nicoleta; Elstner, Marcus

    2013-08-14

    The first proton transfer in the bacteriorhodopsin photocycle takes place during the L → M transition. Structural details of the pre proton transfer L intermediate have been investigated using experiments and computations. Here, we assess L-state structural models by performing hybrid quantum mechanical/molecular mechanical molecular dynamics and excitation energy calculations. The computations suggest that a water-bridged twisted retinal structure gives the closest agreement with the experimental L/bR shift in the excitation energy.

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

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

  20. Lowest singlet excited state and spectroscopy of α-carotene

    NASA Astrophysics Data System (ADS)

    Itoh, Takao

    2011-03-01

    Emission, excitation and absorption spectra of α-carotene have been measured in solvents with different polarizabilities. It is shown that in highly-polarized solvents α-carotene emits weak fluorescence from the S 1( π, π∗) state with the fluorescence origin observed at 14 800 ± 200 cm -1. The relative S 1/S 2 fluorescence intensity ratio tends to increase with increasing solvent polarizability or decreasing the S 1-S 2 energy separation. The obtained spectroscopic data include the Raman spectrum of α-carotene along with the vibrational analyses of the Raman spectrum based on the DFT calculation at the B3LYP/6-31G(d,p) level.

  1. Theoretical study on the excited states of HCN

    SciTech Connect

    Nayak, Malaya K.; Chaudhuri, Rajat K.; Krishnamachari, S.N.L.G.

    2005-05-08

    In the flash-photolysis of oxazole, iso-oxazole, and thiozole a transient band system was observed in the region 2500-3050 A. This band system was attributed to a meta-stable form of HCN, i.e., either HNC or triplet HCN. Theoretical investigations have been carried out on the ground and excited states of HCN to characterize this and other experimentally observed transitions. The predicted geometries are compared with the experiment and earlier theoretical calculations. The present calculations show that the band system in the region 2500-3050 A corresponds to the transition 4 {sup 3}-A{sup '}<{sup -}1 {sup 3}-A{sup '} of HCN.

  2. Measurement of Atomic Oscillator Strength Distribution from the Excited States

    SciTech Connect

    Hussain, Shahid; Saleem, M.; Baig, M. A.

    2008-10-22

    Saturation technique has been employed to measure the oscillator strength distribution in spectra of helium lithium using an electrical discharge cell a thermionic diode ion detector respectively. The photoabsorption cross sections in the discrete or bound region (commonly known as f-values) have been determined form the Rydberg series accessed from a particular excited state calibrating it with the absolute value of the photoionization cross section measured at the ionization threshold. The extracted discrete f-values merge into the oscillator strength densities, estimated from the measured photoionization cross sections at different photon energies above the first ionization threshold. The experimental data on helium and lithium show continuity between the discrete and the continuous oscillator strengths across the ionization threshold.

  3. Excited state mass spectra and Regge trajectories of bottom baryons

    NASA Astrophysics Data System (ADS)

    Thakkar, Kaushal; Shah, Zalak; Rai, Ajay Kumar; C. Vinodkumar, P.

    2017-09-01

    We present the mass spectra of radial and orbital excited states of singly heavy bottom baryons; Σb+, Σb-, Ξb-, Ξb0, Λb0 and Ωb-. The QCD motivated hypercentral quark model is employed for the three body description of baryons and the form of confinement potential is hyper Coulomb plus linear. The first order correction to the confinement potential is also incorporated in this work. The semi-electronic decay of Ωb and Ξb are calculated using the spectroscopic parameters of the baryons. The computed results are compared with other theoretical predictions as well as with the available experimental observations. The Regge trajectories are plotted in (n ,M2) plane.

  4. Theoretical description of excited state dynamics in nanostructures

    NASA Astrophysics Data System (ADS)

    Rubio, Angel

    2009-03-01

    There has been much progress in the synthesis and characterization of nanostructures however, there remain immense challenges in understanding their properties and interactions with external probes in order to realize their tremendous potential for applications (molecular electronics, nanoscale opto-electronic devices, light harvesting and emitting nanostructures). We will review the recent implementations of TDDFT to study the optical absorption of biological chromophores, one-dimensional polymers and layered materials. In particular we will show the effect of electron-hole attraction in those systems. Applications to the optical properties of solvated nanostructures as well as excited state dynamics in some organic molecules will be used as text cases to illustrate the performance of the approach. Work done in collaboration with A. Castro, M. Marques, X. Andrade, J.L Alonso, Pablo Echenique, L. Wirtz, A. Marini, M. Gruning, C. Rozzi, D. Varsano and E.K.U. Gross.

  5. The Ground and First Excited Torsional States of Acetic Acid.

    PubMed

    Ilyushin, V. V.; Alekseev, E. A.; Dyubko, S. F.; Podnos, S. V.; Kleiner, I.; Margulès, L.; Wlodarczak, G.; Demaison, J.; Cosléou, J.; Maté, B.; Karyakin, E. N.; Golubiatnikov, G. Yu.; Fraser, G. T.; Suenram, R. D.; Hougen, J. T.

    2001-02-01

    A global fit of microwave and millimeter-wave rotational transitions in the ground and first excited torsional states (v(t) = 0 and 1) of acetic acid (CH(3)COOH) is reported, which combines older measurements from the literature with new measurements from Kharkov, Lille, and NIST. The fit uses a model developed initially for acetaldehyde and methanol-type internal rotor molecules. It requires 34 parameters to achieve a unitless weighted standard deviation of 0.84 for a total of 2518 data and includes A- and E-species transitions with J

  6. Theoretical studies of excited state 1,3 dipolar cycloadditions

    NASA Astrophysics Data System (ADS)

    Belluccci, Michael A.

    The 1,3 dipolar photocycloaddition reaction between 3-hydroxy-4',5,7-trimethoxyflavone (3-HTMF) and methyl cinnamate is investigated in this work. Since its inception in 2004 [JACS, 124, 13260 (2004)], this reaction remains at the forefront in the synthetic design of the rocaglamide natural products. The reaction is multi-faceted in that it involves multiple excited states and is contingent upon excited state intramolecular proton transfer (ESIPT) in 3-HTMF. Given the complexity of the reaction, there remain many questions regarding the underlying mechanism. Consequently, throughout this work we investigate the mechanism of the reaction along with a number of other properties that directly influence it. To investigate the photocycloaddition reaction, we began by studying the effects of different solvent environments on the ESIPT reaction in 3-hydroxyflavone since this underlying reaction is sensitive to the solvent environment and directly influences the cycloaddition. To study the ESIPT reaction, we developed a parallel multi-level genetic program to fit accurate empirical valence bond (EVB) potentials to ab initio data. We found that simulations with our EVB potentials accurately reproduced experimentally determined reaction rates, fluorescence spectra, and vibrational frequency spectra in all solvents. Furthermore, we found that the ultrafast ESIPT process results from a combination of ballistic transfer and intramolecular vibrational redistribution. To investigate the cycloaddition reaction mechanism, we utilized the string method to obtain minimum energy paths on the ab initio potential. These calculations demonstrated that the reaction can proceed through formation of an exciplex in the S1 state, followed by a non-adiabatic transition to the ground state. In addition, we investigated the enantioselective catalysis of the reaction using alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolan-4,5-dimethanol alcohol (TADDOL). We found that TADDOL lowered the energy

  7. The influence of the molecular charge on potential energy curves for the proton transfer in electronic ground and excited states

    NASA Astrophysics Data System (ADS)

    Kowal, Marek; Roszak, Szczepan; Leszczynski, Jerzy

    2001-05-01

    The potential energy curves were studied for the proton transfer in the electronic ground and excited states for the model systems H3O2-, H4O2, and H5O2+. The complete active space self-consistent-field calculations were performed for the ground state optimized structures. The potential energy curves for the proton transfer in the excited states undergo a dramatic change due to the different electronic density distribution as an effect of electronic excitations. In all cases of the studied excited states, the electron population on the transferred proton is higher compared to that in the ground state. The total charge of the system greatly influences the potential curves. Energy separation between ground and excited states is decreased due to the negative charge of the system and is increased when the studied species are positively charged. The vertical excitations of the complex are similar to those in the monomers, but the proton relaxation leads to significant energetical (energy barriers) and structural (H+ position) changes.

  8. Recoil distance transmission method: Measurement of interaction cross sections of excited states with fast rare-isotope beams

    NASA Astrophysics Data System (ADS)

    Kobayashi, N.; Whitmore, K.; Iwasaki, H.

    2016-09-01

    The possible appearance of nuclear halos in ground and excited states close to the particle-decay threshold is of great importance in the investigation of nuclear structure and few-body correlations at the limit of stability. In order to obtain direct evidence of the halo structure manifested in nuclear excited states, we have considered a new method to measure the interaction cross sections of excited states. The combination of the transmission method and the recoil distance Doppler-shift method with a plunger device enables us to measure the number of interactions of the excited states in a target. Formulae to determine the interaction cross section are derived, and key issues to realize measurements are discussed. Dominant sources of errors are uncertainties in the excited-state lifetimes and γ-ray yields. We examine prototype experiments and perform simulations to study the impact of each uncertainty on the final result. This method provides a novel opportunity to perform cross section measurements on the excited states of rare isotopes.

  9. Experimental and theoretical dipole moments of purines in their ground and lowest excited singlet states

    NASA Astrophysics Data System (ADS)

    Aaron, Jean-Jacques; Diabou Gaye, Mame; Párkányi, Cyril; Cho, Nam Sook; Von Szentpály, László

    1987-01-01

    The ground-state dipole moments of seven biologically important purines (purine, 6-chloropurine, 6-mercaptopurine, hypoxanthine, theobromine, theophylline and caffeine) were determined at 25°C in acetic acid (all the above compounds with the exception of purine) and in ethyl acetate (purine, theophylline and caffeine). Because of its low solubility, it was not possible to measure the dipole moment of uric acid. The first excited singlet-state dipole moments were obtained on the basis of the Bakhshiev and Chamma—Viallet equations using the variation of the Stokes shift with the solvent dielectric constant-refractive index term. The theoretical dipole moments for all the purines listed above and including uric acid were calculated by combining the use of the PPP (π-LCI-SCF-MO) method for the π-contribution to the overall dipole moment with the σ-contribution obtained as a vector sum of the σbond moments and group moments. The experimental and theoretical values were compared with the data available in the literature for some of the purines under study. For several purines, the calculations were carried out for different tautomeric forms. Excited singlet-state dipole moments are smaller than the ground-state values by 0.8 to 2.2 Debye units for all purines under study with the exception of 6-chloropurine. The effects of the structure upon the ground- and excited-state dipole moments of the purines are discussed.

  10. Beyond Time-Dependent Density Functional Theory Using Only Single Excitations: Methods for Computational Studies of Excited States in Complex Systems.

    PubMed

    Herbert, John M; Zhang, Xing; Morrison, Adrian F; Liu, Jie

    2016-05-17

    Single-excitation methods, namely, configuration interaction singles and time-dependent density functional theory (TDDFT), along with semiempirical versions thereof, represent the most computationally affordable electronic structure methods for describing electronically excited states, scaling as [Formula: see text] absent further approximations. This relatively low cost, combined with a treatment of electron correlation, has made TDDFT the most widely used excited-state quantum chemistry method over the past 20+ years. Nevertheless, certain inherent problems (beyond just the accuracy of this or that exchange-correlation functional) limit the utility of traditional TDDFT. For one, it affords potential energy surfaces whose topology is incorrect in the vicinity of any conical intersection (CI) that involves the ground state. Since CIs are the conduits for transitions between electronic states, the TDDFT description of photochemistry (internal conversion and intersystem crossing) is therefore suspect. Second, the [Formula: see text] cost can become prohibitive in large systems, especially those that involve multiple electronically coupled chromophores, for example, the antennae structures of light-harvesting complexes or the conjugated polymers used in organic photovoltaics. In such cases, the smallest realistic mimics might already be quite large from the standpoint of ab initio quantum chemistry. This Account describes several new computational methods that address these problems. Topology around a CI can be rigorously corrected using a "spin-flip" version of TDDFT, which involves an α → β spin-flipping transition in addition to occupied → virtual excitation of one electron. Within this formalism, singlet states are generated via excitation from a high-spin triplet reference state, doublets from a quartet, etc. This provides a more balanced treatment of electron correlation between ground and excited states. Spin contamination is problematic away from the

  11. Lasing due to the excited state in quantum dot lasers

    NASA Astrophysics Data System (ADS)

    Abusaa, M.; Danckaert, J.; Viktorov, E. A.

    2017-07-01

    Quantum Dot Lasers (QDLs) are promising sources of light because of their favorable properties compared to other light sources. Emission in QDLs can access transitions in ground state (GS) and excited state (ES). Lasing due to the ES extends the spectral range and enables the laser to generate high output powers. Thus, lasing action due to the ES or to the dual lasing regime (GS and ES simultaneously) is expected to increase the applicability of QDLs in many future applications. We present a partially microscopic rate equation model that takes into account lasing action due to both the GS and the ES and distinguishes between both types of carriers (electrons and holes). Also, we present all possible steady-state solutions and we apply a stability analysis to the solutions to determine all stable lasing regimes (lasing due to the GS, lasing due to the ES and the dual lasing regime) to highlight the role of ES transitions. Specifically, we address the appearance of lasing due to the ES to the larger population of the ES and hence to the larger gain in higher injected current regimes.

  12. Ultrafast Spectroscopy of Delocalized Excited States of the Hydrated Electron

    SciTech Connect

    Paul F. Barbara

    2005-09-28

    Research under support of this grant has been focused on the understanding of highly delocalized ''conduction-band-like'' excited states of solvated electrons in bulk water, in water trapped in the core of reverse micelles, and in alkane solvents. We have strived in this work to probe conduction-band-like states by a variety of ultrafast spectroscopy techniques. (Most of which were developed under DOE support in a previous funding cycle.) We have recorded the optical spectrum of the hydrated electron for the first time. This was accomplished by applying a photo-detrapping technique that we had developed in a previous funding cycle, but had not yet been applied to characterize the actual spectrum. In the cases of reverse micelles, we have been investigating the potential role of conduction bands in the electron attachment process and the photoinduced detrapping, and have published two papers on this topic. Finally, we have been exploring solvated electrons in isooctane from various perspectives. All of these results strongly support the conclusion that optically accessible, highly delocalized electronic states exist in these various media.

  13. Development of collective structures over noncollective excitations in 139Nd

    NASA Astrophysics Data System (ADS)

    Bhowal, S.; Gangopadhyay, G.; Petrache, C. M.; Ragnarsson, I.; Singh, A. K.; Bhattacharya, S.; Hübel, H.; Neußer-Neffgen, A.; Al-Khatib, A.; Bringel, P.; Bürger, A.; Nenoff, N.; Schönwaßer, G.; Hagemann, G. B.; Herskind, B.; Jensen, D. R.; Sletten, G.; Fallon, P.; Görgen, A.; Bednarczyk, P.; Curien, D.; Korichi, A.; Lopez-Martens, A.; Rao, B. V. T.; Reddy, T. S.; Singh, Nirmal

    2011-08-01

    High-spin states in 139Nd were investigated using the reaction 96Zr(48Ca,5n) at a beam energy of 195 MeV and γ-ray coincidences were acquired with the Euroball spectrometer. Apart from several dipole bands at medium excitation energy, three quadrupole bands have been observed at high spin. Linking transitions connecting two of the high-spin bands to low-energy states have been observed. Calculations based on the cranked-Nilsson-Strutinsky formalism have been used to assign configurations for the high-spin quadrupole bands.

  14. Watching ultrafast barrierless excited-state isomerization of pseudocyanine in real time.

    PubMed

    Dietzek, Benjamin; Yartsev, Arkady; Tarnovsky, Alexander N

    2007-05-03

    The photoinduced excited-state processes in 1,1'-diethyl-2,2'-cyanine iodine are investigated using femtosecond time-resolved pump-probe spectroscopy. Using a broad range of probe wavelengths, the relaxation of the initially prepared excited-state wavepacket can be followed down to the sink region. The data directly visualize the directed downhill motion along the torsional reaction coordinate and suggest a barrierless excited-state isomerization in the short chain cyanine dye. Additionally, ultrafast ground-state hole and excited-state hole replica broadening is observed. While the narrow excited-state wavepacket broadens during pump-probe overlap, the ground-state hole burning dynamics takes place on a significantly longer time-scale. The experiment reported can be considered as a direct monitoring of the shape and the position of the photoprepared wavepacket on the excited-state potential energy surface.

  15. Probing ground and low-lying excited states for HIO{sub 2} isomers

    SciTech Connect

    Souza, Gabriel L. C. de; Brown, Alex

    2014-12-21

    We present a computational study on HIO{sub 2} molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10{sup −3})

  16. Probing ground and low-lying excited states for HIO2 isomers.

    PubMed

    de Souza, Gabriel L C; Brown, Alex

    2014-12-21

    We present a computational study on HIO2 molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10(-3)).

  17. Probing ground and low-lying excited states for HIO2 isomers

    NASA Astrophysics Data System (ADS)

    de Souza, Gabriel L. C.; Brown, Alex

    2014-12-01

    We present a computational study on HIO2 molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10-3).

  18. Neutron star structure and collective excitations of finite nuclei

    NASA Astrophysics Data System (ADS)

    Paar, N.; Moustakidis, Ch. C.; Marketin, T.; Vretenar, D.; Lalazissis, G. A.

    2014-07-01

    A method is introduced that establishes relations between properties of collective excitations in finite nuclei and the phase transition density nt and pressure Pt at the inner edge separating the liquid core and the solid crust of a neutron star. A theoretical framework that includes the thermodynamic method, relativistic nuclear energy density functionals, and the quasiparticle random-phase approximation is employed in a self-consistent calculation of (nt,Pt) and collective excitations in nuclei. Covariance analysis shows that properties of charge-exchange dipole transitions, isovector giant dipole and quadrupole resonances, and pygmy dipole transitions are correlated with the core-crust transition density and pressure. A set of relativistic nuclear energy density functionals, characterized by systematic variation of the density dependence of the symmetry energy of nuclear matter, is used to constrain possible values for (nt,Pt). By comparing the calculated excitation energies of giant resonances, energy-weighted pygmy dipole strength, and dipole polarizability with available data, we obtain the weighted average values: nt=0.0955±0.0007 fm-3 and Pt=0.59±0.05 MeV fm-3. This approach crucially depends on experimental results for collective excitations in nuclei and, therefore, accurate measurements are necessary to further constrain the structure of the crust of neutron stars.

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

    SciTech Connect

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

    2014-05-14

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

  20. Quartic force fields for excited electronic states: rovibronic reference data for the 1 (2)A' and 1 (2)A″ states of the isoformyl radical, HOC.

    PubMed

    Morgan, W James; Fortenberry, Ryan C

    2015-01-25

    Quartic force fields (QFFs) have been shown to be an effective, accurate, and relatively compact means of computing rovibrational spectroscopic data for numerous molecules with numerous applications. However, excited states have been nearly excluded from the this approach since most accurate QFFs are based on the "gold standard" coupled cluster singles, doubles, and perturbative triples [CCSD(T)] method which is not readily extended to excited states. In this work, rovibronic spectroscopic data is provided for the isoformyl radical, a molecule of significance in combustion and astrochemistry, both through the traditional means of variational access to excited states with CCSD(T) and in the novel extension of QFFs routinely to treat electronically excited states through the standard coupled cluster excited state approach, equation of motion (EOM) CCSD. It is shown here that the new EOM-based QFF provides structural parameters and rotational constants that are quite close to those from a related CCSD(T)-based QFF for the 1 (2)A(″) excited state of HOC. The anharmonic vibrational frequency percent differences between the two QFFs are less than 0.4% for the O-H stretch, less than 1.9% for the C-O stretch, and around 3.0% for the bend. Even so, the pure excited state EOM-QFF anharmonic frequencies are still very good abinitio representations that may be applied to systems where electronically excited states are not variationally accessible. Additionally, rovibrational spectroscopic data is provided for the 1 (2)A(') ground state of HOC and for both the ground and excited state of DOC.

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

    SciTech Connect

    Kaptan, Y. Herzog, B.; Schöps, O.; Kolarczik, M.; Woggon, U.; Owschimikow, N.; Röhm, A.; Lingnau, B.; Lüdge, K.; Schmeckebier, H.; Arsenijević, D.; Bimberg, D.; Mikhelashvili, V.; Eisenstein, G.

    2014-11-10

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

  2. Microwave Spectroscopy of the Excited Vibrational States of Methanol

    NASA Astrophysics Data System (ADS)

    Pearson, John; Daly, Adam M.; Bermúdez, Celina

    2015-06-01

    Methanol is the simplest molecule with a three-fold internal rotation and the observation of its νb{8} band served the primary catalyst for the development of internal rotation theory(a,b). The 75 subsequent years of investigation into the νb{8} band region have yielded a large number assignments, numerous high precision energy levels and a great deal of insight into the coupling of νb{t}=3 & 4 with νb{8}, νb{7}, νb{11} and other nearby states(c). In spite of this progress numerous assignment mysteries persist, the origin of almost half the far infrared laser lines remain unknown and all attempts to model the region quantum mechanically have had very limited success. The C3V internal rotation Hamiltonian has successfully modeled the νb{t}=0,1 & 2 states of methanol and other internal rotors(d). However, successful modeling of the coupling between torsional bath states and excited small amplitude motion remains problematic and coupling of multiple interacting excited small amplitude vibrations featuring large amplitude motions remains almost completely unexplored. Before such modeling can be attempted, identifying the remaining low lying levels of νb{7} and νb{11} is necessary. We present an investigation into the microwave spectrum of νb{7}, νb{8} and νb{11} along with the underlying torsional bath states in νb{t}=3 and νb{t}= 4. (a) A. Borden, E.F. Barker J. Chem. Phys., 6, 553 (1938). (b) J. S. Koehler and D. M. Dennison, Phys. Rev. 57, 1006 (1940). (c) R. M. Lees, Li-Hong Xu, J. W. C. Johns, B. P. Winnewisser, and M. Lock, J. Mol. Spectrosc. 243, 168 (2007). (d) L.-H. Xu, J. Fisher, R.M. Lees, H.Y. Shi, J.T. Hougen, J.C. Pearson, B.J. Drouin, G.A. Blake, R. Braakman J. Mol. Spectrosc., 251, 305 (2008).

  3. Coherence, Energy and Charge Transfers in De-Excitation Pathways of Electronic Excited State of Biomolecules in Photosynthesis

    NASA Astrophysics Data System (ADS)

    Bohr, Henrik G.; Malik, F. Bary

    2013-11-01

    The observed multiple de-excitation pathways of photo-absorbed electronic excited state in the peridinin-chlorophyll complex, involving both energy and charge transfers among its constituents, are analyzed using the bio-Auger (B-A) theory. It is also shown that the usually used Förster-Dexter theory, which does not allow for charge transfer, is a special case of B-A theory. The latter could, under appropriate circumstances, lead to excimers.

  4. Excitation energy dependence of excited states dynamics in all- trans-carotenes determined by femtosecond absorption and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Kosumi, Daisuke; Yanagi, Kazuhiro; Nishio, Tomohiro; Hashimoto, Hideki; Yoshizawa, Masayuki

    2005-06-01

    Ultrafast relaxation kinetics in β-carotene and lycopene has been investigated by femtosecond absorption and fluorescence spectroscopies using tunable excitation pulses. The transient signals induced by the photoexcitation with larger excess energy have broader bands and longer lifetimes both in the 11Bu+and21Ag- excited states. The excess vibrational energy remains longer than several picoseconds and slows the relaxation kinetics in carotenoids.

  5. Red and blue shift of liquid water's excited states: A many body perturbation study

    NASA Astrophysics Data System (ADS)

    Ziaei, Vafa; Bredow, Thomas

    2016-08-01

    In the present paper, accurate optical absorption spectrum of liquid H2O is calculated in the energy range of 5-20 eV to probe the nature of water's excited states by means of many body perturbation approach. Main features of recent inelastic X-ray measurements are well reproduced, such as a bound excitonic peak at 7.9 eV with a shoulder at 9.4 eV as well as the absorption maximum at 13.9 eV, followed by a broad shoulder at 18.4 eV. The spectrum is dominated by excitonic effects impacting the structures of the spectrum at low and higher energy regimes mixed by single particle effects at high energies. The exciton distribution of the low-energy states, in particular of S1, is highly anisotropic and localized mostly on one water molecule. The S1 state is essentially a HOCO-LUCO (highest occupied crystal orbital - lowest unoccupied crystal orbital) transition and of intra-molecular type, showing a localized valence character. Once the excitation energy is increased, a significant change in the character of the electronically excited states occurs, characterized through emergence of multiple quasi-particle peaks at 7.9 eV in the quasi-particle (QP) transition profile and in the occurring delocalized exciton density distribution, spread over many more water molecules. The exciton delocalization following a change of the character of excited states at around 7.9 eV causes the blue shift of the first absorption band with respect to water monomer S1. However, due to reduction of the electronic band gap from gas to liquid phase, following enhanced screening upon condensation, the localized S1 state of liquid water is red-shifted with respect to S1 state of water monomer. For higher excitations, near vertical ionization energy (11 eV), quasi-free electrons emerge, in agreement with the conduction band electron picture. Furthermore, the occurring red and blue shift of the excited states are independent of the coupling of resonant and anti-resonant contributions to the

  6. Hedgehog excitations in double-exchange magnetism: Energetics and electronic structure

    NASA Astrophysics Data System (ADS)

    Pekker, David; Goldbart, Paul; Salamon, Myron; Abanov, Alexander

    2004-03-01

    Topological hedgehog excitations of the magnetic state are believed to play an important role in the three-dimensional ferromagnet-to-paramagnet phase transition. This is true not only in Heisenberg magnets but also in double-exchange magnets, for which the transition is accompanied by a metal-insulator transition. The energetics and electronic structure of hedgehog excitations in double-exchange systems are investigated using a model in which the electrons move through a lattice of classical spins, to which they are coupled via Hund's Rule interactions. The core energy of hedgehog excitations is determined, as is the extent to which charge is expelled from the hedgehog cores. In settings involving pairs of hedgehogs, the manner in which the electronic energetics determines the magnetic structure is explored variationally, especially in the region between the hedgehogs.

  7. Modal parameter extraction from large operating structures using ambient excitation

    SciTech Connect

    James, G.H. III; Carne, T.G.; Mayes, R.L.

    1995-12-31

    A technique called the Natural Excitation Technique or has been developed to response extract response parameters from large operational structure when subjected to random and unmeasured forces such as wind, road noise, aerodynamics, or waves. Six applications of NExT to ambient excitation testing and NExT analysis are surveyed in this paper with a minimum of technical detail. In the first application, NExT was applied to a controlled-yaw Horizontal-Axis Wind Turbine (HAWT). By controlling the yaw degree of freedom an important class of rotating coordinate system effects are reduced. A new shape extraction procedure was applied to this data set with good results. The second application was to a free-yaw HAWT. The complexity of the response has prompted further analytical studies and the development of a specialized visualization package. The third application of NExT was to a parked three-bladed Vertical-Axis Wind Turbine (VAWT) in which traditional modal testing could not excite all modes of interest. The shape extraction process used cross-correlation functions directly in a time-domain shape-fitting routine. The fourth application was to ground transportation systems. Ongoing work to improve driver and passenger comfort in tractor-trailer vehicles and to refine automobile body and tire models will use NExT. NExT has been used to process ambient vibration data for Finite Element Model correlation and is being used to study Structural Health Monitoring with ambient excitation. Shape fitting was performed using amplitude and phase information taken directly from the cross-spectra. The final application is to an offshore structure. This work is on-going, however initial studies have found a high-modal density, high noise content, and sparse data set.

  8. Nature of the open state in long polynucleotide double helices: possibility of soliton excitations.

    PubMed Central

    Englander, S W; Kallenbach, N R; Heeger, A J; Krumhansl, J A; Litwin, S

    1980-01-01

    The existence of transiently open states in DNA and synthetic polynucleotide double helices has been demonstrated by hydrogen exchange measurements; base pairs reversibly separate and reclose, exposing nucleotide protons to exchange with solvent protons. Recently it has been possible to define the equilibrium, kinetic, and activation parameters of the major open state that determines base pair hydrogen exchange. However, there is no direct information at the moment about the conformation of the open form. Here we consider the possibility that the low energy and slow opening and closing rates observed reflect a deformation involving several adjacent base pairs. Assuming a mobile open unit capable of diffusing along the double helix, we find that available data are consistent with structures of 10 or so adjacent open pairs. It is further suggested that these structures correspond to thermally induced soliton excitations of the double helix, which retain coherence by sharing the energy of a twist deformation among several base pairs. Solitons are nonlinear excitations that can travel as coherent solitary waves, and have been recognized as an important mechanism for mediating conformational changes in polymers and condensed systems generally. Comparison of the double helix with simple mechanical analogs suggests that soliton excitations may well exist within DNA chains, and the present analysis shows that the hydrogen exchange open state is consistent with these. PMID:6938969

  9. Peak earthquake response of structures under multi-component excitations

    NASA Astrophysics Data System (ADS)

    Song, Jianwei; Liang, Zach; Chu, Yi-Lun; Lee, George C.

    2007-12-01

    Accurate estimation of the peak seismic responses of structures is important in earthquake resistant design. The internal force distributions and the seismic responses of structures are quite complex, since ground motions are multi-directional. One key issue is the uncertainty of the incident angle between the directions of ground motion and the reference axes of the structure. Different assumed seismic incidences can result in different peak values within the scope of design spectrum analysis for a given structure and earthquake ground motion record combination. Using time history analysis to determine the maximum structural responses excited by a given earthquake record requires repetitive calculations to determine the critical incident angle. This paper presents a transformation approach for relatively accurate and rapid determination of the maximum peak responses of a linear structure subjected to three-dimensional excitations within all possible seismic incident angles. The responses can be deformations, internal forces, strains and so on. An irregular building structure model is established using SAP2000 program. Several typical earthquake records and an artificial white noise are applied to the structure model to illustrate the variation of the maximum structural responses for different incident angles. Numerical results show that for many structural parameters, the variation can be greater than 100%. This method can be directly applied to time history analysis of structures using existing computer software to determine the peak responses without carrying out the analyses for all possible incident angles. It can also be used to verify and/or modify aseismic designs by using response spectrum analysis.

  10. Characterization of adsorption and electronic excited states of quercetin on titanium dioxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Zdyb, Agata; Krawczyk, Stanisław

    2016-03-01

    Adsorption of quercetin on colloidal titanium dioxide nanoparticles in ethanol and its excited-state electronic structure were investigated by means of electronic and vibrational spectroscopies. The changes in electronic charge redistribution as reflected by the dipole moment difference, ∆μ, between the ground and excited electronic states were measured with electroabsorption spectroscopy and analyzed using results of TD DFT computations. Adsorption of quercetin causes a red shift of its absorption spectrum. Raman spectra of quercetin analyzed with reference to analogous data for morin indicate binding of quercetin through the hydroxy groups of the catechol moiety. The difference dipole moment, which is 5.5 D in free quercetin, increases to 11.8 D in opposite direction in adsorbed quercetin, and is associated with charge-transfer to the Ti atom. The computed transition energy, intensity, vector Δμ and molecular orbitals involved in the electronic transition at different molecular configurations indicate a bidentate chelating mode of binding of quercetin.

  11. The repopulation of electronic states upon vibrational excitation of niobium carbide clusters

    NASA Astrophysics Data System (ADS)

    Chernyy, V.; Logemann, R.; Bakker, J. M.; Kirilyuk, A.

    2016-07-01

    We study the infrared (IR) resonant heating of neutral niobium carbide clusters probed through ultraviolet photoionization spectroscopy. The IR excitation not only changes the photoionization spectra for the photon energies above the ionization threshold, but also modulates ion yield for energies significantly below it. An attempt to describe the experimental spectra using either Fowler's theory or thermally populated vibrational states was not successful. However, the data can be fully modeled by vibrationally and rotationally broadened discrete electronic levels obtained from Density Functional Theory (DFT) calculations. The application of this method to spectra with different IR pulse energies not only yields information about the excited electronic states in the vicinity of the HOMO level, populated by manipulation of the vibrational coordinates of a cluster, but also can serve as an extra indicator for the cluster isomeric structure and corresponding DFT-calculated electronic levels.

  12. Excited state electron transfer after visible light absorption by the Co(I) state of vitamin B12.

    PubMed

    Achey, Darren; Brigham, Erinn C; DiMarco, Brian N; Meyer, Gerald J

    2014-11-11

    The first example of excited state electron transfer from cob(I)alamin is reported herein. Vitamin B12 was anchored to a mesoporous TiO2 thin film and electrochemically reduced to the cob(I)alamin form. Pulsed laser excitation resulted in rapid excited state electron transfer, ket > 10(8) s(-1), followed by microsecond interfacial charge recombination to re-form cob(I)alamin. The supernucleophilic cob(I)alamin was found to be a potent photoreductant. The yield of excited state electron transfer was found to be excitation wavelength dependent. The implications of this dependence are discussed.

  13. Ultrafast branching in the excited state of coumarin and umbelliferone.

    PubMed

    Krauter, Caroline M; Möhring, Jens; Buckup, Tiago; Pernpointner, Markus; Motzkus, Marcus

    2013-11-07

    In the present work we have explored the ultrafast relaxation network of coumarin and umbelliferone (7-hydroxy-coumarin) using time-resolved femtosecond spectroscopy and quantum chemical calculations. Despite the importance of the photophysical properties of coumarin derivatives for applications in biomedicine, the low fluorescence quantum yield of coumarin itself has not been fully understood so far. On the basis of our combined experimental and theoretical results we suggest a model for the ultrafast decay after photoexcitation incorporating two parallel radiationless relaxation pathways: one within the initially excited state via ring opening and the other one by transition into a dark state along the carbonyl stretching mode. The fluorescence quantum yield is determined by the position of the branching point relative to the Franck-Condon region which is strongly influenced by interactions with the environment and the substitution pattern. This model is finally capable of giving a comprehensive account of the striking differences observed in the photophysical behavior of coumarin as opposed to umbelliferone.

  14. Orbitally Excited States of Quarkonia in a Nonrelativistic Model

    NASA Astrophysics Data System (ADS)

    Bhaghyesh; Vijaya Kumar, K. B.; Ma, Yong-Liang

    Having succeeded in predicting the S wave spectra and decays of cbar {c} and bbar {b} mesons, Bhaghyesh, K. B. Vijaya Kumar and A. P. Monteiro, J. Phys. G: Nucl. Part. Phys. 38, 085001 (2011), in this article, we apply our nonrelativistic quark model to calculate the spectra and decays of the orbitally excited states (P- and D-waves) of heavy quarkonia. The full Qbar {Q} potential used in our model consists of a Hulthen potential and a confining linear potential. The spin hyperfine, spin-orbit and tensor interactions are introduced to obtain the masses of the P- and D-wave states. The three-dimensional harmonic oscillator wave function is employed as a trial wave function to obtain the mass spectra. The model parameters and the wave function that reproduce the mass spectra of cbar {c} and bbar {b} mesons are used to investigate their decay properties. The two-photon decay widths, two-gluon decay widths and E1 radiative decay widths are calculated. The obtained values are compared with the experimental results and those obtained from other theoretical models.

  15. Photoactivated excited states of DNA repair photolyase: Dynamical and semiempircal identification

    NASA Astrophysics Data System (ADS)

    Zheng, Xuehe; Ly, Ngan M.; Stuchebrukhov, Alexei A.

    DNA damage caused by UV light radiation is often naturally repaired in a process initiated by excited state electron transfer from the photoactivated photolyase enzyme to the DNA cyclobutane pyrimidine dimer lesion. The active cofactor in the excited state electron transfer in the photolyase is the two-electron fully reduced form of the flavin adenine dinucleotide (FADH-). To calculate electron tunneling matrix element and model the DNA binding with photolyase, the LUMO of the FADH- calculated using extended Huckel method was previously chosen from the SCF wavefunctions. Recently, the DNA-photolyase complex was crystallized in its bound form, in good agreement with our previous model in even minute details at the active site. Here we carry out molecular dynamics simulation of the entire complex using the new experimental structure of Anacystis nidulans and identify the low-lying photoactivated states of the enzyme for the dynamical confirmations. Our results from ZINDO/S CIS calculations are compared with experimental UV spectra, and their implications for excited state electron transfer and energy transfer are discussed.0

  16. Excited-state singlet manifold and oscillatory features of a nonatetraeniminium retinal chromophore model.

    PubMed

    Cembran, Alessandro; Bernardi, Fernando; Olivucci, Massimo; Garavelli, Marco

    2003-10-15

    In this paper we use ab initio multireference Møller-Plesset second-order perturbation theory computations to map the first five singlet states (S(0), S(1), S(2), S(3), and S(4)) along the initial part of the photoisomerization coordinate for the isolated rhodopsin chromophore model 4-cis-gamma-methylnona-2,4,6,8-tetraeniminium cation. We show that this information not only provides an explanation for the spectral features associated to the chromophore in solution but also, subject to a tentative hypothesis on the effect of the protein cavity, may be employed to explain/assign the ultrafast near-IR excited-state absorption, stimulated emission, and transient excited-state absorption bands observed in rhodopsin proteins (e.g. rhodopsin and bacteriorhodopsin). We also show that the results of vibrational frequency computations reveal a general structure for the first (S(1)) excited-state energy surface of PSBs that is consistent with the existence of the coherent oscillatory motions observed both in solution and in bacteriorhodopsin.

  17. Excited-state symmetry breaking of linear quadrupolar chromophores: A transient absorption study

    NASA Astrophysics Data System (ADS)

    Dozova, Nadia; Ventelon, Lionel; Clermont, Guillaume; Blanchard-Desce, Mireille; Plaza, Pascal

    2016-11-01

    The photophysical properties of two highly symmetrical quadrupolar chromophores were studied by both steady-state and transient absorption spectroscopy. Their excited-state behavior is dominated by the solvent-induced Stokes shift of the stimulated-emission band. The origin of this shift is attributed to symmetry breaking that confers a non-vanishing dipole moment to the excited state of both compounds. This dipole moment is large and constant in DMSO, whereas symmetry breaking appears significantly slower and leading to smaller excited-state dipole in toluene. Time-dependant increase of the excited-state dipole moment induced by weak solvation is proposed to explain the results in toluene.

  18. Photophysical behavior of doubly bridged d7-d7 metal-metal bonded compounds - The crystal structure and the excited- and ground-state electronic spectra of Re2(CO)6(dmpm)2 (dmpm = bis/dimethylphosphino/ methane)

    NASA Technical Reports Server (NTRS)

    Milder, Steven J.; Castellani, Michael P.; Weakley, Timothy J. R.; Tyler, David R.; Miskowski, Vincent M.; Stiegman, A. E.

    1990-01-01

    Re2(CO)6(dmpm)2 shows photophysical behavior in a rigid medium that differs dramatically from that observed in fluid solution. In a hydrocarbon glass at 77 K, metal-metal bond homolysis is suppressed and an intense phosphorescence is observed. The transient absorption spectrum, which shows only weak transitions to the red of the ground state 1(sigma-sigma asterisk) transition, permits assignment of the emitting state to a 3(sigma-sigma asterisk) transition. The crystal structure of Re2(CO)6(dmpm)2 is also reported. The ground-state electronic structure is discussed relative to the structural data.

  19. Photophysical behavior of doubly bridged d7-d7 metal-metal bonded compounds - The crystal structure and the excited- and ground-state electronic spectra of Re2(CO)6(dmpm)2 (dmpm = bis/dimethylphosphino/ methane)

    NASA Technical Reports Server (NTRS)

    Milder, Steven J.; Castellani, Michael P.; Weakley, Timothy J. R.; Tyler, David R.; Miskowski, Vincent M.; Stiegman, A. E.

    1990-01-01

    Re2(CO)6(dmpm)2 shows photophysical behavior in a rigid medium that differs dramatically from that observed in fluid solution. In a hydrocarbon glass at 77 K, metal-metal bond homolysis is suppressed and an intense phosphorescence is observed. The transient absorption spectrum, which shows only weak transitions to the red of the ground state 1(sigma-sigma asterisk) transition, permits assignment of the emitting state to a 3(sigma-sigma asterisk) transition. The crystal structure of Re2(CO)6(dmpm)2 is also reported. The ground-state electronic structure is discussed relative to the structural data.

  20. Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy.

    PubMed

    Lockard, Jenny V; Rachford, Aaron A; Smolentsev, Grigory; Stickrath, Andrew B; Wang, Xianghuai; Zhang, Xiaoyi; Atenkoffer, Klaus; Jennings, Guy; Soldatov, Alexander; Rheingold, Arnold L; Castellano, Felix N; Chen, Lin X

    2010-12-09

    The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ-(t)Bu(2)pz)](2) (ppy = 2-phenylpyridine; (t)Bu(2)pz = 3,5-di-tert-butylpyrazolate) is studied by X-ray transient absorption (XTA) spectroscopy to reveal the transient electronic and nuclear geometry. DFT calculations predict that the lowest energy triplet excited state, assigned to a metal-metal-to-ligand charge transfer (MMLCT) transition, has a contraction in the Pt-Pt distance. The Pt-Pt bond length and other structural parameters extracted from fitting the experimental XTA difference spectra from full multiple scattering (FMS) and multidimensional interpolation calculations indicates a metal-metal distance decrease by approximately 0.2 Å in the triplet excited state. The advantages and challenges of this approach in resolving dynamic transient structures of nonbonding or weak-bonding dinuclear metal complexes in solution are discussed.

  1. Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

    DTIC Science & Technology

    2016-06-03

    provide interpretation of absorption spectra with respect to molecular structure for excitation by electromagnetic waves at frequencies within the...IR and UV-visible ranges. The absorption spectrum corresponding to excitation states of As-H2O complexes consisting of relatively small numbers of...As emphasized previously [17], the absorption spectrum of H2O clusters should be of significance for interpretation of absorption spectra

  2. Calculation of excited-state properties using general coupled-cluster and configuration-interaction models.

    PubMed

    Kállay, Mihály; Gauss, Jürgen

    2004-11-15

    Using string-based algorithms excitation energies and analytic first derivatives for excited states have been implemented for general coupled-cluster (CC) models within CC linear-response (LR) theory which is equivalent to the equation-of-motion (EOM) CC approach for these quantities. Transition moments between the ground and excited states are also considered in the framework of linear-response theory. The presented procedures are applicable to both single-reference-type and multireference-type CC wave functions independently of the excitation manifold constituting the cluster operator and the space in which the effective Hamiltonian is diagonalized. The performance of different LR-CC/EOM-CC and configuration-interaction approaches for excited states is compared. The effect of higher excitations on excited-state properties is demonstrated in benchmark calculations for NH(2) and NH(3). As a first application, the stationary points of the S(1) surface of acetylene are characterized by high-accuracy calculations.

  3. Analytic energy gradient of excited electronic state within TDDFT/MMpol framework: Benchmark tests and parallel implementation

    SciTech Connect

    Zeng, Qiao; Liang, WanZhen

    2015-10-07

    The time-dependent density functional theory (TDDFT) has become the most popular method to calculate the electronic excitation energies, describe the excited-state properties, and perform the excited-state geometric optimization of medium and large-size molecules due to the implementation of analytic excited-state energy gradient and Hessian in many electronic structure software packages. To describe the molecules in condensed phase, one usually adopts the computationally efficient hybrid Quantum Mechanics/Molecular Mechanics (QM/MM) models. Here, we extend our previous work on the energy gradient of TDDFT/MM excited state to account for the mutual polarization effects between QM and MM regions, which is believed to hold a crucial position in the potential energy surface of molecular systems when the photoexcitation-induced charge rearrangement in the QM region is drastic. The implementation of a simple polarizable TDDFT/MM (TDDFT/MMpol) model in Q-Chem/CHARMM interface with both the linear response and the state-specific features has been realized. Several benchmark tests and preliminary applications are exhibited to confirm our implementation and assess the effects of different treatment of environmental polarization on the excited-state properties, and the efficiency of parallel implementation is demonstrated as well.

  4. Exploring ground states and excited states of spin-1 Bose-Einstein condensates by continuation methods

    SciTech Connect

    Chen, Jen-Hao; Chern, I-Liang; Wang Weichung

    2011-03-20

    A pseudo-arclength continuation method (PACM) is employed to compute the ground state and excited state solutions of spin-1 Bose-Einstein condensates (BEC). The BEC is governed by the time-independent coupled Gross-Pitaevskii equations (GPE) under the conservations of the mass and magnetization. The coupling constants that characterize the spin-independent and spin-exchange interactions are chosen as the continuation parameters. The continuation curve starts from a ground state or an excited state with very small coupling parameters. The proposed numerical schemes allow us to investigate the effect of the coupling constants and study the bifurcation diagrams of the time-independent coupled GPE. Numerical results on the wave functions and their corresponding energies of spin-1 BEC with repulsive/attractive and ferromagnetic/antiferromagnetic interactions are presented. Furthermore, we reveal that the component separation and population transfer between the different hyperfine states can only occur in excited states due to the spin-exchange interactions.

  5. Resonance Raman and photoluminescence excitation profiles and excited-state dynamics in CdSe nanocrystals

    NASA Astrophysics Data System (ADS)

    Baker, Joshua A.; Kelley, David F.; Kelley, Anne Myers

    2013-07-01

    Resonance Raman excitation profiles for the longitudinal optical (LO) phonon fundamental and its first overtone have been measured for organic ligand capped, wurtzite form CdSe nanocrystals of ˜3.2 nm diameter dissolved in chloroform. The absolute differential Raman cross-section for the fundamental is much larger when excited at 532 or 543 nm, on the high-frequency side of the lowest-wavelength absorption maximum, than for excitation in the 458-476 nm range although the absorbance is higher at the shorter wavelengths. That is, the quantum yield for resonance Raman scattering is reduced for higher-energy excitation. In contrast, the photoluminescence quantum yield is relatively constant with wavelength. The optical absorption spectrum and the resonance Raman excitation profiles and depolarization dispersion curves are reproduced with a model for the energies, oscillator strengths, electron-phonon couplings, and dephasing rates of the multiple low-lying electronic excitations. The Huang-Rhys factor for LO phonon in the lowest excitonic transition is found to lie in the range S = 0.04-0.14. The strong, broad absorption feature about 0.5 eV above the lowest excitonic peak, typically labeled as the 1P3/21Pe transition, is shown to consist of at least two significant components that vary greatly in the magnitude of their electron-phonon coupling.

  6. Nature of the lowest excited states of neutral polyenyl radicals and polyene radical cations

    NASA Astrophysics Data System (ADS)

    Starcke, Jan Hendrik; Wormit, Michael; Dreuw, Andreas

    2009-10-01

    Due to the close relation of the polyenyl radicals C2n+1H2n+3• and polyene radical cations C2nH2n+2•+ to the neutral linear polyenes, one may suspect their excited states to possess substantial double excitation character, similar to the famous S1 state of neutral polyenes and thus to be equally problematic for simple excited state theories. Using the recently developed unrestricted algebraic-diagrammatic construction scheme of second order perturbation theory and the equation-of-motion coupled-cluster method, the vertical excitation energies, their corresponding oscillator strengths, and the nature of the wave functions of the lowest excited electronic states of the radicals are calculated and analyzed in detail. For the polyenyl radicals two one-photon allowed states are found as D1 and D4 states, with two symmetry-forbidden D2 and D3 states in between, while in the polyene radical cations D1 and D2 are allowed and D3 is forbidden. The order of the states is conserved with increasing chain length. It is found that all low-lying excited states exhibit a significant but similar amount of doubly excited configuration in their wave functions of 15%-20%. Using extrapolation, predictions for the excitation energies of the five lowest excited states of the polyene radical cations are made for longer chain lengths.

  7. TDDFT study on the excited-state proton transfer of 8-hydroxyquinoline: key role of the excited-state hydrogen-bond strengthening.

    PubMed

    Lan, Sheng-Cheng; Liu, Yu-Hui

    2015-03-15

    Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations have been employed to study the excited-state intramolecular proton transfer (ESIPT) reaction of 8-hydroxyquinoline (8HQ). Infrared spectra of 8HQ in both the ground and the lowest singlet excited states have been calculated, revealing a red-shift of the hydroxyl group (-OH) stretching band in the excited state. Hence, the intramolecular hydrogen bond (O-H···N) in 8HQ would be significantly strengthened upon photo-excitation to the S1 state. As the intramolecular proton-transfer reaction occurs through hydrogen bonding, the ESIPT reaction of 8HQ is effectively facilitated by strengthening of the electronic excited-state hydrogen bond (O-H···N). As a result, the intramolecular proton-transfer reaction would occur on an ultrafast timescale with a negligible barrier in the calculated potential energy curve for the ESIPT reaction. Therefore, although the intramolecular proton-transfer reaction is not favorable in the ground state, the ESIPT process is feasible in the excited state. Finally, we have identified that radiationless deactivation via internal conversion (IC) becomes the main dissipative channel for 8HQ by analyzing the energy gaps between the S1 and S0 states for the enol and keto forms.

  8. On the population of triplet excited states of 6-aza-2-thiothymine.

    PubMed

    Gobbo, João Paulo; Borin, Antonio Carlos

    2013-07-11

    The mechanisms of population of the lowest excited triplet states of 6-aza-2-thiothymine were investigated by means of CASPT2//CASSCF quantum-chemical calculations, with extensive atomic natural orbital basis sets of double-ζ quality (ANO-L-VDZP). Several key structures corresponding to equilibrium geometries, surface crossings, minimum energy paths, and linear interpolation in internal coordinates were used to explain the ability to sensitize molecular oxygen. After population of the S2(1)(ππ*) state, the system evolves to the state minimum. At this point, and along the minimum energy path of the (1)(ππ*) state, two main mechanisms related to the triplet and singlet manifolds can be visualized, leading the system to the lowest triplet state, T1(3)(ππ*).

  9. State-to-state chemistry and rotational excitation of CH+ in photon-dominated regions

    NASA Astrophysics Data System (ADS)

    Faure, A.; Halvick, P.; Stoecklin, T.; Honvault, P.; Epée Epée, M. D.; Mezei, J. Zs.; Motapon, O.; Schneider, I. F.; Tennyson, J.; Roncero, O.; Bulut, N.; Zanchet, A.

    2017-07-01

    We present a detailed theoretical study of the rotational excitation of CH+ due to reactive and non-reactive collisions involving C+(2P), H2, CH+, H and free electrons. Specifically, the formation of CH+ proceeds through the reaction between C+(2P) and H_2(ν _H_2 = 1, 2), while the collisional (de)excitation and destruction of CH+ is due to collisions with hydrogen atoms and free electrons. State-to-state and initial-state-specific rate coefficients are computed in the kinetic temperature range 10-3000 K for the inelastic, exchange, abstraction and dissociative recombination processes using accurate potential energy surfaces and the best scattering methods. Good agreement, within a factor of 2, is found between the experimental and theoretical thermal rate coefficients, except for the reaction of CH+ with H atoms at kinetic temperatures below 50 K. The full set of collisional and chemical data are then implemented in a radiative transfer model. Our non-LTE calculations confirm that the formation pumping due to vibrationally excited H2 has a substantial effect on the excitation of CH+ in photon-dominated regions. In addition, we are able to reproduce, within error bars, the far-infrared observations of CH+ towards the Orion Bar and the planetary nebula NGC 7027. Our results further suggest that the population of ν _H_2 = 2 might be significant in the photon-dominated region of NGC 7027.

  10. Electronic spectra and excited state dynamics of pentafluorophenol: Effects of low-lying πσ∗ states

    NASA Astrophysics Data System (ADS)

    Karmakar, Shreetama; Mukhopadhyay, Deb Pratim; Chakraborty, Tapas

    2015-05-01

    Multiple fluorine atom substitution effect on photophysics of an aromatic chromophore has been investigated using phenol as the reference system. It has been noticed that the discrete vibronic structure of the S1←S0 absorption system of phenol vapor is completely washed out for pentafluorophenol (PFP), and the latter also shows very large Stokes shift in the fluorescence spectrum. For excitations beyond S1 origin, the emission yield of PFP is reduced sharply with increase in excess vibronic energy. However, in a collisional environment like liquid hydrocarbon, the underlying dynamical process that drives the non-radiative decay is hindered drastically. Electronic structure theory predicts a number of low-lying dark electronic states of πσ∗ character in the vicinity of the lowest valence ππ∗ state of this molecule. Tentatively, we have attributed the excitation energy dependent non-radiative decay of the molecule observed only in the gas phase to an interplay between the lowest ππ∗ and a nearby dissociative πσ∗ state. Measurements in different liquids reveal that some of the dark excited states light up with appreciable intensity only in protic liquids like methanol