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Sample records for excited state model

  1. 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.

  2. 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.

  3. 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.

  4. Excited-state polarizabilities of solvated molecules using cubic response theory and the polarizable continuum model

    NASA Astrophysics Data System (ADS)

    Ferrighi, Lara; Frediani, Luca; Ruud, Kenneth

    2010-01-01

    The theory and an implementation of the solvent contribution to the cubic response function for the polarizable continuum model for multiconfigurational self-consistent field wave functions is presented. The excited-state polarizability of benzene, para-nitroaniline, and nitrobenzene has been obtained from the double residue of the cubic response function calculated in the presence of an acetonitrile and dioxane solvent. The calculated excited-state polarizabilities are compared to results obtained from the linear response function of the explicitly optimized excited states.

  5. Entropy, chaos, and excited-state quantum phase transitions in the Dicke model.

    PubMed

    Lóbez, C M; Relaño, A

    2016-07-01

    We study nonequilibrium processes in an isolated quantum system-the Dicke model-focusing on the role played by the transition from integrability to chaos and the presence of excited-state quantum phase transitions. We show that both diagonal and entanglement entropies are abruptly increased by the onset of chaos. Also, this increase ends in both cases just after the system crosses the critical energy of the excited-state quantum phase transition. The link between entropy production, the development of chaos, and the excited-state quantum phase transition is more clear for the entanglement entropy.

  6. Modeling the Excited States of Biological Chromophores within Many-Body Green's Function Theory.

    PubMed

    Ma, Yuchen; Rohlfing, Michael; Molteni, Carla

    2010-01-12

    First-principle many-body Green's function theory (MBGFT) has been successfully used to describe electronic excitations in many materials, from bulk crystals to nanoparticles. Here we assess its performance for the calculations of the excited states of biological chromophores. MBGFT is based on a set of Green's function equations, whose key ingredients are the electron's self-energy Σ, which is obtained by Hedin's GW approach, and the electron-hole interaction, which is described by the Bethe-Salpeter equation (BSE). The GW approach and the BSE predict orbital energies and excitation energies with high accuracy, respectively. We have calculated the low-lying excited states of a series of model biological chromophores, related to the photoactive yellow protein (PYP), rhodopsin, and the green fluorescent protein (GFP), obtaining a very good agreement with the available experimental and accurate theoretical data; the order of the excited states is also correctly predicted. MBGFT bridges the gap between time-dependent density functional theory and high-level quantum chemistry methods, combining the efficiency of the former with the accuracy of the latter: this makes MBGFT a promising method for studying excitations in complex biological systems.

  7. Excited state absorption in glasses activated with rare earth ions: Experiment and modeling

    NASA Astrophysics Data System (ADS)

    Piatkowski, Dawid; Mackowski, Sebastian

    2012-10-01

    We present semiempirical approach based on the Judd-Ofelt theory and apply it for modeling the spectral properties of fluoride glasses activated with the rare earth (RE) ions. This method provide a powerful tool for simulating both ground state absorption (GSA) and excited state absorption (ESA) spectra of RE ions, e.g. Nd3+, Ho3+, Er3+ and Tm3+ in the ZBLAN glass matrix. The results of theoretical calculations correspond to the experimentally measured data. We also demonstrate that the spectra obtained using the presented approach are applicable in the analysis of up-conversion excitation schemes in these optoelectronically relevant materials.

  8. Modeling the doubly excited state with time-dependent Hartree-Fock and density functional theories

    NASA Astrophysics Data System (ADS)

    Isborn, Christine M.; Li, Xiaosong

    2008-11-01

    Multielectron excited states have become a hot topic in many cutting-edge research fields, such as the photophysics of polyenes and in the possibility of multiexciton generation in quantum dots for the purpose of increasing solar cell efficiency. However, obtaining multielectron excited states has been a major obstacle as it is often done with multiconfigurational methods, which involve formidable computational cost for large systems. Although they are computationally much cheaper than multiconfigurational wave function based methods, linear response adiabatic time-dependent Hartree-Fock (TDHF) and density functional theory (TDDFT) are generally considered incapable of obtaining multielectron excited states. We have developed a real-time TDHF and adiabatic TDDFT approach that is beyond the perturbative regime. We show that TDHF/TDDFT is able to simultaneously excite two electrons from the ground state to the doubly excited state and that the real-time TDHF/TDDFT implicitly includes double excitation within a superposition state. We also present a multireference linear response theory to show that the real-time electron density response corresponds to a superposition of perturbative linear responses of the S0 and S2 states. As a result, the energy of the two-electron doubly excited state can be obtained with several different approaches. This is done within the adiabatic approximation of TDDFT, a realm in which the doubly excited state has been deemed missing. We report results on simple two-electron systems, including the energies and dipole moments for the two-electron excited states of H2 and HeH+. These results are compared to those obtained with the full configuration interaction method.

  9. Efficient Deactivation of a Model Base Pair via Excited-State Hydrogen Transfer

    NASA Astrophysics Data System (ADS)

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

    2004-12-01

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

  10. A Model of Electronically-Excited States of N_2 and its Extreme-Ultraviolet Spectrum.

    NASA Astrophysics Data System (ADS)

    Heays, A. N.; Lewis, B. R.; Gibson, S. T.

    2013-06-01

    The nitrogen molecule is a long-studied and difficult problem in molecular spectroscopy, and many important details of its interaction with radiation remain unexplained. A principal problem of continuing interest concerns the resonant photoabsorption and resultant predissociation of N_2 when exposed to extreme-ultraviolet radiation. A model of the relevant excited states of N_2 has been developed in order to quantify their interactions and reproduce photoabsorption and photodissociation cross sections between 100 000 and 118 500 cm^{-1} (100 and 84 nm). This solves the radial Schrödinger equation within a coupled-channels formulation for new diabatic potential-energy curves, homogeneous and heterogeneous state mixing, and electronic transition moments for the optically allowed transitions. The accidental predissociation of {}^1Π_u states between 100 000 and 112 500 cm^{-1} has been quantitatively modelled by spin-orbit coupling these to a set of {}^3Π_u and {}^3Σ_u^+ states which includes unbound members. Following reference to a large experimental database, the model is both accurate and comprehensive and may be used to simulate synthetic cross sections for any temperature or isotopologue. These are suitable for use in high-resolution photochemical models of atmospheric and astrophysical environments.

  11. Low-lying excited states in armchair polyacene within Pariser-Parr-Pople model: A density matrix renormalization group study

    SciTech Connect

    Das, Mousumi

    2014-03-28

    We studied the nature of the ground state and low-lying excited states of armchair polyacene oligomers (Polyphenanthrene) within long-range Pariser-Parr-Pople model Hamiltonian with up to 14 monomers using symmetrized density matrix renormalization group technique. The ground state of all armchair polyacenes studied is found to be singlet. The results show that lowest singlet dipole allowed excited state has higher energy for armchair polyacenes as compared to linear fused polyacenes. Moreover, unlike linear fused polyacenes, the lowest singlet excited state of these oligomers is always found to lie below the lowest dipole forbidden two-photon state indicating that these armchair polyacene oligomers strongly fluoresce. The calculations of low-lying excitations on singly and triply electron doped armchair polyacene oligomers show a low energy band with strong transition dipole moment that coupled to charge conductivity. This implies armchair polyacene posses novel field-effect transistor properties.

  12. The electronic excited states of a model organic endoperoxide: A comparison of TD-DFT and ab initio methods

    NASA Astrophysics Data System (ADS)

    Corral, Inés; González, Leticia

    2007-10-01

    The vertical excited spectrum of a model endoperoxide (cyclohexadieneendoperoxide) has been calculated using time dependent density functional theory (TD-DFT), resolution of the identity second order approximate coupled-cluster theory (RI-CC2), multiconfigurational complete active space self consistent field (CASSCF) and second order multi-state perturbation theory (MS-CASPT2). All theoretical methods predict the charge transfer πOO∗→πCC∗, and the πOO∗→σOO∗ excitation to be the lowest absorbing excited states. CASSCF optimized geometries for these states provide some hints about the photodissociation mechanisms as well as the emission spectrum of the molecule.

  13. Numerical Study of Excited States in the Shastry-Sutherland Model

    NASA Astrophysics Data System (ADS)

    Munehisa, Tomo; Munehisa, Yasuko

    2003-01-01

    We investigate excited states of the Shastry-Sutherland model using a kind of variational method. Starting from various trial states which include one or two triplet dimers, we numerically pursue the best evaluation of the energy for each set of quantum numbers. We present the energy difference as a function of either the coupling ratio or the momentum and compare them with the perturbative calculations. Our data suggest that the helical order phase exists between the singlet dimer phase and the magnetically ordered phase. In comparison with the experimental data we can estimate the intra-dimer coupling J and the inter-dimer coupling J' for SrCu2(BO3)2: J'/J=0.65 and J=87 K.

  14. Excited state distribution of reflected hydrogen atoms at metal surfaces - Development of theoretical models

    NASA Astrophysics Data System (ADS)

    Kato, D.; Kenmotsu, T.; Ohya, K.; Tanabe, T.

    2009-06-01

    Numerical methods were developed to study single electron capture by translating hydrogen atoms above metal surfaces. The present method gives predictions for hitherto unknown population distribution of excited species in hydrogen atoms reflected at the metal surfaces. The excited state abundance was calculated for Mo surface. Kinetic energy distribution of the reflected atoms was taken into account with the aid of the Monte-Carlo simulation code (ACAT). Energy distribution associated with the 3d 2 excited state in reflected neutrals consistently explains peak energy variation with incident energies of Doppler-shifted D α lines measured by Tanabe et al. Occupation probability of the magnetic sub-levels is obtained to be highly polarized. It suggests strong anisotropy in angular distribution of photon emission from the excited states created via the surface electron capture.

  15. Analytic model for low energy excitation states and phase transitions in spin-ice systems

    NASA Astrophysics Data System (ADS)

    López-Bara, F. I.; López-Aguilar, F.

    2017-04-01

    Low energy excitation states in magnetic structures of the so-called spin-ices are produced via spin flips among contiguous tetrahedra of their crystal structure. These spin flips generate entities which mimic magnetic dipoles in every two tetrahedra according to the dumbbell model. When the temperature increases, the spin-flip processes are transmitted in the lattice, generating so-called Dirac strings, which constitute structural entities that can present mimetic behavior similar to that of magnetic monopoles. In recent studies of both specific heat and ac magnetic susceptibility, two (even possibly three) phases have been shown to vary the temperature. The first of these phases presents a sharp peak in the specific heat and another phase transition occurs for increasing temperature whose peak is broader than that of the former phase. The sharp peak occurs when there are no free individual magnetic charges and temperature of the second phase transition coincides with the maximum proliferation of free deconfined magnetic charges. In the present paper, we propose a model for analyzing the low energy excitation many-body states of these spin-ice systems. We give analytical formulas for the internal energy, specific heat, entropy and their temperature evolution. We study the description of the possible global states via the nature and structure of their one-body components by means of the thermodynamic functions. Below 0.37 K, the Coulomb-like magnetic charge interaction can generate a phase transition to a condensation of pole–antipole pairs, possibly having Bose–Einstein structure which is responsible for the sharp peak of the first phase transition. When there are sufficient free positive and negative charges, the system tends to behave as a magnetic plasma, which implies the broader peak in the specific heat appearing at higher temperature than the sharper experimental peak.

  16. 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.

  17. Excited-state quantum phase transitions in the two-spin elliptic Gaudin model.

    PubMed

    Relaño, Armando; Esebbag, Carlos; Dukelsky, Jorge

    2016-11-01

    We study the integrability of the two-spin elliptic Gaudin model for arbitrary values of the Hamiltonian parameters. The limit of a very large spin coupled to a small one is well described by a semiclassical approximation with just one degree of freedom. Its spectrum is divided into bands that do not overlap if certain conditions are fulfilled. In spite of the fact that there are no quantum phase transitions in each of the band heads, the bands show excited-state quantum phase transitions separating a region in which the parity symmetry is broken from another region in which time-reversal symmetry is broken. We derive analytical expressions for the critical energies in the semiclassical approximation, and confirm the results by means of exact diagonalizations for large systems.

  18. Conductor-like screening model for relaxed excited states: Implementation in the semiempirical method MSINDO.

    PubMed

    Krause, Katharina; Bredow, Thomas

    2014-03-15

    Two approaches to treat solvent polarization and reorientation effects for excited states of molecules and surfaces have been implemented in the recently developed MSINDO-sCIS method (Gadaczek, Krause, Hintze, Bredow, J. Chem. Theory Comput. 2011, 7, 3675). They allow for an efficient calculation of analytical energy gradients and hence open the opportunity to investigate fluorescence effects or photochemical reactions in solution for large molecules that are difficult to treat with high-level methods. Both approaches are based on the conductor-like screening model (COSMO) (Klamt and Schüürmann, J. Chem. Soc., Perkin Trans. 1993, 2, 799) in combination with the configuration interaction singles (CIS) method (Foresman, Head-Gordon, Pople, and Frisch, J. Phys. Chem. 1992, 96, 135). The paper gives a brief outline of the theoretical background. As a first application, solvent shifts of three well-studied, environment-sensitive fluorescent dyes (Kucherak, Didier, Mély, and Klymchenko, J. Phys. Chem. Lett. 2010, 1, 616) have been calculated and compared with experimental results and standard time-dependent density functional theory. A statistical evaluation of MSINDO-COSMO-sCIS is provided for a set of 39 molecules suggested recently by Jacquemin et al. (Jacquemin, Planchat, Adamo, and Mennucci, J. Chem. Theory Comput. 2012, 8, 2359). Calculated vertical and adiabatic excitation energies and fluorescence energies are compared to experimental data.

  19. 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.

  20. Decay widths of ground-state and excited {Xi}{sub b} baryons in a nonrelativistic quark model

    SciTech Connect

    Limphirat, Ayut; Kobdaj, Chinorat; Suebka, Prasart; Yan, Yupeng

    2010-11-15

    Decay processes of ground and excited bottom baryons are studied in the {sup 3}P{sub 0} nonrelativistic quark model with all model parameters fixed in the sector of light quarks. Using as an input the recent mass of {Xi}{sub b} and the theoretical masses of {Xi}{sub b}{sup *} and {Xi}{sub b}{sup '}, narrow decay widths are predicted for the ground-state bottom baryons {Xi}{sub b}{sup *} and {Xi}{sub b}{sup '}. The work predicts large decay widths, about 100 MeV for the {rho}-type orbital excitation states of {Xi}{sub b}.

  1. 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.

  2. 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.

  3. Model-free measurement of the excited-state fraction in a 85Rb magneto-optical trap

    NASA Astrophysics Data System (ADS)

    Veshapidze, G.; Bang, J.-Y.; Fehrenbach, C. W.; Nguyen, H.; DePaola, B. D.

    2015-05-01

    In many experiments involving magneto-optical traps (MOTs), it is imperative to know the fraction of atoms left in an excited state by the cooling and trapping lasers. In most cases, researchers have used formulas that were derived for simple two-level systems interacting with a single beam of light having a well-defined polarization, and in the absence of magnetic or electric fields. However, a MOT environment is much more complex than this. Here we directly measure the excited fraction in a MOT of 85Rb atoms in a model-independent manner for a wide range of trapping conditions. We then fit our measured fractions to an ansatz based on a simple model. Knowing only the trapping laser's total intensity and detuning from resonance, one can then use this ansatz to accurately predict the excited fraction. The work is a companion piece to similar measurements on a MOT of 87Rb.

  4. Uniform Treatment of Solute-Solvent Dispersion in the Ground and Excited Electronic States of the Solute Based on a Solvation Model with State-Specific Polarizability.

    PubMed

    Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

    2013-08-13

    We present a new kind of treatment of the solute-solvent dispersion contribution to the free energy of solvation using a solvation model with state-specific polarizability (SMSSP). To evaluate the solute-solvent dispersion contribution, the SMSSP model utilizes only two descriptors, namely, the spherically averaged dipole polarizability of the solute molecule (either in its ground or excited electronic state) and the refractive index of the solvent. The model was parametrized over 643 ground-state solvation free energy data for 231 solutes in 14 nonpolar, non-hydrogen-bonding solvents. We show that the SMSSP model is applicable to solutes in both the ground and the excited electronic state. For example, in comparison to available experimental data, the model yields qualitatively accurate predictions of the solvatochromic shifts for a number of systems where solute-solvent dispersion is the dominant contributor to the shift.

  5. Hydrogen-bonding modulation of excited-state properties of flavins in a model of aqueous confined environment.

    PubMed

    Valle, Lorena; Vieyra, Faustino E Morán; Borsarelli, Claudio D

    2012-06-01

    The singlet and triplet excited states properties of lumiflavin (LF), riboflavin (RF), flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD) in reversed micelles (RM) of sodium docusate (AOT) in n-hexane solutions were evaluated as a function of the water to surfactant molar ratio, w(0) = [H(2)O]/[AOT], by both steady-state and time-resolved absorption and fluorescence spectroscopy. The results indicated that hydrogen-bonding interactions between the isoalloxazine ring of the flavins with the water molecules of the micellar interior play a crucial role on the modulation of the excited state properties of the flavins. Fluorescence dynamic experiments in the RM, allowed the calculation of similar values for both the internal rotational time of the flavins (θ(i)) and the hydrogen-bonding relaxation time (τ(HB)), e.g.≈ 7 and 1.5 ns at w(0) = 1 and 20, respectively. In turn, the triplet state lifetimes of the flavins were also enlarged in RM solutions at low w(0), without modifications of their quantum yields. A hydrogen bonding relaxation model is proposed to explain the singlet excited state properties of the flavins, while the changes of the triplet state decays of the flavins were related with the global composition and strength of the hydrogen bonding network inside of the RM.

  6. 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.

  7. Low-Scaling Quantum Chemistry Approach to Excited-State Properties via an ab Initio Exciton Model: Application to Excitation Energy Transfer in a Self-Assembled Nanotube.

    PubMed

    Morrison, Adrian F; Herbert, John M

    2015-11-05

    We introduce a charge-embedding scheme for an excited-state quantum chemistry method aimed at weakly interacting molecular aggregates. The Hamiltonian matrix for the aggregate is constructed in a basis of direct products of configuration-state functions for the monomers, and diagonalization of this matrix affords excitation energies within ∼0.2 eV of the corresponding supersystem calculation. Both the basis states and the coupling matrix elements can be computed in a distributed way, resulting in an algorithm whose time-to-solution is independent of the number of chromophores, and we report calculations on systems with almost 55 000 basis functions using fewer than 450 processors. In a semiconducting organic nanotube, we find evidence of ultrafast, coherent dynamics followed by energy localization driven by static disorder. Truncation of the model system has a qualitative effect on the energy-transfer dynamics, demonstrating the importance of simulating an extended portion of the nanotube, which is not feasible using traditional quantum chemistry.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  10. Bound state - excitation in ion-ion collisions related to X-ray lasers modelling

    SciTech Connect

    Stancalie, V.; Sureau, A.; Klisnick, A.

    1995-12-31

    As in the earlier work of Walling and Weisheit we used the Seaton`s semi-classical, impact parameter formulation of Coulomb excitation for a variety of inelastic ion-ion collisions, involved in laser-produced soft X-ray lasers with Li-like aluminum ions, 1s{sup 2} nl configuration. Energy levels has been calculated by direct SCF method including the spin-orbit interaction. Our definition of the electric 2{sup {lambda}} - pole line strength, S{sup {lambda}}, is consistent with that of Sobelman. The ion-ion collision processes have been considered for a wide range of temperature between 500 eV to 30 eV, with a particular interest in the last part of plasma evolution time, when complications such as non-Maxwellian particle distributions, radiation fields and transient plasma conditions can be neglected, and when the plasma electrons and ions have comparable temperatures.

  11. 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

  12. 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.

  13. Photonics of a conjugated organometallic Pt-Ir polymer and its model compounds exhibiting hybrid CT excited states.

    PubMed

    Soliman, Ahmed M; Fortin, Daniel; Zysman-Colman, Eli; Harvey, Pierre D

    2012-04-13

    Trans- dichlorobis(tri-n-butylphosphine)platinum(II) reacts with bis(2- phenylpyridinato)-(5,5'-diethynyl-2,2'-bipyridine)iridium(III) hexafluorophosphate to form the luminescent conjugated polymer poly[trans-[(5,5'-ethynyl-2,2'-bipyridine)bis(2- phenylpyridinato)-iridium(III)]bis(tri-n-butylphosphine)platinum(II)] hexafluorophosphate ([Pt]-[Ir])n. Gel permeation chromatography indicates a degree of polymerization of 9 inferring the presence of an oligomer. Comparison of the absorption and emission band positions and their temperature dependence, emission quantum yields, and lifetimes with those for models containing only the [Pt] or the [Ir] units indicates hybrid excited states including features from both chromophores.

  14. On the accuracy of the general, state-specific polarizable-continuum model for the description of correlated ground- and excited states in solution.

    PubMed

    Mewes, Jan-Michael; Herbert, John M; Dreuw, Andreas

    2017-01-04

    Equilibrium and non-equilibrium formulations of the state-specific polarizable-continuum model (SS-PCM) are evaluated in combination with correlated ground- and excited-state densities provided by the algebraic-diagrammatic construction method (ADC) for the polarization propagator via the computationally efficient intermediate-state representation (ISR) formalism. Since the influence of the SS-PCM onto quantum-chemical method is naturally limited to the presence of the apparent surface charges in the one-electron Hamiltonian and hence fully contained in the polarized MOs, the herein presented solvent model can be combined with all implemented orders and variants of ADC. Employing ADC/SS-PCM, the symmetric, ionized dimers of neon, ethene and nitromethane are investigated. Their broken-symmetry wavefunctions exhibit a low-lying charge-transfer state that is symmetry-equivalent to the ground state. This curious though ultimately artificial feature is convenient as it allows for a direct comparison of ADC/SS-PCM for the CT state to the Møller-Plesset/PCM description of the ground state. The agreement down to 0.02 eV for a wide range of dielectric constants validates the ADC/SS-PCM approach. Eventually, the relaxed potential-energy surfaces of the ground and lowest excited states of 4-(N,N)-dimethylaminobenzonitrile in cyclohexane and acetonitrile are computed, and it is demonstrated that the ADC(2)/SS-PCM approach affords excellent agreement with experimental fluorescence data. Only at the ADC(3) level of theory, however, the experimentally observed solvent-dependent dual fluorescence can be explained.

  15. 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.

  16. Excitation dynamics in Phycoerythrin 545: modeling of steady-state spectra and transient absorption with modified Redfield theory.

    PubMed

    Novoderezhkin, Vladimir I; Doust, Alexander B; Curutchet, Carles; Scholes, Gregory D; van Grondelle, Rienk

    2010-07-21

    We model the spectra and excitation dynamics in the phycobiliprotein antenna complex PE545 isolated from the unicellular photosynthetic cryptophyte algae Rhodomonas CS24. The excitonic couplings between the eight bilins are calculated using the CIS/6-31G method. The site energies are extracted from a simultaneous fit of the absorption, circular dichroism, fluorescence, and excitation anisotropy spectra together with the transient absorption kinetics using the modified Redfield approach. Quantitative fit of the data enables us to assign the eight exciton components of the spectra and build up the energy transfer picture including pathways and timescales of energy relaxation, thus allowing a visualization of excitation dynamics within the complex.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Exact ensemble density functional theory for excited states in a model system: Investigating the weight dependence of the correlation energy

    NASA Astrophysics Data System (ADS)

    Deur, Killian; Mazouin, Laurent; Fromager, Emmanuel

    2017-01-01

    Ensemble density functional theory (eDFT) is an exact time-independent alternative to time-dependent DFT (TD-DFT) for the calculation of excitation energies. Despite its formal simplicity and advantages in contrast to TD-DFT (multiple excitations, for example, can be easily taken into account in an ensemble), eDFT is not standard, which is essentially due to the lack of reliable approximate exchange-correlation (x c ) functionals for ensembles. Following Smith et al. [Phys. Rev. B 93, 245131 (2016), 10.1103/PhysRevB.93.245131], we propose in this work to construct an exact eDFT for the nontrivial asymmetric Hubbard dimer, thus providing more insight into the weight dependence of the ensemble x c energy in various correlation regimes. For that purpose, an exact analytical expression for the weight-dependent ensemble exchange energy has been derived. The complementary exact ensemble correlation energy has been computed by means of Legendre-Fenchel transforms. Interesting features like discontinuities in the ensemble x c potential in the strongly correlated limit have been rationalized by means of a generalized adiabatic connection formalism. Finally, functional-driven errors induced by ground-state density-functional approximations have been studied. In the strictly symmetric case or in the weakly correlated regime, combining ensemble exact exchange with ground-state correlation functionals gives better ensemble energies than when calculated with the ground-state exchange-correlation functional. However, when approaching the asymmetric equiensemble in the strongly correlated regime, the former approximation leads to highly curved ensemble energies with negative slope which is unphysical. Using both ground-state exchange and correlation functionals gives much better results in that case. In fact, exact ensemble energies are almost recovered in some density domains. The analysis of density-driven errors is left for future work.

  10. 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).

  11. Modeling excitable systems: Reentrant tachycardia

    NASA Astrophysics Data System (ADS)

    Lancaster, Jarrett L.; Hellen, Edward H.; Leise, Esther M.

    2010-01-01

    Excitable membranes are an important type of nonlinear dynamical system, and their study can be used to provide a connection between physical and biological circuits. We discuss two models of excitable membranes important in cardiac and neural tissues. One model is based on the Fitzhugh-Nagumo equations, and the other is based on a three-transistor excitable circuit. We construct a circuit that simulates reentrant tachycardia and its treatment by surgical ablation. This project is appropriate for advanced undergraduates as a laboratory capstone project or as a senior thesis or honors project and can also be a collaborative project, with one student responsible for the computational predictions and another for the circuit construction and measurements.

  12. 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.

  13. 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.

  14. 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.

  15. Mass spectra and decays of ground and orbitally excited cb¯ states in nonrelativistic quark model

    NASA Astrophysics Data System (ADS)

    Monteiro, Antony Prakash; Bhat, Manjunath; Vijaya Kumar, K. B.

    2017-02-01

    The complete spectrum of cb¯ states is obtained in a phenomenological nonrelativistic quark model (NRQM), which consists of a confinement potential and one gluon exchange potential (OGEP) as effective quark-antiquark potential. We make predictions for the radiative decay (E1 and M1) widths and weak decay widths of cb¯ states in the framework of NRQM formalism.

  16. 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.

  17. 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).

  18. 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.

  19. 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.

  20. Excitation Spectrum in the Friedberg-Lee Model

    NASA Astrophysics Data System (ADS)

    Kowata, H.; Arima, M.

    2001-03-01

    The excitation spectrum of a nucleon with spin 1/2 is examined using the Friedberg-Lee model containing constituent quarks and a scalar meson. An appropriate method of quantization for the non-linear meson field is employed by taking account of the non-topological soliton existing at the classical level. Our model space for the nucleon resonances includes the three quark plus one meson state, in addition to the pure three quark state. The excitation spectrum in this model space reveals that the positive parity state appears as the first excited state associated with the 0s-excitation of the scalar meson. The meson excitation also generates an additional negative parity state apart from the well-known 0p-excitation of the quark.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. Effects of low-lying excitations on ground-state energy and energy gap of the Sherrington-Kirkpatrick model in a transverse field

    NASA Astrophysics Data System (ADS)

    Koh, Yang Wei

    2016-04-01

    We present an extensive numerical study of the Sherrington-Kirkpatrick model in a transverse field. Recent numerical studies of quantum spin glasses have focused on exact diagonalization of the full Hamiltonian for small systems (≈20 spins). However, such exact numerical treatments are difficult to apply on larger systems. We propose making an approximation by using only a subspace of the full Hilbert space spanned by low-lying excitations consisting of one-spin-flipped and two-spin-flipped states. The approximation procedure is carried out within the theoretical framework of the Hartree-Fock approximation and configuration interaction. Although not exact, our approach allows us to study larger system sizes comparable to that achievable by state-of-the-art quantum Monte Carlo simulations. We calculate two quantities of interest due to recent advances in quantum annealing, the ground-state energy and the energy gap between the ground and first excited states. For the energy gap, we derive a formula that enables it to be calculated using just the ground-state wave function, thereby circumventing the need to diagonalize the Hamiltonian. We calculate the scalings of the energy gap and the leading correction to the extensive part of the ground-state energy with system size, which are difficult to obtain with current methods.

  7. 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.

  8. 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.

  9. An analysis of single-phase self-excited induction generators: Model development and steady-state calculations

    SciTech Connect

    Ojo, O.; Bhat, I.

    1995-06-01

    The need for alternative and renewable energy sources for utility and autonomous applications especially in remote places has focused attention on the use of electric generators connected to a source of mechanical power such as wind and minihydro turbines. In particular, induction and reluctance generators have great potential. The modeling and steady-state performance of single-phase induction generators based on the principles harmonic balance is set forth in this paper. Magnetizing flux linkage saturation and flux dependent core loss resistances are included. Experimental results are provided to justify analytical approach and steady-state calculations.

  10. 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.

  11. 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.

  12. 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}

  13. Excited Electronic and Vibrational State Decomposition of Energetic Materials and Model Systems on Both Nanosecond and Femtosecond Time Scales

    DTIC Science & Technology

    2014-07-22

    decomposition following electronic excitation, conical intersections, potential energy surfaces, mass spectrometry, laser induced fluorescense, laser ablation...products and their energy content and partition, and parent molecule potential energy surfaces and conical intersections. (a) Papers published in...through conical intersections, The Journal of Physical Chemistry A, (09 2011): 0. doi: 10.1021/jp109150u Zijun Yu, Elliot R. Bernstein

  14. Modeling Excited States in TiO2 Nanoparticles: On the Accuracy of a TD-DFT Based Description

    SciTech Connect

    Berardo, Enrico; Hu, Hanshi; Shevlin, S. A.; Woodley, Scott M.; Kowalski, Karol; Zwijnenburg, Martijn A.

    2014-03-11

    We have investigated the suitability of Time-Dependent Density Functional Theory (TD-DFT) to describe vertical low-energy excitations in naked and hydrated titanium dioxide nanoparticles through a comparison with results from Equation-of-Motion Coupled Cluster (EOM-CC) quantum chemistry methods. We demonstrate that for most TiO2 nanoparticles TD-DFT calculations with commonly used exchange-correlation (XC-)potentials (e.g. B3LYP) and EOM-CC methods give qualitatively similar results. Importantly, however, we also show that for an important subset of structures, TD-DFT gives qualitatively different results depending upon the XC-potential used and that in this case only TD-CAM-B3LYP and TD-BHLYP calculations yield results that are consistent with those obtained using EOM-CC theory. Moreover, we demonstrate that the discrepancies for such structures arise from a particular combination of defects, excitations involving which are charge-transfer excitations and hence are poorly described by XC-potentials that contain no or low fractions of Hartree-Fock like exchange. Finally, we discuss that such defects are readily healed in the presence of ubiquitously present water and that as a result the description of vertical low-energy excitations for hydrated TiO2 nanoparticles is hence non-problematic.

  15. 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.

  16. 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

  17. Ground and excited state proton transfer of the bioactive plant flavonol robinetin in a protein environment: spectroscopic and molecular modeling studies.

    PubMed

    Pahari, Biswa Pathik; Chaudhuri, Sudip; Chakraborty, Sandipan; Sengupta, Pradeep K

    2015-02-12

    We performed spectroscopic and molecular modeling studies to explore the interaction of the bioactive plant flavonol robinetin (3,7,3',4',5'-OH flavone), with the carrier protein human serum albumin (HSA). Multiparametric fluorescence sensing, exploiting the intrinsic "two color" fluorescence of robinetin (comprising excited state intramolecular proton transfer (ESIPT) and charge transfer (CT) emissions) reveals that binding to HSA significantly affects the emission and excitation profiles, with strongly blue-shifted (∼29 nm) normal fluorescence and remarkable increase in the ESIPT fluorescence anisotropy (r) and lifetime (τ). Flavonol-induced HSA (tryptophan) fluorescence quenching data yield the dynamic quenching constant (KD) as 5.42 × 10(3) M(-1) and the association constant (Ks) as 5.59 × 10(4) M(-1). Time-resolved fluorescence anisotropy decay studies show dramatic (∼170 times) increase in the rotational correlation time (τ(rot)), reflecting greatly enhanced restrictions in motion of robinetin in the protein matrix. Furthermore, prominent induced circular dichroism (ICD) bands appear, indicating that the chiral environment of HSA strongly perturbs the electronic transitions of the intrinsically achiral robinetin molecule. Molecular docking calculations suggest that robinetin binds in subdomain IIA of HSA, where specific interactions with basic residues promote ground state proton abstraction and stabilize an anionic species, which is consistent with spectroscopic observations.

  18. 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.

  19. Modeling Molecular Systems at Extreme Pressure by an Extension of the Polarizable Continuum Model (PCM) Based on the Symmetry-Adapted Cluster-Configuration Interaction (SAC-CI) Method: Confined Electronic Excited States of Furan as a Test Case.

    PubMed

    Fukuda, Ryoichi; Ehara, Masahiro; Cammi, Roberto

    2015-05-12

    Novel molecular photochemistry can be developed by combining high pressure and laser irradiation. For studying such high-pressure effects on the confined electronic ground and excited states, we extend the PCM (polarizable continuum model) SAC (symmetry-adapted cluster) and SAC-CI (SAC-configuration interaction) methods to the PCM-XP (extreme pressure) framework. By using the PCM-XP SAC/SAC-CI method, molecular systems in various electronic states can be confined by polarizable media in a smooth and flexible way. The PCM-XP SAC/SAC-CI method is applied to a furan (C4H4O) molecule in cyclohexane at high pressure (1-60 GPa). The relationship between the calculated free-energy and cavity volume can be approximately represented with the Murnaghan equation of state. The excitation energies of furan in cyclohexane show blueshifts with increasing pressure, and the extents of the blueshifts significantly depend on the character of the excitations. Particularly large confinement effects are found in the Rydberg states. The energy ordering of the lowest Rydberg and valence states alters under high-pressure. The pressure effects on the electronic structure may be classified into two contributions: a confinement of the molecular orbital and a suppression of the mixing between the valence and Rydberg configurations. The valence or Rydberg character in an excited state is, therefore, enhanced under high pressure.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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

  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. 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.

  8. 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

  9. 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).

  10. 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.

  11. 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.

  12. The small impact of various partial charge distributions in ground and excited state on the computational Stokes shift of 1-methyl-6-oxyquinolinium betaine in diverse water models

    NASA Astrophysics Data System (ADS)

    Heid, Esther; Harringer, Sophia; Schröder, Christian

    2016-10-01

    The influence of the partial charge distribution obtained from quantum mechanics of the solute 1-methyl-6-oxyquinolinium betaine in the ground- and first excited state on the time-dependent Stokes shift is studied via molecular dynamics computer simulation. Furthermore, the effect of the employed solvent model — here the non-polarizable SPC, TIP4P and TIP4P/2005 and the polarizable SWM4 water model — on the solvation dynamics of the system is investigated. The use of different functionals and calculation methods influences the partial charge distribution and the magnitude of the dipole moment of the solute, but not the orientation of the dipole moment. Simulations based on the calculated charge distributions show nearly the same relaxation behavior. Approximating the whole solute molecule by a dipole results in the same relaxation behavior, but lower solvation energies, indicating that the time scale of the Stokes shift does not depend on peculiarities of the solute. However, the SPC and TIP4P water models show too fast dynamics which can be ascribed to a too large diffusion coefficient and too low viscosity. The calculated diffusion coefficient and viscosity for the SWM4 and TIP4P/2005 models coincide well with experimental values and the corresponding relaxation behavior is comparable to experimental values. Furthermore we found that for a quantitative description of the Stokes shift of the applied system at least two solvation shells around the solute have to be taken into account.

  13. 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.

  14. Proton release from Stentor photoreceptors in the excited states.

    PubMed

    Song, P S; Walker, E B; Auerbach, R A; Robinson, G W

    1981-08-01

    Steady-state and picosecond pulse excitations of the photophobic-phototactic receptors isolated from Stentor coeruleus produced anionic species predominantly in the excited singlet state, although neutral photoreceptors in the ground state were exclusively excited. The same photoreceptor in vivo also emits fluorescence from the excited state of its anionic species, with an excitation spectrum identical to the absorption spectrum of the neutral species in the ground state. The excited state dissociation of protons from the photoreceptor chromophore (stentorin; hypericin covalently linked to protein) efficiently occurs in less than 10 ps. A possible role of the transient-proton release from the photoreceptor, in the signal transduction photoresponse of Stentor, is briefly discussed.

  15. 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.

  16. 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.

  17. The high overtone and combination levels of SF6 revisited at Doppler-limited resolution: A global effective rovibrational model for highly excited vibrational states

    NASA Astrophysics Data System (ADS)

    Faye, M.; Boudon, V.; Loëte, M.; Roy, P.; Manceron, L.

    2017-03-01

    Sulfur hexafluoride is an important prototypal molecule for modeling highly excited vibrational energy flow and multi quanta absorption processes in hexafluoride molecules of technological importance. It is also a strong greenhouse gas of anthropogenic origin. This heavy species, however, features many hot bands at room temperature (at which only 30% of the molecules lie in the ground vibrational state), especially those originating from the lowest, v6=1 vibrational state. Using a cryogenic long path cell with variable optical path length and temperatures regulated between 120 and 163 K, coupled to Synchrotron Radiation and a high resolution interferometer, Doppler-limited spectra of the 2ν1 +ν3 , ν1 +ν2 +ν3 , ν1 +ν3 , ν2 +ν3 , 3ν3, ν2 + 3ν3 and ν1 + 3ν3 from 2000 to 4000 cm-1 near-infrared region has been recorded. Low temperature was used to limit the presence of hot bands. The spectrum has been analyzed thanks to the XTDS software package. Combining with previously observed weak difference bands in the far infrared region involving the v1, v2, v3=1 states, we are thus able to use the tensorial model to build a global fit of spectroscopic parameters for v1=1,2, v2=1, v3=1,2,3. The model constitutes a consistent set of molecular parameters and enable spectral rovibrational simulation for all multi-quanta transitions involving v1, v2 and v3 up to v1-3 = 3 . Tests simulation on rovibrational transitions not yet rovibrationally assigned are presented and compared to new experimental data.

  18. Kinetic Model of Conduction Changes across Excitable Membranes*

    PubMed Central

    Jain, Mahendra K.; Marks, Richard H. L.; Cordes, E. H.

    1970-01-01

    A kinetic model describing conduction changes across excitable membranes is proposed. It assumes that a population of discrete membrane sites is distributed among several distinct functional states determined by the voltage across the membrane. Interconversion of these states is postulated to occur by first-order reactions. It provides a satisfactory description of the central aspects of excitable membrane behavior, including current-time and current-voltage relationships, action potential, and effects of inhibitors. PMID:5289023

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

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

    SciTech Connect

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

    2015-07-21

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

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

    PubMed

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

    2015-07-21

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

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. Nontrivial excited-state coherence due to two uncorrelated partially coherent fields

    NASA Astrophysics Data System (ADS)

    Sadeq, Z. S.

    2015-04-01

    We analyze a model where a closed V system is excited by two uncorrelated partially coherent fields. We use a collisionally broadened cw laser, which is a good model for an experimentally realizable partially coherent field, and show that it is possible to generate excited-state coherences even if the two fields are uncorrelated. This transient coherence can be increased if splitting between the excited states is reduced relative to the radiation coherence time τd. For small excited-state splitting, one can use this scheme to generate a long-lived coherent response in the system.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. THE PHOTOTOXOICITY OF POLYCYCLIC AROMATIC HYDROCARBONS: A THEORETICAL STUDY OF EXCITED STATES AND CORRELATION TO EXPERIMENT

    EPA Science Inventory



    Investigators using models to determine the phototoxic effects of sunlight on polycyclic aromatic hydrocarbons (PAHS) have invoked the excited states of the molecule as important in elucidating the mechanism of these reactions. Energies of actual excited states were calcu...

  12. Excited singlet-state absorption in laser dyes at the XeCl wavelength

    NASA Astrophysics Data System (ADS)

    Taylor, R. S.; Mihailov, S.

    1985-10-01

    The transmission properties of the laser dyes BBQ, PBD, BPBD, α-NPO, p-Quarterphenyl and PPO have been measured using a XeCl (308 nm) excimer laser. A model for the dye saturation which incorporates excited-state absorption was used to estimate the lifetime and the absorption cross section of the first excited singlet-state for each dye.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. The phototoxicity of polycyclic aromatic hydrocarbons: a theoretical study of excited states and correlation to experiment.

    PubMed

    Betowski, Leon D; Enlow, Mark; Riddick, Lee

    2002-06-01

    Investigators using models to determine the phototoxic effects of sunlight on polycyclic aromatic hydrocarbons (PAHs) have invoked the excited states of the molecule as important in elucidating the mechanism of these reactions. Energies of actual excited states were calculated for ten PAHs by several ab initio methods. The main method used for these calculations was the Configuration Interaction approach, modeling excited states as combinations of single substitutions out of the Hartree-Fock ground state. These calculations correlate well with both experimentally measured singlet and triplet state energies and also previous HOMO-LUMO gap energies that approximate the singlet state energies. The excited state calculations then correlate well with general models of photo-induced toxicity based for the PAHs.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Asymptotic properties of mathematical models of excitability.

    PubMed

    Biktasheva, I V; Simitev, R D; Suckley, R; Biktashev, V N

    2006-05-15

    We analyse small parameters in selected models of biological excitability, including Hodgkin-Huxley (Hodgkin & Huxley 1952 J. Physiol.117, 500-544) model of nerve axon, Noble (Noble 1962 J. Physiol.160, 317-352) model of heart Purkinje fibres and Courtemanche et al. (Courtemanche et al. 1998 Am. J. Physiol.275, H301-H321) model of human atrial cells. Some of the small parameters are responsible for differences in the characteristic time-scales of dynamic variables, as in the traditional singular perturbation approaches. Others appear in a way which makes the standard approaches inapplicable. We apply this analysis to study the behaviour of fronts of excitation waves in spatially extended cardiac models. Suppressing the excitability of the tissue leads to a decrease in the propagation speed, but only to a certain limit; further suppression blocks active propagation and leads to a passive diffusive spread of voltage. Such a dissipation may happen if a front propagates into a tissue recovering after a previous wave, e.g. re-entry. A dissipated front does not recover even when the excitability restores. This has no analogy in FitzHugh-Nagumo model and its variants, where fronts can stop and then start again. In two spatial dimensions, dissipation accounts for breakups and self-termination of re-entrant waves in excitable media with Courtemanche et al. kinetics.

  5. 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

  6. Superposition of Fragment Excitations for Excited States of Large Clusters with Application to Helium Clusters.

    PubMed

    Closser, Kristina D; Ge, Qinghui; Mao, Yuezhi; Shao, Yihan; Head-Gordon, Martin

    2015-12-08

    We develop a local excited-state method, based on the configuration interaction singles (CIS) wave function, for large atomic and molecular clusters. This method exploits the properties of absolutely localized molecular orbitals (ALMOs), which strictly limits the total number of excitations, and results in formal scaling with the third power of the system size for computing the full spectrum of ALMO-CIS excited states. The derivation of the equations and design of the algorithm are discussed in detail, with particular emphasis on the computational scaling. Clusters containing ∼500 atoms were used in evaluating the scaling, which agrees with the theoretical predictions, and the accuracy of the method is evaluated with respect to standard CIS. A pioneering application to the size dependence of the helium cluster spectrum is also presented for clusters of 25-231 atoms, the largest of which results in the computation of 2310 excited states per sampled cluster geometry.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Cross Sections for Electron-impact Excitation of Electronic States in Atoms and Molecules -Application Examples of the BEf-scaling model in Optically-allowed Transitions

    NASA Astrophysics Data System (ADS)

    Kato, Hidetoshi

    2012-10-01

    The differential cross section (DCS) and integral cross section (ICS) measurements of electron-impact electronic excitation for noble gases were reported by many groups. Unfortunately, despite all these endeavours, if we were to characterize the level of agreement between these studies, then we could only conclude that it remains ``patchy'' at best. Hence, we report measurements of DCS and ICS for electron-impact excitation of the lowest electronic states in noble gases (Ne, Ar, Kr and Xe), and compare with results from a scaled Born cross section (BEf-scaling). We have previously found for the He atom and a number of molecules, including H2, O2, CO, H2O, CO2, N2O and C6H6 that the BEf-scaling approach, for calculating ICSs for dipole-allowed electronic-state transitions, can lead to a very accurate description of the various scattering processes from threshold to 2000 eV [1]. Exceptions to this general statement have only been found in those cases where resonance effects due to the temporary capture of the incident electron by the target and contamination from an accidentally degenerate or near-degenerate triplet state have arisen. Our results for noble gases will be presented in detail at the conference.[4pt] [1] H. Kato et al., NIFS Research Report, NIFS-DATA-108, 1 (2009).

  12. From Model Hamiltonians to ab Initio Hamiltonians and Back Again: Using Single Excitation Quantum Chemistry Methods To Find Multiexciton States in Singlet Fission Materials.

    PubMed

    Mayhall, Nicholas J

    2016-09-13

    Due to the promise of significantly enhanced photovoltaic efficiencies, significant effort has been directed toward understanding and controlling the singlet fission mechanism. Although accurate quantum chemical calculations would provide a detail-rich view of the singlet fission mechanism, this is complicated by the multiexcitonic nature of one of the key intermediates, the (1)(TT) state. Being described as two simultaneous and singlet-coupled triplet excitations on a pair of nearest neighbor monomers, the (1)(TT) state is inherently a multielectronic excitation. This fact renders most single-reference ab initio quantum chemical methods incapable of providing accurate results. This paper serves two purposes: (1) to demonstrate that the multiexciton states in singlet fission materials can be described using a spin-only Hamiltonian and with each monomer treated as a biradical and (2) to propose a very simple procedure for extracting the values for this Hamiltonian from single-reference calculations. Numerical examples are included for a number of different systems, including dimers, trimers, tetramers, and a cluster comprised of seven chromophores.

  13. 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.

  14. 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.

  15. Methodological CASPT2 study of the valence excited states of an iron-porphyrin complex.

    PubMed

    Ben Amor, Nadia; Soupart, Adrien; Heitz, Marie-Catherine

    2017-02-01

    The singlet valence excited states of an iron-porphyrin-pyrazine-carbonyl complex are investigated up to the Soret band (about 3 eV) using multi-state complete active space with perturbation at the second order (MS-CASPT2). This complex is a model for the active site of carboxy-hemoglobin/myoglobin. The spectrum of the excited states is rather dense, comprising states of different nature: d→π* transitions, d→d states, π→π* excitations of the porphyrin, and doubly excited states involving simultaneous intra-porphyrin π→π* and d→d transitions. Specific features of the MS-CASPT2 method are investigated. The effect of varying the number of roots in the state average calculation is quantified as well as the consequence of targeted modifications of the active space. The effect of inclusion of standard ionization potential-electron affinity (IPEA) shift in the perturbation treatment is also investigated.

  16. On the nature of excited electronic states in cyanine dyes: implications for visual pigment spectra

    NASA Astrophysics Data System (ADS)

    Dinur, Uri; Honig, Barry; Schulten, Klaus

    1980-06-01

    CNDO/S CI calculations are carried out on polyenes and on cyanine dyes. In contrast to polyenes, doubly excited configurations have a strong effect on the first optically allowed excited state in cyanines. Protonated Schiff bases of retinal are closely related to cyanine dyes, with important consequences for models of visual pigment spectra and photochemistry.

  17. 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.

  18. 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.

  19. 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

  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. 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

  2. Excited state dynamics in photosynthetic reaction center and light harvesting complex 1

    NASA Astrophysics Data System (ADS)

    Strümpfer, Johan; Schulten, Klaus

    2012-08-01

    Key to efficient harvesting of sunlight in photosynthesis is the first energy conversion process in which electronic excitation establishes a trans-membrane charge gradient. This conversion is accomplished by the photosynthetic reaction center (RC) that is, in case of the purple photosynthetic bacterium Rhodobacter sphaeroides studied here, surrounded by light harvesting complex 1 (LH1). The RC employs six pigment molecules to initiate the conversion: four bacteriochlorophylls and two bacteriopheophytins. The excited states of these pigments interact very strongly and are simultaneously influenced by the surrounding thermal protein environment. Likewise, LH1 employs 32 bacteriochlorophylls influenced in their excited state dynamics by strong interaction between the pigments and by interaction with the protein environment. Modeling the excited state dynamics in the RC as well as in LH1 requires theoretical methods, which account for both pigment-pigment interaction and pigment-environment interaction. In the present study we describe the excitation dynamics within a RC and excitation transfer between light harvesting complex 1 (LH1) and RC, employing the hierarchical equation of motion method. For this purpose a set of model parameters that reproduce RC as well as LH1 spectra and observed oscillatory excitation dynamics in the RC is suggested. We find that the environment has a significant effect on LH1-RC excitation transfer and that excitation transfers incoherently between LH1 and RC.

  3. Interpretation of unusual absorption bandwidths and resonance Raman intensities in excited state mixed valence.

    PubMed

    Lockard, Jenny V; Valverde, Guadalupe; Neuhauser, Daniel; Zink, Jeffrey I; Luo, Yun; Weaver, Michael N; Nelsen, Stephen F

    2006-01-12

    Excited state mixed valence (ESMV) occurs in molecules in which the ground state has a symmetrical charge distribution but the excited state possesses two or more interchangeably equivalent sites that have different formal oxidation states. Although mixed valence excited states are relatively common in both organic and inorganic molecules, their properties have only recently been explored, primarily because their spectroscopic features are usually overlapped or obscured by other transitions in the molecule. The mixed valence excited state absorption bands of 2,3-di-p-anisyl-2,3-diazabicyclo[2.2.2]octane radical cation are well-separated from others in the absorption spectrum and are particularly well-suited for detailed analysis using the ESMV model. Excited state coupling splits the absorption band into two components. The lower energy component is broader and more intense than the higher energy component. The absorption bandwidths are caused by progressions in totally symmetric modes, and the difference in bandwidths is caused by the coordinate dependence of the excited state coupling. The Raman intensities obtained in resonance with the high and low energy components differ significantly from those expected based on the oscillator strengths of the bands. This unexpected observation is a result of the excited state coupling and is explained by both the averaging of the transition dipole moment orientation over all angles for the two types of spectroscopies and the coordinate-dependent coupling. The absorption spectrum is fit using a coupled two-state model in which both symmetric and asymmetric coordinates are included. The physical meaning of the observed resonance Raman intensity trends is discussed along with the origin of the coordinate-dependent coupling. The well-separated mixed valence excited state spectroscopic components enable detailed electronic and resonance Raman data to be obtained from which the model can be more fully developed and tested.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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).

  16. 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

  17. Communication: Momentum-resolved quantum interference in optically excited surface states.

    PubMed

    Chan, Wai-Lun; Tritsch, John; Dolocan, Andrei; Ligges, Manuel; Miaja-Avila, Luis; Zhu, X-Y

    2011-07-21

    Surface states play essential roles in condensed matter physics, e.g., as model two-dimensional (2D) electron gases and as the basis for topological insulators. Here, we demonstrate quantum interference in the optical excitation of 2D surface states using the model system of C(60)/Au(111). These surface states are transiently populated and probed in a femtosecond time- and angle-resolved two-photon photoemission experiment. We observe quantum interference within the excited populations of these surface states as a function of parallel momentum vector. Such quantum interference in momentum space may allow one to control 2D transport properties by optical fields.

  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. 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.

  20. 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.

  1. 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.

  2. 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."

  3. 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."

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Excited state properties of peridinin: Observation of a solvent dependence of the lowest excited singlet state lifetime and spectral behavior unique among carotenoids

    SciTech Connect

    Bautista, J.A.; Connors, R.E.; Raju, B.B.; Hiller, R.G.; Sharples, F.P.; Gosztola, D.; Wasielewski, M.R.; Frank, H.A.

    1999-10-14

    The spectroscopic properties and dynamic behavior of peridinin in several different solvents were studied by steady-state absorption, fluorescence, and transient optical spectroscopy. The lifetime of the lowest excited singlet state of peridinin is found to be strongly dependent on solvent polarity and ranges from 7 ps in the strongly polar solvent trifluoroethanol to 172 ps in the nonpolar solvents cyclohexane and benzene. The lifetimes show no obvious correlation with solvent polarizability, and hydrogen bonding of the solvent molecules to peridinin is not an important factor in determining the dynamic behavior of the lowest excited singlet state. The wavelengths of emission maxima, the quantum yields of fluorescence, and the transient absorption spectra are also affected by the solvent environment. A model consistent with the data and supported by preliminary semiempirical calculations invokes the presence of a charge transfer state in the excited state manifold of peridinin to account for the observations. The charge transfer state most probably results from the presence of the lactone ring in the {pi}-electron conjugation of peridinin analogous to previous findings on aminocoumarins and related compounds. The behavior of peridinin reported here is highly unusual for carotenoids, which generally show little dependence of the spectral properties and lifetimes of the lowest excited singlet state on the solvent environment.

  10. 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.

  11. 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.

  12. The Millimeter-Wave Spectrum of Methacrolein. Torsion-Rotation Effects in the Excited States

    NASA Astrophysics Data System (ADS)

    Zakharenko, Olena; Motiyenko, R. A.; Aviles Moreno, Juan-Ramon; Huet, T. R.

    2015-06-01

    Last year we reported the analysis of the rotational spectrum of s-trans conformer of methacrolein CH2=C(CH3)CHO in the ground vibrational state. In this talk we report the study of its low lying excited vibrational states. The study is based on room-temperature absorption spectra of methacrolein recorded in the frequency range 150 - 465 GHz using the spectrometer in Lille. The new results include assignment of the first excited torsional state (131 cm-1), and the joint analysis of the vt = 0 and vt = 1 states, that allowed us to improve the model in the frame of Rho-Axis-Method (RAM) Hamiltonian and to remove some strong correlations between parameters. Also we assigned the first excited vibrational state of the skeletal torsion mode (170 cm-1). The inverse sequence of A and E tunneling substates as well as anomalous A-E splittings observed for the rotational lines of vsk = 1 state clearly indicate a coupling between methyl torsion and skeletal torsion. However we were able to fit within experimental accuracy the rotational lines of vsk = 1 state using the RAM Hamiltonian. Because of the inversion of the A and E tunneling substates the rotational lines of the vsk = 1 states were assumed to belong to a virtual first excited torsional state. Finally, we assigned several low-Ka rotational transitions of the excited vibrational states above 200 cm-1 but their analysis is complicated by different rotation-vibration interactions. In particular there is an evidence of the Fermi-type resonance between the second excited torsional state and the first excited state of the in-plane skeletal bending mode (265 cm-1). Support from the French Laboratoire d'Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d'Investissements d'Avenir is acknowledged. Zakharenko O. et al., 69th ISMS, 2014, TI01

  13. 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.

  14. 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.

  15. Electron Impact Excitation of Xenon from the Ground State and the Metastable State to the 5p57p Levels

    NASA Astrophysics Data System (ADS)

    Chen, Zhan-Bin; Dong, Chen-Zhong; Xie, Lu-You; Jiang, Jun

    2014-03-01

    Electron impact excitation cross sections from the ground state and the lowest metastable state 5p56s J = 2 to the excited states of the 5p57p configuration of xenon are calculated systematically using the fully relativistic distorted wave method. Special attention is paid to the configuration interaction effects in the wave-function expansion of target states. The results are in good agreement with the recent experimental data by Jung et al. [Phys. Rev. A 80 (2009) 062708] over the measured energy range. These accurate theoretical results can be used in the modeling and diagnosis of plasmas containing xenon.

  16. Depopulation of highly excited singlet states of DNA model compounds: quantum yields of 193 and 245 nm photoproducts of pyrimidine monomers and dinucleoside monophosphates.

    PubMed

    Gurzadyan, G G; Görner, H

    1996-02-01

    Formation of uracil and orotic acid photodimers, uridine and 5'-UMP photohydrates, TpT photodimers and (6-4)photoproducts, dCpT photohydrates and (6-4)photoproducts and UpU, CpC and CpU photohydrates were studied in neutral deoxygenated aqueous solution at room temperature upon irradiation at either 193 or 254 nm. The photoproducts were identified and quantified and the contribution from photoionization to substrate decomposition, using lambda irr = 193 nm, was separated. The ratio of the quantum yields of respective stable products, eta = phi 193/phi 254, is indicative of the yield of internal conversion from the second to the first excited singlet state, S2-->S1. For the observed photodimers eta decreases from 0.94 for uracil to 0.7 for TpT and further to 0.55 for orotic acid. For the (6-4)photoproducts of TpT and dCpT eta = 0.5-0.8 and for the photohydrates in the cases of UpU, CpC, CpU and dCpT eta ranges from 0.55 to 1.

  17. A SPONTANEOUS STATE OF WEAKLY CORRELATED SYNAPTIC EXCITATION AND INHIBITION IN VISUAL CORTEX

    PubMed Central

    TAN, A. Y. Y.; ANDONI, S.; PRIEBE, N. J.

    2013-01-01

    Cortical spontaneous activity reflects an animal’s behavioral state and affects neural responses to sensory stimuli. The correlation between excitatory and inhibitory synaptic input to single neurons is a key parameter in models of cortical circuitry. Recent measurements demonstrated highly correlated synaptic excitation and inhibition during spontaneous “up-and-down” states, during which excitation accounted for approximately 80% of inhibitory variance (Shu et al., 2003; Haider et al., 2006). Here we report in vivo whole-cell estimates of the correlation between excitation and inhibition in the rat visual cortex under pentobarbital anesthesia, during which up-and-down states are absent. Excitation and inhibition are weakly correlated, relative to the up-and-down state: excitation accounts for less than 40% of inhibitory variance. Although these correlations are lower than when the circuit cycles between up-and-down states, both behaviors may arise from the same circuitry. Our observations provide evidence that different correlational patterns of excitation and inhibition underlie different cortical states. PMID:23727451

  18. 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.

  19. Quantum dimensions from local operator excitations in the Ising model

    NASA Astrophysics Data System (ADS)

    Caputa, Paweł; Rams, Marek M.

    2017-02-01

    We compare the time evolution of entanglement measures after local operator excitation in the critical Ising model with predictions from conformal field theory. For the spin operator and its descendants we find that Rényi entropies of a block of spins increase by a constant that matches the logarithm of the quantum dimension of the conformal family. However, for the energy operator we find a small constant contribution that differs from the conformal field theory answer equal to zero. We argue that the mismatch is caused by the subtleties in the identification between the local operators in conformal field theory and their lattice counterpart. Our results indicate that evolution of entanglement measures in locally excited states not only constraints this identification, but also can be used to extract non-trivial data about the conformal field theory that governs the critical point. We generalize our analysis to the Ising model away from the critical point, states with multiple local excitations, as well as the evolution of the relative entropy after local operator excitation and discuss universal features that emerge from numerics.

  20. 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}.

  1. 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).

  2. 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.

  3. Reactions of 5-methylcytosine cation radicals in DNA and model systems: thermal deprotonation from the 5-methyl group vs. excited state deprotonation from sugar

    PubMed Central

    Adhikary, Amitava; Kumar, Anil; Palmer, Brian J.; Todd, Andrew D.; Heizer, Alicia N.; Sevilla, Michael D.

    2014-01-01

    Purpose To study the formation and subsequent reactions of the 5-methyl-2′-deoxycytidine cation radical (5-Me-2′-dC•+) in nucleosides and DNA-oligomers and compare to one electron oxidized thymidine. Materials and methods Employing electron spin resonance (ESR), cation radical formation and its reactions were investigated in 5-Me-2′-dC, thymidine (Thd) and their derivatives, in fully double stranded (ds) d[GC*GC*GC*GC*]2 and in the 5-Me-C/A mismatched, d[GGAC*AAGC:CCTAATCG], where C* = 5-Me-C. Results We report 5-Me-2′-dC•+ production by one-electron oxidation of 5-Me-2′-dC by Cl2•− via annealing in the dark at 155 K. Progressive annealing of 5-Me-2′-dC•+ at 155 K produces the allylic radical (C-CH2•). However, photoexcitation of 5-Me-2′-dC•+ by 405 nm laser or by photoflood lamp leads to only C3′• formation. Photoexcitation of N3-deprotonated thyminyl radical in Thd and its 5′-nucleotides leads to C3′• formation but not in 3′-TMP which resulted in the allylic radical (U-CH2•) and C5′• production. For excited 5-Me-2′,3′-ddC•+, absence of the 3′-OH group does not prevent C3′• formation. For d[GC*GC*GC*GC*]2 and d[GGAC*AAGC:CCTAATCG], intra-base paired proton transferred form of G cation radical (G(N1-H)•:C(+H+)) is found with no observable 5-Me-2′-dC•+ formation. Photoexcitation of (G(N1-H)•:C(+H+)) in d[GC*GC*GC*GC*]2 produced only C1′• and not the expected photoproducts from 5-Me-2′-dC•+. However, photoexcitation of (G(N1-H)•:C(+H+)) in d[GGAC*AAGC:CCTAATCG] led to C5′• and C1′• formation. Conclusions C-CH2• formation from 5-Me-2′-dC•+ occurs via ground state deprotonation from C5-methyl group on the base. In the excited 5-Me-2′-dC•+ and 5-Me-2′,3′-ddC•+, spin and charge localization at C3′ followed by deprotonation leads to C3′• formation. Thus, deprotonation from C3′ in the excited cation radical is kinetically controlled and sugar C-H bond energies are

  4. 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.

  5. A numerical method to model excitable cells.

    PubMed Central

    Joyner, R W; Westerfield, M; Moore, J W; Stockbridge, N

    1978-01-01

    We have extended a fast, stable, and accurate method for the numerical solution of cable equations to include changes in geometry and membrane properties in order to model a single excitable cell realistically. In addition, by including the provision that the radius may be a function of distance along an axis, we have achieved a general and powerful method for simulating a cell with any number of branched processes, any or all of which may be nonuniform in diameter, and with no restriction on the branching pattern. PMID:656539

  6. Impacts on Air Quality due to Photosensitized Production of Excited State O2 (1Δg) by PAHs and Oxy-PAHs in the Lower Atmosphere: An Experimental and Computational Modeling Approach

    NASA Astrophysics Data System (ADS)

    Montoya, G. A.; Carreras-Sospedra, M.; Montoya, J.; Dabdub, D.; Foster, K. L.

    2014-12-01

    Complex reactions between hydroxyl radicals (OH) and volatile organic compounds (VOCs) in the lower atmosphere have a high impact on the formation/fates of airborne toxic chemicals, polycyclic aromatic hydrocarbons (PAHs), and particulate matter.1 Recently, air quality models have been implemented to identify OH sources, but have underpredicted OH concentrations. Studies suggest that O2 (1Δg) is produced via an energy transfer (ET) mechanism initiated by the electronic excitation of PAH and oxygenated-PAH. Energy transfer involves the formation of triplet excited state PAH which is then quenched by the surrounding ground state O2 (3∑g) resulting in excited state O2 (1Δg) formation. Excited state O2 (1Δg) is known to readily react with mono-olefins to produce organic hydroperoxides.2,3 Furthermore, the organic hydroperoxide can photodegrade to yield OH. In this study, a Nd:YAG laser coupled to a time-resolved near infrared detector was used to obtain quantum yields of O2 (1Δg) production by irradiating PAHs and oxy-PAHs at both 355 nm and 532 nm in different solvents. Select PAHs, primarily emitted by combustion engines (e.g. pyrene and benzo[a]pyrene), and their oxygenated forms (oxy-PAHs) have been identified as highly efficient O2 (1Δg) photosensitizers. For example, the measured quantum yield for pyrene in toluene was 0.90 ± 0.02. The measured quantum yields were used to calculate the photochemical rate constants for O2 (1Δg) production via ET from electronically excited PAHs and oxy-PAHs. These results were incorporated into the University of California, Irvine-California Institute of Technology (UCI-CIT) model to assess the impact on OH concentrations and the overall air quality of the South Coast Air Basin of California. References 1 Finlayson-Pitts, B.J., and J. N. Pitts (1997), Science, 276(5315),1045-1052. 2 Foote, C. S. (1968), Accts. Chem. Res., 1, 104-110; Gollnick, K. (1968), Adv. Photochem., 6, 1-112; Kearns, D. R. (1971), Chem. Rev., 71, 395

  7. Excited-state hydrogen atom transfer reaction in solvated 7-hydroxy-4-methylcoumarin.

    PubMed

    De Silva, Nuwan; Minezawa, Noriyuki; Gordon, Mark S

    2013-12-12

    Excited-state enol to keto tautomerization of 7-hydroxy-4-methylcoumarin (C456) with three water molecules (C456:3H2O), is theoretically investigated using time-dependent density functional theory (TDDFT) combined with the polarizable continuum model and 200 waters explicitly modeled with the effective fragment potential. The tautomerization of C456 in the presence of three water molecules is accompanied by an asynchronous quadruple hydrogen atom transfer reaction from the enol to the keto tautomer in the excited state. TDDFT with the PBE0 functional and the DH(d,p) basis set is used to calculate the excited-state reaction barrier height, absorption (excitation), and fluorescence (de-excitation) energies. These results are compared with the available experimental and theoretical data. In contrast to previous work, it is predicted here that the coumarin 456 system undergoes a hydrogen atom transfer, not a proton transfer. The calculated reaction barrier of the first excited state of C456:3H2O with 200 water molecules is found to be -0.23 kcal/mol without zero-point energy (-5.07 kcal/mol with zero point energy, i.e., the activation energy).

  8. 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

  9. 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.

  10. 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.

  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. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. Steady-state solutions of cell volume in a cardiac myocyte model elaborated for membrane excitation, ion homeostasis and Ca2+ dynamics.

    PubMed

    Cha, Chae Young; Noma, Akinori

    2012-08-21

    The cell volume continuously changes in response to varying physiological conditions, and mechanisms underlying volume regulation have been investigated in both experimental and theoretical studies. Here, general formulations concerning cell volume change are presented in the context of developing a comprehensive cell model which takes Ca(2+) dynamics into account. Explicit formulas for charge conservation and steady-state volumes of the cytosol and endoplasmic reticulum (ER) are derived in terms of membrane potential, amount of ions, Ca(2+)-bound buffer molecules, and initial cellular conditions. The formulations were applied to a ventricular myocyte model which has plasma-membrane Ca(2+) currents with dynamic gating mechanisms, Ca(2+)-buffering reactions with diffusive and non-diffusive buffer proteins, and Ca(2+) uptake into or release from the sarcoplasmic reticulum (SR) accompanied by compensatory cationic or anionic currents through the SR membrane. Time-dependent volume changes in cardiac myocytes induced by varying extracellular osmolarity or by action potential generation were successfully simulated by the novel formulations. Through application of bifurcation analysis, the existence and uniqueness of steady-state solutions of the cell volume were validated, and contributions of individual ion channels and transporters to the steady-state volume were systematically analyzed. The new formulas are consistent with previous fundamental theory derived from simple models of minimum compositions. The new formulations may be useful for examination of the relationship between cell function and volume change in other cell types.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Derivation of a model of the exciter of a brushless synchronous machine

    NASA Astrophysics Data System (ADS)

    Vleeshouwers, J. M.

    1992-06-01

    The modeling of the brushless exciter for a machine used in a wind turbine is addressed. A brushless exciter reduces the susceptability of the machine to atmospheric conditions and therefore the need for maintenance compared to a synchronous machine equipped with brushes and sliprings. Furthermore, no large excitation winding power supply is needed. In large wind turbines which apply a synchronous machine, these advantages will be vital. A brushless exciter is usually constructed as a small synchronous machine with rectifier. According to manufacturers, exciters are designed to function as a current transformer. The method which has been developed in an earlier resarch project to model the synchronous machine with rectifier is concluded to be applicable to model the exciter, provided that the effect of resistances on the commutation may be neglected. This restricts the technique to modeling exciters of machines in the 100 kW range and larger. For smaller exciters the existing modeling approach is not applicable. Measurements of a small exciter (of a 37.5 kVa machine) show that higher harmonics in the exciter significantly contribute to its behavior. Based on experimental data a simple linear first order dynamic model was developed for the small exciter. The model parameters can be deduced from the steady state current gain and a simple dynamic experiment.

  4. Is dipole moment a valid descriptor of excited state's charge-transfer character?

    PubMed

    Petelenz, Piotr; Pac, Barbara

    2013-11-20

    In the ongoing discussion on excited states of the pentacene crystal, dipole moment values have been recently invoked to gauge the CT admixture to excited states of Frenkel parentage in a model cluster. In the present paper, a simple dimer model is used to show that, in general, the dipole moment is not a valid measure of the CT contribution. This finding eliminates some apparent disagreement between the computational results published by different research groups. The implications of our results and other related aspects of cluster-type quantum chemistry calculations are discussed in the context of the standing literature dispute concerning the mechanism of singlet fission in the pentacene crystal, notably the role of charge transfer contributions vs the involvement of an excimer-like doubly excited intermediate (D state).

  5. Equilibrium excited state and emission spectra of molecular aggregates from the hierarchical equations of motion approach.

    PubMed

    Jing, Yuanyuan; Chen, Liping; Bai, Shuming; Shi, Qiang

    2013-01-28

    The hierarchical equations of motion (HEOM) method was applied to calculate the emission spectra of molecular aggregates using the Frenkel exciton model. HEOM equations for the one-exciton excited state were first propagated until equilibration. The reduced density operator and auxiliary density operators (ADOs) were used to characterize the coupled system-bath equilibrium. The dipole-dipole correlation functions were then calculated to obtain the emission spectra of model dimers, and the B850 band of light-harvesting complex II (LH2) in purple bacteria. The effect of static disorder on equilibrium excited state and the emission spectra of LH2 was also explicitly considered. Several approximation schemes, including the high temperature approximation (HTA) of the HEOM, a modified version of the HTA, the stochastic Liouville equation approach, the perturbative time-local and time-nonlocal generalized quantum master equations, were assessed in the calculation of the equilibrium excited state and emission spectra.

  6. Control by decoherence: weak field control of an excited state objective

    SciTech Connect

    Katz, Gil; Ratner, Mark A.; Kosloff, Ronnie

    2010-01-01

    Coherent control employing a broadband excitation is applied to a branching reaction in the excited state. In a weak field for an isolated molecule, a control objective is only frequency dependent. This means that phase control of the pulse cannot improve the objective beyond the best frequency selection. Once the molecule is put into a dissipative environment a new timescale emerges. In this study, we demonstrate that the dissipation allows us to achieve coherent control of branching ratios in the excited state. The model studied contains a nuclear coordinate and three electronic states: the ground and two coupled diabatic excited states. The influence of the environment is modeled by the stochastic surrogate Hamiltonian. The excitation is generated by a Gaussian pulse where the phase control introduced a chirp to the pulse. For sufficient relaxation, we find significant control in the weak field depending on the chirp rate. The observed control is rationalized by a timing argument caused by a focused wavepacket. The initial non-adiabatic crossing is enhanced by the chirp. This is followed by energy relaxation which stabilizes the state by having an energy lower than the crossing point.

  7. Electro-optical parameters in excited states of some spectrally active molecules

    NASA Astrophysics Data System (ADS)

    Benchea, Andreea Celia; Closca, Valentina; Rusu, Cristina Marcela; Morosanu, Cezarina; Dorohoi, Dana Ortansa

    2014-08-01

    The spectral shifts measured in different solvents are expressed as functions of the solvent macroscopic parameters. The value of the correlation coefficient multiplying the functions of electric permittivity was determined by statistical means. The correlation coefficient depends on the electric dipole moment of the spectrally active molecules. The electro-optical parameters in the ground state of the solute molecules can be approximated by molecular modeling. The excited state parameters are usually estimated using the results obtained both by HyperChem Programme and solvatochromic study. The importance of this approximate method is that it offers information about of the excited state of solute molecule for which our measuring possibilities are very restrictive. The information about the excited electronic state is affected by the limits in which the theories of liquid solutions are developed. Our results refer to two molecules of vitamins from B class, namely B3 and B6.

  8. 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.

  9. 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.

  10. 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.

  11. Stochastic modeling of the Chandler wobble and its excitation

    NASA Astrophysics Data System (ADS)

    Brzezinski, A.; Rajner, M.

    2012-12-01

    The Chandler wobble (CW) is the most important rotational eigenmode of the Earth. Its parameters, the frequency F (or, equivalently, the period T) and the quality factor Q should be known as best as possible because 1) they appear in the equation of polar motion, and 2) they are closely related to various geophysical parameters. Here we report an attempt to derive improved estimate of the CW parameters. We apply stochastic models to express the free wobble excitation and the measurements noise. These models are used to derive the state-space formulation which is the base for application of the Kalman filter for analysis of the related observations. The Chandler wobble parameters are derived either from analysis of the polar motion data alone or from simultaneous processing of polar motion and geophysical excitation data. Our estimates of F and Q are finally compared to the earlier results.

  12. 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.

  13. Optical Pulse Interactions in Nonlinear Excited State Materials

    DTIC Science & Technology

    2008-07-14

    for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching data sources...Paperwork Reduction Project (0704-0188) Washington, DC 20503. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1 . REPORT DATE (DD-MM-YYYY) 14...Excited State Materials 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550-04- 1 -0219 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Potasek

  14. 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.

  15. 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.

  16. 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.

  17. Wave-packet model for excitation by ultrashort pulses

    NASA Astrophysics Data System (ADS)

    Suominen, Kalle-Antti; Garraway, Barry M.; Stenholm, Stig

    1992-03-01

    In this paper we discuss the excitation of a localized molecular ground-state wave function by a short laser pulse. With a one-dimensional approach we show when it is possible to excite a considerable fraction of the ground state without too much distortion of the shape of the wave packet. This is of interest in time-resolved molecular experiments where an excited wave packet is often taken as the initial state. We solve the two coupled wave equations numerically and compare results to an analytical approximation based on the Rosen-Zener model. The validity of the approximation and its breakdown is considered in detail. Special attention is paid to the effect of lengthening the pulse duration and the consequences of the accompanying number of Rabi flops occurring in the area theorem. When the approximation breaks down, the wave packet becomes distorted and spread out, but there are still interesting coherence effects due to the interplay between the Rabi flopping and the molecular dynamics; these are displayed and discussed. Finally, the relationship to other works and possible generalizations are presented.

  18. 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

  19. Neutron correlations in the decay of the first excited state of 11Li

    NASA Astrophysics Data System (ADS)

    Smith, J. K.; Baumann, T.; Bazin, D.; Brown, J.; DeYoung, P. A.; Frank, N.; Jones, M. D.; Kohley, Z.; Luther, B.; Marks, B.; Spyrou, A.; Stephenson, S. L.; Thoennessen, M.; Volya, A.

    2016-11-01

    The decay of unbound excited 11Li was measured after being populated by a two-proton removal from a 13B beam at 71 MeV/nucleon. Decay energy spectra and Jacobi plots were obtained from measurements of the momentum vectors of the 9Li fragment and neutrons. A resonance at an excitation energy of ∼1.2 MeV was observed. The kinematics of the decay are equally well fit by a simple dineutron-like model or a phase-space model that includes final state interactions. A sequential decay model can be excluded.

  20. 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}.

  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. Controlling the Excited-State Dynamics of Nuclear Spin Isomers Using the Dynamic Stark Effect.

    PubMed

    Waldl, Maria; Oppel, Markus; González, Leticia

    2016-07-14

    Stark control of chemical reactions uses intense laser pulses to distort the potential energy surfaces of a molecule, thus opening new chemical pathways. We use the concept of Stark shifts to convert a local minimum into a local maximum of the potential energy surface, triggering constructive and destructive wave-packet interferences, which then induce different dynamics on nuclear spin isomers in the electronically excited state of a quinodimethane derivative. Model quantum-dynamical simulations on reduced dimensionality using optimized ultrashort laser pulses demonstrate a difference of the excited-state dynamics of two sets of nuclear spin isomers, which ultimately can be used to discriminate between these isomers.

  3. Exploring the Photophysical Properties of Molecular Systems Using Excited State Accelerated ab Initio Molecular Dynamics.

    PubMed

    Ortiz-Sánchez, Juan Manuel; Bucher, Denis; Pierce, Levi C T; Markwick, Phineus R L; McCammon, J Andrew

    2012-08-14

    In the present work, we employ excited state accelerated ab initio molecular dynamics (A-AIMD) to efficiently study the excited state energy landscape and photophysical topology of a variety of molecular systems. In particular, we focus on two important challenges for the modeling of excited electronic states: (i) the identification and characterization of conical intersections and crossing seams, in order to predict different and often competing radiationless decay mechanisms, and (ii) the description of the solvent effect on the absorption and emission spectra of chemical species in solution. In particular, using as examples the Schiff bases formaldimine and salicylidenaniline, we show that A-AIMD can be readily employed to explore the conformational space around crossing seams in molecular systems with very different photochemistry. Using acetone in water as an example, we demonstrate that the enhanced configurational space sampling may be used to accurately and efficiently describe both the prominent features and line-shapes of absorption and emission spectra.

  4. Excited state two photon absorption of a charge transfer radical dimer in the near infrared.

    PubMed

    Schiccheri, Nicola; Meneghetti, Moreno

    2005-06-02

    Nonlinear transmission measurements of a solution of radical dimers of tetramethyl-tetrathiafulvalene, (TMTTF+)2, recorded with 9 ns laser pulses at 1064 nm are reported and interpreted on the basis of a multiphoton absorption process. One finds that the process can be interpreted with a sequence of three photon absorption, the first being a one photon absorption related to the intermolecular charge transfer process characteristic of the dimers and the second a two photon absorption from the excited state created with the first process. A model calculation allows one to obtain the value of the two photon absorption cross section which is found to be several orders of magnitude larger than those usually found for two photon absorbing systems excited from the ground state. These results show the importance of an excited-state population for obtaining large nonlinear optical responses.

  5. 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.

  6. Quantum mechanical identification of quadrupolar plasmonic excited states in silver nanorods

    SciTech Connect

    Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C.

    2016-10-27

    Quadrupolar plasmonic modes in noble metal nanoparticles have gained interest in recent years for various sensing applications. Although quantum mechanical studies have shown that dipolar plasmons can be modeled in terms of excited states where several to many excitations contribute coherently to the transition dipole moment, new approaches are needed to identify the quadrupolar plasmonic states. We show that quadrupolar states in Ag nanorods can be identified using the semiempirical INDO/SCI approach by examining the quadrupole moment of the transition density. The main longitudinal quadrupolar states occur at higher energies than the longitudinal dipolar states, in agreement with previous classical electrodynamics results, and have collective plasmonic character when the nanorods are sufficiently long. In conclusion, the ability to identify these states will make it possible to evaluate the differences between dipolar and quadrupolar plasmons that are relevant for sensing applications.

  7. Quantum mechanical identification of quadrupolar plasmonic excited states in silver nanorods

    DOE PAGES

    Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C.

    2016-10-27

    Quadrupolar plasmonic modes in noble metal nanoparticles have gained interest in recent years for various sensing applications. Although quantum mechanical studies have shown that dipolar plasmons can be modeled in terms of excited states where several to many excitations contribute coherently to the transition dipole moment, new approaches are needed to identify the quadrupolar plasmonic states. We show that quadrupolar states in Ag nanorods can be identified using the semiempirical INDO/SCI approach by examining the quadrupole moment of the transition density. The main longitudinal quadrupolar states occur at higher energies than the longitudinal dipolar states, in agreement with previous classicalmore » electrodynamics results, and have collective plasmonic character when the nanorods are sufficiently long. In conclusion, the ability to identify these states will make it possible to evaluate the differences between dipolar and quadrupolar plasmons that are relevant for sensing applications.« less

  8. Optically Excited Entangled States in Organic Molecules Illuminate the Dark.

    PubMed

    Upton, L; Harpham, M; Suzer, O; Richter, M; Mukamel, S; Goodson, T

    2013-06-20

    We utilize quantum entangled photons to carry out nonlinear optical spectroscopy in organic molecules with an extremely small number of photons. For the first time, fluorescence is reported as a result of entangled photon absorption in organic nonlinear optical molecules. Selectivity of the entangled photon absorption process is also observed and a theoretical model of this process is provided. Through these experiments and theoretical modeling it is found that while some molecules may not have strong classical nonlinear optical properties due to their excitation pathways; these same excitation pathways may enhance the entangled photon processes. It is found that the opposite is also true. Some materials with weak classical nonlinear optical effects may exhibit strong non-classical nonlinear optical effects. Our entangled photon fluorescence results provide the first steps in realizing and demonstrating the viability of entangled two-photon microscopy, remote sensing, and optical communications.

  9. 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.

  10. Influence of a polarizable surrounding on the electronically excited states of aggregated perylene materials.

    PubMed

    Bellinger, Daniel; Settels, Volker; Liu, Wenlan; Fink, Reinhold F; Engels, Bernd

    2016-06-30

    To tune the efficiency of organic semiconductor devices it is important to understand limiting factors as trapping mechanisms for excitons or charges. An understanding of such mechanisms deserves an accurate description of the involved electronical states in the given environment. In this study, we investigate how a polarizable surrounding influences the relative positions of electronically excited states of dimers of different perylene dyes. Polarization effects are particularly interesting for these systems, because gas phase computations predict that the CT states lie slightly above the corresponding Frenkel states. A polarizable environment may change this energy order because CT states are thought to be more sensitive to a polarizable surrounding than Frenkel states. A first insight we got via a TD-HF approach in combination with a polarizable continuum model (PCM). These give limited insights because TD-HF overestimates excitation energies of CT states. However, SCS-CC2 approaches, which are sufficiently accurate, cannot easily be used in combination with continuum solvent models. Hence, we developed two approaches to combine gas phase SCS-CC2 results with solvent effects based on TD-HF computations. Their accuracies were finally checked via ADC(2)//COSMO computations. The results show that for perylene dyes a polarizable surrounding alone does not influence the energetic ordering of CT and Frenkel states. Variations in the energy order of the states only result from nuclear relaxation effects after the excitation process. © 2016 Wiley Periodicals, Inc.

  11. 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.

  12. Finding Matrix Product State Representations of Highly Excited Eigenstates of Many-Body Localized Hamiltonians

    NASA Astrophysics Data System (ADS)

    Yu, Xiongjie; Pekker, David; Clark, Bryan K.

    2017-01-01

    A key property of many-body localized Hamiltonians is the area law entanglement of even highly excited eigenstates. Matrix product states (MPS) can be used to efficiently represent low entanglement (area law) wave functions in one dimension. An important application of MPS is the widely used density matrix renormalization group (DMRG) algorithm for finding ground states of one-dimensional Hamiltonians. Here, we develop two algorithms, the shift-and-invert MPS (SIMPS) and excited state DMRG which find highly excited eigenstates of many-body localized Hamiltonians. Excited state DMRG uses a modified sweeping procedure to identify eigenstates, whereas SIMPS applies the inverse of the shifted Hamiltonian to a MPS multiple times to project out the targeted eigenstate. To demonstrate the power of these methods, we verify the breakdown of the eigenstate thermalization hypothesis in the many-body localized phase of the random field Heisenberg model, show the saturation of entanglement in the many-body localized phase, and generate local excitations.

  13. The Paternò-Büchi reaction: importance of triplet states in the excited-state reaction pathway.

    PubMed

    Brogaard, Rasmus Y; Schalk, Oliver; Boguslavskiy, Andrey E; Enright, Gary D; Hopf, Henning; Raev, Vitaly; Tarcoveanu, Eliza; Sølling, Theis I; Stolow, Albert

    2012-06-28

    The Paternò-Büchi (PB) reaction between an excited carbonyl compound and an alkene has been widely studied, but so far little is known about the excited-state dynamics of the reaction. In this investigation, we used a compound in which a formyl and a vinyl group are attached to a [2.2]paracyclophane in order to obtain a model system in pre-reactive conformation for the PB reaction. We studied the excited-state dynamics of the isolated molecule in a molecular beam using femtosecond time-resolved photoelectron spectroscopy and ab initio calculations. The results show that inter-system crossing within two picoseconds competes efficiently with the reaction in the singlet manifold. Thus, the PB reaction in this model system takes place in the triplet state on a time scale of nanoseconds. This result stresses the importance of triplet states in the excited-state pathway of the PB reaction involving aromatic carbonyl compounds, even in situations in which the reacting moieties are in immediate vicinity.

  14. 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.

  15. Investigations into photo-excited state dynamics in colloidal quantum dots

    NASA Astrophysics Data System (ADS)

    Singh, Gaurav

    Colloidal Quantum dots (QDs) have garnered considerable scientific and technological interest as a promising material for next generation solar cells, photo-detectors, lasers, bright light-emitting diodes (LEDs), and reliable biomarkers. However, for practical realization of these applications, it is crucial to understand the complex photo-physics of QDs that are very sensitive to surface chemistry and chemical surroundings. Depending on the excitation density, QDs can support single or multiple excitations. The first part of this talk addresses evolution of QD excited state dynamics in the regime of low excitation intensity. We use temperature-resolved time-resolved fluorescence spectroscopy to study exciton dynamics from picoseconds to microseconds and use kinetic modeling based on classical electron transfer to show the effect of surface trap states on dynamics of ground-state exciton manifold in core-shell CdSe/CdS QDs. We show that the thickness of CdS shell plays an important role in interaction of CdSe core exciton states with nanocrystal environment, and find that a thicker shell can minimize the mixing of QD exciton states with surface trap states. I will then present an investigation into the dynamics of multiply-excited states in QDs. One of the key challenges in QD spectroscopy is to reliably distinguish multi- from single-excited states that have similar lifetime components and spectroscopic signatures. I will describe the development of a novel multi-pulse fluorescence technique to selectively probe multi-excited states in ensemble QD samples and determine the nature of the multi-excited state contributing to the total fluorescence even in the limit of low fluorescent yields. We find that in our sample of CdSe/CdS core/shell QDs the multi-excited emission is dominated by emissive trion states rather than biexcitons. Next, I will discuss the application of this technique to probe exciton-plasmon coupling in layered hybrid films of QD/gold nanoparticles

  16. 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).

  17. Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques

    DOE PAGES

    Couch, David E.; Kapteyn, Henry C.; Murnane, Margaret M.; ...

    2017-03-17

    Here, understanding the ultrafast dynamics of highly-excited electronic states of small molecules is critical for a better understanding of atmospheric and astrophysical processes, as well as for designing coherent control strategies for manipulating chemical dynamics. In highly excited states, nonadiabatic coupling, electron-electron interactions, and the high density of states govern dynamics. However, these states are computationally and experimentally challenging to access. Fortunately, new sources of ultrafast vacuum ultraviolet pulses, in combination with electron-ion coincidence spectroscopies, provide new tools to unravel the complex electronic landscape. Here we report time-resolved photoelectron-photoion coincidence experiments using 8 eV pump photons to study the highlymore » excited states of acetone. We uncover for the first time direct evidence that the resulting excited state consists of a mixture of both ny → 3p and π → π* character, which decays with a time constant of 330 fs. In the future, this approach can inform models of VUV photochemistry and aid in designing coherent control strategies for manipulating chemical reactions.« less

  18. Characterizing the Locality of Diabatic States for Electronic Excitation Transfer by Decomposing the Diabatic Coupling

    SciTech Connect

    Vura-Weis, Josh; Newton, M. D.; Wasielewski, Michael R; Subotnik, J.E.

    2010-12-09

    A common strategy to calculate electronic coupling matrix elements for charge or energy transfer is to take the adiabatic states generated by electronic structure computations and rotate them to form localized diabatic states. In this paper, we show that, for intermolecular transfer of singlet electronic excitation, usually we cannot fully localize the electronic excitations in this way. Instead, we calculate putative initial and final states with small excitation tails caused by weak interactions with high energy excited states in the electronic manifold. These tails do not lead to substantial changes in the total diabatic coupling between states, but they do lead to a different partitioning of the total coupling between Coulomb (Förster), exchange (Dexter), and one-electron components. The tails may be reduced by using a multistate diabatic model or eliminated entirely by truncation (denoted as “chopping”). Without more information, we are unable to conclude with certainty whether the observed diabatic tails are a physical reality or a computational artifact. This research suggests that decomposition of the diabatic coupling between chromophores into Coulomb, exchange, and one-electron components may depend strongly on the number of states considered, and such results should be treated with caution.

  19. 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.

  20. 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.

  1. Spectroscopic consequences of a mixed valence excited state: quantitative treatment of a dihydrazine diradical dication.

    PubMed

    Lockard, Jenny V; Zink, Jeffrey I; Konradsson, Asgeir E; Weaver, Michael N; Nelsen, Stephen F

    2003-11-05

    A model for the quantitative treatment of molecular systems possessing mixed valence excited states is introduced and used to explain observed spectroscopic consequences. The specific example studied in this paper is 1,4-bis(2-tert-butyl-2,3-diazabicyclo[2.2.2]oct-3-yl)-2,3,5,6-tetramethylbenzene-1,4-diyl dication. The lowest energy excited state of this molecule arises from a transition from the ground state where one positive charge is associated with each of the hydrazine units, to an excited state where both charges are associated with one of the hydrazine units, that is, a Hy-to-Hy charge transfer. The resulting excited state is a Class II mixed valence molecule. The electronic emission and absorption spectra, and resonance Raman spectra, of this molecule are reported. The lowest energy absorption band is asymmetric with a weak low-energy shoulder and an intense higher energy peak. Emission is observed at low temperature. The details of the absorption and emission spectra are calculated for the coupled surfaces by using the time-dependent theory of spectroscopy. The calculations are carried out in the diabatic basis, but the nuclear kinetic energy is explicitly included and the calculations are exact quantum calculations of the model Hamiltonian. Because the transition involves the transfer of an electron from the hydrazine on one side of the molecule to the hydrazine on the other side and vice versa, the two transitions are antiparallel and the transition dipole moments have opposite signs. Upon transformation to the adiabatic basis, the dipole moment for the transition to the highest energy adiabatic surface is nonzero, but that for the transition to the lowest surface changes sign at the origin. The energy separation between the two components of the absorption spectrum is twice the coupling between the diabatic basis states. The bandwidths of the electronic spectra are caused by progressions in totally symmetric modes as well as progressions in the modes

  2. Total photoionization cross-sections of excited electronic states by the algebraic diagrammatic construction-Stieltjes-Lanczos method

    NASA Astrophysics Data System (ADS)

    Ruberti, M.; Yun, R.; Gokhberg, K.; Kopelke, S.; Cederbaum, L. S.; Tarantelli, F.; Averbukh, V.

    2014-05-01

    Here, we extend the L2 ab initio method for molecular photoionization cross-sections introduced in Gokhberg et al. [J. Chem. Phys. 130, 064104 (2009)] and benchmarked in Ruberti et al. [J. Chem. Phys. 139, 144107 (2013)] to the calculation of total photoionization cross-sections of molecules in electronically excited states. The method is based on the ab initio description of molecular electronic states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. The intermediate state representation of the dipole operator in the ADC basis is used to compute the transition moments between the excited states of the molecule. We compare the results obtained using different levels of the many-body theory, i.e., ADC(1), ADC(2), and ADC(2)x for the first two excited states of CO, N2, and H2O both at the ground state and the excited state equilibrium or saddle point geometries. We find that the single excitation ADC(1) method is not adequate even at the qualitative level and that the inclusion of double electronic excitations for description of excited state photoionization is essential. Moreover, we show that the use of the extended ADC(2)x method leads to a substantial systematic difference from the strictly second-order ADC(2). Our calculations demonstrate that a theoretical modelling of photoionization of excited states requires an intrinsically double excitation theory with respect to the ground state and cannot be achieved by the standard single excitation methods with the ground state as a reference.

  3. Total photoionization cross-sections of excited electronic states by the algebraic diagrammatic construction-Stieltjes-Lanczos method.

    PubMed

    Ruberti, M; Yun, R; Gokhberg, K; Kopelke, S; Cederbaum, L S; Tarantelli, F; Averbukh, V

    2014-05-14

    Here, we extend the L2 ab initio method for molecular photoionization cross-sections introduced in Gokhberg et al. [J. Chem. Phys. 130, 064104 (2009)] and benchmarked in Ruberti et al. [J. Chem. Phys. 139, 144107 (2013)] to the calculation of total photoionization cross-sections of molecules in electronically excited states. The method is based on the ab initio description of molecular electronic states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. The intermediate state representation of the dipole operator in the ADC basis is used to compute the transition moments between the excited states of the molecule. We compare the results obtained using different levels of the many-body theory, i.e., ADC(1), ADC(2), and ADC(2)x for the first two excited states of CO, N2, and H2O both at the ground state and the excited state equilibrium or saddle point geometries. We find that the single excitation ADC(1) method is not adequate even at the qualitative level and that the inclusion of double electronic excitations for description of excited state photoionization is essential. Moreover, we show that the use of the extended ADC(2)x method leads to a substantial systematic difference from the strictly second-order ADC(2). Our calculations demonstrate that a theoretical modelling of photoionization of excited states requires an intrinsically double excitation theory with respect to the ground state and cannot be achieved by the standard single excitation methods with the ground state as a reference.

  4. Hydrological excitation of polar motion by different variables of the GLDAS models

    NASA Astrophysics Data System (ADS)

    Wińska, Małgorzata; Nastula, Jolanta

    Continental hydrological loading, by land water, snow, and ice, is an element that is strongly needed for a full understanding of the excitation of polar motion. In this study we compute different estimations of hydrological excitation functions of polar motion (Hydrological Angular Momentum - HAM) using various variables from the Global Land Data Assimilation System (GLDAS) models of land hydrosphere. The main aim of this study is to show the influence of different variables for example: total evapotranspiration, runoff, snowmelt, soil moisture to polar motion excitations in annual and short term scale. In our consideration we employ several realizations of the GLDAS model as: GLDAS Common Land Model (CLM), GLDAS Mosaic Model, GLDAS National Centers for Environmental Prediction/Oregon State University/Air Force/Hydrologic Research Lab Model (Noah), GLDAS Variable Infiltration Capacity (VIC) Model. Hydrological excitation functions of polar motion, both global and regional, are determined by using selected variables of these GLDAS realizations. First we compare a timing, spectra and phase diagrams of different regional and global HAMs with each other. Next, we estimate, the hydrological signal in geodetically observed polar motion excitation by subtracting the atmospheric -- AAM (pressure + wind) and oceanic -- OAM (bottom pressure + currents) contributions. Finally, the hydrological excitations are compared to these hydrological signal in observed polar motion excitation series. The results help us understand which variables of considered hydrological models are the most important for the polar motion excitation and how well we can close polar motion excitation budget in the seasonal and inter-annual spectral ranges.

  5. 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.

  6. 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

  7. 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.

  8. 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).

  9. Survey of Excited State Neutron Spectroscopic Factors for Z=8-28 Nuclei

    NASA Astrophysics Data System (ADS)

    Tsang, M. B.; Lee, Jenny; Su, S. C.; Dai, J. Y.; Horoi, M.; Liu, H.; Lynch, W. G.; Warren, S.

    2009-02-01

    We have extracted 565 neutron spectroscopic factors of sd and fp shell nuclei by systematically analyzing more than 2000 measured (d, p) angular distributions. We are able to compare 125 of the extracted spectroscopic factors to values predicted by large-basis shell-model calculations and evaluate the accuracies of spectroscopic factors predicted by different shell-model interactions in these regions. We find that the spectroscopic factors predicted for most excited states of sd-shell nuclei using the latest USDA or USDB interactions agree with the experimental values. For fp shell nuclei, the inability of the current models to account for the core excitation and fragmentation of the states leads to considerable discrepancies. In particular, the agreement between data and shell-model predictions for Ni isotopes is not better than a factor of 2 using either the GXPF1A or the XT interaction.

  10. Coulomb excitation of ground band rotational states in /sup 249/Bk

    SciTech Connect

    Bemis, C.E. Jr.; McGowan, F.K.; Ford, J.L.C. Jr.; Milner, W.T.; Robinson, R.L.; Stelson, P.H.

    1982-03-01

    Coulomb-excitation probabilities for the first few members of the 7/2/sup +/(633up-arrow) ground-state rotational band in /sup 249/Bk have been determined with 17.06-MeV /sup 4/He ions. These previously know excited states include the 9/2/sup +/ (41.8-keV), 11/2/sup +/ (93.7-keV), and 13/2/sup +/ (155.8-keV) members of the 7/2/sup +/(633up-arrow) band. Within experimental uncertainties, the Coulomb-excitation probabilities for these rotational states are reproduced by calculated values when only E2 excitations are considered with an intrinsic quadrupole moment, Q/sub 20/, of 12.70 +- 0.24 eb in the rigid rotor limit. The deduced ground-state spectroscopic quadrupole moment is 5.93 +- 0.11 eb. Intraband M1 transition rates have been deduced by combining the Q/sub 20/ result with other experimental data. Within the rotational model, a ground-state magnetic moment of +3.45 +- 0.10 ..mu../sub N/ is indicated.

  11. Symmetry-adapted excited states for the T1u⊗hg Jahn-Teller system

    NASA Astrophysics Data System (ADS)

    Qiu, Q. C.; Dunn, J. L.; Bates, C. A.

    2001-08-01

    Jahn-Teller (JT) systems typically contain a set of equivalent-energy wells in the lowest adiabatic potential-energy surface (APES). Quantum-mechanical tunneling between these wells (the dynamic JT effect) must be allowed for by taking appropriate symmetrized combinations of oscillator-type states associated with the wells. It is important to be able to describe the excited states of such systems for a number of reasons. One particular reason is that they are required for the calculation of second-order vibronic reduction factors, which in turn are useful for modeling experimental data using effective Hamiltonians. In this paper, projection-operator techniques are used to obtain general expressions for the symmetry-adapted excited states of the icosahedral T1u⊗hg JT system for the case of D5d minima in the APES. Analytical expressions for the states and their energies for one-phonon excitation are given explicitly. The energies of a selection of states with two-phonon excitations are also obtained and plotted. The results obtained in this paper are applicable to the C-60 molecule.

  12. State-specific transport properties of partially ionized flows of electronically excited atomic gases

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    State-to-state approach for theoretical study of transport properties in atomic gases with excited electronic degrees of freedom of both neutral and ionized species is developed. The dependence of atomic radius on the electronic configuration of excited atoms is taken into account in the transport algorithm. Different cutoff criteria for increasing atomic radius are discussed and the limits of applicability for these criteria are evaluated. The validity of a Slater-like model for the calculation of state-resolved transport coefficients in neutral and ionized atomic gases is shown. For ionized flows, a method of evaluation for effective cross-sections of resonant charge-transfer collisions is suggested. Accurate kinetic theory algorithms for modelling the state-specific transport properties are applied for the prediction of transport coefficients in shock heated flows. Based on the numerical observations, different distributions over electronic states behind the shock front are considered. For the Boltzmann-like distributions at temperatures greater than 14,000 K, an important effect of electronic excitation on the partial thermal conductivity and viscosity coefficients is found for both neutral and ionized atomic gases: increasing radius of excited atoms causes a strong decrease in these transport coefficients. Similarly, the presence of electronically excited states with increased atomic radii leads to reduced diffusion coefficients. Nevertheless the overall impact of increasing effective cross-sections on the transport properties just behind the shock front under hypersonic reentry conditions is found to be minor since the populations of high-lying electronic energy levels behind the shock waves are low.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. γ -ray spectroscopy of low-lying excited states and shape competition in 194Os

    NASA Astrophysics Data System (ADS)

    Daniel, T.; Kisyov, S.; Regan, P. H.; Marginean, N.; Podolyák, Zs.; Marginean, R.; Nomura, K.; Rudigier, M.; Mihai, R.; Werner, V.; Carroll, R. J.; Gurgi, L. A.; Oprea, A.; Berry, T.; Serban, A.; Nita, C. R.; Sotty, C.; Suvaila, R.; Turturica, A.; Costache, C.; Stan, L.; Olacel, A.; Boromiza, M.; Toma, S.

    2017-02-01

    The properties of excited states in the neutron-rich nucleus 194Os have been investigated using the 192Os(18O,16O )194Os reaction with an 80 MeV beam provided by the IFIN-HH Laboratory, Bucharest. Discrete γ -ray decays from excited states have been measured using the hybrid HPGe-LaBr3(Ce ) array RoSPHERE. The current work identifies a number of previously unreported low-lying nonyrast states in 194Os as well as the first measurement of the half-life of the yrast 2+ state of 302(50) ps. This is equivalent to a B (E 2 :2+→0+) =45 (16 ) W.u. and intrinsic quadrupole deformation of βeff=0.14 (1 ) . The experimental results are compared with Hartree-Fock-Bogoliubov-interacting-boson-model calculations and are consistent with a reduction in a quadrupole collectivity in Os isotopes with increasing neutron number.

  18. β decay of 129Cd and excited states in 129In

    NASA Astrophysics Data System (ADS)

    Taprogge, J.; Jungclaus, A.; Grawe, H.; Nishimura, S.; Doornenbal, P.; Lorusso, G.; Simpson, G. S.; Söderström, P.-A.; Sumikama, T.; Xu, Z. Y.; Baba, H.; Browne, F.; Fukuda, N.; Gernhäuser, R.; Gey, G.; Inabe, N.; Isobe, T.; Jung, H. S.; Kameda, D.; Kim, G. D.; Kim, Y.-K.; Kojouharov, I.; Kubo, T.; Kurz, N.; Kwon, Y. K.; Li, Z.; Sakurai, H.; Schaffner, H.; Steiger, K.; Suzuki, H.; Takeda, H.; Vajta, Zs.; Watanabe, H.; Wu, J.; Yagi, A.; Yoshinaga, K.; Benzoni, G.; Bönig, S.; Chae, K. Y.; Coraggio, L.; Covello, A.; Daugas, J.-M.; Drouet, F.; Gadea, A.; Gargano, A.; Ilieva, S.; Kondev, F. G.; Kröll, T.; Lane, G. J.; Montaner-Pizá, A.; Moschner, K.; Mücher, D.; Naqvi, F.; Niikura, M.; Nishibata, H.; Odahara, A.; Orlandi, R.; Patel, Z.; Podolyák, Zs.; Wendt, A.

    2015-05-01

    The β decay of 129Cd, produced in the relativistic fission of a 238U beam, was experimentally studied at the RIBF facility at the RIKEN Nishina Center. From the γ radiation emitted after the β decays, a level scheme of 129In was established comprising 31 excited states and 69 γ -ray transitions. The experimentally determined level energies are compared to state-of-the-art shell-model calculations. The half-lives of the two β -decaying states in 129Cd were deduced and the β feeding to excited states in 129In were analyzed. It is found that, as in most cases in the Z <50 , N ≤82 region, both decays are dominated by the ν 0 g7 /2→π 0 g9 /2 Gamow-Teller transition, although the contribution of first-forbidden transitions cannot be neglected.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Jahn-Teller stabilization energies for ZnS:Mn and ZnSe:Mn excited states obtained by the angular overlap model

    NASA Astrophysics Data System (ADS)

    Stavrev, K. K.; Kynev, K. D.; Nikolov, G. St.

    1988-06-01

    Linear Jahn-Teller coupling constants are obtained by the angular overlap model. A comparison with the data published recently [Parrot et al., J. Chem. Phys. 87, 1463 (1987)] is made in order to demonstrate the considerable improvement in the calculated Jahn-Teller coefficients when the parameters of the angular overlap model are extracted from a spectral analysis of the systems under consideration.

  4. Capturing Invisible Motions in the Transition from Ground to Rare Excited States of T4 Lysozyme L99A.

    PubMed

    Schiffer, Jamie M; Feher, Victoria A; Malmstrom, Robert D; Sida, Roxana; Amaro, Rommie E

    2016-10-18

    Proteins commonly sample a number of conformational states to carry out their biological function, often requiring transitions from the ground state to higher-energy states. Characterizing the mechanisms that guide these transitions at the atomic level promises to impact our understanding of functional protein dynamics and energy landscapes. The leucine-99-to-alanine (L99A) mutant of T4 lysozyme is a model system that has an experimentally well characterized excited sparsely populated state as well as a ground state. Despite the exhaustive study of L99A protein dynamics, the conformational changes that permit transitioning to the experimentally detected excited state (∼3%, ΔG ∼2 kcal/mol) remain unclear. Here, we describe the transitions from the ground state to this sparsely populated excited state of L99A as observed through a single molecular dynamics (MD) trajectory on the Anton supercomputer. Aside from detailing the ground-to-excited-state transition, the trajectory samples multiple metastates and an intermediate state en route to the excited state. Dynamic motions between these states enable cavity surface openings large enough to admit benzene on timescales congruent with known rates for benzene binding. Thus, these fluctuations between rare protein states provide an atomic description of the concerted motions that illuminate potential path(s) for ligand binding. These results reveal, to our knowledge, a new level of complexity in the dynamics of buried cavities and their role in creating mobile defects that affect protein dynamics and ligand binding.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. On the saturation of Tb phosphors under cathode-ray excitation. I. Excited-state absorption in Tb-activated phosphor powders

    NASA Astrophysics Data System (ADS)

    Nieuwesteeg, K. J. B. M.; Raue, R.; Busselt, W.

    1990-12-01

    Optical transitions between the 5D4 excited state of the Tb3+ (4f)8 configuration and the crystal-field split components of the (4f)7(5d) configuration are observed using high-resolution laser excitation of Tb-doped powder samples at room temperature. Excited-state absorption spectra of Tb3+ in YAG, YAGaG, Y2SiO5, and LaOBr are presented. Superimposed on the broadband excitation spectrum of these transitions we find the relatively narrow 4f→4f lines. We present a theoretical model for interpreting the 4f→5d transitions, which predicts a strict proportionality between the (4f)8 5D4→(4f)7(5d) and the (4f)8 7F6→(4f)7(5d) transitions. This model is used to estimate the optical-absorption cross section for the former transitions. Although the terminating 4f levels lie at the same energy as the 5d bands, the 4f→4f transitions can be interpreted on the basis of the Judd-Ofelt theory. We derived a method for calibration of the Tb3+ 4f→5d fluorescence-excitation spectra from powder samples. For YAG:Tb, the resulting optical cross sections were confirmed by direct-absorption measurements on a Tb3+ -doped epitaxial YAG layer. To our knowledge, this is the first time that the probabilities for excited-state absorption to highly excited 5d and 4f states in Tb3+ have been obtained theoretically and experimentally from Tb-doped powder materials.

  10. Modeling coherent excitation energy transfer in photosynthetic light harvesting systems

    NASA Astrophysics Data System (ADS)

    Huo, Pengfei

    2011-12-01

    Recent non-linear spectroscopy experiments suggest the excitation energy transfer in some biological light harvesting systems initially occurs coherently. Treating such processes brings significant challenge for conventional theoretical tools that usually involve different approximations. In this dissertation, the recently developed Iterative Linearized Density Matrix (ILDM) propagation scheme, which is non-perturbative and non-Markovian is extended to study coherent excitation energy transfer in various light harvesting complexes. It is demonstrated that the ILDM approach can successfully describe the coherent beating of the site populations on model systems and gives quantitative agreement with both experimental results and the results of other theoretical methods have been developed recently to going beyond the usual approximations, thus providing a new reliable theoretical tool to study this phenomenon. This approach is used to investigate the excited energy transfer dynamics in various experimentally studied bacteria light harvesting complexes, such as Fenna-Matthews-Olsen (FMO) complex, Phycocyanin 645 (PC645). In these model calculations, quantitative agreement is found between computed de-coherence times and quantum beating pattens observed in the non-linear spectroscopy. As a result of these studies, it is concluded that the stochastic resonance behavior is important in determining the optimal throughput. To begin addressing possible mechanics for observed long de-coherence time, various models which include correlation between site energy fluctuations as well as correlation between site energy and inter-site coupling are developed. The influence of both types of correlation on the coherence and transfer rate is explored using with a two state system-bath hamiltonian parametrized to model the reaction center of Rhodobacter sphaeroides bacteria. To overcome the disadvantages of a fully reduced approach or a full propagation method, a brownian dynamics

  11. 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).

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

    SciTech Connect

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

    2015-05-21

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

  14. The End of Superdeformation: De-excitation to Spherical States in Lead Isotopes

    NASA Astrophysics Data System (ADS)

    Cizewski, Jolie A.

    1997-04-01

    Numerous examples of superdeformed rotational bands at high angular momenta have been observed in medium and heavy mass nuclei. The A ~190 region has been especially rich - superdeformed (SD) excitations have been identified in at least 22 isotopes and a large fraction of these bands have γ-ray energies which are simply related. However, the fundamental properties of excitation energy and spin-parity have only recently between determined. The first candidate for a discrete transition which links the SD band to ``normal" deformed (ND) excitations was observed in ^194Pb.(M. J. Brinkman, et al., Phys. Rev. C53), R1461 (1996). Subsequently, many transitions which connect SD and ND excitations in ^194Hg were observed, which allowed the determination of the excitation energy and spin.footnote T. L. Khoo, et al., Phys. Rev. Lett. 76, 1583 (1996). In ^194Pb as many as 12 discrete transitionsfootnote A. Lopez-Martens, et al., Phys. Lett. B380, 18 (1996) and K. Hauschild, et al., Phys. Rev. C (1996). have now been identified with the Eurogam or Gammasphere arrays of γ-ray detectors. This has allowed model-independent determinations of the excitation energy, spin, and parity of these states. The decay of the SD to ND states has been suggested to proceed via mixing between SD and ND excitations with similar excitation energies and angular momenta,(E. Vigezzi, et al., Phys. Lett. B249), 163 (1990). and allows a probe of the complex character of excitations at moderate temperatures in the ND well. In addition, the quasi-continuous spectrum of transitions which link SD and ND excitations can be used to probe level density and pairing degrees of freedom in hot, ND nuclei.footnote T. Dossing, et al., Phys. Rev. Lett. 75, 1276 (1995); A. Lopez-Martens, et al., PRL 77, 1707 (1996); and D.P. McNabb, et al., BAPS 41, 1237 (1996). Studies of the deexcitation of SD bands will be reviewed with a focus on the Pb isotopes.

  15. 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.

  16. 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.

  17. Enhanced negative ion formation via electron attachment to electronically-excited states

    SciTech Connect

    Pinnaduwage, L.A. |

    1995-12-31

    Recent basic studies on electron attachment to laser-excited molecules show that electron attachment to electronically-excited states can have orders of magnitude larger cross sections compared to the respective ground electronic states. Even though systematic studies have not been conducted, there are indications that electronically-excited states may play a significant role in negative ion formation in gas discharges. The high-lying Rydberg states could be of particular significance since, (i) their production efficiencies are high, and (ii) they have comparatively long lifetimes. Such states could be populated in discharge sources via direct electron impact or via excitation transfer from metastable states of inert gases.

  18. 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.

  19. 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.

  20. Slow State Transitions of Sustained Neural Oscillations by Activity-Dependent Modulation of Intrinsic Excitability

    PubMed Central

    Fröhlich, Flavio; Bazhenov, Maxim; Timofeev, Igor; Steriade, Mircea; Sejnowski, Terrence J.

    2010-01-01

    Little is known about the dynamics and mechanisms of transitions between tonic firing and bursting in cortical networks. Here, we use a computational model of a neocortical circuit with extracellular potassium dynamics to show that activity-dependent modulation of intrinsic excitability can lead to sustained oscillations with slow transitions between two distinct firing modes: fast run (tonic spiking or fast bursts with few spikes) and slow bursting. These transitions are caused by a bistability with hysteresis in a pyramidal cell model. Balanced excitation and inhibition stabilizes a network of pyramidal cells and inhibitory interneurons in the bistable region and causes sustained periodic alternations between distinct oscillatory states. During spike-wave seizures, neocortical paroxysmal activity exhibits qualitatively similar slow transitions between fast run and bursting. We therefore predict that extracellular potassium dynamics can cause alternating episodes of fast and slow oscillatory states in both normal and epileptic neocortical networks. PMID:16763023

  1. Electronic Excited States in Amorphous MEH-PPV Polymers from Large-Scale First Principles Calculations.

    PubMed

    Ma, Haibo; Qin, Ting; Troisi, Alessandro

    2014-03-11

    The electronic excited states of amorphous polymeric semiconductor MEH-PPV are investigated by first principles quantum chemical calculations based on trajectories from classical molecular dynamics simulations. We inferred an average conjugation length of ∼5-7 monomers for lowest vertical excitations of amorphous MEH-PPV at room temperature and verified that the normal definition of a chromophore in a polymer based on purely geometric "conjugation breaks" is not always valid in amorphous polymers and a rigorous definition can be only on the basis of the evaluation of the polymer excited state wave function. The charge transfer character is observed to be nearly invariant for all excited states in low energy window while the exciton delocalization extent is found to increase with energy. The interchain excitonic couplings for amorphous MEH-PPV are shown to be usually smaller than 10 meV suggesting that the transport mechanism across chain can be described by incoherent hopping. All these observations about the energetic and spatial distribution of the excitons in polymer as well as their couplings provide important qualitative insights and useful quantitative information for constructing a realistic model for exciton migration dynamics in amorphous polymer materials.

  2. Coherent Excitation of Lithium to Rydberg States and Application to Rydberg Atom Optics

    NASA Astrophysics Data System (ADS)

    Stevens, G.; Widmer, M.; Tudorica, F.; Iu, C.-H.; Metcalf, H.

    1996-05-01

    We present a theoretical analysis of several schemes for coherently exciting lithium atoms in a thermal beam to Rydberg states in a four level/three laser system, previously discussed by Oreg et al.(J. Oreg et al.), Phys. Rev. A 45, 4888 (1992). The time evolution of the dressed states and their populations are calculated numerically, solving the optical Bloch equations by a fourth order Runge-Kutta integration. Our code closely models actual experimental conditions, including spontaneous decay, beam profiles, intensities and detunings. Large Rydberg populations (50%) around n=15 may be obtained by non-adiabatic excitation, with each laser power on the order of 1 mW. We discuss the effects of an externally controlled time dependent detuning in the Rydberg state, for example as produced by atoms traversing an inhomogeneous electric field. An understanding of this excitation mechanism is important for large angle reflection of coherently excited atoms using field gradients. Some primitive ideas of Stark-Rydberg atom optics are presented.

  3. Evolution of spin excitations into the superconducting state in FeTe1-xSex

    NASA Astrophysics Data System (ADS)

    Lumsden, M. D.; Christianson, A. D.; Goremychkin, E. A.; Nagler, S. E.; Mook, H. A.; Stone, M. B.; Abernathy, D. L.; Guidi, T.; MacDougall, G. J.; de La Cruz, C.; Sefat, A. S.; McGuire, M. A.; Sales, B. C.; Mandrus, D.

    2010-03-01

    The origin of the superconducting state in the recently discovered Fe-based materials is the subject of intense scrutiny. Neutron scattering and NMR (ref. 8) measurements have already demonstrated a strong correlation between magnetism and superconductivity. A central unanswered question concerns the nature of the normal-state spin fluctuations that may be responsible for the pairing. Here we present inelastic neutron scattering measurements from large single crystals of superconducting and non-superconducting Fe1+yTe1-xSex. These measurements indicate a spin fluctuation spectrum dominated by two-dimensional incommensurate excitations extending to energies greater than 250meV. Most importantly, the spin excitations in Fe1+yTe1-xSex have four-fold symmetry about the (1, 0) wavevector (square-lattice (π,π) point). Moreover, the excitations are described by the identical wavevector and can be characterized by the same model as the normal-state spin excitations in the high-TC cuprates. These results demonstrate commonality between the magnetism in these classes of materials, which perhaps extends to a common origin for superconductivity.

  4. 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.

  5. Modeling Excitable Systems Coupled Through External Medium

    NASA Astrophysics Data System (ADS)

    Noorbakhsh, Javad; Mehta, Pankaj

    2013-03-01

    Excitable systems are stable dynamical systems in which any input beyond a threshold results in a significant output. This behavior is ubiquitous in nature and is seen in biological systems such as Dictyostelium discoideum amoeba and neurons to oscillatory chemical reactions. In this work we will focus on transition to oscillation in populations of excitable systems coupled through an external medium and will study their synchronization. We will describe a mechanism to tune the frequency of oscillations using an external input and will study the effects of stochasticity and inhomogeneity on the collective behavior of the system. Furthermore we will include diffusion into the dynamics of the external medium and will study formation of spatial patterns, their characteristics and their robustness to different factors.

  6. 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.

  7. 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

    Franck-Condon region, but we describe a "spin-complete" version of the theory in which proper spin eigenstates are obtained by construction. For systems of coupled chromophores, we have developed an ab initio version of the Frenkel-Davydov exciton model in which collective excitations of the system are expanded in a basis of excited states computed for individual chromophores. The monomer calculations are trivially parallelizable, as is computation of the coupling matrix elements needed to construct the exciton Hamiltonian, and systems containing hundreds of chromophores can be tackled on commodity hardware. This enables calculations on organic semiconductors, where even small model systems exhibit a semicontinuum of excited states that renders traditional TDDFT computationally challenging. Despite including only single excitations on each monomer, the exciton model can describe entangled spins on two or more monomers, an effect that is responsible for excitation energy transfer between chromophores, for example, in singlet fission. Excitonic approximations can also be applied to the TDDFT equations themselves, and a particularly promising application is to describe the effects of environment on an excitation that is localized on a single chromophore. This "local excitation approximation" to TDDFT allows an essentially arbitrary number of solvent molecules to be included in the calculation in a highly parallelizable way such that the time-to-solution increases only very slowly as additional solvent molecules are added. It is therefore possible to converge the calculation with respect to describing an ever-larger portion of the environment at a quantum-mechanical level.

  8. 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.

  9. 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.

  10. Heat capacity for systems with excited-state quantum phase transitions

    NASA Astrophysics Data System (ADS)

    Cejnar, Pavel; Stránský, Pavel

    2017-03-01

    Heat capacities of model systems with finite numbers of effective degrees of freedom are evaluated using canonical and microcanonical thermodynamics. Discrepancies between both approaches, which are observed even in the infinite-size limit, are particularly large in systems that exhibit an excited-state quantum phase transition. The corresponding irregularity of the spectrum generates a singularity in the microcanonical heat capacity and affects smoothly the canonical heat capacity.

  11. Rotationally resolved IR-diode laser studies of ground-state CO2 excited by collisions with vibrationally excited pyridine.

    PubMed

    Johnson, Jeremy A; Kim, Kilyoung; Mayhew, Maurine; Mitchell, Deborah G; Sevy, Eric T

    2008-03-27

    Relaxation of highly vibrationally excited pyridine (C5NH5) by collisions with carbon dioxide has been investigated using diode laser transient absorption spectroscopy. Vibrationally hot pyridine (E' = 40,660 cm(-1)) was prepared by 248 nm excimer laser excitation followed by rapid radiationless relaxation to the ground electronic state. Pyridine then collides with CO2, populating the high rotational CO2 states with large amounts of translational energy. The CO2 nascent rotational population distribution of the high-J (J = 58-80) tail of the 00(0)0 state was probed at short times following the excimer laser pulse to measure rate constants and probabilities for collisions populating these CO2 rotational states. Doppler spectroscopy was used to measure the CO2 recoil velocity distribution for J = 58-80 of the 00(0)0 state. The energy-transfer distribution function, P(E,E'), from E' - E approximately 1300-7000 cm(-1) was obtained by re-sorting the state-indexed energy-transfer probabilities as a function of DeltaE. P(E,E') is fit to an exponential or biexponential function to determine the average energy transferred in a single collision between pyridine and CO2. Also obtained are fit parameters that can be compared to previously studied systems (pyrazine, C6F6, methylpyrazine, and pyrimidine/CO2). Although the rotational and translational temperatures that describe pyridine/CO2 energy transfer are similar to previous systems, the energy-transfer probabilities are much smaller. P(E,E') fit parameters for pyridine/CO2 and the four previously studied systems are compared to various donor molecular properties. Finally, P(E,E') is analyzed in the context of two models, one indicating that P(E,E') shape is primarily determined by the low-frequency out-of-plane donor vibrational modes, and the other that indicates that P(E,E') shape can be determined from how the donor molecule final density of states changes with DeltaE.

  12. Level density parameters from excitation cross sections of isomeric states

    NASA Astrophysics Data System (ADS)

    Skakun, E. A.; Batij, V. G.

    1992-03-01

    Cross section ratios were measured for the production of the isomeric pairs99m,gRh,101m,gRh,102m,gRh,104m,gRh and108m,gIn in the (p,n)-reaction,107m,gIn and109m,gIn in the ( p, γ)-reaction over the energy range up to 9 MeV, and116m,gSb and118m,gSb in the (α, n)-reaction up to 24 MeV. The experimental results for these nuclei as well as for other isometric pairs excited in the ( p, n)-reaction were analysed in the frame of the statistical model for extracting the level density parameter values in the vicinity of closed nucleon shells. The level density parameter behaviour is discussed in the range of nuclear mass numbers under study.

  13. Spectroscopy of ground and excited states of pseudoscalar and vector charmonium and bottomonium

    NASA Astrophysics Data System (ADS)

    Negash, Hluf; Bhatnagar, Shashank

    2016-07-01

    In this paper, we calculate the mass spectrum, weak decay constants, two photon decay widths, and two-gluon decay widths of ground (1S) and radially excited (2S, 3S,…) states of pseudoscalar charmoniuum and bottomonium such as ηc and ηb, as well as the mass spectrum and leptonic decay constants of ground state (1S), excited (2S, 1D, 3S, 2D, 4S,…, 5D) states of vector charmonium and bottomonium such as J/ψ, and Υ, using the formulation of Bethe-Salpeter equation under covariant instantaneous ansatz (CIA). Our results are in good agreement with data (where ever available) and other models. In this framework, from the beginning, we employ a 4 × 4 representation for two-body (qq¯) BS amplitude for calculating both the mass spectra as well as the transition amplitudes. However, the price we have to pay is to solve a coupled set of equations for both pseudoscalar and vector quarkonia, which we have explicitly shown get decoupled in the heavy-quark approximation, leading to mass spectral equation with analytical solutions for both masses, as well as eigenfunctions for all the above states, in an approximate harmonic oscillator basis. The analytical forms of eigenfunctions for ground and excited states so obtained are used to evaluate the decay constants and decay widths for different processes.

  14. 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.

  15. The excited states of stilbene and stilbenoid donor-acceptor dye systems. A theoretical study

    NASA Astrophysics Data System (ADS)

    Rettig, Wolfgang; Strehmel, Bernd; Majenz, Wilfried

    1993-07-01

    Semiempirical calculations within the CNDO/S framework are used to characterize the nature of the "phantom-singlet" excited state P * (double-bond twisted geometry) of stilbene and stilbenoid donor-acceptor dye systems including the laser dyes DCM and DASPMI. P * is highly polar (closed shell "hole-pair" nature) for weakly perturbed stilbenes but for larger donor-acceptor strength, the order of ground and excited state is reversed, and P * becomes of small polarity ("dot-dot" nature), fully consistent with the established model of biradicaloid states. For stilbene, a slight geometric symmetry reduction is necessary in order to localize the orbitals on the subunits. Only then are the calculated results consistent with those for methyl-substituted stilbene. The localized orbital description of twisted stilbene shows that P * contains negligible doubly excited character and possesses a very small gap to the ground state contrary to what is stated in the previous literature. The planar systems are also investigated and correlated with Dähne's triad rule of polymethine systems.

  16. Laboratory Characterization and Astrophysical Detection in Orion KL of Higher Excited Vibrational States of Vinyl Cyanide

    NASA Astrophysics Data System (ADS)

    López, Alicia; Tercero, Belén; Cernicharo, Jose; Kisiel, Zbigniew; Pszczółkowski, Lech; Bermúdez, Celina; Alonso, José L.; Medvedev, Ivan; Neese, Christopher F.; Drouin, Brian; Daly, Adam M.; Marcelino, Nuria; Viti, Serena; Calcutt, Hannah

    2014-06-01

    Vinyl cyanide (acrylonitrile, H_2C=CHC≡N) is an interstellar molecule that was classified as a 'weed' since transitions in its isotopic species and vibrationally excited states have already been detected and need to be accounted for in searches for complex organic molecules. Presently we extend the systematic analysis of the laboratory rotational spectrum of vinyl cyanide to 9 new excited vibrational states with vibrational energies above 550 cm-1 (785K). The spectroscopic analysis is based on the broadband 50-1900 GHz spectrum combined from results from the participating spectroscopic laboratories and covering a total of 1235 GHz. The studied states come in the form of polyads of perturbing vibrational states, and such perturbations also affect the strong, low-K_a transitions used for astrophysical detection. It is therefore crucial to account for such effects in order to produce reliable linelists. The experimental data for three new polyads were fitted to experimental accuracy using Coriolis and Fermi perturbation models. Multiple transitions in the lowest of these polyads (and in other excited vibrational states and isotopic species of vinyl cyanide) were detected in the millimetre survey of the Orion-KL Nebula made with the IRAM 30-m radiotelescope.

  17. Excited triplet states as photooxidants in surface waters

    NASA Astrophysics Data System (ADS)

    Canonica, S.

    2012-12-01

    The chromophoric components of dissolved organic matter (DOM) are generally the main absorbers of sunlight in surface waters and therefore a source of transient reactants under irradiation. Such short-lived species can be relevant for the fate of various classes of chemical contaminants in the aquatic environment. The present contribution focuses on the role of excited triplet states of chromophoric DOM, 3CDOM*, as transient photooxidants initiating the transformation and degradation of organic chemical contaminants. An early study [1] indicated that 3CDOM* may play a dominant role in the photo-induced transformation of electron-rich phenols, a conclusion which was later fortified by the results of transient absorption investigations using aromatic ketones as model photosensitizers [2] and by a recent careful analysis of the effect of oxygen concentration on transformation rates [3]. The variety of aquatic contaminants shown to be affected by triplet-induced oxidation has kept increasing, phenylurea herbicides [4], sulfonamide antibiotics [5] and some phytoestrogens [6] being prominent examples. Recent research has shown that the triplet-induced transformation of specific contaminants, especially aromatic nitrogen compounds, could be inhibited by the presence of DOM, very probably due to its antioxidant moieties [7]. While such moieties are not relevant for the quenching of 3CDOM*, they are expected to react with it in a similar way as the studied contaminants. Analogous reactions can be postulated to occur in liquid or solid phases of the atmospheric environment, as demonstrated in the case of HONO formation [8]. References 1. Canonica, S.; Jans, U.; Stemmler, K.; Hoigné, J. Transformation kinetics of phenols in water: Photosensitization by dissolved natural organic material and aromatic ketones. Environ. Sci. Technol. 1995, 29 (7), 1822-1831. 2. Canonica, S.; Hellrung, B.; Wirz, J. Oxidation of phenols by triplet aromatic ketones in aqueous solution. J. Phys

  18. 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.

  19. Scaling of collision strengths for highly-excited states of ions of the H- and He-like sequences

    NASA Astrophysics Data System (ADS)

    Fernández-Menchero, L.; Del Zanna, G.; Badnell, N. R.

    2016-08-01

    Emission lines from highly-excited states (n ≥ 5) of H- and He-like ions have been detected in astrophysical sources and fusion plasmas. For such excited states, R-matrix or distorted wave calculations for electron-impact excitation are very limited, due to the large size of the atomic basis set needed to describe them. Calculations for n ≥ 6 are also not generally available. We study the behaviour of the electron-impact excitation collision strengths and effective collision strengths for the most important transitions used to model electron collision dominated astrophysical plasmas, solar, for example. We investigate the dependence on the relevant parameters: the principal quantum number n or the nuclear charge Z. We also estimate the importance of coupling to highly-excited states and the continuum by comparing the results of different sized calculations. We provide analytic formulae to calculate the electron-impact excitation collision strengths and effective collision strengths to highly-excited states (n ≥ 8) of H- and He-like ions. These extrapolated effective collision strengths can be used to interpret astrophysical and fusion plasma via collisional-radiative modelling. Tables of atomic data for Si xiii and S xv are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/592/A135

  20. 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.

  1. 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.

  2. Ferrimagnetism and single-particle excitations in a periodic Anderson model on the honeycomb lattice

    NASA Astrophysics Data System (ADS)

    Seki, Kazuhiro; Shirakawa, Tomonori; Zhang, Qinfang; Li, Tao; Yunoki, Seiji

    2015-04-01

    By using the variationalcluster approximation and cluster perturbation theory, we investigate the magnetism and single-particle excitations of a periodic Anderson model on the honeycomb lattice as an effective model for the single-side hydrogenated graphene, namely, graphone. We calculate the magnetic moment as a function of U (Coulomb interaction on impurity sites) with showing that the ground state is ferrimagneticfor any U > 0. We then calculate the single-particle excitations and show that the single-particle excitations are gapless and exhibit quadratic dispersion relation near the Fermi energy.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Light-induced self-nitrosation of polycyclic phenols with nitrosamine. Excited state proton transfer

    SciTech Connect

    Chow, Y.L.; Wu, Z.Z.

    1987-08-19

    Photoexcitation of polycyclic phenols in the presence of N-nitrosodimethylamine caused the self-nitrosation of the phenols to give 1,2- or 1,4-quinone monooximes. With use of naphthols as models the key step of the photonitrosation was shown to be a dual sensitization process from the lowest singlet excited state of naphthols by proton transfer followed by energy migration within an exciplex to cause the known homolysis of the nitrosamine; it is assumed that the resulting radical species undergo nitrosation of naphtholates. The crucial requirement of the excited state proton transfer (ESPT) reaction is established by quenching of the photonitrosation by general bases, such as water and TEA, with quenching rate constants close to those of naphthol fluorescence by these bases.

  8. Nonlinear vibrational-state excitation and piezoelectric energy conversion in harmonically driven granular chains

    NASA Astrophysics Data System (ADS)

    Chong, C.; Kim, E.; Charalampidis, E. G.; Kim, H.; Li, F.; Kevrekidis, P. G.; Lydon, J.; Daraio, C.; Yang, J.

    2016-05-01

    This article explores the excitation of different vibrational states in a spatially extended dynamical system through theory and experiment. As a prototypical example, we consider a one-dimensional packing of spherical particles (a so-called granular chain) that is subject to harmonic boundary excitation. The combination of the multimodal nature of the system and the strong coupling between the particles due to the nonlinear Hertzian contact force leads to broad regions in frequency where different vibrational states are possible. In certain parametric regions, we demonstrate that the nonlinear Schrödinger equation predicts the corresponding modes fairly well. The electromechanical model we apply predicts accurately the conversion from the obtained mechanical energy to the electrical energy observed in experiments.

  9. Effect of an excited-state optical transition on the linewidth enhancement factor of quantum dot lasers

    SciTech Connect

    Zhukov, A. E. Savelyev, A. V.; Maximov, M. V.; Shernyakov, Yu. M.; Arakcheeva, E. M.; Zubov, F. I.; Krasivichev, A. A.; Kryzhanovskaya, N. V.

    2012-02-15

    An analytical expression is derived for the linewidth enhancement factor of a quantum-dot laser, which makes it possible to describe its dependence on optical loss and photon density in an explicit form. The model accounts for refractive index variations at the ground-state optical transition due to gain/absorption variations upon the first excited-state transition in quantum dots. It is shown that a decrease in optical loss, an increase in saturated gain, and an increase in the energy separation between the excited-state and ground-state transitions results in a decrease in the {alpha} factor both at and above the lasing threshold.

  10. Excited electronic states from a variational approach based on symmetry-projected Hartree–Fock configurations

    SciTech Connect

    Jiménez-Hoyos, Carlos A.; Rodríguez-Guzmán, R.; Scuseria, Gustavo E.

    2013-12-14

    Recent work from our research group has demonstrated that symmetry-projected Hartree–Fock (HF) methods provide a compact representation of molecular ground state wavefunctions based on a superposition of non-orthogonal Slater determinants. The symmetry-projected ansatz can account for static correlations in a computationally efficient way. Here we present a variational extension of this methodology applicable to excited states of the same symmetry as the ground state. Benchmark calculations on the C{sub 2} dimer with a modest basis set, which allows comparison with full configuration interaction results, indicate that this extension provides a high quality description of the low-lying spectrum for the entire dissociation profile. We apply the same methodology to obtain the full low-lying vertical excitation spectrum of formaldehyde, in good agreement with available theoretical and experimental data, as well as to a challenging model C{sub 2v} insertion pathway for BeH{sub 2}. The variational excited state methodology developed in this work has two remarkable traits: it is fully black-box and will be applicable to fairly large systems thanks to its mean-field computational cost.

  11. Exotic and excited-state radiative transitions in charmonium from lattice QCD

    SciTech Connect

    Dudek, Jozef J.; Edwards, Robert G.; Thomas, Christopher E.

    2009-05-01

    We compute, for the first time using lattice QCD methods, radiative transition rates involving excited charmonium states, states of high spin and exotics. Utilizing a large basis of interpolating fields we are able to project out various excited state contributions to three-point correlators computed on quenched anisotropic lattices. In the first lattice QCD calculation of the exotic $1^{-+}$ $\\eta_{c1}$ radiative decay, we find a large partial width $\\Gamma(\\eta_{c1} \\to J/\\psi \\gamma) \\sim 100 \\,\\mathrm{keV}$. We find clear signals for electric dipole and magnetic quadrupole transition form factors in $\\chi_{c2} \\to J/\\psi \\gamma$, calculated for the first time in this framework, and study transitions involving excited $\\psi$ and $\\chi_{c1,2}$ states. We calculate hindered magnetic dipole transition widths without the sensitivity to assumptions made in model studies and find statistically significant signals, including a non-exotic vector hybrid candidate $Y_{\\mathrm{hyb?}} \\to \\et

  12. Exotic and excited-state radiative transitions in charmonium from lattice QCD

    DOE PAGES

    Dudek, Jozef J.; Edwards, Robert G.; Thomas, Christopher E.

    2009-05-01

    We compute, for the first time using lattice QCD methods, radiative transition rates involving excited charmonium states, states of high spin and exotics. Utilizing a large basis of interpolating fields we are able to project out various excited state contributions to three-point correlators computed on quenched anisotropic lattices. In the first lattice QCD calculation of the exoticmore » $$1^{-+}$$ $$\\eta_{c1}$$ radiative decay, we find a large partial width $$\\Gamma(\\eta_{c1} \\to J/\\psi \\gamma) \\sim 100 \\,\\mathrm{keV}$$. We find clear signals for electric dipole and magnetic quadrupole transition form factors in $$\\chi_{c2} \\to J/\\psi \\gamma$$, calculated for the first time in this framework, and study transitions involving excited $$\\psi$$ and $$\\chi_{c1,2}$$ states. We calculate hindered magnetic dipole transition widths without the sensitivity to assumptions made in model studies and find statistically significant signals, including a non-exotic vector hybrid candidate $Y_{\\mathrm{hyb?}} \\to \\et« less

  13. Chemical bonding in excited states: Energy transfer and charge redistribution from a real space perspective.

    PubMed

    Jara-Cortés, Jesús; Guevara-Vela, José Manuel; Martín Pendás, Ángel; Hernández-Trujillo, Jesús

    2017-05-15

    This work provides a novel interpretation of elementary processes of photophysical relevance from the standpoint of the electron density using simple model reactions. These include excited states of H2 taken as a prototype for a covalent bond, excimer formation of He2 to analyze non-covalent interactions, charge transfer by an avoided crossing of electronic states in LiF and conical interesections involved in the intramolecular scrambling in C2 H4 . The changes of the atomic and interaction energy components along the potential energy profiles are described by the interacting quantum atoms approach and the quantum theory of atoms in molecules. Additionally, the topological analysis of one- and two-electron density functions is used to explore basic reaction mechanisms involving excited and degenerate states in connection with the virial theorem. This real space approach allows to describe these processes in a unified way, showing its versatility and utility in the study of chemical systems in excited states. © 2017 Wiley Periodicals, Inc.

  14. Two-photon excitation into low-energy singlet states of anthracene in mixed crystals

    NASA Astrophysics Data System (ADS)

    Bree, A.; Leyderman, A.; Taliani, C.

    1985-08-01

    The two-photon excitation spectrum of the first excited state of anthracene in fluorene and biphenyl at 4.2 K has been measured. Intensity is induced into the origin by the static dipole moment of fluorene, and into b 1u vibrons through coupling to an A g state near 29400 cm -1; the nature of this A g state is discussed.

  15. Electron delocalization and aromaticity in low-lying excited states of archetypal organic compounds.

    PubMed

    Feixas, Ferran; Vandenbussche, Jelle; Bultinck, Patrick; Matito, Eduard; Solà, Miquel

    2011-12-14

    Aromaticity is a property usually linked to the ground state of stable molecules. Although it is well-known that certain excited states are unquestionably aromatic, the aromaticity of excited states remains rather unexplored. To move one step forward in the comprehension of aromaticity in excited states, in this work we analyze the electron delocalization and aromaticity of a series of low-lying excited states of cyclobutadiene, benzene, and cyclooctatetraene with different multiplicities at the CASSCF level by means of electron delocalization measures. While our results are in agreement with Baird's rule for the aromaticity of the lowest-lying triplet excited state in annulenes having 4nπ-electrons, they do not support Soncini and Fowler's generalization of Baird's rule pointing out that the lowest-lying quintet state of benzene and septet state of cyclooctatetraene are not aromatic.

  16. Self-Exciting Point Process Modeling of Conversation Event Sequences

    NASA Astrophysics Data System (ADS)

    Masuda, Naoki; Takaguchi, Taro; Sato, Nobuo; Yano, Kazuo

    Self-exciting processes of Hawkes type have been used to model various phenomena including earthquakes, neural activities, and views of online videos. Studies of temporal networks have revealed that sequences of social interevent times for individuals are highly bursty. We examine some basic properties of event sequences generated by the Hawkes self-exciting process to show that it generates bursty interevent times for a wide parameter range. Then, we fit the model to the data of conversation sequences recorded in company offices in Japan. In this way, we can estimate relative magnitudes of the self excitement, its temporal decay, and the base event rate independent of the self excitation. These variables highly depend on individuals. We also point out that the Hawkes model has an important limitation that the correlation in the interevent times and the burstiness cannot be independently modulated.

  17. Excited state property of hardly photodissociable heme-CO adduct studied by time-dependent density functional theory.

    PubMed

    Ohta, Takehiro; Pal, Biswajit; Kitagawa, Teizo

    2005-11-10

    While most of CO-bound hemes are easily photodissociated with a quantum yield of nearly unity, we occasionally encounter a CO-heme which appears hardly photodissociable under the ordinary measurement conditions of resonance Raman spectra using CW laser excitation and a spinning cell. This study aims to understand such hemes theoretically, that is, the excited-state properties of the five-coordinate heme-CO adduct (5cH) as well as the 6c heme-CO adduct (6cH) with a weak axial ligand. Using a hybrid density functional theory, we scrutinized the properties of the ground and excited spin states of the computational models of a 5cH and a water-ligated 6cH (6cH-H(2)O) and compared these properties with those of a photodissociable imidazole-ligated 6cH (6cH-Im). Jahn-Teller softening for the Fe-C-O bending potential in the a(1)-e excited state was suggested. The excited-state properties of 6cH-Im and 5cH were further studied with time-dependent DFT theory. The reaction products of 6cH-Im and 5cH were assumed to be quintet and triplet states, respectively. According to the time-dependent DFT calculations, the Q excited state of 6cH-Im, which is initially a pure pi-pi state, crosses the Fe-CO dissociative state (2A') without large elongation of the Fe-CO bond. In contrast, the Q state of the 5cH does not cross the Fe-CO dissociative state but results in the formation of the excited spin state with a bent Fe-C-O. Consequently, photoisomerization from linear to bent Fe-C-O in the 5cH is a likely mechanism for apparent nonphotodissociation.

  18. Lifetimes and branching ratios of excited anion states

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

    Relativistic configuration-interaction transition probability calculations have been performed for several anion cases of our recent lanthanideootnotetextS. M. O'Malley and D. R. Beck, Phys. Rev. A 79, 012511 (2009). and actinideootnotetextS. M. O'Malley and D. R. Beck, Phys. Rev. A 80, 032514 (2009). studies. In particular, we identified an E1 transition (˜3680 nm) in La^- that may prove more useful in laser-cooling applications than the previously proposed Os^- candidateootnotetextA. Kellerbauer and J. Walz, New J. Phys. 8, 45 (2006).. We also explored long-lived states in Lu^- and Lr^- which are restricted to M2 decay by selection rules. Finally, we found sufficient mixing between a weakly-bound alternate-configuration Pr^- level and a nearby resonance to result in a lifetime (M1/E2) similar to other excited levels despite a two-electron difference between the dominant configurations. The details of the Pr^- calculations serve as further confirmation of the utility of our universal jls restrictions on 4f^n and 5f^n portions of lanthanide and actinide wave functions, but we find that a similar application to d^k electron subgroups in transition metals (Os^-) has a much smaller impact on the complexity of our calculations.

  19. Electronic excitation of ground state atoms by collision with heavy gas particles

    NASA Technical Reports Server (NTRS)

    Hansen, C. Frederick

    1993-01-01

    point where the initial and final potentials cross, or at least come very close. Therefore, this mechanism would be applicable to the case where a gas is initially at very low temperature suddenly subjected to high energy heavy particle bombardment. This situation would model the measurement of excitation cross section by molecular beam techniques, for example. The purpose is to report values of cross sections and rate coefficients for collision excitation of ground state atoms estimated with the Landau-Zener transition theory and to compare results with measurement of excitation cross sections for a beam of Hydrogen atoms impacting Argon atom targets. Some very dubious approximations are used, and the comparison with measurement is found less than ideal, but results are at least consistent within order of magnitude. The same model is then applied to the case of N-N atom collisions, even though the approximations then become even more doubtful. Still the rate coefficients obtained are at least plausible in both magnitude and functional form, and as far as I am aware these are the only estimates available for such rate coefficients.

  20. 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

  1. Vibrational dynamics of aniline (N2)1 clusters in their first excited singlet state

    NASA Astrophysics Data System (ADS)

    Hineman, M. F.; Kim, S. K.; Bernstein, E. R.; Kelley, D. F.

    1992-04-01

    The first excited singlet state S1 vibrational dynamics of aniline(N2)1 clusters are studied and compared to previous results on aniline(CH4)1 and aniline(Ar)1. Intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP) rates fall between the two extremes of the CH4 (fast IVR, slow VP) and Ar (slow IVR, fast VP) cluster results as is predicted by a serial IVR/VP model using Fermi's golden rule to describe IVR processes and a restricted Rice-Ramsperger-Kassel-Marcus (RRKM) theory to describe unimolecular VP rates. The density of states is the most important factor determining the rates. Two product states, 00 and 10b1, of bare aniline and one intermediate state ˜(00) in the overall IVR/VP process are observed and time resolved measurements are obtained for the 000 and ˜(000) transitions. The results are modeled with the serial mechanism described above.

  2. Excited state absorption spectrum of chlorophyll a obtained with white-light continuum.

    PubMed

    De Boni, L; Correa, D S; Pavinatto, F J; dos Santos, D S; Mendonça, C R

    2007-04-28

    The study of excited state properties of chlorophyll a is a subject of foremost interest, given that it plays important roles in biological process and has also been proposed for applications in photonics. This work reports on the excited state absorption spectrum of chlorophyll a solution from 460 to 700 nm, obtained through the white-light continuum Z-scan technique. Saturation of absorption was observed due to the ground state depletion, induced by the white-light continuum region that is resonant with the Q band of chlorophyll a. The authors also observed reverse saturation of absorption related to the excitation from the first excited state to a higher energy level for wavelengths below 640 nm. An energy-level diagram, based on the electronic states of chlorophyll a, was employed to interpret their results, revealing that more states than the ones related to the Q and B bands participate in the excited state absorption of this molecule.

  3. Excited-state mixed valence in a diphenyl hydrazine cation: Spectroscopic consequences of coupling and transition dipole moment orientation.

    PubMed

    Lockard, Jenny V; Zink, Jeffrey I; Trieber Ii, Dwight A; Konradsson, Asgeir E; Weaver, Michael N; Nelsen, Stephen F

    2005-02-17

    A quantitative model of mixed-valence excited-state spectroscopy is developed and applied to 2,3-diphenyl-2,3-diazabicyclo[2.2.2]octane. The lowest-energy excited state of this molecule arises from a transition from the ground state, where the charge is located on the hydrazine bridge, to an excited state where the charge is associated with one phenyl group or the other. Coupling splits the absorption band into two components with the lower-energy component being the most intense. The sign of the coupling, derived by using a neighboring orbital model, is positive. The transition dipole moments consist of parallel and antiparallel vector components, and selection rules for each are derived. Bandwidths are caused by progressions in totally symmetric modes determined from resonance Raman spectroscopic analysis. The absorption, emission, and Raman spectra are fit simultaneously with one parameter set.

  4. Direct Electron Impact Excitation of Rydberg-Valence States of Molecular Nitrogen

    NASA Astrophysics Data System (ADS)

    Malone, C. P.; Johnson, P. V.; Liu, X.; Ajdari, B.; Muleady, S.; Kanik, I.; Khakoo, M. A.

    2012-12-01

    Collisions between electrons and neutral N2 molecules result in emissions that provide an important diagnostic probe for understanding the ionospheric energy balance and the effects of space weather in upper atmospheres. Also, transitions to singlet ungerade states cause N2 to be a strong absorber of solar radiation in the EUV spectral range where many ro-vibrational levels of these Rydberg-valence (RV) states are predissociative. Thus, their respective excitation and emission cross sections are important parameters for understanding the [N]/[N2] ratio in the thermosphere of nitrogen dominated atmospheres. The following work provides improved constraints on absolute and relative excitation cross sections of numerous RV states of N2, enabling more physically accurate atmospheric modeling. Here, we present recent integral cross sections (ICSs) for electron impact excitation of RV states of N2 [6], which were based on the differential cross sections (DCSs) derived from electron energy-loss (EEL) spectra of [5]. This work resulted in electronic excitation cross sections over the following measured vibrational levels: b 1Πu (v‧=0-14), c3 1Πu (v‧=0-3), o3 1Πu (v‧=0-3), b‧ 1Σu+ (v‧=0-10), c‧4 1Σu+ (v‧=0-3), G 3Πu (v‧=0-3), and F 3Πu (v‧=0-3). We further adjusted the cross sections of the RV states by extending the vibronic contributions to unmeasured v‧-levels via the relative excitation probabilities (REPs) as discussed in [6]. This resulted in REP-scaled ICSs over the following vibrational levels for the singlet ungerade states: b(0-19), c3(0-4), o3(0-4), b‧(0-16), and c‧4(0-8). Comparison of the ICSs of [6] with available EEL based measurements, theoretical calculations, and emission based work generally shows good agreement within error estimations, except with the recent reevaluation provided by [1]. Further, we have extended these results, using the recent EEL data of [3], to include the unfolding of better resolved features above ~13

  5. Excitation spectra and spin gap of the half-filled Holstein-Hubbard model

    NASA Astrophysics Data System (ADS)

    Hohenadler, Martin; Assaad, Fakher F.

    2013-02-01

    Single- and two-particle excitation spectra of the one-dimensional, half-filled Holstein-Hubbard model are calculated using the continuous-time quantum Monte Carlo method. In the metallic phase, the results are consistent with a Luther-Emery liquid that has gapped spin and single-particle excitations but a gapless charge mode. However, given the initially exponential dependence of the spin gap on the backscattering matrix element, the numerical excitation spectra appear gapless in the weak-coupling regime, and therefore resemble those of a Luttinger liquid. The Mott phase has the expected charge gap and gapless spin excitations. The Peierls state shows a charge, spin, and single-particle gap, a soft phonon mode, backfolded shadow bands, and soliton excitations. Arguments and numerical evidence for the existence of a nonzero spin gap throughout the metallic phase are provided in terms of equal-time spin and charge correlation functions.

  6. An excitation-pattern model for the starling (Sturnus vulgaris).

    PubMed

    Buus, S; Klump, G M; Gleich, O; Langemann, U

    1995-07-01

    This paper develops and tests an excitation-pattern model for the starling. Like excitation-pattern models for humans [e.g., Zwicker, Acustica 6, 365-381 (1956); Florentine and Buus, J. Acoust. Soc. Am. 70, 1646-1654 (1981)], the model for starlings provides a unified account of a large body of data. The foundation of the model is a critical-band scale, which is derived as an equal-distance scale according to a cochlear-map function. The cochlear-map function is determined as a best-fitting function to physiological data relating characteristic frequency (CF) of auditory-nerve fibers to their place of innervation on the basilar papilla. Excitation patterns are derived from auditory-nerve measurements of levels at CF necessary to produce firing rates equal to those evoked by a test tone. The shape of these excitation patterns is independent of level and frequency when plotted on a cochlear-distance scale. The resulting model indicates that 10-dB bandwidths of auditory-nerve tuning curves and frequency DLs can be approximated as equal distances along the basilar papilla. Predictions of level discrimination are in good agreement with the data, except below 20 dB SL. Overall, the present work indicates that excitation-pattern models account for a wide range of auditory phenomena in both humans and starlings, when the models take into account differences in critical-band scales, absolute thresholds, excitation-pattern slopes, and growth of excitation, which is linear in starlings, but nonlinear in humans.

  7. Activity of upper electron-excited states in bioluminescence of coelenterates

    NASA Astrophysics Data System (ADS)

    Belogurova, N. V.; Alieva, R. R.; Kudryasheva, N. S.

    2009-04-01

    The involvement of upper electron-excited states as the primary excited states into bioluminescence of coelenterates was experimentally verified. A series of fluorescent molecules was used as foreign energy acceptors in this bioluminescent reaction. The fluorescent aromatic compounds - pyrene, 2-methoxy-naphtalene, naphthalene, and 1,4-diphenylbutadiene - were selected, with fluorescent state energies ranging from 26,700 to 32,500 cm -1. Excitation of these molecules by Forster singlet-singlet energy transfer from S of bioluminescence emitter and by light absorption were excluded. The weak sensitized fluorescence of three compounds was found in the course of bioluminescent reaction. Energy of the upper electron-excited states of the bioluminescent emitter was located around 31,000 cm -1. Localization of the primary excitation on a carbonyl group of coelenteramide molecule is discussed. Comparison of the primary excitation in bioluminescent processes of coelenterates and bacteria is provided.

  8. Comparison of different models of geophysical excitation in nutation

    NASA Astrophysics Data System (ADS)

    Ron, Cyril; Vondrák, Jan

    2015-04-01

    Celestial pole offsets caused by the excitations of geophysical fluids (atmosphere, ocean) and geomagnetic fields (geomagnetic jerks) are computed for a non-rigid Earth model to account for the realistic Earth's response by using the integration of the broad-band Liouville equations. The results are compared with the celestial pole offsets observed by Very Long-Baseline Interferometry. In our previous study we demonstrated that the application of a synthetic excitation in the epoch of the geomagnetic jerks improves significantly the agreement between the integrated and observed celestial pole offsets. In the presented study we focus on the analysis of differencies between the integrated series excited by different models of geophysical fluids, the U.S. model NCEP/NCAR and the European models ERA supplemented with the ocean model OMCT provided by GFZ Potsdam.

  9. Multi-pathway excited state relaxation of adenine oligomers in aqueous solution: a joint theoretical and experimental study.

    PubMed

    Banyasz, Akos; Gustavsson, Thomas; Onidas, Delphine; Changenet-Barret, Pascale; Markovitsi, Dimitra; Improta, Roberto

    2013-03-11

    The singlet excited states of adenine oligomers, model systems widely used for the understanding of the interaction of ultraviolet radiation with DNA, are investigated by fluorescence spectroscopy and time-dependent (TD) DFT calculations. Fluorescence decays, fluorescence anisotropy decays, and time-resolved fluorescence spectra are recorded from the femtosecond to the nanosecond timescales for single strand (dA)20 in aqueous solution. These experimental observations and, in particular, the comparison of the fluorescence behavior upon UVC and UVA excitation allow the identification of various types of electronic transitions with different energy and polarization. Calculations performed for up to five stacked 9-methyladenines, taking into account the solvent, show that different excited states are responsible for the absorption in the UVC and UVA spectral domains. Independently of the number of bases, bright excitons may evolve toward two types of excited dimers having π-π* or charge-transfer character, each one distinguished by its own geometry and spectroscopic signature. According to the picture arising from the joint experimental and theoretical investigation, UVC-induced fluorescence contains contribution from 1) exciton states with a different degree of localization, decaying within a few ps, 2) "neutral" excited dimers decaying on the sub-nanosecond timescale, being the dominant species, and 3) charge-transfer states decaying on the nanosecond timescale. The majority of the photons emitted upon UVA excitation are related to charge-transfer states.

  10. Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

    DOE PAGES

    Zhang, Wenkai; Kjaer, Kasper S.; Alonso-Mori, Roberto; ...

    2016-08-25

    Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover – the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN–) ligands and one 2,2'-bipyridine (bpy) ligand. This enables MLCTmore » excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN)4(bpy)]2–. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. Here, we conclude that the MLCT excited state of [Fe(CN)4(bpy)]2– decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2'-bipyridine)3]2+ by more than two orders of magnitude.« less

  11. Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

    SciTech Connect

    Zhang, Wenkai; Kjaer, Kasper S.; Alonso-Mori, Roberto; Bergmann, Uwe; Chollet, Matthieu; Fredin, Lisa A.; Hadt, Ryan G.; Hartsock, Robert W.; Harlang, Tobias; Kroll, Thomas; Kubicek, Katharina; Lemke, Henrik T.; Liang, Huiyang W.; Liu, Yizhu; Nielsen, Martin M.; Persson, Petter; Robinson, Joseph S.; Solomon, Edward I.; Sun, Zheng; Sokaras, Dimosthenis; van Driel, Tim B.; Weng, Tsu -Chien; Zhu, Diling; Warnmark, Kenneth; Sundstrom, Villy; Gaffney, Kelly J.

    2016-08-25

    Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover – the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN) ligands and one 2,2'-bipyridine (bpy) ligand. This enables MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN)4(bpy)]2–. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. Here, we conclude that the MLCT excited state of [Fe(CN)4(bpy)]2– decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2'-bipyridine)3]2+ by more than two orders of magnitude.

  12. Ab Initio Calculations of Singlet and Triplet Excited States of Chlorine Nitrate and Nitric Acid

    NASA Technical Reports Server (NTRS)

    Grana, Ana M.; Lee, Timothy J.; Head-Gordon, Martin; Langhoff, Stephen R. (Technical Monitor)

    1994-01-01

    Ab initio calculations of vertical excitations to singlet and triplet excited states of chlorine nitrate and nitric acid are reported. The nature of the electronic transitions are examined by decomposing the difference density into the sum of detachment and attachment densities. Counterparts for the three lowest singlet excited states of nitric acid survive relatively unperturbed in chlorine nitrate, while other low-lying singlet states of chlorine nitrate appear to be directly dissociative in the ClO chromophore. These results suggest an assignment of the two main peaks in the experimental chlorine nitrate absorption spectrum. In addition, triplet vertical excitations and the lowest optimized triplet geometries of both molecules are studied.

  13. Effect of Turbulence Modeling on an Excited Jet

    NASA Technical Reports Server (NTRS)

    Brown, Clifford A.; Hixon, Ray

    2010-01-01

    The flow dynamics in a high-speed jet are dominated by unsteady turbulent flow structures in the plume. Jet excitation seeks to control these flow structures through the natural instabilities present in the initial shear layer of the jet. Understanding and optimizing the excitation input, for jet noise reduction or plume mixing enhancement, requires many trials that may be done experimentally or computationally at a significant cost savings. Numerical simulations, which model various parts of the unsteady dynamics to reduce the computational expense of the simulation, must adequately capture the unsteady flow dynamics in the excited jet for the results are to be used. Four CFD methods are considered for use in an excited jet problem, including two turbulence models with an Unsteady Reynolds Averaged Navier-Stokes (URANS) solver, one Large Eddy Simulation (LES) solver, and one URANS/LES hybrid method. Each method is used to simulate a simplified excited jet and the results are evaluated based on the flow data, computation time, and numerical stability. The knowledge gained about the effect of turbulence modeling and CFD methods from these basic simulations will guide and assist future three-dimensional (3-D) simulations that will be used to understand and optimize a realistic excited jet for a particular application.

  14. Excited-state lifetime of adenine near the first electronic band origin

    NASA Astrophysics Data System (ADS)

    Kang, Hyuk; Chang, Jinyoung; Lee, Sang Hak; Ahn, Tae Kyu; Kim, Nam Joon; Kim, Seong Keun

    2010-10-01

    The excited-state lifetime of supersonically cooled adenine was measured in the gas phase by femtosecond pump-probe transient ionization as a function of excitation energy between 36 100 and 37 500 cm-1. The excited-state lifetime of adenine is ˜2 ps around the 0-0 band of the L1b ππ ∗ state (36 105 cm-1). The lifetime drops to ˜1 ps when adenine is excited to the L1a ππ ∗ state with the pump energy at 36 800 cm-1 and above. The excited-state lifetimes of L1a and L1b ππ∗ states are differentiated in accordance with previous frequency-resolved and computational studies.

  15. Excited-state annihilation process involving a cyclometalated platinum(II) complex

    SciTech Connect

    Maestri, M.; Sandrini, D. ); von Zelewsky, A.; Deuschel-Cornioley, C. )

    1991-05-29

    The Pt(tpy)(ppz) complex exhibits strong luminescence with a relatively long excited-state lifetime (15.3 {mu}s) in deaerated acetonitrile solution, at room temperature and at low excitation intensity, and can be easily involved in excited-state quenching processes. The {sub 3}CT excited state is, in fact, quenched (1) by oxygen (k{sub q} {congruent} 10{sup 9} M{sup {minus}1} s{sup {minus}1}), (2) by the ground-state complex (k{sub q} = 5.7 {times} 10{sup 7} M{sup {minus}1} s{sup {minus}1}), and (3) by another {sup 3}CT excited state in an annihilation process, which is practically diffusion controlled (k{sub 3} > 6 {times} 10{sup 9} M{sup {minus}1} s{sup {minus}1}). The ground-state quenching and the annihilation process most probably occur via an excimer formation mechanism. 46 refs., 3 figs.

  16. Intramolecular excited-state proton-transfer studies on flavones in different environments

    NASA Astrophysics Data System (ADS)

    Kumar, Sanjay; Jain, Sapan K.; Sharma, Neera; Rastogi, Ramesh C.

    2001-02-01

    The absorption and fluorescence spectra of some biologically active flavones have been studied as a function of the acidity (pH/H 0) of the solution. Dissociation constants have been determined for the ground and first excited singlet states. The results are compared with those obtained from Forster-Weller calculations. The acidity constants obtained by fluorimetric titration method are in complete agreement (in most of the systems) with ground state data indicating a excited state deactivation prior to prototropic equilibration. Compared to umbelliferones, flavones are only weakly fluorescent in alkaline solution. This behaviour is explained by the small energy difference between the singlet excited state and triplet excited state giving rise to more efficient intersystem crossing. Most of the flavones studied here undergo adiabatic photodissociation in the singlet excited state indicating the formation of an exciplex or a phototautomer.

  17. Modeling K,ATP-Dependent Excitability in Pancreatic Islets

    PubMed Central

    Silva, Jonathan R.; Cooper, Paige; Nichols, Colin G.

    2014-01-01

    In pancreatic β-cells, K,ATP channels respond to changes in glucose to regulate cell excitability and insulin release. Confirming a high sensitivity of electrical activity to K,ATP activity, mutations that cause gain of K,ATP function cause neonatal diabetes. Our aim was to quantitatively assess the contribution of K,ATP current to the regulation of glucose-dependent bursting by reproducing experimentally observed changes in excitability when K,ATP conductance is altered by genetic manipulation. A recent detailed computational model of single cell pancreatic β-cell excitability reproduces the β-cell response to varying glucose concentrations. However, initial simulations showed that the model underrepresents the significance of K,ATP activity and was unable to reproduce K,ATP conductance-dependent changes in excitability. By altering the ATP and glucose dependence of the L-type Ca2+ channel and the Na-K ATPase to better fit experiment, appropriate dependence of excitability on K,ATP conductance was reproduced. Because experiments were conducted in islets, which contain cell-to-cell variability, we extended the model from a single cell to a three-dimensional model (10×10×10 cell) islet with 1000 cells. For each cell, the conductance of the major currents was allowed to vary as was the gap junction conductance between cells. This showed that single cell glucose-dependent behavior was then highly variable, but was uniform in coupled islets. The study highlights the importance of parameterization of detailed models of β-cell excitability and suggests future experiments that will lead to improved characterization of β-cell excitability and the control of insulin secretion. PMID:25418087

  18. Experimental investigation of shell-model excitations of 89Zr up to high spin

    NASA Astrophysics Data System (ADS)

    Saha, S.; Palit, R.; Sethi, J.; Trivedi, T.; Srivastava, P. C.; Kumar, S.; Naidu, B. S.; Donthi, R.; Jadhav, S.; Biswas, D. C.; Garg, U.; Goswami, A.; Jain, H. C.; Joshi, P. K.; Mukherjee, G.; Naik, Z.; Nag, S.; Nanal, V.; Pillay, R. G.; Saha, S.; Singh, A. K.

    2012-09-01

    Near yrast states in 89Zr were investigated up to high spin using the fusion evaporation reaction 80Se(13C, 4n) at an incident beam energy of 50 MeV. Excited levels of 89Zr have been observed up to ˜10 MeV excitation energy and spin ˜37/2ℏ using the prompt gamma spectroscopy technique with the Indian National Gamma Array (INGA). The angular distribution, directional correlation, and polarization measurements were carried out to assign the spin and parity of the newly reported states. The structures of both the positive and negative parity states up to highest spin observed in the present experiment have been compared with shell-model calculations using two recently developed residual interactions, JUN45 and jj44b. The role of proton excitations from p3/2 and f5/2 orbitals to the g9/2 orbital for the higher spin states has been discussed.

  19. Oceanic Excitations On Polar Motion: A Cross Comparison Among Models

    NASA Astrophysics Data System (ADS)

    Zhou, Y.; Chen, J.; Liao, X.; Wilson, C. R.

    2004-12-01

    Recent studies based on various oceanic general circulation models (OGCMs) demonstrated that the oceans are a major contributor to polar motion excitations. In this paper, we analyze and compare observed non-atmospheric polar motion excitations with oceanic angular momentum (OAM) variations determined from four OGCMs, which include the parallel ocean climate model (POCM), a barotropic ocean model (BOM), the Estimating the Circulation and Climate of the Ocean (ECCO) non-data-assimilating model (ECCO-NDA), and the ECCO data-assimilating model (ECCO-DA). The data to be analyzed span a 5-year¡_s overlapped period from 1993 to 1997. At annual time scale, these four OAM estimates do not agree well with each other, while POCM shows relatively larger discrepancies than other three models. At intraseasonal time scales, ECCO-DA yields the best agreement with observations, and reduces the variance of non-atmospheric excitations by about 60%, 10-20% more than those explained by other three models. However, at the very short periods of 4-20 days, the BOM estimates could explain about half of the observed variance, twice as much as that by ECCO-NDA, and also shows considerably better correlation with observations. Due to different modeling schemes and methods, significant discrepancies could arise with respect to the quantity of modeling large-scale oceanic mass redistribution and current variation. A clear understanding of global oceanic contributions to polar motion excitation still remains a challenge.

  20. Solvent effects on the excited-state processes of protochlorophyllide: a femtosecond time-resolved absorption study.

    PubMed

    Dietzek, B; Kiefer, W; Hermann, G; Popp, J; Schmitt, M

    2006-03-09

    The excited-state dynamics of protochlorophyllide a, a porphyrin-like compound and, as substrate of the NADPH/protochlorophyllide oxidoreductase, a precursor of chlorophyll biosynthesis, is studied by femtosecond absorption spectroscopy in a variety of solvents, which were chosen to mimic different environmental conditions in the oxidoreductase complex. In the polar solvents methanol and acetonitrile, the excited-state dynamics differs significantly from that in the nonpolar solvent cyclohexane. In methanol and acetonitrile, the relaxation dynamics is multiexponential with three distinguishable time scales of 4.0-4.5 ps for vibrational relaxation and vibrational energy redistribution of the initially excited S1 state, 22-27 ps for the formation of an intermediate state, most likely with a charge transfer character, and 200 ps for the decay of this intermediate state back to the ground state. In the nonpolar solvent cyclohexane, only the 4.5 ps relaxational process can be observed, whereas the intermediate intramolecular charge transfer state is not populated any longer. In addition to polarity, solvent viscosity also affects the excited-state processes. Upon increasing the viscosity by adding up to 60% glycerol to a methanolic solution, a deceleration of the 4 and 22 ps decay rates from the values in pure methanol is found. Apparently not only vibrational cooling of the S1 excited state is slowed in the more viscous surrounding, but the formation rate of the intramolecular charge transfer state is also reduced, suggesting that nuclear motions along a reaction coordinate are involved in the charge transfer. The results of the present study further specify the model of the excited-state dynamics in protochlorophyllide a as recently suggested (Chem. Phys. Lett. 2004, 397, 110).

  1. Subpicosecond spin dynamics of excited states in the topological insulator Bi2Te3

    NASA Astrophysics Data System (ADS)

    Sánchez-Barriga, J.; Battiato, M.; Krivenkov, M.; Golias, E.; Varykhalov, A.; Romualdi, A.; Yashina, L. V.; Minár, J.; Kornilov, O.; Ebert, H.; Held, K.; Braun, J.

    2017-03-01

    Using time-, spin-, and angle-resolved photoemission, we investigate the ultrafast spin dynamics of hot electrons on the surface of the topological insulator Bi2Te3 following optical excitation by femtosecond-infrared pulses. We observe two surface-resonance states above the Fermi level coexisting with a transient population of Dirac fermions that relax in ˜2 ps. One state disperses up to ˜0.4 eV just above the bulk continuum, and the other one at ˜0.8 eV inside a projected bulk band gap. At the onset of the excitation, both states exhibit a reversed spin texture with respect to that of the transient Dirac bands, in agreement with our one-step photoemission calculations. Our data reveal that the high-energy state undergoes spin relaxation within ˜0.5 ps, a process that triggers the subsequent spin dynamics of both the Dirac cone and the low-energy state, which behave as two dynamically locked electron populations. We discuss the origin of this behavior by comparing the relaxation times observed for electrons with opposite spins to the ones obtained from a microscopic Boltzmann model of ultrafast band cooling introduced into the photoemission calculations. Our results demonstrate that the nonequilibrium surface dynamics is governed by electron-electron rather than electron-phonon scattering, with a characteristic time scale unambiguously determined by the complex spin texture of excited states above the Fermi level. Our findings reveal the critical importance of detecting momentum and energy-resolved spin textures with femtosecond resolution to fully understand the subpicosecond dynamics of transient electrons on the surface of topological insulators.

  2. E2 transitions between excited single-phonon states: Role of ground-state correlations

    NASA Astrophysics Data System (ADS)

    Kamerdzhiev, S. P.; Voitenkov, D. A.

    2016-11-01

    The probabilities for E2 transitions between low-lying excited 3- and 5- single-phonon states in the 208Pb and 132Sn magic nuclei are estimated on the basis of the theory of finite Fermi systems. The approach used involves a new type of ground-state correlations, that which originates from integration of three (rather than two, as in the random-phase approximation) single-particle Green's functions. These correlations are shown to make a significant contribution to the probabilities for the aforementioned transitions.

  3. Pentacyano-N,N-dimethylaniline in the excited state. Only locally excited state emission, in spite of the large electron affinity of the pentacyanobenzene subgroup.

    PubMed

    Zachariasse, Klaas A; Druzhinin, Sergey I; Galievsky, Victor A; Demeter, Attila; Allonas, Xavier; Kovalenko, Sergey A; Senyushkina, Tamara A

    2010-12-23

    Pentacyano-N,N-dimethylaniline (PCDMA) does not undergo an intramolecular charge transfer (ICT) reaction, even in the strongly polar solvent acetonitrile (MeCN), in clear contrast to 4-(dimethylamino)benzonitrile (DMABN). Within the twisted ICT (TICT) model, this is unexpected, as the electron affinity of the pentacyanobenzene moiety of PCDMA is much larger than that of the benzonitrile subgroup in DMABN. According to the TICT model, the energy of the ICT state of PCDMA would be 2.05 eV (∼16550 cm(-1)) lower than that of DMABN, on the basis of the reduction potentials E(A(-)/A) of pentacyanobenzene (-0.29 V vs saturated calomel electrode (SCE)) and benzonitrile (-2.36 V vs SCE), more than enough to compensate for the decrease in energy of the locally excited (LE) state of PCDMA (E(S(1)) = 19990 cm(-1)) relative to that of DMABN (E(S(1)) = 29990 cm(-1)). This absence of a LE → ICT reaction shows that the TICT hypothesis does not hold for PCDMA in the singlet excited state, similar to what was found for DMABN, N-phenylpyrrole, and their derivatives. In this connection, the six dicyano-substituted dimethylanilines are also discussed. The energy gap ΔE(S(1),S(2)) between the two lowest singlet excited states is, at 7170 cm(-1) for PCDMA in MeCN, considerably larger than that for DMABN (2700 cm(-1) in n-hexane, smaller in MeCN). The absence of ICT is therefore in accord with the planar ICT (PICT) model, which considers a sufficiently small ΔE(S(1),S(2)) to be an important condition determining whether an ICT reaction will take place. The fluorescence quantum yield of PCDMA is very small: Φ(LE) = 0.0006 in MeCN at 25 °C, predominantly due to LE → S(0) internal conversion (IC), as the intersystem crossing yield Φ(ISC) is practically zero (<0.01). From the LE fluorescence decay time of 27 ps for PCDMA in MeCN at 25 °C, a radiative rate constant k(f)(LE) = 2 × 10(7) s(-1) results, comparable to the k(f)(LE) of DMABN (6.5 × 10(7) s(-1)) and 2,4,6-tricyano

  4. Energy Dependence of the Ruthenium(II)-Bipyridine Metal-to-Ligand-Charge-Transfer Excited State Radiative Lifetimes: Effects of ππ*(bipyridine) Mixing.

    PubMed

    Thomas, Ryan A; Tsai, Chia Nung; Mazumder, Shivnath; Lu, I Chen; Lord, Richard L; Schlegel, H Bernhard; Chen, Yuan Jang; Endicott, John F

    2015-06-18

    The variations in band shape with excited state energy found for the triplet metal to ligand charge transfer ((3)MLCT) emission spectra of ruthenium-bipyridine (Ru-bpy) chromophores at 77 K have been postulated to arise from excited state/excited state configurational mixing. This issue is more critically examined through the determination of the excited state energy dependence of the radiative rate constants (kRAD) for these emissions. Experimental values for kRAD were determined relative to known literature references for Ru-bpy complexes. When the lowest energy excited states are metal centered, kRAD can be anomalously small and such complexes have been identified using density functional theory (DFT) modeling. When such complexes are removed from the energy correlation, there is a strong (3)MLCT energy-dependent contribution to kRAD in addition to the expected classical energy cubed factor for complexes with excited state energies greater than 10 000 cm(-1). This correlates with the DFT calculations which show significant excited state electronic delocalization between a π(bpy-orbital) and a half-filled dπ*-(Ru(III)-orbital) for Ru-bpy complexes with (3)MLCT excited state energies greater than about 16 000 cm(-1). Overall, this work implicates the "stealing" of emission bandshapes as well as intensity from the higher energy, strongly allowed bpy-centered singlet ππ* excited state.

  5. Proton-hole and core-excited states in the semi-magic nucleus 131In82

    NASA Astrophysics Data System (ADS)

    Taprogge, J.; Jungclaus, A.; Grawe, H.; Borzov, I. N.; Nishimura, S.; Doornenbal, P.; Lorusso, G.; Simpson, G. S.; Söderström, P.-A.; Sumikama, T.; Xu, Z. Y.; Baba, H.; Browne, F.; Fukuda, N.; Gernhäuser, R.; Gey, G.; Inabe, N.; Isobe, T.; Jung, H. S.; Kameda, D.; Kim, G. D.; Kim, Y.-K.; Kojouharov, I.; Kubo, T.; Kurz, N.; Kwon, Y. K.; Li, Z.; Sakurai, H.; Schaffner, H.; Shimizu, Y.; Steiger, K.; Suzuki, H.; Takeda, H.; Vajta, Zs.; Watanabe, H.; Wu, J.; Yagi, A.; Yoshinaga, K.; Benzoni, G.; Bönig, S.; Chae, K. Y.; Coraggio, L.; Daugas, J.-M.; Drouet, F.; Gadea, A.; Gargano, A.; Ilieva, S.; Itaco, N.; Kondev, F. G.; Kröll, T.; Lane, G. J.; Montaner-Pizá, A.; Moschner, K.; Mücher, D.; Naqvi, F.; Niikura, M.; Nishibata, H.; Odahara, A.; Orlandi, R.; Patel, Z.; Podolyák, Zs.; Wendt, A.

    2016-11-01

    The β decay of the N = 83 nucleus 131Cd has been studied at the RIBF facility at the RIKEN Nishina Center. The main purpose of the study was to identify the position of the 1p_{3/2} and 0f_{5/2} proton-hole states and the energies of core-excited configurations in the semi-magic nucleus 131In. From the radiation emitted following the β decay, a level scheme of 131In was established and the β feeding to each excited state determined. Similarities between the single-particle transitions observed in the β decays of the N = 83 isotones 132In and 131Cd are discussed. Finally the excitation energies of several core-excited configurations in 131In are compared to QRPA and shell-model calculations.

  6. Decoherence dynamics of coherent electronic excited states in the photosynthetic purple bacterium Rhodobacter sphaeroides

    NASA Astrophysics Data System (ADS)

    Liang, Xian-Ting; Zhang, Wei-Min; Zhuo, Yi-Zhong

    2010-01-01

    In this paper, we present a theoretical description to the quantum coherence and decoherence phenomena of energy transfer in photosynthesis observed in a recent experiment [Science 316, 1462 (2007)]. As a successive two-color laser pulses with selected frequencies cast on a sample of the photosynthetic purple bacterium Rb. sphaeroides two resonant excitations of electrons in chromophores can be generated. However, this effective two-level subsystem will interact with its protein environment and decoherence is inevitable. We describe this subsystem coupled with its environment as a dynamical spin-boson model. The non-Markovian decoherence dynamics is described using a quasiadiabatic propagator path integral (QUAPI) approach. With the photon-induced effective time-dependent level splitting energy and level flip coupling coefficient between the two excited states and the environment-induced non-Markovian decoherence dynamics, our theoretical result is in good agreement with the experimental data.

  7. Evaluating Electronic Couplings for Excited State Charge Transfer Based on Maximum Occupation Method ΔSCF Quasi-Adiabatic States.

    PubMed

    Liu, Junzi; Zhang, Yong; Bao, Peng; Yi, Yuanping

    2017-02-14

    Electronic couplings of charge-transfer states with the ground state and localized excited states at the donor/acceptor interface are crucial parameters for controlling the dynamics of exciton dissociation and charge recombination processes in organic solar cells. Here we propose a quasi-adiabatic state approach to evaluate electronic couplings through combining maximum occupation method (mom)-ΔSCF and state diabatization schemes. Compared with time-dependent density functional theory (TDDFT) using global hybrid functional, mom-ΔSCF is superior to estimate the excitation energies of charge-transfer states; moreover it can also provide good excited electronic state for property calculation. Our approach is hence reliable to evaluate electronic couplings for excited state electron transfer processes, which is demonstrated by calculations on a typical organic photovoltaic system, oligothiophene/perylenediimide complex.

  8. A Doubles Correction to Electronic Excited States from Configuration Interaction in the Space of Single Substitutions

    NASA Technical Reports Server (NTRS)

    Head-Gordon, Martin; Rico, Rudolph J.; Lee, Timothy J.; Oumi, Manabu

    1994-01-01

    A perturbative correction to the method of configuration interaction with single substitutions (CIS) is presented. This CIS(D) correction approximately introduces the effect of double substitutions which are absent in CIS excited states. CIS(D) is a second-order perturbation expansion of the coupled-cluster excited state method, restricted to single and double substitutions, in a series in which CIS is zeroth order, and the first-order correction vanishes. CIS (D) excitation energies are size consistent and the calculational complexity scales with the fifth power of molecular size, akin to second-order Moller-Plesset theory for the ground state. Calculations on singlet excited states of ethylene, formaldehyde, acetaldehyde, butadiene and benzene show that CIS (D) is a uniform improvement over CIS. CIS(D) appears to be a promising method for examining excited states of large molecules, where more accurate methods are not feasible.

  9. 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.

  10. Steady-state responses of a belt-drive dynamical system under dual excitations

    NASA Astrophysics Data System (ADS)

    Ding, Hu

    2016-02-01

    The stable steady-state periodic responses of a belt-drive system with a one-way clutch are studied. For the first time, the dynamical system is investigated under dual excitations. The system is simultaneously excited by the firing pulsations of the engine and the harmonic motion of the foundation. Nonlinear discrete-continuous equations are derived for coupling the transverse vibration of the belt spans and the rotations of the driving and driven pulleys and the accessory pulley. The nonlinear dynamics is studied under equal and multiple relations between the frequency of the firing pulsations and the frequency of the foundation motion. Furthermore, translating belt spans are modeled as axially moving strings. A set of nonlinear piecewise ordinary differential equations is achieved by using the Galerkin truncation. Under various relations between the excitation frequencies, the time histories of the dynamical system are numerically simulated based on the time discretization method. Furthermore, the stable steady-state periodic response curves are calculated based on the frequency sweep. Moreover, the convergence of the Galerkin truncation is examined. Numerical results demonstrate that the one-way clutch reduces the resonance amplitude of the rotations of the driven pulley and the accessory pulley. On the other hand, numerical examples prove that the resonance areas of the belt spans are decreased by eliminating the torque-transmitting in the opposite direction. With the increasing amplitude of the foundation excitation, the damping effect of the one-way clutch will be reduced. Furthermore, as the amplitude of the firing pulsations of the engine increases, the jumping phenomena in steady-state response curves of the belt-drive system with or without a one-way clutch both occur.

  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. Integrative Systems Models of Cardiac Excitation Contraction Coupling

    PubMed Central

    Greenstein, Joseph L.; Winslow, Raimond L.

    2010-01-01

    Excitation-contraction coupling in the cardiac myocyte is mediated by a number of highly integrated mechanisms of intracellular Ca2+ transport. The complexity and integrative nature of heart cell electrophysiology and Ca2+-cycling has led to an evolution of computational models that have played a crucial role in shaping our understanding of heart function. An important emerging theme in systems biology is that the detailed nature of local signaling events, such as those that occur in the cardiac dyad, have important consequences at higher biological scales. Multi-scale modeling techniques have revealed many mechanistic links between micro-scale events, such as Ca2+ binding to a channel protein, and macro-scale phenomena, such as excitation-contraction coupling gain. Here we review experimentally based multi-scale computational models of excitation-contraction coupling and the insights that have been gained through their application. PMID:21212390

  13. Molecular dynamics of excited state intramolecular proton transfer: 3-hydroxyflavone in solution

    SciTech Connect

    Bellucci, Michael A.; Coker, David F.

    2012-05-21

    The ultrafast enol-keto photoisomerization in the lowest singlet excited state of 3-hydroxyflavone is investigated using classical molecular dynamics in conjunction with empirical valence bond (EVB) potentials for the description of intramolecular interactions, and a molecular mechanics and variable partial charge model, dependent on transferring proton position, for the description of solute-solvent interactions. A parallel multi-level genetic program was used to accurately fit the EVB potential energy surfaces to high level ab initio data. We have studied the excited state intramolecular proton transfer (ESIPT) reaction in three different solvent environments: methylcyclohexane, acetonitrile, and methanol. The effects of the environment on the proton transfer time and the underlying mechanisms responsible for the varied time scales of the ESIPT reaction rates are analyzed. We find that simulations with our EVB potential energy surfaces accurately reproduce experimentally determined reaction rates, fluorescence spectra, and vibrational frequency spectra in all three solvents. Furthermore, we find that the ultrafast ESIPT process results from a combination of ballistic transfer, and intramolecular vibrational redistribution, which leads to the excitation of a set of low frequency promoting vibrational modes. From this set of promoting modes, we find that an O-O in plane bend and a C-H out of plane bend are present in all three solvents, indicating that they are fundamental to the ultrafast proton transfer. Analysis of the slow proton transfer trajectories reveals a solvent mediated proton transfer mechanism, which is diffusion limited.

  14. Emergence of nontrivial magnetic excitations in a spin-liquid state of kagomé volborthite

    PubMed Central

    Watanabe, Daiki; Sugii, Kaori; Shimozawa, Masaaki; Suzuki, Yoshitaka; Yajima, Takeshi; Ishikawa, Hajime; Hiroi, Zenji; Shibauchi, Takasada; Matsuda, Yuji; Yamashita, Minoru

    2016-01-01

    When quantum fluctuations destroy underlying long-range ordered states, novel quantum states emerge. Spin-liquid (SL) states of frustrated quantum antiferromagnets, in which highly correlated spins fluctuate down to very low temperatures, are prominent examples of such quantum states. SL states often exhibit exotic physical properties, but the precise nature of the elementary excitations behind such phenomena remains entirely elusive. Here, we use thermal Hall measurements that can capture the unexplored property of the elementary excitations in SL states, and report the observation of anomalous excitations that may unveil the unique features of the SL state. Our principal finding is a negative thermal Hall conductivity κxy which the charge-neutral spin excitations in a gapless SL state of the 2D kagomé insulator volborthite Cu3V2O7(OH)2⋅2H2O exhibit, in much the same way in which charged electrons show the conventional electric Hall effect. We find that κxy is absent in the high-temperature paramagnetic state and develops upon entering the SL state in accordance with the growth of the short-range spin correlations, demonstrating that κxy is a key signature of the elementary excitation formed in the SL state. These results suggest the emergence of nontrivial elementary excitations in the gapless SL state which feel the presence of fictitious magnetic flux, whose effective Lorentz force is found to be less than 1/100 of the force experienced by free electrons. PMID:27439874

  15. Emergence of nontrivial magnetic excitations in a spin-liquid state of kagomé volborthite.

    PubMed

    Watanabe, Daiki; Sugii, Kaori; Shimozawa, Masaaki; Suzuki, Yoshitaka; Yajima, Takeshi; Ishikawa, Hajime; Hiroi, Zenji; Shibauchi, Takasada; Matsuda, Yuji; Yamashita, Minoru

    2016-08-02

    When quantum fluctuations destroy underlying long-range ordered states, novel quantum states emerge. Spin-liquid (SL) states of frustrated quantum antiferromagnets, in which highly correlated spins fluctuate down to very low temperatures, are prominent examples of such quantum states. SL states often exhibit exotic physical properties, but the precise nature of the elementary excitations behind such phenomena remains entirely elusive. Here, we use thermal Hall measurements that can capture the unexplored property of the elementary excitations in SL states, and report the observation of anomalous excitations that may unveil the unique features of the SL state. Our principal finding is a negative thermal Hall conductivity [Formula: see text] which the charge-neutral spin excitations in a gapless SL state of the 2D kagomé insulator volborthite Cu3V2O7(OH)2[Formula: see text]2H2O exhibit, in much the same way in which charged electrons show the conventional electric Hall effect. We find that [Formula: see text] is absent in the high-temperature paramagnetic state and develops upon entering the SL state in accordance with the growth of the short-range spin correlations, demonstrating that [Formula: see text] is a key signature of the elementary excitation formed in the SL state. These results suggest the emergence of nontrivial elementary excitations in the gapless SL state which feel the presence of fictitious magnetic flux, whose effective Lorentz force is found to be less than 1/100 of the force experienced by free electrons.

  16. 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.

  17. Oceanic excitations on polar motion: a cross comparison among models

    NASA Astrophysics Data System (ADS)

    Zhou, Y. H.; Chen, J. L.; Liao, X. H.; Wilson, C. R.

    2005-08-01

    Recent studies based on various ocean general circulation models (OGCMs) demonstrate that the oceans are a major contributor to polar motion excitations. In this paper, we analyse and compare observed non-atmospheric polar motion excitations with oceanic angular momentum (OAM) variations determined from four OGCMs, which include the parallel ocean climate model (POCM), a barotropic ocean model (BOM), the Estimating the Circulation and Climate of the Ocean (ECCO) non-data-assimilating model (ECCO-NDA) and the ECCO data-assimilating model (ECCO-DA). The data to be analysed span a 5-yr overlapped period from 1993 to 1997. At annual timescale, considerable discrepancies exist between POCM and the other three models, which result mainly from differences in annual components of the forcing wind fields. At semi-annual timescale, however, POCM shows better phase agreement with observed non-atmospheric polar motion excitation than the other three ocean models. At intraseasonal timescales, ECCO-DA yields better agreement with observations, and reduces the variance of non-atmospheric excitations by ~60 per cent, 10-20 per cent more than those explained by the other three models. However, at the very short periods of 4-20 days, the BOM estimates could explain about half of the observed variance, twice as much as that by ECCO-NDA, and also shows considerably better correlation with observations. Due to different modelling schemes and methods, significant discrepancies could arise with respect to the quality of modelling large-scale oceanic mass redistribution and current variation. A complete understanding of global oceanic contributions to polar motion excitation still remains a challenge.

  18. Modeling the acoustic excitation of a resonator

    NASA Astrophysics Data System (ADS)

    Mandre, Shreyas; Mahadevan, Lakshminarayanan

    2007-11-01

    The sounding of a beverage bottle when blown on is a familiar but very little understood phenomenon. A very similar mechanism is used by musical wind instruments, like organ pipes and flutes, for sound production. This phenomenon falls under the general umbrella of flow induced oscillations and is representative of a more generic mechanism. The modeling of this phenomenon essentially involves two components. The first is the resonator, which bears the oscillations and this component is very well understood. The resonator, however, needs an external energy input to sustain the oscillations, which is provided by the jet of air blown. The dynamics of the jet and its interaction with the resonator is the primary focus of this talk. In particular, we provide a linearized model based on first principles to explain the feedback of energy from the jet to the resonator and compare the predictions with experimental results.

  19. Exotic and excited-state meson spectroscopy and radiative transitions from lattice QCD

    SciTech Connect

    Christopher Thomas

    2010-09-01

    We discuss recent progress in extracting the excited meson spectrum and radiative transition form factors using lattice QCD. We mention results in the charmonium sector, including the first lattice QCD calculation of radiative transition rates involving excited charmonium states, highlighting results for high spin and exotic states. We present recent results on a highly excited isovector meson spectrum from dynamical anisotropic lattices. Using carefully constructed operators we show how the continuum spin of extracted states can be reliably identified and confidently extract excited states, states with exotic quantum numbers and states of high spin. This spectrum includes the first spin-four state extracted from lattice QCD. We conclude with some comments on future prospects.

  20. Ground and excited state dipole moments of coumarin 337 laser dye

    NASA Astrophysics Data System (ADS)

    Raikar, U. S.; Tangod, V. B.; Mannopantar, S. R.; Mastiholi, B. M.

    2010-11-01

    This paper reports that the effects of spectral properties of coumarin 337 laser dye have been investigated in different solvents considering solvent parameters like dielectric constant ( є) and refractive index ( n) of different solvent polarities. The ground state ( μg) and excited state ( μe) dipole moments are calculated using Lippert's, Bakhshiev's, and Kawski-Chamma-Viallet's equations. In all these three equations the variation of Stokes shift was used to calculate the excited state ( μe) dipole moment. It is observed that the Bakhshiev method is comparatively better than the other two methods for ground state and excited state dipole moment calculations. The angle between the excited state and ground state dipole moments is also calculated.

  1. Electronically Excited States in Poly(p-phenylenevinylene): Vertical Excitations and Torsional Potentials from High-Level Ab Initio Calculations

    PubMed Central

    2013-01-01

    Ab initio second-order algebraic diagrammatic construction (ADC(2)) calculations using the resolution of the identity (RI) method have been performed on poly-(p-phenylenevinylene) (PPV) oligomers with chain lengths up to eight phenyl rings. Vertical excitation energies for the four lowest π–π* excitations and geometry relaxation effects for the lowest excited state (S1) are reported. Extrapolation to infinite chain length shows good agreement with analogous data derived from experiment. Analysis of the bond length alternation (BLA) based on the optimized S1 geometry provides conclusive evidence for the localization of the defect in the center of the oligomer chain. Torsional potentials have been computed for the four excited states investigated and the transition densities divided into fragment contributions have been used to identify excitonic interactions. The present investigation provides benchmark results, which can be used (i) as reference for lower level methods and (ii) give the possibility to parametrize an effective Frenkel exciton Hamiltonian for quantum dynamical simulations of ultrafast exciton transfer dynamics in PPV type systems. PMID:23427902

  2. 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.

  3. Ultrafast internal conversion of excited cytosine via the lowest pipi electronic singlet state.

    PubMed

    Merchán, Manuela; Serrano-Andrés, Luis

    2003-07-09

    Computational evidence at the CASPT2 level supports that the lowest excited state pipi* contributes to the S1/S0 crossing responsible for the ultrafast decay of singlet excited cytosine. The computed radiative lifetime, 33 ns, is consistent with the experimentally derived value, 40 ns. The nOpi* state does not play a direct role in the rapid repopulation of the ground state; it is involved in a S2/S1 crossing. Alternative mechanisms through excited states pisigma* or nNpi* are not competitive in cytosine.

  4. Excited-state wavepacket and potential reconstruction by coherent anti-Stokes Raman scattering.

    PubMed

    Avisar, David; Tannor, David J

    2015-01-28

    Among the major challenges in the chemical sciences is controlling chemical reactions and deciphering their mechanisms. Since much of chemistry occurs in excited electronic states, in the last three decades scientists have employed a wide variety of experimental techniques and theoretical methods to recover excited-state potential energy surfaces and the wavepackets that evolve on them. These methods have been partially successful but generally do not provide a complete reconstruction of either the excited state wavepacket or potential. We have recently proposed a methodology for reconstructing excited-state molecular wavepackets and the corresponding potential energy surface [Avisar and Tannor, Phys. Rev. Lett., 2011, 106, 170405]. In our approach, the wavepacket is represented as a superposition of the set of vibrational eigenfunctions of the molecular ground-state Hamiltonian. We assume that the multidimensional ground-state potential surface is known, and therefore these vibrational eigenfunctions are known as well. The time-dependent coefficients of the basis functions are obtained by experimental measurement of the resonant coherent anti-Stokes Raman scattering (CARS) signal. Our reconstruction strategy has several significant advantages: (1) the methodology requires no a priori knowledge of any excited-state potential. (2) It applies to dissociative as well as to bound excited-state potentials. (3) It is general for polyatomics. (4) The excited-state potential surface is reconstructed simultaneously with the wavepacket. Apart from making a general contribution to the field of excited-state spectroscopy, our method provides the information on the excited-state wavepacket and potential necessary to design laser pulse sequences to control photochemical reactions.

  5. CHEMI-IONIZATION IN SOLAR PHOTOSPHERE: INFLUENCE ON THE HYDROGEN ATOM EXCITED STATES POPULATION

    SciTech Connect

    Mihajlov, Anatolij A.; Ignjatovic, Ljubinko M.; Sreckovic, Vladimir A.; Dimitrijevic, Milan S. E-mail: mihajlov@ipb.ac.rs

    2011-03-15

    In this paper, the influence of chemi-ionization processes in H*(n {>=} 2) + H(1s) collisions, as well as the influence of inverse chemi-recombination processes on hydrogen atom excited-state populations in solar photosphere, are compared with the influence of concurrent electron-atom and electron-ion ionization and recombination processes. It has been found that the considered chemi-ionization/recombination processes dominate over the relevant concurrent processes in almost the whole solar photosphere. Thus, it is shown that these processes and their importance for the non-local thermodynamic equilibrium modeling of the solar atmosphere should be investigated further.

  6. Simulations of fluorescence solvatochromism in substituted PPV oligomers from excited state molecular dynamics with implicit solvent

    SciTech Connect

    Bjorgaard, J. A.; Nelson, T.; Kalinin, K.; Kuzmenko, V.; Velizhanin, K. A.; Tretiak, S.

    2015-04-28

    In this study, an efficient method of treating solvent effects in excited state molecular dynamics (ESMD) is implemented and tested by exploring the solvatochromic effects in substituted p-phenylene vinylene oligomers. A continuum solvent model is used which has very little computational overhead. This allows simulations of ESMD with solvent effects on the scale of hundreds of picoseconds for systems of up to hundreds of atoms. At these time scales, solvatochromic shifts in fluoresence spectra can be described. Solvatochromic shifts in absorption and fluorescence spectra from ESMD are compared with time-dependent density functional theory calculations and experiments.

  7. Excitation of single proton states in ( p, α) reactions

    NASA Astrophysics Data System (ADS)

    Gadioli, E.; Erba, E. Gadioli; Guazzoni, P.; Luinetti, M.; Zetta, L.; Berg, G. P. A.; Meissburger, J.; von Rossen, P.; Römer, J. G. M.; Prasuhn, D.; Paul, D.

    1986-06-01

    A high resolution experiment, using the BIG KARL spectrometer has been made to identify the levels of 141 Pr excited in the 144 Nd(p,α) reaction at 25 MeV. It has been found that only levels with a dominant single proton component are populated with appreciable intensity.

  8. Lifetime measurement of excited states in /sup 105/Ag

    SciTech Connect

    Mittal, V.K.; Govil, I.M.

    1986-11-01

    The levels up to about 2.1 MeV in /sup 105/Ag were excited via /sup 105/Pd(p,n..gamma..) reaction. For the first time, lifetimes of energy levels at 1023, 1042, 1097, 1166, 1243, 1295, 1328, 1386, 1442, 1543, 1558, 1587, 1719, 1923, and 2081 keV have been measured using the Doppler shift attenuation technique.

  9. 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.

  10. Protolytic dissociation of cyano derivatives of naphthol, biphenyl and phenol in the excited state: A review

    NASA Astrophysics Data System (ADS)

    Szczepanik, Beata

    2015-11-01

    The excited state proton transfer (ESPT) has been extensively studied for hydroxyarenes, phenols, naphthols, hydroxystilbenes, etc., which undergo large enhancement of acidity upon electronic excitation, thus classified as photoacids. The changes of acidic character in the excited state of cyano-substituted derivatives of phenol, hydroxybiphenyl and naphthol are reviewed in this paper. The acidity constants pKa in the ground state (S0), pKa∗ in the first singlet excited state (S1) and the change of the acidity constant in the excited state ΔpKa for the discussed compounds are summarized and compared. The results of the acidity studies show, that the "electro-withdrawing" CN group in the molecules of naphthol, hydroxybiphenyl and phenol causes dramatic increase of their acidity in the excited state in comparison to the ground state. This effect is greatest for the cyanonaphthols (the doubly substituted CN derivatives are almost as strong as a mineral acid in the excited state), comparable for cyanobiphenyls, and smaller for phenol derivatives. The increase of acidity enables proton transfer to various organic solvents, and the investigation of ESPT can be extended to a variety of solvents besides water. The results of theoretical investigations were also presented and used for understanding the protolytic equilibria of cyano derivatives of naphthol, hydroxybiphenyl and phenol.

  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. Electron-impact excitation of the low-lying electronic states of formaldehyde

    NASA Technical Reports Server (NTRS)

    Chutjian, A.

    1974-01-01

    Electron-impact excitation has been observed at incident electron energies of 10.1 and 20.1 eV to the first five excited electronic states of formaldehyde lying at and below the 1B2 state at 7.10 eV. These excitations include two new transitions in the energy-loss range 5.6-6.2 eV and 6.7-7.0 eV which have been detected for the first time, either through electron-impact excitation or photon absorption. The differential cross sections of these new excitations are given at scattering angles between 15 and 135 deg. These cross-section ratios peak at large scattering angles - a characteristic of triplet - singlet excitations. The design and performance of the electron-impact spectrometer used in the above observations is outlined and discussed.

  13. Solvent-induced configuration mixing and triplet excited-state inversion: insights from transient absorption and transient dc photoconductivity measurements.

    PubMed

    She, Chunxing; Rachford, Aaron A; Wang, Xianghuai; Goeb, Sébastien; El-Ballouli, Ala'a O; Castellano, Felix N; Hupp, Joseph T

    2009-10-14

    Solvent-induced excited-state configuration mixing in a Pt(II) diimine chromophore with phenylene ethynylene containing acetylide ligands, [Pt((t)Bu2bpy)(PE3)2] (1), was characterized by nanosecond transient absorption spectroscopy and transient dc photoconductivity (TDCP). The mixing is a result of closely spaced triplet charge transfer (3CT) and intraligand-localized (3IL) triplet energy levels that are finely tuned with solvent polarity as ascertained by their parent model chromophores [Pt((t)Bu2bpy)(PE1)2] (2) and [Pt(P2)(PE3)2] (3), respectively. The absorption difference spectrum of the mixed triplet state is dramatically different from those of the 3CT and 3IL state model chromophores. The 3CT, 3IL and configuration-mixed triplet states led to distinct TDCP signals. The TDCP response is of negative polarity for 3CT excited states but of positive polarity for 3IL excited states. TDCP transients for 1 in mixed solvents are a combination of signals from the 3IL and 3CT states, with the signal magnitude depending on the polarity of solvent composition. The fraction of 3CT state character in the configurationally mixed excited state was quantified by TDCP to be approximately 0.24 in pure benzene, while it decreased to approximately 0.05 in 20 : 80 (v : v) benzene-CH2Cl2. The charge transfer fraction appears to increase slightly to approximately 0.11 in the lower polarity 20 : 80 n-hexane-CH2Cl2 medium. TDCP is shown to be a useful tool for the identification of the lowest excited state in electrically neutral metal-organic chromophores.

  14. Estimation of first excited singlet-state dipole moments of aminoanthraquinones by solvatochromic method.

    PubMed

    Siddlingeshwar, B; Hanagodimath, S M

    2009-04-01

    The ground state (micro(g)) and the excited state (micro(e)) dipole moments of three substituted anthraquinones, namely 1-aminoanthracene-9,10-dione (AAQ), 1-(methylamino)anthracence-9,10-dione (MAQ) and 1,5-diaminoanthracene-9,10-dione (DAQ) were estimated in various solvents. The dipole moments (micro(g) and micro(e)) were estimated from Lippert, Bakhshiev, Kawski-Chamma-Viallet, McRae and Suppan equations by using the variation of Stokes shift with the solvent dielectric constant and refractive index. The excited state dipole moments were also calculated by using the variation of Stokes shift with microscopic solvent polarity parameter (Epsilon(T)(N)). It was observed that dipole moment values of excited states (micro(e)) were higher than corresponding ground state values (micro(g)), indicating a substantial redistribution of the pi-electron densities in a more polar excited state for all the molecules investigated.

  15. Estimation of first excited singlet-state dipole moments of aminoanthraquinones by solvatochromic method

    NASA Astrophysics Data System (ADS)

    Siddlingeshwar, B.; Hanagodimath, S. M.

    2009-04-01

    The ground state ( μg) and the excited state ( μe) dipole moments of three substituted anthraquinones, namely 1-aminoanthracene-9,10-dione (AAQ), 1-(methylamino)anthracence-9,10-dione (MAQ) and 1,5-diaminoanthracene-9,10-dione (DAQ) were estimated in various solvents. The dipole moments ( μg and μe) were estimated from Lippert, Bakhshiev, Kawski-Chamma-Viallet, McRae and Suppan equations by using the variation of Stokes shift with the solvent dielectric constant and refractive index. The excited state dipole moments were also calculated by using the variation of Stokes shift with microscopic solvent polarity parameter ( ETN). It was observed that dipole moment values of excited states ( μe) were higher than corresponding ground state values ( μg), indicating a substantial redistribution of the π-electron densities in a more polar excited state for all the molecules investigated.

  16. Excited-state lifetime of propadienylidene, l-C3H2.

    PubMed

    Noller, Bastian; Margraf, Markus; Schröter, Christian; Schultz, Thomas; Fischer, Ingo

    2009-07-14

    The excited-state dynamics of the singlet carbene propadienylidene, l-C(3)H(2), were investigated by femtosecond time-resolved photoionisation. The carbene was excited into the C (1)A(1) state with 250 nm pulses and the subsequent excited state dynamics were probed by multiphoton ionization with 800 nm pulses. The lifetime of the C (1)A(1) state was determined to be 70 fs. In agreement with recent nanosecond experiments, we assume that the carbene deactivates to the electronic ground state where it subsequently dissociates. Since propadienylidene was generated from 3-bromo-1-iodopropyne, two further radical intermediates were studied, IC(3)H(2) and C(3)H(2)Br. For both species, an ultrafast excited state decay was observed with an upper limit of 40 fs for the respective lifetimes.

  17. Local conformations and excited state dynamics of porphyrins and nucleic acids by 2-dimensional fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Widom, Julia R.

    Biological systems present many challenges to researchers attempting to study them using spectroscopy. Low specificity, low sensitivity, and broad and overlapping lineshapes limit the amount of information that can be obtained in experiments. Two-dimensional fluorescence spectroscopy (2D FS) is a highly sensitive and information-rich spectroscopic technique that was developed to study the conformations and excited state dynamics of systems exhibiting exciton coupling. In this dissertation, I describe a variety of extensions of 2D FS that further increase its utility for the study of biological systems. I describe experiments on a dimer of zinc tetraphenylporphyrin embedded in a membrane, in which the signals from two conformational subpopulations were separated in order to study the thermodynamics of their interconversion. I present proof-of-principle experiments on nucleic acids that utilize fluorescence resonance energy transfer to separate signals from different subpopulations. I also describe experiments in which 2D FS was performed using ultraviolet excitation to determine the conformation of a dinucleotide of a fluorescent analogue of the nucleic acid base adenine. I discuss experiments on porphyrin dimers in which 2D FS was used as a probe of excited state dynamics. Finally, I present model calculations for a proposed variation of 2D FS in which entangled photons would be used as the excitation source. These calculations suggest that this approach has the potential to yield significantly narrower spectral lineshapes than conventional 2D FS. These experiments and calculations yield new insight into the systems investigated and establish a `toolbox' of variations of 2D FS that can be used to gain as much information as possible from experiments on challenging systems such as protein-DNA complexes.

  18. Estimation of ground and excited state dipole moments of some laser dyes

    NASA Astrophysics Data System (ADS)

    Biradar, D. S.; Siddlingeshwar, B.; Hanagodimath, S. M.

    2008-03-01

    The ground state ( μg) and the excited state ( μe) dipole moments of three laser dyes namely 2, 5-diphenyl-1, 3, 4- oxadiazole (PPD), 2, 2″-dimethyl-p-terphenyl (DMT) and 1, 3-diphenyl benzene (MT) were studied at room temperature in various solvents. The ground state dipole moments ( μg) of all the three laser dyes were determined experimentally by Guggenheim method. The excited state dipole moments ( μe) were estimated from Lippert's, Bakshiev's and Chamma Viallet's equations by using the variation of the Stokes shift with the solvent dielectric constant and refractive index. Ground and excited state dipole moments were evaluated by means of solvatochromic shift method and also the excited state dipole moments are determined in combination with ground state dipole moments. It was observed that dipole moment values of excited states ( μe) were higher than corresponding ground state values ( μg), indicating a substantial redistribution of the π-electron densities in a more polar excited state for all the dyes investigated.

  19. Three-dimensional quantum calculations on the ground and excited state vibrations of ethylene

    NASA Astrophysics Data System (ADS)

    Groenenboom, Gerrit Cornelis

    Three dimensional potential energy surfaces of the ground and excited states of ethylene were calculated at the MRCEPA (Multi Reference Coupled Electronic Pair Approximation) level. The modes included are the torsion, the CC stretch, and the symmetric scissors. Full vibrational calculations were performed using the Lanczos/grid method. The avoided crossing between the V and the R state was dealt with in a diabetic model. The ground state results agree within 3 up to the highest vibrational level known experimentally. The origin and the maximum of the V back arrow N band are calculated at 5.68 and 7.82 eV, respectively, approximately 0.2 eV above the somewhat ambiguous experimental values. This work considerably diminishes the existing gap of approximately 0.5 eV between theory and experiment.

  20. Pulsed CO2 laser pumped by an all solid-state magnetic exciter

    NASA Astrophysics Data System (ADS)

    Shimada, T.; Noda, K.; Obara, M.; Midorikawa, K.

    1985-11-01

    An all solid-state exciter, which consists of a Silicon Controlled Rectifier (SCR) switched pulse transformer and a three stage magnetic pulse compressor, has been successfully used for pulsed CO2 laser excitation. Using the exciter, output laser energy of 240 mJ has been obtained at 1 pps under sealed-off conditions. Since this laser has no discharge switch, long lifetime operation with high repetition rate (HRR) is anticipated.

  1. Excited state absorption of pump radiation as a loss mechanism in solid-state lasers

    SciTech Connect

    Kliewer, M.L.; Powell, R.C.

    1989-08-01

    The characteristics of optical pumping dynamics occurring in laser-pumped rare earth-doped, solid-state laser materials were investigated by using a tunable alexandrite laser to pump Y/sub 3/Al/sub 5/O/sub 12/:Nd/sup 3+/ in an optical cavity. It was found that the slope efficiency of the Nd laser operation depends strongly on the wavelength of the pump laser. For pump wavelengths resulting in low slope efficiencies, intense fluorescence emission is observed from the sample in the blue-green spectral region. This is attributed to the excited state absorption of pump photons which occurs during radiationless relaxation from the pump band to the metastable state. This type of process will be an important loss mechanism for monochromatic pumping of laser systems at specific pump wavelengths.

  2. Excited-state absorption of pump radiation as a loss mechanism in solid-state lasers

    SciTech Connect

    Kliewer, M.L.; Powell, R.C.

    1989-08-01

    The characteristics of optical pumping dynamics occuring in laser-pumped rare earth-doped, solid-state laser materials were investigated by using a tunable alexandrite laser to pump Y3Al5O12:Nd(3+) in an optical cavity. It was found that the slope efficiency of the Nd laser operation depends strongly on the wavelength of the pump laser. For pump wavelength resulting in low slope efficiencies, intense fluorescence emission is observed form the sample in the blue-green spectral region. This is attributed to the excited state absorption of pump photons which occurs during radiationless relaxation from the pump band to the metastable state. This type of process will be an important loss mechanism for monochromatic pumping of laser systems at specific pump wavelengths.

  3. Excited state absorption of pump radiation as a loss mechanism in solid-state lasers

    NASA Technical Reports Server (NTRS)

    Kliewer, Michael L.; Powell, Richard C.

    1989-01-01

    The characteristics of optical pumping dynamics in laser-pumped, rare-earth-doped, solid-state laser materials are investigated by using a tunable alexandrite laser to pump Y3Al5O12:Nd(3+) in an optical cavity. It is found that the slope efficiency of the Nd laser operation depends strongly on the wavelength of the pump laser. For pump wavelengths resulting in low slope efficiencies, intense fluorescence emission is observed from the sample in the blue-green spectral region. This is attributed to the excited-state absorption of pump photons which occurs during radiationless relaxation from the pump band to the metastable state. This type of process is an important loss mechanism for monochromatic pumping of laser systems at specific pump wavelengths.

  4. Detection of the torsionally excited state of methanol in Orion A

    NASA Technical Reports Server (NTRS)

    Lovas, F. J.; Suenram, R. D.; Snyder, L. E.; Hollis, J. M.; Lees, R. M.

    1982-01-01

    Torsionally excited methanol has been detected in Orion A, where three emission lines observed in the region of 93-100 GHz coincide with laboratory measurements of three methanol transitions. Torsionally excited methanol may therefore be used as a novel temperature probe, since this state lies near 200 per cm above the ground state, or about 290 K. No emission was detected from the transition arising from levels near 300 per cm, or approximately 430 K above the ground state.

  5. Theoretical and experimental study on the intramolecular charge transfer excited state of the new highly fluorescent terpyridine compound

    NASA Astrophysics Data System (ADS)

    Song, Peng; Sun, Shi-Guo; Liu, Jian-Yong; Xu, Yong-Qian; Han, Ke-Li; Peng, Xiao-Jun

    2009-10-01

    Experimental and theoretical methods have been used to investigate the relaxation dynamics and photophysical properties of the donor-acceptor compound 4'-(4-N,N-diphenylaminophenyl)-2,2':6',2″-terpyridine (DPAPT), a compound which is found to exhibit efficient intramolecular charge transfer emission in polar solvents with relatively large Stokes shifts and strong solvatochromism. The difference between the ground and excited state dipole moments (Δ μ) is estimated to be 13.7 D on the basis of Lippert-Mataga models. To gain insight into the relaxation dynamics of DPAPT in the excited state, the potential energy curves for conformational relaxation are calculated. From the frontier molecular orbital (MO) pictures at the geometry of the twisted ICT excited state, the intramolecular charger transfer mainly takes place from HOMO (triphenylamine) to LUMO (terpyridine) in this donor-acceptor system.

  6. Dark excited States of carotenoid regulated by bacteriochlorophyll in photosynthetic light harvesting.

    PubMed

    Nakamura, Ryosuke; Nakagawa, Katsunori; Nango, Mamoru; Hashimoto, Hideki; Yoshizawa, Masayuki

    2011-03-31

    In photosynthesis, carotenoids play important roles in light harvesting (LH) and photoprotective functions, which have been described mainly in terms of two singlet excited states of carotenoids: S(1) and S(2). In addition to the "dark" S(1) state, another dark state, S*, was recently identified and its involvement in photosynthetic functions was determined. However, there is no consistent picture concerning its nature or the mechanism of its formation. One particularly anomalous behavior obtained from femtosecond transient absorption (TA) spectroscopy is that the S*/S(1) population ratio depends on the excitation intensity. Here, we focus on the effect of nearby bacteriochlorophyll (BChl) on the relaxation dynamics of carotenoid in the LH complex. We performed femtosecond TA spectroscopy combined with pre-excitation of BChl in the reconstituted LH1 complex from Rhodospirillum rubrum S1. We observed that the energy flow from S(1), including its vibrationally excited hot states, to S* occurs only when nearby BChl is excited into Q(y), resulting in an increase in S*/S(1). We also examined the excitation-intensity dependence of S*/S(1) by conventional TA spectroscopy. A comparison between the pre-excitation effect and excitation-intensity dependence shows a strong correlation of S*/S(1) with the number of BChls excited into Q(y). In addition, we observed an increase in triplet formation as the S* population increased, indicating that S* is an electronic excited state that is the precursor to triplet formation. Our findings provide an explanation for observed spectroscopic features, including the excitation-intensity dependences debated so far, and offer new insights into energy deactivation mechanisms inherent in the LH antenna.

  7. Ultrafast excited-state proton transfer from dicyano-naphthol

    NASA Astrophysics Data System (ADS)

    Carmeli, I.; Huppert, D.; Tolbert, L. M.; Haubrich, J. E.

    1996-09-01

    The rate of proton transfer from electronically excited 5,8-dicyano-2-naphthol (DCN2) to the solvent is studied by time-resolved fluorescence. Unlike most naphthol derivatives, excited DCN2 is a strong acid ( pK ∗ 2≈ -4.5 ) and therefore is capable of transferring protons to alcohols and other moderate proton acceptor solvents. The rate constant of proton transfer, κd, at low temperatures (< 250 K) is slightly larger than the inverse dielectric relaxation time, 1/τ D and has the same activation energy of the dielectric relaxation. On the other hand, at temperatures above 250 K the temperature dependence of the proton transfer rate decreases monotonically with increasing temperature, while the dielectric relaxation activation energy maintains the low temperature value.

  8. Critical Assessment of TD-DFT for Excited States of Open-Shell Systems: I. Doublet-Doublet Transitions.

    PubMed

    Li, Zhendong; Liu, Wenjian

    2016-01-12

    A benchmark set of 11 small radicals is set up to assess the performance of time-dependent density functional theory (TD-DFT) for the excited states of open-shell systems. Both the unrestricted (U-TD-DFT) and spin-adapted (X-TD-DFT) formulations of TD-DFT are considered. For comparison, the well-established EOM-CCSD (equation-of-motion coupled-cluster with singles and doubles) is also used. In total, 111 low-lying singly excited doublet states are accessed by all the three approaches. Taking the MRCISD+Q (multireference configuration interaction with singles and doubles plus the Davidson correction) results as the benchmark, it is found that both U-TD-DFT and EOM-CCSD perform well for those states dominated by singlet-coupled single excitations (SCSE) from closed-shell to open-shell, open-shell to vacant-shell, or closed-shell to vacant-shell orbitals. However, for those states dominated by triplet-coupled single excitations (TCSE) from closed-shell to vacant-shell orbitals, both U-TD-DFT and EOM-CCSD fail miserably due to severe spin contaminations. In contrast, X-TD-DFT provides balanced descriptions of both SCSE and TCSE. As far as the functional dependence is concerned, it is found that, when the Hartree-Fock ground state does not suffer from the instability problem, both global hybrid (GH) and range-separated hybrid (RSH) functionals perform grossly better than pure density functionals, especially for Rydberg and charge-transfer excitations. However, if the Hartree-Fock ground state is instable or nearly instable, GH and RSH tend to underestimate severely the excitation energies. The SAOP (statistically averaging of model orbital potentials) performs more uniformly than any other density functionals, although it generally overestimates the excitation energies of valence excitations. Not surprisingly, both EOM-CCSD and adiabatic TD-DFT are incapable of describing excited states with substantial double excitation characters.

  9. Excited states in the active media of oxygen - iodine lasers

    SciTech Connect

    Azyazov, V N

    2009-11-30

    A review of investigations of kinetic processes in active media oxygen - iodine lasers (OILs) performed in the last decade is presented. The mechanisms of pumping and quenching of electronically and vibrationally excited O{sub 2} and I{sub 2} molecules are considered, and dissociation mechanisms of I{sub 2} in the active medium of the OIL are analysed. The values of kinetic constants of processes proceeding in the active media of OILs are recommended. (review)

  10. Excited State Electronic Properties of Sodium Iodide and Cesium Iodide

    SciTech Connect

    Campbell, Luke W.; Gao, Fei

    2013-05-01

    We compute from first principles the dielectric function, loss function, lifetime and scattering rate of quasiparticles due to electronic losses, and secondary particle spectrum due to plasmon decay in two scintillating alkali halides, sodium iodide and cesium iodide. Particular emphasis is placed on quasiparticles within several multiples of the band gap from the band edges. A theory for the decay spectra of plasmons and other electronic excitations in crystals is presented. Applications to Monte Carlo radiation transport codes are discussed.

  11. Protolytic dissociation of cyanophenols in ground and excited states in alcohol and water solutions

    NASA Astrophysics Data System (ADS)

    Szczepanik, Beata; Styrcz, Stanisław

    2011-08-01

    The effect of cyano substituents on acidity in ground and excited states of mono- and dicyanophenols was investigated. The equilibrium dissociation constants of 3,4-dicyanophenol in ground and lowest excited states in water solution and the change of these constants in the excited state during the transfer to the ground state for o-, m-, p-cyanophenol and 3,4-dicyanophenol in alcohol and water solutions were determined. It was shown that the cyano substitution increases the acidity of ortho-, meta- and dicyano-derivative in ground state in comparison to the phenol, which makes the anions of these derivatives appear in solutions from methanol to 1-butanol. In the excited state the acidity of investigated compounds changes significantly in comparison to the ground state. 3,4-Dicyanophenol is the strongest acid in the lowest excited singlet state, while p-cyanophenol is the weakest one in both alcohol and water solutions. The distribution of the electronic charge and dipole moments of all investigated cyanophenols in ground and excited states were determined on the basis of ab initio calculations using the GAMESS program.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  13. Precise control of state-selective excitation in stimulated Raman scattering

    SciTech Connect

    Zhang Shian; Zhang Hui; Jia Tianqing; Wang Zugeng; Sun Zhenrong; Shi Junhui

    2010-10-15

    Multiphoton transitions can be manipulated by tailoring the ultrashort laser pulse. In this paper, we propose two schemes for achieving precise control of the selective excitation between two excited states in stimulated Raman-scattering process. We theoretically demonstrate that by properly designing the spectral phase distribution, the stimulated Raman transition probability for one excited state is kept at zero or a maximal value, while that for the other excited state can be continuously tuned over a wide range. Furthermore, the influence of the spectral bandwidth on the tunable range by the two schemes is discussed. We conclude that these schemes have significant application to the selective excitation of femtosecond coherent anti-Stokes Raman scattering.

  14. Model State Efforts.

    ERIC Educational Resources Information Center

    Morgan, Gwen

    Models of state involvement in training child care providers are briefly discussed and the employers' role in training is explored. Six criteria for states that are taken as models are identified, and four are described. Various state activities are described for each criterion. It is noted that little is known about employer and other private…

  15. Ultrafast excited state hydrogen atom transfer in salicylideneaniline driven by changes in aromaticity.

    PubMed

    Gutiérrez-Arzaluz, Luis; Cortés-Guzmán, Fernando; Rocha-Rinza, Tomás; Peón, Jorge

    2015-12-21

    We investigated two important unresolved issues on excited state intramolecular proton transfer (ESIPT) reactions, i.e., their driving force and the charge state of the transferred species by means of quantum chemical topology. We related changes in the aromaticity of a molecule after electron excitation to reaction dynamics in an excited state. Additionally, we found that the conveyed particle has a charge intermediate between that of a bare proton and a neutral hydrogen atom. We anticipate that the analysis presented in this communication will yield valuable insights into ESIPT and other similar photochemical reactions.

  16. Nonequilibrium solvent effects in Born-Oppenheimer molecular dynamics for ground and excited electronic states

    NASA Astrophysics Data System (ADS)

    Bjorgaard, J. A.; Velizhanin, K. A.; Tretiak, S.

    2016-04-01

    The effects of solvent on molecular processes such as excited state relaxation and photochemical reaction often occurs in a nonequilibrium regime. Dynamic processes such as these can be simulated using excited state molecular dynamics. In this work, we describe methods of simulating nonequilibrium solvent effects in excited state molecular dynamics using linear-response time-dependent density functional theory and apparent surface charge methods. These developments include a propagation method for solvent degrees of freedom and analytical energy gradients for the calculation of forces. Molecular dynamics of acetaldehyde in water or acetonitrile are demonstrated where the solute-solvent system is out of equilibrium due to photoexcitation and emission.

  17. Defect States in Copper Indium Gallium Selenide Solar Cells from Two-Wavelength Excitation Photoluminescence Spectroscopy

    SciTech Connect

    Jensen, Soren A.; Dippo, Patricia; Mansfield, Lorelle M.; Glynn, Stephen; Kuciauskas, Darius

    2016-11-21

    We use two-wavelength excitation photoluminescence spectroscopy to probe defect states in CIGS thin films. Above-Eg excitation is combined with a tunable IR bias light that modulates the population of the defect states. We find that IR illumination in the range of 1400-2000 nm (0.62-0.89 eV) causes a reduction of the PL intensity, the magnitude of which scales linearly with IR power. Further, KF post deposition treatment has only a modest influence on the effect of the IR excitation. Initial data suggest that we have developed an optical characterization tool for band-gap defect states.

  18. Nonequilibrium solvent effects in Born-Oppenheimer molecular dynamics for ground and excited electronic states

    SciTech Connect

    Bjorgaard, Josiah August; Velizhanin, Kirill A.; Tretiak, Sergei

    2016-04-15

    The effects of solvent on molecular processes such as excited state relaxation and photochemical reaction often occurs in a nonequilibrium regime. Dynamic processes such as these can be simulated using excited state molecular dynamics. In this paper, we describe methods of simulating nonequilibrium solvent effects in excited state molecular dynamics using linear-response time-dependent density functional theory and apparent surface charge methods. These developments include a propagation method for solvent degrees of freedom and analytical energy gradients for the calculation of forces. Finally, molecular dynamics of acetaldehyde in water or acetonitrile are demonstrated where the solute-solvent system is out of equilibrium due to photoexcitation and emission.

  19. Excited-State Proton-Transfer-Induced Trapping Enhances the Fluorescence Emission of a Locked GFP Chromophore.

    PubMed

    Liu, Xiang-Yang; Chang, Xue-Ping; Xia, Shu-Hua; Cui, Ganglong; Thiel, Walter

    2016-02-09

    The chemical locking of the central single bond in core chromophores of green fluorescent proteins (GFPs) influences their excited-state behavior in a distinct manner. Experimentally, it significantly enhances the fluorescence quantum yield of GFP chromophores with an ortho-hydroxyl group, while it has almost no effect on the photophysics of GFP chromophores with a para-hydroxyl group. To unravel the underlying physical reasons for this different behavior, we report static electronic structure calculations and nonadiabatic dynamics simulations on excited-state intramolecular proton transfer, cis-trans isomerization, and excited-state deactivation in a locked ortho-substituted GFP model chromophore (o-LHBI). On the basis of our previous and present results, we find that the S1 keto species is responsible for the fluorescence emission of the unlocked o-HBI and the locked o-LHBI species. Chemical locking does not change the parts of the S1 and S0 potential energy surfaces relevant to enol-keto tautomerization; hence, in both chromophores, there is an ultrafast excited-state intramolecular proton transfer that takes only 35 fs on average. However, the locking effectively hinders the S1 keto species from approaching the keto S1/S0 conical intersections so that most of trajectories are trapped in the S1 keto region for the entire 2 ps simulation time. Therefore, the fluorescence quantum yield of o-LHBI is enhanced compared with that of unlocked o-HBI, in which the S1 excited-state decay is efficient and ultrafast. In the case of the para-substituted GFP model chromophores p-HBI and p-LHBI, chemical locking hardly affects their efficient excited-state deactivation via cis-trans isomerization; thus, the fluorescence quantum yields in these chromophores remain very low. The insights gained from the present work may help to guide the design of new GFP chromophores with improved fluorescence emission and brightness.

  20. Excited-State Proton-Transfer-Induced Trapping Enhances the Fluorescence Emission of a Locked GFP Chromophore

    PubMed Central

    2016-01-01

    The chemical locking of the central single bond in core chromophores of green fluorescent proteins (GFPs) influences their excited-state behavior in a distinct manner. Experimentally, it significantly enhances the fluorescence quantum yield of GFP chromophores with an ortho-hydroxyl group, while it has almost no effect on the photophysics of GFP chromophores with a para-hydroxyl group. To unravel the underlying physical reasons for this different behavior, we report static electronic structure calculations and nonadiabatic dynamics simulations on excited-state intramolecular proton transfer, cis–trans isomerization, and excited-state deactivation in a locked ortho-substituted GFP model chromophore (o-LHBI). On the basis of our previous and present results, we find that the S1 keto species is responsible for the fluorescence emission of the unlocked o-HBI and the locked o-LHBI species. Chemical locking does not change the parts of the S1 and S0 potential energy surfaces relevant to enol–keto tautomerization; hence, in both chromophores, there is an ultrafast excited-state intramolecular proton transfer that takes only 35 fs on average. However, the locking effectively hinders the S1 keto species from approaching the keto S1/S0 conical intersections so that most of trajectories are trapped in the S1 keto region for the entire 2 ps simulation time. Therefore, the fluorescence quantum yield of o-LHBI is enhanced compared with that of unlocked o-HBI, in which the S1 excited-state decay is efficient and ultrafast. In the case of the para-substituted GFP model chromophores p-HBI and p-LHBI, chemical locking hardly affects their efficient excited-state deactivation via cis–trans isomerization; thus, the fluorescence quantum yields in these chromophores remain very low. The insights gained from the present work may help to guide the design of new GFP chromophores with improved fluorescence emission and brightness. PMID:26744782

  1. Electronic excited states of CO/sub 2/: An electron impact investigation

    SciTech Connect

    McDiarmid, R.; Doering, J.P.

    1984-01-15

    The electronic excited states of CO/sub 2/ were restudied by variable incident energy, variable angle electron impact spectroscopy. In this study, valence states of mixed configurations were distinguished from pure Rydberg states. Our results are incompatible with the theoretical description of CO/sub 2/, in which only two valence singlet states are located.

  2. Dynamics of the Chemistry of Electronically Excited Atoms in Defined Quantum States.

    DTIC Science & Technology

    1980-08-15

    excited atom concentration by atomic absorption spectroscopy in the vacuum ultraviolet (6). Relatively efficient electronic to vibrational energy transfer...by the use of atomic absorption spectroscopy , permitted observation of both ground and electronically excited state bromine atoms. The deactivation of

  3. Modeling of autoresonant control of a parametrically excited screen machine

    NASA Astrophysics Data System (ADS)

    Abolfazl Zahedi, S.; Babitsky, Vladimir

    2016-10-01

    Modelling of nonlinear dynamic response of a screen machine described by the nonlinear coupled differential equations and excited by the system of autoresonant control is presented. The displacement signal of the screen is fed to the screen excitation directly by means of positive feedback. Negative feedback is used to fix the level of screen amplitude response within the expected range. The screen is anticipated to vibrate with a parametric resonance and the excitation, stabilization and control response of the system are studied in the stable mode. Autoresonant control is thoroughly investigated and output tracking is reported. The control developed provides the possibility of self-tuning and self-adaptation mechanisms that allow the screen machine to maintain a parametric resonant mode of oscillation under a wide range of uncertainty of mass and viscosity.

  4. Fast and slow excited-state intramolecular proton transfer in 3-hydroxychromone: a two-state story?

    PubMed

    Perveaux, Aurelie; Lorphelin, Maxime; Lasorne, Benjamin; Lauvergnat, David

    2017-02-16

    The photodynamics of 3-hydroxychromone in its first-excited singlet electronic state (bright state of ππ* character) is investigated with special emphasis given to two types of reaction pathways: the excited-state intramolecular-proton-transfer coordinate and the hydrogen-torsion coordinate linking the excited cis and trans isomers. A newly-found conical intersection with the second-excited singlet electronic state (dark state of nπ* character) is suspected to be, to some extent, the reason for the slower rate constant. This hypothesis based on quantum-chemistry calculations is supported by quantum-dynamics simulations in full dimensionality. They show significant transfer of electronic population and provide consistently a vibronic interpretation for the forbidden band in the UV absorption spectrum.

  5. On the origin of ultrafast nonradiative transitions in nitro-polycyclic aromatic hydrocarbons: Excited-state dynamics in 1-nitronaphthalene

    NASA Astrophysics Data System (ADS)

    Reichardt, Christian; Vogt, R. Aaron; Crespo-Hernández, Carlos E.

    2009-12-01

    The electronic energy relaxation of 1-nitronaphthalene was studied in nonpolar, aprotic, and protic solvents in the time window from femtoseconds to microseconds. Excitation at 340 or 360 nm populates the Franck-Condon S1(ππ ∗) state, which is proposed to bifurcate into two essentially barrierless nonradiative decay channels with sub-200 fs lifetimes. The first main decay channel connects the S1 state with a receiver Tn state that has considerable nπ∗ character. The receiver Tn state undergoes internal conversion to populate the vibrationally excited T1(ππ∗) state in 2-4 ps. It is shown that vibrational cooling dynamics in the T1 state depends on the solvent used, with average lifetimes in the range from 6 to 12 ps. Furthermore, solvation dynamics competes effectively with vibrational cooling in the triplet manifold in primary alcohols. The relaxed T1 state undergoes intersystem crossing back to the ground state within a few microseconds in N2-saturated solutions in all the solvents studied. The second minor channel involves conformational relaxation of the bright S1 state (primarily rotation of the NO2-group) to populate a dissociative singlet state with significant charge-transfer character and negligible oscillator strength. This dissociative channel is proposed to be responsible for the observed photochemistry in 1-nitronaphthalene. Ground- and excited-state calculations at the density functional level of theory that include bulk and explicit solvent effects lend support to the proposed mechanism where the fluorescent S1 state decays rapidly and irreversibly to dark excited states. A four-state kinetic model is proposed that satisfactorily explains the origin of the nonradiative electronic relaxation pathways in 1-nitronaphthalene.

  6. 7-Hydroxyquinoline-8-carbaldehydes. 1. Ground- and excited-state long-range prototropic tautomerization.

    PubMed

    Vetokhina, Volha; Nowacki, Jacek; Pietrzak, Mariusz; Rode, Michał F; Sobolewski, Andrzej L; Waluk, Jacek; Herbich, Jerzy

    2013-09-26

    Ground- and excited-state long-range prototropic tautomerization were studied for a series of 7-hydroxyquinoline-8-carbaldehydes (7-HQCs) by (1)H and (13)C NMR spectroscopy, photostationary and time-resolved UV-vis spectroscopic methods, and quantum chemical computations. These molecules represent trifunctional proton-donating/accepting systems that have been proposed to serve as models of a reversible optically driven molecular switch composed of two moieties: a molecular "frame" (7-hydroquinolines, 7-HQs) and a proton "crane" (carbaldehyde group). The NMR and electronic absorption spectra indicate a solvent-dependent equilibrium between two tautomeric forms, OH (7-quinolinol)) and NH (7(1H)-quinolinone), already in the ground state of all the compounds under study (7-hydroxy-2-methoxy-4-methylquinoline-8-carbaldehyde, HMMQC, shows only a trace of the NH form in highly polar and/or protic media). Electronic absorption and fluorescence of 7-HQCs are rationalized in terms of the ground- and excited-state hydrogen atom transfer (HAT). This process was identified by comparing the UV-vis spectroscopic properties of 7-HQCs with those of 7-HQs, synthetic precursors of the former, as well as with the characteristics of corresponding protonated cations and deprotonated anions (part 2). The experimental results are corroborated by the density functional theory (DFT) and ab initio computations, which shed some light on the differences in photophysics between variously substituted 7-HQCs.

  7. Excited-state positronium formation in positron-hydrogen collisions under weakly coupled plasmas

    NASA Astrophysics Data System (ADS)

    Rej, Pramit; Ghoshal, Arijit

    2016-06-01

    The effect of screening of weakly coupled plasma on positronium (Ps) formation in excited states in the scattering of a positron from the ground state of a hydrogen atom has been investigated using a distorted wave theory which includes screened dipole polarization potential. The effect of external plasma has been incorporated by using the Debye-Hückel screening model of the interacting charge particles. Variationally determined simple hydrogenic wave functions have been used to obtain the distorted wave scattering amplitude in a closed form. Effects of plasma screening on the differential and total cross sections have been studied in detail in the energy range 20-300 eV of incident positron. For the free atomic case, our results agree nicely with some of the most accurate results available in the literature. To the best of our knowledge, such a study on the differential and total cross sections for Ps formation in highly excited states in positron-hydrogen collisions under weakly coupled plasma is reported first time in the literature.

  8. Effect of xanthophyll composition on the chlorophyll excited state lifetime in plant leaves and isolated LHCII

    NASA Astrophysics Data System (ADS)

    Johnson, Matthew P.; Zia, Ahmad; Horton, Peter; Ruban, Alexander V.

    2010-07-01

    Xanthophyll excited states have been implicated by transient absorption and two-photon excitation studies in playing a key role in the regulation of photosynthetic light harvesting via photoprotective energy dissipation. For any proposed quenching mechanism to be effective it must reduce the chlorophyll excited state lifetime from 2 ns to ˜0.5-0.4 ns. In the presented study the effect of xanthophyll composition on the chlorophyll excited state lifetime in Arabidopsis leaves in the light harvesting ( F m) and photoprotective (NPQ) states was determined. The data was compared to the chlorophyll excited state lifetime of native isolated LHCII and CP26 in detergent micelles with varying xanthophyll composition. It was found that although the differences in xanthophyll composition between LHC complexes from various Arabidopsis mutants were sufficient to explain the varying F m lifetime (and varying PSII efficiency), they were not of a sufficient scale to fully explain the observed differences in the NPQ lifetimes. Only when the LHC complexes were exposed to a low detergent/low pH media, a condition known to mimic the conformational state of LHCII associated with NPQ in vivo, were variations in excited state lifetime large enough to explain the differences observed in leaves. Furthermore, the data reveal that the replacement of lutein by either zeaxanthin or violaxanthin in the internal xanthophyll binding sites of LHCII and CP26 reduces the efficiency of energy dissipation in the photoprotective state in leaves and isolated complexes.

  9. 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.

  10. Dynamics of the binding of acridine dyes to DNA investigated by triplet excited state probe techniques

    SciTech Connect

    Geacintov, N.E.; Waldmeyer, J.; Kuzmin, V.A.; Kolubayev, T.

    1981-11-26

    The binding of the polynuclear aromatic dyes acridine orange (AO) and proflavin (PF) to DNA in aqueous phosphate buffer solution at 25 +- 1/sup 0/C has been studied by measuring the properties of the triplet excited states of these dyes. The triplet lifetimes can be measured either by triplet-triplet absorption flash photolysis techniques or by delayed fluorescence methods. The triplet lifetimes of AO vary from about 0.5 ms with no DNA present to 20 to 35 ms at DNA concentration above 10/sup -3/M expressed in concentration of DNA phosphate (P), or at (P)/(D) ratios above 1000 ((D) is the dye concentration). At all DNA concentrations the decay profiles are exponential, except at high excitation intensities where nonexponentialities, attributed to triplet-triplet annihilation, become apparent. Similar results are observed with PF-DNA solutions. The exponentiality of the triplet decay at all DNA concentrations is attributed to rapid association and dissociation of the dye-DNA complexes on the time scales of the triplet lifetimes. A simplified one-step binding model is utilized to describe this effect. A dissociation rate of AO-DNA complexes greater than or equal to 10/sup 3/s/sup -1/ has been estimated from these results. It is shown that a detailed study of the triplet lifetime vs. DNA concentration provides a novel method for the estimation of the apparent equilibrium association constant K* for dye molecules in the triplet excited state and DNA. For AO, K* approx. = 10/sup 5/ M/sup -1/, while for PF it is approx. = 3 x 10/sup 4/ M/sup -1/. These values are of the same order of magnitude as the ground-state dye-DNA equilibrium association constants measured by others.

  11. Excited-state hadron masses from lattice QCD

    NASA Astrophysics Data System (ADS)

    Morningstar, C.; Bulava, J.; Foley, J.; Jhang, Y. C.; J, K. J.; Lenkner, D.; Wong, C. H.

    2012-09-01

    Progress in computing the spectrum of excited baryons and mesons in lattice QCD is described. Large sets of spatially-extended hadron operators are used. The need for multi-hadron operators in addition to single-hadron operators is emphasized, necessitating the use of a new stochastic method of treating the low-lying modes of quark propagation which exploits Laplacian Heaviside quark-field smearing. A new glueball operator is tested and computing the mixing of this glueball operator with a quark-antiquark operator and multiple two-pion operators is shown to be feasible.

  12. Noncollisional excitation of low-lying states in gaseous nebulae

    NASA Technical Reports Server (NTRS)

    Rubin, Robert H.

    1986-01-01

    Consideration is given to the effects of processes other than electron collisional excitation on the energy level populations of species of C, N, and O. It is found that dielectronic as well as direct-radiative recombination may contribute significantly and in some cases be the major input to populating the low-lying metastable levels. It is concluded that the most pronounced changes occur when there is a large effective recombination coefficient to a level and when T(e) is low. The most dramatic change among the forbidden lines occurs for the O II forbidden lines.

  13. Populating excited states of incoherent atoms using coherent light.

    NASA Technical Reports Server (NTRS)

    Mcilrath, T. J.; Carlsten, J. L.

    1972-01-01

    Study of the influence of various experimental parameters on the interaction between a multimode high-intensity laser light and the absorbing atoms of an atomic gas. Using a simplified treatment of line broadening which does not include correlations between momentum-changing collisions and pressure-broadening collisions, expressions are obtained that show the effect of pressure, laser-pulse length, and intensity on the excitation. It is found that, as long as the dephasing time of the atomic system is sufficiently short, the interaction reduces to a two-body collision between the atoms and photons, where coherence effects do not occur.

  14. M1 excitation in Sm isotopes and the proton-neutron sdg interacting boson model

    NASA Astrophysics Data System (ADS)

    Mizusaki, Takahiro; Otsuka, Takaharu; Sugita, Michiaki

    1991-10-01

    The magnetic-dipole scissors mode in spherical to deformed Sm isotopes is studied in terms of the proton-neutron sdg interacting boson model, providing a good agreement with recent experiment by Ziegler et al. The present calculation correctly reproduces the increase of M1 excitation strength in going from spherical to deformed nuclei. It is suggested that there may be 1+ states which do not correspond to the scissors mode but absorb certain M1 strength from the ground state.

  15. Modeling Endovascular MRI Coil Coupling with Transmit RF Excitation

    PubMed Central

    Venkateswaran, Madhav; Unal, Orhan; Hurley, Samuel; Samsonov, Alexey; Wang, Peng; Fain, Sean; Kurpad, Krishna

    2016-01-01

    Objective To model inductive coupling of endovascular coils with transmit RF excitation for selecting coils for MRI-guided interventions. Methods Independent and computationally efficient FEM models are developed for the endovascular coil, cable, transmit excitation and imaging domain. Electromagnetic and circuit solvers are coupled to simulate net B1+ fields and induced currents and voltages. Our models are validated using the Bloch Siegert B1+ mapping sequence for a series-tuned multimode coil, capable of tracking, wireless visualization and high resolution endovascular imaging. Results Validation shows good agreement at 24, 28 and 34 μT background RF excitation within experimental limitations. Quantitative coil performance metrics agree with simulation. A parametric study demonstrates trade off in coil performance metrics when varying number of coil turns. Tracking, imaging and wireless marker multimode coil features and their integration is demonstrated in a pig study. Conclusion Developed models for the multimode coil were successfully validated. Modeling for geometric optimization and coil selection serves as a precursor to time-consuming and expensive experiments. Specific applications demonstrated include parametric optimization, coil selection for a cardiac intervention and an animal imaging experiment. Significance Our modular, adaptable and computationally efficient modeling approach enables rapid comparison, selection and optimization of inductively-coupled coils for MRI-guided interventions. PMID:26960218

  16. Interplay of collective and single-particle properties of excited states of deformable odd nuclei {sup 155}Eu and {sup 161}Tm

    SciTech Connect

    Sharipov, Sh.; Ermamatov, M. J. Bayimbetova, J. K.

    2008-02-15

    The properties of excited states of two deformable odd nuclei are investigated within the nonadiabatic model previously developed by the present authors. The results of relevant calculations are compared with available experimental data.

  17. Direct observation of metal-to-ligand charge-transfer (MLCT) excited states of pentaammineruthenium(II) complexes

    SciTech Connect

    Winkler, J.R.; Netzel, T.L.; Creutz, C.; Sutin, N.

    1987-04-15

    Excited-state difference spectra and lifetimes are reported for Ru(tpy)/sub 2//sup 2 +/ (tpy = 2,2',2''-terpyridine) and a series of pentaammineruthenium(II) complexes. The initially formed excited states (generated by approx. 25-ps excitation with 532-nm light) are well modeled by a Ru/sup III/(L/sup .-/) electronic configuration (L is an aromatic, N-heterocyclic ligand) since an excellent correspondence is found between their absorption features and those of (L/sup .-)H/sup +/ radicals. The transients are, therefore, assigned as MLCT states. The Ru(tpy)/sub 2//sup 2 +/ excited-state lifetime is 250 ps. The Ru(NH/sub 3/)/sub 5/L/sup 2 +/ excited-state lifetimes vary from less than or equal to 20 (L = protonated pyrazine, protonated 4,4'-bipyridine, and 4-acetylpyridine) to approx. 200 (L = pyrazine, isonicotinamide, 4,4'-bipyridine) ps in water at approx. 22/sup 0/C. Ammine aquation products, Ru(NH/sub 3/)/sub 4/(H/sub 2/O)L/sup 2 +/, are also observed and are shown to result from multiphoton absorption of the ps-excitation pulses. The MLCT states of Ru(NH/sub 3/)/sub 5/L/sup 2 +/ (L = pz or 4,4'-bpy) undergo protonation by solvent water and deactivation to Ru(NH/sub 3/)/sub 5/LH/sup 3 +/; rate constants for proton loss from the protonated species (Ru(NH/sub 3/)/sub 5/LH/sup 3 +/ + H/sub 2/O ..-->.. Ru(NH/sub 3/)/sub 5/L/sup 2 +/ + H/sub 3/O/sup +/) are (2-3) x 10/sup 7/ s/sup -1/ and 2 x 10/sup 5/ s/sup -1/ for L = pz and 4,4'-bpy, respectively. The Ru(NH/sub 3/)/sub 5/L/sup 2 +/ MLCT-excited-state lifetimes are discussed in terms of the lowest excited state tuning model of Ford and co-workers.

  18. Characterizing the Locality of Diabatic States forElectronic Excitation Transfer By Decomposing theDiabatic Coupling

    SciTech Connect

    Newton, M.D.; Vura-Weis, J.; Wasielewski, M.R.; Subotnik, J.E.

    2010-10-19

    A common strategy to calculate electronic coupling matrix elements for charge or energy transfer is to take the adiabatic states generated by electronic structure computations and rotate them to form localized diabatic states. In this paper, we show that, for intermolecular transfer of singlet electronic excitation, usually we cannot fully localize the electronic excitations in this way. Instead, we calculate putative initial and final states with small excitation tails caused by weak interactions with high energy excited states in the electronic manifold. These tails do not lead to substantial changes in the total diabatic coupling between states, but they do lead to a different partitioning of the total coupling between Coulomb (Forster), exchange (Dexter), and one-electron components. The tails may be reduced by using a multistate diabatic model or eliminated entirely by truncation (denoted as 'chopping'). Without more information, we are unable to conclude with certainty whether the observed diabatic tails are a physical reality or a computational artifact. This research suggests that decomposition of the diabatic coupling between chromophores into Coulomb, exchange, and one-electron components may depend strongly on the number of states considered, and such results should be treated with caution.

  19. Collective magnetic excitations of C4-symmetric magnetic states in iron-based superconductors

    NASA Astrophysics Data System (ADS)

    Scherer, Daniel D.; Eremin, Ilya; Andersen, Brian M.

    2016-11-01

    We study the collective magnetic excitations of the recently discovered C4-symmetric spin-density-wave states of iron-based superconductors with particular emphasis on their orbital character based on an itinerant multiorbital approach. This is important since the C4-symmetric spin-density-wave states exist only at moderate interaction strengths where damping effects from a coupling to the continuum of particle-hole excitations strongly modify the shape of the excitation spectra compared to predictions based on a local moment picture. We uncover a distinct orbital polarization inherent to magnetic excitations in C4-symmetric states, which provide a route to identify the different commensurate magnetic states appearing in the continuously updated phase diagram of the iron-pnictide family.

  20. Inelastic WIMP-nucleus scattering to the first excited state in 125Te

    NASA Astrophysics Data System (ADS)

    Vergados, J. D.; Avignone, F. T., III; Kortelainen, M.; Pirinen, P.; Srivastava, P. C.; Suhonen, J.; Thomas, A. W.

    2016-11-01

    The direct detection of dark matter constituents, in particular the weakly interacting massive particles (WIMPs), is considered central to particle physics and cosmology. In this paper we study transitions to the excited states, possible in nuclei which have sufficiently low-lying excited states. Examples considered previously were the first excited states of 127I, 129Xe and 83Kr. Here, we examine 125Te, which offers some advantages and is currently being considered as a target. In all these cases the extra signature of the gamma rays following the de-excitation of these states has definite advantages over the purely nuclear recoil and in principle such a signature can be exploited experimentally. A brief discussion of the experimental feasibility is given in the context of the CUORE experiment.

  1. Comments on the determination of excited state dipole moment of molecules using the method of solvatochromism.

    PubMed

    Kawski, A; Bojarski, P

    2011-11-01

    The present note comments on several publications which appeared in different journals containing many inaccurate statements and lacking honest citations of basic papers dealing with the application of solvatochromism to determine excited state dipole moments.

  2. Radical ions and excited states in radiolysis. Optically detected time resolved EPR

    SciTech Connect

    Trifunac, A.D.; Smith, J.P.

    1981-01-01

    Excited-state production and radical-ion recombination kinetics in pulse-irradiated solutions of aromatic solutes in cyclohexane are studied by a new method of optical detection of time-resolved electron paramagnetic resonance (EPR) spectra. 7 figures.

  3. Permanent Magnet Synchronous Condenser with Solid State Excitation

    SciTech Connect

    Hsu, Ping; Muljadi, Eduard; Wu, Ziping; Gao, Wenzhong

    2015-10-05

    A synchronous condenser consists of a free-spinning wound-field synchronous generator and a field excitation controller. In this paper, we propose a synchronous generator that employs a permanent magnet synchronous generator (PMSG) instead of a wound-field machine. PMSGs have the advantages of higher efficiency and reliability. In the proposed configuration, the reactive power control is achieved by a voltage source converter connected in series with the PMSG and the grid. The converter varies the phase voltage of the PMSG so as to create the same effect of over or under excitation in a wound-field machine. The converter output voltage level controls the amount and the direction of the produced reactive power and the voltage's phase is kept in-phase with the grid voltage except a slight phase can be introduced so that some power can be drawn from the grid for maintaining the DC bus voltage level of the converter. Since the output voltage of the converter is only a fraction of the line voltage, its VA rating is only a fraction of the rating of the PMSG. The proposed scheme is shown to be effective by computer simulation.

  4. Energies of low-lying excited states of linear polyenes.

    PubMed

    Christensen, Ronald L; Galinato, Mary Grace I; Chu, Emily F; Howard, Jason N; Broene, Richard D; Frank, Harry A

    2008-12-11

    Room temperature absorption and emission spectra of the all-trans isomers of decatetraene, dodecapentaene, tetradecahexaene, and hexadecaheptaene have been obtained in a series of nonpolar solvents. The resolved vibronic features in the optical spectra of these model systems allow the accurate determination of S(0) (1(1)A(g)(-)) --> S(2) (1(1)B(u)(+)) and S(1) (2(1)A(g)(-)) --> S(0) (1(1)A(g)(-)) electronic origins as a function of solvent polarizability. These data can be extrapolated to predict the transition energies in the absence of solvent perturbations. The effects of the terminal methyl substituents on the transition energies also can be estimated. Franck-Condon maxima in the absorption and emission spectra were used to estimate differences between S(0) (1(1)A(g)(-)) --> S(1) (2(1)A(g)(-)) and S(0) (1(1)A(g)(-)) --> S(2) (1(1)B(u)(+)) electronic origins and "vertical" transition energies. Experimental estimates of the vertical transition energies of unsubstituted, all-trans polyenes in vacuum as a function of conjugation length are compared with long-standing multireference configuration interaction (MRCI) treatments and with more recent ab initio calculations of the energies of the 2(1)A(g)(-) (S(1)) and 1(1)B(u)(+) (S(2)) states.

  5. Switching between ground and excited states by optical feedback in a quantum dot laser diode

    SciTech Connect

    Virte, Martin; Breuer, Stefan; Sciamanna, Marc; Panajotov, Krassimir

    2014-09-22

    We demonstrate switching between ground state and excited state emission in a quantum-dot laser subject to optical feedback. Even though the solitary laser emits only from the excited state, we can trigger the emission of the ground state by optical feedback. We observe recurrent but incomplete switching between the two emission states by variation of the external cavity length in the sub-micrometer scale. We obtain a good qualitative agreement of experimental results with simulation results obtained by a rate equation that accounts for the variations of the feedback phase.

  6. Excited-state absorption in bacteriochlorophyll a-protein from the green photosynthetic bacterium Prosthecochloris aestuarii: Reinterpretation of the absorption difference spectrum

    SciTech Connect

    Amerongen, H. van; Struve, W.S. )

    1991-10-31

    Excited-state absorption arising from transitions between singly and doubly excited exciton components in strongly coupled photosynthetic antennae profoundly influences the absorption difference spectra observed in pump-probe spectroscopy. Model calculations of the absorption difference spectrum in the BChl a-protein complex from P. aestuarii are compared with the experimental spectrum.

  7. Reproducibility and Comparability of Computational Models for Astrocyte Calcium Excitability

    PubMed Central

    Manninen, Tiina; Havela, Riikka; Linne, Marja-Leena

    2017-01-01

    The scientific community across all disciplines faces the same challenges of ensuring accessibility, reproducibility, and efficient comparability of scientific results. Computational neuroscience is a rapidly developing field, where reproducibility and comparability of research results have gained increasing interest over the past years. As the number of computational models of brain functions is increasing, we chose to address reproducibility using four previously published computational models of astrocyte excitability as an example. Although not conventionally taken into account when modeling neuronal systems, astrocytes have been shown to take part in a variety of in vitro and in vivo phenomena including synaptic transmission. Two of the selected astrocyte models describe spontaneous calcium excitability, and the other two neurotransmitter-evoked calcium excitability. We specifically addressed how well the original simulation results can be reproduced with a reimplementation of the models. Additionally, we studied how well the selected models can be reused and whether they are comparable in other stimulation conditions and research settings. Unexpectedly, we found out that three of the model publications did not give all the necessary information required to reimplement the models. In addition, we were able to reproduce the original results of only one of the models completely based on the information given in the original publications and in the errata. We actually found errors in the equations provided by two of the model publications; after modifying the equations accordingly, the original results were reproduced more accurately. Even though the selected models were developed to describe the same biological event, namely astrocyte calcium excitability, the models behaved quite differently compared to one another. Our findings on a specific set of published astrocyte models stress the importance of proper validation of the models against experimental wet

  8. Relative entropy of excited states in two dimensional conformal field theories

    NASA Astrophysics Data System (ADS)

    Sárosi, Gábor; Ugajin, Tomonori

    2016-07-01

    We study the relative entropy and the trace square distance, both of which measure the distance between reduced density matrices of two excited states in two dimensional conformal field theories. We find a general formula for the relative entropy between two primary states with the same conformal dimension in the limit of a single small interval and find that in this case the relative entropy is proportional to the trace square distance. We check our general formulae by calculating the relative entropy between two generalized free fields and the trace square distance between the spin and disorder operators of the critical Ising model. We also give the leading term of the relative entropy in the small interval expansion when the two operators have different conformal dimensions. This turns out to be universal when the CFT has no primaires lighter than the stress tensor. The result reproduces the previously known special cases.

  9. The effect of charge state on electron excitation by slow protons in simple metal

    NASA Astrophysics Data System (ADS)

    Marouf, S.; Boudouma, Y.; Chami, A. C.

    2016-01-01

    We investigate the energy and angular distributions of conduction band electrons excited by slowly moving protons. An improved method for the description of target response was developed assuming a convenient spherical symmetry of the screened potential. The velocity dependent screening parameter of the trial potential is adjusted in a self-consistent way using an extension of the Friedel sum rule. As positive projectile can be ionized or neutralized by interaction with the target, we should include the different charge states fractions of the protons to determine the doubly differential cross section (DDCS) for the secondary electron emission. A comparison of the double differential cross section using the Density Functional Theory (DFT) is presented. The energy loss of moving proton is also discussed with explicit inclusion of the different charge states and compared to the available experimental data in order to check the validity of the proposed model.

  10. Contribution of excited states to stellar weak-interaction rates in odd-A nuclei

    NASA Astrophysics Data System (ADS)

    Sarriguren, P.

    2016-05-01

    Weak-interaction rates, including β decay and electron capture, are studied in several odd-A nuclei in the p f -shell region at various densities and temperatures of astrophysical interest. Special attention is paid to the relative contribution to these rates of thermally populated excited states in the decaying nucleus. The nuclear structure involved in the weak processes is studied within a quasiparticle random-phase approximation with residual interactions in both particle-hole and particle-particle channels on top of a deformed Skyrme Hartree-Fock mean field with pairing correlations. In the range of densities and temperatures considered, it is found that the total rates do not differ much from the rates of the ground state fully populated. In any case, the changes are not larger than the uncertainties due to the nuclear-model dependence of the rates.

  11. Optical excitation of trapping states in Fe doped InP

    NASA Astrophysics Data System (ADS)

    Giessner, J.

    1983-06-01

    The knowledge that defect states affect the performance and speed of semiconductors is well known. Defect and trapping states are categorized according to their sex (hole or electron trap), energy in the gap and capture cross sections. The Deep Level Transient Spectroscopy (DLTS) technique that is useful for electrical pulsing, becomes increasingly profitable using optical pulsing. The optical pulsing was accomplished using a simple, but efficient, infrared light emitting diode (LED). The LED had the fortunate property that with decreasing temperature, the average energy output of the LED stayed about equal to the bandgap for the 3-5 semiconductor InP. Because of these findings, emphasis was put on Fe-doped Inp using LED excitation. These particular samples are being studied by Naval Research Labs (NRL) in connection with lasing that results from Fe transitions. Models were set up for both the p+n junction and Fe transitions to help explain experimental results obtained.

  12. Coherent excitation of a two-state system by a train of short pulses

    NASA Astrophysics Data System (ADS)

    Vitanov, Nikolay V.; Knight, Peter L.

    1995-09-01

    A theoretical nonperturbative study of the coherent excitation of a two-state system by N consecutive equally spaced identical pulses is presented. General relations between the evolution matrix elements in the cases of one and N pulses are obtained in a closed form. For pulse envelopes allowing analytical solutions, these relations enable analytical treatment of pulse-train excitation; for pulses that can only be treated numerically, they shorten the computations by a factor of N. The relations show that the multiple-pulse excitation of a two-state system can be considered as a quantum analog of the diffraction grating. The interaction dynamics substantially depends on the way the train is produced because the phase shift that is accumulated by the probability amplitudes due to the free evolution of the system during and between the pulses differs. In the limit of weak excitation, the results recover earlier conclusions based on perturbative treatments. Simple formulas are derived for the conditions for complete population inversion (CPI) and complete population return (CPR), which differ from the single-pulse ones. These general results are applied to four particular cases that allow analytical solutions: resonant, rectangular, Rosen-Zener, and Allen-Eberly pulses. A common feature in all these cases is that the number and the amplitude of oscillations in the state populations increase with the number of pulses, while their width decreases. For rectangular pulses, CPI is possible below a given value of the ratio between the detuning and the pulse area; this value increases nearly linearly with the number of pulses. For the Rosen-Zener model, CPI is found to be possible for two and more pulses, while it is impossible for a single non-resonant pulse. It is shown that for a given number of pulses there is an upper limit on the detuning for which CPI can be observed; this limit increases logarithmically with the number of pulses. For the Allen-Eberly model, CPR is

  13. Geometric constraints in semiclassical initial value representation calculations in Cartesian coordinates: excited states.

    PubMed

    Issack, Bilkiss B; Roy, Pierre-Nicholas

    2007-01-14

    The authors show that a recently proposed approach [J. Chem. Phys. 123, 084103 (2005)] for the inclusion of geometric constraints in semiclassical initial value representation calculations can be used to obtain excited states of weakly bound complexes. Sample calculations are performed for free and constrained rare gas clusters. The results show that the proposed approach allows the evaluation of excited states with reasonable accuracy when compared to exact basis set calculations.

  14. 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.

  15. Non-orthogonal configuration interaction for the calculation of multielectron excited states

    NASA Astrophysics Data System (ADS)

    Sundstrom, Eric J.; Head-Gordon, Martin

    2014-03-01

    We apply Non-orthogonal Configuration Interaction (NOCI) to molecular systems where multielectron excitations, in this case double excitations, play a substantial role: the linear polyenes and β-carotene. We demonstrate that NOCI when applied to systems with extended conjugation, provides a qualitatively correct wavefunction at a fraction of the cost of many other multireference treatments. We also present a new extension to this method allowing for purification of higher-order spin states by utilizing Generalized Hartree-Fock Slater determinants and the details for computing ⟨S2⟩ for the ground and excited states.

  16. Non-orthogonal configuration interaction for the calculation of multielectron excited states

    SciTech Connect

    Sundstrom, Eric J. Head-Gordon, Martin

    2014-03-21

    We apply Non-orthogonal Configuration Interaction (NOCI) to molecular systems where multielectron excitations, in this case double excitations, play a substantial role: the linear polyenes and β-carotene. We demonstrate that NOCI when applied to systems with extended conjugation, provides a qualitatively correct wavefunction at a fraction of the cost of many other multireference treatments. We also present a new extension to this method allowing for purification of higher-order spin states by utilizing Generalized Hartree-Fock Slater determinants and the details for computing 〈S{sup 2}〉 for the ground and excited states.

  17. Experimental validation of a theoretical model of dual wavelength photoacoustic (PA) excitation in fluorophores

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Fluorophores, such as exogenous dyes and genetically expressed proteins, exhibit radiative relaxation with long excited state lifetimes. This can be exploited for PA detection based on dual wavelength excitation using pump and probe wavelengths that coincide with the absorption and emission spectra, respectively. While the pump pulse raises the fluorophore to a long-lived excited state, simultaneous illumination with the probe pulse reduces the excited state lifetime due to stimulated emission (SE).This leads to a change in thermalized energy, and hence PA signal amplitude, compared to single wavelength illumination. By introducing a time delay between pump and probe pulses, the change in PA amplitude can be modulated. Since the effect is not observed in endogenous chromophores, it provides a contrast mechanism for the detection of fluorophores via PA difference imaging. In this study, a theoretical model of the PA signal generation in fluorophores was developed and experimentally validated. The model is based on a system of coupled rate equations, which describe the spatial and temporal changes in the population of the molecular energy levels of a fluorophore as a function of pump-probe energy and concentration. This allows the prediction of the thermalized energy distribution, and hence the time-resolved PA signal amplitude. The model was validated by comparing its predictions to PA signals measured in solutions of rhodamine 6G, a well-known laser dye, and Atto680, a NIR fluorophore.

  18. 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.

  19. Excited-State Energies and Electronic Couplings of DNA Base Dimers

    SciTech Connect

    Kozak, Christopher R.; Kistler, Kurt A.; Lu, Zhen; Matsika, Spiridoula

    2010-02-04

    The singlet excited electronic states of two π-stacked thymine molecules and their splittings due to electronic coupling have been investigated with a variety of computational methods. Focus has been given on the effect of intermolecular distance on these energies and couplings. Single-reference methods, CIS, CIS(2), EOMCCSD, TDDFT, and the multireference method CASSCF, have been used, and their performance has been compared. It is found that the excited-state energies are very sensitive to the applied method but the couplings are not as sensitive. Inclusion of diffuse functions in the basis set also affects the excitation energies significantly but not the couplings. TDDFT is inadequate in describing the states and their coupling, while CIS(2) gives results very similar to EOM-CCSD. Excited states of cytosine and adenine π-stacked dimers were also obtained and compared with those of thymine dimers to gain a more general picture of excited states in π-stacked DNA base dimers. The coupling is very sensitive to the relative position and orientation of the bases, indicating great variation in the degree of delocalization of the excited states between stacked bases in natural DNA as it fluctuates.

  20. Photochemistry of excited-state species in natural waters: a role for particulate organic matter.

    PubMed

    Cottrell, Barbara A; Timko, Stephen A; Devera, Lianne; Robinson, Alice K; Gonsior, Michael; Vizenor, Ashley E; Simpson, André J; Cooper, William J

    2013-09-15

    Laser flash photolysis (LFP) was used to characterize a triplet excited state species isolated from Black River and San Joaquin wetlands particulate organic matter (POM). The solubilized organic matter, isolated from POM by pH-independent diffusion in distilled water, was named PdOM. UV-visible absorption spectroscopy, excitation-emission matrix spectroscopy (EEMs), and (1)H NMR were used to characterize the PdOM. While LFP of dissolved organic matter (DOM) is known to generate the solvated electron, LFP of the PdOM transient in argon-, air-, and nitrous oxide-saturated solutions indicated that this was a triplet excited state species ((3)PdOM*). The lifetime and the reactivity of (3)PdOM* with sorbic acid, a triplet state quencher, were compared with that of the triplet excited state of benzophenone, a DOM proxy. A second excited state species (designated DOM*), with a longer lifetime, was reported in a number of previous studies but not characterized. The lifetime of DOM*, measured for seventeen organic matter isolates, lignin, tannic acid, and three wetlands plant extracts, was shown to differentiate allochthonous from autochthonous DOM. (3)POM* and DOM* were also observed in lake water and a constructed wetlands' water. Aqueous extracts of fresh and aged plant material from the same wetland were shown to be one source of these excited state species. This study provides evidence of a role for POM in the photochemistry of natural and constructed wetland waters.

  1. Laser pulse trains for controlling excited state dynamics of adenine in water.

    PubMed

    Petersen, Jens; Wohlgemuth, Matthias; Sellner, Bernhard; Bonačić-Koutecký, Vlasta; Lischka, Hans; Mitrić, Roland

    2012-04-14

    We investigate theoretically the control of the ultrafast excited state dynamics of adenine in water by laser pulse trains, with the aim to extend the excited state lifetime and to suppress nonradiative relaxation processes. For this purpose, we introduce the combination of our field-induced surface hopping method (FISH) with the quantum mechanical-molecular mechanical (QM/MM) technique for simulating the laser-driven dynamics in the condensed phase under explicit inclusion of the solvent environment. Moreover, we employ parametric pulse shaping in the frequency domain in order to design simplified laser pulse trains allowing to establish a direct link between the pulse parameters and the controlled dynamics. We construct pulse trains which achieve a high excitation efficiency and at the same time keep a high excited state population for a significantly extended time period compared to the uncontrolled dynamics. The control mechanism involves a sequential cycling of the population between the lowest and higher excited states, thereby utilizing the properties of the corresponding potential energy surfaces to avoid conical intersections and thus to suppress the nonradiative decay to the ground state. Our findings provide a means to increase the fluorescence yield of molecules with an intrinsically very short excited state lifetime, which can lead to novel applications of shaped laser fields in the context of biosensing.

  2. 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.

  3. Intermolecular electron transfer from naphthalene derivatives in the higher triplet excited states.

    PubMed

    Sakamoto, Masanori; Cai, Xichen; Hara, Michihiro; Fujitsuka, Mamoru; Majima, Tetsuro

    2004-08-11

    Intermolecular electron transfer (ELT) from a series of naphthalene derivatives (NpD) in the higher triplet excited states (T(n)) to carbon tetrachloride (CCl(4)) in Ar-saturated acetonitrile was observed using the two-color two-laser flash photolysis method. The ELT efficiency depended on the driving force of ELT. Since the ELT from the T(n) state occurred competitively with the internal conversion (IC, T(n) --> T(1)) and the triplet energy transfer (ENT), the ELT became apparent only when sufficient free energy change of ELT was attained. On the other hand, ELT from the T(1) state was not observed, although ELT from the T(1) state with sufficiently long lifetime has a slightly exothermic driving force. The fast ELT from the T(n) state and lack of the reactivity of the T(1) state were explained well by the "sticky" dissociative electron-transfer model based on one-electron reductive attachment to CCl(4) leading to the C-Cl bond cleavage.

  4. Highly excited {Sigma}{sup -} states of molecular hydrogen

    SciTech Connect

    Argoubi, F.; Bezzaouia, S.; Oueslati, H.; Telmini, M.; Jungen, Ch.

    2011-05-15

    We report calculations of H{sub 2} {Sigma}{sup -} states using a variational R-matrix approach combined with multichannel quantum defect theory. Several Rydberg series converging to the 2p{pi} state of the H{sub 2}{sup +} ion core are established and their mutual channel interactions characterized. The influence of the external electron on the chemical bond is found to be particularly strong in these electronically and chemically weakly bound states.

  5. Multiple hydrogen bonding in excited states of aminopyrazine in methanol solution: time-dependent density functional theory study.

    PubMed

    Chai, Shuo; Yu, Jie; Han, Yong-Chang; Cong, Shu-Lin

    2013-11-01

    Aminopyrazine (AP) and AP-methanol complexes have been theoretically studied by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The excited-state hydrogen bonds are discussed in detail. In the ground state the intermolecular multiple hydrogen bonds can be formed between AP molecule and protic solvents. The AP monomer and hydrogen-bonded complex of AP with one methanol are photoexcited initially to the S2 state, and then transferred to the S1 state via internal conversion. However the complex of AP with two methanol molecules is directly excited to the S1 state. From the calculated electronic excited energies and simulated absorption spectra, we find that the intermolecular hydrogen bonds are strengthened in the electronic excited states. The strengthening is confirmed by the optimized excited-state geometries. The photochemical processes in the electronic excited states are significantly influenced by the excited-state hydrogen bond strengthening.

  6. Steady-state photoluminescent excitation characterization of semiconductor carrier recombination

    SciTech Connect

    Bhosale, J. S.; Moore, J. E.; Wang, X.; Bermel, P.; Lundstrom, M. S.

    2016-01-15

    Photoluminescence excitation spectroscopy is a contactless characterization technique that can provide valuable information about the surface and bulk recombination parameters of a semiconductor device, distinct from other sorts of photoluminescent measurements. For this technique, a temperature-tuned light emitting diode (LED) has several advantages over other light sources. The large radiation density offered by LEDs from near-infrared to ultraviolet region at a low cost enables efficient and fast photoluminescence measurements. A simple and inexpensive LED-based setup facilitates measurement of surface recombination velocity and bulk Shockley-Read-Hall lifetime, which are key parameters to assess device performance. Under the right conditions, this technique can also provide a contactless way to measure the external quantum efficiency of a solar cell.

  7. Steady-state photoluminescent excitation characterization of semiconductor carrier recombination.

    PubMed

    Bhosale, J S; Moore, J E; Wang, X; Bermel, P; Lundstrom, M S

    2016-01-01

    Photoluminescence excitation spectroscopy is a contactless characterization technique that can provide valuable information about the surface and bulk recombination parameters of a semiconductor device, distinct from other sorts of photoluminescent measurements. For this technique, a temperature-tuned light emitting diode (LED) has several advantages over other light sources. The large radiation density offered by LEDs from near-infrared to ultraviolet region at a low cost enables efficient and fast photoluminescence measurements. A simple and inexpensive LED-based setup facilitates measurement of surface recombination velocity and bulk Shockley-Read-Hall lifetime, which are key parameters to assess device performance. Under the right conditions, this technique can also provide a contactless way to measure the external quantum efficiency of a solar cell.

  8. Excited-State Geometry Optimization with the Density Matrix Renormalization Group, as Applied to Polyenes.

    PubMed

    Hu, Weifeng; Chan, Garnet Kin-Lic

    2015-07-14

    We describe and extend the formalism of state-specific analytic density matrix renormalization group (DMRG) energy gradients, first used by Liu et al. [J. Chem. Theor. Comput. 2013, 9, 4462]. We introduce a DMRG wave function maximum overlap following technique to facilitate state-specific DMRG excited-state optimization. Using DMRG configuration interaction (DMRG-CI) gradients, we relax the low-lying singlet states of a series of trans-polyenes up to C20H22. Using the relaxed excited-state geometries, as well as correlation functions, we elucidate the exciton, soliton, and bimagnon ("single-fission") character of the excited states, and find evidence for a planar conical intersection.

  9. Excited-state spectroscopy for producing ultracold ground-state NaRb molecule

    NASA Astrophysics Data System (ADS)

    Wang, Dajun; Zhu, Bing; Guo, Mingyang; Li, Xiaoke; Lu, Bo; Wang, Fudong; Ye, Xin; Vexiau, Romain; Luc, Eliane; Bouloufa-Maafa, Nadia; Dulieu, Olivier

    2015-05-01

    We report a joint experimental and theoretical investigation on the excited states of NaRb molecule. In particular, we focus on the A1Σ+ /b3 Π admixture which is a promising intermediate state for transferring weakly-bound NaRb Feshbach molecules to the v = 0 level of the X1Σ+ state. Based on RKR potentials obtained from conventional molecular spectroscopy [1], we identified several levels which satisfy the requirements for efficient two-photon population transfer. Starting from a pure sample of NaRb Feshbach molecules, we have experimentally observed most of these levels. The detailed characterization of these levels, including their transition strengths and singlet/triplet mixing ratios, as well as searching of the v = 0 level of the X1Σ+ state with two-photon Autler-Townes spectroscopy, are well underway. This work is jointly supported by Agence Nationale de la Recherche (#ANR-13-IS04-0004-01) and Hong Kong Research Grant Council (#A-CUHK403/13) through the COPOMOL project.

  10. Contrasting the Excited-State Dynamics of the Photoactive Yellow Protein Chromophore: Protein versus Solvent Environments

    PubMed Central

    Vengris, Mikas; van der Horst, Michael A.; Zgrablić, Goran; van Stokkum, Ivo H. M.; Haacke, Stefan; Chergui, Majed; Hellingwerf, Klaas J.; van Grondelle, Rienk; Larsen, Delmar S.

    2004-01-01

    Wavelength- and time-resolved fluorescence experiments have been performed on the photoactive yellow protein, the E46Q mutant, the hybrids of these proteins containing a nonisomerizing “locked” chromophore, and the native and locked chromophores in aqueous solution. The ultrafast dynamics of these six systems is compared and spectral signatures of isomerization and solvation are discussed. We find that the ultrafast red-shifting of fluorescence is associated mostly with solvation dynamics, whereas isomerization manifests itself as quenching of fluorescence. The observed multiexponential quenching of the protein samples differs from the single-exponential lifetimes of the chromophores in solution. The locked chromophore in the protein environment decays faster than in solution. This is due to additional channels of excited-state energy dissipation via the covalent and hydrogen bonds with the protein environment. The observed large dispersion of quenching timescales observed in the protein samples that contain the native pigment favors both an inhomogeneous model and an excited-state barrier for isomerization. PMID:15345563

  11. Effect of nuclear-reaction mechanisms on the population of excited nuclear states and isomeric ratios

    NASA Astrophysics Data System (ADS)

    Skobelev, N. K.

    2016-07-01

    Experimental data on the cross sections for channels of fusion and transfer reactions induced by beams of radioactive halo nuclei and clustered and stable loosely bound nuclei were analyzed, and the results of this analysis were summarized. The interplay of the excitation of single-particle states in reaction-product nuclei and direct reaction channels was established for transfer reactions. Respective experiments were performed in stable (6Li) and radioactive (6He) beams of the DRIBs accelerator complex at the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, and in deuteron and 3He beams of the U-120M cyclotron at the Nuclear Physics Institute, Academy Sciences of Czech Republic (Řež and Prague, Czech Republic). Data on subbarrier and near-barrier fusion reactions involving clustered and loosely bound light nuclei (6Li and 3He) can be described quite reliably within simple evaporation models with allowance for different reaction Q-values and couple channels. In reactions involving halo nuclei, their structure manifests itself most strongly in the region of energies below the Coulomb barrier. Neutron transfer occurs with a high probability in the interactions of all loosely bound nuclei with light and heavy stable nuclei at positive Q-values. The cross sections for such reactions and the respective isomeric ratios differ drastically for nucleon stripping and nucleon pickup mechanisms. This is due to the difference in the population probabilities for excited single-particle states.

  12. Effect of CTAB and SDS micelles on the excited state equilibria of some indole probes

    NASA Astrophysics Data System (ADS)

    Sharma, Neera; Jain, Sapan K.; Rastogi, Ramesh C.

    2007-11-01

    The absorption and fluorescence spectral characteristics of some biologically active indoles have been studied as a function of acidity and basicity (H_/pH/H o) in cationic (cetyltrimethylammonium bromide, CTAB), anionic (sodium dodecylsulphate, SDS) and aqueous phases at a given surfactant concentration. The prototropic equilibrium reactions of these probes have been studied in aqueous and micellar phases and apparent excited state acidity constant (pKa*) values are calculated. The probes show formation of different species on changing pH. Various species present in water, CTAB and SDS have been identified and the equilibrium constants have been determined by Fluorimetric Titration method. The fluorescence spectral data suggest the formation of oxonium ion through the excited state proton transfer reaction in highly acidic media and formation of photoproducts due to the base catalyzed auto-oxidative reaction in basic aqueous solutions. Variations in the apparent pKa* value have been observed in different media. The change in the apparent p Ka values depends upon the solubilising power of the micelles, as well as on the location of the protonating site in the molecule. The observation about increase in pKa* values in SDS and decrease in CTAB compared to pure water for various equilibria is consistent with the pseudophase ion-exchange (PIE) model.

  13. Model-independent measurement of the excited fraction in a magneto-optical trap

    SciTech Connect

    Shah, M. H.; Trachy, M. L.; Veshapidze, G.; DePaola, B. D.; Camp, H. A.; Gearba, M. A.

    2007-05-15

    In many experiments involving a magneto-optical trap (MOT) it is of great importance to know the fraction of atoms placed in an excited state due to the trapping process. Generally speaking, researchers have had to use overly simplistic and untested models to estimate this fraction. In this work, the excited fractions of {sup 87}Rb atoms in a MOT are directly measured using a charge transfer technique, for a range of MOT parameters. Simple models are then fit to the measured fractions. Using the results of this work, the excited fraction of {sup 87}Rb atoms trapped in a MOT can be accurately estimated with knowledge of only the trapping laser intensity and detuning. The results are, at most, only weakly dependent on other MOT parameters.

  14. Blackbody-induced decay, excitation and ionization rates for Rydberg states in hydrogen and helium atoms

    NASA Astrophysics Data System (ADS)

    Glukhov, I. L.; Nekipelov, E. A.; Ovsiannikov, V. D.

    2010-06-01

    New features of the blackbody-induced radiation processes on Rydberg atoms were discovered on the basis of numerical data for the blackbody-induced decay Pdnl(T), excitation Penl(T) and ionization Pionnl(T) rates of nS, nP and nD Rydberg states calculated together with the spontaneous decay rates Pspnl in neutral hydrogen, and singlet and triplet helium atoms for some values of the principal quantum number n from 10 to 500 at temperatures from T = 100 K to 2000 K. The fractional rates Rd(e, ion)nl(T) = Pnld(e, ion)(T)/Pspnl equal to the ratio of the induced decay (excitation, ionization) rates to the rate of spontaneous decay were determined as functions of T and n in every series of states with a given angular momentum l = 0, 1, 2. The calculated data reveal an essential difference between the asymptotic dependence of the ionization rate Pionnl(T) and the rates of decay and excitation Pd(e)nl(T)~T/n2. The departures appear in each Rydberg series for n > 100 and introduce appreciable corrections to the formula of Cooke and Gallagher. Two different approximation formulae are proposed on the basis of the numerical data, one for Rd(e)nl(T) and another one for Rionnl(T), which reproduce the calculated values in wide ranges of principal quantum number from n = 10 to 1000 and temperatures between T = 100 K and T = 2000 K with an accuracy of 2% or better. Modified Fues' model potential approach was used for calculating matrix elements of bound-bound and bound-free radiation transitions in helium.

  15. An experimentally validated bimorph cantilever model for piezoelectric energy harvesting from base excitations

    NASA Astrophysics Data System (ADS)

    Erturk, A.; Inman, D. J.

    2009-02-01

    Piezoelectric transduction has received great attention for vibration-to-electric energy conversion over the last five years. A typical piezoelectric energy harvester is a unimorph or a bimorph cantilever located on a vibrating host structure, to generate electrical energy from base excitations. Several authors have investigated modeling of cantilevered piezoelectric energy harvesters under base excitation. The existing mathematical modeling approaches range from elementary single-degree-of-freedom models to approximate distributed parameter solutions in the sense of Rayleigh-Ritz discretization as well as analytical solution attempts with certain simplifications. Recently, the authors have presented the closed-form analytical solution for a unimorph cantilever under base excitation based on the Euler-Bernoulli beam assumptions. In this paper, the analytical solution is applied to bimorph cantilever configurations with series and parallel connections of piezoceramic layers. The base excitation is assumed to be translation in the transverse direction with a superimposed small rotation. The closed-form steady state response expressions are obtained for harmonic excitations at arbitrary frequencies, which are then reduced to simple but accurate single-mode expressions for modal excitations. The electromechanical frequency response functions (FRFs) that relate the voltage output and vibration response to translational and rotational base accelerations are identified from the multi-mode and single-mode solutions. Experimental validation of the single-mode coupled voltage output and vibration response expressions is presented for a bimorph cantilever with a tip mass. It is observed that the closed-form single-mode FRFs obtained from the analytical solution can successfully predict the coupled system dynamics for a wide range of electrical load resistance. The performance of the bimorph device is analyzed extensively for the short circuit and open circuit resonance

  16. Analysis and simulation for a model of electron impact excitation/deexcitation and ionization/recombination

    SciTech Connect

    Yan, Bokai; Caflisch, Russel E.; Barekat, Farzin; Cambier, Jean-Luc

    2015-10-15

    This paper describes a kinetic model and a corresponding Monte Carlo simulation method for excitation/deexcitation and ionization/recombination by electron impact in a plasma free of external fields. The atoms and ions in the plasma are represented by continuum densities and the electrons by a particle distribution. A Boltzmann-type equation is formulated and a corresponding H-theorem is formally derived. An efficient Monte Carlo method is developed for an idealized analytic model of the excitation and ionization collision cross sections. To accelerate the simulation, the reduced rejection method and binary search method are used to overcome the singular rate in the recombination process. Numerical results are presented to demonstrate the efficiency of the method on spatially homogeneous problems. The evolution of the electron distribution function and atomic states is studied, revealing the possibility under certain circumstances of system relaxation towards stationary states that are not the equilibrium states, a potential non-ergodic behavior.

  17. Triplet excited state spectra and dynamics of carotenoids from the thermophilic purple photosynthetic bacterium Thermochromatium tepidum

    SciTech Connect

    Niedzwiedzki, Dariusz; Kobayashi, Masayuki; Blankenship, R. E.

    2011-01-13

    Light-harvesting complex 2 from the anoxygenic phototrophic purple bacterium Thermochromatium tepidum was purified and studied by steady-state absorption, fluorescence and flash photolysis spectroscopy. Steady-state absorption and fluorescence measurements show that carotenoids play a negligible role as supportive energy donors and transfer excitation to bacteriochlorophyll-a with low energy transfer efficiency of ~30%. HPLC analysis determined that the dominant carotenoids in the complex are rhodopin and spirilloxanthin. Carotenoid excited triplet state formation upon direct (carotenoid) or indirect (bacteriochlorophyll-a Q{sub x} band) excitation shows that carotenoid triplets are mostly localized on spirilloxanthin. In addition, no triplet excitation transfer between carotenoids was observed. Such specific carotenoid composition and spectroscopic results strongly suggest that this organism optimized carotenoid composition in the light-harvesting complex 2 in order to maximize photoprotective capabilities of carotenoids but subsequently drastically suppressed their supporting role in light-harvesting process.

  18. 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.

  19. 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.

  20. Excitation-inhibition discoordination in rodent models of mental disorders

    PubMed Central

    Fenton, André A.

    2015-01-01

    Animal models of mental illness provide a foundation for evaluating hypotheses for the mechanistic causes of mental illness. Neurophysiological investigations of neural network activity in rodent models of mental dysfunction are reviewed from the conceptual framework of the discoordination hypothesis, which asserts that failures of neural coordination cause cognitive deficits in the judicious processing and use of information. Abnormal dynamic coordination of excitatory and inhibitory neural discharge in pharmacological and genetic rodent models support the discoordination hypothesis. These observations suggest excitation-inhibition discoordination and aberrant neural circuit dynamics as causes of cognitive impairment as well as therapeutic targets for cognition-promoting treatments. PMID:25895430

  1. Control of multiple excited image states around segmented carbon nanotubes

    SciTech Connect

    Knörzer, J. Fey, C.; Sadeghpour, H. R.; Schmelcher, P.

    2015-11-28

    Electronic image states around segmented carbon nanotubes can be confined and shaped along the nanotube axis by engineering the image potential. We show how several such image states can be prepared simultaneously along the same nanotube. The inter-electronic distance can be controlled a priori by engineering tubes of specific geometries. High sensitivity to external electric and magnetic fields can be exploited to manipulate these states and their mutual long-range interactions. These building blocks provide access to a new kind of tailored interacting quantum systems.

  2. Excitation model of pacemaker cardiomyocytes of cardiac conduction system

    NASA Astrophysics Data System (ADS)

    Grigoriev, M.; Babich, L.

    2015-11-01

    Myocardium includes typical and atypical cardiomyocytes - pacemakers, which form the cardiac conduction system. Excitation from the atrioventricular node in normal conditions is possible only in one direction. Retrograde direction of pulses is impossible. The most important prerequisite for the work of cardiomyocytes is the anatomical integrity of the conduction system. Changes in contractile force of the cardiomyocytes, which appear periodically, are due to two mechanisms of self-regulation - heterometric and homeometric. Graphic course of the excitation pulse propagation along the heart muscle more accurately reveals the understanding of the arrhythmia mechanism. These models have the ability to visualize the essence of excitation dynamics. However, they do not have the proper forecasting function for result estimation. Integrative mathematical model enables further investigation of general laws of the myocardium active behavior, allows for determination of the violation mechanism of electrical and contractile function of cardiomyocytes. Currently, there is no full understanding of the topography of pacemakers and ionic mechanisms. There is a need for the development of direction of mathematical modeling and comparative studies of the electrophysiological arrangement of cells of atrioventricular connection and ventricular conduction system.

  3. Multiphoton Rabi oscillations between highly excited Stark states of potassium

    SciTech Connect

    He Yonglin

    2011-11-15

    We have applied a nonperturbative resonant theory to study the Rabi frequency of microwave multiphoton transitions between two Rydberg states of potassium in a static electric field. The Stark electric dipole moments used to calculate the Rabi frequency are determined by the Stark states' wave functions, which are obtained by the diagonalization method. The frequencies of the Rabi oscillations are in good agreement with either experimental ones or ones calculated by the time-dependent close-coupling method and the Floquet theory. Furthermore, we are able to show that the size of avoided crossings between the (n+2)s and (n,3) states can be predicted from the Stark electric dipole moment and the difference of the two Stark states' energy at a given resonance.

  4. 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.

  5. Mechanistic photodecarboxylation of pyruvic acid: Excited-state proton transfer and three-state intersection

    SciTech Connect

    Chang, Xue-Ping; Fang, Qiu Cui, Ganglong

    2014-10-21

    Photodissociation dynamics of pyruvic acid experimentally differs from that of commonly known ketones. We have employed the complete active space self-consistent field and its multi-state second-order perturbation methods to study its photodissociation mechanism in the S{sub 0}, T{sub 1}, and S{sub 1} states. We have uncovered four nonadiabatic photodecarboxylation paths. (i) The S{sub 1} system relaxes via an excited-state intramolecular proton transfer (ESIPT) to a hydrogen-transferred tautomer, near which an S{sub 1}/S{sub 0} conical intersection funnels the S{sub 1} to S{sub 0} state. Then, some trajectories continue completing the decarboxylation reaction in the S{sub 0} state; the remaining trajectories via a reverse hydrogen transfer return to the S{sub 0} minimum, from which a thermal decarboxylation reaction occurs. (ii) Due to a small S{sub 1} −T{sub 1} energy gap and a large S{sub 1}/T{sub 1} spin-orbit coupling, an efficient S{sub 1} → T{sub 1} intersystem crossing process happens again near this S{sub 1}/S{sub 0} conical intersection. When decaying to T{sub 1} state, a direct photodecarboxylation proceeds. (iii) Prior to ESIPT, the S{sub 1} system first decays to the T{sub 1} state via an S{sub 1} → T{sub 1} intersystem crossing; then, the T{sub 1} system evolves to a hydrogen-transferred tautomer. Therefrom, an adiabatic T{sub 1} decarboxylation takes place due to a small barrier of 7.7 kcal/mol. (iv) Besides the aforementioned T{sub 1} ESIPT process, there also exists a comparable Norrish type I reaction in the T{sub 1} state, which forms the ground-state products of CH{sub 3}CO and COOH. Finally, we have found that ESIPT plays an important role. It closes the S{sub 1}-T{sub 1} and S{sub 1}-S{sub 0} energy gaps, effecting an S{sub 1}/T{sub 1}/S{sub 0} three-state intersection region, and mediating nonadiabatic photodecarboxylation reactions of pyruvic acid.

  6. 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.

  7. Singlet excited-state behavior of uracil and thymine in aqueous solution: a combined experimental and computational study of 11 uracil derivatives.

    PubMed

    Gustavsson, Thomas; Bányász, Akos; Lazzarotto, Elodie; Markovitsi, Dimitra; Scalmani, Giovanni; Frisch, Michael J; Barone, Vincenzo; Improta, Roberto

    2006-01-18

    The excited-state properties of uracil, thymine, and nine other derivatives of uracil have been studied by steady-state and time-resolved spectroscopy. The excited-state lifetimes were measured using femtosecond fluorescence upconversion in the UV. The absorption and emission spectra of five representative compounds have been computed at the TD-DFT level, using the PBE0 exchange-correlation functional for ground- and excited-state geometry optimization and the Polarizable Continuum Model (PCM) to simulate the aqueous solution. The calculated spectra are in good agreement with the experimental ones. Experiments show that the excited-state lifetimes of all the compounds examined are dominated by an ultrafast (<100 fs) component. Only 5-substituted compounds show more complex behavior than uracil, exhibiting longer excited-state lifetimes and biexponential fluorescence decays. The S(0)/S(1) conical intersection, located at CASSCF (8/8) level, is indeed characterized by pyramidalization and out of plane motion of the substituents on the C5 atom. A thorough analysis of the excited-state Potential Energy Surfaces, performed at the PCM/TD-DFT(PBE0) level in aqueous solution, shows that the energy barrier separating the local S(1) minimum from the conical intersection increases going from uracil through thymine to 5-fluorouracil, in agreement with the ordering of the experimental excited-state lifetime.

  8. Estimation of ground and excited state dipole moments of Oil Red O by solvatochromic shift methods

    NASA Astrophysics Data System (ADS)

    Sıdır, İsa; Gülseven Sıdır, Yadigar

    2015-01-01

    Absorption and fluorescence spectra of Oil Red O (abbreviated as ORO) are recorded in various solvents with different polarity in the range of 250-900 nm, at room temperature. The solvatochromic shift methods have been used to determine the ground state (μg) and excited state (μe) dipole moments depending on dielectric constant and refractive index functions. It is observed that fluorescence spectra show positive solvatochromism whereas absorption spectra do not indicates sensitive behavior to solvent polarity. Excited state dipole moment is found as higher than those of ground state for all of the used methods and it is attributed to more polar excited state of ORO. Theoretical μg has been determined by quantum chemical calculations using DFT and semi empirical methods. HOMO, LUMO, molecular electrostatic potential (MEP) and solvent accessible surface of ORO are calculated by using DFT-B3LYP method.

  9. 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.

  10. Estimation of ground and excited state dipole moments of Oil Red O by solvatochromic shift methods.

    PubMed

    Sıdır, İsa; Gülseven Sıdır, Yadigar

    2015-01-25

    Absorption and fluorescence spectra of Oil Red O (abbreviated as ORO) are recorded in various solvents with different polarity in the range of 250-900 nm, at room temperature. The solvatochromic shift methods have been used to determine the ground state (μg) and excited state (μe) dipole moments depending on dielectric constant and refractive index functions. It is observed that fluorescence spectra show positive solvatochromism whereas absorption spectra do not indicates sensitive behavior to solvent polarity. Excited state dipole moment is found as higher than those of ground state for all of the used methods and it is attributed to more polar excited state of ORO. Theoretical μg has been determined by quantum chemical calculations using DFT and semi empirical methods. HOMO, LUMO, molecular electrostatic potential (MEP) and solvent accessible surface of ORO are calculated by using DFT-B3LYP method.

  11. Intrinsic excitability state of local neuronal population modulates signal propagation in feed-forward neural networks

    NASA Astrophysics Data System (ADS)

    Han, Ruixue; Wang, Jiang; Yu, Haitao; Deng, Bin; Wei, Xilei; Qin, Yingmei; Wang, Haixu

    2015-04-01

    Reliable signal propagation across distributed brain areas is an essential requirement for cognitive function, and it has been investigated extensively in computational studies where feed-forward network (FFN) is taken as a generic model. But it is still unclear how distinct local network states, which are intrinsically generated by synaptic interactions within each layer, would affect the ability of FFN to transmit information. Here we investigate the impact of such network states on propagating transient synchrony (synfire) and firing rate by a combination of numerical simulations and analytical approach. Specifically, local network dynamics is attributed to the competition between excitatory and inhibitory neurons within each layer. Our results show that concomitant with different local network states, the performance of signal propagation differs dramatically. For both synfire propagation and firing rate propagation, there exists an optimal local excitability state, respectively, that optimizes the performance of signal propagation. Furthermore, we find that long-range connections strongly change the dependence of spiking activity propagation on local network state and propose that these two factors work jointly to determine information transmission across distributed networks. Finally, a simple mean field approach that bridges response properties of long-range connectivity and local subnetworks is utilized to reveal the underlying mechanism.

  12. Intrinsic excitability state of local neuronal population modulates signal propagation in feed-forward neural networks.

    PubMed

    Han, Ruixue; Wang, Jiang; Yu, Haitao; Deng, Bin; Wei, Xilei; Qin, Yingmei; Wang, Haixu

    2015-04-01

    Reliable signal propagation across distributed brain areas is an essential requirement for cognitive function, and it has been investigated extensively in computational studies where feed-forward network (FFN) is taken as a generic model. But it is still unclear how distinct local network states, which are intrinsically generated by synaptic interactions within each layer, would affect the ability of FFN to transmit information. Here we investigate the impact of such network states on propagating transient synchrony (synfire) and firing rate by a combination of numerical simulations and analytical approach. Specifically, local network dynamics is attributed to the competition between excitatory and inhibitory neurons within each layer. Our results show that concomitant with different local network states, the performance of signal propagation differs dramatically. For both synfire propagation and firing rate propagation, there exists an optimal local excitability state, respectively, that optimizes the performance of signal propagation. Furthermore, we find that long-range connections strongly change the dependence of spiking activity propagation on local network state and propose that these two factors work jointly to determine information transmission across distributed networks. Finally, a simple mean field approach that bridges response properties of long-range connectivity and local subnetworks is utilized to reveal the underlying mechanism.

  13. 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.

  14. Permanent Magnet Synchronous Condenser with Solid State Excitation: Preprint

    SciTech Connect

    Hsu, P.; Muljadi, E.; Wu, Z.; Gao, W.

    2015-04-07

    A typical synchronous condenser (SC) consists of a free-spinning, wound-field synchronous generator and a field excitation controller. In this paper, we propose an SC that employs a permanent magnet synchronous generator (PMSG) instead of a wound-field machine. PMSGs have the advantages of higher efficiency and reliability. In the proposed configuration, the reactive power control is achieved by a voltage converter controller connected in series to the PMSG. The controller varies the phase voltage of the PMSG and creates the same effect on the reactive power flow as that of an over- or underexcited wound-field machine. The controller’s output voltage magnitude controls the amount of the reactive power produced by the SC. The phase of the controller’s output is kept within a small variation from the grid voltage phase. This small phase variation is introduced so that a small amount of power can be drawn from the grid into the controller to maintain its DC bus voltage. Because the output voltage of the controller is only a fraction of the line voltage, its VA rating is only a fraction of the rating of the PMSG. The proposed scheme is shown to be effective by computer simulations.

  15. Theory of chemical reactions of vibronically excited H/sub 2/(B /sup 1/. sigma. /sup +//sub u/). I. Prediction of a strongly bound excited state of H/sub 4/

    SciTech Connect

    Nicolaides, C.A.; Theodorakopoulos, G.; Petsalakis, I.D.

    1984-02-15

    MRD--CI calculations were carried out on the potential energy surfaces of the ground and first excited singlet of the same symmetry of H/sub 4/, which predict a bound excited state with respect to H/sub 2/+H(/sub 2/ (B /sup 1/..sigma../sup +//sub u/) of 3.1 eV at a geometry of trigonal pyramid. This geometry was predicted theoretically according to a model of chemical bonding for ''maximum ionicity excited states.'' At the minimum and the three dimensional space surrounding it, there is a near touching of the excited with the ground state hypersurfaces. This fact has implications for the spectroscopy and photochemistry of the H/sub 2/+H(/sub 2/ system.

  16. Ultrafast excited-state dynamics in vitamin B12 and related cob(III)alamins.

    PubMed

    Shiang, Joseph J; Cole, Allwyn G; Sension, Roseanne J; Hang, Kun; Weng, Yuxiang; Trommel, Jenna S; Marzilli, Luigi G; Lian, Tianquan

    2006-01-25

    Femtosecond transient IR and visible absorption spectroscopies have been employed to investigate the excited-state photophysics of vitamin B12 (cyanocobalamin, CNCbl) and the related cob(III)alamins, azidocobalamin (N3Cbl), and aquocobalamin (H2OCbl). Excitation of CNCbl, H2OCbl, or N3Cbl results in rapid formation of a short-lived excited state followed by ground-state recovery on time scales ranging from a few picoseconds to a few tens of picoseconds. The lifetime of the intermediate state is influenced by the sigma-donating ability of the axial ligand, decreasing in the order CNCbl > N3Cbl > H2OCbl, and by the polarity of the solvent, decreasing with increasing solvent polarity. The peak of the excited-state visible absorption spectrum is shifted to ca. 490 nm, and the shape of the spectrum is characteristic of weak axial ligands, similar to those observed for cob(II)alamin, base-off cobalamins, or cobinamides. Transient IR spectra of the upper CN and N3 ligands are red-shifted 20-30 cm(-1) from the ground-state frequencies, consistent with a weakened Co-upper ligand bond. These results suggest that the transient intermediate state can be attributed to a corrin ring pi to Co 3d(z2) ligand to metal charge transfer (LMCT) state. In this state bonds between the cobalt and the axial ligands are weakened and lengthened with respect to the corresponding ground states.

  17. 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.

  18. Meteorological Excitations of Polar Motion for an Earth Model with Frequency-dependent Responses

    NASA Astrophysics Data System (ADS)

    Chen, W.; Ray, J.; Li, J.; Huang, C.; Shen, W.

    2013-12-01

    Polar motion excitation involves the mass redistributions and motions of the Earth system relative to the mantle, as well as the frequency-dependent rheology of the Earth, where the latter has recently been modeled in the form of complex and frequency-dependent Love numbers and polar motion excitation transfer functions. At seasonal and intra-seasonal time scales, polar motions are dominated by angular momentum fluctuations due to mass redistributions and relative motions in the atmosphere, oceans, and continental water, snow and ice. In this study, we compare the geophysical excitations derived from various global atmospheric, oceanic and hydrological models (NCEP, ECCO, ERA40, ERAinterim and ECMWF operational products), and construct two model sets LDC1 and LDC2 by combining the above models with a least difference method, which selects FFT coefficients of the above data series closest to those of the geodetic excitation at each frequency to build a new series. Comparisons between the geodetic excitation (derived from the polar motion series IERS EOP 08 C04) and the geophysical excitations (based on those meteorological models) imply that the atmospheric models are the most reliable while the hydrological ones suffer from significant uncertainties; that the ERAinterim is, in general, the best model set among the original ones, but the combined models LDC1 and LDC2 are much better than ERAinterim; and that applying the frequency-dependent transfer functions to LDC1 and LDC2 improves their agreements with the geodetic excitation. Thus, we conclude that the combined models LDC1 and LDC2 are reliable, and the complex and frequency-dependent Love numbers and polar motion excitation transfer functions are well modeled. This study is supported in parts by the National 973 Project of China (No. 2013CB733305), the National Natural Science Foundation of China (No. 41174011, 41128003 and 11073044), and the Open Fund of the State Key Laboratory of Geodesy and Earth

  19. Meteorological excitations of polar motion for an Earth model with frequency-dependent responses

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Ray, Jim; Li, JianCheng; Shen, WenBin; Huang, ChengLi

    2014-05-01

    Polar motion excitation involves the mass redistributions and motions of the Earth system relative to the mantle, as well as the frequency-dependent rheology of the Earth, where the latter has recently been modeled in the form of complex and frequency-dependent Love numbers and polar motion excitation transfer functions. At seasonal and intra-seasonal time scales, polar motions are dominated by angular momentum fluctuations due to mass redistributions and relative motions in the atmosphere, oceans, and continental water, snow and ice. In this study, we compare the geophysical excitations derived from various global atmospheric, oceanic and hydrological models (NCEP, ECCO, ERA40, ERAinterim and ECMWF operational products), and construct two model sets LDC1 and LDC2 by combining the above models with a least difference method, which selects FFT coefficients of the above data series closest to those of the geodetic excitation at each frequency to build a new series. Comparisons between the geodetic excitation (derived from the polar motion series IERS EOP 08 C04) and the geophysical excitations (based on those meteorological models) imply that the atmospheric models are the most reliable while the hydrological ones suffer from significant uncertainties; that the ERAinterim is, in general, the best model set among the original ones, but the combined models LDC1 and LDC2 are much better than ERAinterim; and that applying the frequency-dependent transfer functions to LDC1 and LDC2 improves their agreements with the geodetic excitation. Thus, we conclude that the combined models LDC1 and LDC2 are reliable, and the complex and frequency-dependent Love numbers and polar motion excitation transfer functions are well modeled. This study is supported in parts by the National 973 Project of China (No. 2013CB733301 and 2013CB733305), the National Natural Science Foundation of China (No. 41174011, 41128003 and 11073044), and the Open Fund of the State Key Laboratory of Geodesy

  20. High power repetitive excimer lasers pumped by an all solid state magnetic exciter

    NASA Astrophysics Data System (ADS)

    Kobayashi, Osamu; Noda, Koji; Shimada, Tsutomu; Obara, Minoru

    1986-01-01

    In a high repetition rate excimer laser operation, the lifetime of the exciter is one of the most important problems. To attain a nearly endless lifetime of the excimer laser exciter, an all-solid-state exciter has been developed which consists of a high-voltage transformer switched by a silicon-controlled rectifier, producing a pulse whose energy and duration are 11.2 J and 8 microns, respectively, and a three-stage magnetic compressor. With a 1.4-ohm dummy load, output peak power, energy/pulse, and pulse duration were 100 MW, 5.2 J, and 100 ns, respectively. The electrical efficiency of the exciter was 47 percent. The energy loss of 6 J in the exciter was due both to the core loss and the transfer loss. It should be noted that the time jitter between the SCR gate input pulse and the output voltage pulse was less than 12 ns.

  1. 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.

  2. Benchmarks for electronically excited states: CASPT2, CC2, CCSD, and CC3

    NASA Astrophysics Data System (ADS)

    Schreiber, Marko; Silva-Junior, Mario R.; Sauer, Stephan P. A.; Thiel, Walter

    2008-04-01

    A benchmark set of 28 medium-sized organic molecules is assembled that covers the most important classes of chromophores including polyenes and other unsaturated aliphatic compounds, aromatic hydrocarbons, heterocycles, carbonyl compounds, and nucleobases. Vertical excitation energies and one-electron properties are computed for the valence excited states of these molecules using both multiconfigurational second-order perturbation theory, CASPT2, and a hierarchy of coupled cluster methods, CC2, CCSD, and CC3. The calculations are done at identical geometries (MP2/6-31G*) and with the same basis set (TZVP). In most cases, the CC3 results are very close to the CASPT2 results, whereas there are larger deviations with CC2 and CCSD, especially in singlet excited states that are not dominated by single excitations. Statistical evaluations of the calculated vertical excitation energies for 223 states are presented and discussed in order to assess the relative merits of the applied methods. CC2 reproduces the CC3 reference data for the singlets better than CCSD. On the basis of the current computational results and an extensive survey of the literature, we propose best estimates for the energies of 104 singlet and 63 triplet excited states.

  3. Ionization potential for excited S states of the lithium atom

    SciTech Connect

    Puchalski, M.; KePdziera, D.; Pachucki, K.

    2010-12-15

    Nonrelativistic, relativistic, quantum electrodynamic, and finite nuclear mass corrections to the energy levels are obtained for the nS{sub 1/2},n=3,...,9 states of the lithium atom. Computational approach is based on the explicitly correlated Hylleraas functions with the analytic integration and recursion relations. Theoretical predictions for the ionization potential of nS{sub 1/2} states and transition energies nS{sub 1/2{yields}}2S{sub 1/2} are compared to known experimental values for {sup 6,7}Li isotopes.

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

    PubMed

    Zhang, Yuyuan; Beckstead, Ashley A; Hu, Yuesong; Piao, Xijun; Bong, Dennis; Kohler, Bern

    2016-11-30

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

  5. Excited State Trends in Bidirectionally Expanded Closed-Shell PAH and PANH Anions.

    PubMed

    Fortenberry, Ryan C; Moore, Megan M; Lee, Timothy J

    2016-09-22

    Some anions are known to exhibit excited states independent of external forces such as dipole moments and induced polarizabilities. Such states exist simply as a result of the stabilization of valence accepting orbitals whereby the binding energy of the extra electron is greater than the valence excitation energy. Closed-shell anions are interesting candidates for such transitions since their ground-state, spin-paired nature makes the anions more stable from the beginning. Consequently, this work shows the point beyond which deprotonated, closed-shell polycyclic aromatic hydrocarbons (PAHs) and those PAHs containing nitrogen heteroatoms (PANHs) will exhibit valence excited states. This behavior has already been demonstrated in some PANHs and for anistropically extended PAHs. This work establishes a general trend for PAHs/PANHs of arbitrary size and directional extension, whether in one dimension or two. Once seven six-membered rings make up a PAH/PANH, valence excited states are present. For most classes of PAHs/PANHs, this number is closer to four. Even though most of these excited states are weak absorbers, the sheer number of PAHs present in various astronomical environments should make them significant contributors to astronomical spectra.

  6. Many-electron aspects of molecular promotion in ion-atom collisions - Production of core-excited states of Li in Li/+/-He collisions

    NASA Technical Reports Server (NTRS)

    Elston, S. B.; Vane, C. R.; Schumann, S.

    1979-01-01

    Production of core-excited autoionizing states of neutral Li having configurations of the form 1snln(prime)l(prime) has been observed over the impact-energy range from 10-50 keV. Although the results for production of all such states is remarkably consistent with a quasi-molecular-excitation model proposed by Stolterfoht and Leithaeuser (1976), production of individual lines in the observed spectra exhibits collision-velocity dependencies indicative of considerably more complex processes, including processes which appear to be inherently two-electron in nature. Excitation functions are presented for (1s2s/2/)/2/S, 1s(2s2p/3/P)/2/P, 1s(2s2p/1/P)/2/P, and (1s2p/2/)/2/D core-excited state of Li and for total core excitation.

  7. Impact of dynamic orbital correlations on magnetic excitations in the normal state of iron-based superconductors

    NASA Astrophysics Data System (ADS)

    Lee, Wei-Cheng; Lv, Weicheng; Tranquada, J. M.; Phillips, Philip W.

    2012-09-01

    We show here that orbital degrees of freedom produce a distinct signature in the magnetic excitation spectrum of iron-based superconductors above the magnetic ordering temperature. Because dxz and dyz orbitals are strongly connected with Fermi surface topology, the nature of magnetic excitations can be modified significantly due to the presence of either static or fluctuating orbital correlations. Within a five-orbital itinerant model, we show that static orbital order generally leads to an enhancement of commensurate magnetic excitations even when the original Fermi surface lacks nesting at (π,0) or (0,π). When long-range orbital order is absent, Gaussian fluctuations beyond the standard random-phase approximation capture the effects of fluctuating orbital correlations on the magnetic excitations. We find that commensurate magnetic excitations can also be enhanced if the orbital correlations are strong. Our results offer a natural explanation for the incommensurate-to-commensurate transformation observed in a recent neutron scattering measurement (Xu , arXiv:1201.4404), and we propose that this unusual transformation is an important signature to distinguish orbital from spin physics in the normal state of pnictides. Implications for the magnetic and superconducting states are discussed.

  8. Excitable Oscillators as Models for Central Pattern Generators

    NASA Astrophysics Data System (ADS)

    Taylor, David; Holmes, Philip; Cohen, Avis H.

    Chains of coupled oscillators have been used to model the central pattern generator for locomotion in lamprey1,2,3, as well as electrical waves in the mammalian small intestine4. In this paper we examine a variation on the equations for the coupled oscillators used in a number of these papers. In particular, we investigate the effect of modeling the uncoupled oscillators as excitable. The motivation behind this is that it may provide some insight into the electrical activity of the lamprey spinal cord with brainstem attached5

  9. Polar motion excitations for an Earth model with frequency-dependent responses: 2. Numerical tests of the meteorological excitations

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Ray, Jim; Shen, WenBin; Huang, ChengLi

    2013-09-01

    motion excitation involves mass redistributions and motions of the Earth system relative to the mantle, as well as the frequency-dependent rheology of the Earth, where the latter has recently been modeled in the form of frequency-dependent Love numbers and polar motion transfer functions. At seasonal and intraseasonal time scales, polar motions are dominated by angular momentum fluctuations due to mass redistributions and relative motions in the atmosphere, oceans, and continental water, snow, and ice. In this study, we compare the geophysical excitations derived from various global atmospheric, oceanic, and hydrological models (NCEP, ECCO, ERA40, ERAinterim, and ECMWF operational products), and construct two model sets LDC1 and LDC2 by combining the above models with a least difference method. Comparisons between the geodetic excitation (derived from the polar motion series IERS EOP 08 C04) and the geophysical excitations (based on those meteorological models) imply that the atmospheric models are the most reliable while the hydrological ones are the most inaccurate; that the ERAinterim is, in general, the best model set among the original ones, but the combined models LDC1 and LDC2 are much better than ERAinterim; and that applying the frequency-dependent transfer functions to LDC1 and LDC2 improves their agreements with the geodetic excitation. Thus, we conclude that the combined models LDC1 and LDC2 are reliable, and the frequency-dependent Love numbers and polar motion transfer functions are well modeled.

  10. Lifetime measurement of excited low-spin states via the (p, p‧ γ) reaction

    NASA Astrophysics Data System (ADS)

    Hennig, A.; Derya, V.; Mineva, M. N.; Petkov, P.; Pickstone, S. G.; Spieker, M.; Zilges, A.

    2015-09-01

    In this paper a method for lifetime measurements in the sub-picosecond regime via the Doppler-shift attenuation method (DSAM) following the inelastic proton scattering reaction is presented. In a pioneering experiment we extracted the lifetimes of 30 excited low-spin states of 96Ru, taking advantage of the coincident detection of scattered protons and de-exciting γ-rays as well as the large number of particle and γ-ray detectors provided by the SONIC@HORUS setup at the University of Cologne. The large amount of new experimental data shows that this technique is suited for the measurement of lifetimes of excited low-spin states, especially for isotopes with a low isotopic abundance, where (n ,n‧ γ) or - in case of investigating dipole excitations - (γ ,γ‧) experiments are not feasible due to the lack of sufficient isotopically enriched target material.

  11. Half-life of the first excited state of {sup 201}Hg

    SciTech Connect

    Meot, V.; Morel, P.; Gosselin, G.

    2007-06-15

    The lifetime of the first excited state of {sup 201}Hg, populated by the {sup 201}Tl electron capture decay and subsequent {gamma}-ray transitions, has been measured for the first time. This measurement has been carried out using a coincidence between an internal conversion electron and a {gamma}-ray. The half-life of 81{+-}5 ns has been obtained and B(E2) and B(M1) values were deduced and compared to previous estimates. With these reduced matrix elements, the excitation rate of the first excited state of {sup 201}Hg in plasma have been calculated in the frame of a Nuclear excitation by electronic transition (NEET) process.

  12. Electron impact excitation and dissociation of N2 via the b 1Pi(u) state

    NASA Technical Reports Server (NTRS)

    Ratliff, J. M.; James, G. K.; Trajmar, S.; Ajello, J. M.; Shemansky, D. E.

    1991-01-01

    Electron impact excitation of the b 1Pi(u) state in N2 plays a prominent role in the dissociation of the molecule and thus in the production of atomic nitrogen in planetary atmospheres. Electron impact excitation cross sections combined with electron-impact-induced fluorescence measurements can yield the corresponding dissociation cross sections. Serious discrepancies exist among excitation cross sections reported in the literature. To clarify the situation, these cross sections were measured at two impact energies using electron energy loss spectroscopy. The new results are in agreement with recent values deduced from optical measurements and fall midway between previous results which are too high or low by factors of 2.

  13. Imaging Excited-State Dynamics of Doped He Nanodroplets in Real-Time.

    PubMed

    von Vangerow, Johannes; Coppens, François; Leal, Antonio; Pi, Martí; Barranco, Manuel; Halberstadt, Nadine; Stienkemeier, Frank; Mudrich, Marcel

    2017-01-05

    The real-time dynamics of excited alkali metal atoms (Rb) attached to quantum fluid He nanodroplets is investigated using femtosecond imaging spectroscopy and time-dependent density functional theory. We disentangle the competing dynamics of desorption of excited Rb atoms off the He droplet surface and solvation inside the droplet interior as the Rb atom is ionized. For Rb excited to the 5p and 6p states, desorption occurs on starkly differing time scales (∼100 versus ∼1 ps, respectively). The comparison between theory and experiment indicates that desorption proceeds either impulsively (6p) or in a transition regime between impulsive dissociation and complex desorption (5p).

  14. Nonequilibrium solvent effects in Born-Oppenheimer molecular dynamics for ground and excited electronic states.

    PubMed

    Bjorgaard, J A; Velizhanin, K A; Tretiak, S

    2016-04-21

    The effects of solvent on molecular processes such as excited state relaxation and photochemical reaction often occurs in a nonequilibrium regime. Dynamic processes such as these can be simulated using excited statemolecular dynamics. In this work, we describe methods of simulating nonequilibrium solvent effects in excited statemolecular dynamics using linear-response time-dependent density functional theory and apparent surface charge methods. These developments include a propagation method for solvent degrees of freedom and analytical energy gradients for the calculation of forces. Molecular dynamics of acetaldehyde in water or acetonitrile are demonstrated where the solute-solvent system is out of equilibrium due to photoexcitation and emission.

  15. Quantal Density Functional Theory(Q-DFT) of Degenerate Ground and Excited States

    NASA Astrophysics Data System (ADS)

    Sahni, Viraht; Pan, Xiaoyin

    2002-03-01

    We present here Q-DFT (V.Sahni et al, PRL 87), 113002 (2001), and references therein. of degenerate states with degeneracy g. We describe : (a) The transformation from a degenerate ground or excited pure state of the interacting system to an S (single Slater determinant) system of noninteracting Fermions with equivalent density, total energy, and ionization potential; (b) The construction of g S systems to reproduce a subspace ensemble density and energy. The density and energy are defined via the ensemble density matrix formed from the degenerate ground or excited pure states of the interacting system; (c) The construction of an S system with a g-fold degenerate highest occupied level, (which leads to g Slater determinants (C.A. Ullrich and W. Kohn, PRL 87), 093001(2001).), to reproduce the ground or excited state ensemble density and energy.

  16. Watson-Crick base pairing controls excited-state decay in natural DNA.

    PubMed

    Bucher, Dominik B; Schlueter, Alexander; Carell, Thomas; Zinth, Wolfgang

    2014-10-13

    Excited-state dynamics are essential to understanding the formation of DNA lesions induced by UV light. By using femtosecond IR spectroscopy, it was possible to determine the lifetimes of the excited states of all four bases in the double-stranded environment of natural DNA. After UV excitation of the DNA duplex, we detected a concerted decay of base pairs connected by Watson-Crick hydrogen bonds. A comparison of single- and double-stranded DNA showed that the reactive charge-transfer states formed in the single strands are suppressed by base pairing in the duplex. The strong influence of the Watson-Crick hydrogen bonds indicates that proton transfer opens an efficient decay path in the duplex that prohibits the formation or reduces the lifetime of reactive charge-transfer states.

  17. Fluorescence following excited-state protonation of riboflavin at N(5).

    PubMed

    Quick, Martin; Weigel, Alexander; Ernsting, Nikolaus P

    2013-05-09

    Excited-state protonation of riboflavin in the oxidized form is studied in water. In the -1 < pH < 2 range, neutral and N(1)-protonated riboflavin coexist in the electronic ground state. Transient absorption shows that the protonated form converts to the ground state in <40 fs after optical excitation. Broadband fluorescence upconversion is therefore used to monitor solvation and protonation of the neutral species in the excited singlet state exclusively. A weak fluorescence band around 660 nm is assigned to the product of protonation at N(5). Its radiative rate and quantum yield relative to neutral riboflavin are estimated. Protonation rates agree with proton diffusion times for H(+) concentrations below 5 M but increase at higher acidities, where the average proton distance is below the diameter of the riboflavin molecule.

  18. Sideband excitation of trapped ions by rapid adiabatic passage for manipulation of motional states

    SciTech Connect

    Watanabe, T.; Nomura, S.; Toyoda, K.; Urabe, S.

    2011-09-15

    We describe an analysis and experimental results of the manipulation of motional states of a single trapped {sup 40}Ca{sup +} ion based on sideband excitation by rapid adiabatic passage. When the sideband transition is excited by rapid adiabatic passage, adiabaticity may be affected by ac Stark shifts. We investigate the influence of ac Stark shifts and compensate for these shifts with an additional laser field. This makes the population transfer by rapid adiabatic passage more robust with respect to experimental parameters. Finally, we manipulate the motional states and generate motional Fock states of a single {sup 40}Ca{sup +} ion by rapid adiabatic passage with ac Stark compensation.

  19. Discrimination of nuclear spin isomers exploiting the excited state dynamics of a quinodimethane derivative

    SciTech Connect

    Obaid, Rana; Kinzel, Daniel; Oppel, Markus González, Leticia

    2014-10-28

    Despite the concept of nuclear spin isomers (NSIs) exists since the early days of quantum mechanics, only few approaches have been suggested to separate different NSIs. Here, a method is proposed to discriminate different NSIs of a quinodimethane derivative using its electronic excited state dynamics. After electronic excitation by a laser field with femtosecond time duration, a difference in the behavior of several quantum mechanical operators can be observed. A pump-probe experimental approach for separating these different NSIs is then proposed.

  20. Discrimination of nuclear spin isomers exploiting the excited state dynamics of a quinodimethane derivative.

    PubMed

    Obaid, Rana; Kinzel, Daniel; Oppel, Markus; González, Leticia

    2014-10-28

    Despite the concept of nuclear spin isomers (NSIs) exists since the early days of quantum mechanics, only few approaches have been suggested to separate different NSIs. Here, a method is proposed to discriminate different NSIs of a quinodimethane derivative using its electronic excited state dynamics. After electronic excitation by a laser field with femtosecond time duration, a difference in the behavior of several quantum mechanical operators can be observed. A pump-probe experimental approach for separating these different NSIs is then proposed.