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Sample records for 29s excited states

  1. Excited states

    Lim, Edward C

    1974-01-01

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

  2. Excited states v.6

    Lim, Edward C

    2013-01-01

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

  3. Excited states 2

    Lim, Edward C

    2013-01-01

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

  4. Excited states 4

    Lim, Edward C

    2013-01-01

    Excited States, Volume 4 is a collection of papers that deals with the excited states of molecular activity. One paper investigates the resonance Raman spectroscopy as the key to vibrational-electronic coupling. This paper reviews the basic theory of Raman scattering; it also explains the derivation of the Raman spectra, excitation profiles, and depolarization ratios for simple resonance systems. Another paper reviews the magnetic properties of triplet states, including the zero-field resonance techniques, the high-field experiments, and the spin Hamiltonian. This paper focuses on the magnetic

  5. Excited Charm States

    Characteristics of mass spectra and decays of orbitally excited charm mesons and baryons, expected on the basis of quark models and Heavy Quark Symmetry, are briefly described. The difficulties associated with measurements on these excited states are discussed. The accuracy and reliability of currently available experimental information is examined. The reasons, for the widely accepted spin-parity assignments to the observed excited mesons and baryons, are stated. Finally, the experimental data, with the accepted spin-parity assignments, is compared with expectations based on quark models and Heavy Quark Symmetry

  6. β-delayed proton decay of 29S

    The 28Si(3He,2n) reaction at 32 MeV has been used to produce 29S; delayed protons have been observed following the positron decay of 29S to proton unbound levels in 29P. The half-life of 29S was measured to be 187 +- 6 ms which, combined with previous results, gives a weighted average value of 188.0 +- 4.3 ms. Precise level energies have confirmed several recently observed states in 29P from 4.0 to 9.5 MeV in excitation energy. From the intensities of these proton groups and assuming isospin purity for the lowest T = 3/2 level in 29P, absolute log ft values for each transition were determined. The measured excitation energies and β decay transition rates to levels in 29P are compared to recent shell-model calculations

  7. Excited States in 207Rn

    罗万居; 郭应祥; 周小红; 张玉虎; 雷相国; 刘忠; 郑勇; 柳敏良; 何建军; 竺礼华; 温书贤

    2003-01-01

    Excited states in 207Rn are investigated via the 196Pt(16O,Sn)207Rn reaction at beam energies from 85 to 95 MeV using techniques of in-beam γ-ray spectroscopy. Measurements ofγ-ray excitation function, x - γ and γ - γ- t coincidences are performed with ten BGO(AC)HPGe detectors. Based on these measurements, a level scheme of207Rn, including 17 γ-rays and 18 levels, is established. Spins for most of the levels are proposed according to the measured DCO ratios. The level structure is compared with a weak-coupling calculation using the interaction energies extracted from neighbouring nuclei.

  8. Excited state Intramolecular Proton Transfer in Anthralin

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

    1998-01-01

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

  9. Excited states in Pd99

    Sihotra, S.; Naik, Z.; Kumar, S.; Singh, K.; Goswamy, J.; Singh, N.; Kumar, R.; Singh, R. P.; Muralithar, S.; Bhowmik, R. K.; Palit, R.; Mehta, D.

    2011-02-01

    Excited states in the Pd99 nucleus populated in the As75(Si28, p3n) fusion-evaporation reaction at Elab=120 MeV have been investigated through in-beam γ-ray spectroscopic techniques using an array of Compton-suppressed clover detectors. The level scheme is established up to excitation energy ~11.5 MeV and spin ~25ℏ with the addition of about 60 new transitions. The level structures observed in Pd99 have been interpreted in the framework of a microscopic theory based on the deformed Hartree-Fock and angular momentum projection techniques. Band structures at lower spins are based on the low-Ω νg7/2 and νd5/2 orbitals, and those at higher spins are reproduced for the π(g9/2)5⊗π(g7/2)⊗ν(g7/2)2⊗ν(h11/2)2⊗ν(g9/2)-1 and π(g9/2)6⊗ν(g9/2)10⊗ν(g7/2)2⊗ν(h11/2) configurations. The octupole correlations in Pd99 have been inferred from new interband E1 transitions linking the ΔI=1 states of the bands based on the νh11/2 and νd5/2 orbitals (Δl=3, Δj=3, and Δπ=-1) with the deduced B(E1) values ~10-6 W.u.

  10. The mechanisms of Excited states in enzymes

    Petersen, Frederic Nicolas Rønne; Bohr, Henrik

    2010-01-01

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

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

    Lim, Edward C

    2013-01-01

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

  12. Excited states of {sup 15}C

    Cappuzzello, F.; Orrigo, S.E.A.; Cunsolo, A.; Allia, M.C.; Lazzaro, A.; Nociforo, C.; Winfield, J.S. [Istituto Nazionale di Fisica Nucleare, Lab. Nazionali del Sud, Catania (Italy); Lazzaro, A. [Catania Univ., Dipt. Fisica (Italy); Lenske, H. [Giessen Univ. (Germany). Inst. fuer Theoretische Physik; Beaumel, D.; Fortier, S. [Institut de Physique Nucleaire, (IN2P3/CNRS) 91 - Orsay (France); Foti, A. [Istituto Nazionale di Fisica Nucleare, Catania (Italy)

    2004-03-01

    The N{sup 15}(Li{sup 7},Be{sup 7})C{sup 15} reaction at 55 MeV incident energy was studied at forward angles in order to explore the C{sup 15} excitation energy spectrum. The C{sup 15} ground state and the states at E{sub x} = 0.77, 6.77, 7.30, 8.50 MeV excitation energies were populated. The energy resolution ({approx} 250 keV) allowed the identification of these transitions each for Be{sup 7} ground and first-excited state at E{sub x} = 0.429 MeV. Quasi-particle random phase approximation (QRPA) calculations reproduce the C{sup 15} level structure below 1.5 MeV excitation energy. The strength observed at higher excitation energies probably arises from core-excited components of C{sup 15}. (authors)

  13. Excited-state dynamics of astaxanthin aggregates

    Fuciman, M.; Durchan, Milan; Šlouf, V.; Kesan, G.; Polívka, Tomáš

    2013-01-01

    Roč. 568, č. 1 (2013), s. 21-25. ISSN 0009-2614 Institutional support: RVO:60077344 Keywords : astaxanthin * aggregates * excited states Subject RIV: BO - Biophysics Impact factor: 1.991, year: 2013

  14. Excited state g factors in Te125

    Chamoli, S. K.; Stuchbery, A. E.; East, M. C.

    2009-11-01

    The transient-field technique has been used to measure, with considerably improved precision, the g factors of the 3/2+ and 5/2+ states in Te125 at 444 and 463 keV, respectively, relative to the g factor of the first excited state in Te126. Together with shell model and weak-coupling core-excitation model calculations, the g-factor measurements provide insight into the orbital occupation of the odd neutron for the low-excitation states in Te125. A new 9/2+ level at 1029 keV, together with a firm 7/2+ spin assignment for the level at 1018 keV, identifies candidate states for the coupling of the s1/2 neutron to the 4+ core excitation.

  15. Excited-state properties of hydrophilic carotenoids

    Fuciman, M.; Chábera, P.; Naqvi, K.R.; Melo, T.B.; Sliwka, H.R.; Partali, V.; Lockwood, S.; Jackson, H.L.; Polívka, Tomáš

    - : -, 2009. s. 408. ISBN N. [International Conference on Photochemistry /24./. 19.07.2009-24.07.2009, Toledo] Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * excited-state dynamics * femtosecond spectroscopy Subject RIV: BO - Biophysics

  16. Excitation Halo States of 12B

    林承键; 刘祖华; 张焕乔; 吴岳伟; 杨峰; 阮明

    2001-01-01

    Angular distributions for the 11 B(d,p)12 B transfer reactions have been measured at E1ab = 11.8 Me V. The asymp-totic normalization coefficients (ANC) of the ground state, the second and third excitation states for 12B ( 11 B+n) are extracted from the differential cross sections at three forward angles. With these ANCs, the root-mean-square radii are calculated for these three states. The results show that the second and third excitation states of 12B are neutron halo states.

  17. Rearrangements in ground and excited states

    de Mayo, Paul

    2013-01-01

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

  18. Excited states of 129Xe

    Here investigation of the observed yrast and excited bands in 129Xe populated by the heavy-ion fusion reaction 124Sn(11B, p5n)129Xe has been presented. An isotopically enriched (99.9%) self-supporting 124Sn target of thickness 2.2 mg/cm2 was utilized. The experiment was performed at the Linac accelerator facility at the Tata Institute of Fundamental Research (TIFR), Mumbai, India. The experimental set-up, called the Indian National Gamma Array (INGA), consisted of 21 Compton suppressed clover HPGe detectors. Two of these detectors were placed at 23°, three at 40°, three at 65°, four at 90°, three at 140°, three at 115° and three at 157° with respect to the beam direction. The triple gamma coincidence data were collected in the event-by-event mode

  19. Photoionization of excited molecular states using multiphoton excitation techniques

    Photoelectron spectra are reported for three photon resonant, four photon ionization of H2 via the B 1Σ/sub u/+, v = 7 (J = 2,4) and C 1π/sub u'/, v = 0-4 (J = 1) levels and of N2 via the o31π/sub u'/, v = 1,2, b 1π/sub u'/, v = 3-5, and c 1π/sub u'/, v = 0 levels. The results reflect both the spectroscopy and the dynamics of photoionization of excited molecular states and are discussed in terms of the selection rules for photoionization and the relative probabilities of photoionization from Rydberg and valence states. In some cases, in accordance with the Franck-Condon principle, the results demonstrate that resonant multiphoton ionization through Rydberg states may be a powerful technique for the production of electronic, vibrational, and rotational state selected ions. However, in other cases, systematic departures from Franck-Condon factors are observed, which reflect the more subtle dynamics of excited state photoionization. 23 references, 6 figures, 2 tables

  20. Photoionization of excited molecular states using multiphoton excitation techniques

    Dehmer, Patricia M. [Argonne National Laboratory (ANL), Argonne, IL (United States); Pratt, Stephen T. [Argonne National Laboratory (ANL), Argonne, IL (United States); Dehmer, Joseph L. [Argonne National Laboratory (ANL), Argonne, IL (United States)

    1984-01-01

    Photoelectron spectra are reported for three photon resonant, four photon ionization of H₂ via the B ¹Σu⁺, v = 7 (J = 2,4) and C ¹Πu v = 0-4 (J = 1) levels and of N₂ via the o₃ ¹Πu, v = 1,2, b ¹Πu, v = 3-5, and c ¹Πu, v = 0 levels. The results reflect both the spectroscopy and the dynamics of photoionization of excited molecular states and are discussed in terms of the selection rules for photoionization and the relative probabilities of photoionization from Rydberg and valence states. In some cases, in accordance with the Franck-Condon principle, the results demonstrate that resonant multiphoton ionization through Rydberg states may be a powerful technique for the production of electronic, vibrational, and rotational state selected ions. However, in other cases, systematic departures from Franck-Condon factors are observed, which reflect the more subtle dynamics of excited state photoionization.

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

    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).

  2. Application of the coherent state formalism to multiply excited states

    A general expression is obtained for the matrix element of an m-body operator between coherent states constructed from multiple orthogonal coherent boson species. This allows the coherent state formalism to be applied to states possessing an arbitrarily large number of intrinsic excitation quanta. For illustration, the formalism is applied to the two-dimensional vibron model (U(3) model), to calculate the energies of all excited states in the large-N limit

  3. Nodal Variational Principle for Excited States

    Zahariev, Federico; Levy, Mel

    2016-01-01

    It is proven that the exact excited-state wavefunction and energy may be obtained by minimizing the energy expectation value of a trial wave function that is constrained only to have the correct nodes of the state of interest. This excited-state nodal minimum principle has the advantage that it requires neither minimization with the con- straint of wavefunction orthogonality to all lower eigenstates nor the antisymmetry of the trial wavefunctions. It is also found that the minimization over the entire space can be partitioned into several in- terconnected minimizations within the individual nodal regions, and the exact excited-state energy may be obtained by a minimization in just one or several of these nodal regions. For the proofs of the the- orem, it is observed that the many-electron eigenfunction, restricted to a nodal region, is equivalent to a ground state wavefunction of one electron in a higher dimensional space; and an explicit excited-state energy variational expression is obtained by generalizing...

  4. Computing Correct Truncated Excited State Wavefunctions

    Bacalis, N C; Zang, J; Karaoulanis, D

    2016-01-01

    We demonstrate that, if a truncated expansion of a wave function 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.

  5. Impact of ground- and excited-state aromaticity on cyclopentadiene and silole excitation energies and excited-state polarities.

    Jorner, Kjell; Emanuelsson, Rikard; Dahlstrand, Christian; Tong, Hui; Denisova, Aleksandra V; Ottosson, Henrik

    2014-07-21

    A new qualitative model for estimating the properties of substituted cyclopentadienes and siloles in their lowest ππ* excited states is introduced and confirmed through quantum chemical calculations, and then applied to explain earlier reported experimental excitation energies. According to our model, which is based on excited-state aromaticity and antiaromaticity, siloles and cyclopentadienes are cross-hyperconjugated "aromatic chameleons" that adapt their electronic structures to conform to the various aromaticity rules in different electronic states (Hückel's rule in the π(2) electronic ground state (S0) and Baird's rule in the lowest ππ* excited singlet and triplet states (S1 and T1)). By using pen-and-paper arguments, one can explain polarity changes upon excitation of substituted cyclopentadienes and siloles, and one can tune their lowest excitation energies by combined considerations of ground- and excited-state aromaticity/antiaromaticity effects. Finally, the "aromatic chameleon" model can be extended to other monocyclic compound classes of potential use in organic electronics, thereby providing a unified view of the S0, T1, and S1 states of a range of different cyclic cross-π-conjugated and cross-hyperconjugated compound classes. PMID:25043523

  6. Excited state properties of aryl carotenoids

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

    2010-01-01

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

  7. Excited-state properties of hydrophilic carotenoids

    Chábera, P.; Naqvi, K.R.; Melo, T.B.; Sliwka, H.R.; Partali, V.; Lockwood, S.; Nodolski, G.; Polívka, Tomáš

    Nové Hrady : Academic and University Center, 2008. s. 40. [ESF Workshop on Novel Methods in Exploring Carotenoid Excited State Dynamics. 21.09.2008-25.09.2008, Nové Hrady] Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * biophysics Subject RIV: BO - Biophysics

  8. Femtosecond spectroscopy of reacting excited states

    Thanks to recent advance of ultra short pulse lasers, we are now able to observe ultra fast phenomena taking place in a time scale as short as 10 fs. This time scale is the time scale of the nuclear motion of molecules, and the observation of coherent nuclear wavepacket motion is a central issue of femtosecond spectroscopy. One of the dreams of chemists is to see chemical reactions, i.e., the change of chemical bonds, in real time. In a sense, observation of the wavepacket motion of reacting molecules is realization of this dream. However, the significance of the coherent nuclear motion in chemical reactions is still unclear for polyatomic molecules where the reaction coordinate does not simply correspond to the change of a particular chemical bond. To discuss the relation between the initial coherent wavepacket motion and the reaction coordinate, we studied several fundamental photochemical reactions in solution, i.e., photoisomerization of cis-stilbene, photodissociation of diphenylcyclopropenone and excited-state intramolecular proton transfer of 10-hydorxybenzoquinoline, using two-color pump-probe spectroscopy with time resolution of 30-70 fs. The photoisomerization of cis-stilbene proceeds in the S1 state in a time scale of ∼1 ps. Time-resolved absorption of cis-stilbene in cyclohexane (pump 315 nm; probe 660 nm) clearly showed an oscillatory feature, which was attributed to the ∼220 cm-1 wavepacket motion in the S1 state. The dephasing time of the wavepacket motion was 0.21±0.04 ps, which was much shorter than the isomerization time of S1 cis-stilbene (1.25 ps). This indicates that a fast dephasing of the vibrational coherence takes place before isomerization. The result of the experiments on the solvent dependence demonstrated that the dephasing rate and isomerization rate do not correlate with each other, indicating that the observed wavepacket motion is not directly coupled with the isomerization coordinate. Photoexcitation to the S2 state of

  9. Rearrangements in ground and excited states

    de Mayo, Paul

    2013-01-01

    Rearrangements in Ground and Excited States, Volume 2 covers essays on the theoretical approach of rearrangements; the rearrangements involving boron; and the molecular rearrangements of organosilicon compounds. The book also includes essays on the polytopal rearrangement at phosphorus; the rearrangement in coordination complexes; and the reversible thermal intramolecular rearrangements of metal carbonyls. Chemists and people involved in the study of rearrangements will find the book invaluable.

  10. Extension of LCAO to excited states

    Koval, Peter; Foerster, Dietrich

    2009-01-01

    We extend the LCAO (Linear Combination of Atomic Orbitals) method to excited states by constructing a particularly simple basis in the space of orbital products. The residual error of our procedure vanishes exponentially with the number of products and our procedure avoids auxiliary sets of fitting functions and their intrinsic ambiguities. As an application of our technique, we compute the Kohn--Sham density response function $\\chi_{0}$ for a molecule consisting of $N$ atoms in $O(N^{2}N_{\\o...

  11. Excited States in Solution through Polarizable Embedding

    Olsen, Jógvan Magnus; Aidas, Kestutis; Kongsted, Jacob

    2010-01-01

    We present theory and implementation of an advanced quantum mechanics/molecular mechanics (QM/MM) approach using a fully self-consistent polarizable embedding (PE) scheme. It is a polarizable layered model designed for effective yet accurate inclusion of an anisotropic medium in a quantum mechani......, nanoparticles and solute−solvent systems. Here, we present numerical examples of solvent shifts and excited-state properties related to a set of organic molecules in aqueous solution....

  12. Identification of excited states in conjugated polymers

    Hartwell, L J

    2003-01-01

    This thesis reports quasi steady state photoinduced absorption measurements from three conjugated polymers: polypyridine (PPy), polyfluorene (PFO) and the emeraldine base (EB) form of polyaniline. The aim of these experiments was to determine the nature of the photoexcited states existing in these materials in the millisecond time domain, as this has important consequences for the operation of real devices manufactured using these materials. The results from the photoinduced absorption experiments are closely compared with published results from pulse radiolysis experiments. In all cases there is very good correspondence between the two data sets, which has enabled the photoexcited states to be assigned with a high degree of confidence. Quasi steady-state photoinduced absorption involves the measurement of the change in absorption of a material in response to optical excitation with a laser beam. The changes in absorption are small, so a instrument was developed and optimised for each different sample. Lock-i...

  13. Holographic Construction of Excited CFT States

    Christodoulou, Ariana

    2016-01-01

    We present a systematic construction of bulk solutions that are dual to CFT excited states. The bulk solution is constructed perturbatively in bulk fields. The linearised solution is universal and depends only on the conformal dimension of the primary operator that is associated with the state via the operator-state correspondence, while higher order terms depend on detailed properties of the operator, such as its OPE with itself and generally involve many bulk fields. We illustrate the discussion with the holographic construction of the universal part of the solution for states of two dimensional CFTs, either on $R \\times S^1$ or on $R^{1,1}$. We compute the 1-point function both in the CFT and in the bulk, finding exact agreement. We comment on the relation with other reconstruction approaches.

  14. Ultrafast excited-state dynamics of isocytosine.

    Szabla, Rafał; Góra, Robert W; Šponer, Jiří

    2016-07-27

    The alternative nucleobase isocytosine has long been considered as a plausible component of hypothetical primordial informational polymers. To examine this hypothesis we investigated the excited-state dynamics of the two most abundant forms of isocytosine in the gas phase (keto and enol). Our surface-hopping nonadiabatic molecular dynamics simulations employing the algebraic diagrammatic construction to the second order [ADC(2)] method for the electronic structure calculations suggest that both tautomers undergo efficient radiationless deactivation to the electronic ground state with time constants which amount to τketo = 182 fs and τenol = 533 fs. The dominant photorelaxation pathways correspond to ring-puckering (ππ* surface) and C[double bond, length as m-dash]O stretching/N-H tilting (nπ* surface) for the enol and keto forms respectively. Based on these findings, we infer that isocytosine is a relatively photostable compound in the gas phase and in these terms resembles biologically relevant nucleobases. The estimated S1 [radiolysis arrow - arrow with voltage kink] T1 intersystem crossing rate constant of 8.02 × 10(10) s(-1) suggests that triplet states might also play an important role in the overall excited-state dynamics of the keto tautomer. The reliability of ADC(2)-based surface-hopping molecular dynamics simulations was tested against multireference quantum-chemical calculations and the potential limitations of the employed ADC(2) approach are briefly discussed. PMID:27346684

  15. Dynamic hyperpolarizabilities of excited states of hydrogen

    On the basis of the generalized Sturm expansion of the radial part of the Coulomb Green function, a computational method is proposed and numerical results are presented for the dynamic hyperpolarizability γ and the corrections E(4) (quadratic in the light intensity) to the quasi-energy of the ground and excited states of hydrogen with principal quantum numbers n ≤ 5 in a monochromatic light field. In this approach, the problem is reduced to the summation of well-convergent double series of the hypergeometric kind, which ensures reliable numerical results both for states with a large n, and in a wide range of field frequencies ω, including the above-threshold frequency range of (ℎ/2π)ω >> vertical bar En vertical bar (vertical bar En vertical bar is the ionization potential of the state |nlm> under investigation). We consider the frequency dependence of γ and E(4), their differences for the cases of linear and circular polarizations of the field, and the relation between their real and imaginary parts, which determine the laser field-induced corrections to the position and width of energy levels. For n = 5, the significant role of mixing the vertical bar nlm> states with different values of l by a laser field in the region of resonances on intermediate bound states is demonstrated. The linear (in intensity) corrections to the photoionization cross section for excited states are analyzed and the threshold intensity corresponding to the onset of atomic level stabilization is estimated for a number of states with n = 3 and n = 5

  16. Excited states of muonium in atomic hydrogen

    V S Kulhar

    2006-06-01

    Muonium formation in excited states in muon-hydrogen charge-exchange collision is investigated using a method developed in a previous paper. Differential cross-section results are found to resemble positronium formation cross-section results of positron-hydrogen charge-exchange problem. Forward differential and integrated cross-sections are computed for muon energy of 2 keV and higher. Total muonium formation cross-sections are computed using Jackson and Schiff scaling rules. Muonium formation cross-section results obtained from proton-hydrogen charge-exchange cross-section results, using velocity scaling are compared with the results of the present calculation.

  17. Excited state dynamics of DNA bases

    Kleinermanns, K.; Nachtigallová, Dana; de Vries, M. S.

    2013-01-01

    Roč. 32, č. 2 (2013), s. 308-342. ISSN 0144-235X R&D Projects: GA ČR GAP208/12/1318 Grant ostatní: National Science Foundation(US) CHE-0911564; NASA(US) NNX12AG77G; Deutsche Forschungsgemeinschaft(DE) SFB 663; Deutsche Forschungsgemeinschaft(DE) KI 531-29 Institutional support: RVO:61388963 Keywords : DNA bases * nucleobases * excited state * dynamics * computations * gas phase * conical intersections Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.920, year: 2013

  18. Excited state halos in 10Be

    The structure of certain bound excited states in 10Be have been shown to have exotic features because of their weak binding and cluster-like configurations. In this article, we investigate E1 and E2 transitions between these states and compare the findings with recent experimental results. We compare the predictions of two types of structure calculations: a microscopic multicluster model and an ab initio no-core shell model. Both predict very similar transition strengths. By considering the relative contributions from the various matrix elements contributing to the transitions arising from the coupling of different 9Bexn configurations in the wave functions making up the states, we conclude that the very weak B(E1;2-→21+) can only be understood if the 2- state (with a separation energy of its predominantly 1s1/2 neutron of just 0.548 MeV) is a clear halo state. Other nearby states, such as the 22+, do not exhibit a clear halo signature because of the less than clean decoupling into the well-defined 9Be core plus halo neutron

  19. Excited-state relaxation of some aminoquinolines

    B. M. Uzhinov

    2006-04-01

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

  20. Lifetimes of excited states in 164Hf

    Lifetimes of excited states in 164Hf were measured using the Doppler-shift recoil-distance method. Gamma-gamma coincidences at eleven target-stopper distances were measured using the twelve Compton-suppressed Ge-detectors of the OSIRIS spectrometer. From the coincidence spectra the intensities of the Doppler-shifted and unshifted γ-lines were determined. The quadrupole moments Qt of transitions within the rotational bands derived from the lifetimes are constant within the experimental uncertainties up to the 18+ state. The Qt value for the transition between the ground- and the neutron i213/2 band (s-band) which is strongly reduced compared to the values of the in-band transitions is used to deduce a band interaction energy of 34 keV≤V≤57 keV. (orig.)

  1. Lifetimes of 167Yb excited states

    Lifetimes of 167Yb excited states arising at the decay of 167Lu → 167Yb monoisotope have been determined using eγ and γγ delayed coincidence methods. The time spectrometers mounted on the base of a magnetic lens β-spectrometer and a scintillation detector, a scintillation and a Ge(Li) detectors, a scintillation and Si(Li)-detectors are used. 167Yb level fifetimes are measured with energies of 29 keV (Tsub(1/2)=13.5(7) ns), 78 keV (Tsub(1/2=0.84(4) ns), 178 keV (Tsub(1/2)167Yb investigated levels are analysed. On the basis of intrarotational transitions internal quadrupole momenta of 5/2-/523/, 3/2-/512/ and 1/2-/521/ bands have been determined

  2. Excited state quantum phase transitions in many-body systems

    Phenomena analogous to ground state quantum phase transitions have recently been noted to occur among states throughout the excitation spectra of certain many-body models. These excited state phase transitions are manifested as simultaneous singularities in the eigenvalue spectrum (including the gap or level density), order parameters, and wave function properties. In this article, the characteristics of excited state quantum phase transitions are investigated. The finite-size scaling behavior is determined at the mean-field level. It is found that excited state quantum phase transitions are universal to two-level bosonic and fermionic models with pairing interactions

  3. Representation of electronic excited states by conditional wavefunction

    Koichiro, Yamaguchi; Yoshiaki, Ito; Takeshi, Mukoyama

    2000-03-01

    Hartree-Fock scheme is an ordinary method to calculate the zeroth order approximation for non-relativistic electronic excited states of atoms and molecules. The accuracy of zeroth order hamiltonian affects the efficiency of higher order estimation of the Hamiltonian and the Green's function. To improve the preciseness of zeroth order Hamiltonian, we try to include the relaxation of electronic excited states into zeroth order approximation by using conditional wavefunction representation instead of Hartree-Fock method. Our method is illustrated by the calculation of electronic double-excited states of Helium and single-excited states of Neon. Further extention of our formulation for multiple-exfcited states are also discussed.

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

    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 2 molecule

  5. Excited states in DNA strands investigated by ultrafast laser spectroscopy.

    Chen, Jinquan; Zhang, Yuyuan; Kohler, Bern

    2015-01-01

    Ultrafast laser experiments on carefully selected DNA model compounds probe the effects of base stacking, base pairing, and structural disorder on excited electronic states formed by UV absorption in single and double DNA strands. Direct π-orbital overlap between two stacked bases in a dinucleotide or in a longer single strand creates new excited states that decay orders of magnitude more slowly than the generally subpicosecond excited states of monomeric bases. Half or more of all excited states in single strands decay in this manner. Ultrafast mid-IR transient absorption experiments reveal that the long-lived excited states in a number of model compounds are charge transfer states formed by interbase electron transfer, which subsequently decay by charge recombination. The lifetimes of the charge transfer states are surprisingly independent of how the stacked bases are oriented, but disruption of π-stacking, either by elevating temperature or by adding a denaturing co-solvent, completely eliminates this decay channel. Time-resolved emission measurements support the conclusion that these states are populated very rapidly from initial excitons. These experiments also reveal the existence of populations of emissive excited states that decay on the nanosecond time scale. The quantum yield of these states is very small for UVB/UVC excitation, but increases at UVA wavelengths. In double strands, hydrogen bonding between bases perturbs, but does not quench, the long-lived excited states. Kinetic isotope effects on the excited-state dynamics suggest that intrastrand electron transfer may couple to interstrand proton transfer. By revealing how structure and non-covalent interactions affect excited-state dynamics, on-going experimental and theoretical studies of excited states in DNA strands can advance understanding of fundamental photophysics in other nanoscale systems. PMID:25326834

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

    Azuma, T.; Nakano, Y.; Metoki, K.; Hatakeyama, A.; Nakai, Y.; Komaki, K.; Yamazaki, Y.; Takada, E.; Murakami, T.

    2009-11-01

    Convoy electrons emitted from 416 MeV/u heliumlike Ar16+ ions excited by three-dimensional resonant coherent excitation (3D-RCE) have been explored. The 1s electron in the ground state was excited to the 2p state by a periodic crystal field during the passage through a Si crystal and released into the continuum by collisions with target atoms to form a cusp-shaped peak in the energy distribution, referred to as convoy electron. Under the resonance condition, we found not only enhancement of the convoy electron yield but also significant narrowing in the energy distribution, reflecting the initial bound state momentum distribution of the excited ions. This suggests that RCE is well-suited to study fast ion collisions involving the specific excited state.

  7. Exact ensemble density-functional theory for excited states

    Yang, Zeng-hui; Pribram-Jones, Aurora; Burke, Kieron; Needs, Richard J; Ullrich, Carsten A

    2014-01-01

    We construct exact Kohn-Sham potentials for the ensemble density-functional theory (EDFT) of excited states from the ground and excited states of helium. The exchange-correlation potential is compared with current approximations, which miss prominent features. The ensemble derivative discontinuity is tested, and the virial theorem is proven and illustrated.

  8. Charge-displacement analysis for excited states

    Ronca, Enrico, E-mail: enrico@thch.unipg.it; Tarantelli, Francesco, E-mail: francesco.tarantelli@unipg.it [Istituto CNR di Scienze e Tecnologie Molecolari, via Elce di Sotto 8, I-06123 Perugia (Italy); Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, via Elce di Sotto 8, I-06123 Perugia (Italy); Pastore, Mariachiara, E-mail: chiara@thch.unipg.it; Belpassi, Leonardo; De Angelis, Filippo [Istituto CNR di Scienze e Tecnologie Molecolari, via Elce di Sotto 8, I-06123 Perugia (Italy); Angeli, Celestino; Cimiraglia, Renzo [Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Ferrara, via Borsari 46, I-44100 Ferrara (Italy)

    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.

  9. Bogoliubov Excited States and the Lyth Bound

    Aravind, Aditya; Paban, Sonia

    2014-01-01

    We show that Bogoliubov excited scalar and tensor modes do not alleviate Planckian evolution during inflation if one assumes that $r$ and the Bogoliubov coefficients are approximately scale invariant. We constrain the excitation parameter for the scalar fluctuations, $\\beta$, and tensor perturbations, $\\tilde{\\beta}$, by requiring that there be at least three decades of scale invariance in the scalar and tensor power spectrum. For the scalar fluctuations this is motivated by the observed nearly scale invariant scalar power spectrum. For the tensor fluctuations this assumption may be shown to be valid or invalid by future experiments.

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

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

  11. Density functional theory generalized to degenerate excited states

    In this paper it is shown that the density functional theory can be generalized to systems with degenerate excited states. There is a one-to-one map between the subspace, spanned by the ground state and any one of the first degenerate excited states, and the sum of their densities. But only a one way correspondence exists between external potential and subspace, as well as between external potential and the sum of densities. The extension of the Hohenberg-Kohn-Sham theory for degenerate excited states has also been developed. (author)

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

    Theophilou, Iris; Thanos, S

    2014-01-01

    Photoinduced charge transfer processes play a key role for novel photovoltaic phenomena and devices. Thus, the development of ab initio methods that allow for accurate and computationally inexpensive treatment of charge transfer excitations is a topic that attracts nowadays a lot of scientific attention. In this paper we extend an approach recently introduced for the description of single and double excitations (M. Tassi, I. Theophilou and S. Thanos, Int. J. Quantum Chem., {113}, 690 (2013), M. Tassi, I. Theophilou and S. Thanos, J. Chem. Phys. {138}, 124107 (2013)) to allow for the description of intermolecular charge transfer excitations. For the description of an excitation where an electron is transferred from a donor system to an acceptor one, it is necessary to keep the excited state orthogonal to the ground sate in order to avoid variational collapse. These conditions are achieved by decomposing the subspace spanned by the Hartree-Fock (HF) ground state orbitals to four subspaces: The subspace spanned ...

  13. 18Ne Excited States Two-Proton Decay

    de Napoli, M.; Rapisarda, E.; Raciti, G.; Cardella, G.; Amorini, F.; Giacoppo, F.; Sfienti, C.

    2008-04-01

    Two-proton radioactivity studies have been performed on excited states of 18Ne produced by 20Ne fragmentation at the FRS of the Laboratori Nazionali del Sud and excited via Coulomb excitation on a 209Pb target. The 18Ne levels decay has been studied by complete kinematical reconstruction. In spite of the low statistic, the energy and angular correlations of the emitted proton pairs indicate the presence of 2He emission toghether with the democratic decay.

  14. Energy levels of Sm2+ excited state

    The energy levels of excited configurations 4f5u'l' of Sm2+ calculated in detail by using unitary group approach are covered. The energy expressions with slater integral as parameters are given and the spin-orbit coupling is considered according to the Russell-Saunders approximation. The coupling parameters λ of the main energy levels are also calculated in the paper

  15. Photoionization of excited states of neon-like Mg III

    Narendra Singh; Man Mohan

    2002-04-01

    The close coupling -matrix method is used to calculate cross-sections for photoionization of Mg III from its first three excited states. Configuration interaction wave functions are used to represent two target states of Mg III retained in the -matrix expansion. The positions and effective quantum numbers for the Rydberg series converging to the excited state 2226 \\ 2 of the residual ion, are predicted.

  16. Quantum entanglement of localized excited states at finite temperature

    Caputa, Pawel; Simón, Joan; Štikonas, Andrius(School of Mathematics and Maxwell Institute for Mathematical Sciences, University of Edinburgh, King’s Buildings, Edinburgh, EH9 3FD, U.K.); Takayanagi, Tadashi

    2015-01-01

    In this work we study the time evolutions of (Renyi) entanglement entropy of locally excited states in two dimensional conformal field theories (CFTs) at finite temperature.We consider excited states created by acting with local operators on thermal states and give both field theoretic and holographic calculations. In free field CFTs, we find that the growth of Renyi entanglement entropy at finite temperature is reduced compared to the zero temperature result by a small quantity proportional ...

  17. Excited state systematics in extracting nucleon electromagnetic form factors

    Capitani, Stefano; von Hippel, Georg; Jäger, Benjamin; Knippschild, Bastian; Meyer, Harvey B; Rae, Thomas D; Wittig, Hartmut

    2012-01-01

    We present updated preliminary results for the nucleon electromagnetic form factors for non-perturbatively $\\mathcal{O}(a)$ improved Wilson fermions in $N_f=2$ QCD measured on the CLS ensembles. The use of the summed operator insertion method allows us to suppress the influence of excited states in our measurements. A study of the effect that excited state contaminations have on the $Q^2$ dependence of the extracted nucleon form factors may then be made through comparisons of the summation method to standard plateau fits, as well as to excited state fits.

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

    The author reports coincidence measurements made on the He+ + Ne and He+ + He systems. The complex population amplitudes for the magnetic sublevels of the investigated excited states, Ne(2p43s2)1D and He(2p2)1D, were completely determined and possible excitation mechanisms are described. (Auth.)

  19. Coherent excitation of a single atom to a Rydberg state

    Miroshnychenko, Yevhen; Gaëtan, Alpha; Evellin, Charles;

    2010-01-01

    We present the coherent excitation of a single Rubidium atom to the Rydberg state 58d3/2 using a two-photon transition. The experimental setup is described in detail, as are experimental techniques and procedures. The coherence of the excitation is revealed by observing Rabi oscillations between...

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

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

    2015-12-01

    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. PMID:26609558

  1. Vibronic coupling in the excited-states of carotenoids.

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

    2016-04-20

    The ultrafast femtochemistry of carotenoids is governed by the interaction between electronic excited states, which has been explained by the relaxation dynamics within a few hundred femtoseconds from the lowest optically allowed excited state S2 to the optically dark state S1. Extending this picture, some additional dark states (3A and 1B) and their interaction with the S2 state have also been suggested to play a major role in the ultrafast deactivation of carotenoids and their properties. Here, we investigate the interaction between such dark and bright electronic excited states of open chain carotenoids, particularly its dependence on the number of conjugated double bonds (N). We focus on the ultrafast wave packet motion on the excited potential surface, which is modified by the interaction between bright and dark electronic states. Such a coupling between electronic states leads to a shift of the vibrational frequency during the excited-state evolution. In this regard, pump-degenerate four-wave mixing (pump-DFWM) is applied to a series of carotenoids with different numbers of conjugated double bonds N = 9, 10, 11 and 13 (neurosporene, spheroidene, lycopene and spirilloxanthin, respectively). Moreover, we demonstrate in a closed-chain carotenoid (lutein) that the coupling strength and therefore the vibrational shift can be tailored by changing the energy degeneracy between the 1B and 1B states via solvent interaction. PMID:27055720

  2. Quantification of Entanglement Entropies for Doubly Excited States in Helium

    In this work, we study the quantum entanglement for doubly excited resonance states in helium by using highly correlated Hylleraas type functions to represent such states of the two-electron system. The doubly-excited resonance states are determined by calculation of density of resonance states under the framework of the stabilization method. The spatial (electron–electron orbital) entanglement measures for the low-lying doubly excited 2s2, 2s3s, and 2p21 Se states are carried out. Once a resonance state wave function is obtained, the linear entropy and von Neumann entropy for such a state are quantified using the Schmidt-Slater decomposition method. To check the consistence, linear entropy is also determined by solving analytically the needed four-electron (12-dimensional) integrals. (author)

  3. Optimal control of peridinin excited-state dynamics

    Chábera, P.; Dietzek, B.; Yartsev, A.; Polívka, Tomáš

    Nové Hrady: Academic and University Center, 2008. s. 15. [ESF Workshop on Novel Methods in Exploring Carotenoid Excited State Dynamics. 21.09.2008-25.09.2008, Nové Hrady] Keywords : peridinin * biophysics Subject RIV: BO - Biophysics

  4. Ultrafast Excited-State Dynamics in Biological Environments

    Fürstenberg, Alexandre; Vauthey, Eric

    2007-01-01

    We discuss and illustrate by several examples how the ultrafast excited-state dynamics of a chromophore can be altered when changing its environment from a homogenous solution to a biological molecule such as proteins or nucleic acids.

  5. Boson analysis of the excited O+ state in Ge isotopes

    Motivated by attemp to explain the strong variation in energy of the excited O+ state in even Ge isotopes in terms of a simple collective configuration, a boson mapping is introduced for proton, neutron and proton-neutron pairing

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

    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.

  7. Controlling Chimera States - The influence of excitable units

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

    2015-01-01

    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...

  8. Investigation into chromophore excited-state coupling in allophycocyanin

    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.

  9. Photoacoustic imaging of the excited state lifetime of fluorophores

    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.

  10. Metastable states of highly excited heavy ions

    Pegg, D. J.; Griffin, P. M.; Sellin, I. A.; Smith, W. W.; Donnally, B.

    1973-01-01

    Description of the method used and results obtained in an experimental study of the metastable states of highly stripped heavy ions, aimed at determining the lifetimes of such states by the rates of autoionization and radiation. The significance and limitations of the results presented are discussed.

  11. Excited-state Halo of 14C

    2002-01-01

    Neutron capture processes on carbon isotope play an important role in astrophysics ranging fromnucleosynthesis in the stellar helium and carbon burning stages to possibly inhomogeneous big bangmodels. The capture rate in astrophysical environments strongly depends on the structure of these carbonnuclei. For example, the first 1/2+ state in 13C is a neutron halo state, and these results in an enormous

  12. Microwave spectroscopy of furfural in vibrationally excited states

    Motiyenko, R. A.; Alekseev, E. A.; Dyubko, S. F.

    2007-07-01

    The results of microwave spectrum investigation of the excited vibrational states of furfural in the frequency range between 49 and 149 GHz are reported. In total 15 excited vibrational states (9 for trans-furfural and 6 for cis-furfural) were assigned and analyzed. Six of the 15 investigated states were assigned for the first time. Accurate values of rigid rotor and quartic centrifugal distortion constants of asymmetric top Hamiltonian have been determined for 13 excited states. Also for some states several sextic and octic level constants were needed in order to fit the data within experimental accuracy. The vt = 3 and vs = 1, va = 1 states of trans-furfural were found to be strongly perturbed and only rotational transitions with low Ka values can be reliably identified in this study.

  13. Neutral Excitations in the Gaffnian state

    Kang, Byungmin; Moore, Joel E.

    The Fractional Quantum Hall Effect (FQHE) is one of the most well-studied systems having topological order. Starting with the pioneering work by Laughlin, the model wave function approach has been shown to provide essential information for understanding topological order in gapped incompressible states. We study a model wave function called the Gaffnian state which is believed to represent a gapless, strongly correlated state that is very different from conventional metals. To understand this exotic gapless state better, we provide a representation in which the pairing structure of the Gaffnian state becomes more explicit. We employ the single-mode approximation of the Girvin-MacDonald-Platzman (GMP) mode, which is a neutral collective exitation mode, in order to have a physical picture of the gaplessness of the Gaffnian state. In particular, we discuss how to extract systematically the relevant physics in the long-distance, large electron number limit of the FQH states using a numerical calculation with relatively few electrons.

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

    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. PMID:25960203

  15. Controlling chimera states: The influence of excitable units

    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.

  16. Shape vibration and quasiparticle excitations in the lowest 0+ excited state in erbium isotopes

    Chen, Fang-Qi; Egido, J. Luis

    2016-06-01

    The ground and first excited 0+ states of the -172Er156 isotopes are analyzed in the framework of the generator coordinate method. The shape parameter β is used to generate wave functions with different deformations which together with the two-quasiparticle states built on them provide a set of states. An angular momentum and particle number projection of the latter spawn the basis states of the generator coordinate method. With this ansatz and using the separable pairing plus quadrupole interaction we obtain a good agreement with the experimental spectra and E 2 transition rates up to moderate spin values. The structure of the wave functions suggests that the first excited 0+ states in the soft Er isotopes are dominated by shape fluctuations, while in the well deformed Er isotopes the two-quasiparticle states are more relevant. In between, both degrees of freedom are necessary.

  17. Shape vibrations and quasiparticle excitations in the lowest 0+ excited state of the Erbium isotopes

    Chen, Fang-Qi

    2016-01-01

    The ground and first excited 0+ states of the {156-172}Er isotopes are analyzed in the framework of the generator coordinate method. The shape parameter beta is used to generate wave functions with different deformations which together with the two-quasiparticle states built on them provide a set of states. An angular momentum and particle number projection of the latter spawn the basis states of the generator coordinate method. With this ansatz and using the separable pairing plus quadrupole interaction we obtain a good agreement with the experimental spectra and E2 transition rates up to moderate spin values. The structure of the wave functions suggests that the first excited 0+ states in the soft Er isotopes are dominated by shape fluctuations, while in the well deformed Er isotopes the two-quasiparticle states are more relevant. In between both degrees of freedom are necessary .

  18. Cluster structure in highly-excited states of light nuclei

    The cluster structure in the highly-excited states of light nuclei are investigated using the multi-cluster model. For this purpose, we propose a developed treatment method of the multi-cluster model. The method consists of two parts: One is a systematic construction method of the multi-cluster Pauli-allowed states. Another is a truncation method of the large model space of the multi-cluster system. We show that we can easily solve the equation of the orthogonality condition model (OCM) for complex multi-cluster systems by the use of the method. We apply the multi-cluster models 3α, 4α, 12C + 2α and 16O + 2α to 12C, 16O, 20Ne and 24Mg, respectively. As shown in the Ikeda diagram, these models open a very interesting problem not only of the cluster structure in the highly-excited states of those nuclei but also of the structure change between different cluster structures. We show a typical example of the 16O + 2α model for 24Mg ; 1) many excited states with the 20Ne-α cluster structure are obtained at excitation energies above 10 MeV, 2) the 16O-8Be cluster states are obtained at the energy region higher than 20 MeV, and 3) the very interesting states with the α-16O-α linear-chain-like structure are predicted at about 20 MeV excitation energy. (author)

  19. Doubly excited 3P(e) resonant states in Ps(-)

    Ho, Y. K.; Bhatia, A. K.

    1992-01-01

    Doubly excited 3P(e) resonant states in Ps(-) are calculated using a method of complex-coordinate rotation. Resonance parameters (both resonance positions and widths) for doubly excited states associated with the n = 2, 3, 4, 5, and 6 thresholds of positronium atoms are evaluated using elaborate Hylleraas-type functions. In addition to ten Feshbach-type resonances lying below various Ps thresholds, three shape resonances were identified, one each lying above the n = 2, 4, and 6 Ps thresholds. It is further noted that the energy levels for the present 3P(e) states are nearly degenerate with respect to the previously calculated 1P(0) states. Such a symmetric character suggests that the highly and doubly excited Ps(-), similar to its counterpart in H(-), would exhibit rovibrational behaviors analogous to those of XYX triatomic molecules.

  20. Neutron halos in the excited states for N=127 isotones

    SUN Qin; GUO Jian-You

    2009-01-01

    Properties of the ground states and the excited states of N=127 isotones are investigated by using the nonlinear relativistic mean field theory with the interactions PK1. By analyzing the rms of proton and neutron, the single particle energies of valence nucleon and the density distributions of neutron, proton and the last neutron, it can be found that there exists a neutron halo in the excited states of 3d5/2, 4s1/2 and 3d3/2 in 209Pb. It is also predicted that there exists a neutron halo in the excited states of 3d5/2, 4s1/2 and 3d3/2 in 207Hg, 208Tl, 210Bi and 211Po.

  1. Excited states and transition metal compounds with quantum Monte Carlo

    Bande, Annika

    2007-01-01

    To the most challenging electron structure calculations belong weak interactions, excited state calculations, transition metals and properties. In this work the performance of variational (VMC) and fixed-node diffusion quantum Monte Carlo (FN-DMC) is tested for challenging electron structure problems using the quantum Monte Carlo amolqc code by Lüchow et al. The transition metal compounds under consideration are vanadium oxides. Here excitation, ionization, oxygen atom and molecule abstractio...

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

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

    2014-04-28

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

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

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

    1994-01-01

    A combination of steady-state and dynamic spectral measurements are used to provide new insights into the nature of the excited-state processes of all-trans-1,4-diphenyl-1,3-butadiene and several analogs: 1,4-diphenyl- 1,3-cyclopentadiene, 1,1,4,4-tetraphenylbutadiene, 1,2,3,4-tetraphenyl-1...

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

    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

  5. Excited-state dynamics of astaxanthin aggregates

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

    2013-05-01

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

  6. Quantum entanglement of localized excited states at finite temperature

    Caputa, Pawel; Simón, Joan; Štikonas, Andrius; Takayanagi, Tadashi

    2015-01-01

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

  7. Quantum Entanglement of Localized Excited States at Finite Temperature

    Caputa, Pawel; Stikonas, Andrius; Takayanagi, Tadashi

    2014-01-01

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

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

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

    2015-09-01

    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. PMID:26575896

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

    Robinson, David

    2014-12-01

    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. PMID:26583218

  10. Coupled cluster calculations of ground and excited states of nuclei

    The standard and renormalized coupled cluster methods with singles, doubles, and noniterative triples and their generalizations to excited states, based on the equation of motion coupled cluster approach, are applied to the He4 and O16 nuclei. A comparison of coupled cluster results with the results of the exact diagonalization of the Hamiltonian in the same model space shows that the quantum chemistry inspired coupled cluster approximations provide an excellent description of ground and excited states of nuclei. The bulk of the correlation effects is obtained at the coupled cluster singles and doubles level. Triples, treated noniteratively, provide the virtually exact description

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

    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.

  12. Equations of state for self-excited MHD generator studies

    We have constructed a state-of-the-art equation of state (EOS) for argon covering the temperature density range attainable by currently proposed self-excited MHD generators. The EOS for conditions in the flow channel was obtained primarily by a non-ideal plasma code (ACTEX) that is based on a many body activity expansion. For conditions in the driver chamber the EOS was primarily obtained from a fluid code (HDFP) that calculates the fluid properties from perturbation theory based on the insulator interatomic pair potential but including electronic excitations. The results are in agreement with several sets of experimental data in the 0.6 - 91 GPa pressure range

  13. Equations of state for self-excited MHD generator studies

    Rogers, F.J.; Ross, M.; Haggin, G.L.; Wong, L.K.

    1980-02-26

    We have constructed a state-of-the-art equation of state (EOS) for argon covering the temperature density range attainable by currently proposed self-excited MHD generators. The EOS for conditions in the flow channel was obtained primarily by a non-ideal plasma code (ACTEX) that is based on a many body activity expansion. For conditions in the driver chamber the EOS was primarily obtained from a fluid code (HDFP) that calculates the fluid properties from perturbation theory based on the insulator interatomic pair potential but including electronic excitations. The results are in agreement with several sets of experimental data in the 0.6 - 91 GPa pressure range.

  14. Kinetic studies following state-selective laser excitation

    The objective of this contract is the study of state-to-state, electronic energy transfer reactions following two-photon laser excitation. We have chosen to study reactions of Xe 5p5np because of their relevance to the XeCl excimer laser. We are studying deactivation reactions in collisions with heavy atoms such as Ar, Kr, and Xe and reactive collisions with chlorides. The reactants are excited by multiphoton laser absorption. Product channels are observed by their fluorescence, or by laser induced fluorescence using a second color laser. 36 refs., 16 figs., 5 tabs

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

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

  16. Attosecond dynamics of electron correlation in doubly excited atomic states

    We have solved the time-dependent Schroedinger equation describing the simultaneous interaction of the He 1s2s 1S state with two laser-generated pulses of trapezoidal or Gaussian shape, of duration 86 fs and of frequencies ω1=1.453 au and ω2=1.781 au. The system is excited to the energy region of two strongly correlated doubly excited states, chosen for this study according to specific criteria. It is demonstrated quantitatively that, provided one focuses on the dynamics occurring within the attosecond timescale, the corresponding orbital configurations, 2s2p and 2p3d 1P0, exist as nonstationary states, with occupation probabilities that are oscillating as the states decay exponentially into the 1sεp continuum, during and after the laser-atom interaction. It follows that it is feasible to probe by attosecond pulses the motion of configurations of electrons as they correlate via the total Hamiltonian. For the particular system studied here, the probe pulses could register the oscillating doubly excited configurations by de-exciting to the He 1s3d 1D state, which emits at 6680 A. (author). Letter-to-the-editor

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

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

  18. Wave packet dynamics in molecular excited electronic states

    We theoretically explore the use of UV pump – UV probe schemes to resolve in time the dynamics of nuclear wave packets in excited electronic states of the hydrogen molecule. The pump pulse ignites the dynamics in singly excited states, that will be probed after a given time delay by a second identical pulse that will ionize the molecule. The field-free molecular dynamics is first explored by analyizing the autocorrelation function for the pumped wave packet and the excitation probabilities. We investigate both energy and angle differential ionization probabilities and demonstrate that the asymmetry induced in the electron angular distributions gives a direct map of the time evolution of the pumped wave packet

  19. Excited charmonium states from Bethe-Salpeter equation

    Sauli, Vladimir

    2011-01-01

    We solve the Bethe-Salpeter equation for a system of a heavy quark-antiquark pair interacting with a screened linear confining potential. First we show the spinless QFT model is inadequate and fail to describe even gross feature of the quarkonia spectrum. In order to get reliable description the spine degrees of freedom has to be considered. Within the approximation employed we reasonably reproduce known radial excitation of vector charmonium. The BSE favors relatively large string breaking scale $\\mu\\simeq 350MeV$ . Using free charm quark propagators we observe that $J/\\Psi$ is the only charmonium left bellow naive quark-antiquark threshold $2m_c$, while the all excited states are situated above this threshold. Within the numerical method we overcome obstacles related with threshold singularity and discuss the consequences of the use of free propagators for calculation of excited states above the threshold.

  20. Optimal control of peridinin excited-state dynamics

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

    2010-01-01

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

  1. Size dependent deactivation of the excited state of DHICA

    Gauden, Magdalena; Pezzella, Alessandro; Panzella, Lucia;

    2008-01-01

    Melanin is a natural pigment mainly responsible for the protection of skin and eyes from UV damage. 5,6- dihydroxyindole- 2 carboxylic acid (DHICA) is a key melanin building block. We have investigated the excited state dynamics of DHICA as well as its derivatives and oligomeric units using...

  2. Dark excited states of carotenoids: Consensus and controversy

    Polívka, Tomáš; Sundström, V.

    2009-01-01

    Roč. 477, 1-3 (2009), s. 1-11. ISSN 0009-2614 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * excited states * relaxation pathways * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 2.291, year: 2009

  3. Calculation of neutral beam deposition accounting for excited states

    Large-scale neutral-beam auxillary heating of plasmas has led to new plasma operational regimes which are often dominated by fast ions injected via the absorption of an energetic beam of hydrogen neutrals. An accurate simulation of the slowing down and transport of these fast ions requires an intimate knowledge of the hydrogenic neutral deposition on each flux surface of the plasma. As a refinement to the present generation of transport codes, which base their beam deposition on ground-state reaction rates, a new set of routines, based on the excited states of hydrogen, is presented as mechanism for computing the attenuation and deposition of a beam of energetic neutrals. Additionally, the numerical formulations for the underlying atomic physics for hydrogen impacting on the constiuent plasma species is developed and compiled as a numerical database. Sample results based on this excited state model are compared with the ground-state model for simple plasma configurations

  4. Calculation of neutral beam deposition accounting for excited states

    Gianakon, T.A.

    1992-09-01

    Large-scale neutral-beam auxillary heating of plasmas has led to new plasma operational regimes which are often dominated by fast ions injected via the absorption of an energetic beam of hydrogen neutrals. An accurate simulation of the slowing down and transport of these fast ions requires an intimate knowledge of the hydrogenic neutral deposition on each flux surface of the plasma. As a refinement to the present generation of transport codes, which base their beam deposition on ground-state reaction rates, a new set of routines, based on the excited states of hydrogen, is presented as mechanism for computing the attenuation and deposition of a beam of energetic neutrals. Additionally, the numerical formulations for the underlying atomic physics for hydrogen impacting on the constiuent plasma species is developed and compiled as a numerical database. Sample results based on this excited state model are compared with the ground-state model for simple plasma configurations.

  5. Direct excitation of butterfly states in Rydberg molecules

    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.

  6. Optimized resonating valence bond state in square lattice: correlations & excitations

    Z Nourbakhsh

    2009-09-01

    Full Text Available We consider RVB state as a variational estimate for the ground state of Heisenberg antiferromagnet in square lattice. We present numerical calculation of energy, spin-spin correlation function and spin excitation spectrum. We show, that the quantum flactuations reduce of magnetization respect to Neel order. Our results are in good agreement with other methods such as spin-wave calculation and series expansions.

  7. Excited States of the Diatomic Molecule CrHe

    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}.

  8. Coupling of single-particle states to collective excitations

    We discuss the effects of colletive vibrations of the closed shell core on the fragmentation of single-particle states in the neighbouring odd nuclei. A scheme for calculating microscopically these effects is presented. Starting from a Skyrme-type effective interaction, one can obtain the Hartree-Fock spectrum, the core excited states and giant resonances and then the energy-dependent mass operator which determines the fragmentation. Results for the 207Pb are discussed and compared with the data

  9. Photodissociation of N2O: excitation of 1A" states.

    Schinke, Reinhard; Schmidt, Johan A

    2012-11-26

    We investigate the contributions of the lowest two (1)A" states in the UV photodissociation of N(2)O employing three-dimensional potential energy surfaces and transition dipole moment functions. Because the transition dipole moments are much smaller than for the 2 (1)A' state, we conclude that excitation of the (1)A" states has a marginal effect. The dense vibrational spectrum of the quasi-bound 2(1)A" state possibly explains some of the tiny, noise-like structures of the measured absorption spectrum. PMID:22536943

  10. Temperature measurements from relative populations of excited states with INDRA

    For the first time, INDRA has been used to analyse resonances observed in correlation functions, giving thus the possibility to probe the caloric curve (correlation between the excitation energy and the temperature). First results obtained for the reaction 1836Ar+2858Ni at 95 MeV/nucleon are presented where the projectile-like apparent temperature has been evaluated. Moreover, the measured populations of excited states are compared with the predictions of a statistical model which includes an original hypothesis of excluded volume for species at the freeze-out. (author)

  11. Solid-State Excitation Laser for Laser-Ultrasonics

    Schnars, U.; Platz, W.; Mahnke, P.; A. Fix; Frede, M; Neumann, J.; Peuser, P.

    2010-01-01

    The inspection speed of laser-ultrasonics compared with conventional ultrasonic testing is limited by the pulse repetition rate of the excitation laser. The maximum pulse repetition rate reported up to now for CO2-lasers, which are presently used for nearly all systems, is in the range of 400 Hz. In this paper a new approach based on a diode-pumped solid-state laser is discussed, which is currently being developed. This new excitation laser is designed for a repetition rate of 1 kHz and will ...

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

    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

  13. MULTIPLY CHARGED IONS COLLISIONS WITH ATOMS INTO EXCITED STATES

    PanGuangyan

    1990-01-01

    The emission spectra in collisions between Ions and Atoms have been measured by an Optical Multichannel Analysis System (OMA).The experimental results demonstrate that there are two channels of excitation in collision between single charged ions and atoms and three channels of excitation in collision between double charged ions and atoms.Emission cross cestions and excitation cross sections have been obtained.K.Kadota et al and R.Shingal et al suggested that,under the appropriate conditions,the H42+-Li and He2++Na collision systems can be used efficiently to produce a laser of Lyman-α(30,4nm) and Lyman-β(25.6nm)lines via cascade to He+(2P)state.

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

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

  15. Super-atom molecular orbital excited states of fullerenes.

    Johansson, J Olof; Bohl, Elvira; Campbell, Eleanor E B

    2016-09-13

    Super-atom molecular orbitals are orbitals that form diffuse hydrogenic excited electronic states of fullerenes with their electron density centred at the centre of the hollow carbon cage and a significant electron density inside the cage. This is a consequence of the high symmetry and hollow structure of the molecules and distinguishes them from typical low-lying molecular Rydberg states. This review summarizes the current experimental and theoretical studies related to these exotic excited electronic states with emphasis on femtosecond photoelectron spectroscopy experiments on gas-phase fullerenes.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'. PMID:27501970

  16. Controlling excited-state contamination in nucleon matrix elements

    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; Nucleon Matrix Elements NME Collaboration

    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 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. 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.

  17. Excited state dynamics of the astaxanthin radical cation

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

    2010-07-01

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

  18. Controlling Excited-State Contamination in Nucleon Matrix Elements

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

    2016-01-01

    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_...

  19. First observation of excited states in {sup 182}Pb.

    Jenkins, D. G.; Muikku, M.; Greenlees, P. T.; Hauschild, K.; Helarjutta, K.; Jones, P. M.; Julin, R.; Juutinen, S.; Kankaanpaa, H.; Kelsall, N. S.; Kettunen, H.; Kuusiniemi, P.; Leino, M.; Moore, C. J.; Nieminen, P.; O' Leary, C. D.; Page, R. D.; Rakhila, P.; Reviol, W.; Taylor, M. J.; Uusitalo, J.; Wadsworth, R.; Physics; Univ. of York; Univ. of Jyvaskyla; CEA Saclay; Univ. of Liverpool; Univ. of Tennessee

    2000-01-01

    Excited states in the light lead nucleus, {sup 182}Pb, have been observed for the first time, by means of the recoil-decay tagging technique. A rotational band has been observed which has features in common with bands attributed to a prolate configuration in the heavier neutron deficient lead nuclei, {sup 184-188}Pb. A variable moment of inertia fit to the states in this band suggests that the prolate minimum has risen significantly in energy compared to the next even lead nucleus, {sup 184}Pb. This constitutes firm evidence for the minimization of this configuration with respect to the spherical ground state around N=103.

  20. Strong-Field Photoionization as Excited-State Tunneling.

    Serebryannikov, E E; Zheltikov, A M

    2016-03-25

    We show that, in an intense laser field, ultrafast photoionization can occur through quantum pathways that cannot be categorized as multiphoton ionization or ground-state tunneling. In this regime, the subcycle electron-wave-packet dynamics leading to photoionization occurs via electron excited states, from where the electrons tunnel to the continuum within a tiny fraction of the field cycle. For high field intensities, this ionization pathway is shown to drastically enhance the dynamic leakage of the electron wave packet into the continuum, opening an ionization channel that dominates over ground-state electron tunneling. PMID:27058079

  1. Ultrafast excited state dynamics in 9,9'-bifluorenylidene.

    Conyard, Jamie; Heisler, Ismael A; Browne, Wesley R; Feringa, Ben L; Amirjalayer, Saeed; Buma, Wybren Jan; Woutersen, Sander; Meech, Stephen R

    2014-08-01

    9,9'-Bifluorenylidene has been proposed as an alternative and flexible electron acceptor in organic photovoltaic cells. Here we characterize its excited state properties and photokinetics, combining ultrafast fluorescence and transient IR measurements with quantum chemical calculations. The fluorescence decay is ultrafast (sub-100 fs) and remarkably independent of viscosity. This suggests that large scale structure change is not the primary relaxation mode. The ultrafast decay populates a dark state characterized by distinct vibrational and electronic spectra. This state decays with a 6 ps time constant to a hot ground state that ultimately populates the initial state with a 20 ps time constant; these times are also insensitive to solvent viscosity. No metastable intermediate structures are resolved in the photocycle after population of the dark state. The implications of these results for the operation of 9,9'-bifluorenylidene as an electron acceptor and as a potential molecular switch are discussed. PMID:25025227

  2. Negative-parity nucleon excited state in nuclear matter

    Ohtani, Keisuke; Oka, Makoto

    2016-01-01

    Spectral functions of the nucleon and its negative parity excited state in nuclear matter are studied using QCD sum rules and the maximum entropy method (MEM). It is found that in-medium modifications of the spectral functions are attributed mainly to density dependencies of the $\\langle \\bar{q}q \\rangle $ and $\\langle q^{\\dagger}q \\rangle $ condensates. The MEM reproduces the lowest-energy peaks of both the positive and negative parity nucleon states at finite density up to $\\rho \\sim \\rho_N$ (normal nuclear matter density). As the density grows, the residue of the nucleon ground state decreases gradually while the residue of the lowest negative parity excited state increases slightly. On the other hand, the positions of the peaks, which correspond to the total energies of these states, are almost density independent for both parity states. The density dependencies of the effective masses and vector self-energies are also extracted by assuming the mean-field green functions for the peak states. We find that,...

  3. Physical Properties, Exciton Analysis, and Visualization of Core-Excited States: An Intermediate State Representation Approach.

    Wenzel, Jan; Dreuw, Andreas

    2016-03-01

    The theoretical simulation of X-ray absorption spectra is in general a challenging task. However, for small and medium-sized organic molecules, the algebraic diagrammatic construction scheme (ADC) for the polarization operator in combination with the core-valence separation approximation (CVS) has proven to yield core-excitation energies and transition moments with almost quantitative accuracy allowing for reliable construction of X-ray absorption spectra. Still, to understand core-excitation processes in detail, it is not sufficient to only compute energies, but also properties like static dipole moments and state densities are important as they provide deeper insight into the nature of core-excited states. Here, we present for the first time an implementation of the intermediate state representation (ISR) approach in combination with the CVS approximation (CVS-ISR), which gives, in combination with the CVS-ADC method, direct access to core-excited state properties. The performance of the CVS-ADC/CVS-ISR approach is demonstrated by means of small- and medium-sized organic molecules. Besides the calculation of core-excited state dipole moments, advanced analyses of core-excited state densities are performed using descriptors like exciton sizes and distances. Plotting electron and hole densities helps to determine the character of the state, and in particular, the investigation of detachment/attachment densities provides information about orbital relaxation effects that are crucial for understanding core excitations. PMID:26845396

  4. On the nature of highly vibrationally excited states of thiophosgene

    Srihari Keshavamurthy

    2012-01-01

    In this work an analysis of the highly vibrationally excited states of thiophosgene (SCCl2) is made in order to gain insights into some of the experimental observations and spectral features. The states analysed here lie in a spectrally complex region where strong mode mixings are expected due to the overlap of several strong anharmonic Fermi resonances. Two recent techniques, a semiclassical angle space representation of the eigenstates and the parametric variation of the eigenvalues (level-velocities) are used to identify eigenstate sequences exhibiting common localization characteristics. Preliminary results on the influence of highly excited out-of-plane bending modes on the nature of the eigenstates suggest a possible bifurcation in the system.

  5. The effects of doubly excited states on ionization balance

    2006-01-01

    The effects of highly doubly excited states on ionization balance are investigated. In the calculation, A Collisional-Radiative model in Detailed-Configuration-Accounting (DCA) is applied to population calculations for NLTE plasmas. Configuration-averaged rate coefficients that needed in the rate equations are obtained based on the first order perturbation theory. The Hatree-Fock-Slater self-consistent-field method is used to calculate the electron wave functions. The mean ionization stage of high-Z plasma Lu is presented. The comparison shows that the mean ionization stage increases more than 3 stages when doubly excited states 5l6l' and 5l5l' are not included in the population calculations.

  6. Excited states in large molecular systems through polarizable embedding.

    List, Nanna Holmgaard; Olsen, Jógvan Magnus Haugaard; Kongsted, Jacob

    2016-07-27

    In this perspective, we provide an overview of recent work within the polarizable embedding scheme to describe properties of molecules in realistic environments of increasing complexity. After an outline of the theoretical basis for the polarizable embedding model, we discuss the importance of using an accurate embedding potential, and how this may be used to significantly reduce the size of the part of the system treated using quantum mechanics without compromising the accuracy of the final results. Furthermore, we discuss the calculation of local electronic excited states based on response theory. We finally discuss aspects related to two recent extensions of the model (i) effective external field and (ii) polarizable density embedding emphasizing their importance for efficient yet accurate description of excited-state properties in complex environments. PMID:27416749

  7. Algorithm for Computing Excited States in Quantum Theory

    Luo, X. Q.; Jirari, H.; Kroger, H; Moriarty, K.

    2001-01-01

    Monte Carlo techniques have been widely employed in statistical physics as well as in quantum theory in the Lagrangian formulation. However, in the conventional approach, it is extremely difficult to compute the excited states. Here we present a different algorithm: the Monte Carlo Hamiltonian method, designed to overcome the difficulties of the conventional approach. As a new example, application to the Klein-Gordon field theory is shown.

  8. Time evolution of vibration-induced excited state decay

    Menšík, Miroslav; Nešpůrek, Stanislav

    2002-01-01

    Roč. 52, č. 8 (2002), s. 945-962. ISSN 0011-4626 R&D Projects: GA AV ČR IAB1050903; GA AV ČR IAA1050901 Institutional research plan: CEZ:AV0Z4050913 Keywords : excited state decay * exciton-phonon interaction Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 0.311, year: 2002

  9. Clustered Chimera States in Systems of Type-I Excitability

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

    2014-01-01

    Chimera is a fascinating phenomenon of coexisting synchronized and desynchronized behaviour that was discovered in networks of nonlocally coupled identical phase oscillators over ten years ago. Since then, chimeras were found in numerous theoretical and experimental studies and more recently in models of neuronal dynamics as well. In this work, we consider a generic model for a saddle-node bifurcation on a limit cycle representative for neural excitability type I. We obtain chimera states wit...

  10. Minimal-excitation states for electron quantum optics using levitons

    Dubois, J.; Jullien, T.; Portier, F.; Roche, P.; Cavanna, A.; Jin, Y.; Wegscheider, W.; Roulleau, P.; Glattli, D. C.

    2013-10-01

    The on-demand generation of pure quantum excitations is important for the operation of quantum systems, but it is particularly difficult for a system of fermions. This is because any perturbation affects all states below the Fermi energy, resulting in a complex superposition of particle and hole excitations. However, it was predicted nearly 20 years ago that a Lorentzian time-dependent potential with quantized flux generates a minimal excitation with only one particle and no hole. Here we report that such quasiparticles (hereafter termed levitons) can be generated on demand in a conductor by applying voltage pulses to a contact. Partitioning the excitations with an electronic beam splitter generates a current noise that we use to measure their number. Minimal-excitation states are observed for Lorentzian pulses, whereas for other pulse shapes there are significant contributions from holes. Further identification of levitons is provided in the energy domain with shot-noise spectroscopy, and in the time domain with electronic Hong-Ou-Mandel noise correlations. The latter, obtained by colliding synchronized levitons on a beam splitter, exemplifies the potential use of levitons for quantum information: using linear electron quantum optics in ballistic conductors, it is possible to imagine flying-qubit operation in which the Fermi statistics are exploited to entangle synchronized electrons emitted by distinct sources. Compared with electron sources based on quantum dots, the generation of levitons does not require delicate nanolithography, considerably simplifying the circuitry for scalability. Levitons are not limited to carrying a single charge, and so in a broader context n-particle levitons could find application in the study of full electron counting statistics. But they can also carry a fraction of charge if they are implemented in Luttinger liquids or in fractional quantum Hall edge channels; this allows the study of Abelian and non-Abelian quasiparticles in the

  11. Spin radical enhanced magnetocapacitance effect in intermolecular excited states.

    Zang, Huidong; Wang, Jianguo; Li, Mingxing; He, Lei; Liu, Zitong; Zhang, Deqing; Hu, Bin

    2013-11-14

    This article reports the magnetocapacitance effect (MFC) based on both pristine polymer MEH-PPV and its composite system doped with spin radicals (6R-BDTSCSB). We observed that a photoexcitation leads to a significant positive MFC in the pristine MEH-PPV. Moreover, we found that a low doping of spin radicals in polymer MEH-PPV causes a significant change on the MFC signal: an amplitude increase and a line-shape narrowing under light illumination at room temperature. However, no MFC signal was observed under dark conditions in either the pristine MEH-PPV or the radical-doped MEH-PPV. Furthermore, the magnitude increase and line-shape narrowing caused by the doped spin radicals are very similar to the phenomena induced by increasing the photoexcitation intensity. Our studies suggest that the MFC is essentially originated from the intermolecular excited states, namely, intermolecular electron-hole pairs, generated by a photoexcitation in the MEH-PPV. More importantly, by comparing the effects of spin radicals and electrically polar molecules on the MFC magnitude and line shape, we concluded that the doped spin radicals can have the spin interaction with intermolecular excited states and consequently affect the internal spin-exchange interaction within intermolecular excited states in the development of MFC. Clearly, our experimental results indicate that dispersing spin radicals forms a convenient method to enhance the magnetocapacitance effect in organic semiconducting materials. PMID:24144347

  12. Doubly excited triplet states of highly stripped ions

    Transition energies, Coulomb repulsions and effective quantum numbers have been calculated for the doubly excited Nsnp: 3P0 (for N=2, n=N,..,5); Nsnd: 3De (for N=2, n=N+1,..,5) and Npnd: 3F0 (for N=2, n=N+1,..,5) states for the highly stripped ions Na9+,Mg10+,Al11+,Si12+,P13+ and S14+. Time-dependent perturbation theory has been applied to calculate such transitions properties. A time-dependent harmonic perturbation causes simultaneous excitation of both the electrons with a change of spin state. The doubly excited energy levels and the analytic representation of their wave functions are obtained by identifying the poles of an appropriately constructed linearized variational functional with respect to driving frequency. Most of the results are new. The transition energies and effective quantum numbers of 2s2p: 3P0 states of all the ions agree well with the only available experimental data. (orig.)

  13. Entanglement Temperature and Entanglement Entropy of Excited States

    Wong, Gabriel; Zayas, Leopoldo A Pando; Vaman, Diana

    2013-01-01

    We derive a general relation between the ground state entanglement Hamiltonian and the physical stress tensor within the path integral formalism. For spherical entangling surfaces in a CFT, we reproduce the \\emph{local} ground state entanglement Hamiltonian derived by Casini, Huerta and Myers. The resulting reduced density matrix can be interpreted as a state of local thermal equilibrium with a spatially varying "entanglement temperature." Using the entanglement Hamiltonian, we calculate the first order change in the entanglement entropy due to changes in conserved charges of the ground state, and find a generalized, local first law-like relation for the entanglement entropy. Our approach provides a field theory derivation and generalization of recent results obtained by holographic techniques. However, we note a discrepancy between our field theoretically derived results for the entanglement entropy of excited states with a non-uniform energy density and current holographic results in the literature. Finally...

  14. Is the Z+(4430) a radially excited state of Ds?

    We present the interpretation that the recently discovered Z+(4430) by the Belle Collaboration can be a radial excitation of the cs-bar state, being consistent with an observed value of the product of branching ratios, B(B0→K±Z±(4430))xB(Z±(4430)→π±ψ')∼10-5. We give an explicit cs-bar candidate for this state by calculating the mass value in our semirelativistic quark potential model and also give a natural understanding for the facts that the decay mode Z→J/ψπ+ has not yet been seen while Z→ψ'π can be seen

  15. Modular Hamiltonian for Excited States in Conformal Field Theory

    Lashkari, Nima

    2016-07-01

    We present a novel replica trick that computes the relative entropy of two arbitrary states in conformal field theory. Our replica trick is based on the analytic continuation of partition functions that break the Zn replica symmetry. It provides a method for computing arbitrary matrix elements of the modular Hamiltonian corresponding to excited states in terms of correlation functions. We show that the quantum Fisher information in vacuum can be expressed in terms of two-point functions on the replica geometry. We perform sample calculations in two-dimensional conformal field theories.

  16. Internal-nuclear conversion of energy of nucleus excited state

    In the work an effect of penetration electrons of internal conversion showing in hindered M1-transitions was studied. At the moment of a nucleus transition from excited state in low state, electron of atomic shell can appear inside a nucleus and the internal conversion of electrons occur. For such transitions nuclear parameter do not equal zero. The analytical method of definition of nuclear parameter is offered from the relation of intensities L1/L2, L1/L3, L2/L3 of internal conversion of electrons. (authors)

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

    Schutz, Katelin

    2014-01-01

    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 c...

  18. Quantum Entanglement of Locally Excited States in Maxwell Theory

    Nozaki, Masahiro

    2016-01-01

    In 4 dimensional Maxwell gauge theory, we study the changes of (Renyi) entangle-ment entropy which are defined by subtracting the entropy for the ground state from the one for the locally excited states generated by acting with the 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.

  19. Excited-State Properties of Molecular Solids from First Principles.

    Kronik, Leeor; Neaton, Jeffrey B

    2016-05-27

    Molecular solids have attracted attention recently in the context of organic (opto)electronics. These materials exhibit unique charge carrier generation and transport phenomena that are distinct from those of conventional semiconductors. Understanding these phenomena is fundamental to optoelectronics and requires a detailed description of the excited-state properties of molecular solids. Recent advances in many-body perturbation theory (MBPT) and density functional theory (DFT) have made such description possible and have revealed many surprising electronic and optical properties of molecular crystals. Here, we review this progress. We summarize the salient aspects of MBPT and DFT as well as various properties that can be described by these methods. These properties include the fundamental gap and its renormalization, hybridization and band dispersion, singlet and triplet excitations, optical spectra, and excitonic properties. For each, we present concrete examples, a comparison to experiments, and a critical discussion. PMID:27090844

  20. Excited-State Properties of Molecular Solids from First Principles

    Kronik, Leeor; Neaton, Jeffrey B.

    2016-05-01

    Molecular solids have attracted attention recently in the context of organic (opto)electronics. These materials exhibit unique charge carrier generation and transport phenomena that are distinct from those of conventional semiconductors. Understanding these phenomena is fundamental to optoelectronics and requires a detailed description of the excited-state properties of molecular solids. Recent advances in many-body perturbation theory (MBPT) and density functional theory (DFT) have made such description possible and have revealed many surprising electronic and optical properties of molecular crystals. Here, we review this progress. We summarize the salient aspects of MBPT and DFT as well as various properties that can be described by these methods. These properties include the fundamental gap and its renormalization, hybridization and band dispersion, singlet and triplet excitations, optical spectra, and excitonic properties. For each, we present concrete examples, a comparison to experiments, and a critical discussion.

  1. Systematic study of double beta decay to excited final states

    A systematic study of two-neutrino double beta (2νββ) decay to the final ground state and excited states is performed within a microscopic quasiparticle random phase approximation (QRPA) model. The excited states are assumed to have the structure of one or two QRPA phonons. This study of the 2νββ decay rates is complemented with the study of single-beta-decay feeding of the relevant nuclei taking part in the double beta process. The Woods-Saxon single-particle energies have been corrected near the Fermi surface by comparing the BCS quasi-particle energies with spectroscopic data of the relevant odd-mass nuclei. Pairing gaps, energy systematics of the Gamow-Teller-States and the available beta-decay data have been used to obtain effective, model-space adapted, two-body matrix elements starting from the G-matrix elements of the Bonn one-boson-exchange potential. This enables a parameter-free calculation of the double Gamow-Teller matrix elements and theoretical prediction of double-beta half lives. The harmonic two-phonon approximation has been used in the beta-decay analysis and the subsequent 2νββ calculations. (authors)

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

    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. Output power of a quantum dot laser: Effects of excited states

    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

  4. Excited state dynamics and isomerization in ruthenium sulfoxide complexes.

    King, Albert W; Wang, Lei; Rack, Jeffrey J

    2015-04-21

    Molecular photochromic compounds are those that interconvert between two isomeric forms with light. The two isomeric forms display distinct electronic and molecular structures and must not be in equilibrium with one another. These light-activated molecular switch compounds have found wide application in areas of study ranging from chemical biology to materials science, where conversion from one isomeric form to another by light prompts a response in the environment (e.g., protein or polymeric material). Certain ruthenium and osmium polypyridine sulfoxide complexes are photochromic. The mode of action is a phototriggered isomerization of the sulfoxide from S- to O-bonded. The change in ligation drastically alters both the spectroscopic and electrochemical properties of the metal complex. Our laboratory has pioneered the preparation and study of these complexes. In particular, we have applied femtosecond pump-probe spectroscopy to reveal excited state details of the isomerization mechanism. The data from numerous complexes allowed us to predict that the isomerization was nonadiabatic in nature, defined as occurring from a S-bonded triplet excited state (primarily metal-to-ligand charge transfer in character) to an O-bonded singlet ground state potential energy surface. This prediction was corroborated by high-level density functional theory calculations. An intriguing aspect of this reactivity is the coupling of nuclear motion to the electronic wave function and how this coupling affects motions productive for isomerization. In an effort to learn more about this coupling, we designed a project to examine phototriggered isomerization in bis-sulfoxide complexes. The goal of these studies was to determine whether certain complexes could be designed in which a single photon excitation event would prompt two sulfoxide isomerizations. We employed chelating sulfoxides in this study and found that both the nature of the chelate ring and the R group on the sulfoxide affect

  5. Theoretical aspects of multiphoton ionization with many resonant excited states

    The variety of the parameters involved in multi-color multi-step ionization makes it a formidable job to obtain a theoretically comprehensible overview of the process. We examine these parameters of such processes as well as commonly used assumptions in theoretical investigations of multiphoton ionization with many resonantly excited levels. The density matrix formalism is adequate to treat resonant multiphoton ionization when the number of the resonant levels involved is not too large, solving the resonantly coupled states separately beyond the lowest order perturbation theory, while the rest of the states are treated perturbatively. An example of such formalism is given for a four-level system ionized with three lasers each of which resonantly couples the adjacent pairs of the atomic states.

  6. Excited states in 146Sm and 147Sm

    The sup(144,146)Nd(α,xn) and sup(146,148)Nd(3He,xn) reactions with Esub(α) = 20 - 43 MeV and E3sub(He) = 19 - 27 MeV are used to investigate excited states in the isotopes 146Sm and 147Sm. The experiments involve measurements of singles γ-ray spectra and conversion electron spectra, γ-ray angular distributions and three parameter (E sub(γ)E sub(γ) time) coincidences. From these experiments information is obtained for states with spin up to I = 13+ and I = 27/2-, respectively, These states are interpeted within the framework of the cluster-vibration model (CVM) as well as the shell model. (author)

  7. Excited states above the proton threshold in {sup 26}Si

    Komatsubara, T. [Institute for Basic Science (IBS), Rare Isotope Science Project, Yuseong-gu Daejeon (Korea, Republic of); Kubono, S.; Ito, Y. [RIKEN, Saitama (Japan); Hayakawa, T.; Shizuma, T. [Japan Atomic Energy Agency, Tokai, Ibaraki (Japan); Ozawa, A.; Ishibashi, Y. [University of Tsukuba, Institute of Physics, Tsukuba, Ibaraki (Japan); Moriguchi, T. [National Cerebral and Cardiovascular Center Research Institute, Suita, Osaka (Japan); Yamaguchi, H.; Kahl, D. [University of Tokyo, Wako Branch, Center for Nuclear Study (CNS), Wako, Saitama (Japan); Hayakawa, S. [Laboratori Nazionali del Sud-INFN, Catania (Italy); Nguyen Binh, Dam [Vietnamese Academy for Science and Technology, Institute of Physics, Hanoi (Viet Nam); Chen, A.A.; Chen, J. [McMaster University, Hamilton, Ontario (Canada); Setoodehnia, K. [University of Notre Dame, Department of Physics, Notre Dame, Indiana (United States); Kajino, T. [National Astronomical Observatory, Tokyo (Japan); University of Tokyo, Department of Astronomy, Graduate School of Science, Tokyo (Japan)

    2014-09-15

    The level scheme above the proton threshold in {sup 26}Si is crucial for evaluating the {sup 25}Al(p, γ){sup 26}Si stellar reaction, which is important for understanding the astrophysical origin of the long-lived cosmic radioactivity {sup 26}Al(T{sub 1/2} = 7.17 x 10{sup 5} y) in the Galaxy. The excited states in {sup 26}Si have been studied using an in-beam γ-ray spectroscopy technique with the {sup 24}Mg({sup 3}He, nγ){sup 26}Si reaction. γ-rays with energies up to 4.6 MeV emitted from excited states in {sup 26}Si have been measured using large volume HPGe detectors. The spin-parity of one of the most important states reported recently at 5890.0keV has been assigned as 0{sup +} by γ-γ angular correlation measurements in this work. (orig.)

  8. Weighing excited nuclear states with a Penning trap mass spectrometer

    We report on high-accuracy mass measurements and isomer identification of 187Pb. In this nuclide, two close-lying isomeric states are known from α-decay studies. With the combined use of the ISOLDE resonance ionization laser ion source and the Penning trap mass spectrometer ISOLTRAP the energy difference of 187Pb and 187mPb was determined to be E = 33(13) keV. This is the lowest isomeric excitation energy ever determined by weighing nuclei. (orig.)

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

    Bohr, Henrik; Malik, F. Bary

    2013-01-01

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

  10. Probing the Locality of Excited States with Linear Algebra.

    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. PMID:26574379

  11. Excitation gap of fractal quantum hall states in graphene

    Luo, Wenchen; Chakraborty, Tapash

    2016-01-01

    In the presence of a magnetic field and an external periodic potential the Landau level spectrum of a two-dimensional electron gas exhibits a fractal pattern in the energy spectrum which is described as the Hofstadter’s butterfly. In this work, we develop a Hartree-Fock theory to deal with the electron-electron interaction in the Hofstadter’s butterfly state in a finite-size graphene with periodic boundary conditions, where we include both spin and valley degrees of freedom. We then treat the butterfly state as an electron crystal so that we could obtain the order parameters of the crystal in the momentum space and also in an infinite sample. A phase transition between the liquid phase and the fractal crystal phase can be observed. The excitation gaps obtained in the infinite sample is comparable to those in the finite-size study, and agree with a recent experimental observation.

  12. 3alpha clustering in the excited states of 16C

    Baba, T; Kimura, M

    2014-01-01

    The alpha cluster states of 16C are investigated by using the antisymmetrized molecular dynamics. It is shown that two different types of alpha cluster states exist: triangular and linear-chain states. The former has an approximate isosceles triangular configuration of alpha particles surrounded by four valence neutrons occupying sd-shell, while the latter has the linearly aligned alpha particles with two sd-shell neutrons and two pf-shell neutrons. It is found that the structure of the linear-chain state is qualitatively understood in terms of the 3/2 pi- and 1/2 sigma- molecular orbit as predicted by molecular-orbital model, but there exists non-negligible Be+alpha+2n correlation. The band-head energies of the triangular and linear-chain rotational bands are 8.0 and 15.5 MeV, and the latter is close to the He+Be threshold energy. It is also shown that the linear-chain state becomes the yrast sstate at J=10 with excitation energy 27.8 MeV owing to its very large moment-of-inertia comparable with hyperdeforma...

  13. Kinetic studies following state-selective laser excitation

    We have made measurements of state-to-state deactivation cross sections and radiative lifetimes for Xe*(6p,6p',7p) and Kr*(5p) states in xenon and krypton buffer gases. These results are relevant to kinetic models and both excimer lasers and the infrared xenon laser; and they are a significant improvement in the precision of the known radiative lifetimes. This type of experiment can now be compared with recent calculations of state-to-state collisional relaxation in rare-gases by Hickman, Huestis, and Saxon. We have also made significant progress in the study of the electronic spectra of small molecules of the rare gases. Spectra have been obtained for Xe2, Xe3, Xe4, and larger clusters. As guidance for the larger clusters of the rare gases we have obtained the first multiphoton spectra for excitons in condensed xenon. In collaboration with research on the multiphoton spectra of the rare gases, we have continued experiments using synchrotron radiation in collaboration with the University of Hamburg. In experiments there we have observed excitation and fluorescence spectra for single xenon atoms at the surface, within the second layer, and within the bulk of large argon clusters

  14. Excited state properties of the astaxanthin radical cation: A quantum chemical study

    Dreuw, Andreas; Starcke, Jan Hendrik; Wachtveitl, Josef

    2010-07-01

    Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT rad + ) are investigated. While the optically allowed excited D 1 and D 3 states are typical ππ∗ excited states, the D 2 and D 4 states are nπ∗ states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed ππ∗ states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.

  15. Excited state properties of the astaxanthin radical cation: A quantum chemical study

    Dreuw, Andreas, E-mail: andreas.dreuw@theochem.uni-frankfurt.de [Institute of Physical and Theoretical Chemistry, Goethe-University Frankfurt, Max von Laue-Str. 7, 60438 Frankfurt am Main (Germany); Starcke, Jan Hendrik; Wachtveitl, Josef [Institute of Physical and Theoretical Chemistry, Goethe-University Frankfurt, Max von Laue-Str. 7, 60438 Frankfurt am Main (Germany)

    2010-07-19

    Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT{sup {center_dot}+}) are investigated. While the optically allowed excited D{sub 1} and D{sub 3} states are typical {pi}{pi}* excited states, the D{sub 2} and D{sub 4} states are n{pi}* states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed {pi}{pi}* states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.

  16. Excited state properties of the astaxanthin radical cation: A quantum chemical study

    Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT·+) are investigated. While the optically allowed excited D1 and D3 states are typical ππ* excited states, the D2 and D4 states are nπ* states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed ππ* states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.

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

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

    2014-12-14

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

  18. Observation of interference effects via four photon excitation of highly excited Rydberg states in thermal cesium vapor

    Kondo, Jorge M; Guttridge, Alex; Wade, Christopher G; De Melo, Natalia R; Adams, Charles S; Weatherill, Kevin J

    2015-01-01

    We report on the observation of Electromagnetically Induced Transparency (EIT) and Absorption (EIA) of highly-excited Rydberg states in thermal Cs vapor using a 4-step excitation scheme. The advantage of this 4-step scheme is that the final transition to the Rydberg state has a large dipole moment and one can achieve similar Rabi frequencies to 2 or 3 step excitation schemes using two orders of magnitude less laser power. Consequently each step is driven by a relatively low power infra-red diode laser opening up the prospect for new applications. The observed lineshapes are in good agreement with simulations based on multilevel optical Bloch equations.

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

    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

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

    The time evolution of electronically excited vitamin B12 (cyanocobalamin) has been observed for the first time in the gas phase. It reveals an ultrafast decay to a state corresponding to metal excitation. This decay is interpreted as resulting from a ring to metal electron transfer. This opens the observation of the excited state of other complex biomimetic systems in the gas phase, the key to the characterisation of their complex evolution through excited electronic states

  1. Breathing-like excited state of the Hoyle state in ${^{12}{\\rm C}}$

    Zhou, Bo; Horiuchi, Hisashi; Ren, Zhongzhou

    2016-01-01

    The existence of the $0_3^+$ and $0_4^+$ states around 10 MeV excitation energy in ${^{12}{\\rm C}}$ is confirmed by a fully microscopic 3$\\alpha$ cluster model. Firstly, a GCM (generator coordinate method) calculation is performed by superposing optimized 2$\\alpha$+$\\alpha$ THSR (Tohsaki-Horiuchi-Schuck-R\\"{o}pke) wave functions with the radius-constraint method. The obtained two excited $0^+$ states above the Hoyle state are consistent with the recently observed states by experiment. Secondly, a variational calculation using the single 2$\\alpha$+$\\alpha$ THSR wave function orthogonalized to the ground and Hoyle states is made and it also supports the existence of the $0_3^+$ state obtained by the GCM calculation. The analysis of the obtained $0_3^+$ state is made by studying its 2$\\alpha$-$\\alpha$ reduced width amplitude, its 2$\\alpha$ correlation function, and the large monopole matrix element between this state and the Hoyle state, which shows that this $0_3^+$ state is a breathing-like excited state of th...

  2. Electronic structure and excited state dynamics in optically excited PTCDA films investigated with two-photon photoemission

    Marks, M.; Sachs, S.; Schwalb, C. H.; Schöll, A.; Höfer, U.

    2013-09-01

    We present an investigation of the electronic structure and excited state dynamics of optically excited 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) thin films adsorbed on Ag(111) using two-photon photoemission spectroscopy (2PPE). 2PPE allows us to study both occupied and unoccupied electronic states, and we are able to identify signals from the highest occupied and the two lowest unoccupied electronic states of the PTCDA thin film in the 2PPE spectra. The energies for occupied states are identical to values from ultraviolet photoelectron spectroscopy. Compared to results from inverse photoelectron spectroscopy (IPES), the 2PPE signals from the two lowest unoccupied electronic states, LUMO and LUMO+1, are found at 0.8 eV and 1.0 eV lower energies, respectively. We attribute this deviation to the different final states probed in 2PPE and IPES and the attractive interaction of the photoexcited electron and the remaining hole. Furthermore, we present a time-resolved investigation of the excited state dynamics of the PTCDA film in the femtosecond time regime. We observe a significantly shorter inelastic excited state lifetime compared to findings from time-resolved photoluminescence spectroscopy of PTCDA single crystals which could originate from excitation quenching by the metal substrate.

  3. Hemispherical Asymmetry from Parity-Violating Excited Initial States

    Ashoorioon, Amjad

    2015-01-01

    We investigate if the hemispherical asymmetry in the CMB is produced from parity-violating excited initial condition. We show that in the limit where the deviations from the Bunch-Davies vacuum is large and the scale of new physics is maximally separated from the inflationary Hubble parameter, the primordial power spectrum is modulated only by dipole and quadrupole terms. Requiring the dipole contribution in the power spectrum accounts for the observed power asymmetry, $A=0.07\\pm0.022$, we show that the amount of quadrupole terms is roughly equal to $A^2$, which is still consistent with the bounds from the CMB. The mean local bispectrum which gets enhanced for the excited initial states is within the $1\\sigma$ bound of Planck 2015 results, $f_{\\rm NL}\\simeq 4.17$, but reachable by future CMB experiments. The amplitude of the local non-gaussianity modulates around this mean value, approximately depending on the angle that the short wavelength mode makes with the preferred direction. The amount of variation max...

  4. Excited states of quantum many-body interacting systems: A variational coupled-cluster description

    Xian, Y.

    2007-01-01

    We extend recently proposed variational coupled-cluster method to describe excitation states of quantum many-body interacting systems. We discuss, in general terms, both quasiparticle excitations and quasiparticle-density-wave excitations (collective modes). In application to quantum antiferromagnets, we reproduce the well-known spin-wave excitations, i.e. quasiparticle magnons of spin $\\pm 1$. In addition, we obtain new, spin-zero magnon-density-wave excitations which has been missing in Ans...

  5. Masses of ground and excited-state hadrons

    Roberts, H L L; Cloet, I C; Roberts, C D

    2011-01-01

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

  6. Masses of Ground- and Excited-State Hadrons

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

    2011-07-01

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

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

    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.

  8. Ultrafast Spectroscopy of Delocalized Excited States of the Hydrated Electron

    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

  9. Foil dissociation of fast molecular ions into atomic excited states

    The intensity and polarizations of light emitted from atomic excited states of dissociated molecular ions were measured. The dissociations are induced when fast molecular ions (50 to 500 keV/amu) are transmitted through thin carbon foils. A calculation of multiple scattering and the Coulomb explosion gives the average internuclear separation of the projectile at the foil surface. Experimentally, the foil thickness is varied to give varying internuclear separations at the foil surface and observe the consequent variation in light yield and optical polarization. Using HeH+ projectiles, factors of 1 to 5 enhancements of the light yields from n = 3, 13P,D states of He I and some He II and H I emissions were observed. The results can be explained in terms of molecular level crossings which provide mixings of the various final states during dissociation of the molecular ions at the exit surface. They suggest a short range surface interaction of the electron pick-up followed by a slow molecular dissociation. Alignment measurements confirm the essential features of the model. Observations of Lyman α emission after dissociation of H2+ amd H3+ show rapid variations in light yield for small internuclear separations at the foil surface

  10. Suppression of Excited-State Contributions to Stellar Reaction Rates

    Rauscher, T

    2013-01-01

    It has been shown in previous work [Phys. Rev. Lett. 101, 191101 (2008); Phys. Rev. C 80, 035801 (2009)] that a suppression of the stellar enhancement factor (SEF) occurs in some endothermic reactions at and far from stability. This effect is re-evaluated using the ground-state contributions to the stellar reaction rates, which were shown to be better suited to judge the importance of excited state contributions than the previously applied SEFs. An update of the tables shown in Phys. Rev. C 80, 035801 (2009) is given. The new evalution finds 2350 cases (out of a full set of 57513 reactions) for which the ground-state contribution is larger in the reaction direction with negative reaction Q-value than in the exothermic direction, thus providing exceptions to the commonly applied Q-value rule. The results confirm the Coulomb suppression effect but lead to a larger number of exceptions than previously found. This is due to the fact that often a large variation in the g.s. contribution does not lead to a sizeable...

  11. Dynamics of the excited state intramolecular charge transfer

    The 6-dodecanoyl-2-dimethylaminonaphtalene (laurdan), a derivative of 6-propanoyl- 2-dimethylaminonaphthalene (prodan), has been used as a fluorescent probe in cell imaging, especially in visualizing the lipid rafts by the generalized polarization (GP) images, where GP=(I440-I490)/(I440+I490) with I being the fluorescence intensity. The fluorescence spectrum of laurdan is sensitive to its dipolar environment due to the intramolecular charge transfer (ICT) process in S1 state, which results in a dual emission from the locally excited (LE) and the ICT states. The ICT process and the solvation of the ICT state are very sensitive to the dipolar nature of the environment. In this work, the ICT of laurdan in ethanol has been studied by femtosecond time resolved fluorescence (TRF), especially TRF spectra measurement without the conventional spectral reconstruction method. TRF probes the excited states exclusively, a unique advantage over the pump/probe transient absorption technique, although time resolution of the TRF is generally lower than transient absorption and the TRF spectra measurement was possible only though the spectral reconstruction. Over the years, critical advances in TRF technique have been made in our group to achieve <50 fs time resolution with direct full spectra measurement capability. Detailed ICT and the subsequent solvation processes can be visualized unambiguously from the TRF spectra. Fig. 1 shows the TRF spectra of laurdan in ethanol at several time delays. Surprisingly, two bands at 433 and 476 nm are clearly visible in the TRF spectra of laurdan even at T = 0 fs. As time increases, the band at 476 nm shifts to the red while its intensity increases. The band at 433 nm also shifts slightly to the red, but loses intensity as time increases. The intensity of the 476 nm band reaches maximum at around 5 ps, where it is roughly twice as intense as that at 0 fs, and stays constant until lifetime decay is noticeable. The spectra were fit by two log

  12. Carotenoid excited states: Mystery of the dark states and their roles in relaxation pathways

    Polívka, Tomáš

    Messina : Universitá di Messina, 2008. s. 36. [ESF Workshop on Ultrafast Excited-State Processes in Condensed Phases. 18.06.2008-21.06.2008, Santa Tecla] Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids Subject RIV: BO - Biophysics

  13. Study of excited states of mass=4 hypernuclei

    The excited states, J=1+, of the mirror hypernuclei sub(Λ)sup(4)H and sub(Λsup(4)He were observed by γ-spectroscopy. These hypernuclei were producted by K- absorption in 6Li and 7Li targets. Their identification was given by the detection and the energy measurement of the mesonic decay products: 53 MeV π- for sub(Λ)sup(4)H and 57 MeV π0 for sub(Λ)sup(4)He. A γ line at (1.04+-0.04) MeV has been observed in coincidence with charged pions in the energy range of 40 to 60 MeV then ascribed to a γ-transition in sub(Λ)sup(4)H. Whereas a second γ-line at (1.15+-0.04) MeV, in coincidence with neutral pions of 45 MeV to 75 MeV, has been ascribed to a γ transition in sub(Λ)sup(4)He. With these new experimental data, the phenomenological Λ-N potential for the S-state interaction was recalculated. It may be concluded that the CSB component of this Λ-N potential is spin-independant and that potentials with intrinsic range of 1.5 fm give the bast fit of the total low energy Λ - p elastic scattering cross-sections and to the experimental Bsub(Λ) value for sub(Λ)sup(3)H

  14. Ground States and Excited States in a Tunable Graphene Quantum Dot

    WANG Lin-Jun; CAO Gang; TU Tao; LI Hai-Ou; ZHOU Cheng; HAO Xiao-Jie; GUO Guang-Can; GUO Guo-Ping

    2011-01-01

    We prepare an etched gate tunable quantum dot in single-layer graphene and present transport measurement in this system. We extract the information of the ground states and excited states of the graphene quantum dot, as denoted by the presence of characteristic Coulomb blockade diamond diagrams. The results demonstrate that the quantum dot in single-layer graphene bodes well in future quantum transport study and quantum computing applications.%@@ We prepare an etched gate tunable quantum dot in single-layer graphene and present transport measurement in this system.We extract the information of the ground states and excited states of the graphene quantum dot, as denoted by the presence of characteristic Coulomb blockade diamond diagrams.The results demonstrate that the quantum dot in single-layer graphene bodes well in future quantum transport study and quantum computing applications.

  15. Ground States and Excited States in a Tunable Graphene Quantum Dot

    We prepare an etched gate tunable quantum dot in single-layer graphene and present transport measurement in this system. We extract the information of the ground states and excited states of the graphene quantum dot, as denoted by the presence of characteristic Coulomb blockade diamond diagrams. The results demonstrate that the quantum dot in single-layer graphene bodes well for future quantum transport study and quantum computing applications. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  16. Excited state dipole moments of chloroanilines and chlorophenols from solvatochromic shifts in electronic absorption spectra: Support for the concept of excited state group moments

    Prabhumirashi, L. S.; Satpute, R. S.

    The dipole moments of isomeric o-, m- and p-chloroanilines and chlorophenols in electronically excited L a and L b states are estimated from solvent induced polarization shifts in electronic absorption spectra. It is observed that μ e( L a) > μ e( L b) > μ g, which is consistent with the general theory of polarization red shift. The μ es are found to be approximately co-linear with the corresponding μ gs. The concept of group moments is extended to aromatic molecules in excited states. This approach is found to be useful in understanding correlations among the excited states of mono- and disubstituted benzenes.

  17. One-photon excitation and dissociation of both weakly bound rotational excited states and vibrational excited states of HD2+ and photofragment branching ratio D+/H+ of the final predissociative states

    The presence of weakly bound rotationally excited initial states of HD2+ lying just below the lowest dissociation limit has been observed as well as quasi-bound, predissociative final states above the dissociation limit resulting from one-photon excitation of those weakly bound states. The excitation of the initial weakly bound and possibly only few quasi-bound states took place with 1064 nm laser radiation. The possibility of one-photon excitation of the vibrationally excited initial HD2+ ions is considered. The centre-of-mass kinetic energy distributions of the D+ and H+ fragment were used to identify the possible initial and final states involved in the transitions leading to these fragments. The fragment ratio D+/H+ is shown to be critically dependent on the ion source pressure. A strong preference is observed for the D++HD dissociation channel over the H++D2 channel at high source gas pressures. The centre-of-mass energy of the resulting H+ and D+ fragments was found to agree with predicted theoretical values, and suggest that among initially excited HD2+ ions, only a few of these lie initially above the lowest dissociation limit. (author)

  18. One-photon excitation and dissociation of both weakly bound rotational excited states and vibrational excited states of HD{sub 2}{sup +} and photofragment branching ratio D{sup +}/H{sup +} of the final predissociative states

    Yousif, F.B. [Centro de Ciencias Fisicas, UNAM, Cuernavaca, Morelos (Mexico)]. E-mail: fbyousif@fis.unam.mx; Cisneros, C.; Urquijo, J. de; Alvarez, I. [Centro de Ciencias Fisicas, UNAM, Cuernavaca, Morelos (Mexico)

    2001-03-14

    The presence of weakly bound rotationally excited initial states of HD{sub 2}{sup +} lying just below the lowest dissociation limit has been observed as well as quasi-bound, predissociative final states above the dissociation limit resulting from one-photon excitation of those weakly bound states. The excitation of the initial weakly bound and possibly only few quasi-bound states took place with 1064 nm laser radiation. The possibility of one-photon excitation of the vibrationally excited initial HD{sub 2}{sup +} ions is considered. The centre-of-mass kinetic energy distributions of the D{sup +} and H{sup +} fragment were used to identify the possible initial and final states involved in the transitions leading to these fragments. The fragment ratio D{sup +}/H{sup +} is shown to be critically dependent on the ion source pressure. A strong preference is observed for the D{sup +}+HD dissociation channel over the H{sup +}+D{sub 2} channel at high source gas pressures. The centre-of-mass energy of the resulting H{sup +} and D{sup +} fragments was found to agree with predicted theoretical values, and suggest that among initially excited HD{sub 2}{sup +} ions, only a few of these lie initially above the lowest dissociation limit. (author)

  19. TDDFT study on the excited-state proton transfer of 8-hydroxyquinoline: Key role of the excited-state hydrogen-bond strengthening

    Lan, Sheng-Cheng; Liu, Yu-Hui

    2015-03-01

    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.

  20. Excited-state spectroscopy of single NV defects in diamond using optically detected magnetic resonance

    Using pulsed optically detected magnetic resonance techniques, we directly probe electron-spin resonance transitions in the excited-state of single nitrogen-vacancy (NV) color centers in diamond. Unambiguous assignment of excited state fine structure is made, based on changes of NV defect photoluminescence lifetime. This study provides significant insight into the structure of the emitting 3E excited state, which is invaluable for the development of diamond-based quantum information processing.

  1. The Need, Benefits, and Demonstration of a Minimization Principle for Excited States

    Bacalis, Naoum C

    2015-01-01

    It is shown that the standard methods of computing excited states in truncated spaces must yield wave functions that, beyond truncation, are in principle veered away from the exact, and a remedy is demonstrated via a presented functional, F$_n$, obeying a minimization principle for excited states. It is further demonstrated that near avoided crossings, between two MCSCF 'flipped roots' the wave function that leads to the excited state has the lowest F$_n$.

  2. Structural and excited-state properties of oligoacene crystals from first principles

    Rangel, Tonatiuh; Berland, Kristian; Sharifzadeh, Sahar; Brown-Altvater, Florian; Lee, Kyuho; Hyldgaard, Per; Kronik, Leeor; Neaton, Jeffrey B.

    2016-01-01

    Molecular crystals are a prototypical class of van der Waals (vdW) bound organic materials with excited state properties relevant for optoelectronics applications. Predicting the structure and excited state properties of molecular crystals presents a challenge for electronic structure theory, as standard approximations to density functional theory (DFT) do not capture long range vdW dispersion interactions and do not yield excited state properties. In this work, we use a combination of DFT in...

  3. Excited states in doubly-odd 98Rh

    Excited states in the 98Rh nucleus were populated in the 75As(28Si, 2p3n) fusion-evaporation reaction using the 120 MeV 28Si beam. The experiment was carried out at Inter University Accelerator Centre (IUAC), New Delhi. The 28Si projectiles were provided by the 15UD Pelletron accelerator. The target ∼ 3 mg/cm2 thick (ΔE ∼ 20 MeV) was prepared by vacuum evaporation of natural 75As on to ∼ 10 mg/cm2 natural Pb backing followed by rolling. The 103Ag compound nucleus produced in the present reaction is found to decay via several reaction channels associated with 5-particle emission, viz., p4n (98Pd), 2p3n (98Rh), and αp3n (95Ru) with relative population of ∼ 4%, 13%, and 2%, respectively, 4-particle emission, viz., p3n (99Pd), 2p2n (99Rh), and αp2n (96Ru) with relative population of ∼ 12%, 26%, and 20%, respectively, and 3-particle emission, viz., p2n (100Pd), α2n (97Rh), and 2αn (94Tc) with relative population of ∼ 9%, 6%, and 2%, respectively

  4. Hertzian spectroscopy application to excited states in accelerated ion beams

    It is shown that accelerated ion beams enables the application of optical hertzian spectrometry methods to be extended to research on the excited states of free ionic systems. The photon beat method has proved especially simple to apply in beam foil geometry because of the unidirectional beam velocity while the beam gas device is suitable for experiments of the energy level crossing type. Only the resonance technique involving direct application of high-frequency magnetic fields poses serious problems because of the high HF powers necessary. So far structure intervals have been measured in ions carrying up to three charges (seven in the special case of Lamb shift measurements) with a precision of a few percent. The interest of these structure studies in free ions is emphasized particularly. The study of hydrogen-like or helium-like ions of high Z allows the fundamental calculations of quantum electrodynamics to be checked with regard to the Lamb shift or the spontaneous emission theory. In more complex electronic systems, optical spectroscopy of accelerated ion beams gives wavelengths with a resolution reaching 10-5, lifetimes with an accuracy better than 10% when the cascade effects are properly studied, and Lande factors with a precision of several % under present technical conditions. The photon beat method concerns hyperfine nuclear effects in light atoms of Z<=20. Another line of research study the hyperfine structure of a given configuration in an isoelectronic sequence

  5. A Simple Hubbard Model for the Excited States of $\\pi$ Conjugated -acene Molecules

    Sadeq, Z S

    2015-01-01

    In this paper we present a model that elucidates in a simple way the electronic excited states of $\\pi$ conjugated -acene molecules such as tetracene, pentacene, and hexacene. We use a tight-binding and truncated Hubbard model written in the electron-hole basis to describe the low lying excitations with reasonable quantitative accuracy. We are able to produce semi-analytic wavefunctions for the electronic states of the system, which allows us to compute the density correlation functions for various states such as the ground state, the first two singly excited states, and the lowest lying doubly excited state. We show that in this lowest lying doubly excited state, a state which has been speculated as to being involved in the singlet fission process, the electrons and holes behave in a triplet like manner.

  6. The Structure of the Nucleon and its Excited States

    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

  7. Photodissociation path in H2 + induced by nonuniform optical near fields: Two-step excitation via vibrationally excited states

    Yamaguchi, Maiku; Nobusada, Katsuyuki

    2016-02-01

    In this paper, effects of the spatial nonuniformity of an optical near field (ONF) on the molecular photodissociation process are presented. The dissociation dynamics of H2 + was theoretically investigated by solving a non-Born-Oppenheimer Schrödinger equation. It was found that in addition to two dissociation mechanisms, which are one-photon and three-photon processes induced by uniform laser light excitation, the nonuniform ONF opens another dissociation path: two-step excitation mediated by vibrationally excited states. The nonuniformity of the ONF causes a transition between vibrational states that is forbidden according to conventional selection rules, leading to the dissociation path. The dependences of photodissociation on the intensity and nonuniformity of the ONF were calculated and the results validated the two-step dissociation mechanism.

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

    Filatov, Mikhail A.

    2015-10-13

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

  9. Probing an Excited-State Atomic Transition Using Hyperfine Quantum Beat Spectroscopy

    Wade, Christopher G; Keaveney, James; Adams, Charles S; Weatherill, Kevin J

    2014-01-01

    We describe a method to observe the dynamics of an excited-state transition in a room temperature atomic vapor using hyperfine quantum beats. Our experiment using cesium atoms consists of a pulsed excitation of the D2 transition, and continuous-wave driving of an excited-state transition from the 6P$_{3/2}$ state to the 7S$_{1/2}$ state. We observe quantum beats in the fluorescence from the 6P$_{3/2}$ state which are modified by the driving of the excited-state transition. The Fourier spectrum of the beat signal yields evidence of Autler-Townes splitting of the 6P$_{3/2}$, F = 5 hyperfine level and Rabi oscillations on the excited-state transition. A detailed model provides qualitative agreement with the data, giving insight to the physical processes involved.

  10. Excited state lifetime during photostimulated desorption of no from a Pt surface

    Magkoev, T. T.

    1998-07-01

    We analyze the rotational energy distribution N(J) for NO molecules desorbed from a Pt (111) surface, taking into account the valence electron excitations, using a simple impulse model. We find a linear dependence between ln N(J) and (Er)1/2, where Er is the rotational energy of the desorbed molecules. The excited state lifetime and the critical residence time in the excited state, evaluated from the given dependences, are close to each other, and in order of magnitude are 10-15 s. We also estimate the frequency and amplitude of the tilting vibrations of the adsorbed molecules in the excited state.

  11. A Dark Excited State of Fluorescent Protein Chromophores, Considered as Brooker Dyes

    Olsen, Seth

    2010-01-01

    The green fluorescent protein (GFP) chromophore is an asymmetric monomethine dye system. In the resonance color theory of dyes, a strong optical excitation arises from interactions of two valence-bond structures with a third, higher structure. We use correlated quantum chemistry to show that the anionic chromophore is a resonant Brooker dye, and that the third structure corresponds to a higher stationary electronic state of this species. The excitation energy of this state should be just below the first excitation energy of the neutral form. This has implications for excited state mechanism in GFPs, which we discuss.

  12. Two-mode excited entangled coherent states and their entanglement properties

    Zhou Dong-Lin; Kuang Le-Man

    2009-01-01

    This paper introduces two types of two-mode excited entangled coherent states(TMEECSs)|Ψ±(α,m,n)>,studies their entanglement characteristics,and investigates the influence of photon excitations on quantum entanglement.It shows that for the state|Ψ+(α,m,m)>the two-mode photon excitations affect seriously entanglement character while the state |Ψ-(α,m,m)>is always a maximally entangled state,and shows how such states can be produced by using cavity quantum electrodynamics and quantum measurements.It finds that the entanglement amount of the TMEECSs is larger than that of the single-mode excited entangled coherent states with the same photon excitation number.

  13. State-averaged Monte Carlo configuration interaction applied to electronically excited states

    Coe, J P

    2014-01-01

    We introduce state-averaging into the method of Monte Carlo configuration interaction (SA-MCCI) to allow the stable and efficient calculation of excited states. We show that excited potential curves for H$_{3}$, including a crossing with the ground state, can be accurately reproduced using a small fraction of the FCI space. A recently introduced error measure for potential curves [J. P. Coe and M. J. Paterson, J. Chem. Phys., 137, 204108 (2012)] is shown to also be a fair approach when considering potential curves for multiple states. We demonstrate that potential curves for LiF using SA-MCCI agree well with the FCI results and the avoided crossing occurs correctly. The seam of conical intersections for CH$_{2}$ found by Yarkony [J. Chem. Phys., 104, 2932 (1996)] is used as a test for SA-MCCI and we compare potential curves from SA-MCCI with FCI results for this system for the first three triplet states. We then demonstrate the improvement from using SA-MCCI on the dipole of the $2$ $^{1}A_{1}$ state of carbo...

  14. Optimization of Ground- and Excited-State Wave Functions and van der Waals Clusters

    A quantum Monte Carlo method is introduced to optimize excited-state trial wave functions. The method is applied in a correlation function Monte Carlo calculation to compute ground- and excited-state energies of bosonic van der Waals clusters of up to seven particles. The calculations are performed using trial wave functions with general three-body correlations

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

    Harbola, Manoj K.; Samal, Prasanjit

    2004-01-01

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

  16. Ultrafast dynamics and excited state deactivation of [Ru(bpy)2Sq]+ (Ru-Sq)

    Excited state dynamics of Ru-Sq has been studied using time resolved transient absorption spectroscopy with a time resolution of about 100fs. [Ru(bpy)2Sq]+, where bpy is the bipyridyl and Sq is the semi quinone is known to have two ground state absorption bands corresponding to two different metal to ligand charge transfer (MLCT) states. The absorption band centered on 460 nm is assigned to Ru(d) to bpy (π*) and the one on 890 nm is assigned to Ru(d) to Sq(π*). Significantly different excited state relaxation dynamics for both the MLCT states have been observed exciting both the bands separately. (author)

  17. Influence of multiple excitation of low lying states and giant resonances on heavy ion inelastic spectra

    The inelastic excitation probabilities of 40Ca, 90Zr and 208Pb impinged by 40Ca projectiles at bombarding energies between 10 and 100 MeV/nucleon are calculated in a model where the excitation amplitudes are evaluated along classical trajectories. The excited states are calculated in the random phase approximation and the nuclear and Coulomb excitations of both low lying states and giant resonances of the target and projectile are taken into account. A general feature of the calculated spectra for near grazing impact parameters and bombarding energies above 20 MeV/nucleon is the presence of broad regularly-spaced structures mainly due to the excitation of multiphonon states built with giant resonances. Cross section estimates for the inelastic excitations are given

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

    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.

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

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

    Kowalczyk, Tim; Le, Khoa; Irle, Stephan

    2016-01-12

    We present an implementation of energies and gradients for the ΔDFTB method, an analogue of Δ-self-consistent-field density functional theory (ΔSCF) within density-functional tight-binding, for the lowest singlet excited state of closed-shell molecules. Benchmarks of ΔDFTB excitation energies, optimized geometries, Stokes shifts, and vibrational frequencies reveal that ΔDFTB provides a qualitatively correct description of changes in molecular geometries and vibrational frequencies due to excited-state relaxation. The accuracy of ΔDFTB Stokes shifts is comparable to that of ΔSCF-DFT, and ΔDFTB performs similarly to ΔSCF with the PBE functional for vertical excitation energies of larger chromophores where the need for efficient excited-state methods is most urgent. We provide some justification for the use of an excited-state reference density in the DFTB expansion of the electronic energy and demonstrate that ΔDFTB preserves many of the properties of its parent ΔSCF approach. This implementation fills an important gap in the extended framework of DFTB, where access to excited states has been limited to the time-dependent linear-response approach, and affords access to rapid exploration of a valuable class of excited-state potential energy surfaces. PMID:26587877

  1. Ground and Excited States of Bipolarons in Two and Three Dimensions

    RUAN Yong-Hong; CHEN Qing-Hu

    2007-01-01

    The properties of large bipolarons in two and three dimensions are investigated by averaging over the relative wavefunction of the two electrons and using the Lee-Low-Pines-Huybrechts variational method. The groundstate (GS) and excited-state energies of the Fr(o)hlich bipolaron for the whole range of electron-phonon coupling constants can be obtained. The energies of the first relaxed excited state (RES) and Franck-Condon (FC) excited state of the bipolaron are also calculated. It is found that the first RES energy is lower than the FC state energy. The comparison of our GS and RES energies with those in literature is also given.

  2. Continuum excitations of $^{26}$O in a three-body model: $0^+$ and $2^+$ states

    Grigorenko, L V

    2015-01-01

    The structure and decay dynamics for $0^+$ and $2^+$ continuum excitations of $^{26}$O are investigated in a three-body $^{24}$O+$n$+$n$ model. Validity of a simple approximation for the cross section profile for long-lived $2n$ emission is demonstrated. Sequence of three $0^+$ monopole ("breathing mode" type) excited states is predicted. These states could probably be interpreted as analogues of Efimov states pushed into continuum by insufficient binding. The possible energies of the $2^+$ states are related to excitation spectrum of $^{25}$O. We discuss possible connection of predicted $^{26}$O spectrum with observations.

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

    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.

  4. Excited triplet states as photooxidants in surface waters

    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

  5. Dual channel nitrogen laser useful for nanosecond excited state studies

    Shipman (1967) adapted the Blumlein discharge circuit to lasers and this method has proved highly useful in producing high peak pulses. The authors describe a double Blumlein producing two 250 kW pulses separated by 15 nanosecs. The dual channel nitrogen laser is designed for use in atomic spectroscopy, the first pulse excites the target atoms while the second pumps another laser whose output is used to study the levels. (U.S.)

  6. Suppression of excited-state effects in lattice determination of nucleon electromagnetic form factors

    von Hippel, G M; Djukanovic, D; Hua, J; Jäger, B; Junnarkar, P; Meyer, H B; Rae, T D; Wittig, H

    2014-01-01

    We study the ability of a variety of fitting techniques to extract the ground state matrix elements of the vector current from ratios of nucleon three- and two-point functions that contain contaminations from excited states. Extending our high-statistics study of nucleon form factors, we are able to demonstrate that the treatment of excited-state contributions in conjunction with approaching the physical pion mass has a significant impact on the $Q^2$-dependence of the form factors.

  7. Heme photolysis occurs by ultrafast excited state metal-to-ring charge transfer.

    Franzen, S.; Kiger, L.; Poyart, C; Martin, J.L.

    2001-01-01

    Ultrafast time-resolved resonance Raman spectra of carbonmonoxy hemoglobin (Hb), nitroxy Hb, and deoxy Hb are compared to determine excited state decay mechanisms for both ligated and unligated hemes. Transient absorption and Raman data provide evidence for a sequential photophysical relaxation pathway common to both ligated and unligated forms of Hb* (photolyzed heme), in which the excited state 1Q decays sequentially: 1Q-->Hb*I-->Hb*II-->Hb ground state. Consistent with the observed kinetic...

  8. Carbazole-containing light- emitting polymers: Properties of excited states

    2003-01-01

    A series of light-emitting conjugated polymers alternatively involving carbazole and bivinylene arylene moieties in the main chain were synthesized via Wittig-Horner type copolymerization. The photoinduced charge transfer process relating to these polymers was investigated by using the technique of fluorescence spectroscopy. The interaction between excited copolymers and C60 in benzene solution was studied. The fluorescence quenching can be well described by the "sphere-of-action" mechanism. It is believed that two basic steps are involved in the quenching process, i.e. the diffusion of excitation within the conjugated polymers and the dissociation of the exctions trapped by fullerene. The radius of the sphere-of-action can be related to the excitation diffusion length, which depends on the lifetime of the exciton. The dynamic fluorescence quenching of the copolymers by another quencher, 1,4-dicyanobenzene (DCB) was also surveyed. Copolymers with different chain conformations show different temperature effects in the dynamic quenching. A planar conformation is beneficial for the quenching via bimolecular collision.

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

    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.

  10. Characterization of ground state entanglement by single-qubit operations and excitation energies

    Giampaolo, S M; Illuminati, F; Verrucchi, P; Giampaolo, Salvatore M.; Illuminati, Fabrizio; Siena, Silvio De; Verrucchi, Paola

    2006-01-01

    We consider single-qubit unitary operations and study the associated excitation energies above the ground state of interacting quantum spins. We prove that there exists a unique operation such that the vanishing of the corresponding excitation energy determines a necessary and sufficient condition for the separability of the ground state. We show that the energy difference associated to factorization exhibits a monotonic behavior with the one-tangle and the entropy of entanglement, including non analiticity at quantum critical points. The single-qubit excitation energy thus provides an independent, directly observable characterization of ground state entanglement, and a simple relation connecting two universal physical resources, energy and nonlocal quantum correlations.

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

    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 S0, T1, and S1 states. We have uncovered four nonadiabatic photodecarboxylation paths. (i) The S1 system relaxes via an excited-state intramolecular proton transfer (ESIPT) to a hydrogen-transferred tautomer, near which an S1/S0 conical intersection funnels the S1 to S0 state. Then, some trajectories continue completing the decarboxylation reaction in the S0 state; the remaining trajectories via a reverse hydrogen transfer return to the S0 minimum, from which a thermal decarboxylation reaction occurs. (ii) Due to a small S1 −T1 energy gap and a large S1/T1 spin-orbit coupling, an efficient S1 → T1 intersystem crossing process happens again near this S1/S0 conical intersection. When decaying to T1 state, a direct photodecarboxylation proceeds. (iii) Prior to ESIPT, the S1 system first decays to the T1 state via an S1 → T1 intersystem crossing; then, the T1 system evolves to a hydrogen-transferred tautomer. Therefrom, an adiabatic T1 decarboxylation takes place due to a small barrier of 7.7 kcal/mol. (iv) Besides the aforementioned T1 ESIPT process, there also exists a comparable Norrish type I reaction in the T1 state, which forms the ground-state products of CH3CO and COOH. Finally, we have found that ESIPT plays an important role. It closes the S1-T1 and S1-S0 energy gaps, effecting an S1/T1/S0 three-state intersection region, and mediating nonadiabatic photodecarboxylation reactions of pyruvic acid

  12. Bound states and entanglement in the excited states of quantum spin chains

    We investigate the entanglement properties of the excited states of the spin- (1/2) Heisenberg (XXX) chain with isotropic antiferromagnetic interactions, by exploiting the Bethe ansatz solution of the model. We consider eigenstates obtained from both real and complex solutions (‘strings’) of the Bethe equations. Physically, the former are states of interacting magnons, whereas the latter contain bound states of groups of particles. We first focus on the situation with few particles in the chain. Using exact results and semiclassical arguments, we derive an upper bound SMAX for the entanglement entropy. This exhibits an intermediate behaviour between logarithmic and extensive, and it is saturated for highly-entangled states. As a function of the eigenstate energy, the entanglement entropy is organized in bands. Their number depends on the number of blocks of contiguous Bethe–Takahashi quantum numbers. In the presence of bound states a significant reduction in the entanglement entropy occurs, reflecting that a group of bound particles behaves effectively as a single particle. Interestingly, the associated entanglement spectrum shows edge-related levels. At a finite particle density, the semiclassical bound SMAX becomes inaccurate. For highly-entangled states SA∝ Lc, with Lc the chord length, signalling the crossover to extensive entanglement. Finally, we consider eigenstates containing a single pair of bound particles. No significant entanglement reduction occurs, in contrast with the few-particle case. (paper)

  13. Effects of crossed states on photoluminescence excitation spectroscopy of InAs quantum dots

    Lin Chien-Hung

    2011-01-01

    Full Text Available Abstract In this report, the influence of the intrinsic transitions between bound-to-delocalized states (crossed states or quasicontinuous density of electron-hole states on photoluminescence excitation (PLE spectra of InAs quantum dots (QDs was investigated. The InAs QDs were different in size, shape, and number of bound states. Results from the PLE spectroscopy at low temperature and under a high magnetic field (up to 14 T were compared. Our findings show that the profile of the PLE resonances associated with the bound transitions disintegrated and broadened. This was attributed to the coupling of the localized QD excited states to the crossed states and scattering of longitudinal acoustical (LA phonons. The degree of spectral linewidth broadening was larger for the excited state in smaller QDs because of the higher crossed joint density of states and scattering rate.

  14. $\\sigma$-SCF: A Direct Energy-targeting Method To Mean-field Excited States

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

    2016-01-01

    The mean-field solutions of electronic excited states are much less accessible than ground state (e.g.\\ Hartree-Fock) solutions. Energy-based optimization methods for excited states, like $\\Delta$-scf, tend to fall into the lowest solution consistent with a given symmetry -- a problem known as "variational collapse". In this work, we combine the ideas of direct energy-targeting and variance-based optimization in order to describe excited states at the mean-field level. The resulting method, $\\sigma$-scf, has several advantages. First, it allows one to target any desired excited state by specifying a single parameter: a guess of the energy of that state. It can therefore, in principle, find \\emph{all} excited states. Second, it avoids variational collapse by using a variance-based, unconstrained local minimization. As a consequence, all states -- ground or excited -- are treated on an equal footing. Third, it provides an alternate approach to locate $\\Delta$-scf solutions that are otherwise inaccessible by the...

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

    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.

  16. Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy.

    Shelby, Megan L; Lestrange, Patrick J; Jackson, Nicholas E; Haldrup, Kristoffer; Mara, Michael W; Stickrath, Andrew B; Zhu, Diling; Lemke, Henrik T; Chollet, Matthieu; Hoffman, Brian M; Li, Xiaosong; Chen, Lin X

    2016-07-20

    Photoexcited Nickel(II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through multiple electronic states following an initial porphyrin-based excitation, some involving metal centered electronic configuration changes that could be harnessed catalytically before excited state relaxation. While a NiTMP excited state present at 100 ps was previously identified by X-ray transient absorption (XTA) spectroscopy at a synchrotron source as a relaxed (d,d) state, the lowest energy excited state (J. Am. Chem. Soc., 2007, 129, 9616 and Chem. Sci., 2010, 1, 642), structural dynamics before thermalization were not resolved due to the ∼100 ps duration of the available X-ray probe pulse. Using the femtosecond (fs) X-ray pulses of the Linac Coherent Light Source (LCLS), the Ni center electronic configuration from the initial excited state to the relaxed (d,d) state has been obtained via ultrafast Ni K-edge XANES (X-ray absorption near edge structure) on a time scale from hundreds of femtoseconds to 100 ps. This enabled the identification of a short-lived Ni(I) species aided by time-dependent density functional theory (TDDFT) methods. Computed electronic and nuclear structure for critical excited electronic states in the relaxation pathway characterize the dependence of the complex's geometry on the electron occupation of the 3d orbitals. Calculated XANES transitions for these excited states assign a short-lived transient signal to the spectroscopic signature of the Ni(I) species, resulting from intramolecular charge transfer on a time scale that has eluded previous synchrotron studies. These combined results enable us to examine the excited state structural dynamics of NiTMP prior to thermal relaxation and to capture intermediates of potential photocatalytic significance. PMID:27286410

  17. Neutral Fermion Excitations in the Moore-Read state at \

    Moller, Gunnar; Wojs, Arkadiusz; Cooper, Nigel R.

    2010-01-01

    We present evidence supporting the weakly paired Moore-Read phase in the half-filled second Landau level, focusing on some of the qualitative features of its excitations. Based on numerical studies, we show that systems with odd particle number at the flux $N_\\phi=2N-3$ can be interpreted as a neutral fermion mode of one unpaired fermion, which is gapped. The mode is found to have two distinct minima, providing a signature that could be observed by photoluminescence. In the presence of two qu...

  18. Thermodynamical property of entanglement entropy for excited states.

    Bhattacharya, Jyotirmoy; Nozaki, Masahiro; Takayanagi, Tadashi; Ugajin, Tomonori

    2013-03-01

    We argue that the entanglement entropy for a very small subsystem obeys a property which is analogous to the first law of thermodynamics when we excite the system. In relativistic setups, its effective temperature is proportional to the inverse of the subsystem size. This provides a universal relationship between the energy and the amount of quantum information. We derive the results using holography and confirm them in two-dimensional field theories. We will also comment on an example with negative specific heat and suggest a connection between the second law of thermodynamics and the strong subadditivity of entanglement entropy. PMID:23496702

  19. Semiclassical hyperspherical matrix elements for helium doubly excited states

    A classical description of the two-electron atom, analogous to the quantum adiabatic hyperspherical channel approach, is presented. The classical problems, analogue to the quantum eigenvalue problem for the great angular momentum operator, and the separated dynamical systems defined by each of the other constants of the motion of the non-interacting system are solved, using the Hamiltonian-Jacobi method. Some matrix elements of the Coulomb interaction terms of the Hamilton for doubly excited helium atom using the Heisenberg correspondence principle are calculated. (author). 26 refs, 4 tabs

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

    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

  1. Structural and excited-state properties of oligoacene crystals from first principles

    Rangel, Tonatiuh; Berland, Kristian; Sharifzadeh, Sahar; Brown-Altvater, Florian; Lee, Kyuho; Hyldgaard, Per; Kronik, Leeor; Neaton, Jeffrey B.

    2016-03-01

    Molecular crystals are a prototypical class of van der Waals (vdW) bound organic materials with excited-state properties relevant for optoelectronics applications. Predicting the structure and excited-state properties of molecular crystals presents a challenge for electronic structure theory, as standard approximations to density functional theory (DFT) do not capture long-range vdW dispersion interactions and do not yield excited-state properties. In this work, we use a combination of DFT including vdW forces, using both nonlocal correlation functionals and pairwise correction methods, together with many-body perturbation theory (MBPT) to study the geometry and excited states, respectively, of the entire series of oligoacene crystals, from benzene to hexacene. We find that vdW methods can predict lattice constants within 1% of the experimental measurements, on par with the previously reported accuracy of pairwise approximations for the same systems. We further find that excitation energies are sensitive to geometry, but if optimized geometries are used MBPT can yield excited-state properties within a few tenths of an eV from experiment. We elucidate trends in MBPT-computed charged and neutral excitation energies across the acene series and discuss the role of common approximations used in MBPT.

  2. Direct excitation of high-orbital-angular-momentum states of rare-gas atoms by electron impact

    Tarr, S.M.; Schiavone, J.A.; Freund, R.S.

    1980-12-01

    Narrow threshold peaks are observed in the excitation functions for high-Rydberg states of the rare-gas atoms. They are considered to be evidence for the direct excitation of high-orbital-angular-momentum (l) states.

  3. Hyperon and charmed baryon masses and nucleon excited states from lattice QCD

    Alexandrou, Constantia

    2014-01-01

    We discuss the status of current dynamical lattice QCD simulations in connection to the emerging results on the strange and charmed baryon spectrum, excited states of the nucleon and the investigation of the structure of scalar mesons.

  4. Notes on entanglement entropy for excites holographic states in 2d

    Rashkov, Radoslav C

    2016-01-01

    In this work we revisit the problem of contributions of excited holographic states to the entanglement entropy in two-dimensional conformal field theories. Using the results of replica trick method we find three expressions for these contributions. First, we express the contribution of the excited states in terms of Aharonov invariants. It is shown that beside the Schwarzian, the one-point functions of descendants of energy-momentum also contribute. Given Schwarz-Christoffel map, the contributions to any order can be easily computed. The second expression relates the entanglement entropy of excited states to Faber polynomials and Grunsky coefficients. Based on the relation of Grunsky coefficiens to tau-funcion of dispersionless Toda hierarchy, we find the third expression for contributions of excited holographic states to the entanglement entropy.

  5. Inelastic WIMP-nucleus scattering to the first excited state in $^{125}$Te

    Vergados, J D; Kortelainen, M; Pirinen, P; Srivastava, P C; Suhonen, J; Thomas, A W

    2016-01-01

    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 some nuclei, which have sufficiently low lying excited states. Examples considered previously were the first excited states of $^{127}$I and $^{129}$Xe and $^{83}$Kr. Here we examine $^{125}$Te, 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.

  6. Theoretical direct WIMP detection rates for inelastic scattering to excited states

    The recent WMAP and Planck data have confirmed that exotic dark matter together with the vacuum energy (cosmological constant) dominate in the flat Universe. Many extensions of the standard model provide dark matter candidates, in particular Weakly Interacting Massive Particles (WIMPs). Thus the direct dark matter detection is central to particle physics and cosmology. Most of the research on this issue has hitherto focused on the detection of the recoiling nucleus. In this paper we study transitions to the excited states, possible in some nuclei, which have sufficiently low lying excited states. Good examples are the first excited states of 127I and 129Xe. We find appreciable branching ratios for the inelastic scattering mediated by the spin cross sections. So, in principle, the extra signature of the gamma ray following the de-excitation of these states can, in principle, be exploited experimentally

  7. Dark excited states of carotenoid in light harvesting complex probing with femtosecond stimulated Raman spectroscopy

    Sakai S.

    2013-03-01

    Full Text Available Vibrational dynamics of dark excited states in carotenoids have been investigated using tunable Raman pump pulses. The S1 state has same vibrational dynamics in light-harvesting complex (LH1 and solution. The S* state in LH1 has similar vibrational modes with the triplet state of carotenoid. However, the so-called S* state in solution does not have the modes and is concluded to be different from the S* state in LH1.

  8. Excited-state absorption and radiative up-conversion in porphyrin-doped gels

    Wang, X.; Yates, L. M., III; Knobbe, Edward T.

    1994-10-01

    Optical absorption and emission behavior have been investigated in aluminosilicate sol-gel materials containing the sodium salt of tetra-4-sulfonatophenylporphyrinatocopper(II). Concentration-dependent nonlinear absorption was observed in the porphyrin-doped specimens. Up-converted optical emission from the second excited doublet band was studied, and a saturated behavior was observed as a function of incoming excitation energies. These phenomena have been attributed to excited state absorption from both doublet and quartet manifolds. Intersystem crossing and quartet-quartet absorption effects are believed to dominate the nonlinear processes, especially in the case of strong excitation. Rate equation analysis also suggests that the quartet manifold is extensively involved for intersystem relaxation and excited state absorption. Good agreement was obtained between experimental observations and the presented rate equations.

  9. Mixed symmetry states and isospin excitation in N = Z nucleus 52Fe

    2008-01-01

    The interacting boson model with isospin (IBM-3) was applied to study the band structure and electromagnetic transition properties of the low-lying states in the even-even N = Z nucleus 52Fe. The isospin excitation states with T = 0, 1 and 2 were identified, and compared with the available data. The study shows that the 2+3 state is the lowest mixed symmetry state in 52Fe. The excitation energy of the second 0+2 state with T = 0 in nucleus 52Fe was identified. The model calculations with the data show a reasonably good agreement.

  10. Multiple-Resonance Local Wave Functions for Accurate Excited States in Quantum Monte Carlo.

    Zulfikri, Habiburrahman; Amovilli, Claudio; Filippi, Claudia

    2016-03-01

    We introduce a novel class of local multideterminant Jastrow-Slater wave functions for the efficient and accurate treatment of excited states in quantum Monte Carlo. The wave function is expanded as a linear combination of excitations built from multiple sets of localized orbitals that correspond to the bonding patterns of the different Lewis resonance structures of the molecule. We capitalize on the concept of orbital domains of local coupled-cluster methods, which is here applied to the active space to select the orbitals to correlate and construct the important transitions. The excitations are further grouped into classes, which are ordered in importance and can be systematically included in the Jastrow-Slater wave function to ensure a balanced description of all states of interest. We assess the performance of the proposed wave function in the calculation of vertical excitation energies and excited-state geometry optimization of retinal models whose π → π* state has a strong intramolecular charge-transfer character. We find that our multiresonance wave functions recover the reference values of the total energies of the ground and excited states with only a small number of excitations and that the same expansion can be flexibly used at very different geometries. Furthermore, significant computational saving can also be gained in the orbital optimization step by selectively mixing occupied and virtual orbitals based on spatial considerations without loss of accuracy on the excitation energy. Our multiresonance wave functions are therefore compact, accurate, and very promising for the calculation of multiple excited states of different character in large molecules. PMID:26761421

  11. Counting the number of excited states in organic semiconductor systems using topology

    Catanzaro, Michael J. [Department of Mathematics, Wayne State University, 656 W. Kirby, Detroit, Michigan 48202 (United States); Shi, Tian [Department of Chemistry, Wayne State University, 5101 Cass Ave., Detroit, Michigan 48202 (United States); Tretiak, Sergei, E-mail: serg@lanl.gov [Theoretical Division, Center for Nonlinear Studies, and Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Chernyak, Vladimir Y., E-mail: chernyak@chem.wayne.edu [Department of Mathematics, Wayne State University, 656 W. Kirby, Detroit, Michigan 48202 (United States); Department of Chemistry, Wayne State University, 5101 Cass Ave., Detroit, Michigan 48202 (United States)

    2015-02-28

    Exciton scattering theory attributes excited electronic states to standing waves in quasi-one-dimensional molecular materials by assuming a quasi-particle picture of optical excitations. The quasi-particle properties at branching centers are described by the corresponding scattering matrices. Here, we identify the topological invariant of a scattering center, referred to as its winding number, and apply topological intersection theory to count the number of quantum states in a quasi-one-dimensional system.

  12. Distribution of populations in excited states of electrodeless discharge lamp of Rb atoms

    TAO ZhiMing; WANG YanFei; HONG YeLong; WANG DongYing; ZHANG ShengNan; ZHUANG Wei; CHEN JingBiao

    2013-01-01

    The intensity of fluorescence spectral lines of Rb atoms in the region of 350-1110 nm is measured in eletrodeless discharge lamp.The population ratio between the excited states is calculated according to the spontaneous transition probabilities with rate equations.At the same time,the population density of energy level is also obtained.The results provide the potential applications of electrodeless discharge lamp in atomic filter and optical frequency reference at higher excited states without a pumping laser.

  13. Sum rule analysis of vector and axial-vector spectral functions with excited states in vacuum

    Hohler, Paul M.; Rapp, Ralf

    2012-01-01

    We simultaneously analyze vector and axial-vector spectral functions in vacuum using hadronic models constrained by experimental data and the requirement that Weinberg-type sum rules are satisfied. Upon explicit inclusion of an excited vector state, viz. rho', and the requirement that the perturbative continua are degenerate in vector and axial-vector channels, we deduce the existence of an excited axial-vector resonance state, a1', in order that the Weinberg sum rules are satisfied. The resu...

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

    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

  15. High-energy excited states in {sup 98}Cd

    Braun, Norbert; Blazhev, Andrey; Jolie, Jan [Institut fuer Kernphysik, Universitaet Koeln (Germany); Boutachkov, Plamen; Gorska, Magda; Grawe, Hubert; Pietri, Stephane [GSI, Darmstadt (Germany); Brock, Tim; Nara Singh, B.S.; Wadsworth, Robert [Department of Physics, University of York, York (United Kingdom); Liu, Zhong [University of Edinburgh, Edinburgh (United Kingdom)

    2009-07-01

    Studies of isomerism in the proton-rich N {approx_equal}Z nuclei around {sup 100}Sn give important insights into the role of proton-neutron pairing and also serve as testing grounds for nuclear models. In summer 2008, an experiment on {sup 96,97,98}Cd was performed using the FRS fragment separator and the RISING germanium array at GSI. These exotic nuclei of interest were produced using fragmentation of a 850 MeV/u {sup 124}Xe beam on a 4 g/cm{sup 2} {sup 9}Be target and finally implanted into an active stopper consisting of 9 double-sided silicon strip detectors. In {sup 98}Cd, a new high-energy isomeric transition was identified. Preliminary results on {sup 98}Cd are presented and their implications for the high-excitation level scheme are discussed.

  16. First observation of excited states in 108Sb

    A spectroscopic study of 108Sb has been carried out as a part of a larger experiment where in total twenty-nine different residual nuclei were identified. This study gives the first information on excited levels in this nucleus. A low-lying two-quasi-particle multiplet together with some of the higher lying levels are discussed within the framework of the nuclear shell model. A rotational, strongly coupled, band is identified as, most likely, being built on the deformed πg9/2-1xνh11/2 configuration in accordance with total routhian surface calculations. Tentative spins and parities are presented as well as B(M1)/B(E2) ratios for some of the transitions in the strongly coupled band. ((orig.))

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

    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.

  18. Relativistic Hartree-Fock-Bogoliubov theory: ground states and excitations

    Long, Wen Hui; Meng, Jie; Giai, Nguyen Van

    The covariant density functional (CDF) theory with the Fock diagrams, the indivisible part of the effective nuclear interaction, is introduced, including both the relativistic Hartree-Fock and its extension -- the relativistic Hartree-Fock-Bogoliubov methods. The specific roles played by Fock diagrams, particularly for the new degrees of freedom associated with the π and ρ-tensor fields and the non-local mean fields, are discussed in determining the nuclear energy functional, the shell structure and the evolution, and nuclear isospin excitations. The existing problems and limits of the CDF theory with Fock terms are also discussed, and the perspective on a new algorithm of dealing with the non-local Fock terms is given.

  19. A theoretical study of electronic excited states of photosynthetic reaction center in Rhodopseudomonas viridis

    2006-01-01

    The electronic singlet vertical excited states of photosynthetic reaction center (PSRC) in Rhodopseudomonas (Rps.) viridis were investigated by ZINDO and INDO/S methods. The effects of the interactions of pigment-pigment and pigment-protein on the electronic excitations were examined. The calculation results showed that the interactions of pigment-pigment and pigment-protein play an important role in reasonably assigning the experimental absorption and circular dichroism (CD) spectra of PSRC in Rps. virids. By comparing the theoretically computed excited states with the experimental absorption and CD spectra, satisfactory assignments of the experimental spectroscopic peaks were achieved.

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

    Sundstrom, Eric J., E-mail: eric.jon.sundstrom@berkeley.edu; Head-Gordon, Martin [Department of Chemistry, University of California Berkeley, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2014-03-21

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

  1. Excited state evolution towards ligand loss and ligand chelation at group 6 metal carbonyl centres.

    Manton, Jennifer C; Amirjalayer, Saeed; Coleman, Anthony C; McMahon, Suzanne; Harvey, Emma C; Greetham, Gregory M; Clark, Ian P; Buma, Wybren Jan; Woutersen, Sander; Pryce, Mary T; Long, Conor

    2014-12-21

    The photochemistry and photophysics of three model "half-sandwich" complexes (η(6)-benzophenone)Cr(CO)3, (η(6)-styrene)Cr(CO)3, and (η(6)-allylbenzene)Cr(CO)3 were investigated using pico-second time-resolved infrared spectroscopy and time-dependent density functional theory methods. The (η(6)-benzophenone)Cr(CO)3 complex was studied using two excitation wavelengths (470 and 320 nm) while the remaining complexes were irradiated using 400 nm light. Two independent excited states were detected spectroscopically for each complex, one an unreactive excited state of metal-to-arene charge-transfer character and the other with metal-to-carbonyl charge transfer character. This second excited state leads to an arrested release of CO on the pico-second time-scale. Low-energy excitation (470 nm) of (η(6)-benzophenone)Cr(CO)3 populated only the unreactive excited state which simply relaxes to the parent complex. Higher energy irradiation (320 nm) induced CO-loss. Irradiation of (η(6)-styrene)Cr(CO)3, or (η(6)-allylbenzene)Cr(CO)3 at 400 nm provided evidence for the simultaneous population of both the reactive and unreactive excited states. The efficiency at which the unreactive excited state is populated depends on the degree of conjugation of the substituent with the arene π-system and this affects the efficiency of the CO-loss process. The quantum yield of CO-loss is 0.50 for (η(6)-allylbenzene)Cr(CO)3 and 0.43 for (η(6)-styrene)Cr(CO)3. These studies provide evidence for the existence of two photophysical routes to CO loss, a minor ultrafast route and an arrested mechanism involving the intermediate population of a reactive excited state. This reactive excited state either relaxes to reform the parent species or eject CO. Thus the quantum yield of the CO-loss is strongly dependent on the excitation wavelength. Time-dependent density functional theory calculations confirm that the state responsible for ultrafast CO-loss has significant metal-centred character while

  2. Study on even-parity highly excited states of the Sm atom

    Zhao Yanhong; Dai Changjian; Ye Shiwei, E-mail: daicj@126.com [School of Science, Tianjin University of Technology, Tianjin 300384 (China)

    2011-10-14

    Spectra of even-parity highly excited states of the Sm atom have been systematically studied using the two-color three-step excitation and photoionization detection method. With three different excitation paths distinguished by three different intermediate states with the 4f{sup 6}6s6p configuration, the atom is resonantly excited to given highly excited states in the energy region between 30 040 and 38 065 cm{sup -1}, where it is detected by photoionization. The wavelength of the second laser is scanned from 440 to 700 nm, while that of the first laser is fixed at 638.96, 636.92 or 627.50 nm. Based on precise calibration of the wavelength, the energy levels of 198 even-parity states are determined with the relative line intensities of the related transitions. A unique value of J, the total angular momentum, is assigned to all detected states by comparing the three spectra obtained with the different excitation paths. Except that the energy levels of 113 states are confirmed in this work, the rest of the information mentioned above has not been previously reported.

  3. The structure of the ground state and low excited states of quantum fluids

    The structure of the ground state of a quantum fluid is described in terms of the pair correlation function and pair-pair correlation function, which are the response functions to first and second order scattering respectively. Results are presented for the pair-pair correlation function of liquid 4He obtained using two methods; a Monte Carlo simulation and a hypernetted chain approximation. These results are used to obtain the solution of the Euler-Lagrange equation for the optimum Jastrow function for the ground state of liquid 4He. The Monte Carlo calculation is in good agreement with the augmented HNC approximation. General properties of the pair correlation function are discussed in terms of its Fourier transform, the liquid structure function. A critical review is given of the present status of the Jastrow theory ( and its generalizations) of the ground state of boson and fermion quantum fluids. The recent extension of the Jastrow theory to include three-body factors by Pandharipande is compared to the earlier theory of Campbell along with a parallel discussion of the theories of the low excited states of the boson fluid by Feynman and Cohen and by Jackson and Feenberg. The importance fo the three-body factors to the quantitative agreement between the theoretical and experimental phonon-roton spectrum of liquid 4He is discussed. (Auth.)

  4. One Neutron Halo in a 12B Excited State

    陈宝秋; 马中玉

    2001-01-01

    The nonlinear relativistic mean field (RMF) theory with a new effective interaction NL3 has been used to inves tigate the bulk properties of the 12B nucleus. The results obtained in the RMF predict one neutron halo in a 12Bexcited state. 12B does not show the neutron halo structure if it is in its ground state.

  5. Photoionization spectra of even-parity states of Sm atom with multistep excitation

    Two-color stepwise excitation and photoionization schemes are adopted to study the spectra of bound even-parity high-lying states of the Sm atom with three different excitation paths via the 4f66s6p 7DJ (J=1, 2 and 3) intermediate states. In order to obtain the information of these high-lying states, the Sm atom in these high-lying states is photoionized with an extra photon. Among 231 states detected in the energy region between 35,545 and 44,225 cm-1, 108 states are newly discovered, while the rest can be identified as the same with the literature. In most cases, comparisons of the spectra corresponding to the three different excitation paths may partially determine the total angular momentum of the observed peaks with the selection rules. In addition, the relative intensities of all related transition lines are given.

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

    Botta-Cantcheff, Marcelo; Silva, Guillermo A

    2015-01-01

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

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

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

    2016-08-01

    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 [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. PMID:27439874

  8. Control of multiple excited Rydberg states around segmented carbon nanotubes

    Schmelcher, Peter; Sadeghpour, Hossein; Knoerzer, Johannes; Fey, Christian

    2016-05-01

    Electronic image Rydberg 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 long-range interacting quantum systems.

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

    Knörzer, J., E-mail: johannes.knoerzer@physnet.uni-hamburg.de; Fey, C., E-mail: christian.fey@physnet.uni-hamburg.de [Zentrum für Optische Quantentechnologien, Universität Hamburg, Luruper Chaussee 149, Hamburg 22761 (Germany); Sadeghpour, H. R. [ITAMP, Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, Massachusetts 02138 (United States); Schmelcher, P. [Zentrum für Optische Quantentechnologien, Universität Hamburg, Luruper Chaussee 149, Hamburg 22761 (Germany); The Hamburg Centre for Ultrafast Imaging, Luruper Chaussee 149, Hamburg 22761 (Germany)

    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.

  10. Study of the giant dipole resonance built on highly excited states in Sn and Dy nuclei

    A study is presented of the giant dipole resonance built on highly excited states. The aim is to get more detailed information on the properties of the GDR and to use it as a tool for the investigation of nuclear structure at high excitation energy. The high energy γ-rays seen from the decay of excited state GDRs in heavy ion fusion reactions reflect the average properties of the states populated by the γ-emission. The measurements at different initial excitation energies of 114Sn provide information on the nuclear level density near the particle separation energy at an average angular momentum of 10ℎ. The study of shape changes at very high spin in 152-156Dy nuclei is presented. A theoretical model developed to describe fusion-evaporation reactions is presented. 149 refs.; 63 figs.; 13 tabs

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

    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.

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

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

    2014-03-15

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

  13. Gapped excitations of unconventional fractional quantum Hall effect states in the second Landau level

    Wurstbauer, U.; Levy, A. L.; Pinczuk, A.; West, K. W.; Pfeiffer, L. N.; Manfra, M. J.; Gardner, G. C.; Watson, J. D.

    2015-12-01

    We report the observation of low-lying collective charge and spin excitations in the second Landau level at ν =2 +1 /3 and also for the very fragile states at ν =2 +2 /5 and 2 +3 /8 in inelastic light scattering experiments. These modes exhibit a clear dependence on filling factor and temperature substantiating the unique access to the characteristic neutral excitation spectra of the incompressible fractional quantum Hall effect (FQHE) states. A detailed mode analysis reveals low-energy modes at around 70 μ eV and a sharp mode slightly below the Zeeman energy interpreted as gap and spin-wave excitation, respectively. The lowest-energy collective charge excitation spectrum at ν =2 +1 /3 exhibits significant qualitative similarities with its cousin state in the lowest Landau level at ν =1 /3 suggesting similar magnetoroton minima in the neutral excitations. The mode energies differ by a scaling of 0.15 indicating different interaction physics in the N =0 and N =1 Landau levels. The striking polarization dependence in elastic and inelastic light scattering is discussed in the framework of anisotropic electron phases that allow for the stabilization of nematic FQHE states. The observed excitation spectra provide new insights by accessing quantum phases in the bulk of electron systems and facilitate comparison with different theoretical descriptions of those enigmatic FQHE states.

  14. Accounting for highly excited states in detailed opacity calculations

    Pain, Jean-Christophe

    2015-01-01

    In multiply-charged ion plasmas, a significant number of electrons may occupy high-energy orbitals. These "Rydberg" electrons, when they act as spectators, are responsible for a number of satellites of X-ray absorption or emission lines, yielding a broadening of the red wing of the resonance lines. The contribution of such satellite lines may be important, because of the high degeneracy of the relevant excited configurations which give these large Boltzmann weights. However, it is in general difficult to take these configurations into account since they are likely to give rise to a large number of lines. We propose to model the perturbation induced by the spectators in a way similar to the Partially-Resolved-Transition-Array approach recently published by C. Iglesias. It consists in a partial detailed-line-accounting calculation in which the effect of the Rydberg spectators is included through a shift and width, expressed in terms of the canonical partition functions, which are key-ingredients of the Super-Tr...

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

    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.

  16. Dynamic quenching as a simple test for the mechanism of excited-state reaction

    We report on comparative studies of dynamic fluorescence quenching of 3-hydroxyflavone (3HF) and of its novel analogs by nitric oxide spin compound TEMPO. These dyes exhibit the excited-state intramolecular proton transfer (ESIPT) reaction that allows observation of two separate bands in fluorescence emission - of initially excited form and of the product of ESIPT reaction. In the frame of two-state excited-state reaction formalism, we develop the theory predicting different dependence of intensities at two bands in steady-state spectra in the cases of thermodynamic and kinetic control of ESIPT. In line with these predictions, the quenching changes strongly the distribution of intensities between these bands for 3HF but does not change it for the novel compounds whose excited states exhibit strong charge transfer character. Based on these findings, we suggest that the quenching of fluorescence by an efficient collisional quencher can be a simple and convenient method using only the steady-state experiment for distinguishing the excited-state reactions occurring under thermodynamic or under kinetic controls. This method can be used for large-scale screening of a series of compounds - potential candidates for application in fluorescence sensor and biosensor technologies

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

    Resonance Raman and electronic absorption spectra are reported for the S0 and T1 states of the carotenoids β-carotene, zeaxanthin, echinenone, canthaxanthin, dihydroxylycopene, astaxanthin, decapreno(C50)-β-carotene, β-apo-8'-carotenal, and ethyl β-apo-8'-carotenoate. The results reveal qualitatively similar ground-state spectra and similar frequency shifts in all observed resonance Raman modes between S0 and T1, regardless of carotenoid structure. Examinations of the relationship of the putative C--C and C==C frequencies in S0 and T1 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 T1 states of carotenoids and in the S1 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 S1 lifetime (of the 1B/sub u/ and/or the 1A/sub g/* states) of β-carotene in benzene is less than 1 ps

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

    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.

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

    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.

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

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

    2016-09-14

    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. PMID:27391126

  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

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

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

  3. Coherent secondary emission from resonantly excited two-exciton states

    Birkedal, Dan

    2000-01-01

    The coherent interaction of light and the electronic states of semiconductors near the fundamental bandgap has been a very active topic of research since the advent of ultrafast lasers. While many of the ultrafast nonlinear properties of semiconductors have been well explained within mean field...

  4. Sputtering of Ag atoms into metastable excited states

    Staudt, C.; Wucher, A.; Bastiaansen, J.; Philipsen, V.; Vervaecke, F.; Vandeweert, E.; Lievens, P.; Silverans, R. E.; Šroubek, Zdeněk

    2002-01-01

    Roč. 66, č. 8 (2002), s. 085415/1-085415/12. ISSN 0163-1829 R&D Projects: GA AV ČR IAA1067801 Institutional research plan: CEZ:AV0Z2067918 Keywords : sputtering * molecular electronic states Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.327, year: 2002

  5. Stretching of hydrogen-bonded OH in the lowest singlet excited electronic state of water dimer.

    Chipman, Daniel M

    2006-01-28

    The lowest singlet excited electronic state of water monomer in the gas phase is strictly dissociative along a OH stretch coordinate but changes its nature when the stretched OH moiety is hydrogen bonded to a neighboring water molecule. This work extends previous exploration of the water dimer excited singlet potential-energy surface, using computational methods that are reliable even at geometries well removed from the ground-state equilibrium. First, the hydrogen-bonded OH moiety is stretched far enough to establish the existence of a barrier that is sufficient to support a quasibound vibrational state of the OH oscillator near the Franck-Condon region. Second, the constraint of an icelike structure is relaxed, and it is found that a substantial fraction of liquidlike structures also supports a quasibound vibrational state. These potential-energy explorations on stretching of the hydrogen-bonded OH moiety in a water dimer are discussed as a model for understanding the initial dynamics upon excitation into the lowest excited singlet state of condensed water. The possibility is raised that the excited-state lifetime may be long enough to allow for exciton migration, which would provide a mechanism for energy transport in condensed water phases. PMID:16460160

  6. How To Reach Intense Luminescence for Compounds Capable of Excited-State Intramolecular Proton Transfer?

    Skonieczny, Kamil; Yoo, Jaeduk; Larsen, Jillian M; Espinoza, Eli M; Barbasiewicz, Michał; Vullev, Valentine I; Lee, Chang-Hee; Gryko, Daniel T

    2016-05-23

    Photoinduced intramolecular direct arylation allows structurally unique compounds containing phenanthro[9',10':4,5]imidazo[1,2-f]phenanthridine and imidazo[1,2-f]phenanthridine skeletons, which mediate excited-state intramolecular proton transfer (ESIPT), to be efficiently synthesized. The developed polycyclic aromatics demonstrate that the combination of five-membered ring structures with a rigid arrangement between a proton donor and a proton acceptor provides a means for attaining large fluorescence quantum yields, exceeding 0.5, even in protic solvents. Steady-state and time-resolved UV/Vis spectroscopy reveals that, upon photoexcitation, the prepared protic heteroaromatics undergo ESIPT, converting them efficiently into their excited-state keto tautomers, which have lifetimes ranging from about 5 to 10 ns. The rigidity of their structures, which suppresses nonradiative decay pathways, is believed to be the underlying reason for the nanosecond lifetimes of these singlet excited states and the observed high fluorescence quantum yields. Hydrogen bonding with protic solvents does not interfere with the excited-state dynamics and, as a result, there is no difference between the occurrences of ESIPT processes in MeOH versus cyclohexane. Acidic media has a more dramatic effect on suppressing ESIPT by protonating the proton acceptor. As a result, in the presence of an acid, a larger proportion of the fluorescence of ESIPT-capable compounds originates from their enol excited states. PMID:27062363

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

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

    1999-01-01

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

  8. Excited doublet and quartet states of SiP: a high level theoretical investigation

    Doublet and quartet states of the SiP molecule dissociating into the four lowest dissociation channels are characterized theoretically at a high-level of correlation treatment (multireference single and double excitation configuration interaction). Potential energy curves give a global view of the manifold of possible electronic states. For selected states, dipole and transition moment functions, and transition probabilities and radiative lifetimes are also reported as well as an extensive set of spectroscopic constants. A new 2Π state offers another likely route for exploring transitions to excited vibrational states of both X2Π and A2Σ+ states. A detailed set of data for the quartet states is expected to provide valuable information for the experimental identification of these states

  9. Lifetime measurement of excited low-spin states via the $(p,p^{\\prime}\\gamma$) reaction

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

    2015-01-01

    In this article 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 $^{96}$Ru, taking advantage of the coincident detection of scattered protons and de-exciting $\\gamma$-rays as well as the large number of particle and $\\gamma$-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 $(n,n^{\\prime}\\gamma$) or - in case of investigating dipole excitations - ($\\gamma,\\gamma^{\\prime}$) experiments are not feasible due to the lack of sufficient isotopically enriched target material.

  10. Structural Influence on Excited State Dynamics in Simple Amines

    Klein, Liv Bærenholdt

    Simple amines are basic model system of nitrogen-containing chromophores that appear widely in nature. They are also ideal systems for detailed investigation of nonadiabatic dynamical processes and ultrafast temporal evolution of electronic states of the Rydberg type. This investigation, combining...... experiments with calculations, provides new insight into the nature of the internal conversion processes that mediate the dynamical evolution between Rydberg states, and how structural variations in simple amine system have a large impact on the non-adiabatic processes. The experimental method of choice is...... sensitive collection of photoelectron spectra. In particular, the angleresolved data available from the VMI approach provides highly detailed mechanistic insight about the relaxation pathways. One striking novel nding is that for tertiary amines, the critical factor driving the non-adiabatic dynamics is the...

  11. First Observation of Excited States in 140 Dy

    A new 7 μs isomer in the drip line nucleus 140Dy was selected from the products of the 54Fe(315 MeV) + 92Mo reaction by a recoil mass spectrometer and studied with recoil-delayed γ-γ coincidences. Five cascading γ transitions were interpreted as the decay of an Iπ = 8- ( ν 9/2 - [514] x ν 7/2+ [404] ) K isomer via the ground state band. (author)

  12. Charge properties of cuprates: ground state and excitations

    Waidacher, Christoph

    2000-01-01

    This thesis analyzes charge properties of (undoped) cuprate compounds from a theoretical point of view. The central question considered here is: How does the dimensionality of the CU-O sub-structure influence its charge degrees of freedom? The model used to describe the Cu-O sub-structure is the three- (or multi-) band Hubbard model. Analytical approaches are employed (ground-state formalism for strongly correlated systems, Mori-Zwanzig projection technique) as well as numerical simulations (...

  13. Production of excited beauty states in Z decays

    A data sample of about 3.0 million hadronic Z decays collected by the ALEPH experiment at LEP in the years 1991 through 1994 is used to make an inclusive selection of B hadron events. In this event sample 4227±140±252 B* mesons in the decay B* → Bγ and 1944 ± 108 ± 161 B**u,d mesons decaying into a B meson and a charged pion are reconstructed. Here and in the following B**u,d denotes the eight L=1 (bu) and (bd) states and their charge conjugate. For the well established B* meson the following quantities are obtained: ΔM=MB*-MB=(45.30±0.35±0.87) MeV/c2 and NB*/(NB+NB*)=(77.1±2.6±7.0)%. The angular distribution of the photons in the B* rest frame is used to measure the relative contribution of longitudinal B* polarization states to be σL/(σL+σT)=(33±6±5)%. In the M(Bπ)-M(B) mass difference resonance structure is observed at (424±4±10) MeV/c2, for which the shape and position is consistent with the expectation for B**u,d states decaying into B(*)π±. The relative production rate is determined to be BR(Z→b→B**u,d)/BR(Z→b→ Bu,d)=[27.9±.6(stat)±5.9(syst)+3.9-5.6(model)]%. where the third error reflects the uncertainty due to different production and decay models for the broad B**u,d states. (orig.)

  14. Coupled state analysis of electron excitations in asymmetric collision systems

    A coupled channel formalism is presented, using relativistic basis states of the target atom. Screening effects are incorporated by means of an effective potential of Hartree-Fock-Slater type. Relativistic wave packets are employed for the description of the continuum. The impact parameter dependence of the K-hole production in p-Ag collisions is calculated, including quadrupole contributions of the projectile Coulomb potential. The results are compared with experimental data. (orig.)

  15. Delta(1232) isobar excitations and the ground state of nuclei

    Frick, T; Kaiser, S.; Müther, Herbert; Polls Martí, Artur; Entem, D R; Machleidt, R.

    2002-01-01

    The influence of $\\Delta$ isobar components on the ground state properties of nuclear systems is investigated for nuclear matter as well as finite nuclei. Many-body wave functions, including isobar configurations, and binding energies are evaluated employing the framework of the coupled-cluster theory. It is demonstrated that the effect of isobar configurations depends in a rather sensitive way on the model used for the baryon-baryon interaction. As examples for realistic baryon-baryon intera...

  16. Separable interactions and excited states in open-shell nuclei

    The relevant matrix elements of the Hamiltonian for a RPA description of collective states in open-shell nuclei are determined. For separable interactions it is found necessary to include the particle-particle and particle-hole interactions simultaneously. The energy-weighted sum rule for the electromagnetic operator (with angular momentum I) is greatly reduced by the use of the pairing interaction with the same angular momentum. (author)

  17. The hyperfine splitting of the ground state and first excited state of holmium in yttrium hydroxide

    We have studied the field dependence of the hyperfine splitting of 165Ho in yttrium hydroxide by spin echo NMR at liquid helium temperatures and in fields up to 8 T. Hyperfine spectra have been obtained from the electronic ground state and from the first excited state. The measured hyperfine splittings are compared with theoretical results obtained by diagonalizing the complete electronic-nuclear Hamiltonian for the nominally 5I8 ground multiplet of Ho3+, using crystal field parameters derived from optical spectroscopy. There is close agreement between the measured and calculated quadrupolar and octupolar splittings, but we find a significant difference between the measured and calculated dipolar splittings, especially when allowance is made for J mixing. Agreement is restored, to within the uncertainties, if the currently accepted value of the dipolar hyperfine coupling coefficient for the free Ho3+ ion is reduced by 1.3%. Independent evidence for a reduction of that order will be presented in a later publication. The ratio of nuclear to electronic antishielding factors for Ho3+ is found to be γN/γE=148±10, in close agreement with the value obtained in pure holmium hydroxide. (author)

  18. Determination of state-to-state electron-impact rate coefficients between Ar excited states: a review of combined diagnostic experiments in afterglow plasmas

    Zhu, Xi-Ming; Cheng, Zhi-Wen; Carbone, Emile; Pu, Yi-Kang; Czarnetzki, Uwe

    2016-08-01

    Electron-impact excitation processes play an important role in low-temperature plasma physics. Cross section and rate coefficient data for electron-impact processes from the ground state to excited states or between two excited states are required for both diagnostics and modeling works. However, the collisional processes between excited states are much less investigated than the ones involving the ground state due to various experimental challenges. Recently, a method for determining electron excitation rate coefficients between Ar excited states in afterglow plasmas was successfully implemented and further developed to obtain large sets of collisional data. This method combines diagnostics for electron temperature, electron density, and excited species densities and kinetic modeling of excited species, from which the electron excitation rate coefficients from one of the 1s states to the other 1s states or to one of 2p or 3p states are determined (states are in Paschen’s notation). This paper reviews the above method—namely the combined diagnostics and modeling in afterglow plasmas. The results from other important approaches, including electron-beam measurement of cross sections, laser pump-probe technique for measuring rate coefficients, and theoretical calculations by R-matrix and distorted-wave models are also discussed. From a comparative study of these results, a fitted mathematical expression of excitation rate coefficients is obtained for the electron temperature range of 1–5 eV, which can be used for the collisional-radiative modeling of low-temperature Ar plasmas. At last, we report the limitations in the present dataset and give some suggestions for future work in this area.

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

    Jiménez-Hoyos, Carlos A; Scuseria, Gustavo E

    2013-01-01

    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$_2$ 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 $C_{2v}$ insertion pathway for BeH$_2$. The variational excited state methodolo...

  20. Excited-state hydroxyl maser polarimetry: Who ate all the {\\pi}s?

    Green, James A; McClure-Griffiths, Naomi M

    2015-01-01

    We present polarimetric maser observations with the Australia Telescope Compact Array (ATCA) of excited-state hydroxyl (OH) masers. We observed 30 fields of OH masers in full Stokes polarization with the Compact Array Broadband Backend (CABB) at both the 6030 and 6035 MHz excited-state OH transitions, and the 6668-MHz methanol maser transition, detecting 70 sites of maser emission. Amongst the OH we found 112 Zeeman pairs, of which 18 exhibited candidate {\\pi} components. This is the largest single full polarimetric study of multiple sites of star formation for these frequencies, and the rate of 16% {\\pi} components clearly indicates the {\\pi} component exists, and is comparable to the percentage recently found for ground-state transitions. This significant percentage of {\\pi} components, with consistent proportions at both ground- and excited-state transitions, argues against Faraday rotation suppressing the {\\pi} component emission. Our simultaneous observations of methanol found the expected low level of p...

  1. Tracking excited-state charge and spin dynamics in iron coordination complexes

    Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe;

    2014-01-01

    states and possible transitions result in phenomena too complex to unravel when faced with the indirect sensitivity of optical spectroscopy to spin dynamics(5) and the flux limitations of ultrafast X-ray sources(6,7). Such a situation exists for archetypal poly-pyridyl iron complexes, such as [Fe(2......Crucial to many light-driven processes in transition metal complexes is the absorption and dissipation of energy by 3d electrons(1-4). But a detailed understanding of such non-equilibrium excited-state dynamics and their interplay with structural changes is challenging: a multitude of excited......,2'-bipyridine)(3)](2+), where the excited-state charge and spin dynamics involved in the transition from a low-to a high-spin state (spin crossover) have long been a source of interest and controversy(6-15). Here we demonstrate that femtosecond resolution X-ray fluorescence spectroscopy, with its sensitivity to...

  2. ALMA imaging study of methyl formate (HCOOCH$_{3}$) in the torsionally excited states towards Orion KL

    Sakai, Yusuke; Hirota, Tomoya

    2015-01-01

    We recently reported the first identification of rotational transitions of methyl formate (HCOOCH$_{3}$) in the second torsionally excited state toward Orion Kleinmann-Low (KL) observed with the Nobeyama 45 m telescope. In combination with the identified transitions of methyl formate in the ground state and the first torsional excited state, it was found that there is a difference in rotational temperature and vibrational temperature, where the latter is higher. In this study, high spatial resolution analysis by using Atacama Large Millimeter/Submillimeter Array (ALMA) science verification data was carried out to verify and understand this difference. Toward the Compact Ridge, two different velocity components at 7.3 and 9.1 km s$^{-1}$ were confirmed, while a single component at 7.3 km s$^{-1}$ was identified towards the Hot Core. The intensity maps in the ground, first, and second torsional excited states have quite similar distributions. Using extensive ALMA data, we determined the rotational and vibration...

  3. Vibronic resonances sustain excited state coherence in light harvesting proteins at room temperature

    Novelli, Fabio; Roozbeh, Ashkan; Wilk, Krystyna E; Curmi, Paul M G; Davis, Jeffrey A

    2015-01-01

    Until recently it was believed that photosynthesis, a fundamental process for life on earth, could be fully understood with semi-classical models. However, puzzling quantum phenomena have been observed in several photosynthetic pigment-protein complexes, prompting questions regarding the nature and role of these effects. Recent attention has focused on discrete vibrational modes that are resonant or quasi-resonant with excitonic energy splittings and strongly coupled to these excitonic states. Here we report a series of experiments that unambiguously identify excited state coherent superpositions that dephase on the timescale of the excited state lifetime. Low energy (56 cm-1) oscillations on the signal intensity provide direct experimental evidence for the role of vibrational modes resonant with excitonic splittings in sustaining coherences involving different excited excitonic states at physiological temperature.

  4. Photoemission from excited states in rare gas solids by combining synchrotronradiation with a laser

    A new spectroscopic method has been developed to study excited states in rare gas solids: Excitons and conductionband-states are populated by synchrotron radiation (photon energy hwSR=5 - 30 eV). Subsequently electrons from these bound or conduction band-states are excited above the vacuum level of the solid by a pulsed dye laser (hwL=1.9 - 3.7 eV). This experimental technique was applied to solid Xe, Kr, Ar and Ne. (orig./GSCH)

  5. Laser frequency stabilization to excited state transitions using electromagnetically induced transparency in a cascade system.

    Abel, R.P.; Mohapatra, A. K.; Bason, M. G.; Pritchard, J D; Weatherill, K. J.; Raitzsch, U.; Adams, C. S.

    2009-01-01

    We demonstrate laser frequency stabilization to excited state transitions using cascade electromagnetically induced transparency. Using a room temperature Rb vapor cell as a reference, we stabilize a first diode laser to the D2 transition and a second laser to a transition from the intermediate 5P3/2 state to a highly excited state with principal quantum number n = 19–70. A combined laser linewidth of 280±50 kHz over a 100 μs time period is achieved. This method may be applied generally to an...

  6. Quantum Entanglement and Shannon Information Entropy for the Doubly Excited Resonance State in Positronium Negative Ion

    Chien-Hao Lin

    2015-09-01

    Full Text Available In the present work, we report an investigation on quantum entanglement in the doubly excited 2s2 1Se resonance state of the positronium negative ion by using highly correlated Hylleraas type wave functions, determined by calculation of the density of resonance states with the stabilization method. Once the resonance wave function is obtained, the spatial (electron-electron orbital entanglement entropies (von Neumann and linear can be quantified using the Schmidt decomposition method. Furthermore, Shannon entropy in position space, a measure for localization (or delocalization for such a doubly excited state, is also calculated.

  7. Negative-continuum dielectronic recombination into excited states of highly-charged ions

    Artemyev, A. N.; Shabaev, V. M.; Stöhlker, Th; Surzhykov, A. S.

    2009-01-01

    The recombination of a free electron into a bound state of bare, heavy nucleus under simultaneous production of bound-electron--free-positron pair is studied within the framework of relativistic first--order perturbation theory. This process, denoted as "negative-continuum dielectronic recombination" leads to a formation of not only the ground but also the singly- and doubly-excited states of the residual helium-like ion. The contributions from such an excited--state capture to the total as w...

  8. Nucleon, Delta and Omega excited state spectra at three pion mass values

    The energies of the excited states of the Nucleon, Delta and Omega are computed in lattice QCD, using two light quarks and one strange quark on anisotropic lattices. The calculations are performed at three values of the pion mass: 392(4), 438(3) and 521(3) MeV. We employ the variational method with a basis of about ten interpolating operators enabling six energies to be distinguished clearly in each irreducible representation of the octahedral group. We compare our calculations of nucleon excited states with the low-lying experimental spectrum. There is reasonable agreement for the pattern of states.

  9. Excited states in the neutron deficient nuclei 138Sm and 139Eu

    Excited states in the two N=76 nuclei 138Sm and 139Eu have been identified via 32S induced reactions on different targets using γ-ray spectroscopy methods. Lifetimes have been measured with the Doppler shift recoil distance technique, showing the coexistence of a large nuclear deformation (β-0.24) with excitations of single particle character. The E2 transition strengths in the odd-even nucleus 139Eu and in its core 138Sm are discussed. (orig.)

  10. Quantum-chemical study of electronically excited states ofprotolytic forms of vanillic acid

    Vusovich, O. V.; Tchaikovskaya, O. N.; I. V. Sokolova; Vasileva, N. Y.

    2015-01-01

    The paper describes an analysis of possible ways of deactivation of electronically excited states of 4-hydroxy- 3-methoxy-benzoic acid (vanillic acid) and its protolytic forms with the use of quantum-chemical methods INDO/S (intermediate neglect of differential overlap with a spectroscopic parameterization) and MEP (molecular electrostatic potential). The ratio of radiative and non-radiative deactivation channels of the electronic excitation energy is established. The rate constants of photop...

  11. On the importance of excited state dynamic response electron correlation in polarizable embedding methods

    Eriksen, Janus J.; Sauer, Stephan P. A.; Mikkelsen, Kurt Valentin;

    2012-01-01

    a great portion of the inherent PE-RPA error when the observable is the solvatochromic shift. We furthermore demonstrate that whenever the change in density resulting from the ground state-excited state electronic transition in the solute is not associated with a significant change in the electric field...

  12. Excitation of exciton states on a curved surface

    Silotia, Poonam; Prasad, Vinod

    2016-05-01

    Excitonic transitions on the surface of a sphere have been studied in he presence of external static electric and laser fields. The spectrum and the various coupling matrix elements, (for n = 1 , 2 , 3), between few states of exciton have been evaluated in the absence and presence of excitonic Coulombic interaction with different values of dielectric constant. Variation of various physical quantities: energy eigenvalues, transition probability, orientational and alignment parameter, has been shown to have strong dependence on the laser field and static electric field.

  13. Fluorescence excitation and ultraviolet absorption spectra and theoretical calculations for benzocyclobutane: Vibrations and structure of its excited S{sub 1}(π,π{sup *}) electronic state

    Shin, Hee Won; Ocola, Esther J.; Laane, Jaan, E-mail: laane@mail.chem.tamu.edu [Department of Chemistry, Texas A and M University, College Station, Texas 77843-3255 (United States); Kim, Sunghwan [National Center for Biotechnology Information, National Library of Medicine, National Institutes of Health, Department of Health and Human Services, 8600 Rockville Pike, Bethesda, Maryland 20894 (United States)

    2014-01-21

    The fluorescence excitation spectra of jet-cooled benzocyclobutane have been recorded and together with its ultraviolet absorption spectra have been used to assign the vibrational frequencies for this molecule in its S{sub 1}(π,π{sup *}) electronic excited state. Theoretical calculations at the CASSCF(6,6)/aug-cc-pVTZ level of theory were carried out to compute the structure of the molecule in its excited state. The calculated structure was compared to that of the molecule in its electronic ground state as well as to the structures of related molecules in their S{sub 0} and S{sub 1}(π,π{sup *}) electronic states. In each case the decreased π bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S{sub 0} and S{sub 1}(π,π{sup *}) states were remarkably harmonic in contrast to the other bicyclic molecules. The decreases in the frequencies of the out-of-plane skeletal modes reflect the increased floppiness of these bicyclic molecules in their S{sub 1}(π,π{sup *}) excited state.

  14. An intramolecular charge transfer state of carbonyl carotenoids: implications for excited state dynamics of apo-carotenals and retinal

    Polívka, Tomáš; Kaligotla, S.; Chábera, P.; Frank, H.A.

    2011-01-01

    Roč. 13, č. 22 (2011), s. 1463-9076. ISSN 1463-9076 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoid * retinal * excited-state dynamics * charge-transfer state Subject RIV: BO - Biophysics Impact factor: 3.573, year: 2011

  15. Production of excited beauty states in Z decays

    Buskulic, Damir; De Bonis, I; Décamp, D; Ghez, P; Goy, C; Lees, J P; Lucotte, A; Minard, M N; Odier, P; Pietrzyk, B; Ariztizabal, F; Chmeissani, M; Crespo, J M; Efthymiopoulos, I; Fernández, E; Fernández-Bosman, M; Gaitan, V; Garrido, L; Martínez, M; Orteu, S; Pacheco, A; Padilla, C; Palla, Fabrizio; Pascual, A; Perlas, J A; Sánchez, F; Teubert, F; Colaleo, A; Creanza, D; De Palma, M; Farilla, A; Gelao, G; Girone, M; Iaselli, Giuseppe; Maggi, G; Maggi, M; Marinelli, N; Natali, S; Nuzzo, S; Ranieri, A; Raso, G; Romano, F; Ruggieri, F; Selvaggi, G; Silvestris, L; Tempesta, P; Zito, G; Huang, X; Lin, J; Ouyang, Q; Wang, T; Xie, Y; Xu, R; Xue, S; Zhang, J; Zhang, L; Zhao, W; Bonvicini, G; Cattaneo, M; Comas, P; Coyle, P; Drevermann, H; Engelhardt, A; Forty, Roger W; Frank, M; Hagelberg, R; Harvey, J; Jacobsen, R; Janot, P; Jost, B; Knobloch, J; Lehraus, Ivan; Markou, C; Martin, E B; Mato, P; Meinhard, H; Minten, Adolf G; Miquel, R; Oest, T; Palazzi, P; Pater, J R; Pusztaszeri, J F; Ranjard, F; Rensing, P E; Rolandi, Luigi; Schlatter, W D; Schmelling, M; Schneider, O; Tejessy, W; Tomalin, I R; Venturi, A; Wachsmuth, H W; Wiedenmann, W; Wildish, T; Witzeling, W; Wotschack, J; Ajaltouni, Ziad J; Bardadin-Otwinowska, Maria; Barrès, A; Boyer, C; Falvard, A; Gay, P; Guicheney, C; Henrard, P; Jousset, J; Michel, B; Monteil, S; Montret, J C; Pallin, D; Perret, P; Podlyski, F; Proriol, J; Rossignol, J M; Saadi, F; Fearnley, Tom; Hansen, J B; Hansen, J D; Hansen, J R; Hansen, P H; Nilsson, B S; Kyriakis, A; Simopoulou, Errietta; Siotis, I; Vayaki, Anna; Zachariadou, K; Blondel, A; Bonneaud, G R; Brient, J C; Bourdon, P; Passalacqua, L; Rougé, A; Rumpf, M; Tanaka, R; Valassi, Andrea; Verderi, M; Videau, H L; Candlin, D J; Parsons, M I; Focardi, E; Parrini, G; Corden, M; Delfino, M C; Georgiopoulos, C H; Jaffe, D E; Antonelli, A; Bencivenni, G; Bologna, G; Bossi, F; Campana, P; Capon, G; Chiarella, V; Felici, G; Laurelli, P; Mannocchi, G; Murtas, F; Murtas, G P; Pepé-Altarelli, M; Dorris, S J; Halley, A W; ten Have, I; Knowles, I G; Lynch, J G; Morton, W T; O'Shea, V; Raine, C; Reeves, P; Scarr, J M; Smith, K; Smith, M G; Thompson, A S; Thomson, F; Thorn, S; Turnbull, R M; Becker, U; Braun, O; Geweniger, C; Graefe, G; Hanke, P; Hepp, V; Kluge, E E; Putzer, A; Rensch, B; Schmidt, M; Sommer, J; Stenzel, H; Tittel, K; Werner, S; Wunsch, M; Beuselinck, R; Binnie, David M; Cameron, W; Colling, D J; Dornan, Peter J; Konstantinidis, N P; Moneta, L; Moutoussi, A; Nash, J; San Martin, G; Sedgbeer, J K; Stacey, A M; Dissertori, G; Girtler, P; Kneringer, E; Kuhn, D; Rudolph, G; Bowdery, C K; Brodbeck, T J; Colrain, P; Crawford, G; Finch, A J; Foster, F; Hughes, G; Sloan, Terence; Whelan, E P; Williams, M I; Galla, A; Greene, A M; Kleinknecht, K; Quast, G; Raab, J; Renk, B; Sander, H G; Wanke, R; Zeitnitz, C; Aubert, Jean-Jacques; Bencheikh, A M; Benchouk, C; Bonissent, A; Bujosa, G; Calvet, D; Carr, J; Diaconu, C A; Etienne, F; Thulasidas, M; Nicod, D; Payre, P; Rousseau, D; Talby, M; Abt, I; Assmann, R W; Bauer, C; Blum, Walter; Brown, D; Dietl, H; Dydak, Friedrich; Ganis, G; Gotzhein, C; Jakobs, K; Kroha, H; Lütjens, G; Lutz, Gerhard; Männer, W; Moser, H G; Richter, R H; Rosado-Schlosser, A; Schael, S; Settles, Ronald; Seywerd, H C J; Stierlin, U; Saint-Denis, R; Wolf, G; Alemany, R; Boucrot, J; Callot, O; Cordier, A; Courault, F; Davier, M; Duflot, L; Grivaz, J F; Heusse, P; Jacquet, M; Kim, D W; Le Diberder, F R; Lefrançois, J; Lutz, A M; Musolino, G; Nikolic, I A; Park, H J; Park, I C; Schune, M H; Simion, S; Veillet, J J; Videau, I; Abbaneo, D; Azzurri, P; Bagliesi, G; Batignani, G; Bettarini, S; Bozzi, C; Calderini, G; Carpinelli, M; Ciocci, M A; Ciulli, V; Dell'Orso, R; Fantechi, R; Ferrante, I; Foà, L; Forti, F; Giassi, A; Giorgi, M A; Gregorio, A; Ligabue, F; Lusiani, A; Marrocchesi, P S; Messineo, A; Rizzo, G; Sanguinetti, G; Sciabà, A; Spagnolo, P; Steinberger, Jack; Tenchini, Roberto; Tonelli, G; Triggiani, G; Vannini, C; Verdini, P G; Walsh, J; Betteridge, A P; Blair, G A; Bryant, L M; Cerutti, F; Gao, Y; Green, M G; Johnson, D L; Medcalf, T; Mir, L M; Perrodo, P; Strong, J A; Bertin, V; Botterill, David R; Clifft, R W; Edgecock, T R; Haywood, S; Edwards, M; Maley, P; Norton, P R; Thompson, J C; Bloch-Devaux, B; Colas, P; Duarte, H; Emery, S; Kozanecki, Witold; Lançon, E; Lemaire, M C; Locci, E; Marx, B; Pérez, P; Rander, J; Renardy, J F; Rossowsky, A; Roussarie, A; Schuller, J P; Schwindling, J; Si Mohand, D; Trabelsi, A; Vallage, B; Johnson, R P; Kim, H Y; Litke, A M; McNeil, M A; Taylor, G; Beddall, A; Booth, C N; Boswell, R; Cartwright, S L; Combley, F; Dawson, I; Köksal, A; Letho, M; Newton, W M; Rankin, C; Thompson, L F; Böhrer, A; Brandt, S; Cowan, G D; Feigl, E; Grupen, Claus; Lutters, G; Minguet-Rodríguez, J A; Rivera, F; Saraiva, P; Smolik, L; Van Gemmeren, P; Apollonio, M; Bosisio, L; Della Marina, R; Giannini, G; Gobbo, B; Ragusa, F; Rothberg, J E; Wasserbaech, S R; Armstrong, S R; Bellantoni, L; Elmer, P; Feng, Z; Ferguson, D P S; Gao, Y S; González, S; Grahl, J; Harton, J L; Hayes, O J; Hu, H; McNamara, P A; Nachtman, J M; Orejudos, W; Pan, Y B; Saadi, Y; Schmitt, M; Scott, I J; Sharma, V; Turk, J; Walsh, A M; Wu Sau Lan; Wu, X; Yamartino, J M; Zheng, M; Zobernig, G

    1996-01-01

    A data sample of about 3.0 million hadronic Z decays collected by the ALEPH experiment at LEP in the years 1991 through 1994, is used to make an inclusive selection of B~hadron events. In this event sample 4227 \\pm 140 \\pm 252 B^* mesons in the decay B^* \\to B \\gamma and 1944 \\pm 108 \\pm 161 B^{**} mesons decaying into a B~meson and a charged pion are reconstructed. For the well established B^* meson the following quantities areobtained: \\Delta M = M_{B^*} - M_{B} = (45.30\\pm 0.35\\pm 0.87)~\\mathrm{MeV}/c^2 and N_{B^*}/(N_B+N_{B^*}) = (77.1 \\pm 2.6 \\pm 7.0)\\%. The angular distribution of the photons in the B^* rest frame is used to measure the relative contribution of longitudinal B^* polarization states to be \\sigma_L/(\\sigma_L + \\sigma_T)= (33 \\pm 6 \\pm 5)\\%. \\\\ Resonance structure in the M(B\\pi)-M(B) mass difference is observed at (424 \\pm 4 \\pm 10)~\\mathrm{MeV}/c^2. Its shape and position is in agreement with the expectation for B^{**}_{u,d} states decaying into B_{u,d}^{(*)} \\pi^\\pm. The signal is therefo...

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

    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

  17. Excited states structure and processes: Understanding organic light-emitting diodes at the molecular level

    Photo- or electro-excited states in polyatomic molecules, aggregates, and conjugated polymers are at the center of organic light-emitting diodes (OLEDs). These can decay radiatively or non-radiatively, determining the luminescence quantum efficiency of molecular materials. According to Kasha’s rule, light-emission is dictated by the lowest-lying excited state. For conjugated polymers, the electron correlation effect can lead the lowest-lying excited state to the even-parity 2Ag state which is non-emissive. To understand the nature of the low-lying excited state structure, we developed the density matrix renormalization group (DMRG) theory and its symmetrization scheme for quantum chemistry applied to calculate the excited states structure. We found there are three types of 1Bu/2Ag crossover behaviors: with electron correlation strength U, with bond length alternation, and with conjugation length. These directly influence the light-emitting property. For the electro-excitation, carriers (electron and hole) are injected independently, forming both singlet and triplet excited bound states with statistically 25% and 75% portions, respectively. We found that the exciton formation rate can depend on spin manifold, and for conjugated polymers, the singlet exciton can have larger formation rate leading to the internal electroluminescence quantum efficiency larger than the 25% spin statistical limit. It is originated from the interchain electron correlation as well as intrachain lattice relaxation. For the dipole allowed emissive state, the radiative decay process via either spontaneous emission or stimulated emission can be computed from electronic structure plus vibronic couplings. The challenging issue lies in the non-radiative decay via non-adiabatic coupling and/or spin–orbit coupling. We developed a unified correlation function formalism for the excited state radiative and non-radiative decay rates. We emphasized the low-frequency mode mixing (Duschinsky rotation

  18. Generalized variational principle for excited states using nodes of trial functions

    The familiar variational principle provides an upper bound to the ground-state energy of a given Hamiltonian. This allows one to optimize a trial wave function by minimizing the expectation value of the energy. This approach is also trivially generalized to excited states, so that given a trial wave function of a certain symmetry, one can compute an upper bound to the lowest-energy level of that symmetry. In order to generalize further and build an upper bound of an arbitrary excited state of the desired symmetry, a linear combination of basis functions is generally used to generate an orthogonal set of trial functions, all bounding their respective states. However, sometimes a compact wave-function form is sought, and a basis-set expansion is not desirable or possible. Here we present an alternative generalization of the variational principle to excited states that does not require explicit orthogonalization to lower-energy states. It is valid for one-dimensional systems and, with additional information, to at least some n-dimensional systems. This generalized variational principle exploits information about the nodal structure of the trial wave function, giving an upper bound to the exact energy without the need to build a linear combination of basis functions. To illustrate the theorem we apply it to a nontrivial example: the 1s2s 1 S excited state of the helium atom.

  19. Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density Functional Theory

    Yu-ling Chu; Zhong Yang; Zhe-feng Pan; Jing Liu; Yue-yi Han; Yong Ding; Peng Song

    2012-01-01

    Density functional theory and time-dependent density-functional theory have been used to investigate the photophysical properties and relaxation dynamics of dimethylaminobenzophenone (DMABP) and its hydrogen-bonded DMABP-MeOH dimer.It is found that,in nonpolar aprotic solvent,the transitions from S0 to S1 and S2 states of DMABP have both n→π* and π→π* characters,with the locally excited feature mainly located on the C=O group and the partial CT one characterized by electron transfer mainly from the dimethylaminophenyl group to the C=O group.But when the intermolecular hydrogen bond C=O…H-O is formed,the highly polar intramolecular charge transfer character switches over to the first excited state of DMABP-MeOH dimer and the energy difference between the two lowlying electronically excited states increases.To gain insight into the relaxation dynamics of DMABP and DMABP-MeOH dimer in the excited state,the potential energy curves for conformational relaxation are calculated.The formation of twisted intramolecular charge transfer state via diffusive twisting motion of the dimethylamino/dimethylaminophenyl groups is found to be the major relaxation process.In addition,the decay of the S1 state of DMABP-MeOH dimer to the ground state,through nonradiative intermolecular hydrogen bond stretching vibrations,is facilitated by the formation of the hydrogen bond between DMABP and alcohols.

  20. Mid-infrared ultrafast laser pulses induced third harmonic generation in nitrogen molecules on an excited state

    Hongqiang Xie; Guihua Li; Jinping Yao; Wei Chu; Ziting Li; Bin Zeng; Zhanshan Wang; Ya Cheng

    2015-01-01

    We report on generation of third harmonic from nitrogen molecules on the excited state with a weak driver laser pulse at a mid-infrared wavelength. The excited nitrogen molecules are generated using a circularly polarized intense femtosecond pulse which produces energetic electrons by photoionization to realize collisional excitation of nitrogen molecules. Furthermore, since the third harmonic is generated using a pump-probe scheme, it enables investigation of the excited-state dynamics of ni...

  1. Two-step excitation of an auto-ionized state of the Ba atom associated with two-photon excitation of an intermediate state

    An experimental and theoretical study is performed of the angular photoelectron distribution for three-photon ionization of Ba atoms through the 2ω-excited intermediate state 6p2(1S0) and the auto-ionized state 6p8s(3P1). Rotation of the polarization plane of dye-laser radiation allowed us to investigate the photoelectron angular distribution. Electrons were counted with the help of a time-of-flight electron spectrometer. The density-matrix formalism is used to obtain expressions for the angular dependence of the differential ionization probability. Possible experiments are discussed

  2. Determination of ground and excited state dipole moments via electronic Stark spectroscopy: 5-methoxyindole

    Wilke, Josefin; Wilke, Martin; Schmitt, Michael, E-mail: mschmitt@uni-duesseldorf.de [Institut für Physikalische Chemie, Heinrich-Heine-Universität, D-40225 Düsseldorf (Germany); Meerts, W. Leo, E-mail: leo.meerts@science.ru.nl [Institute for Molecules and Materials, Radboud University, NL-6525 AS Nijmegen (Netherlands)

    2016-01-28

    The dipole moments of the ground and lowest electronically excited singlet state of 5-methoxyindole have been determined by means of optical Stark spectroscopy in a molecular beam. The resulting spectra arise from a superposition of different field configurations, one with the static electric field almost parallel to the polarization of the exciting laser radiation, the other nearly perpendicular. Each field configuration leads to different intensities in the rovibronic spectrum. With an automated evolutionary algorithm approach, the spectra can be fit and the ratio of both field configurations can be determined. A simultaneous fit of two spectra with both field configurations improved the precision of the dipole moment determination by a factor of two. We find a reduction of the absolute dipole moment from 1.59(3) D to 1.14(6) D upon electronic excitation to the lowest electronically excited singlet state. At the same time, the dipole moment orientation rotates by 54{sup ∘} showing the importance of the determination of the dipole moment components. The dipole moment in the electronic ground state can approximately be obtained from a vector addition of the indole and the methoxy group dipole moments. However, in the electronically excited state, vector addition completely fails to describe the observed dipole moment. Several reasons for this behavior are discussed.

  3. Determination of ground and excited state dipole moments via electronic Stark spectroscopy: 5-methoxyindole

    The dipole moments of the ground and lowest electronically excited singlet state of 5-methoxyindole have been determined by means of optical Stark spectroscopy in a molecular beam. The resulting spectra arise from a superposition of different field configurations, one with the static electric field almost parallel to the polarization of the exciting laser radiation, the other nearly perpendicular. Each field configuration leads to different intensities in the rovibronic spectrum. With an automated evolutionary algorithm approach, the spectra can be fit and the ratio of both field configurations can be determined. A simultaneous fit of two spectra with both field configurations improved the precision of the dipole moment determination by a factor of two. We find a reduction of the absolute dipole moment from 1.59(3) D to 1.14(6) D upon electronic excitation to the lowest electronically excited singlet state. At the same time, the dipole moment orientation rotates by 54∘ showing the importance of the determination of the dipole moment components. The dipole moment in the electronic ground state can approximately be obtained from a vector addition of the indole and the methoxy group dipole moments. However, in the electronically excited state, vector addition completely fails to describe the observed dipole moment. Several reasons for this behavior are discussed

  4. Excited-state hydroxyl maser catalogue from the methanol multibeam survey -- I. Positions and Variability

    Avison, A; Fuller, G A; Caswell, J L; Green, J A; Breen, S L; Ellingsen, S P; Gray, M D; Pestalozzi, M; Thompson, M A; Voronkov, M A

    2016-01-01

    We present the results of the first complete unbaised survey of the Galactic Plane for 6035-MHz excited-state hydroxyl masers undertaken as part of the Methanol Multibeam Survey. These observations cover the Galactic longitude ranges $186^{\\circ}< l < 60^{\\circ}$ including the Galactic Centre. We report the detection of 127 excited-state hydroxyl masers within the survey region, 47 being new sources. The positions of new detections were determined from interferometric observations with the Australia Telescope Compact Array. We discuss the association of 6035-MHz masers in our survey with the 6668-MHz masers from the MMB Survey, finding 37 likely methanol-excited-state hydroxyl masers maser pairs with physical separations of <=0.03pc and 55 pairings separated by <=0.1pc. Using these we calculate for the first time an excited-state hydroxyl maser life time of between 3.3x10^3 and 8.3x10^3 years. We also discuss the variability of the 6035-MHz masers and detection rates of counterpart 6030-MHz excite...

  5. Efficient Excitation of a Symmetric Collective Atomic State with a Single-Photon Through Dipole Blockade

    HONG Fang-Yu; XIONG Shi-Jie; FU Jing-Li; ZHU Zhi-Yan

    2013-01-01

    In the famous quantum communication scheme developed by Duan et al.[L.M.Duan,M.D.Lukin,J.L.Cirac,and P.Zoller,Nature (London) 414 (2001) 413],the probability of successful generating a symmetric collective atomic state with a single-photon emitted have to be far smaller than 1 to obtain an acceptable entangled state.Based on strong dipole-dipole interaction between two Rydberg atoms,two simultaneous excitations in an atomic ensemble are greatly suppressed,which makes it possible to excite a mesoscopic cold atomic ensemble into a near-ideal singly-excited symmetric collective state accompanied by a signal-photon with near unity success probability.

  6. Excited state coherent dynamics in light-harvesting complexes from photosynthetic marine algae

    Richards, G. H.; Wilk, K. E.; Curmi, P. M. G.; Quiney, H. M.; Davis, J. A.

    2012-08-01

    We explore coherence dynamics in light-harvesting complexes and their interactions with other electronic states and vibrational modes. This is achieved by utilizing a two-colour four-wave mixing spectroscopy to excite and analyse a specific coherence pathway in the phycocyanin-645 (PC645) light-harvesting complex. We observe the dephasing rate increase as a function of temperature and oscillations in the signal intensity as a function of waiting time which reveals coherent excitation of pathways not directly resonant with the laser pulses. This coherent excitation of non-resonant electronic states implies strong coupling to phonon modes, which is necessary if coherent energy transfer between non-resonant states is to play any role in photosynthetic energy transfer.

  7. Excited state coherent dynamics in light-harvesting complexes from photosynthetic marine algae

    We explore coherence dynamics in light-harvesting complexes and their interactions with other electronic states and vibrational modes. This is achieved by utilizing a two-colour four-wave mixing spectroscopy to excite and analyse a specific coherence pathway in the phycocyanin-645 (PC645) light-harvesting complex. We observe the dephasing rate increase as a function of temperature and oscillations in the signal intensity as a function of waiting time which reveals coherent excitation of pathways not directly resonant with the laser pulses. This coherent excitation of non-resonant electronic states implies strong coupling to phonon modes, which is necessary if coherent energy transfer between non-resonant states is to play any role in photosynthetic energy transfer. (paper)

  8. Parametric scaling of neutral and ion excited state densities in an argon helicon source

    McCarren, D.; Scime, E.

    2016-04-01

    We report measurements of the absolute density and temperature of ion and neutral excited states in an argon helicon source. The excited ion state density, which depends on ion density, electron density, and electron temperature, increases sharply with increasing magnetic field in the source. The neutral argon metastable density measurements are consistent with an increasing ionization fraction with increasing magnetic field strength. The ion temperature shows no evidence of increased heating with increasing magnetic field strength (which has only been observed in helicon sources operating at driving frequencies close to the lower hybrid frequency). The measurements were obtained through cavity ring down spectroscopy, a measurement technique that does not require the target excited state to be metastable or part of a fluorescence scheme; and is therefore applicable to any laser accessible atomic or ionic transition in a plasma.

  9. Investigation of two-photon absorption induced excited state absorption in a fluorenyl-based chromophore.

    Li, Changwei; Yang, Kun; Feng, Yan; Su, Xinyan; Yang, Junyi; Jin, Xiao; Shui, Min; Wang, Yuxiao; Zhang, Xueru; Song, Yinglin; Xu, Hongyao

    2009-12-01

    Two-photon absorption induced excited state absorption in the solution of a new fluorenyl-based chromophore is investigated by a time-resolved pump-probe technique using femtosecond pulses. With the help of an additional femtosecond open-aperture Z-scan technique, numerical simulations based on a three-energy level model are used to interpret the experimental results, and we determine the nonlinear optical parameters of this new chromophore uniquely. Large two-photon absorption cross section and excited state absorption cross section for singlet excited state are obtained, indicating a good candidate for optical limiting devices. Moreover, the influence of two-beam coupling induced energy transfer in neat N,N'-dimethylformamide solvent is also considered, although this effect is strongly restrained by the instantaneous two-photon absorption. PMID:19894682

  10. Organic nanophotonic materials: the relationship between excited-state processes and photonic performances.

    Zhang, Wei; Zhao, Yong Sheng

    2016-07-12

    Nanophotonics have recently captured broad attention because of their great potential in information processing and communication, which may allow rates and bandwidth beyond what is feasible in the realm of electronics. Organic materials could be well suitable for such applications due to their ability to generate, transmit, modulate and detect light in their lightweight and flexible nanoarchitectures. Their distinct nanophotonic properties strongly depend on their extrinsic morphologies and intrinsic molecular excited-state processes. In this feature article, we mainly focus on a comprehensive understanding of the relationship between molecular excited-state processes and the advanced photonic functionalities of organic micro/nano-crystals in recent organic nanophotonic research, and then expect to provide enlightenment for the design and development of tiny photonic devices with broadband tunable properties by tailoring the excited-state processes of organic microcrystals. PMID:26883812

  11. Precision Excited State Lifetime Measurements for Atomic Parity Violation and Atomic Clocks

    Sell, Jerry; Patterson, Brian; Gearba, Alina; Snell, Jeremy; Knize, Randy

    2016-05-01

    Measurements of excited state atomic lifetimes provide a valuable test of atomic theory, allowing comparisons between experimental and theoretical transition dipole matrix elements. Such tests are important in Rb and Cs, where atomic parity violating experiments have been performed or proposed, and where atomic structure calculations are required to properly interpret the parity violating effect. In optical lattice clocks, precision lifetime measurements can aid in reducing the uncertainty of frequency shifts due to the surrounding blackbody radiation field. We will present our technique for precisely measuring excited state lifetimes which employs mode-locked ultrafast lasers interacting with two counter-propagating atomic beams. This method allows the timing in the experiment to be based on the inherent timing stability of mode-locked lasers, while counter-propagating atomic beams provides cancellation of systematic errors due to atomic motion to first order. Our current progress measuring Rb excited state lifetimes will be presented along with future planned measurements in Yb.

  12. Production and transport of the excited states of projectile ions in ion-solid interaction

    In ion-solid collisions, more excited states of projectile ions with high angular momenta l are populated than in ion-atom collisions. The use of 13.6 MeV/u Ar18+ projectile ions and solid carbon targets allowed us to study Ar17+ excited states initially populated by electron capture. Using various targets with increasing thickness from 3.5 to 200 μg/cm2, the evolution of excited states from the single collision condition to the population equilibrium was investigated. We observed the evolution of the Lyman line intensities as a function of the ion transit time inside the target (sensitive to core state population) and as a function of the ion time of flight behind the target (sensitive to Rydberg state population). To explain the experimental results, a complete theoretical analysis of the transport of excited states inside the medium was performed. We used two different collisional models. The first one is a rate equation model based on a statistical description of binary collisions of the projectile with target atoms. The second one is a classical transport theory based on an equation describing the motion of the projectile electron on a classical orbit perturbed by a stochastic force. A comparison with experiment shows that such a collisional approach allows to interpret the excited l-state population, but fails in describing the core state population. The observed l mixing in these states is much larger than predicted by the models. The polarization of the medium induced by the projectile ion, with both models do not take into account, could be responsible for this mixing by means of the Stark effect. (author)

  13. Describing excited state relaxation and localization in TiO2 nanoparticles using TD-DFT

    We have investigated the description of excited state relaxation in naked and hydrated TiO2 nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials; B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to be the inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree-Fock Like Exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT-problems for certain particles. We hypothesize that the spurious stabilization of CT-states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries than those obtained using TD-CAM-B3LYP or TD-BHLYP. In conclusion, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in naked and hydrated TiO2 nanoparticles is predicted to be associated with a large Stokes' shift

  14. Excited states in the doubly closed shell nucleus $^{132}_{50}Sn_{82}$

    Bjørnstad, T; Ewan, G T; Jonson, B; Kawade, K; Kérek, A; Mattsson, S; Sistemich, K

    1982-01-01

    New excited states in the nucleus /sup 1/ /sup 32/Sn have been identified from gamma gamma coincidence measurements. Strong beta feeding to a state at 7.210 keV was established. This level is interpreted as a 6^{-} state formed after a\\pig/sup -1//sub 9/2/ to nu g/sup -1//sub 7/2/GT beta ^{-} transition from the 7^{-} ground state of /sup 132/In. The deexcitation of the 7210 keV state passes through a 4351 keV state, providing support for a 3^{-} assignment of this level.

  15. Even-parity states of the Sm atom with stepwise excitation

    Li Ming; Dai Chang-Jian; Xie Jun

    2011-01-01

    Two-colour stepwise excitation and photoionization schemes are adopted to study the spectra of high-lying states of the Sm atom. These bound even-parity states are excited with three different excitation paths from the 4f66s6p7DJ (J = 1, 2, 3) intermediate states, respectively. They are probed by photoionization process with an extra photon driving them to the continuum states. In this experiment, 270 states are detected in an energy range from 36160 cm-1 to 42250 cm-1, 109 of which are newly discovered, while the rest of them are confirmed to be the energy levels reported previously. Furthermore, based on the J-momentum selection rules of three excitation paths, a unique assignment of J-momentum for all observed states is determined, eliminating all remaining ambiguities in the literature. Finally, 53 single-colour transitions originating from the scanning laser are also identified. For all the relevant transitions, the information about their relative intensities is also given in the paper.

  16. Even-parity states of the Sm atom with stepwise excitation

    Two-colour stepwise excitation and photoionization schemes are adopted to study the spectra of high-lying states of the Sm atom. These bound even-parity states are excited with three different excitation paths from the 4f66s6p7DJ (J = 1, 2, 3) intermediate states, respectively. They are probed by photoionization process with an extra photon driving them to the continuum states. In this experiment, 270 states are detected in an energy range from 36160 cm−1 to 42250 cm−1, 109 of which are newly discovered, while the rest of them are confirmed to be the energy levels reported previously. Furthermore, based on the J-momentum selection rules of three excitation paths, a unique assignment of J-momentum for all observed states is determined, eliminating all remaining ambiguities in the literature. Finally, 53 single-colour transitions originating from the scanning laser are also identified. For all the relevant transitions, the information about their relative intensities is also given in the paper. (atomic and molecular physics)

  17. Resonance search for quark excitation in the gamma + jet final state at CMS

    Sharma, Varun

    2014-01-01

    This poster presents a search for excited quarks (q*) decaying into a $\\gamma$ + jet final state at $\\sqrt{\\rm s}$= 8 TeV with the CMS experiment, using the dataset corresponding to an integrated luminosity of 19.7 $\\,\\text{fb}^\\text{-1}$ collected during 2012 data taking at the LHC. Photons and jets with high transverse momentum are selected to search for a resonance peak in the $\\gamma$ + jet invariant mass distribution. The 95\\% confidence level upper limits on cross section times branching ratio are evaluated as a function of excited quark mass (Mq*). We exclude at 95\\% CL excited quarks with 0.7 $<$ Mq* $<$ 3.5 TeV for standard model couplings, and present exclusions of excited quark mass as a function of coupling strength.

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

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

  19. Resonance charge exchange between excited states in slow proton-hydrogen collisions

    The theory of resonance charge exchange in slow collisions of a proton with a hydrogen atom in the excited state is developed. It extends the Firsov-Demkov theory of resonance charge exchange to the case of degenerate initial and final states. The theory is illustrated by semiclassical and quantum calculations of charge exchange cross sections between states with n=2 in parabolic and spherical coordinates. The results are compared with existing close-coupling calculations.

  20. Charge sensing of excited states in an isolated double quantum dot

    C. Johnson, A.; M. Marcus, C.; P. Hanson, M.;

    2005-01-01

    Pulsed electrostatic gating combined with capacitive charge sensing is used to perform excited state spectroscopy of an electrically isolated double-quantum-dot system. The tunneling rate of a single charge moving between the two dots is affected by the alignment of quantized energy levels......; measured tunneling probabilities thereby reveal spectral features. Two pulse sequences are investigated, one of which, termed latched detection, allows measurement of a single tunneling event without repetition. Both provide excited-state spectroscopy without electrical contact to the double-dot system....

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

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

  2. Quantum entanglement for two electrons in the excited states of helium-like systems

    Lin, Yen-Chang; Ho, Yew Kam

    2013-01-01

    The quantum entanglement for the two electrons in the excited states of the helium-like atom/ions is investigated using the two-electron wave functions constructed by the B-spline basis. As a measure of the spatial (electron-electron orbital) entanglement, the von Neumann entropy and linear entropy of the reduced density matrix are calculated for the 1s2s 1,3S excited states for systems with some selected Z values from Z=2 to Z=100. Results for the helium atom are compared with other availabl...

  3. Derivative couplings between TDDFT excited states obtained by direct differentiation in the Tamm-Dancoff approximation

    Working within the Tamm-Dancoff approximation, we calculate the derivative couplings between time-dependent density-functional theory excited states by assuming that the Kohn-Sham superposition of singly excited determinants represents a true electronic wavefunction. All Pulay terms are included in our derivative coupling expression. The reasonability of our approach can be established by noting that, for closely separated electronic states in the infinite basis limit, our final expression agrees exactly with the Chernyak-Mukamel expression (with transition densities from response theory). Finally, we also validate our approach empirically by analyzing the behavior of the derivative couplings around the T1/T2 conical intersection of benzaldehyde

  4. Study of intermediates from transition metal excited-state electron-transfer reactions

    Hoffman, M. Z.

    1992-07-01

    Conventional and fast-kinetics techniques of photochemistry, photophysics, radiation chemistry, and electrochemistry were used to study the intermediates involved in transition metal excited-state electron-transfer reactions. These intermediates were excited state of Ru(II) and Cr(III) photosensitizers, their reduced forms, and species formed in reactions of redox quenchers and electron-transfer agents. Of particular concern was the back electron-transfer reaction between the geminate pair formed in the redox quenching of the photosensitizers, and the dependence of its rate on solution medium and temperature in competition with transformation and cage escape processes.

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

    Dupuy, Nicolas, E-mail: nicolas.dupuy@impmc.upmc.fr [Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, Université Pierre et Marie Curie, case 115, 4 place Jussieu, 75252 Paris Cedex 05 (France); Bouaouli, Samira, E-mail: samira.bouaouli@lct.jussieu.fr [Laboratoire de Chimie Théorique, Université Pierre et Marie Curie, case 115, 4 place Jussieu, 75252 Paris Cedex 05 (France); Mauri, Francesco, E-mail: francesco.mauri@impmc.upmc.fr; Casula, Michele, E-mail: michele.casula@impmc.upmc.fr [CNRS and Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, Université Pierre et Marie Curie, case 115, 4 place Jussieu, 75252 Paris Cedex 05 (France); Sorella, Sandro, E-mail: sorella@sissa.it [International School for Advanced Studies (SISSA), Via Beirut 2-4, 34014 Trieste, Italy and INFM Democritos National Simulation Center, Trieste (Italy)

    2015-06-07

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

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

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

    2015-06-01

    We study the ionization energy, electron affinity, and the π → π(∗) ((1)La) excitation energy of the anthracene molecule, by means of variational quantum Monte Carlo (QMC) methods based on a Jastrow correlated antisymmetrized geminal power (JAGP) wave function, developed on molecular orbitals (MOs). The MO-based JAGP ansatz allows one to rigorously treat electron transitions, such as the HOMO → LUMO one, which underlies the (1)La excited state. We present a QMC optimization scheme able to preserve the rank of the antisymmetrized geminal power matrix, thanks to a constrained minimization with projectors built upon symmetry selected MOs. We show that this approach leads to stable energy minimization and geometry relaxation of both ground and excited states, performed consistently within the correlated QMC framework. Geometry optimization of excited states is needed to make a reliable and direct comparison with experimental adiabatic excitation energies. This is particularly important in π-conjugated and polycyclic aromatic hydrocarbons, where there is a strong interplay between low-lying energy excitations and structural modifications, playing a functional role in many photochemical processes. Anthracene is an ideal benchmark to test these effects. Its geometry relaxation energies upon electron excitation are of up to 0.3 eV in the neutral (1)La excited state, while they are of the order of 0.1 eV in electron addition and removal processes. Significant modifications of the ground state bond length alternation are revealed in the QMC excited state geometry optimizations. Our QMC study yields benchmark results for both geometries and energies, with values below chemical accuracy if compared to experiments, once zero point energy effects are taken into account. PMID:26049481

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

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

  8. Variation of Excited-State Dynamics in Trifluoromethyl Functionalized C60 Fullerenes

    Park, Jaehong; Ramirez, Jessica J.; Clikeman, Tyler T.; Larson, Bryon W.; Boltalina, Olga V.; Strauss, Steven H.; Rumbles, Garry

    2016-09-07

    We report on electronically excited-state dynamics of three different trifluoromethyl C60 fullerenes (TMFs, C60(CF3)n: C60/4-1, C60/6-2, and C60/10-1, featuring four, six, and ten trifluoromethyl groups, respectively) using steady-state and time-resolved optical spectroscopy as well as ultrafast pump/probe transient absorption spectroscopy. C60/4-1 and C60/6-2 dissolved in toluene solvent show near-unity S1--T1 intersystem crossing quantum yield (..phi..ISC), ca. 1 ns S1-state lifetimes, and microsecond-timescale T1-state lifetimes, which are typical of the fullerene class. On the other hand, C60/10-1 exhibits a dominant sub-nanosecond nonradiative S1--S0 relaxation mechanism and negligible ..phi..ISC, therefore decreasing the average excited-state lifetime (..tau..avg) by about 5 orders of magnitude compared to that of C60/4-1 and C60/6-2 (..tau..avg approx. 17 us and 54 us for C60/4-1 and C60/6-2, respectively, whereas ..tau..avg approx. 100 ps for C60/10-1). These excited-state characteristics of C60/4-1 and C60/6-2 are preserved in polymer matrix, suggesting that fullerene/polymer interactions do not modulate intrinsic photophysics of trifluoromethyl-substituted fullerenes. The contrasting excited- state study results of C60/4-1 and C60/6-2 to that of C60/10-1 infer that intrinsic optical properties and excited-state dynamics can be affected by the substitution on the fullerene.

  9. Variation of excited-state dynamics in trifluoromethyl functionalized C60 fullerenes.

    Park, Jaehong; Ramirez, Jessica J; Clikeman, Tyler T; Larson, Bryon W; Boltalina, Olga V; Strauss, Steven H; Rumbles, Garry

    2016-08-17

    We report on electronically excited-state dynamics of three different trifluoromethyl C60 fullerenes (TMFs, C60(CF3)n: C60/4-1, C60/6-2, and C60/10-1, featuring four, six, and ten trifluoromethyl groups, respectively) using steady-state and time-resolved optical spectroscopy as well as ultrafast pump/probe transient absorption spectroscopy. C60/4-1 and C60/6-2 dissolved in toluene solvent show near-unity S1 → T1 intersystem crossing quantum yield (ΦISC), ca. 1 ns S1-state lifetimes, and microsecond-timescale T1-state lifetimes, which are typical of the fullerene class. On the other hand, C60/10-1 exhibits a dominant sub-nanosecond nonradiative S1 → S0 relaxation mechanism and negligible ΦISC, therefore decreasing the average excited-state lifetime (τavg) by about 5 orders of magnitude compared to that of C60/4-1 and C60/6-2 (τavg ≈ 17 μs and 54 μs for C60/4-1 and C60/6-2, respectively, whereas τavg ≈ 100 ps for C60/10-1). These excited-state characteristics of C60/4-1 and C60/6-2 are preserved in polymer matrix, suggesting that fullerene/polymer interactions do not modulate intrinsic photophysics of trifluoromethyl-substituted fullerenes. The contrasting excited-state study results of C60/4-1 and C60/6-2 to that of C60/10-1 infer that intrinsic optical properties and excited-state dynamics can be affected by the substitution on the fullerene. PMID:27485768

  10. Minimization principle for non degenerate excited states (independent of orthogonality to lower lying known approximants)

    Bacalis, Naoum C

    2016-01-01

    The computation of small concise and comprehensible excited state wave functions is needed because many electronic processes occur in excited states. But since the excited energies are saddle points in the Hilbert space of wave functions, the standard computational methods, based on orthogonality to lower lying approximants, resort to huge and incomprehensible wave functions, otherwise, the truncated wave function is veered away from the exact. The presented variational principle for excited states, Fn, is demonstrated to lead to the correct excited eigenfunction in necessarily small truncated spaces. Using Hylleraas coordinates for He 1S 1s2s, the standard method based on the theorem of Hylleraas - Unheim, and MacDonald, yields misleading main orbitals 1s1s' and needs a series expansion of 27 terms to be corrected, whereas minimizing Fn goes directly to the corect main orbitals, 1s2s, and can be adequately improved by 8 terms. Fn uses crude, rather inaccurate, lower lying approximants and does not need ortho...

  11. Self-energy correction to the hyperfine splitting for excited states

    The self-energy corrections to the hyperfine splitting is evaluated for higher excited states in hydrogenlike ions using an expansion in the binding parameter Zα, where Z is the nuclear-charge number and α is the fine-structure constant. We present analytic results for D, F, and G states, and for a number of highly excited Rydberg states, with principal quantum numbers in the range 13≤n≤16, and orbital angular momenta l=n-2 and l=n-1. A closed-form analytic expression is derived for the contribution of high-energy photons, valid for any state with l≥2 and arbitrary n, l, and total angular momentum j. The low-energy contributions are written in the form of generalized Bethe logarithms and evaluated for selected states.

  12. Excited-state dynamics in light-harvesting complex of Rhodobacter sphaeroides

    LIU KangJun; LIU WeiMin; YAN YongLi; DONG ZhiWei; XU ChunHe; QIAN ShiXiong

    2008-01-01

    Photodynamics of peripheral antenna complexes, light-harvesting complex (LH2) of Rhodobacter (Rb) Sphaeroides 601, was studied using femtosecond pump-probe technique at different laser wavelengths. The obtained results reveal dramatic dynamical evolutions within B800 and B850 absorption bands of antenna complexes LH2. At excitation wavelength around 835 nm, a sharp photobleaching signal was observed which was assigned to the contribution of the two-exciton state, which was further confirmed by the power dependence measurement. Rate equations with eight-level scheme were used to calculate the population evolution in LH2 and the transient dynamics under femtosecond pulse excitation. The research results prove that not only the transition from ground state to one-exciton state but also that from one-exciton state to two-exciton state contribute to the photodynamics of B850.

  13. Carbon nanorings with inserted acenes: breaking symmetry in excited state dynamics.

    Franklin-Mergarejo, R; Alvarez, D Ondarse; Tretiak, S; Fernandez-Alberti, S

    2016-01-01

    Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation to the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications. PMID:27507429

  14. Extended Eckart Theorem and New Variation Method for Excited States of Atoms

    Xiong, Zhuang; Bacalis, N C; Zhou, Qin

    2016-01-01

    We extend the Eckart theorem, from the ground state to excited statew, which introduces an energy augmentation to the variation criterion for excited states. It is shown that the energy of a very good excited state trial function can be slightly lower than the exact eigenvalue. Further, the energy calculated by the trial excited state wave function, which is the closest to the exact eigenstate through Gram-Schmidt orthonormalization to a ground state approximant, is lower than the exact eigenvalue as well. In order to avoid the variation restrictions inherent in the upper bound variation theory based on Hylleraas, Undheim, and McDonald [HUM] and Eckart Theorem, we have proposed a new variation functional Omega-n and proved that it has a local minimum at the eigenstates, which allows approaching the eigenstate unlimitedly by variation of the trial wave function. As an example, we calculated the energy and the radial expectation values of Triplet-S(even) Helium atom by the new variation functional, and by HUM a...

  15. Structure of low-lying states in 140Sm studied by Coulomb excitation

    Klintefjord, M.; Hadyńska-KlÈ©k, K.; Görgen, A.; Bauer, C.; Bello Garrote, F. L.; Bönig, S.; Bounthong, B.; Damyanova, A.; Delaroche, J.-P.; Fedosseev, V.; Fink, D. A.; Giacoppo, F.; Girod, M.; Hoff, P.; Imai, N.; Korten, W.; Larsen, A.-C.; Libert, J.; Lutter, R.; Marsh, B. A.; Molkanov, P. L.; Naïdja, H.; Napiorkowski, P.; Nowacki, F.; Pakarinen, J.; Rapisarda, E.; Reiter, P.; Renstrøm, T.; Rothe, S.; Seliverstov, M. D.; Siebeck, B.; Siem, S.; Srebrny, J.; Stora, T.; Thöle, P.; Tornyi, T. G.; Tveten, G. M.; Van Duppen, P.; Vermeulen, M. J.; Voulot, D.; Warr, N.; Wenander, F.; De Witte, H.; Zielińska, M.

    2016-05-01

    The electromagnetic structure of 140Sm was studied in a low-energy Coulomb excitation experiment with a radioactive ion beam from the REX-ISOLDE facility at CERN. The 2+ and 4+ states of the ground-state band and a second 2+ state were populated by multistep excitation. The analysis of the differential Coulomb excitation cross sections yielded reduced transition probabilities between all observed states and the spectroscopic quadrupole moment for the 21+ state. The experimental results are compared to large-scale shell model calculations and beyond-mean-field calculations based on the Gogny D1S interaction with a five-dimensional collective Hamiltonian formalism. Simpler geometric and algebraic models are also employed to interpret the experimental data. The results indicate that 140Sm shows considerable γ softness, but in contrast to earlier speculation no signs of shape coexistence at low excitation energy. This work sheds more light on the onset of deformation and collectivity in this mass region.

  16. Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

    Van Tassle, Aaron Justin

    2006-09-01

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

  17. The structure of low-lying states in ${}^{140}$Sm studied by Coulomb excitation

    Klintefjord, M; Görgen, A; Bauer, C; Garrote, F L Bello; Bönig, S; Bounthong, B; Damyanova, A; Delaroche, J-P; Fedosseev, V; Fink, D A; Giacoppo, F; Girod, M; Hoff, P; Imai, N; Korten, W; Larsen, A C; Libert, J; Lutter, R; Marsh, B A; Molkanov, P L; Naïdja, H; Napiorkowski, P; Nowacki, F; Pakarinen, J; Rapisarda, E; Reiter, P; Renstrøm, T; Rothe, S; Seliverstov, M D; Siebeck, B; Siem, S; Srebrny, J; Stora, T; Thöle, P; Tornyi, T G; Tveten, G M; Van Duppen, P; Vermeulen, M J; Voulot, D; Warr, N; Wenander, F; De Witte, H; Zielińska, M

    2016-01-01

    The electromagnetic structure of $^{140}$Sm was studied in a low-energy Coulomb excitation experiment with a radioactive ion beam from the REX-ISOLDE facility at CERN. The $2^+$ and $4^+$ states of the ground-state band and a second $2^+$ state were populated by multi-step excitation. The analysis of the differential Coulomb excitation cross sections yielded reduced transition probabilities between all observed states and the spectroscopic quadrupole moment for the $2_1^+$ state. The experimental results are compared to large-scale shell model calculations and beyond-mean-field calculations based on the Gogny D1S interaction with a five-dimensional collective Hamiltonian formalism. Simpler geometric and algebraic models are also employed to interpret the experimental data. The results indicate that $^{140}$Sm shows considerable $\\gamma$ softness, but in contrast to earlier speculation no signs of shape coexistence at low excitation energy. This work sheds more light on the onset of deformation and collectivit...

  18. Carbon nanorings with inserted acenes: breaking symmetry in excited state dynamics

    Franklin-Mergarejo, R.; Alvarez, D. Ondarse; Tretiak, S.; Fernandez-Alberti, S.

    2016-08-01

    Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation to the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications.

  19. Influence of Protonation State on the Excited State Dynamics of a Photobiologically Active Ru(II) Dyad.

    Reichardt, Christian; Sainuddin, Tariq; Wächtler, Maria; Monro, Susan; Kupfer, Stephan; Guthmuller, Julien; Gräfe, Stefanie; McFarland, Sherri; Dietzek, Benjamin

    2016-08-18

    The influence of ligand protonation on the photophysics of a ruthenium (Ru) dyad bearing the 2-(1-pyrenyl)-1H-imidazo[4,5-f][1,10]-phenanthroline (ippy) ligand was investigated by time-resolved transient absorption spectroscopy. It was found that changes in the protonation state of the imidazole group led to changes in the electronic configuration of the lowest lying excited state. Formation of the fully deprotonated imidazole anion resulted in excited state signatures that were consistent with a low-lying intraligand (IL) triplet state. This assignment was supported by time-dependent density functional theory (TDDFT) calculations. IL triplet states have been suggested to be potent mediators of photodynamic effects. Thus, these results are of interest in the design of Ru metal complexes as photosensitizers (PSs) for photodynamic therapy (PDT). PMID:27459188

  20. Relativistic time-dependent density functional calculations for the excited states of the cadmium dimer

    Kullie, Ossama, E-mail: kullie@uni-kassel.de [Institute de Chimie de Strasbourg, CNRS et Université de Strasbourg, Laboratoire de Chimie Quantique, 4 rue Blaise Pascal, 67070 Strasbourg (France); Theoretical Physics, Institute for Physics, Department of Mathematics and Natural Science, University of Kassel (Germany)

    2013-03-29

    Highlights: ► The achievement of CAMB3LYP functional for excited states in framework of TD-DFT. ► Relativistic 4-components calculations for the excited states of the Cd{sub 2} dimer. ► Relativistic Spin-Free calculations for the excited states of Cd{sub 2} dimer. ► A comparison of the achievements of different types of DFT approximations upon Cd{sub 2}. - Abstract: In this paper we present a time-dependent density functional study for the ground-state as well the 20-lowest laying excited states of the cadmium dimer Cd{sub 2}, we analyze its spectrum obtained from all electrons calculations performed with time-depended density functional for the relativistic Dirac-Coulomb- and relativistic spin-free-Hamiltonian as implemented in DIRAC-PACKAGE. The calculations were obtained with different density functional approximations, and a comparison with the literature is given as far as available. Our result is very encouraging, especially for the lowest excited states of this dimer, and is expected to be enlightened for similar systems. The result shows that only long-range corrected functionals such as CAMB3LYP, gives the correct asymptotic behavior for the higher states. A comparable but less satisfactory results were obtained with B3LYP and PBE0 functionals. Spin-free-Hamiltonian is shown to be very efficient for systems containing heavy elements such as Cd{sub 2} in frameworks of (time-dependent) density functional without introducing large errors.

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

    Fernandez-Menchero, L; Badnell, N R

    2016-01-01

    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 ...

  2. Lifetimes of ultralong-range Rydberg molecules in vibrational ground and excited states

    Butscher, Bjoern; Bendkowsky, Vera; Nipper, Johannes; Balewski, Jonathan B; Kukota, Ludmila; Loew, Robert; Pfau, Tilman [5. Physikalisches Institut, Universitaet Stuttgart, Pfaffenwaldring 57, 70569 Stuttgart (Germany); Li, Weibin; Pohl, Thomas; Rost, Jan Michael, E-mail: b.butscher@physik.uni-stuttgart.de [Max-Planck-Institut fuer Physik komplexer Systeme, Noethnitzer Str. 38, 01187 Dresden (Germany)

    2011-09-28

    Since their first experimental observation, ultralong-range Rydberg molecules consisting of a highly excited Rydberg atom and a ground state atom [1, 2] have attracted the interest in the field of ultracold chemistry [3, 4]. Especially the intriguing properties such as size, polarizability and type of binding they inherit from the Rydberg atom are of interest. An open question in the field is the reduced lifetime of the molecules compared to the corresponding atomic Rydberg states [2]. In this paper we present an experimental study on the lifetimes of the {sup 3}{Sigma}(5s - 35s) molecule in its vibrational ground state and in an excited state. We show that the lifetimes depend on the density of ground state atoms and that this can be described in the frame of a classical scattering between the molecules and ground state atoms. We also find that the excited molecular state has an even more reduced lifetime compared to the ground state which can be attributed to an inward penetration of the bound atomic pair due to imperfect quantum reflection that takes place in the special shape of the molecular potential [5].

  3. Positive-parity excited states of the nucleon in quenched lattice QCD

    Positive-parity spin-(1/2) excitations of the nucleon are explored in lattice QCD. The variational method is used in this investigation and several correlation matrices are employed. As our focus is on the utility and methodology of the variational approach, we work in the quenched approximation to QCD. Various sweeps of Gaussian fermion-field smearing are applied at the source and at the sink of χ1χ1 and χ1χ2 correlation functions to obtain a large basis of operators. Using several different approaches for constructing basis interpolators, we demonstrate how improving the basis can split what otherwise might be interpreted as a single state into multiple eigenstates. Consistency of the extracted excited energy states are explored over various dimensions of the correlation matrices. The use of large correlation matrices is emphasized for the reliable extraction of the excited eigenstates of QCD.

  4. Electron impact excitation of 2p and 3p states of hydrogen at intermediate energies

    A coupled-channel-optical (CCO) calculation with 9 and 12 atomic states supplemented with the continuum optical potentials for the stronger coupling channels has been performed for the electron impact excitation of hydrogen. The calculated n = 2 and n = 3 differential cross sections and the reduced Stokes parameters are comparable with the state-of-the art calculations. There is closer agreement between the present calculations and the experimental measurements for the reduced Stokes parameters P-bar1 and P-bar3 in the n = 2p excitation at 54.4 eV. The present CCO calculations also display good accord with the limited experimental data for the reduced Stokes parameters in the n = 3p excitation. (authors)

  5. Resonance-enhanced photon excitation spectroscopy of the even-parity autoionizing Rydberg states of Kr

    2009-01-01

    Kr atoms were produced in their metastable states 4p55s [3/2]2 and 4p55s’ [1/2]0 in a pulsed DC dis-charge in a beam,and subsequently excited to the even-parity autoionizing Rydberg states 4p5np’ [3/2]1,2,[1/2]1 and 4p5nf’ [5/2]3 using single photon excitation.The excitation spectra of the even-parity autoionizing resonance series from the metastable Kr were obtained by recording the autoionized Kr+ ions with time-of-flight ion detection in the photon energy range of 29000-40000 cm1.A wealth of autoionizing resonances were newly observed,from which more precise and more systematic spec-troscopic data of the level energy and quantum defects were derived.

  6. Excited eigenmodes in magnetic vortex states of soft magnetic half-spheres and spherical caps

    We studied the magnetization dynamics of excitation modes in special geometrical confinements of soft magnetic half-spheres and spherical caps in magnetic vortex states using finite-element micromagnetic numerical calculations. We found additional fine features of the zeroth- and first-order gyrotropic modes and asymmetric m = +1 and m = −1 azimuthal spin-wave modes, which detailed information is unobtainable from two-dimensional mesh-cell based numerical calculations. Moreover, we examined the perpendicular bias field dependence of the excited eigenmodes, which data provide for an efficient means of control over the excited modes. Such numerical calculations offer additional details or new underlying physics on dynamic features in arbitrary-shape magnetic nano-elements such as half-spheres and spherical caps in magnetic vortex states

  7. First experimental evidence of 2He decay from 18Ne excited states

    Rapisarda, E; Cardella, G; De Napoli, M; Raciti, G; Sfienti, C

    2010-01-01

    Two-proton decay from 18Ne excited states has been studied by complete kinematical detection of the decay products. The 18Ne nucleus has been produced as a radioactive beam by 20Ne projectile fragmentation at 45 AMeV on a 9Be target, using the FRIBs in-flight facility of the LNS. The 18Ne at 33 AMeV incident energy has been excited via Coulomb excitation on a natPb target. The correlated 2p emission has been disentangled from the uncorrelated 2p emission using a high granularity particle detector setup allowing the reconstruction of momentum and angle correlations of the two emitted protons. The obtained results unambiguously show that the 6.15 MeV 18Ne state two-proton decay proceeds through 2He emission (31%) and democratic or virtual sequential decay (69%).

  8. Experimental Evidence of He2 Decay from Ne18 Excited States

    Raciti, G.; Cardella, G.; de Napoli, M.; Rapisarda, E.; Amorini, F.; Sfienti, C.

    2008-05-01

    Two-proton decay from Ne18 excited states has been studied by complete kinematical reconstruction of the decay products. The Ne18 nucleus has been produced as a radioactive beam by Ne20 primary projectile fragmentation at 45AMeV incident energy on a Be target. The Ne18 at 33AMeV incident energy has been excited via Coulomb excitation on a Pbnat target. The obtained results unambiguously show that the 6.15 MeV Ne18 state two-proton decay proceeds through a He2 diproton resonance (31%) and democratic or virtual sequential decay (69%). The quoted branching ratio has been deduced from relative angle and momentum correlations of the emitted proton pairs.

  9. Exact ground and excited states of an antiferromagnetic quantum spin model

    A quasi-one-dimensional spin model which consists of a chain of octahedra of spins has been suggested for which a certain parameter regime of the Hamiltonian, the ground state, can be written down exactly. The ground state is highly degenerate and can be other than a singlet. Also, several excited states can be constructed exactly. The ground state is a local RVB state for which resonance is confined to rings of spins. Some exact numerical results for an octahedron of spins have also been reported. (author). 16 refs, 2 figs, 1 tab

  10. Singlet and triplet excited states and intersystem crossing in free-base porphyrin: TDDFT and DFT/MRCI study.

    Perun, Serhiy; Tatchen, Jörg; Marian, Christel M

    2008-02-01

    Extensive time-dependent DFT (TDDFT) and DFT/multireference configuration interaction (MRCI) calculations are performed on the singlet and triplet excited states of free-base porphyrin, with emphasis on intersystem crossing processes. The equilibrium geometries, as well as the vertical and adiabatic excitation energies of the lowest singlet and triplet excited states are determined. Single and double proton-transfer reactions in the first excited singlet state are explored. Harmonic vibrational frequencies are calculated at the equilibrium geometries of the ground state and of the lowest singlet and triplet excited states. Furthermore, spin-orbit coupling matrix elements of the lowest singlet and triplet states and their numerical derivatives with respect to nuclear displacements are computed. It is shown that opening of an unprotonated pyrrole ring as well as excited-state single and double proton transfer inside the porphyrin cavity lead to crossings of the potential energy curves of the lowest singlet and triplet excited states. It is also found that displacements along out-of-plane normal modes of the first excited singlet state cause a significant increase of the , , and spin-orbit coupling matrix elements. These phenomena lead to efficient radiationless deactivation of the lowest excited states of free-base porphyrin via intercombination conversion. In particular, the S1-->T1 population transfer is found to proceed at a rate of approximately 10(7) s(-1) in the isolated molecule. PMID:18189251

  11. Observation of excited-state excitons and band-gap renormalization in hole-doped carbon nanotubes using photoluminescence excitation spectroscopy

    Kimoto, Yoshio; Okano, Makoto; Kanemitsu, Yoshihiko

    2013-01-01

    The higher Rydberg states of the E11 exciton in undoped and hole-doped single-walled carbon nanotubes (SWCNTs) were studied using one- and two-photon photoluminescence excitation spectroscopy. Increasing the hole-dopant concentration resulted in a redshift of the first excited state (2g) and a blueshift of the ground state (1u) of the E11 exciton. From the redshift of higher Rydberg states, we found that a reduction of the band-gap energy occurs in hole-doped SWCNTs. These findings show that ...

  12. Ground and excited states of KNiF3: An ab initio cluster-model approach

    Casanovas, Jordi; Illas, Francesc

    1994-08-01

    Finite cluster models and a variety of ab initio wave functions have been used to study the electronic structure of bulk KNiF3. Several electronic states, including the ground state and some charge-transfer excited states, have been considered. The study of the cluster-model wave functions has permitted an understanding of the nature of the chemical bond in the electronic ground state. This is found to be highly ionic and the different ionic and covalent contributions to the bonding have been identified and quantified. Finally, we have studied the charge-transfer excited states leading to the optical gap and have found that calculated and experimental values are in good agreement. The wave functions corresponding to these excited states have also been analyzed and show that although KNiF3 may be described as a ligand-to-metal charge-transfer insulator there is a strong configuration mixing with the metal-to-metal charge-transfer states.

  13. What can we learn from excited state GDR measurements in heavy ion reactions?

    The status of measurements of the giant dipole resonance (GDR) built on the excited states are reviewed. The study of the GDR as a function of angular momentum and temperature is expected to throw light on the evolution of the strength function with spin and temperature

  14. Measurement of double beta decay of 100Mo to excited states in the NEMO 3 experiment

    The double beta decay of 100Mo to the 01+ and 21+ excited states of 100Ru is studied using the NEMO 3 data. After the analysis of 8024 h of data the half-life for the two-neutrino double beta decay of 100Mo to the excited 01+ state is measured to be T1/2(2ν)=[5.7-0.9+1.3(stat.)+/-0.8(syst.)]x1020 y. The signal-to-background ratio is equal to 3. Information about energy and angular distributions of emitted electrons is also obtained. No evidence for neutrinoless double beta decay to the excited 01+ state has been found. The corresponding half-life limit is T1/2(0ν)(0+->01+)>8.9x1022 y (at 90% C.L.). The search for the double beta decay to the 21+ excited state has allowed the determination of limits on the half-life for the two neutrino mode T1/2(2ν)(0+->21+)>1.1x1021 y (at 90% C.L.) and for the neutrinoless mode T1/2(0ν)(0+->21+)>1.6x1023 y (at 90% C.L.)

  15. Effect of carotenoid structure on excited-state dynamics of carbonyl carotenoids

    Chábera, P.; Fuciman, M.; Hříbek, P.; Polívka, Tomáš

    2009-01-01

    Roč. 11, - (2009), s. 8795-8703. ISSN 1463-9076 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : excited-state dynamics * carbonyl carotenoids * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 4.116, year: 2009

  16. Measurement of double beta decay of 100Mo to excited states in the NEMO 3 experiment

    Arnold, R; Baker, J; Barabash, A S; Bongrand, M; Broudin, G; Brudanin, V; Caffrey, A J; Egorov, V; Etienvre, A I; Fatemi-Ghomi, N; Hubert, F; Hubert, P; Jerie, J; Jollet, C; Jullian, S; King, S; Kochetov, O; Konovalov, S I; Kovalenko, V; Lalanne, D; Lamhamdi, T; Leccia, F; Lemière, Y; Longuemare, C; Lutter, G; Marquet, C; Mauger, F; Nachab, A; Ohsumi, H; Perrot, F; Piquemal, F; Reyss, J L; Ricol, J S; Saakyan, R; Sarazin, X; Shitov, Y; Simard, L; Simkovic, F; Smolnikov, A; Stekl, I; Suhonen, J; Sutton, C S; Szklarz, G; Söldner-Rembold, S; Thomas, J; Timkin, V; Tretyak, V; Umatov, V; Vanyushin, I A; Vasilev, V; Vorobel, V; Vylov, T; Vàla, L; Hubert, Ph.; Marquet, Ch.; Shitov, Yu.; Vylov, Ts.

    2007-01-01

    The double beta decay of 100Mo to the 0^+_1 and 2^+_1 excited states of 100Ru is studied using the NEMO 3 data. After the analysis of 8024 h of data the half-life for the two-neutrino double beta decay of 100Mo to the excited 0^+_1 state is measured to be T^(2nu)_1/2 = [5.7^{+1.3}_{-0.9}(stat)+/-0.8(syst)]x 10^20 y. The signal-to-background ratio is equal to 3. Information about energy and angular distributions of emitted electrons is also obtained. No evidence for neutrinoless double beta decay to the excited 0^+_1 state has been found. The corresponding half-life limit is T^(0nu)_1/2(0^+ --> 0^+_1) > 8.9 x 10^22 y (at 90% C.L.). The search for the double beta decay to the 2^+_1 excited state has allowed the determination of limits on the half-life for the two neutrino mode T^(2nu)_1/2(0^+ --> 2^+_1) > 1.1 x 10^21 y (at 90% C.L.) and for the neutrinoless mode T^(0nu)_1/2(0^+ --> 2^+_1) > 1.6 x 10^23 y (at 90% C.L.).

  17. From chlorophyll a towards bacteriochlorophyll a: Excited-state processes of modified pigments

    Teuchner, K.; Stiel, H.; Leupold, D; Katheder, Ingrid; Scheer, Hugo

    1994-01-01

    By means of fluorescence spectroscopy and nonlinear absorption experiments, excited-state processes of the modified pigments [3-acetyl]-chlorophyll a, [31-OH]-bacteriochlorophyll a and [3-vinyl]-bacteriochlorophyll a were investigated and compared with those of chlorophyll a and bacteriochlorophyll a.

  18. Double Beta Decays into Excited States in $^{110}$Pd and $^{102}$Pd

    Lehnert, B; Degering, D; Hult, M; Laubenstein, M; Wester, T; Zuber, K

    2016-01-01

    A search for double beta decays of $^{110}$Pd and $^{102}$Pd into excited states of the daughter nuclides has been performed using three ultra-low background gamma-spectrometry measurements in the Felsenkeller laboratory, Germany, the HADES laboratory, Belgium and at the LNGS, Italy. The combined Bayesian analysis of the three measurements sets improved half-life limits for the $2\

  19. Resonance raman and absorption spectra of isomeric retinals in their lowest excited triplet states

    Wilbrandt, Robert Walter; Jensen, N.-H.; Houee-Levin, C.

    1985-01-01

    The triplet-triplet absorption spectra of 9-cis and all-trans-retinal as well as the time-resolved resonance Raman spectra of the lowest electronically excited triplet states of 9-cis-, 11-cis, 13-cis and all-trans-retinal in aromatic solvents at room temperature were obtained under conditions en...

  20. A Theoretical Study of Super-Excited States of F2

    ZHANG Wei-Hua; HE Chun-long; HAO Yu-Song; MO Yu-Xiang; Li Jia-Ming

    2007-01-01

    In the framework of quantum defect theory, we study super-excited states of F2 molecules which can dissociate into F+(3P2,1,0) and F-(1So) ion-pair. Based on our calculation, we present a vibrational resolved assignment of the high precision photofragment yield spectra for F- from the F2 ion-pair production.

  1. Generation of motional Fock states of a trappedion in the mediate-excitation regime

    Zheng Shi-Biao

    2004-01-01

    We propose a scheme to prepare Fock states for the vibrational motion of a trapped ion. Unlike previous schemes,the present scheme works in the mediate-excitation regime, in which the corresponding Rabi frequency is equal to the trap frequency. Thus, the required time is greatly shortened, which is important in view of decoherence.

  2. DILEPTON DECAY OF GIANT-RESONANCES BUILT ON EXCITED-STATES OF SI-28

    BUDA, A; BACELAR, JC; BALANDA, A; SUJKOWSKI, Z; VANDERWOUDE, A; BERSCH, R; CHING, H; DIOSZEGI, [No Value; HOFMAN, DJ; PAUL, P; SCHADMAND, S; VARMA, R

    1995-01-01

    Nuclear states in Si-28 were populated at an initial excitation energy E* = 50 MeV via the isospin T = 0 reaction O-16 + C-12. The dilepton- and photon-decay yields were measured simultaneously for the first time up to transition energies of 30 MeV. Statistical decay calculations describe well both

  3. Excited state absorption in chromium doped Li2B4O7 glass

    Koepke, Cz; Wisniewski, K.; Grinberg, M.; Majchrowski, A.; Han, T. P. J.

    2001-03-01

    Excited state absorption (ESA) measurements of the Cr:Li2B4O7 glass (Cr:LBO-glass) along with preliminary interpretation are presented. The presence of chromium in its tri- (d3) and hexa- (d0) valence states is observed. Both Cr3+ and Cr6+ ions appear to contribute in the de-excitation processes and can be attributed in the ESA spectra under excitation wavelengths at 308 nm, 488 nm, 515 nm and 610 nm. The ESA spectra detected with UV excitation have been interpreted in terms of transitions in the framework of the Cr5+O- centre, which forms after charge-transfer-type absorption in the [CrO4]2- group. Assumption of the double-electron state of the 3d22p4 electronic configuration together with crystal-field-split states of the 3d12p5 configuration allowed us to reproduce the obtained ESA spectra. The ESA spectra of the Cr3+ ions have different characteristics and are related to transitions to the conduction band.

  4. Stark effect of interfering electronic states: Localization of the nπ* excitations in toluquinone

    Galaup, J. P.; Trommsdorff, H. P.

    1984-04-01

    High-precision Stark measurements on oriented single crystals of toluquinone at low temperatures have been performed and lead to an assessment of the electronic parenthood of the levels giving rise to the complex spectral region of interference between the two nearby nπ* excited states. The origin bands of the lowest excited singlet and triplet states are characterized by a measure of their factor-group splittings and an evaluation of the change in dipole moment and in polarizability upon excitation. The value of the change in dipole moment is shown to vary strongly between different vibrational levels of the lower state and an evaluation of the degree of localization of the electronic excitation on one CO group is made. The previous assignment of the second nπ* state is confirmed by the sign of the corresponding Stark shift. From measurements on crystals having been oriented in an electric field the absolute orientation of the polar crystal as well as the sign of the pyroelectric coefficient are proposed.

  5. Excited-state properties of phenolic carotenoids from green sulphur bacteria

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

    Nové Hrady : Academic and University Center, 2008. s. 43. [ESF Workshop on Novel Methods in Exploring Carotenoid Excited State Dynamics. 21.09.2008-25.09.2008, Nové Hrady] Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids Subject RIV: BO - Biophysics

  6. Effect of carotenoid structure on excited state dynamics of carbonyl carotenoids

    Chábera, P.; Fuciman, M.; Hříbek, P.; Polívka, Tomáš

    Messina : Universitá di Messina, 2008. s. 53. [ESF Workshop on Ultrafast Excited-State Processes in Condensed Phases. 18.06.2008-21.06.2008, Santa Tecla] Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * carotenoid structure Subject RIV: BO - Biophysics

  7. Ponderomotive dressing of doubly-excited states with intensity-controlled laser light

    Ding Thomas

    2013-03-01

    Full Text Available We laser-dress several doubly-excited states in helium. Tuning the coupling-laser intensity from perturbative to the strong-coupling regime, we are able to measure phases imprinted on the two-electron wavefunctions, and observe a new continuum coupling mechanism.

  8. Symmetry-breaking intramolecular charge transfer in the excited state of meso-linked BODIPY dyads

    Whited, Matthew T.

    2012-01-01

    We report the synthesis and characterization of symmetric BODIPY dyads where the chromophores are attached at the meso position, using either a phenylene bridge or direct linkage. Both molecules undergo symmetry-breaking intramolecular charge transfer in the excited state, and the directly linked dyad serves as a visible-light-absorbing analogue of 9,9′-bianthryl.

  9. THE ACQM THEORETICAL CALCULATION OF LOW—LYING EXCITED STATES FOR HeH

    Q.Q.GOU; Z.Y.Huang; 等

    1990-01-01

    The Low-lying excited states of HeH have been calculated by arrangement channel quantum mechanics(ACQM),The calculated potential curves,equilibrium geometry,Rc.dissociation energy Dc.harmonic vibration frequency ω0 and quadratic force coustant F2 are comparable with Ci calculations.

  10. Time-, angle- and kinetic-energy-resolved photoelectron spectroscopy of highly excited states of NO

    We investigate non-adiabatic dynamics of NO molecules that are photo-excited in the vacuum ultraviolet photon energy range using time-resolved velocity map imaging. Highly excited valence and Rydberg states are populated with a tunable (147–151 nm) femtosecond laser pulse and then ionized by a time-delayed near-IR laser pulse. Three main contributions are observed in the photoelectron kinetic spectra with corresponding electron yields that show pronounced oscillations. Two oscillations are assigned to ro-vibronic coupling in the valence-Rydberg mixture of the B′2Δ(v=7) and 4dδ N2Δ(v = 0) states and the B2Π(v = 25) and 4pπ K2Π(v = 1) states, respectively. We assign a third oscillation to originate from a coupling between two Rydberg states. (paper)

  11. Quantum fluctuations of mesoscopic damped mutual capacitance coupled double resonance RLC circuit in thermal excitation state

    XU Xing-Lei

    2007-01-01

    Mesoscopic damped mutual capacitance coupled double resonance circuit is quantized by the method of damped harmonic oscillator quantization. Hamiltonian is diagonalized by the method of unitary transformation. The energy spectra of this circuit are given. The quantum fluctuations of the charge and current of each loop are investigated by the method of thermofield dynamics (TFD) in thermal excitation state,thermal squeezed vacuum state,thermal vacuum state and vacuum state. It is shown that the quantum fluctuations of the charge and current are related to not only circuit inherent parameter and coupled magnitude,but also quantum number of excitation,squeezed coefficients,squeezed angle and environmental temperature. And the quantum fluctuations increase with the increase of temperature and decay with time.

  12. Determination of natural radiative lifetimes and Lande factors for highly excited F states in cesium

    Natural radiative lifetimes and Lande gsub(J) factors for several highly excited F states in cesium were measured using time-resolved fluorescence spectroscopy. The F states were excited from the 52D5/2 state with a pulse-modulated CW dye layer, and the delayed-coincidence method was employed to record decay curves, which in some experiments exhibited Zeeman quantum beats. A further CW dye laser was used to produce the necessary population in the 52D5/2 state. The lifetimes in the sequence 11-162F7/2 follow a nsup(x) scaling law with x=2.76 and the Lande factors agree with the predicted value, 1.143. (orig.)

  13. Excited states and electrochromism of radical cation of the carotenoid astaxanthin

    Krawczyk, Stanisław

    1998-09-01

    Radical cations of the carotenoid astaxanthin were generated by chemical oxidation with Fe(Cl) 3, and their absorption and electroabsorption (Stark) spectra at temperatures about 150 K were recorded in the spectral range from 5900 to 26000 cm -1 (380 to 1700 nm), covering two absorptive electronic transitions from D 0 (ground) to D 1 and D 2 excited states. The changes in static polarizability are negative and equal -40±10 A 3 for D 0→D 1 and -105±15 A 3 for D 0→D 2, pointing that dominant contribution to polarizabilities results from the coupling of D 1 and D 2 with the ground state. An approximate localization of the next excited state with ground-state parity is estimated based on arguments from perturbation theory.

  14. Excited-state spectroscopy of singly, doubly and triply-charmed baryons from lattice QCD

    Padmanath, M. [Tata Institute; Edwards, Robert G. [JLAB; Mathur, Nilmani [Tata Institute; Peardon, Michael [Trinity College

    2014-07-01

    We present the ground and excited state spectra of singly, doubly and triply-charmed baryons by using dynamical lattice QCD. A large set of baryonic operators that respect the symmetries of the lattice and are obtained after subduction from their continuum analogues are utilized. These operators transform as irreducible representations of SU(3)F symmetry for flavour, SU(4) symmetry for Dirac spins of quarks and O(3) symmetry for orbital angular momenta. Using novel computational techniques correlation functions of these operators are generated and the variational method is exploited to extract excited states. The lattice spectra that we obtain have baryonic states with well-defined total spins up to 7/2 and the low lying states remarkably resemble the expectations of quantum numbers from SU(6)ⓍO(3) symmetry.

  15. Excited-state PAW Potentials: Modelling Hot-Dense Plasmas From First Principles

    Hollebon, Patrick; Vinko, Sam; Ciricosta, Orlando; Wark, Justin

    2015-11-01

    Finite temperature density functional theory has proven to be a successful means of modelling warm and hot dense plasma systems, including the calculation of transport properties, equation of state and ionization potential depression. Such methods take into account the non-negligible influence of quantum mechanics on the electronic structure of these strongly coupled systems. We apply excited state frozen core potentials to model general core-hole states in high density plasma, allowing for the calculation of the electronic structure of a range of ionic configurations. The advantages of using excited-state potentials are explored and we investigate their application towards various response function calculations, with the results shown to be in good agreement with all-electron calculations at finite-temperatures.

  16. Iodine molecule covalente excited states as determined by threshold electron spectrometry

    SLOBODAN MACURA

    2000-06-01

    Full Text Available The iodine molecule has been investigated by a threshold electron spectrometer in the incident electron energy range from 1.00 eV to 3.5eV. From the threshold electron spectrum contributions for excitation of three states known from optical spectrometry have been subtracted. The remaining signal has been interpreted by four curves similar in shape to those in absorption otpical spectroscopy into antibonding energy states. The detected maxima have been attributed to the following valence excited states of the iodine molecule: 3P2u(2u, 3P0u-(0u-, 3P2g(2g, and 3P1g(1g, respectively. With the knowledge of the energy ranges within which the signal from a particular state appears, the predicted values of equilibrium distances of iodine atom nuclei and estimated values of vibrational transition frequency potential energy curves have been constructed, too.

  17. The excited states of the neutral and ionized carbon in the regenerative sooting discharges

    We report the mechanisms of production and the state of excitation of the neutral and singly charged monatomic carbon in the regenerative soot as a function of the discharge parameters in graphite hollow cathode (HC) sources. Two distinctly different source configurations have been investigated. Comparisons of the level densities of various charged states of C1 have identified the regenerative properties of the C radicals in graphite HC soot

  18. Single-atom detection of ytterbium by selective laser excitation field ionization from Rydberg states

    Detection of single atoms Yb has been achieved using the method of electric-field ionization from the high-lying Rydberg states. Atoms of Yb in a beam were excited in three steps to a 17-p state by radiation of three pulsed dye lasers. The statistics of an atom's appearance in the interaction volume have been studied in the single-ion counting regime at low beam density

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

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

    2007-03-01

    Excited-state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulphonate, HPTS) to acetate in methanol has been studied by steady-state and time-resolved fluorescence spectroscopy. The rate constant of direct proton transfer from pyranine to acetate (1) is calculated to be ∼ 1 × 109 M-1 s-1. This is slower by about two orders of magnitude than that in bulk water (8 × 1010 M-1 s-1) at 4 M acetate.

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

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

  1. Structure of excited states in nuclei near doubly magic 100SN

    The three neutron-deficient nuclei 94Pd, 98Cd and 104Sn in the vicinity of 100Sn were investigated by means of in-beam γ-ray spectroscopy of excited states. The isomeric decays in 94Pd and 98Cd were studied for the first time with an exclusive experimental setup for delayed γ-ray detection with complete exit channel identification based on information from neutron and charged-particle filter detectors. The structure of excited states of 94Pd showed the first indication of increasing proton-neutron interaction towards the N=Z line in this region of nuclei, that in turn might be related to increased proton-neutron pairing correlations predicted in Tz=0 nuclei. The closest neighbours of 100Sn with two active particles, 98Cd and 102Sn, are now known with their lowest excited states. The measured reduced transition probabilities for the decay of the isomeric 8+ and 6+ states in 98Cd and 102Sn, respectively, allowed to extract an effective quadrupole charge for neutron and proton in this region of nuclei based on the high configurational purity of the states. While the neutron effective charge appeared to be large and in agreement with expectation, the proton effective charge value is very small (eπ≤1). This controversial result, which would indicate that 100Sn is a very good closed shell nucleus with respect to quadrupole excitation, is not understood. An experimental reason for this result, related to existence of a core excited isomer, observed in the experiment by means of its half life but not γ-rays, which may have escaped observation, can not be definitely excluded and is left as possible explanation. (orig.)

  2. Picosecond spectral relaxation of curcumin excited state in toluene–alcohol mixtures

    Saini, R.K.; Das, K., E-mail: kaustuv@rrcat.gov.in

    2013-12-15

    Excited state photophysics of Curcumin in a binary solvent mixture of toluene and five different alcohols (Methanol, Ethanol, 1-Propanol, 1-Butanol and 1-Octanol) are compared with an instrument time resolution of ∼40 ps. As the alcohol mole-fraction is varied from zero to unity, the observed trends in the fluorescence quantum yield and lifetime of the pigment in toluene–alcohol mixtures changes significantly in going from Methanol to 1-Octanol. This is attributed to the different degree of modulation of the non-radiative rates associated with the excited state intermolecular H bonding between the pigment and the alcohol. Fluorescence decays taken at the red edge of the emission spectrum started to show measurable rise times (200–30 ps) the magnitude of which decreased gradually with increasing alcohol mole-fraction. As a consequence the solvation times in the binary mixture were observed to slow down considerably at certain solvent compositions compared to that in neat alcohol. However, in toluene-1-Octanol mixture, the rise times and corresponding solvation times did not show a dependence on the 1-Octanol mole-fraction. The observed results suggest that viscosity, polarity and hydrogen bonding property of the alcohol solvent plays an important role in the excited state processes of the pigment in toluene–alcohol mixture. -- Highlights: • Excited state photophysics of Curcumin in a binary solvent mixture of toluene and five different alcohols were studied. • The observed trends in the fluorescence properties are attributed to intermolecular H bonding between the pigment and the alcohol. • Except 1-Octanol, the average solvation times of the pigment were observed to depend upon alcohol mole-fraction. • Viscosity, polarity and hydrogen bonding play an important role in the excited state processes of the pigment.

  3. Structure of excited states in nuclei near doubly magic {sup 100}SN

    Gorska, M.

    1998-11-01

    The three neutron-deficient nuclei {sup 94}Pd, {sup 98}Cd and {sup 104}Sn in the vicinity of {sup 100}Sn were investigated by means of in-beam {gamma}-ray spectroscopy of excited states. The isomeric decays in {sup 94}Pd and {sup 98}Cd were studied for the first time with an exclusive experimental setup for delayed {gamma}-ray detection with complete exit channel identification based on information from neutron and charged-particle filter detectors. The structure of excited states of {sup 94}Pd showed the first indication of increasing proton-neutron interaction towards the N=Z line in this region of nuclei, that in turn might be related to increased proton-neutron pairing correlations predicted in T{sub z}=0 nuclei. The closest neighbours of {sup 100}Sn with two active particles, {sup 98}Cd and {sup 102}Sn, are now known with their lowest excited states. The measured reduced transition probabilities for the decay of the isomeric 8{sup +} and 6{sup +} states in {sup 98}Cd and {sup 102}Sn, respectively, allowed to extract an effective quadrupole charge for neutron and proton in this region of nuclei based on the high configurational purity of the states. While the neutron effective charge appeared to be large and in agreement with expectation, the proton effective charge value is very small (e{sub {pi}}{<=}1). This controversial result, which would indicate that {sup 100}Sn is a very good closed shell nucleus with respect to quadrupole excitation, is not understood. An experimental reason for this result, related to existence of a core excited isomer, observed in the experiment by means of its half life but not {gamma}-rays, which may have escaped observation, can not be definitely excluded and is left as possible explanation. (orig.)

  4. Picosecond spectral relaxation of curcumin excited state in toluene–alcohol mixtures

    Excited state photophysics of Curcumin in a binary solvent mixture of toluene and five different alcohols (Methanol, Ethanol, 1-Propanol, 1-Butanol and 1-Octanol) are compared with an instrument time resolution of ∼40 ps. As the alcohol mole-fraction is varied from zero to unity, the observed trends in the fluorescence quantum yield and lifetime of the pigment in toluene–alcohol mixtures changes significantly in going from Methanol to 1-Octanol. This is attributed to the different degree of modulation of the non-radiative rates associated with the excited state intermolecular H bonding between the pigment and the alcohol. Fluorescence decays taken at the red edge of the emission spectrum started to show measurable rise times (200–30 ps) the magnitude of which decreased gradually with increasing alcohol mole-fraction. As a consequence the solvation times in the binary mixture were observed to slow down considerably at certain solvent compositions compared to that in neat alcohol. However, in toluene-1-Octanol mixture, the rise times and corresponding solvation times did not show a dependence on the 1-Octanol mole-fraction. The observed results suggest that viscosity, polarity and hydrogen bonding property of the alcohol solvent plays an important role in the excited state processes of the pigment in toluene–alcohol mixture. -- Highlights: • Excited state photophysics of Curcumin in a binary solvent mixture of toluene and five different alcohols were studied. • The observed trends in the fluorescence properties are attributed to intermolecular H bonding between the pigment and the alcohol. • Except 1-Octanol, the average solvation times of the pigment were observed to depend upon alcohol mole-fraction. • Viscosity, polarity and hydrogen bonding play an important role in the excited state processes of the pigment

  5. Triplet excited state properties in variable gap π-conjugated donor–acceptor–donor chromophores

    Cekli, Seda

    2016-02-12

    A series of variable band-gap donor–acceptor–donor (DAD) chromophores capped with platinum(II) acetylide units has been synthesized and fully characterized by electrochemical and photophysical methods, with particular emphasis placed on probing triplet excited state properties. A counter-intuitive trend of increasing fluorescence quantum efficiency and lifetime with decreasing excited state energy (optical gap) is observed across the series of DAD chromophores. Careful study of the excited state dynamics, including triplet yields (as inferred from singlet oxygen sensitization), reveals that the underlying origin of the unusual trend in the fluorescence parameters is that the singlet–triplet intersystem crossing rate and yield decrease with decreasing optical gap. It is concluded that the rate of intersystem crossing decreases as the LUMO is increasingly localized on the acceptor unit in the DAD chromophore, and this result is interpreted as arising because the extent of spin–orbit coupling induced by the platinum heavy metal centers decreases as the LUMO is more localized on the acceptor. In addition to the trend in intersystem crossing, the results show that the triplet decay rates follow the Energy Gap Law correlation over a 1.8 eV range of triplet energy and 1000-fold range of triplet decay rates. Finally, femtosecond transient absorption studies for the DAD chromophores reveals a strong absorption in the near-infrared region which is attributed to the singlet excited state. This spectral band appears to be general for DAD chromophores, and may be a signature of the charge transfer (CT) singlet excited state.

  6. Nuclear asymptotic normalization coefficients and neutron halo of the excited states

    The authors have extracted the nuclear asymptotic normalization coefficients for the virtual transitions 12B ↔ 11B + n and 13C ↔12C + n via two transfer reactions 11B(d, p)12B and 12C(d, p)13C. With these coefficients, root-mean-square radii for the valence neutron in 12B and 13C have been calculated. Authors' results show that the second (Jπ = 2-), third (Jπ = 1-) excited states in 12B, and the first (Jπ = 1/2+) excited state in 13C are neutron halo states, whereas the third (Jπ = 5/2+) excited state in 13C is a neutron skin state. The retard effects of the Coulomb potential and the orbital angular momentum on halo formation have been quantitatively examined. A unified scaling law for the mean-square radius versus the effective nucleon separation energy is established for the systems with a neutron or proton in a weekly bound state

  7. Microscopic description of Coulomb and nuclear excitation of multiphonon states in $^{40}$Ca + $^{40}$Ca collisions

    N. Andres; Catara, F.; Lanza, E. G.; Chomaz, Ph.; FALLOT M.; Scarpaci, J.A.

    2001-01-01

    We calculate the inelastic scattering cross sections to populate one- and two-phonon states in heavy ion collisions with both Coulomb and nuclear excitations. Starting from a microscopic approach based on RPA, we go beyond it in order to treat anharmonicities and non-linear terms in the exciting field. These anharmonicities and non-linearities are shown to have important effects on the cross sections both in the low energy part of the spectrum and in the energy region of the Double Giant Quad...

  8. Excitation into high-lying states in Li3+–H collisions

    Ibaaz, Aicha; Esteban Hernandez, Rosa; Dubois, Alain; Sisourat, Nicolas

    2016-04-01

    We have studied the excitation of atomic hydrogen by fully-stripped lithium ion impact in the intermediate energy range using a new and efficient implementation of the two-center atomic orbital approach with Gaussian-type orbitals. Partial and state-selective cross sections have been obtained for excitation up to H(6 h). A careful investigation of the convergence of the results with respect to the basis set has been performed which allows us to estimate the accuracy of the cross sections. Furthermore, our calculations provide an explanation for the discrepancies between previous calculations on this collision system.

  9. Fermi-coupled spherically adapted effective states in the collisionless multiphoton excitation of SF6

    A calculation method for the collisionless multiphoton excitation of SF6 by intense CO2 laser light up to a chain of parallel nν3, (n - 1)ν3 + ν2 + ν6 ... vibrational-rotational ladders linked by Fermi interaction is described. Spherically adapted effective states suitable to the purpose are defined, and matrix elements for multiphoton excitation in the rotating wave approximation effective hamiltonian formalism are given in this basis. The method is aimed at the investigation of population transfer between the cited parallel vibrational ladders, and is suitable for computer-calculation programmation. (orig.)

  10. Fermi-coupled spherically adapted effective states in the collisionless multiphoton excitation of SF 6

    Di Lauro, C.; Lattanzi, F.

    1982-10-01

    A calculation method for the collisionless multiphoton excitation of SF 6 by intense CO 2 laser light up to a chain of parallel nv3, ( n - 1) v3 + v2 + v6 … vibrational-rotational ladders linked by Fermi interaction is described. Spherically adapted effective states suitable to the purpose are defined, and matrix elements for multiphoton excitation in the rotatingwave approximation effective hamiltonian formalism are given in this basis. The method is aimed at the investigation of population transfer between the cited parallel vibrational ladders, and is suitable for computer-calculation programmation.

  11. Numerical computation of dynamically important excited states of many-body systems

    Łącki, Mateusz; Delande, Dominique; Zakrzewski, Jakub

    2012-07-01

    We present an extension of the time-dependent density matrix renormalization group, also known as the time evolving block decimation algorithm, allowing for the computation of dynamically important excited states of one-dimensional many-body systems. We show its practical use for analyzing the dynamical properties and excitations of the Bose-Hubbard model describing ultracold atoms loaded in an optical lattice from a Bose-Einstein condensate. This allows for a deeper understanding of nonadiabaticity in experimental realizations of insulating phases.

  12. Excited state polarizabilities for CC2 using the resolution-of-the-identity approximation.

    Graf, Nora K; Friese, Daniel H; Winter, Nina O C; Hättig, Christof

    2015-12-28

    We report an implementation of static and frequency-dependent excited state polarizabilities for the approximate coupled cluster single and doubles model CC2 as analytic second derivatives of an excited state quasienergy Lagrangian. By including appropriate conditions for the normalization and the phase of the eigenvectors, divergent secular terms are avoided. This leads to response equations in a subspace orthogonal to the unperturbed eigenvectors. It is shown how these projected equations can be solved without storage of the double excitation part of the eigenvectors. By exploiting the resolution-of-the-identity approximation and a numerical Laplace transformation, the quadratic scaling of the main memory demands of RI-CC2 with the system size could be preserved. This enables calculations of excited state polarizabilities for large molecules, e.g., linear polyacenes up to decacene with almost 2500 basis functions on a single compute node within a few days. For a test set of molecules where measurements are available as reference data, we compare the orbital-relaxed and unrelaxed CC2 approaches with experiment to validate its accuracy. The approach can be easily extended to other response methods, in particular CIS(D∞). The latter gives results which, in the orbital-relaxed case, are within a few percent of the CC2 values, while coupled cluster singles results deviate typically by about 20% from orbital-relaxed CC2 and experimental reference data. PMID:26723652

  13. Role of excited state solvent fluctuations on time-dependent fluorescence Stokes shift

    Li, Tanping, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu; Kumar, Revati, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States)

    2015-11-07

    We explore the connection between the solvation dynamics of a chromophore upon photon excitation and equilibrium fluctuations of the solvent. Using molecular dynamics simulations, fluorescence Stokes shift for the tryptophan in Staphylococcus nuclease was examined using both nonequilibrium calculations and linear response theory. When the perturbed and unperturbed surfaces exhibit different solvent equilibrium fluctuations, the linear response approach on the former surface shows agreement with the nonequilibrium process. This agreement is excellent when the perturbed surface exhibits Gaussian statistics and qualitative in the case of an isomerization induced non-Gaussian statistics. However, the linear response theory on the unperturbed surface breaks down even in the presence of Gaussian fluctuations. Experiments also provide evidence of the connection between the excited state solvent fluctuations and the total fluorescence shift. These observations indicate that the equilibrium statistics on the excited state surface characterize the relaxation dynamics of the fluorescence Stokes shift. Our studies specifically analyze the Gaussian fluctuations of the solvent in the complex protein environment and further confirm the role of solvent fluctuations on the excited state surface. The results are consistent with previous investigations, found in the literature, of solutes dissolved in liquids.

  14. Role of excited state solvent fluctuations on time-dependent fluorescence Stokes shift

    Li, Tanping; Kumar, Revati

    2015-11-01

    We explore the connection between the solvation dynamics of a chromophore upon photon excitation and equilibrium fluctuations of the solvent. Using molecular dynamics simulations, fluorescence Stokes shift for the tryptophan in Staphylococcus nuclease was examined using both nonequilibrium calculations and linear response theory. When the perturbed and unperturbed surfaces exhibit different solvent equilibrium fluctuations, the linear response approach on the former surface shows agreement with the nonequilibrium process. This agreement is excellent when the perturbed surface exhibits Gaussian statistics and qualitative in the case of an isomerization induced non-Gaussian statistics. However, the linear response theory on the unperturbed surface breaks down even in the presence of Gaussian fluctuations. Experiments also provide evidence of the connection between the excited state solvent fluctuations and the total fluorescence shift. These observations indicate that the equilibrium statistics on the excited state surface characterize the relaxation dynamics of the fluorescence Stokes shift. Our studies specifically analyze the Gaussian fluctuations of the solvent in the complex protein environment and further confirm the role of solvent fluctuations on the excited state surface. The results are consistent with previous investigations, found in the literature, of solutes dissolved in liquids.

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

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

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

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

    2009-01-01

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

  17. Role of excited state solvent fluctuations on time-dependent fluorescence Stokes shift

    We explore the connection between the solvation dynamics of a chromophore upon photon excitation and equilibrium fluctuations of the solvent. Using molecular dynamics simulations, fluorescence Stokes shift for the tryptophan in Staphylococcus nuclease was examined using both nonequilibrium calculations and linear response theory. When the perturbed and unperturbed surfaces exhibit different solvent equilibrium fluctuations, the linear response approach on the former surface shows agreement with the nonequilibrium process. This agreement is excellent when the perturbed surface exhibits Gaussian statistics and qualitative in the case of an isomerization induced non-Gaussian statistics. However, the linear response theory on the unperturbed surface breaks down even in the presence of Gaussian fluctuations. Experiments also provide evidence of the connection between the excited state solvent fluctuations and the total fluorescence shift. These observations indicate that the equilibrium statistics on the excited state surface characterize the relaxation dynamics of the fluorescence Stokes shift. Our studies specifically analyze the Gaussian fluctuations of the solvent in the complex protein environment and further confirm the role of solvent fluctuations on the excited state surface. The results are consistent with previous investigations, found in the literature, of solutes dissolved in liquids

  18. Fermionic Basis in Conformal Field Theory and Thermodynamic Bethe Ansatz for Excited States

    Hermann Boos

    2011-01-01

    Full Text Available We generalize the results of [Comm. Math. Phys. 299 (2010, 825-866] (hidden Grassmann structure IV to the case of excited states of the transfer matrix of the six-vertex model acting in the so-called Matsubara direction. We establish an equivalence between a scaling limit of the partition function of the six-vertex model on a cylinder with quasi-local operators inserted and special boundary conditions, corresponding to particle-hole excitations, on the one hand, and certain three-point correlation functions of conformal field theory (CFT on the other hand. As in hidden Grassmann structure IV, the fermionic basis developed in previous papers and its conformal limit are used for a description of the quasi-local operators. In paper IV we claimed that in the conformal limit the fermionic creation operators generate a basis equivalent to the basis of the descendant states in the conformal field theory modulo integrals of motion suggested by A. Zamolodchikov (1987. Here we argue that, in order to completely determine the transformation between the above fermionic basis and the basis of descendants in the CFT, we need to involve excitations. On the side of the lattice model we use the excited-state TBA approach. We consider in detail the case of the descendant at level 8.

  19. Red and blue shift of liquid water's excited states: A many body perturbation study

    Ziaei, Vafa; Bredow, Thomas

    2016-08-01

    In the present paper, accurate optical absorption spectrum of liquid H2O is calculated in the energy range of 5-20 eV to probe the nature of water's excited states by means of many body perturbation approach. Main features of recent inelastic X-ray measurements are well reproduced, such as a bound excitonic peak at 7.9 eV with a shoulder at 9.4 eV as well as the absorption maximum at 13.9 eV, followed by a broad shoulder at 18.4 eV. The spectrum is dominated by excitonic effects impacting the structures of the spectrum at low and higher energy regimes mixed by single particle effects at high energies. The exciton distribution of the low-energy states, in particular of S1, is highly anisotropic and localized mostly on one water molecule. The S1 state is essentially a HOCO-LUCO (highest occupied crystal orbital - lowest unoccupied crystal orbital) transition and of intra-molecular type, showing a localized valence character. Once the excitation energy is increased, a significant change in the character of the electronically excited states occurs, characterized through emergence of multiple quasi-particle peaks at 7.9 eV in the quasi-particle (QP) transition profile and in the occurring delocalized exciton density distribution, spread over many more water molecules. The exciton delocalization following a change of the character of excited states at around 7.9 eV causes the blue shift of the first absorption band with respect to water monomer S1. However, due to reduction of the electronic band gap from gas to liquid phase, following enhanced screening upon condensation, the localized S1 state of liquid water is red-shifted with respect to S1 state of water monomer. For higher excitations, near vertical ionization energy (11 eV), quasi-free electrons emerge, in agreement with the conduction band electron picture. Furthermore, the occurring red and blue shift of the excited states are independent of the coupling of resonant and anti-resonant contributions to the

  20. Theoretical study of autoionizing states and lifetimes in multiply excited argon

    Autoionization transition rates have been calculated for a representative selection of spectroscopic terms of multiply excited argon atoms. The states selected consist of two highly excited electrons in the Rydberg states (n = 4,5), together with one or two vacancies in the valence shell (n = 3) and a single vacancy in the inner shell (n = 2). Configuration mixing was found to be important. The eigenvalues and eigenstates were found by the truncated diagonalization method (i.e., QHQ is diagonalized). The effect of term splitting was included by calculating the contributions of the quadrupole terms in the interelectron repulsive potentials. The applicability of the msnp +- classification scheme suggested by Cooper, Fano, and Prats for helium was investigated for the outer electrons. Among the doubly excited outer-shell states found here are pairs of states which predominantly have the characteristics of 45sp + and 45sp - levels. However, states of the less-ionized system show less +- character because the shielding of the nucleus by the core electrons removes the degeneracy in energy of 4s5p and 5s4p levels, so there is less mixing when there is more shielding. The lifetimes of the valence-electron (n = 3) shell decay range from approximately 10-17 to approximately 10-13 sec. The lifetimes of the highly excited electrons separate into two widely disparate ranges: from approximately 10-17 to approximately 10-16 sec and from approximately 10-13 to approximately 10-11 sec. The outer-shell states that have lifetimes shorter than the inner shell are those from which it is energetically possible for an electron to fall to a 4s, 4p, or 3d subshell, while the longer lifetimes are for states which can decay only to the n = 3 core

  1. Isoscalar monopole and dipole excitations of cluster states and giant resonances in 12C

    Kanada-En'yo, Yoshiko

    2016-05-01

    The isoscalar monopole (ISM) and dipole (ISD) excitations in 12C are investigated theoretically with the shifted antisymmetrized molecular dynamics (AMD) plus 3 α -cluster generator coordinate method (GCM). The small-amplitude vibration modes are described by coherent one-particle one-hole excitations expressed by a small shift of single-nucleon Gaussian wave functions within the AMD framework, whereas the large-amplitude cluster modes are incorporated by superposing 3 α -cluster wave functions in the GCM. The coupling of the excitations in the intrinsic frame with the rotation and parity transformation is taken into account microscopically by the angular-momentum and parity projections. The present a calculation that describes the ISM and ISD excitations over a wide energy region covering cluster modes in the low-energy region and the giant resonances in the high-energy region, although the quantitative description of the high-energy part is not satisfactory. The low-energy ISM and ISD strengths of the cluster modes are enhanced by the distance motion between α clusters, and they split into a couple of states because of the angular motion of α clusters. The low-energy ISM strengths exhaust 26% of the energy-weighted sum rule, which is consistent with the experimental data for the 12C(02+; 7.65 MeV) and 12C(03+; 10.3 MeV) measured by (e ,e') ,(α ,α') , and (6Li,6Li' ) scatterings. In the calculated low-energy ISD strengths, two 1- states (the 11- and 12- states) with the significant strengths are obtained over E =10 -15 MeV. The results indicate that the ISD excitations can be a good probe to experimentally search for new cluster states such as the 12C(12-) obtained in the present calculation.

  2. Calculations of three-dimensional magnetic excitations in permalloy nanostructures with vortex state

    Dynamic susceptibility spectra of the vortex state in nanorings and nanodots are studied using three-dimensional micromagnetic simulations. Spatial maps of the susceptibility have enabled identification of various resonance modes. For an exciting field along the x axis, several resonance peaks appear for a thin dot, including a core mode, whereas only one main resonance peak is detected for a ring corresponding to a volume mode with uniform magnetization perpendicular to the exciting field (x direction). A low-frequency resonance peak related to a surface mode and a high-frequency resonance peak viewed as an edge mode are additionally observed for a thick ring. These three resonance modes (surface, volume and edge modes) which correspond to low, intermediate and high-frequency resonance peaks, respectively, are also captured for an exciting field along the y axis. In addition, a mixed edge and volume mode is revealed at a higher frequency.

  3. Transient spectra of photo-excited states in double exchange model

    We investigate photo-induced effect in strongly correlated electron systems where conduction electrons couple with localized spins. In particular, the photo-induced phenomena in a charge-ordered insulator associated with antiferromagnetic order are examined. Transient excitation spectra are calculated by the exact diagonalization method in one-dimensional extended double exchange model. We find that in the photo-excited states, finite spectral weights in the one-particle excitation spectra appear inside the insulating gap and its band width increases with increasing time. This change of the electronic structure is correlated with the time development of the localized spin correlation. These results indicate that a strong coupling between spin and charge governs the photo-induced phenomena in this system.

  4. Transient spectra of photo-excited states in double exchange model

    Kanamori, Yu; Ishihara, Sumio [Department of Physics, Tohoku University, Aramaki-Aoba, Sendai, 980-8578 (Japan); Matsueda, Hiroaki, E-mail: ykanamori@cmpt.phys.tohoku.ac.j [Sendai National College of Technology, Ayashi, Sendai, 989-3128 (Japan)

    2009-02-01

    We investigate photo-induced effect in strongly correlated electron systems where conduction electrons couple with localized spins. In particular, the photo-induced phenomena in a charge-ordered insulator associated with antiferromagnetic order are examined. Transient excitation spectra are calculated by the exact diagonalization method in one-dimensional extended double exchange model. We find that in the photo-excited states, finite spectral weights in the one-particle excitation spectra appear inside the insulating gap and its band width increases with increasing time. This change of the electronic structure is correlated with the time development of the localized spin correlation. These results indicate that a strong coupling between spin and charge governs the photo-induced phenomena in this system.

  5. Pion inelastic scattering to the first three excited states of lithium-6

    Using the Energetic Pion Channel and Spectrometer system at the Clinton P. Anderson Meson Physics Facility, differential cross sections were measured for π+ inelastic scattering to the 3+, T=0, 2.185-MeV, 0+, T=1, 3.563-MeV, and 2+, T=0, 4.25-MeV states of 6Li at incident pion energies of 120 and 180 MeV and laboratory scattering angles between 150 and 470. Excitation functions were measured at a constant momentum transfer of approximately 109 MeV/c for incident pion energies from 100 to 260 MeV. The constant momentum transfer corresponds to the maxima of the angular distributions for π+ inelastic scattering to the 3.563-MeV level. Microscopic calculations using the distorted-wave impulse approximation (DWIA) agree well with the measured angular distributions and excitation functions for the 2.185- and 4.25-MeV levels. However, microscopic DWIA calculations do not adequately reproduce the measured angular distributions for the 3.563-MeV level and fail to reproduce the observed anomalous excitation function. The shape of the 3.563-MeV excitation function is similar to that previously observed for π+- inelastic scattering to the 1+, T=1, 15.11-MeV state of 12C. The same mechanism may be responsible for the observed excitation functions of both ΔS=ΔT=1 transitions. A possible mechanism is the direct excitation of Δ particle-nucleon hole (Δ-h) components in the final state wave functions. Within the Δ-h model interpretation, the peak of the 3.563-MeV excitation function is reproduced with an estimated probability amplitude for the Δ-h component of the 3.563-MeV state with respect to the ground state of 0.01 less than or equal to β less than or equal to 0.13, a range of values of β consistent with the range estimated for the 15.11-MeV level of 12C (0.026 less than or equal to β less than or equal to 0.096)

  6. Equation-of-motion coupled cluster method for the description of the high spin excited states

    Musiał, Monika; Lupa, Łukasz; Kucharski, Stanisław A.

    2016-04-01

    The equation-of-motion (EOM) coupled cluster (CC) approach in the version applicable for the excitation energy (EE) calculations has been formulated for high spin components. The EE-EOM-CC scheme based on the restricted Hartree-Fock reference and standard amplitude equations as used in the Davidson diagonalization procedure yields the singlet states. The triplet and higher spin components require separate amplitude equations. In the case of quintets, the relevant equations are much simpler and easier to solve. Out of 26 diagrammatic terms contributing to the R1 and R2 singlet equations in the case of quintets, only R2 operator survives with 5 diagrammatic terms present. In addition all terms engaging three body elements of the similarity transformed Hamiltonian disappear. This indicates a substantial simplification of the theory. The implemented method has been applied to the pilot study of the excited states of the C2 molecule and quintet states of C and Si atoms.

  7. Highly selective population of two excited states in nonresonant two-photon absorption

    Zhang Hui; Zhang Shi-An; Sun Zhen-Rong

    2011-01-01

    A nonresonant two-photon absorption process can be manipulated by tailoring the ultra-short laser pulse.In this paper,we theoretically demonstrate a highly selective population of two excited states in the nonresonant two-photon absorption process by rationally designing a spectral phase distribution.Our results show that one excited state is maximally populated while the other state population is widely tunable from zero to the maximum value.We believe that the theoretical results may play an important role in the selective population of a more complex nonlinear process comprising nonresonant two-photon absorption,such as resonance-mediated(2+1)-three-photon absorption and (2+1)-resonant multiphoton ionization.

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

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

    2015-05-21

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

  9. Analytic study of some excited state effects in a slightly bent Renner-Teller molecule

    Vertesi, T [Institute of Nuclear Research of the Hungarian Academy of Sciences, H-4001 Debrecen, PO Box 51 (Hungary); Englman, R [Soreq NRC, Yavne 81800 (Israel)

    2008-01-28

    The two lowest electronic states (arising from X{sup 2}{pi}{sub u}) are treated analytically with inclusion of excited state effects in a slightly bent Renner-Teller acetylene molecular ion. The aim is to explain the anomalous values of approximately {pi} for the integrated non-adiabatic coupling term (NACT), recently obtained by ab initio calculations, as, e.g., in Halasz et al (2007 J. Chem. Phys. 126 154309). These occur when the molecular path twice coincides with symmetrically placed positions of degeneracies (conical intersections). However, the admixture of excited states into X{sup 2}{pi}{sub u} removes these coincidences, creates two aligned conical intersections in a planar arrangement and perturbationally reduces the integrated NACT from its value of {pi}.

  10. Analytic study of some excited state effects in a slightly bent Renner Teller molecule

    Vértesi, T.; Englman, R.

    2008-01-01

    The two lowest electronic states (arising from X2Πu) are treated analytically with inclusion of excited state effects in a slightly bent Renner-Teller acetylene molecular ion. The aim is to explain the anomalous values of approximately π for the integrated non-adiabatic coupling term (NACT), recently obtained by ab initio calculations, as, e.g., in Halász et al (2007 J. Chem. Phys. 126 154309). These occur when the molecular path twice coincides with symmetrically placed positions of degeneracies (conical intersections). However, the admixture of excited states into X2Πu removes these coincidences, creates two aligned conical intersections in a planar arrangement and perturbationally reduces the integrated NACT from its value of π.

  11. Approximating electronically excited states with equation-of-motion linear coupled-cluster theory

    A new perturbative approach to canonical equation-of-motion coupled-cluster theory is presented using coupled-cluster perturbation theory. A second-order Møller-Plesset partitioning of the Hamiltonian is used to obtain the well known equation-of-motion many-body perturbation theory equations and two new equation-of-motion methods based on the linear coupled-cluster doubles and linear coupled-cluster singles and doubles wavefunctions. These new methods are benchmarked against very accurate theoretical and experimental spectra from 25 small organic molecules. It is found that the proposed methods have excellent agreement with canonical equation-of-motion coupled-cluster singles and doubles state for state orderings and relative excited state energies as well as acceptable quantitative agreement for absolute excitation energies compared with the best estimate theory and experimental spectra

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

    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

  13. Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission.

    Sakuma, Takao; Sakai, Hayato; Araki, Yasuyuki; Mori, Tadashi; Wada, Takehiko; Tkachenko, Nikolai V; Hasobe, Taku

    2016-03-24

    Intramolecular singlet fission (ISF) is a promising photophysical process to construct more efficient light energy conversion systems as one excited singlet state converts into two excited triplet states. Herein we synthesized and evaluated bent-shaped pentacene dimers as a prototype of ISF to reveal intrinsic characters of triplet states (e.g., lifetimes of triplet excited states). In this study, meta-phenylene-bridged TIPS-pentacene dimer (PcD-3Ph) and 2,2'-bipheynyl bridged TIPS-pentacene dimer (PcD-Biph) were newly synthesized as bent-shaped dimers. In the steady-state spectroscopy, absorption and emission bands of these dimers were fully characterized, suggesting the appropriate degree of electronic coupling between pentacene moieties in these dimers. In addition, the electrochemical measurements were also performed to check the electronic interaction between two pentacene moieties. Whereas the successive two oxidation peaks owing to the delocalization were observed in a directly linked-pentacene dimer (PcD) by a single bond, the cyclic voltammograms in PcD-Biph and PcD-3Ph implied the weaker interaction compared to that of p-phenylene-bridged TIPS-pentacene dimer (PcD-4Ph) and PcD. The femtosecond and nanosecond transient absorption spectra clearly revealed the slower ISF process in bent-shaped pentacene dimers (PcD-Biph and PcD-3Ph), more notably, the slower relaxation of the excited triplet states in PcD-Biph and PcD-3Ph. Namely, the quantum yields of triplet states (ΦT) by ISF approximately remain constant (ca. 180-200%) in all dimer systems, whereas the lifetimes of the triplet excited states became much longer (up to 360 ns) in PcD-Biph as compared to PcD-4Ph (15 ns). Additionally, the lifetimes of the corresponding triplet states in PcD-Biph and PcD-3Ph were sufficiently affected by solvent viscosity. In particular, the lifetimes of PcD-Biph triplet state in THF/paraffin (1.0 μs) increased up to approximately three times as compared to that in THF

  14. Excited-state absorption of a bipyridyl platinum(II) complex with alkynyl-benzothiazolylfluorene units.

    Pritchett, Timothy M; Sun, Wenfang; Zhang, Bingguang; Ferry, Michael J; Li, Yunjing; Haley, Joy E; Mackie, David M; Shensky, William; Mott, Andrew G

    2010-05-01

    The singlet excited-state lifetime of a bipyridyl platinum(II) complex containing two alkynyl-benzothiazolylfluorene units was determined to be 145+/-105 ps by fitting femtosecond transient difference absorption data, and the triplet quantum yield was measured to be 0.14. A ground-state absorption cross section of 6.1 x 10(-19) cm(2) at 532 nm was deduced from UV-visible absorption data. Excited-state absorption cross sections of (6.7+/-0.1) x 10(-17) cm(2) (singlet) and (4.6+/-0.1) x 10(-16) cm(2) (triplet) were obtained by using a five-level dynamic model to fit open-aperture Z scans at picosecond and nanosecond pulse widths and a variety of pulse energies. For this complex, the ratio of the triplet excited-state absorption cross section to the ground-state absorption cross section--long used as a figure of merit for reverse saturable absorbers--thus stands at 754, to our knowledge the largest ever reported at 532 nm wavelength. PMID:20436550

  15. A theoretical study on the wavepacket dynamics in the excited states of aromatic biomolecules

    The relaxation of the low-lying excited states of 9H-adenine through conical intersections of the dissociative “1πσ”* excited state with the lowest “1ππ”* excited state and the electronic-structure calculations and wave packet dynamics simulation. Adiabatic and quasidiabatic potential-energy surfaces and coupling elements were calculated as a function of the NH stretch coordinate of the azine group and the out-of-plane angle of the hydrogen atom, employing multireference configuration-interaction (MRCI) as well as restricted-active-space self-consistent-field (RASSCF) methods. Characteristic properties of the “1πσ”*-“1ππ”* and “1πσ”*-S0 conical intersections such as the diabatic-to-adiabatic mixing angle, the geometric phase of the adiabatic electronic wave functions, the derivative coupling, as well as adiabatic and diabatic trasition-dipole-moment surfaces were investigated in detail. Time-dependent wave packet simulations reveal an ultrafast relaxations dynamics of the optically-allowed lowest “1ππ”* state driven by vibronic coupling between strongly coupled electronic states that add to our understanding of the origin of the intrinsic photostability of the building blocks of life. (author)

  16. Open-shell nuclei and excited states from multireference normal-ordered Hamiltonians

    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.

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

    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.

  18. Investigation of the structure of the intermediate-energy excited states of the deformed nuclei

    This paper reports that at present, the comprehensive experimental information is available on the properties of low-lying states of atomic nuclei which allows one to describe on a microscopic level the basic regularities of their simplest excitations. The use of the neutron spectroscopy methods formed the experimental basis for studying complex highly excited states lying with a high density in the nucleon binding energy region. They are mainly described in the framework of the statistical approach. At the same time, the study of the transitional region of intermediate excitation (3 MeV approx-lt E approx-lt Bn) has not long ago been undertaken. These states are very complicated in structure and their density is so high that the traditional experimental methods of studying and microscopic describing nuclear states developed for the low-energy regions turned out to be ineffective and inapplicable. The statistical methods also cannot describe to the full the properties of intermediate states since, as experiment shows, different structural effects arise systematically in this energy region

  19. Photoluminescence and excited states dynamics in PbWO{sub 4}:Pr{sup 3+} crystals

    Auffray, E. [CERN, Geneva 23, Geneva (Switzerland); Korjik, M. [Institute for Nuclear Problems, 11 Bobruiskaya, 220020 Minsk (Belarus); Shalapska, T. [Institute of Physics, University of Tartu, Riia 142, 51014 Tartu (Estonia); Zazubovich, S., E-mail: svet@fi.tartu.ee [Institute of Physics, University of Tartu, Riia 142, 51014 Tartu (Estonia)

    2014-10-15

    Luminescence and photo-thermally stimulated defects creation processes are studied for a Pr{sup 3+}-doped PbWO{sub 4} crystal at 4.2–400 K under excitation in the band-to-band, exciton, and charge-transfer transitions regions, as well as in the Pr{sup 3+}-related absorption bands. Emission spectra of Pr{sup 3+} centers depend on the excitation energy, indicating the presence of Pr{sup 3+} centers of two types. The origin of these centers is discussed. The 2.03–2.06 eV emission, arising from the {sup 1}D{sub 2}→{sup 3}H{sub 4} transitions of Pr{sup 3+} ions, is found to be effectively excited in a broad intense absorption band peaking at 4.2 K at 3.92 eV. By analogy with some other Pr{sup 3+}-doped compounds, this band is suggested to arise from an electron transfer from an impurity Pr{sup 3+} ion to the crystal lattice W{sup 6+} or Pb{sup 2+} ions. The dynamics of the Pr{sup 3+}-related excited states is clarified. In the PbWO{sub 4}:Pr crystal studied, the concentration of single oxygen and lead vacancies as traps for electrons and holes is found to be negligible. - Highlights: • Luminescence and defects creation processes in PbWO{sub 4}:Pr single crystal investigated. • Existence of Pr{sup 3+}-related luminescence centers of two types revealed. • Charge transfer origin of the intense 3.92 eV absorption/excitation band suggested. • Dynamics of the Pr{sup 3+}-related excited states clarified. • Negligible concentration of single oxygen and lead vacancies in PbWO{sub 4}:Pr concluded.

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

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

    2009-01-01

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

  1. State specific multireference Møller–Plesset perturbation theory: A few applications to ground, excited and ionized states

    Graphical abstract: We have investigated various interesting and computationally challenging systems [H2O, H2O+, BeC, MgC, CO+, Be3, benzene, trimethylenemethanes and 1,2,3-tridehydrobenzene] in either their ground, or excited/ionized states via SS-MRMPPT method. Highlights: ►Spin-free SS-MRPT method is employed for ground or excited/ionized states. ► SS-MRPT is formally elegant and cost/accuracy ratio of the method is impressive. ► We have computed PES, optimized geometries and ionization/excitation energies. ► We found that it is effective when the states of interest acquire SR or MR characters. ► Our results can meaningfully be compared with other established theoretical estimates. - Abstract: We provide further tests and illustrations of the complete active space based state specific multireference Møller–Plesset perturbation theory (SS-MRMPPT) which opens the way for the treatment of dynamic correlations in situations containing significant static correlations also in an accurate, size- extensive and intruder free manner enjoying at the same time a very favorable computational cost. We have investigated various interesting and computationally challenging systems [H2O, H2O+, BeC, MgC, CO+, Be3, benzene, trimethylenemethane and 1,2,3-tridehydrobenzene] in either their ground, or excited/ionized states. It is found that SS-MRMPPT calculations provide very encouraging results which can be meaningfully compared with other state-of-the-art theoretical estimates. Present results convincingly indicate that the SS-MRMPPT method is not only successful in portraying situations that warrant MR description but also performs acceptably good in cases where a naive single-reference method is enough which reinforces the claim that the SS-MRMPPT is a very useful and flexible ab initio method.

  2. Electron attachment to excited states of silane: Implications for plasma processing discharges

    Observation of enhanced negative-ion formation in ArF endash excimer endash laser irradiated silane was reported in a recent paper [L. A. Pinnaduwage, M. Z. Martin, and L. G. Christophorou, Appl. Phys. Lett. 65, 2571 (1994)]. In that paper, preliminary evidence was presented to show that highly excited electronic states of silane or its photofragments could be responsible for the observed enhanced negative-ion formation. In the present paper, we report evidence, obtained using a new experimental technique, that the electron attaching species are high-Rydberg (HR) states of silane indirectly populated via laser irradiation and show that an absolute lower bound for the corresponding electron attachment rate constant is ∼4x10-7cm3s-1. The initial capture of the electron by the HR states is likely to be a diabatic process and the large polarizabilities associated with the HR states appear to be responsible for the observed large electron attachment rate constants. We also measured electron attachment to thermally excited vibrational states of the ground electronic state of silane, which showed no measurable electron attachment up to 750 K. Implications of these observations in modeling of silane discharges used for plasma processing of amorphous silicon are discussed. It is also pointed out that large negative ion formation observed in many open-quotes weakly electronegativeclose quotes plasma processing gas discharges could be due to enhanced electron attachment to HR states: such states could be populated via direct electron impact and/or via excitation transfer from the metastable states of rare gases that are commonly used in these processing discharges. copyright 1997 American Institute of Physics

  3. Recombination rates and excited state formation and collisional destruction in plasma-afterglows

    The dissociative recombination process for heavy diatomic molecular ions capturing electrons, Hg2+ + e- reversible arrows (Hg2/sup *>)/sub r/ → Hg/sup */+ Hg, has been studied using a plasma/afterglow method. Microwave techniques are employed to generate the plasma, measure the electron density decay and control the electron temperature. Optical spectrometric observations of afterglow radiation are also performed. The recombination coefficient, α(Hg2+) and the excited states of mercury produced by this process are determined as a function of electron temperature. We also measured the two-body collisional destruction rates and partial recombination rates for the argon excited states, 5p12, 5p23, 6s12, 4d12, 4d01, 4d00, 4d33, 4d34, 5d33, 5d34, 4p00/sup prime/, and 4p00, produced by dissociative recombination of Ar2+ ions by measuring the variation of the intensity of radiation from these states with argon pressure. (Production and destruction of a few xenon excited states were also studied qualitatively in this respect.) The collisional destruction (quenching) rate coefficients for the argon states range from approx. 2 x 10-11cm3/sec to approx. 2 x 10-10 cm3/s The quenching rates for the states lying above the ground state of Ar2+ provide an upper bound on the associative ionization rates for these states. The states which have large collisional destruction rates (approx. 2 x 10-10cm3/s) are found to have large partial recombination coefficients

  4. Phonon-like excitations in the two-state Bose-Hubbard model

    I.V. Stasyuk

    2015-12-01

    Full Text Available The spectrum of phonon-like collective excitations in the system of Bose-atoms in optical lattice (more generally, in the system of quantum particles described by the Bose-Hubbard model is investigated. Such excitations appear due to displacements of particles with respect to their local equilibrium positions. The two-level model taking into account the transitions of bosons between the ground state and the first excited state in potential wells, as well as interaction between them, is used. Calculations are performed within the random phase approximation in the hard-core boson limit. It is shown that excitation spectrum in normal phase consists of the one exciton-like band, while in the phase with BE condensate an additional band appears. The positions, spectral weights and widths of bands strongly depend on chemical potential of bosons and temperature. The conditions of stability of a system with respect to the lowering of symmetry and displacement modulation are discussed.

  5. Evolution of l-photon excited thermo vacuum state in a single-mode damping channel

    He, Rui; Fan, Hong-Yi

    2016-01-01

    In this paper, we investigate how a kind of non-Gaussian states (l-photon excited thermo vacuum state Cla†l|0(β)>) evolves in a single-mode damping channel. We find that it evolves into a Laguerre-polynomial-weighted real-fictitious squeezed thermo vacuum state, which exhibits strong decoherence and its original nonclassicality fades. In particular, when l = 0, in this damping process the thermo squeezing effect decreases while the fictitious-mode vacuum becomes chaotic. In overcoming the difficulty of calculation, we employ the summation method within ordered product of operators, a new generating function formula about two-variable Hermite polynomials is derived.

  6. NLIE for hole excited states in the sine-Gordon model with two boundaries

    We derive a nonlinear integral equation (NLIE) for some bulk excited states of the sine-Gordon model on a finite interval with general integrable boundary interactions, including boundary terms proportional to the first time derivative of the field. We use this NLIE to compute numerically the dimensions of these states as a function of scale, and check the UV and IR limits analytically. We also find further support for the ground-state NLIE by comparison with boundary conformal perturbation theory (BCPT), boundary truncated conformal space approach (BTCSA) and the boundary analogue of the Luescher formula

  7. Ground state and excitations of a Bose-Einstein condensate of atoms and their diatomic bound states

    We study theoretically a many-body system of spinless atoms and their diatomic bound states (or molecules) which form a single Bose-Einstein condensate at zero temperature. The equilibrium states of such a system and its dynamics are analyzed within the Gross-Pitaevskii approach. It is shown that the system exhibits two phases depending on binding energy value: it can be in the states with atomic-molecular condensate or molecular condensate. The basic thermodynamic characteristics of the two phases and their stability conditions are obtained. Both phases are characterized by two branches of collective excitations. The first branch is acoustic mode and the second one is gapfull

  8. Laboratory Characterization and Astrophysical Detection of Vibrationally Excited States of Vinyl Cyanide in Orion-KL

    López, A; Kisiel, Z; Daly, A M; Bermúdez, C; Calcutt, H; Marcelino, N; Viti, S; Drouin, B J; Medvedev, I R; Neese, C F; Pszczółkowski, L; Alonso, J L; Cernicharo, J

    2014-01-01

    New laboratory data of CH$_2$CHCN (vinyl cyanide) in its ground and vibrationally excited states at the microwave to THz domain allow searching for these excited state transitions in the Orion-KL line survey. Frequency-modulated spectrometers combined into a single broadband 50-1900 GHz spectrum provided measurements of CH$_2$CHCN covering a spectral range of 18-1893 GHz, whose assignments was confirmed by Stark modulation spectra in the 18-40 GHz region and by ab-initio anharmonic force field calculations. For analyzing the emission lines of CH$_2$CHCN species detected in Orion-KL we used the excitation and radiative transfer code (MADEX) at LTE conditions. The rotational transitions of the ground state of this molecule emerge from four cloud components of hot core nature which trace the physical and chemical conditions of high mass star forming regions in the Orion-KL Nebula. The total column density of CH$_2$CHCN in the ground state is (3.0$\\pm$0.9)x10$^{15}$ cm$^{-2}$. We report on the first interstellar ...

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

    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 C2 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 C2v insertion pathway for BeH2. 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

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

    Jiménez-Hoyos, Carlos A. [Department of Chemistry, Rice University, Houston, Texas 77005 (United States); Rodríguez-Guzmán, R.; Scuseria, Gustavo E. [Department of Chemistry, Rice University, Houston, Texas 77005 (United States); Department of Physics and Astronomy, Rice University, Houston, Texas 77005 (United States)

    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. Excited-state evolution probed by convoy-electron emission in relativistic heavy-ion collisions

    Takabayashi, Y.; Ito, T.; Azuma, T.; Komaki, K.; Yamazaki, Y.; Tawara, H.; Takada, E.; Murakami, T.; Seliger, M.; Tökési, K.; O. Reinhold, C.; Burgdörfer, J.

    2003-10-01

    We present a joint experimental and theoretical study of convoy-electron emission resulting from highly-charged-ion transport through carbon foils at moderately relativistic speeds. Energy spectra of electrons ejected at 0° have been measured for 390 MeV/u hydrogen-like Ar17+ ions and 460 MeV/u (β=v/c=0.74,γ=1.49) Fe25+ (1s), Fe24+ (1s2), and Fe23+ (1s22s) incident on carbon foils with thicknesses from 25 to 8700 μg/cm2. Due to this unprecedented wide range of thicknesses, the sequential excitation and ionization of initially deeply bound electrons to highly excited states and continuum states can be followed in considerable detail. The analysis of the spectra is aided by simulations based on the classical transport theory which has been extended to relativistic energies and to multielectron projectiles. The motion of the projectile electron inside the solid target is calculated taking into account the Coulomb potential of the projectile ion and the multiple stochastic collisions with target cores and target electrons. Different phases of the convoy-electron emissions can be disentangled: direct ejection to the continuum, the transient buildup of an excited-state wave packet followed by ionization, and postionization modification of the continuum spectrum. We find good agreement between experiment and simulation for the evolution of charge states and the emission spectrum.

  12. Pulsed excitation of Rydberg-atom-pair states in an ultracold Cs gas

    Saßmannshausen, Heiner; Deiglmayr, Johannes

    2015-01-01

    Pulsed laser excitation of a dense ultracold Cs vapor has been used to study the pairwise interactions between Cs atoms excited to $n$p$_{3/2}$ Rydberg states of principal quantum numbers in the range $n=22-36$. Molecular resonances were observed that correspond to excitation of Rydberg-atom-pair states correlated not only to the $n$p$_{3/2}+n$p$_{3/2}$ dissociation asymptotes, but also to $n$s$_{1/2}+(n+1)$s$_{1/2}$, $n$s$_{1/2}+n'$f$_{j}$, and $(n-4)$f$_{j}+(n-3)$f$_{j}$ $(j=5/2,7/2)$ dissociation asymptotes. These pair resonances are interpreted as arising from dipole-dipole, and higher long-range-interaction terms between the Rydberg atoms on the basis of i) their spectral positions, ii) their response to static and pulsed electric fields, and iii) millimeter-wave spectra between pair states correlated to different pair-dissociation asymptotes. The Rydberg-atom--pair states were found to spontaneously decay by Penning ionization and the dynamics of the ionization process were investigated during the first...

  13. Exact finite volume expectation values of local operators in excited states

    Pozsgay, B; Takacs, G

    2014-01-01

    We present a conjecture for the exact expression of finite volume expectation values in excited states in integrable quantum field theories, which is an extension of an earlier conjecture to the case of general diagonal factorized scattering with bound states and a nontrivial bootstrap structure. The conjectured expression is a spectral expansion which uses the exact form factors and the excited state thermodynamic Bethe Ansatz as building blocks. The conjecture is proven for the case of the trace of the energy-moment tensor. Concerning its validity for more general operators, we provide numerical evidence using the truncated conformal space approach. It is found that the expansion fails to be well-defined for small values of the volume in cases when the singularity structure of the TBA equations undergoes a non-trivial rearrangement under some critical value of the volume. Despite these shortcomings, the conjectured expression is expected to be valid for all volumes for most of the excited states, and as an ...

  14. Lifetimes and branching ratios of excited states in La-, Os-, Lu-, Lr-, and Pr-

    Relativistic configuration-interaction calculations have been performed for all possible E1, M1, and E2 transitions between bound anion states of La- and Os-. We pay particular attention to E1 transitions in each case that may be of use in laser cooling of these anions. Although the La- transition energy is approximately one-third of the Os- transition, our results indicate that the Einstein A coefficient is nearly two orders of magnitude larger, which would lead to more efficient laser cooling. We have also explored long-lived opposite-parity excited states in Lu- and Lr- which are restricted to M2 decay by selection rules. Finally, in Pr-, we find sufficient mixing between a weakly bound excited 4f25d26s2 state with a nearby 4f36s26p resonance to result in a lifetime similar to that of the other excited anion states, despite the fact that the dominant configurations of these M1 and E2 transitions differ by two electrons.

  15. Probing ground and low-lying excited states for HIO2 isomers

    We present a computational study on HIO2 molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10−3)

  16. Probing ground and low-lying excited states for HIO{sub 2} isomers

    Souza, Gabriel L. C. de [Departamento de Química, Universidade Federal de Mato Grosso, Cuiabá, Mato Grosso 78060-900 (Brazil); Instituto de Ciências Exatas e Tecnologia, Universidade Federal do Amazonas, Itacoatiara, Amazonas 69100-000 (Brazil); Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada); Brown, Alex, E-mail: alex.brown@ualberta.ca [Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada)

    2014-12-21

    We present a computational study on HIO{sub 2} molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10{sup −3})

  17. A relativistic time-dependent density functional study of the excited states of the mercury dimer

    Kullie, Ossama, E-mail: kullie@uni-kassel.de, E-mail: ossama.kullie@unistra.fr [Institute de Chimie de Strasbourg, CNRS et Université de Strasbourg, Laboratoire de Chimie Quantique, 4 rue Blaise Pascal, 67070 Strasbourg, France and Theoretical Physics, Institute for Physics, Department of Mathematics and Natural Science, University of Kassel, D-34127 Kassel (Germany)

    2014-01-14

    In previous works on Zn{sub 2} and Cd{sub 2} dimers we found that the long-range corrected CAMB3LYP gives better results than other density functional approximations for the excited states, especially in the asymptotic region. In this paper, we use it to present a time-dependent density functional (TDDFT) study for the ground-state as well as the excited states corresponding to the (6s{sup 2} + 6s6p), (6s{sup 2} + 6s7s), and (6s{sup 2} + 6s7p) atomic asymptotes for the mercury dimer Hg{sub 2}. We analyze its spectrum obtained from all-electron calculations performed with the relativistic Dirac-Coulomb and relativistic spinfree Hamiltonian as implemented in DIRAC-PACKAGE. A comparison with the literature is given as far as available. Our result is excellent for the most of the lower excited states and very encouraging for the higher excited states, it shows generally good agreements with experimental results and outperforms other theoretical results. This enables us to give a detailed analysis of the spectrum of the Hg{sub 2} including a comparative analysis with the lighter dimers of the group 12, Cd{sub 2}, and Zn{sub 2}, especially for the relativistic effects, the spin-orbit interaction, and the performance of CAMB3LYP and is enlightened for similar systems. The result shows, as expected, that spinfree Hamiltonian is less efficient than Dirac-Coulomb Hamiltonian for systems containing heavy elements such as Hg{sub 2}.

  18. Aqueous secondary organic aerosol (SOA) production from the oxidation of phenols by triplet excited state organics

    Smith, J.; Yu, L.; Zhang, Q.; Anastasio, C.

    2011-12-01

    Recent literature has shown that atmospheric condensed-phase chemistry can play a significant role in the evolution of organic aerosols, including the formation of secondary organic aerosol (SOA). SOA formation from the oxidation of volatile organic compounds (VOCs) in the aqueous phase has largely focused on oxidations involving the hydroxyl radical and other oxidants, such as photochemically created triplet excited states, have not been fully investigated. Phenolic compounds are one of the primary carbon emission classes from biomass and wood combustion and have significant water solubility. Once in the aqueous phase, phenolic compounds can react with the triplet excited states of non-phenolic aromatic carbonyls (NPCs), particle-bound organics that are also emitted in large quantities from wood combustion. The oxidation of phenolic species in the condensed phase by triplet excited states can result in the production of SOA. A main goal of this study was to investigate bulk solution reaction kinetics under atmospherically relevant conditions in order to ascertain how these reactions can impact aqueous-phase SOA production. In our experiments, we studied the reactions of five phenols (phenol, guaiacol, syringol, catechol, and resorcinol) with the triplet state of 3,4-dimethoxybenzaldehyde (34-DMB) during simulated solar radiation. We have characterized the impacts of pH, ionic strength and reactant concentrations on the reaction behavior of this system. In addition, we analyzed the SOA formed using high-resolution aerosol mass spectrometry, ion chromatography, and liquid chromatography-mass spectrometry to infer the reaction mechanisms. Our evidence suggests that under atmospherically relevant conditions, triplet excited states can be the dominant oxidant of phenolics and contribute significantly to the total SOA budget.

  19. Characterising excited states in and around the semi-magic nucleus $^{68}$ Ni using Coulomb excitation and one-neutron transfer

    It is proposed to investigate the structure of excited states in $^{68;70}$Ni(Z = 28;N = 40; 42) via the measurement of electromagnetic matrix elements in a Coulomb excitation experiment in order to study the N = 40 harmonic-oscillator shell and the Z = 28 proton shell closures. The measured B(E2) values connecting low-lying 0$^{+}$ and 2$^{+}$ can be compared to shell-model predictions. It is also proposed to perform the one-neutron transfer reaction ${d}$($^{68}$Ni,$^{69}$Ni)${p}$, with the aim of populating excited states in$^{69}$Ni. Comparisons with the states populated in the recently performed ${d}$($^{66}$Ni,$^{67}$Ni)${p}$ reaction will be useful in determining the role of the neutron $d_{5/2}$ orbital in the semi-magic properties of $^{68}$Ni.

  20. The ground and excited state potential energy surfaces of nitromethane related to its dissociation dynamics after excitation at 193 nm

    The relevant low-lying singlet and triplet potential energy surfaces in the photolysis of nitromethane have been studied by using the multistate extension of the multiconfigurational second-order perturbation theory in conjunction with large atomic natural orbital-type basis sets. The proposed mechanism for the photolytic decomposition of CH3NO2 provides a consistent and reinterpreted picture of the available experimental results. Two reaction paths are found in the photolysis of nitromethane after excitation at 193 nm: (1) Major Channel, CH3NO2(1A')+hν(193 nm)→CH3NO2(2A'')→(lim(lu-tag)lu-tag(bu(IC))))CH3NO2(2A')→CH3(1A1')+NO2(1 2B1)→(lim(lu-tag(-hν')lu-tag(bu(IC))))CH3(1A1')+NO2(1 2A1)→(lim(lu-tag(193 nm)lu-tag(bu(hν))))CH3(1A1')+NO(A 2Σ+)+αO(3P)+βO(1D). (2) Minor Channel, CH3NO2(1A')+hν(193 nm)→CH3NO2(2A'')→CH3(1A1')+NO2(1 2A2)→CH3(1A1')+NO(X 2Π)+αO(3P)+βO(1D), being α and β fractional numbers. No ionic species are found in any dissociation path. Additionally, the respective low-lying Rydberg states of nitromethane and nitrogen dioxide have been studied too.

  1. Production and transport of the excited states of projectile ions in ion-solid interaction; Production et transport des etats excites du projectile en interaction ion-solide

    Lamour, E

    1997-11-01

    In ion-solid collisions, more excited states of projectile ions with high angular momenta l are populated than in ion-atom collisions. The use of 13.6 MeV/u Ar{sup 18+} projectile ions and solid carbon targets allowed us to study Ar{sup 17+} excited states initially populated by electron capture. Using various targets with increasing thickness from 3.5 to 200 {mu}g/cm{sup 2}, the evolution of excited states from the single collision condition to the population equilibrium was investigated. We observed the evolution of the Lyman line intensities as a function of the ion transit time inside the target (sensitive to core state population) and as a function of the ion time of flight behind the target (sensitive to Rydberg state population). To explain the experimental results, a complete theoretical analysis of the transport of excited states inside the medium was performed. We used two different collisional models. The first one is a rate equation model based on a statistical description of binary collisions of the projectile with target atoms. The second one is a classical transport theory based on an equation describing the motion of the projectile electron on a classical orbit perturbed by a stochastic force. A comparison with experiment shows that such a collisional approach allows to interpret the excited l-state population, but fails in describing the core state population. The observed l mixing in these states is much larger than predicted by the models. The polarization of the medium induced by the projectile ion, with both models do not take into account, could be responsible for this mixing by means of the Stark effect. (author)

  2. Search of the first excited states 0+ of 108Cd and106Cd

    108Cd and 106Cd nuclei have been studied from the β+/EC decay of 108In and 106In using the isocele II isotope separator working on-line with the Orsay synchrocyclotron. In order to produce indium nuclei, a molten tin target is irradiated by protons (E = 200 MeV) or 3He (E = 270 MeV). The comparison of saturation activity measured after mass separation with the one measured before mass-separation has allowed us to determine the average delay-time of indium isotopes and the overall efficiency of the separator. Single γ rays, conversion electrons rays, γ-γ-t and γ-e--t coincidence measurements have been performed to build level schemes of 108Cd and 106Cd. In 108Cd, the first excited 0+ state has been established unambiguously. This state preferably decays to the 22+ and not to the 21+ as it does in the even-even neighbouring Cd nuclei. An excited 0+ state is proposed in 106Cd. These states could not be interpreted as headstate of collective band corresponding to a shape different from the ground state one. On the other hand, the model of G. Alaga (vibrator + two proton holes), as well as the IBA2 F. Iachello one seem to be able to describe the low-lying states properties. Finally, the feeding balance and the deduced log ft values have led us to discuss the possible values of the 108In and 106In isomeric state spins

  3. Study of 2p and 4p-2t excited states in 18F

    Proton induced reactions on the 17O nucleus lead principally to the formation of 2p states in 18F. Resonant 17O(p,p) scattering and the 17O(p,α0)14N reaction have been used to form such states for incident energies between 1.4 and 3MeV. The analysis of the elastic scattering excitation functions led to the determination of three positive parity states having a dominant (dsub(5/2)dsub(3/2)) configuration, Esub(x)(Jsup(π),T)=7.406MeV (1+,0), 7.692MeV (3+), and 8.239MeV (4+,1). The positive parity state at 7.585MeV (1+) seems to present a mixture of 2p an 4p-2t configurations. Seven negative parity states, have also been identified and spins proposed. The excitation function of the 17O(p,α0)14N reaction shows eight resonance or complex resonant structures but it has not been possible to give detailed nuclear properties of the corresponding states. Angular distributions of α-particles led to a limitation of possible spin values for six of these states

  4. Relaxation dynamics in the excited states of a ketocyanine dye probed by femtosecond transient absorption spectroscopy

    Jahur A Mondal; Sandeep Verma; Hirendra N Ghosh; Dipak K Palit

    2008-01-01

    Relaxation dynamics of the excited singlet states of 2,5-bis-(N-methyl-N-1,3-propdienylaniline)-cyclopentanone (MPAC), a ketocyanine dye, have been investigated using steady-state absorption and emission as well as femtosecond time-resolved absorption spectroscopic techniques. Following photoexcitation using 400 nm light, the molecule is excited to the S2 state, which is fluorescent in rigid matrices at 77 K. S2 state is nearly non-fluorescent in solution and has a very short lifetime (0.5 ± 0.2 ps). In polar aprotic solvents, the S1 state follows a complex multi-exponential relaxation dynamics consisting of torsional motion of the donor groups, solvent re-organization as well as photoisomerization processes. However, in alcoholic solvents, solvent re-organization via intermolecular hydrogen-bonding interaction is the only relaxation process observed in the S1 state. In trifluoroethanol, a strong hydrogen bonding solvent, conversion of the non-hydrogen-bonded form, which is formed following photoexcitation, to the hydrogen-bonded complex has been clearly evident in the relaxation process of the S1 state.

  5. Beyond Time-Dependent Density Functional Theory Using Only Single Excitations: Methods for Computational Studies of Excited States in Complex Systems.

    Herbert, John M; Zhang, Xing; Morrison, Adrian F; Liu, Jie

    2016-05-17

    Single-excitation methods, namely, configuration interaction singles and time-dependent density functional theory (TDDFT), along with semiempirical versions thereof, represent the most computationally affordable electronic structure methods for describing electronically excited states, scaling as [Formula: see text] absent further approximations. This relatively low cost, combined with a treatment of electron correlation, has made TDDFT the most widely used excited-state quantum chemistry method over the past 20+ years. Nevertheless, certain inherent problems (beyond just the accuracy of this or that exchange-correlation functional) limit the utility of traditional TDDFT. For one, it affords potential energy surfaces whose topology is incorrect in the vicinity of any conical intersection (CI) that involves the ground state. Since CIs are the conduits for transitions between electronic states, the TDDFT description of photochemistry (internal conversion and intersystem crossing) is therefore suspect. Second, the [Formula: see text] cost can become prohibitive in large systems, especially those that involve multiple electronically coupled chromophores, for example, the antennae structures of light-harvesting complexes or the conjugated polymers used in organic photovoltaics. In such cases, the smallest realistic mimics might already be quite large from the standpoint of ab initio quantum chemistry. This Account describes several new computational methods that address these problems. Topology around a CI can be rigorously corrected using a "spin-flip" version of TDDFT, which involves an α → β spin-flipping transition in addition to occupied → virtual excitation of one electron. Within this formalism, singlet states are generated via excitation from a high-spin triplet reference state, doublets from a quartet, etc. This provides a more balanced treatment of electron correlation between ground and excited states. Spin contamination is problematic away from the

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

    Olsen, Thomas; Schiøtz, Jakob

    2008-01-01

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

  7. Characterization of adsorption and electronic excited states of quercetin on titanium dioxide nanoparticles

    Zdyb, Agata; Krawczyk, Stanisław

    2016-03-01

    Adsorption of quercetin on colloidal titanium dioxide nanoparticles in ethanol and its excited-state electronic structure were investigated by means of electronic and vibrational spectroscopies. The changes in electronic charge redistribution as reflected by the dipole moment difference, ∆μ, between the ground and excited electronic states were measured with electroabsorption spectroscopy and analyzed using results of TD DFT computations. Adsorption of quercetin causes a red shift of its absorption spectrum. Raman spectra of quercetin analyzed with reference to analogous data for morin indicate binding of quercetin through the hydroxy groups of the catechol moiety. The difference dipole moment, which is 5.5 D in free quercetin, increases to 11.8 D in opposite direction in adsorbed quercetin, and is associated with charge-transfer to the Ti atom. The computed transition energy, intensity, vector Δμ and molecular orbitals involved in the electronic transition at different molecular configurations indicate a bidentate chelating mode of binding of quercetin.

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

    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. PMID:27300876

  9. Proteolytic Equilibria of Vanillic Acid in the Ground and Excited States

    Vusovich, O. V.; Tchaikovskaya, O. N.; Sokolova, I. V.; Vasil‧eva, N. Yu.

    2016-03-01

    Proteolytic equilibria of vanillic acid in aqueous solutions were studied using electronic spectroscopy. The pH ranges for anionic, dianionic, cationic, and neutral forms of vanillic acid in the ground and excited states were determined. The electron density distribution on atoms in the proteolytic forms was determined using quantum-chemistry methods. The anion formed as a result of dissociation of the carboxylic acid. The dianion formed in the presence of two and more equivalents of alkali as a result of proton loss from the phenol and carboxylic acid. The vanillic acid cation formed via protonation of the carbonyl oxygen. Differences in spectral features of the proteolytic forms in the ground and excited states were observed.

  10. Excitation of high orbital angular momentum Rydberg states with Laguerre-Gauss beams

    Rodrigues, J. D.; Marcassa, L. G.; Mendonça, J. T.

    2016-04-01

    We consider the excitation of Rydberg states through photons carrying an intrinsic orbital angular momentum degree of freedom. Laguerre-Gauss modes, with a helical wave-front structure, correspond to such a set of laser beams, which carry {{\\ell }}0 units of orbital angular momentum in their propagation direction, with ℓ 0 the winding number. We demonstrate that, in a proper geometry setting, this orbital angular momentum can be transferred to the internal degrees of freedom of the atoms, thus violating the standard dipole selection rules. Higher orbital angular momentum states become accessible through a single photon excitation process. We investigate how the spacial structure of the Laguerre-Gauss beam affects the radial coupling strength, assuming the simplest case of hydrogen-like wavefunctions. Finally we discuss a generalization of the angular momentum coupling, in order to include the effects of the fine and hyperfine splitting, in the context of the Wigner-Eckart theorem.

  11. Excitation of high orbital angular momentum Rydberg states with Laguerre-Gauss beams

    Rodrigues, J D; Mendonça, J T

    2015-01-01

    We consider the excitation of Rydberg states through photons carrying an intrinsic orbital angular momentum degree of freedom. Laguerre-Gauss modes, with a helical wave-front structure, correspond to such a set of laser beams, which carry some units of orbital angular momentum in their propagation direction. We demonstrate that, in a proper geometrical setting, this orbital angular momentum can be transferred to the internal degrees of freedom of the atoms, thus violating the standard dipolar selection rules. Higher orbital angular momentum states become accessible through a single photon excitation process. We investigate how the spacial structure of the Laguerre-Gauss beam affects the radial coupling strength, assuming the simplest case of hydrogen-like wavefunctions. Finally we discuss a generalization of the angular momentum coupling, in order to include the effects of the fine and hyperfine splitting, in the context of the Wigner-Eckart theorem.

  12. Comparison of calculation methods for the tunnel splitting at excited states of biaxial spin models

    Cui Xiao-Bo; Chen Zhi-De

    2004-01-01

    We present the calculation and comparison of tunnel splitting at excited levels of biaxial spin models by various methods, including the generalized instanton method, the generalized path integral method for coherent spin states,the perturbation method, and the exact method by numerical diagonalization of the Hamiltonian. It is found that,for integer spin with spin number around 10, tunnel splitting predicted by the generalized path integral for coherent spin states is about 10-n times of the exact numerical result for the nth excited level, while the ratio of the results of the perturbation method and the exact numerical method diverges in the large spin limit. We thus conclude that the generalized instanton method is the best approximate way for calculating tunnel splitting in spin models.

  13. Excited State Properties of Fluorine-Substituted Hexabenzocoronene: A Quantum-Chemical Characterization

    LI Yuan-Zuo; SUN Yu; LI Yong-Qing; MA Feng-Cai

    2006-01-01

    The first fluorine-substituted hexabenzocoronene has been synthesized and its electronic structure and optical properties have been reported [Q. Zhang, et al., Org. Lett.7 (2005) 5019]. In this letter, the electronic structure and excited state properties of the fluorine-substituted hexabenzocoronene are studied with quantum chemistry method as well as the transition and the charge difference densities. The transition densities show the orientations and strength of the dipole moments and the charge difference densities reveal the orientation and results of the intramolecular charge transfer. The calculated transition energies and oscillator strengths are consistent with the experimental data, and the theoretical results of transition and charge difference densities are valuable to understanding the excited state properties of the fluorine-substituted hexabenzocoronene.

  14. Investigation of the ββ decay of 96Zr to excited states in 96Mo

    The two-neutrino mode of double beta decay (2νββ) of 96Zr is investigated both theoretically and experimentally. The calculations, using the quasiparticle random phase approximation approach, show that for 96Zr the detection of 2νββ transitions to the two first excited states in the daughter nuclide will be possible in the very near future. On the experimental side, new, most stringent limits on half-lives for the double beta decay of 96Zr to excited states in 96Mo have been obtained with a 430 cm3 'well-type' germanium detector. They range between 5x1019 and 8x1019 years (90% CL). (author)

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

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

  16. Excitation of continuum states in sup 7 Li and their decay by quantum tunneling

    Utsunomiya, H; Yamagata, T; Ohta, M; Aoki, Y; Hirota, K; Ieki, K; Iwata, Y; Katori, K; Hamada, S; Lui, Y W; Schmitt, R P; Typel, S; Baur, G

    1999-01-01

    Strong forward-backward asymmetries were found in the recent alpha-t coincidence measurement of Coulomb breakup of 42 MeV- sup 7 Li via continuum states. The competition between E1 and E2 multipolarities and higher order effects in Coulomb excitation were investigated by solving the time-dependent Schroedinger equation. It is shown that higher order effects are an essential ingredient to the observed large asymmetries. The relevant reaction mechanism is discussed.

  17. Coherent excitation transferring via dark state in light-harvesting process

    Dong, H.; Xu, D. Z.; Sun, C. P.

    2011-01-01

    We study the light absorption and energy transferring in a donor-acceptor system with a bionic structure. In the optimal case with uniform couplings, it is found that the quantum dynamics of this seemingly complicated system is reduced as a three-level system of $\\Lambda$-type. With this observation, we show that the dark state based electromagnetically-induced transparency (EIT) effect could enhance the energy transfer efficiency, through a quantum interference effect suppressing the excited...

  18. Beta-decay of 95Te to excitation states of 95Mo

    The energies spins, parities, magnetic dipole and electric quadrupole moments of the ground and excited states of 95Mo as well as the probabilities of electromagnetic transition between them have been calculated in the framework of the dynamic collective model. The β+-decay 95Tc → 95Mo have been described. The calculation values are in a good agreement with the experimental data from Nuclear Data Sheets and Evaluated Nuclear Structure Data File

  19. Energetics of Excited States in the Conjugated Polymer Poly(3-hexylthiophene)

    Deibel, Carsten; Mack, Daniel; Gorenflot, Julien; Schoell, Achim; Krause, Stefan; Reinert, Friedrich; Rauh, Daniel; Dyakonov, Vladimir

    2010-01-01

    There is an enormous potential in applying conjugated polymers in novel organic opto-electronic devices such as light emitting diodes and solar cells. Although prototypes and first products exist, a comprehensive understanding of the fundamental processes and energetics involved during photoexcitation is still lacking and limits further device optimisations. Here we report on a unique analysis of the excited states involved in charge generation by photoexcitation. On the model system poly(3-h...

  20. Efficient basis for the Dicke model: II. Wave function convergence and excited states

    An extended bosonic coherent basis has been shown by Chen et al (2008 Phys. Rev. A 78 051801) and Liu T et al (2009 Phys. Rev. A 80 165308) to provide numerically exact solutions of the finite-size Dicke model. The advantages in employing this basis, as compared with the photon number (Fock) basis, are exhibited to be valid for a large region of the Hamiltonian parameter space and many excited states by analyzing the convergence in the wave functions. (paper)

  1. Excited-state relaxation in group IV nanocrystals investigated using optical methods

    Trojánek, F.; Malý, P.; Pelant, Ivan

    Singapore: Pan Stanford Publishing, 2015 - (Valenta, J.; Mirabella, S.), s. 145-175 ISBN 978-981-4463-63-8 R&D Projects: GA ČR(CZ) GBP108/12/G108 Institutional support: RVO:68378271 Keywords : nanocrystals, * excited state, * relaxation, * silicon, * germanium Subject RIV: BM - Solid Matter Physics ; Magnetism https://www.crcpress.com/ Nanotechnology -and-Photovoltaic-Devices-Light-Energy-Harvesting-with-Group/Valenta-Mirabella/9789814463638

  2. Lifetime of the first excited state of the 133Cs nucleus placed in a gold cylinder

    A theoretical investigation has been carried out on how the lifetime of the first excited state of the 133Cs nucleus might be modulated by placing it at the center of a gold cylinder of 0.5 mm in thickness, 2 mm in diameter, and 30 mm in length. At 15 K, the lifetime turns out to be 4.5 % longer, i.e., 6.55 ns, than the usual value (6.27 ± 0.02 ns).

  3. Visualizing overdamped wavepacket motion: Excited-state isomerization of pseudocyanine in viscous solvents

    The isomerization of 1,1'-diethyl-2,2'-cyanine iodide in n-alcohols is studied by femtosecond pump-probe spectroscopy. Using a broad range of probe wavelengths, the dynamics of ground-state bleach recovery, excited-state absorption and stimulation emission are monitored. We attributed the observed spectral evolution to the excited-state torsional motion, which occurs in a barrierless fashion in all solvents investigated. Excitation initiates a fast downhill bond-twisting motion on steep part of the S1 potential. The rate-limiting step of the isomerization is the stochastic bond twisting on a relatively flat part of the potential at the bottom of S1. The dependences of the bond-twisting rates on solvent viscosity are different for the steep and flat parts of the S1 potential. To the best of out knowledge, this work constitutes the first experimental observation of a process for which the viscosity dependence of the reaction rate changes along the reaction coordinate

  4. Effects of Beta-Decays of Excited-State Nuclei on the Astrophysical r-Process

    Famiano, M A; Kajino, T; Otsuki, K; Terasawa, M; Mathews, G J

    2008-01-01

    A rudimentary calculation is employed to evaluate the possible effects of beta- decays of excited-state nuclei on the astrophysical r-process. Single-particle levels calculated with the FRDM are adapted to the calculation of beta-decay rates of these excited-state nuclei. Quantum numbers are determined based on proximity to Nilson model levels. The resulting rates are used in an r-process network calculation in which a supernova hot-bubble model is coupled to an extensive network calculation including all nuclei between the valley of stability and the neutron drip line and with masses A<284. Beta-decay rates are included as functional forms of the environmental temperature. While the decay rate model used is simple and phenomenological, it is consistent across all 3700 nuclei involved in the r-process network calculation. This represents an approximate first estimate to gauge the possible effects of excited-state beta-decays on r-process freeze-out abundances.

  5. Theoretical direct WIMP detection rates for transitions to nuclear excited states

    Vergados, J D; Pirinen, P; Srivastava, P C; Kortelainen, M; Suhonen, J

    2015-01-01

    The recent WMAP and Planck data have confirmed that exotic dark matter together with the vacuum energy (cosmological constant) dominate in the flat Universe. Many extensions of the standard model provide dark matter candidates, in particular Weakly Interacting Massive Particles (WIMPs). Thus the direct dark matter detection is central to particle physics and cosmology. Most of the research on this issue has hitherto focused on the detection of the recoiling nucleus. In this paper we study transitions to the excited states, possible in some nuclei, which have sufficiently low lying excited states. Examples considered previously were the first excited states of $^{127}$I and $^{129}$Xe. We examine here $^{83}$Kr, which offers some kinematical advantages and is currently considered as a possible target. We find appreciable branching ratios for the inelastic scattering mediated by the spin cross sections, with an inelastic event rate of $4.4\\times 10^{-4}$kg$^{-1}$d$^{-1}$. So, the extra signature of the gamma ra...

  6. Proton coupled electron transfer from the excited state of a ruthenium(ii) pyridylimidazole complex.

    Pannwitz, Andrea; Wenger, Oliver S

    2016-04-20

    Proton coupled electron transfer (PCET) from the excited state of [Ru(bpy)2pyimH](2+) (bpy = 2,2'-bipyridine; pyimH = 2-(2'-pyridyl)imidazole) to N-methyl-4,4'-bipyridinium (monoquat, MQ(+)) was studied. While this complex has been investigated previously, our study is the first to show that the formal bond dissociation free energy (BDFE) of the imidazole-N-H bond decreases from (91 ± 1) kcal mol(-1) in the electronic ground state to (43 ± 5) kcal mol(-1) in the lowest-energetic (3)MLCT excited state. This makes the [Ru(bpy)2pyimH](2+) complex a very strong (formal) hydrogen atom donor even when compared to metal hydride complexes, and this is interesting for light-driven (formal) hydrogen atom transfer (HAT) reactions with a variety of different substrates. Mechanistically, formal HAT between (3)MLCT excited [Ru(bpy)2pyimH](2+) and monoquat in buffered 1 : 1 (v : v) CH3CN/H2O was found to occur via a sequence of reaction steps involving electron transfer from Ru(ii) to MQ(+) coupled to release of the N-H proton to buffer base, followed by protonation of reduced MQ(+) by buffer acid. Our study is relevant in the larger contexts of photoredox catalysis and light-to-chemical energy conversion. PMID:27094541

  7. Kinetic studies following state-selective laser excitation: Progress report, March 15, 1988--March 14, 1989

    The objective of this contract is the study of state-to-state, electronic energy transfer reactions following two-photon laser excitation. We have chosen to study reactions of Xe 5p5np because of their relevance to the XeCl excimer laser. We are studying deactivation reactions in collisions with heavy atoms such as Ar, Kr, and Xe and reactive collisions with chlorides. The reactants are excited by multiphoton laser absorption. Product channels are observed by their fluorescence, or by laser induced fluorescence using a second color laser. Reaction rates are measured by observing the time dependent decay of signals from reactant and product channels. In addition we measure interaction potentials of the reactants by laser spectroscopy where the laser induced fluorescence or ionization is measured as a function of laser wavelength (excitation spectra) or by measuring fluorescence spectra at fixed laser frequencies with monochromators. The spectra are obtained in the form of either lineshapes or individual lines from rovibrational transitions of bound states. 11 refs. 4 figs., 3 tabs

  8. Nonadiabtic electron dynamics in densely quasidegenerate states in highly excited boron cluster.

    Yonehara, Takehiro; Takatsuka, Kazuo

    2016-04-28

    Following the previous study on nonadiabatic reaction dynamics including boron clusters [T. Yonehara and K. Takatsuka, J. Chem. Phys. 137, 22A520 (2012)], we explore deep into highly excited electronic states of the singlet boron cluster (B12) to find the characteristic features of the densely quasi-degenerate electronic state manifold, which undergo very frequent nonadiabatic transitions and thereby intensive electronic state mixing among very many of the relevant states. So much so, isolating the individual adiabatic states and tracking the expected potential energy surfaces both lose the physical sense. This domain of molecular situation is far beyond the realm of the Born-Oppenheimer approximation. To survey such a violent electronic state-mixing, we apply a method of nonadiabatic electron wavepacket dynamics, the semiclassical Ehrenfest method. We have tracked those electron wavepackets and found the electronic state mixing looks like an ultrafast diffusion in the Hilbert space, which results in huge fluctuation. Furthermore, due to such a violent mixing, the quantum phases associated with the electronic states are swiftly randomized, and consequently the coherence among the electronic states are lost quickly. Besides, these highly excited states are mostly of highly poly-radical nature, even in the spin singlet manifold and the number of radicals amounts up to 10 electrons in the sense of unpaired electrons. Thus the electronic states are summarized to be poly-radical and decoherent with huge fluctuation in shorter time scales of vibrational motions. The present numerical study sets a theoretical foundation for unknown molecular properties and chemical reactivity of such densely quasi-degenerate chemical species. PMID:27131547

  9. Stepwise excitation and level-crossing spectroscopy of the triplet D states of helium-4

    The fine-structure intervals of the lowest two triplet D states of 4He have been obtained by a new method: Ground-state atoms are excited by a discharge to the triplet metastable state, which then undergoes a two-step optical excitation to the triplet D states, where level-crossing measurements are made. The experimental results for 3D1-3D3 (MHz) are 1400.67 plus-or-minus 0.29 and 591.25 plus-or-minus 0.14 for the 3 3D and 4 3D states, respectively; for 3D2-3D3 (MHz) they are 75.97 plus-or-minus 0.23 and 36.15 plus-or-minus 0.24 for 3 3D and 4 3D. These values are much more precise than the previously available data, obtained by optical, particle-bombardment level crossing, or beam-foil quantum-beat spectroscopy, and are consistent with the previous data except for one case, where a previous measurement of 3 3D2-3 3D3 by electron bombardment level-crossing spectroscopy is believed to be in error. These new experimental values for the fine structures of the triplet D state of 4He clearly indicate the inadequateness of existing theoretical calculations of these fine structures

  10. Recent results related to excited states of 6Be and 10He

    Wolski R.

    2012-12-01

    Full Text Available The 1H(6Li, 6Ben charge-exchange reaction and the 3H(8He,p10He two-neutron transfer reaction were recently carried out at the ACCULINNA fragment separator (FLNR, Dubna to populate the ground and excited states of 6Be and 10He nuclei, respectively. The 6Be ET spectrum (ET is the 6Be energy above its 4He+p+p decay threshold was obtained with high statistics and described by the well-known 0+ ground state of 6Be at ET = 1.37 MeV, the 2+ state at ET = 3.05 MeV and a broad structure extending from 4 to 16 MeV which could be interpreted as the isovector soft dipole mode associated with the 6Li ground state. In the 10He case the 0+ ground state was found at about 2.1(2 MeV (Γ ~ 2 MeV above the 8He+n+n breakup threshold. Angular correlations observed for 10He decay products show prominent interference patterns allowing to draw conclusions about the structure of low-energy excited states: 1-(ET ~ 5 MeV and 2+ (ET ~ 6 MeV.

  11. Hybrid CIS-DFT method to study electric field effects on electronic excited states of ethylene

    Ma Mei-Zhong; Zhu Zheng-He; Chen Xiao-Jun; Xu Guo-Liang; Zhang Yong-Bin; Mao Hua-Ping; Shen Xiao-Hong

    2005-01-01

    The present work is devoted to the study of the effects of external dipole electric field on the molecular structure of ethylene using a hybrid method which combines the single-excitation configuration interactions (CIS) with density functional theory (DFT), i.e. CIS-DFT(B3LYP). It is found that the effects of electric dipole field on the molecular geometry (D2h, D2d and C2v), dipole moment, transition dipole moment, polarizability and, particularly, excitation energy of ethylene are remarkable. The advantages of the hybrid CIS-DFT method are that it can determine the symmetry of molecule and the correct order of excitation as well as the Molecular Orbital (MO) electron configuration;thereby the electronic excitation states of ethylene are easily derived, and most of them are in agreement with those obtained in experiments or references. It may be the first time the effects of external electric field on ethylene molecule have been considered. Compared with other ab initio methods, the CIS-DFT method is relatively accurate and low cost in computation. We expect that it can be used to study other closed-shell molecules.

  12. Photoluminescence and excited states dynamics in PbWO4:Pr3+ crystals

    Auffray, E; Shalapska, T; Zazubovich, S

    2014-01-01

    Luminescence and photo-thermally stimulated defects creation processes are studied for a Pr3+-doped PbWO4 crystal at 4.2-400 K under excitation in the band-to-band, exciton, and charge-transfer transitions regions, as well as in the Pr3+-related absorption bands. Emission spectra of Pr3+ centers depend on the excitation energy, indicating the presence of Pr3+ centers of two types. The origin of these centers is discussed. The 2.03-2.06 eV emission, arising from the D-1(2) -> H-3(4) transitions of Pr3+ ions, is found to be effectively excited in a broad intense absorption band peaking at 4.2 K at 3.92 eV. By analogy with some other Pe(3+)-doped compounds, this band is suggested to arise from an electron transfer from an impurity Pr3+ ion to the crystal lattice W6+ or Pb2+ ions. The dynamics of the Pr3+-related excited states is clarified. In the PbWO4:Pr crystal studied, the concentration of single oxygen and lead vacancies as traps for electrons and holes is found to be negligible.

  13. Investigation of angular momenta and correlation patterns in doubly excited states populated by low velocity double charge exchange

    Rozet, J.P.; Politis, M.F.; Blumenfeld, L.; Vernhet, D.; Wohrer, K.; Touati, A.; Stephan, C.; Chetioui, A.; Roncin, P.; Laurent, H.

    1987-12-01

    Autoionization branching ratios of O/sup 6+/ doubly excited states are shown to depend sensitively on the K, T and L quantum numbers of these states. A measurement of the decay probabilities to 2s and 2p sublevels has been performed for the (3, 3) and (3, 4) doubly excited states populated in the 1.3 keV/u O/sup 8+/ -> He collision. A new technique of X-ray, energy gain coincidence has been used. Results are discussed in terms of possible distributions K, L for the doubly excited states.

  14. Decoherence of quantum excitation of even/odd coherent states in thermal environment

    Mohammadbeigi A; Tavassoly M K

    2016-04-01

    In this paper, we study the decoherence of quantum excitation (photon-added)even/odd coherent states, $((\\^{a})^m|\\alpha_{\\pm}\\rangle)$, in a thermal environment by investigating the variation of negative part of the Wigner quasidistribution function vs. the rescaled time. For this purpose, at first we obtain the time-dependent Wigner function corresponding to the mentioned states in the framework of standard master equation. Then, the time evolution of the Wigner function associated with photon-added even/odd coherent states, as well as the number of added photons $m$ are analysed. It is shown that, in both states, the negative part of the Wigner function decreases with time. By deriving the threshold value of the rescaled time for single photon-added even/odd coherent states, it is also found that, if the rescaled time exceeds the threshold value, the associated Wigner function becomes positive, i.e., the decoherence occurs completely.

  15. Determination of the absolute excited state density of a sodium target by means of beam deflection measurements

    The average deflection of a laser excited, divergent sodium beam with a broad velocity distribution is measured by means of a Langmuir-Taylor detector and exploited for determining the absolute density of the excited state in the interaction area. Simulations of the excitation and deflection process point out that the knowledge of the velocity distribution of the sodium atoms plays a crucial part in obtaining reliable information from deflection measurements. From the comparison of simulated and experimental results we find that in our set-up typically 30% of the sodium atoms are in the excited state when both ground state levels are pumped with an intensity of 35 mW cm-2 from an electro-optically modulated CW laser beam; the corresponding excited state density is 1.5 x 109 cm-3. (Author)

  16. Kinetics studies following state-selective laser excitation. Final progress report, March 15, 1984--July 15, 1993

    Keto, J.W.

    1994-04-01

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

  17. Use of a 3-MV proton accelerator for study of noble gases, including laser ionization of excited states

    The use of a pulsed 3-MV accelerator to study energy pathways in the noble gases is described. The objectives of pathways research are to obtain (1) information on the spectrum of excited states produced by a charged particle in a noble gas, (2) the rate of decay of the various states through various channels as a function of gas pressure, and (3) the modification of the decay channels due to the introduction of foreign species. A new energy pathways model is presented for helium as a general illustration. A method for the study of excited states, using a laser ionization technique is reported. Use is made of a laser which is tuned to a resonance transition between the desired excited state and some higher excited state. Photons in the same pulse photoionize the higher excited state; thus the ionization current vs photon wavelength has a resonance structure. Absolute yields of selected excited states can be obtained whenever the photon fluence per pulse is large enough to saturate the ionization current. A general summary is given of experimental facilities which include a 3-MV Van de Graaff accelerator, electronics for measuring radiation lifetimes, vacuum ultraviolet spectrometers, and a pulsed laser facility for direct study of excited states. Finally, the relevance of pathways research to (1) the interaction of radiation with matter, (2) the development of gas lasers, and (3) methods of ultrasensitive elemental analysis is pointed out

  18. Low-lying states and isospin excitation in the Ge isotopes

    Falih H. Al-Khudair

    2009-01-01

    The level structure of 64-70Ge isotopes has been studied within the framework of the interacting boson model-3 (IBM-3). The symmetry character in the proton and neutron degrees of freedom of the energy levels has been investigated. The isospin excitation states (T>Tz) have been assigned for the 64Ge (N=Z) nucleus. Some intruder states in these nuclei have been suggested. The calculated energy levels and transition probabilities are in good agreement with recent experimental data. The study indicates that the Ge isotopes are in transition from γ-unstable to vibrational.

  19. Doubly excited 3Pe resonance states of two-electron positive ions in Debye plasmas

    Hu, Xiao-Qing; Wang, Yang; Jiang, Zishi; Jiang, Pinghui; Kar, Sabyasachi

    2015-11-01

    We investigate the doubly excited 3Pe resonance states of two-electron positive ions Li+, Be2+, B3+, and C4+ by employing correlated exponential wave functions. In the framework of the stabilization method, we calculate two series (3pnp and 3dnd) of 3Pe resonances below the N = 3 threshold. The 3Pe resonance parameters (resonance energies and widths) are reported for the first time as a function of the screening parameter. For free-atomic cases, comparisons are made with the reported results and few resonance states are reported for the first time.

  20. No Evidence of Isomerism for the First Excited State of {sup 93}Rb

    Miernik, K., E-mail: kmiernik@fuw.edu.pl [Physics Division, Oak Ridge National Laboratory, Oak Ridge Tennessee 37830 (United States); Gross, C.J. [Physics Division, Oak Ridge National Laboratory, Oak Ridge Tennessee 37830 (United States); Grzywacz, R. [Dept. of Physics and Astronomy, University of Tennessee, Knoxville, TN 37996 (United States); Physics Division, Oak Ridge National Laboratory, Oak Ridge Tennessee 37830 (United States); Madurga, M. [Dept. of Physics and Astronomy, University of Tennessee, Knoxville, TN 37996 (United States); Mendez, A.J.; Rykaczewski, K.P.; Stracener, D.W. [Physics Division, Oak Ridge National Laboratory, Oak Ridge Tennessee 37830 (United States); Zganjar, E.F. [Dept. of Physics and Astronomy, Louisiana State University, Baton Rouge, LA 70803 (United States)

    2014-06-15

    The 253.3–keV excited state located in {sup 93}Rb was studied at the Holifield Radioactive Ion Beam Facility in Oak Ridge. This state, described as isomeric in databases, was populated in the decay of {sup 93}Kr produced by proton–induced fission of {sup 238}U and isolated using the isotope separation on–line technique. We report that the 253.3–keV level does not reveal isomerism and the upper limit of the half-life from our measurement is 4 ns. Our findings are supported by previously reported results that were not taken into account in the latest nuclear databases.

  1. Fluorescence and excited state dynamics of the deprotonated Schiff base retinal in proteorhodopsin.

    Bühl, Elena; Braun, Markus; Lakatos, Andrea; Glaubitz, Clemens; Wachtveitl, Josef

    2015-09-01

    The UV light absorbing species of proteorhodopsin with deprotonated Schiff base retinal was investigated using steady-state fluorescence and femtosecond pump-probe spectroscopy. Compared to the all-trans retinal with protonated Schiff base, the deprotonated chromophore absorbs at 365 nm and exhibits a blue-shifted fluorescence spectrum. The unusually long-lived excited state decays bi-exponentially with time constants of 8 ps and 130 ps to form a deprotonated 13-cis retinal as the primary photo-product. PMID:26083266

  2. Excited state Faraday anomalous dispersion optical filters based on indirect laser pumping.

    Yin, Longfei; Luo, Bin; Chen, Zhongjie; Zhong, Lei; Guo, Hong

    2014-02-15

    The direct pump method now used in excited state Faraday anomalous dispersion optical filters (ES-FADOFs) requires that the transition between the target and the ground state is an electric dipole allowed transition and that a laser that operates at the exact pump wavelength is available. This is not always satisfied in practice. An indirect laser pump method for ES-FADOF is proposed and experimentally realized. Compared with the commonly used direct pump method, this indirect pump method can reach the same performance using lasers at very different wavelengths. This method can greatly extend the wavelength range of FADOF and provide a novel scheme for ES-FADOF design. PMID:24562221

  3. Electron impact excitation of the states of Mg, Ca and Sr atoms: Complete experiment results

    Sachin Saxena; Kshamata Muktavat; Rajesh Srivastava

    2004-11-01

    We have used non-relativistic and relativistic distorted wave approximation methods to study the excitation of the 1 states of magnesium ( = 3), calcium ( = 4) and strontium ( = 5) from the ground 1 state. Calculations have been performed for the complete set of parameters $(, \\tilde{L}_{\\bot}^{+}, \\tilde{L}_{\\bot}^{-}, \\tilde{}^{+}, \\tilde{}^{-})$. The results are presented for electron impact energies of 20 and 40 eV. We compare our results obtained from both the non-relativistic and relativistic methods with each other. Good agreement is found on comparison and the importance of relativistic effects is also explored.

  4. Doubly excited 3Pe resonance states of two-electron positive ions in Debye plasmas

    We investigate the doubly excited 3Pe resonance states of two-electron positive ions Li+, Be2+, B3+, and C4+ by employing correlated exponential wave functions. In the framework of the stabilization method, we calculate two series (3pnp and 3dnd) of 3Pe resonances below the N = 3 threshold. The 3Pe resonance parameters (resonance energies and widths) are reported for the first time as a function of the screening parameter. For free-atomic cases, comparisons are made with the reported results and few resonance states are reported for the first time

  5. Intramolecular dynamics and unimolecular reaction. A case study of state-selectively excited nitrogen dioxide

    Quantum levels of the quasibound dissociating NO2 were observed by introduction of PHOFEX spectroscopy in which a yield of photofragment molecules in a specific quantum level is detected as a function of the photolysis energy. Thus, the unimolecular rate constant specific to each quantum level of excited NO2 was determined which shows a stepwise increase when a new product state channel opens. This is a direct experimental proof of the statistical theory of the unimolecular reaction process. Furthermore, the product state distribution indicated quantum fluctuations associated with the individual quasibound eigenstates. (author)

  6. Excited hadrons and the analytical structure of bound-state interaction kernels

    El-Bennich, Bruno; Rojas, Eduardo; Serna, Fernando E

    2016-01-01

    We highlight Hermiticity issues in bound-state equations whose kernels are subject to a highly asymmetric mass and momentum distribution and whose eigenvalue spectrum becomes complex for radially excited states. We trace back the presence of imaginary components in the eigenvalues and wave functions to truncation artifacts and suggest how they can be eliminated in the case of charmed mesons. The solutions of the gap equation in the complex plane, which play a crucial role in the analytic structure of the Bethe-Salpeter kernel, are discussed for several interaction models and qualitatively and quantitatively compared to analytic continuations by means of complex-conjugate pole models fitted to real solutions.

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

    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.

  8. Ab Initio Inverstagation of the Excited States of Nucleobases and Nucleosides

    Szalay, Péter G.; Fogarasi, Géza; Watson, Thomas; Perera, Ajith; Lotrich, Victor; Bartlett, Rod J.

    2011-06-01

    Most living bodies are exposed to sunlight, essential life sustaining processes are using this natural radiation. Sunlight has, however, several components (has a broad "spectrum") and in particular the invisible component (UV, ultraviolet) is harmful for living organisms. Scientists around the word are busy to understand what happens in the cell when it is exposed to light: it seems that the building blocks of cells and in particular those carrying the genetic information (DNA and RNA) are highly protected against this exposition. Our research focuses on the spectral properties of the building blocks of DNA and RNA, the so called nucleobases and nucleosides, in order to understand this mechanism. Due to improvement in computer technology both at hardware and software side we are now able to use the most accurate methods of ab initio quantum chemistry to investigate the spectroscopic properties of these building blocks. These calculations provide direct information on the properties of these molecules but also provide important benchmarks for cheaper methods which can be used for even larger systems. We have calculated the excited state properties for the nucleobases (cytosine, guanine and adenine), their complexes with water and with each other (Watson-Crick base pairs and stacks) as well as corresponding nucleosides at the EOM-CCSD(T)/aug-cc-pVDZ level of theory and try to answer the following questions: (1) how the order of excited states varies in different nucleobases; (2) how hydration influences the excitation energy and order of excited states; (3) is there any effect of the sugar substituent; (4) how do close lying other bases change the spectrum. The calculations involve over hundred correlated electrons and up to thousand basis functions. Such calculations are now routinely available with the recently developed ACESIII code and can make use of hundreds or even several thousand of processors. V. Lotrich, N. Flocke, M. Ponton, A. Yau, A. Perera, E. Deumens

  9. Open-Shell Nuclei and Excited States from Multi-Reference Normal-Ordered Hamiltonians

    Gebrerufael, Eskendr; Roth, Robert

    2015-01-01

    We discuss the approximate inclusion of three-nucleon interactions into ab initio nuclear structure calculations using a multi-reference 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, multi-reference normal ordering opens a path to open-shell nuclei and excited states. Based on different multi-determinantal 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 6-Li, 12-C, and 10-B. We find that this multi-reference normal-ordered two-body approximation is able to capture the effects of the 3N 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 ...

  10. Excited state absorption of Cr/sup 3+/ in low field crystalline hosts

    A simple single configuration coordinate crystal field model has been developed to predict the excited state absorption (ESA) spectra of Cr/sup +3/ in hosts where the /sup 4/T/sub 2g/ is the lowest excited state. Two spin allowed transitions are predicted to lie near 19,000 and 7,000 cm/sup -1/ for Cr/sup 3+/ in a typical fluoride host. On the other hand, ESA from a /sup 2/E lowest excited state is more complex having a number of near infrared and visible transitions to a rich manifold of high energy doublets. To corroborate the model, ESA measurements have been made on GSGG:Cr, GSAG:Cr and K/sub 2/NaScF/sub 6/:Cr over the range 250 nm to 1,750 nm. The higher energy ESA transition was located near 19,000 cm/sup -1/ and is accompanied by bleaching of the strong ground state transitions at 15,500 and 22,000 cm/sup -1/. The lower energy transition was found centered at 8,000 cm/sup -1/ and to be far broader than predicted by a single configuration coordinate model. In addition to these crystal field transitions, intense charge transfer bands were found at 31,000 and 32,000 cm/sup -1/ for GSGG:Cr and GSAG:Cr, respectively, but they are not present in this region for the elpasolite. The peculiar band shape of these charge-transfer transitions suggest that the terminal state of the transition is the host conduction band. Finally, saturation experiments were made at 632.8 nm in order to determine ESA cross sections. Threshold for damage and thermal lensing was found to be near 10 Mwatt/cm/sup 2/ for GSGG, consequently only partial saturation could be achieved. ESA cross sections were extracted from these data with a coupled three level kinetic model

  11. Equation of motion theory for excited states in variational Monte Carlo and the Jastrow antisymmetric geminal power in Hilbert space

    Zhao, Luning

    2016-01-01

    An equation of motion formalism for excited states in variational Monte Carlo is derived and a pilot implementation for the Jastrow-modified antisymmetric geminal power is tested. In single excitations across a range of small molecules, this combination is shown to be intermediate in accuracy between configuration interaction singles and equation of motion coupled cluster with singles and doubles. For double excitations, energy errors are found to be similar to those for coupled cluster.

  12. 2νββ decay of 76Ge into excited states with GERDA phase I

    GERDA Collaboration; Agostini, M.; Allardt, M.; Bakalyarov, A. M.; Balata, M.; Barabanov, I.; Barros, N.; Baudis, L.; Bauer, C.; Becerici-Schmidt, N.; Bellotti, E.; Belogurov, S.; Belyaev, S. T.; Benato, G.; Bettini, A.; Bezrukov, L.; Bode, T.; Borowicz, D.; Brudanin, V.; Brugnera, R.; Budjáš, D.; Caldwell, A.; Cattadori, C.; Chernogorov, A.; D'Andrea, V.; Demidova, E. V.; di Vacri, A.; Domula, A.; Doroshkevich, E.; Egorov, V.; Falkenstein, R.; Fedorova, O.; Freund, K.; Frodyma, N.; Gangapshev, A.; Garfagnini, A.; Gooch, C.; Grabmayr, P.; Gurentsov, V.; Gusev, K.; Hegai, A.; Heisel, M.; Hemmer, S.; Heusser, G.; Hofmann, W.; Hult, M.; Inzhechik, L. V.; Janicskó Csáthy, J.; Jochum, J.; Junker, M.; Kazalov, V.; Kihm, T.; Kirpichnikov, I. V.; Kirsch, A.; Klimenko, A.; Knöpfle, K. T.; Kochetov, O.; Kornoukhov, V. N.; Kuzminov, V. V.; Laubenstein, M.; Lazzaro, A.; Lebedev, V. I.; Lehnert, B.; Liao, H. Y.; Lindner, M.; Lippi, I.; Lubashevskiy, A.; Lubsandorzhiev, B.; Lutter, G.; Macolino, C.; Majorovits, B.; Maneschg, W.; Medinaceli, E.; Mi, Y.; Misiaszek, M.; Moseev, P.; Nemchenok, I.; Palioselitis, D.; Panas, K.; Pandola, L.; Pelczar, K.; Pullia, A.; Riboldi, S.; Rumyantseva, N.; Sada, C.; Salathe, M.; Schmitt, C.; Schneider, B.; Schreiner, J.; Schulz, O.; Schwingenheuer, B.; Schönert, S.; Schütz, A.-K.; Selivanenko, O.; Shirchenko, M.; Simgen, H.; Smolnikov, A.; Stanco, L.; Stepaniuk, M.; Ur, C. A.; Vanhoefer, L.; Vasenko, A. A.; Veresnikova, A.; von Sturm, K.; Wagner, V.; Walter, M.; Wegmann, A.; Wester, T.; Wilsenach, H.; Wojcik, M.; Yanovich, E.; Zavarise, P.; Zhitnikov, I.; Zhukov, S. V.; Zinatulina, D.; Zuber, K.; Zuzel, G.

    2015-11-01

    Two neutrino double beta decay of {}76{Ge} to excited states of {}76{Se} has been studied using data from Phase I of the GERDA experiment. An array composed of up to 14 germanium detectors including detectors that have been isotopically enriched in {}76{Ge} was deployed in liquid argon. The analysis of various possible transitions to excited final states is based on coincidence events between pairs of detectors where a de-excitation γ ray is detected in one detector and the two electrons in the other. No signal has been observed and an event counting profile likelihood analysis has been used to determine Frequentist 90% C.L. bounds for three transitions: {0}{{g}.{{s}}.}+-{2}1+: {T}1/22ν \\gt 1.6× {10}23 yr, {0}{{g}.{{s}}.}+-{0}1+: {T}1/22ν \\gt 3.7× {10}23 yr and {0}{{g}.{{s}}.}+-{2}2+: {T}1/22ν \\gt 2.3× {10}23 yr. These bounds are more than two orders of magnitude larger than those reported previously. Bayesian 90% credibility bounds were extracted and used to exclude several models for the {0}{{g}.{{s}}.}+-{0}1+ transition.

  13. Long-range states in excited ultracold 3He*-4He* dimers

    Cocks, Daniel G; Whittingham, Ian B

    2014-01-01

    Long-range bound states of the excited heteronuclear 3He*--4He* system that dissociate to either 3He(1s2s 3S_1) + 4He(1s2p 3P_j) or 3He(1s2p 3P_j) + 4He(1s2s 3S_1), where j=0, 1, 2, are investigated using both single-channel and multichannel calculations in order to analyse the effects of Coriolis and non-adiabatic couplings. The multichannel calculations predict two groups of resonances above the lowest asymptotic energy. One of these groups dissociates to an atomic pair with the 2p excitation on the fermionic atom and the other dissociates to two asymptotes which correspond to the 2p excitation on either atom. Many of these resonances could be identified with levels in the single-channel calculation although the differences in energies were large. The total parity was found to have a significant influence on the ability to make these identifications. No purely bound states were found, although several resonances with line widths smaller than 1 MHz were obtained.

  14. Excited states of hypernuclei (populated by low energetic separated K- beam)

    Bamberger, A; Haddock, R; Lynen, U; Moszkowski, S; Piekarz, H; Piekarz, J; Pniewski, J; Povh, B; Ritter, H G; Soergel, Volker; Van Oers, W T H

    1972-01-01

    The experimental investigation of hypernuclei up to now has been done using emulsions and bubble chambers and therefore, with only 2 exemptions, all existing knowledge concerns hypernuclear ground states. The investigation of excited states in general is only possible using counter techniques, but these experiments could not be performed due to the low intensity of available K/sup -/-beams. At CERN a low energetic separated K-beam has been built, at which 1000 K /sup -/-mesons per burst can be stopped in a target of 6g/cm/sup 2/ thickness. At this beam an experiment looking for gamma -transitions in excited hypernuclei has been performed. In order to eliminate background gamma -radiation arising from kappa /sup -/ annihilation and de-excitation of residual nuclei, only light targets were used, namely /sup 6/Li, /sup 7/Li, /sup 9/Be, /sup 12/C and /sup 16/O. Hypernuclear transitions were found in /sup 4//sub Lambda /H and /sup 4//sub Lambda /He and possible transitions in /sup 6/Li and /sup 7/Li. The scatterin...

  15. Excited-state dynamics of Si-rhodamine and its aggregates: versatile fluorophores for NIR absorption.

    Kim, Sooyeon; Fujitsuka, Mamoru; Miyata, Mikiji; Majima, Tetsuro

    2016-01-21

    Since it was first reported in 2008, great attention has been paid to Si-rhodamine (SiR) because of its far-red to near-infrared (NIR) absorption/fluorescence and suitability for high-resolution in vivo imaging. However, properties of SiR in the excited state have not been reported, even though they are directly related to its fluorescence. In the present study, the properties of SiR monomers in the excited states are thoroughly characterized for the first time. Moreover, by replacing a phenyl moiety of SiR with a 4-(9-anthryl)phenylene group (SiR-An), we prepared H- and J-aggregates of SiR in the aqueous solution, and succeeded in monitoring exciton formation and annihilation in the aggregates. Interestingly, the relative exciton population in the SiR J-aggregate increases as the excitation power becomes stronger, which is unusual considering that the substantial exciton-exciton annihilation process occurs as more excitons are generated. The results obtained in the present study suggest high versatility of SiR not only as a red fluorophore in the cutting-edge microscopic techniques but also as a NIR absorber in the light harvesting system. PMID:26692043

  16. Two-Component Structure in the Entanglement Spectrum of Highly Excited States.

    Yang, Zhi-Cheng; Chamon, Claudio; Hamma, Alioscia; Mucciolo, Eduardo R

    2015-12-31

    We study the entanglement spectrum of highly excited eigenstates of two known models that exhibit a many-body localization transition, namely the one-dimensional random-field Heisenberg model and the quantum random energy model. Our results indicate that the entanglement spectrum shows a "two-component" structure: a universal part that is associated with random matrix theory, and a nonuniversal part that is model dependent. The nonuniversal part manifests the deviation of the highly excited eigenstate from a true random state even in the thermalized phase where the eigenstate thermalization hypothesis holds. The fraction of the spectrum containing the universal part decreases as one approaches the critical point and vanishes in the localized phase in the thermodynamic limit. We use the universal part fraction to construct an order parameter for measuring the degree of randomness of a generic highly excited state, which is also a promising candidate for studying the many-body localization transition. Two toy models based on Rokhsar-Kivelson type wave functions are constructed and their entanglement spectra are shown to exhibit the same structure. PMID:26765022

  17. Structure of the excited states of 95Mo and beta-decay 95Tc →95Mo

    The energies,spins,parities,magnetic dipole and electric quadrupole moments,and spectroscopic factors of the ground and excited states of 95Mo as well as the reduced probabilities of electromagnetic transitions between them and the reduced probabilities of β-transitions between the ground state of 95Tc and excited states of 95Mo have been calculated in the framework of the dynamic collective model.The theoretical results are compared with experimental values

  18. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited-state

  19. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    Tomin, Vladimir I., E-mail: tomin@apsl.edu.pl; Ushakou, Dzmitryi V.

    2015-10-15

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited-state

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

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

    2016-08-01

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