Population trapping in the excited states using vacuum-induced coherence and adiabatic process

NASA Astrophysics Data System (ADS)

Lal Kumawat, Babu; Kumar, Pardeep; Dasgupta, Shubhrangshu

2018-02-01

We theoretically investigate how population can be trapped in the closely spaced excited levels in presence of vacuum-induced coherence (VIC). We employ delayed pulses to transfer population from a meta-stable state to the excited states. Subsequently, spontaneous emission from these excited states builds coherence between them. This coherence can be probed by using chirping, which leads to the decoupling of the excited states from the ground state thereby ensuring population transfer via delayed pulses. Our results indicate that the existence of VIC leads to the generation of a mixed state in the excited state manifold, where trapping of the population occurs even in the presence of large decay. This trapping may be realized in molecular systems and can be interpreted as a sensitive probe of VIC. We present suitable numerical analysis to support our results.

Laser-induced breakup of helium 3S 1s2s with intermediate doubly excited states

NASA Astrophysics Data System (ADS)

Simonsen, A. S.; Bachau, H.; Førre, M.

2014-02-01

Solving the time-dependent Schrödinger equation in full dimensionality for two electrons, it is found that in the XUV regime the two-photon double ionization dynamics of He(1s2s) is predominantly dictated by the process of resonance enhanced multiphoton ionization via doubly excited states (DESs). We have studied a pump-probe scenario where the full laser-driven breakup of the 3S 1s2s metastable state is dominated by intermediate quasiresonant excitation to doubly excited (autoionizing) states in the 3Po series. Clear evidence of multipath interference effects is revealed in the resulting angular distributions of the ejected electrons in cases where more than one intermediate DES is populated in the process.

Transition rate diagrams - A new approach to the study of selective excitation processes: The spectrum of manganese in a Grimm-type glow discharge

NASA Astrophysics Data System (ADS)

Weiss, Zdeněk; Steers, Edward B. M.; Pickering, Juliet C.; Mushtaq, Sohail

2014-02-01

The emission spectra of manganese observed using a Grimm-type glow discharge in pure argon, argon with 0.3% v/v hydrogen and pure neon were studied in order to identify major excitation and ionization processes of manganese in the plasma. A new procedure is proposed, in which each observed emission line is associated with the corresponding transition between different states of the Mn atom or Mn ion, and, by considering all the observed transitions from and into a specific state, a measure of the total rate is determined at which this state is radiatively populated and depopulated. These resulting population/depopulation rates are then plotted as function of level energy. Such plots, called here “transition rate diagrams”, show the role of individual states in the formation of the observed spectrum and can be used to identify possible selective excitation processes. Also, cascade excitation by radiative decay of higher excited states can be conveniently evaluated in this way. A detailed description of the observed Mn I and Mn II spectra is given for Ar, Ar-H2 and Ne plasmas and relevant excitation/ionization mechanisms are discussed. Matrix effects in analysis of manganese by glow discharge spectroscopy are discussed. A list of important Mn I and Mn II lines excited in the glow discharge plasma is given.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Westlake, Brittany C.; Brennaman, Kyle M.; Concepcion, Javier J.

2011-05-24

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

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

PubMed

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

2011-05-24

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

Experimental Resonance Enhanced Multiphoton Ionization (REMPI) studies of small molecules

NASA Technical Reports Server (NTRS)

Dehmer, J. L.; Dehmer, P. M.; Pratt, S. T.; Ohalloran, M. A.; Tomkins, F. S.

1987-01-01

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

One Photon Can Simultaneously Excite Two or More Atoms.

PubMed

Garziano, Luigi; Macrì, Vincenzo; Stassi, Roberto; Di Stefano, Omar; Nori, Franco; Savasta, Salvatore

2016-07-22

We consider two separate atoms interacting with a single-mode optical or microwave resonator. When the frequency of the resonator field is twice the atomic transition frequency, we show that there exists a resonant coupling between one photon and two atoms, via intermediate virtual states connected by counterrotating processes. If the resonator is prepared in its one-photon state, the photon can be jointly absorbed by the two atoms in their ground state which will both reach their excited state with a probability close to one. Like ordinary quantum Rabi oscillations, this process is coherent and reversible, so that two atoms in their excited state will undergo a downward transition jointly emitting a single cavity photon. This joint absorption and emission process can also occur with three atoms. The parameters used to investigate this process correspond to experimentally demonstrated values in circuit quantum electrodynamics systems.

Multiple-photon excitation of nitrogen vacancy centers in diamond

NASA Astrophysics Data System (ADS)

Ji, Peng; Balili, R.; Beaumariage, J.; Mukherjee, S.; Snoke, D.; Dutt, M. V. Gurudev

2018-04-01

We report the observation of multiphoton photoluminescence excitation (PLE) below the resonant energies of nitrogen vacancy (NV) centers in diamond. The quadratic and cubic dependence of the integrated fluorescence intensity as a function of excitation power indicates a two-photon excitation pathway for the NV- charge state and a three-photon process involved for the neutral NV0 charge state, respectively. Comparing the total multiphoton energy with its single-photon equivalent, the PLE spectra follows the absorption spectrum of single photon excitation. We also observed that the efficiency of photoluminescence for different charge states, as well as the decay time constant, was dependent on the excitation wavelength and power.

Laser-muon spin spectroscopy in liquids - a technique to study the excited state chemistry of transients.

PubMed

Ghandi, Khashayar; Clark, Ian P; Lord, James S; Cottrell, Stephen P

2007-01-21

This study introduces laser-muon spin spectroscopy in the liquid phase, which extends muonium chemistry in liquids to the realm of excited states and enables the detection of muoniated molecules by their spin evolution after laser excitation. This leads to new opportunities to study the Kinetic Isotope Effects (KIEs) of muonium/atomic hydrogen reactions and to probe transient chemistry in radiolysis processes involved in muonium formation, as well as muoniated intermediates in excited states.

Determination of the formation of dark state via depleted spontaneous emission in a complex solvated molecule.

PubMed

Guo, Xunmin; Wang, Sufan; Xia, Andong; Su, Hongmei

2007-07-05

We present a general two-color two-pulse femtosecond pump-dump approach to study the specific population transfer along the reaction coordinate through the higher vibrational energy levels of excited states of a complex solvated molecule via the depleted spontaneous emission. The time-dependent fluorescence depletion provides the correlated dynamical information between the monitored fluorescence state and the SEP "dumped" dark states, and therefore allow us to obtain the dynamics of the formation of the dark states corresponding to the ultrafast photoisomerization processes. The excited-state dynamics of LDS 751 have been investigated as a function of solvent viscosity and solvent polarity, where a cooperative two-step isomerization process is clearly identified within LDS 751 upon excitation.

Excited State Charge Transfer reaction with dual emission from 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile: Spectral measurement and theoretical density functional theory calculation

NASA Astrophysics Data System (ADS)

Jana, Sankar; Dalapati, Sasanka; Ghosh, Shalini; Kar, Samiran; Guchhait, Nikhil

2011-07-01

The excited state intramolecular charge transfer process in donor-chromophore-acceptor system 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile (DMAPPDN) has been investigated by steady state absorption and emission spectroscopy in combination with Density Functional Theory (DFT) calculations. This flexible donor acceptor molecule DMAPPDN shows dual fluorescence corresponding to emission from locally excited and charge transfer state in polar solvent. Large solvatochromic emission shift, effect of variation of pH and HOMO-LUMO molecular orbital pictures support excited state intramolecular charge transfer process. The experimental findings have been correlated with the calculated structure and potential energy surfaces based on the Twisted Intramolecular Charge Transfer (TICT) model obtained at DFT level using B3LYP functional and 6-31+G( d, p) basis set. The theoretical potential energy surfaces for the excited states have been generated in vacuo and acetonitrile solvent using Time Dependent Density Functional Theory (TDDFT) and Time Dependent Density Functional Theory Polarized Continuum Model (TDDFT-PCM) method, respectively. All the theoretical results show well agreement with the experimental observations.

Temperature dependent of IVR investigated by steady-state and time-frequency resolved CARS for liquid nitrobenzene and nitromethane

NASA Astrophysics Data System (ADS)

Yang, Yanqiang; Zhu, Gangbei; Yan, Lin; Liu, Xiaosong; Yang's Ultrafast Spectroscopy Group Team

2017-06-01

Intramolecular vibrational energy redistribution (IVR) is important process in thermal decomposition, shock chemistry and photochemistry. Anti-Stokes Raman scattering is sensitive to the vibrational population in excited states because only vibrational excited states are responsible to the anti-Stokes Raman scattering, does not vibrational ground states. In this report, steady-state anti-Stokes Raman spectroscopy and broad band ultrafast coherent anti-Stokes Raman scattering (CARS) are performed. The steady-state anti-Stokes Raman spectroscopy shows temperature dependent of vibrational energy redistribution in vibrational excited-state molecule, and reveal that, in liquid nitrobenzene, with temperature increasing, vibrational energy is mainly redistributed in NO2 symmetric stretching mode, and phenyl ring stretching mode of νCC. For liquid nitromethane, it is found that, with temperature increasing, vibrational energy concentrate in CN stretching mode and methyl umbrella vibrational mode. In the broad band ultrafast CARS experiment, multiple vibrational modes are coherently excited to vibrational excited states, and the time-frequency resolved CARS spectra show the coincident IVR processes. This work is supported by the National Natural Science Foundation of China (Grant Numbers 21673211 and 11372053), and the Science Challenging Program (Grant Number JCKY2016212A501).

Temporal mapping of photochemical reactions and molecular excited states with carbon specificity

NASA Astrophysics Data System (ADS)

Wang, K.; Murahari, P.; Yokoyama, K.; Lord, J. S.; Pratt, F. L.; He, J.; Schulz, L.; Willis, M.; Anthony, J. E.; Morley, N. A.; Nuccio, L.; Misquitta, A.; Dunstan, D. J.; Shimomura, K.; Watanabe, I.; Zhang, S.; Heathcote, P.; Drew, A. J.

2017-04-01

Photochemical reactions are essential to a large number of important industrial and biological processes. A method for monitoring photochemical reaction kinetics and the dynamics of molecular excitations with spatial resolution within the active molecule would allow a rigorous exploration of the pathway and mechanism of photophysical and photochemical processes. Here we demonstrate that laser-excited muon pump-probe spin spectroscopy (photo-μSR) can temporally and spatially map these processes with a spatial resolution at the single-carbon level in a molecule with a pentacene backbone. The observed time-dependent light-induced changes of an avoided level crossing resonance demonstrate that the photochemical reactivity of a specific carbon atom is modified as a result of the presence of the excited state wavefunction. This demonstrates the sensitivity and potential of this technique in probing molecular excitations and photochemistry.

Nonadiabatic excited-state molecular dynamics modeling of photoinduced dynamics in conjugated molecules.

PubMed

Nelson, Tammie; Fernandez-Alberti, Sebastian; Chernyak, Vladimir; Roitberg, Adrian E; Tretiak, Sergei

2011-05-12

Nonadiabatic dynamics generally defines the entire evolution of electronic excitations in optically active molecular materials. It is commonly associated with a number of fundamental and complex processes such as intraband relaxation, energy transfer, and light harvesting influenced by the spatial evolution of excitations and transformation of photoexcitation energy into electrical energy via charge separation (e.g., charge injection at interfaces). To treat ultrafast excited-state dynamics and exciton/charge transport we have developed a nonadiabatic excited-state molecular dynamics (NA-ESMD) framework incorporating quantum transitions. Our calculations rely on the use of the Collective Electronic Oscillator (CEO) package accounting for many-body effects and actual potential energy surfaces of the excited states combined with Tully's fewest switches algorithm for surface hopping for probing nonadiabatic processes. This method is applied to model the photoinduced dynamics of distyrylbenzene (a small oligomer of polyphenylene vinylene, PPV). Our analysis shows intricate details of photoinduced vibronic relaxation and identifies specific slow and fast nuclear motions that are strongly coupled to the electronic degrees of freedom, namely, torsion and bond length alternation, respectively. Nonadiabatic relaxation of the highly excited mA(g) state is predicted to occur on a femtosecond time scale at room temperature and on a picosecond time scale at low temperature.

Separating Bulk and Surface Contributions to Electronic Excited-State Processes in Hybrid Mixed Perovskite Thin Films via Multimodal All-Optical Imaging.

PubMed

Simpson, Mary Jane; Doughty, Benjamin; Das, Sanjib; Xiao, Kai; Ma, Ying-Zhong

2017-07-20

A comprehensive understanding of electronic excited-state phenomena underlying the impressive performance of solution-processed hybrid halide perovskite solar cells requires access to both spatially resolved electronic processes and corresponding sample morphological characteristics. Here, we demonstrate an all-optical multimodal imaging approach that enables us to obtain both electronic excited-state and morphological information on a single optical microscope platform with simultaneous high temporal and spatial resolution. Specifically, images were acquired for the same region of interest in thin films of chloride containing mixed lead halide perovskites (CH 3 NH 3 PbI 3-x Cl x ) using femtosecond transient absorption, time-integrated photoluminescence, confocal reflectance, and transmission microscopies. Comprehensive image analysis revealed the presence of surface- and bulk-dominated contributions to the various images, which describe either spatially dependent electronic excited-state properties or morphological variations across the probed region of the thin films. These results show that PL probes effectively the species near or at the film surface.

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

Excitation of vacuum ultraviolet spectra of krypton in a cooled gas discharge

NASA Astrophysics Data System (ADS)

Gerasimov, Gennadii N.; Krylov, Boris E.; Hallin, Reinhold

1995-08-01

Results are presented on the experimental study of VUV spectra of krypton excited by a dc discharge in a capillary tube with the wall cooled to the temperature of liquid nitrogen. We studied the 120-200 nm spectral region corresponding to the transitions between the dimer lowest excited states and the weakly bound ground state, 1u, 0u+ yields 0g+. Electron impact, transferring dimers from the ground state into the excited state, is shown to be an efficient excitation mechanism in the 50-650 Torr and the 10-50 mA pressure and current ranges. The spectra obtained and the calculations made corroborate the high rate of this process.

Electron-impact vibrational relaxation in high-temperature nitrogen

NASA Technical Reports Server (NTRS)

Lee, Jong-Hun

1992-01-01

Vibrational relaxation process of N2 molecules by electron-impact is examined for the future planetary entry environments. Multiple-quantum transitions from excited states to higher/lower states are considered for the electronic ground state of the nitrogen molecule N2 (X 1Sigma-g(+)). Vibrational excitation and deexcitation rate coefficients obtained by computational quantum chemistry are incorporated into the 'diffusion model' to evaluate the time variations of vibrational number densities of each energy state and total vibrational energy. Results show a non-Boltzmann distribution of number densities at the earlier stage of relaxation, which in turn suppresses the equilibrium process but affects little the time variation of total vibrational energy. An approximate rate equation and a corresponding relaxation time from the excited states, compatible with the system of flow conservation equations, are derived. The relaxation time from the excited states indicates the weak dependency of the initial vibrational temperature. The empirical curve-fit formula for the improved e-V relaxation time is obtained.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Photofragment Coincidence Imaging of Small I- (H2O)n Clusters Excited to the Charge-transfer-to-solvent State

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neumark, D. E. Szpunar, K. E. Kautzman, A. E. Faulhaber, and D. M.; Kautzman, K.E.; Faulhaber, A.E.

2005-11-09

The photodissociation dynamics of small I{sup -}(H{sub 2}O){sub n} (n = 2-5) clusters excited to their charge-transfer-to-solvent (CTTS) states have been studied using photofragment coincidence imaging. Upon excitation to the CTTS state, two photodissociation channels were observed. The major channel ({approx}90%) is a 2-body process forming neutral I + (H{sub 2}O){sub n} photofragments, and the minor channel is a 3-body process forming I + (H{sub 2}O){sub n-1} + H{sub 2}O fragments. Both process display translational energy (P(E{sub T})) distributions peaking at E{sub T} = 0 with little available energy partitioned into translation. Clusters excited to the detachment continuum rather thanmore » to the CTTS state display the same two channels with similar P(E{sub T}) distributions. The observation of similar P(E{sub T}) distributions from the two sets of experiments suggests that in the CTTS experiments, I atom loss occurs after autodetachment of the excited (I(H{sub 2}O){sub n}{sup -})* cluster, or, less probably, that the presence of the excess electron has little effect on the departing I atom.« less

Excitation and charge transfer in low-energy hydrogen atom collisions with neutral iron

NASA Astrophysics Data System (ADS)

Barklem, P. S.

2018-05-01

Data for inelastic processes due to hydrogen atom collisions with iron are needed for accurate modelling of the iron spectrum in late-type stars. Excitation and charge transfer in low-energy Fe+H collisions is studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multi-channel Landau-Zener model. An extensive calculation including 166 covalent states and 25 ionic states is presented and rate coefficients are calculated for temperatures in the range 1000-20 000 K. The largest rates are found for charge transfer processes to and from two clusters of states around 6.3 and 6.6 eV excitation, corresponding in both cases to active 4d and 5p electrons undergoing transfer. Excitation and de-excitation processes among these two sets of states are also significant. Full Tables and rate coefficient data are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/612/A90

Photophysical study of some 3-benzoylmethyleneindol-2-ones and estimation of ground and excited states dipole moments from solvatochromic methods using solvent polarity parameters

NASA Astrophysics Data System (ADS)

Saroj, Manju K.; Sharma, Neera; Rastogi, Ramesh C.

2012-03-01

3-Benzoylmethyleneindol-2-ones, isatin based chalcones containing donor and acceptor moieties that exhibit excited-state intramolecular charge transfer, have been studied in different solvents by absorption and emission spectroscopy. The excited state behavior of these compounds is strongly dependent on the nature of substituents and the environment. These compounds show multiple emissions arising from a locally excited state and the two states due to intramolecular processes viz. intramolecular charge transfer (ICT) and excited state intramolecular proton transfer (ESIPT). Excited-state dipole moments have been calculated using Stoke-shifts of LE and ICT states using solvatochromic methods. The higher values of dipole moments obtained lead to support the formation of ICT state as one of the prominent species in the excited states of all 3-benzoylmethyleneindol-2-ones. The correlation of the solvatochromic Stokes-shifts with the microscopic solvent polarity parameter (ETN) was found to be superior to that obtained using bulk solvent polarity functions. The absorption and florescence spectral characteristics have been also investigated as a function of acidity and basicity (Ho/pH) in aqueous phase.

Nonadiabatic dynamics simulation of photoisomerization mechanism of the second stablest isomer of N-salicilydenemethylfurylamine

NASA Astrophysics Data System (ADS)

Gao, Aihua; Li, Jianpeng; Wang, Dehua; Ma, Xiaoguang; Wang, Meishan

2018-02-01

The photoisomerization processes of the second stablest isomer in the aromatic Schiff base, N-salicilydenemethylfurylamine, in the gas phase have been studied by static electronic structure calculations and surface-hopping dynamics simulations based on the Zhu-Nakamura theory. Various stable structures are obtained in the optimization because of different orientations of methyl-furyl part with respect to the salicylaldimine part and different orientations of hydroxy group with respect to the benzene ring. Upon photoexcitation into the first excited state, bond isomerization in the salicylaldimine part is completely suppressed until the strong excited-state hydrogen bond is broken. The decay pathway involves two excited-state minima, one in cis-enol form and the other in cis-keto form. After the excited-state proton transfer, twists of bonds lead to a conical intersection between the ground and excited states. After internal conversion around a conical intersection, the molecule is stabilized in cis- or trans-keto form. If the reverse hydrogen transfer process occurs in the ground state, the molecule will finally end up in the cis-enol region. The cis-keto and trans-keto isomers are observed as photoproducts. According to our full-dimensional nonadiabatic dynamics simulations, we find the excited-state intramolecular proton transfer and torsions of three single bonds in the chain to be responsible for photoisomerization of the second stablest isomer of N-salicilydenemethylfurylamine.

Combined TDDFT and AIM Insights into Photoinduced Excited State Intramolecular Proton Transfer (ESIPT) Mechanism in Hydroxyl- and Amino-Anthraquinone Solution.

PubMed

Zheng, Daoyuan; Zhang, Mingzhen; Zhao, Guangjiu

2017-10-23

Time-dependent density functional theory (TDDFT) and atoms in molecules (AIM) theory are combined to study the photoinduced excited state intramolecular proton transfer (ESIPT) dynamics for eight anthraquinones (AQs) derivatives in solution. The calculated absorption and emission spectra are consistent with the available experimental data, verifying the suitability of the theory selected. The systems with the excited-state exothermic proton transfer, such as 1-HAQ, 1,5-DHAQ and TFAQ, emit completely from transfer structure (T), while the reactions for those without ESIPT including 1,4-DHAQ and AAAQ appear to be endothermic. Three reaction properties of three systems (1,8-DHAQ, DCAQ and CAAQ) are between the exothermic and endothermic, sensitive to the solvent. Energy scanning shows that 1,4-DHAQ and AAAQ exhibit the higher ESIPT energy barriers compared to 1-HAQ, 1,5-DHAQ and TFAQ with the "barrierless" ESIPT process. The ESIPT process is facilitated by the strengthening of hydrogen bonds in excited state. With AIM theory, it is observed that the change in electrons density ρ(r) and potential energy density V(r) at BCP position between ground state and excited state are crucial factors to quantitatively elucidate the ESIPT.

TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4‧-dimethylaminoflavonol in ethanol solvent

NASA Astrophysics Data System (ADS)

Wang, Ye; Shi, Ying; Cong, Lin; Li, Hui

2015-02-01

Time-dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate the intramolecular and intermolecular hydrogen bonding dynamics in the first excited (S1) state of 4‧-dimethylaminoflavonol (DMAF) monomer and in ethanol solution. In the DMAF monomer, we demonstrated that the intramolecular charge transfer (ICT) takes place in the S1 state. This excited state ICT process was followed by intramolecular proton transfer. Our calculated results are in good agreement with the mechanism proposed in experimental work. For the hydrogen-bonded DMAF-EtOH complex, it was demonstrated that the intermolecular hydrogen bonds can induce the formation of the twisted intramolecular charge transfer (TICT) state and the conformational twisting is along the C3-C4 bond. Moreover, the intermolecular hydrogen bonds can also facilitate the intermolecular double proton transfer in the TICT state. A stepwise intermolecular double proton transfer process was revealed. Therefore, the intermolecular hydrogen bonds can alter the mechanism of intramolecular charge transfer and proton transfer in the excited state for the DMAF molecule.

Theoretical Studies of Chemical Reactions following Electronic Excitation

NASA Technical Reports Server (NTRS)

Chaban, Galina M.

2003-01-01

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

Up-conversion fluorescence: noncoherent excitation by sunlight.

PubMed

Baluschev, S; Miteva, T; Yakutkin, V; Nelles, G; Yasuda, A; Wegner, G

2006-10-06

We demonstrate up-conversion of noncoherent sunlight realized by ultralow excitation intensity. The bimolecular up-conversion process in our systems relies on the presence of a metastable triplet excited state, and thus has dramatically different photophysical characteristics relative to the other known methods for photon up-conversion (two-photon absorption, parametric processes, second harmonic generation, sequential multiphoton absorption, etc.).

Three-photon Gaussian-Gaussian-Laguerre-Gaussian excitation of a localized atom to a highly excited Rydberg state

NASA Astrophysics Data System (ADS)

Mashhadi, L.

2017-12-01

Optical vortices are currently one of the most intensively studied topics in light-matter interaction. In this work, a three-step axial Doppler- and recoil-free Gaussian-Gaussian-Laguerre-Gaussian (GGLG) excitation of a localized atom to the highly excited Rydberg state is presented. By assuming a large detuning for intermediate states, an effective quadrupole excitation related to the Laguerre-Gaussian (LG) excitation to the highly excited Rydberg state is obtained. This special excitation system radially confines the single highly excited Rydberg atom independently of the trapping system into a sharp potential landscape into the so-called ‘far-off-resonance optical dipole-quadrupole trap’ (FORDQT). The key parameters of the Rydberg excitation to the highly excited state, namely the effective Rabi frequency and the effective detuning including a position-dependent AC Stark shift, are calculated in terms of the basic parameters of the LG beam and of the polarization of the excitation lasers. It is shown that the obtained parameters can be tuned to have a precise excitation of a single atom to the desired Rydberg state as well. The features of transferring the optical orbital and spin angular momentum of the polarized LG beam to the atom via quadrupole Rydberg excitation offer a long-lived and controllable qudit quantum memory. In addition, in contrast to the Gaussian laser beam, the doughnut-shaped LG beam makes it possible to use a high intensity laser beam to increase the signal-to-noise ratio in quadrupole excitation with minimized perturbations coming from stray light broadening in the last Rydberg excitation process.

Ultrafast studies of the excited-state dynamics of copper and nickel phthalocyanine tetrasulfonates: potential sensitizers for the two-photon photodynamic therapy of tumors.

PubMed

Fournier, Michel; Pépin, Claude; Houde, Daniel; Ouellet, René; van Lier, Johan E

2004-01-01

In order to evaluate the potential of copper and nickel phthalocyanine tetrasulfonates as sensitizers for two-photon photodynamic therapy, we conducted kinetic femtosecond measurements of transient absorption and bleaching of their excited state dynamics in aqueous solution. Samples were pumped with 620 nm and 310 nm laser light, which allowed us to study relaxation processes from both the first and second singlet (or doublet for the copper phthalocyanine) excited states. A second excitation from the first excited triplet state, approximately 685 and 105 ps after the first excitation for copper and nickel phthalocyanine tetrasulfonate respectively, was the most efficient way to bring the molecules to an upper triplet state. Presumably this highest triplet state can inflict molecular damage on adjacent biomolecules int eh absence of oxygen, resulting in the desired cytotoxic cellular response. Transient absorption spectra at different fixed delays indicate that optimum efficiency would require that the second photon has a wavelength of approximately 750 nm.

Separating Bulk and Surface Contributions to Electronic Excited-State Processes in Hybrid Mixed Perovskite Thin Films via Multimodal All-Optical Imaging

DOE PAGES

Simpson, Mary Jane; Doughty, Benjamin; Das, Sanjib; ...

2017-07-04

A comprehensive understanding of electronic excited-state phenomena underlying the impressive performance of solution-processed hybrid halide perovskite solar cells requires access to both spatially resolved electronic processes and corresponding sample morphological characteristics. In this paper, we demonstrate an all-optical multimodal imaging approach that enables us to obtain both electronic excited-state and morphological information on a single optical microscope platform with simultaneous high temporal and spatial resolution. Specifically, images were acquired for the same region of interest in thin films of chloride containing mixed lead halide perovskites (CH 3NH 3PbI 3–xCl x) using femtosecond transient absorption, time-integrated photoluminescence, confocal reflectance, and transmissionmore » microscopies. Comprehensive image analysis revealed the presence of surface- and bulk-dominated contributions to the various images, which describe either spatially dependent electronic excited-state properties or morphological variations across the probed region of the thin films. Finally, these results show that PL probes effectively the species near or at the film surface.« less

Promoting Singlet/triplet Exciton Transformation in Organic Optoelectronic Molecules: Role of Excited State Transition Configuration.

PubMed

Chen, Runfeng; Tang, Yuting; Wan, Yifang; Chen, Ting; Zheng, Chao; Qi, Yuanyuan; Cheng, Yuanfang; Huang, Wei

2017-07-24

Exciton transformation, a non-radiative process in changing the spin multiplicity of an exciton usually between singlet and triplet forms, has received much attention recently due to its crucial effects in manipulating optoelectronic properties for various applications. However, current understanding of exciton transformation mechanism does not extend far beyond a thermal equilibrium of two states with different multiplicity and it is a significant challenge to probe what exactly control the transformation between the highly active excited states. Here, based on the recent developments of three types of purely organic molecules capable of efficient spin-flipping, we perform ab initio structure/energy optimization and similarity/overlap extent analysis to theoretically explore the critical factors in controlling the transformation process of the excited states. The results suggest that the states having close energy levels and similar exciton characteristics with same transition configurations and high heteroatom participation are prone to facilitating exciton transformation. A basic guideline towards the molecular design of purely organic materials with facile exciton transformation ability is also proposed. Our discovery highlights systematically the critical importance of vertical transition configuration of excited states in promoting the singlet/triplet exciton transformation, making a key step forward in excited state tuning of purely organic optoelectronic materials.

Measurements of population densities of metastable and resonant levels of argon using laser induced fluorescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nikolić, M.; Newton, J.; Sukenik, C. I.

2015-01-14

We present a new approach to measure population densities of Ar I metastable and resonant excited states in low temperature Ar plasmas at pressures higher than 1 Torr. This approach combines the time resolved laser induced fluorescence technique with the kinetic model of Ar. The kinetic model of Ar is based on calculating the population rates of metastable and resonant levels by including contributions from the processes that affect population densities of Ar I excited states. In particular, we included collisional quenching processes between atoms in the ground state and excited states, since we are investigating plasma at higher pressures. Wemore » also determined time resolved population densities of Ar I 2 p excited states by employing optical emission spectroscopy technique. Time resolved Ar I excited state populations are presented for the case of the post-discharge of the supersonic flowing microwave discharge at pressures of 1.7 and 2.3 Torr. The experimental set-up consists of a pulsed tunable dye laser operating in the near infrared region and a cylindrical resonance cavity operating in TE{sub 111} mode at 2.45 GHz. Results show that time resolved population densities of Ar I metastable and resonant states oscillate with twice the frequency of the discharge.« less

Theoretical study of photoacidity of HCN: the effect of complexation with water.

PubMed

Muchová, Eva; Spirko, Vladimir; Hobza, Pavel; Nachtigallová, Dana

2006-11-14

The character of the hydrogen bonding and the excited state proton transfer (ESPT) in the model system HCN...H(2)O is investigated. The PES of the two lowest excited states of the H(2)O...HCN complex was calculated using the CASPT2 method. The nonadiabatic coupling of the two states of the (pi-->pi*) and (pi-->sigma*) character is responsible for the excited state proton/hydrogen transfer. Compared to the ground state, the barrier for this process is significantly smaller. An increased number of water molecules in the complex with cyclic hydrogen-bonded network causes a large blue shift of the state of the (pi-->sigma*) character. The question of the dissociation of the complex in its excited state is also addressed.

Rotational excitation of the Hoyle state in 12C

NASA Astrophysics Data System (ADS)

Garg, R.; Barton, C.; Diget, C. Aa; Courtin, S.; Fruet, G.; Fynbo, H. O. U.; Howard, A.; Illana, A.; Jenkins, D. G.; Marroquin, I.; Kirsebom, O. S.; Lund, M. V.; Moore, I.; Perea, A.; Refsgaard, J.; Riley, J. E.; Rinta-Antila, S.; Sinclair, L.; Tengblad, O.; IGISOL Collaboration

2018-01-01

12C is synthesised in stars by fusion of three α particles. This process occurs through a resonance in the 12C nucleus, famously known as the Hoyle state. In this state, the 12C nucleus exists as a cluster of α particles. The state is the band-head for a rotational band with the 2+ rotational excitation predicted in the energy region 9 - 11 MeV. This rotational excitation can affect the triple-α process reaction rate by more than an order of magnitude at high temperatures (109 K). Depending on the energy of the resonance, the knowledge of the state can also help determine the structure of the Hoyle state. In the work presented here, the state of interest is populated by beta decay of radioactive 12N ion beam delivered by the IGISOL facility at JYFL, Jyväskylä.

Transient diffraction grating measurements of molecular diffusion in the undergraduate laboratory

NASA Astrophysics Data System (ADS)

Spiegel, Daniel R.; Tuli, Santona

2011-07-01

Diffusion is a central process in many biological, chemical, and physical systems. We describe an experiment that employs the interference of laser beams to allow the measurement of molecular diffusion on submillimeter length scales. The interference fringes of two intersecting pump beams within a dye solution create a sinusoidal distribution of long-lived molecular excited states. A third probe beam is incident at a wavelength at which the indices of refraction of the ground and excited states are different, so the probe beam diffracts from the spatially periodic excited-state pattern. After the pump beams are switched off, the excited-state periodicity washes out as the system diffuses back to equilibrium. The molecular diffusion constant is obtained from the rate constant of the exponential decay of the diffracted beam. It is also possible to measure the excited-state lifetime.

Organic Micro/Nanoscale Lasers.

PubMed

Zhang, Wei; Yao, Jiannian; Zhao, Yong Sheng

2016-09-20

Micro/nanoscale lasers that can deliver intense coherent light signals at (sub)wavelength scale have recently captured broad research interest because of their potential applications ranging from on-chip information processing to high-throughput sensing. Organic molecular materials are a promising kind of ideal platform to construct high-performance microlasers, mainly because of their superiority in abundant excited-state processes with large active cross sections for high gain emissions and flexibly assembled structures for high-quality microcavities. In recent years, ever-increasing efforts have been dedicated to developing such organic microlasers toward low threshold, multicolor output, broadband tunability, and easy integration. Therefore, it is increasingly important to summarize this research field and give deep insight into the structure-property relationships of organic microlasers to accelerate the future development. In this Account, we will review the recent advances in organic miniaturized lasers, with an emphasis on tunable laser performances based on the tailorable microcavity structures and controlled excited-state gain processes of organic materials toward integrated photonic applications. Organic π-conjugated molecules with weak intermolecular interactions readily assemble into regular nanostructures that can serve as high-quality optical microcavities for the strong confinement of photons. On the basis of rational material design, a series of optical microcavities with different structures have been controllably synthesized. These microcavity nanostructures can be endowed with effective four-level dynamic gain processes, such as excited-state intramolecular charge transfer, excited-state intramolecular proton transfer, and excimer processes, that exhibit large dipole optical transitions for strongly active gain behaviors. By tailoring these excited-state processes with molecular/crystal engineering and external stimuli, people have effectively modulated the performances of organic micro/nanolasers. Furthermore, by means of controlled assembly and tunable laser performances, efficient outcoupling of microlasers has been successfully achieved in various organic hybrid microstructures, showing considerable potential for the integrated photonic applications. This Account starts by presenting an overview of the research evolution of organic microlasers in terms of microcavity resonators and energy-level gain. Then a series of strategies to tailor the microcavity structures and excited-state dynamics of organic nanomaterials for the modulation of lasing performances are highlighted. In the following part, we introduce the construction and advanced photonic functionalities of organic-microlaser-based hybrid structures and their applications in integrated nanophotonics. Finally, we provide our outlook on the current challenges as well as the future development of organic microlasers. It is anticipated that this Account will provide inspiration for the development of miniaturized lasers with desired performances by tailoring of excited-state processes and microcavity structures toward integrated photonic applications.

Singlet-to-triplet intermediates and triplet exciton dynamics in pentacene thinfilms

NASA Astrophysics Data System (ADS)

Thorsmolle, Verner; Korber, Michael; Obergfell, Emanuel; Kuhlman, Thomas; Campbell, Ian; Crone, Brian; Taylor, Antoinette; Averitt, Richard; Demsar, Jure

Singlet-to-triplet fission in organic semiconductors is a spin-conserving multiexciton process in which one spin-zero singlet excitation is converted into two spin-one triplet excitations on an ultrafast timescale. Current scientific interest into this carrier multiplication process is largely driven by prospects of enhancing the efficiency in photovoltaic applications by generating two long-lived triplet excitons by one photon. The fission process is known to involve intermediate states, known as correlated triplet pairs, with an overall singlet character, before being interchanged into uncorrelated triplets. Here we use broadband femtosecond real-time spectroscopy to study the excited state dynamics in pentacene thin films, elucidating the fission process and the role of intermediate triplet states. VKT and AJT acknowledge support by the LDRD program at Los Alamos National Laboratory and the Department of Energy, Grant No. DE-FG02-04ER118. MK, MO and JD acknowledge support by the Alexander von Humboldt Foundation.

Direct two-photon excitation of Sm3+, Eu3+, Tb3+, Tb.DOTA-, and Tb.propargylDO3A in solution

NASA Astrophysics Data System (ADS)

Sørensen, Thomas Just; Blackburn, Octavia A.; Tropiano, Manuel; Faulkner, Stephen

2012-07-01

We have observed direct two-photon excitation of samarium, europium and terbium ions in solution upon near IR excitation using a tuneable pulsed light source, and have also studied two-photon processes in a pair of related terbium complexes, namely [Tb.DOTA]- and Tb.propargylDO3A. Direct two-photon excitation of lanthanides is observed in simple systems in the absence of sensitizing chromophores. Where even simple chromophores such as a triple bond are present in the complex, then single and two-photon excitation of chromophore excited states competes with direct two-photon excitation of the ions and is the dominant pathway for sensitizing formation of the lanthanide excited state.

Role of electronic excited N2 in vibrational excitation of the N2 ground state at high latitudes

NASA Astrophysics Data System (ADS)

Campbell, L.; Cartwright, D. C.; Brunger, M. J.; Teubner, P. J. O.

2006-09-01

Vibrationally excited N2 is important in determining the ionospheric electron density and has also been proposed to play a role in the production of NO in disturbed atmospheres. We report here predictions of the absolute vibrational distributions in the ground electronic state of N2 produced by electron impact excitation, at noon and midnight under quiet geomagnetic conditions and disturbed conditions corresponding to the aurora IBCII+ and IBCIII+ at 60°N latitude and 0° longitude, at altitudes between 130 and 350 km. These predictions were obtained from a model which includes thermal excitation and direct electron impact excitation of the vibrational levels of the N2 ground state and its excited electronic states; radiative cascade from all excited electronic states to all vibrational levels of the ground electronic state; quenching by O, O2, and N2; molecular and ambipolar diffusion; and the dominant chemical reactions. Results from this study show that for both aurora and daytime electron environments: (1) cascade from the higher electronic states of N2 determines the population of the higher vibrational levels in the N2 ground state and (2) the effective ground state vibrational temperature for levels greater than 4 in N2 is predicted to be in the range 4000-13000 K for altitudes greater than 200 km. Correspondingly, the associated enhancement factor for the O+ reaction with vibrationally excited N2 to produce NO+ is predicted to increase with increasing altitude (up to a maximum at a height which increases with auroral strength) for both aurora and daytime environments and to increase with increasing auroral strength. The contribution of the cascade from the excited electronic states was evaluated and found to be relatively minor compared to the direct excitation process.

Solvent-dependent activation of intermediate excited states in the energy relaxation pathways of spheroidene.

PubMed

Maiuri, Margherita; Polli, Dario; Brida, Daniele; Lüer, Larry; LaFountain, Amy M; Fuciman, Marcel; Cogdell, Richard J; Frank, Harry A; Cerullo, Giulio

2012-05-14

In carotenoids internal conversion between the allowed (S(2)) and forbidden (S(1)) excited states occurs on a sub-picosecond timescale; the involvement of an intermediate excited state(s) (S(x)) mediating the process is controversial. Here we use high time resolution (sub-20 fs) broadband (1.2-2.5 eV) pump-probe spectroscopy to study the solvent dependence of excited state dynamics of spheroidene, a naturally-occurring carotenoid with ten conjugated double bonds. In the high polarizability solvent, CS(2), we find no evidence of an intermediate state, and the traditional three-level (S(0), S(1), S(2)) model fully accounts for the S(2)→ S(1) process. On the other hand, in the low polarizability solvent, cyclohexane, we find that rapid (~30 fs) relaxation to an intermediate state, S(x), lying between S(1) and S(2) is required to account for the data. We interpret these results as due to a shift of the S(2) energy, which positions the state above or below the energy of S(x) in response to changes in solvent polarizability. This journal is © the Owner Societies 2012

Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.

PubMed

Ghosh, Soumen; Sonnenberger, Andrew L; Hoyer, Chad E; Truhlar, Donald G; Gagliardi, Laura

2015-08-11

The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.

The excited-state decay of 1-methyl-2(1H)-pyrimidinone is an activated process.

PubMed

Ryseck, Gerald; Schmierer, Thomas; Haiser, Karin; Schreier, Wolfgang; Zinth, Wolfgang; Gilch, Peter

2011-07-11

The photophysics of 1-methyl-2(1H)-pyrimidinone (1MP) dissolved in water is investigated by steady-state and time-resolved fluorescence, UV/Vis absorption, and IR spectroscopy. In the experiments, excitation light is tuned to the lowest-energy absorption band of 1MP peaking at 302 nm. At room temperature (291 K) its fluorescence lifetime amounts to 450 ps. With increasing temperature this lifetime decreases and equals 160 ps at 338 K. Internal conversion (IC) repopulating the ground state and intersystem crossing (ISC) to a triplet state are the dominant decay channels of the excited singlet state. At room temperature both channels contribute equally to the decay, that is, the quantum yields of IC and ISC are both approximately 0.5. The temperature dependence of UV/Vis transient absorption signals shows that the activation energy of the IC process (2140 cm(-1)) is higher than that of the ISC process (640 cm(-1)). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carotenoids as electron or excited-state energy donors in artificial photosynthesis: an ultrafast investigation of a carotenoporphyrin and a carotenofullerene dyad.

PubMed

Pillai, Smitha; Ravensbergen, Janneke; Antoniuk-Pablant, Antaeres; Sherman, Benjamin D; van Grondelle, Rienk; Frese, Raoul N; Moore, Thomas A; Gust, Devens; Moore, Ana L; Kennis, John T M

2013-04-07

Photophysical investigations of molecular donor-acceptor systems have helped elucidate many details of natural photosynthesis and revealed design principles for artificial photosynthetic systems. To obtain insights into the factors that govern the partition between excited-state energy transfer (EET) and electron transfer (ET) processes among carotenoids and tetrapyrroles and fullerenes, we have designed artificial photosynthetic dyads that are thermodynamically poised to favor ET over EET processes. The dyads were studied using transient absorption spectroscopy with ∼100 femtosecond time resolution. For dyad , a carotenoporphyrin, excitation to the carotenoid S2 state induces ultrafast ET, competing with internal conversion (IC) to the carotenoid S1 state. In addition, the carotenoid S1 state gives rise to ET. In contrast with biological photosynthesis and many artificial photosynthetic systems, no EET at all was detected for this dyad upon carotenoid S2 excitation. Recombination of the charge separated state takes place in hundreds of picoseconds and yields a triplet state, which is interpreted as a triplet delocalized between the porphyrin and carotenoid moieties. In dyad , a carotenofullerene, excitation of the carotenoid in the S2 band results in internal conversion to the S1 state, ET and probably EET to fullerene on ultrafast timescales. From the carotenoid S1 state EET to fullerene occurs. Subsequently, the excited-state fullerene gives rise to ET from the carotenoid to the fullerene. Again, the charge separated state recombines in hundreds of picoseconds. The results illustrate that for a given rate of EET, the ratio of ET to EET can be controlled by adjusting the driving force for electron transfer.

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

NASA Astrophysics Data System (ADS)

Portnov, Alexander; Epshtein, Michael; Bar, Ilana

2017-06-01

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

Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study

DOE PAGES

Bricker, William P.; Shenai, Prathamesh M.; Ghosh, Avishek; ...

2015-09-08

Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. With modeling this process, non-adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are ablemore » to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function.« less

K-shell excitation studied for H- and He-like bismuth ions in collisions with low-Z target atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoehlker, T.; Ionescu, D.C.; Rymuza, P.

1998-02-01

The formation of excited projectile states via Coulomb excitation is investigated for hydrogenlike and heliumlike bismuth projectiles (Z=83) in relativistic ion-atom collisions. The excitation process was unambiguously identified by observing the radiative decay of the excited levels to the vacant 1s shell in coincidence with ions that did not undergo charge exchange in the reaction target. In particular, owing to the large fine-structure splitting of Bi, the excitation cross sections to the various L-shell sublevels are determined separately. The results are compared with detailed relativistic calculations, showing that both the relativistic character of the bound-state wave functions and the magneticmore » interaction are of considerable importance for the K-shell excitation process in high-Z ions such as Bi. The experimental data confirm the result of the complete relativistic calculations, namely, that the magnetic part of the Li{acute e}nard-Wiechert interaction leads to a significant reduction of the K-shell excitation cross section. {copyright} {ital 1998} {ital The American Physical Society}« less

Fluorescence excitation and excited state intramolecular relaxation dynamics of jet-cooled methyl-2-hydroxy-3-naphthoate

NASA Astrophysics Data System (ADS)

McCarthy, Annemarie; Ruth, Albert A.

2013-11-01

Two distinct S0 → S1 fluorescence excitation spectra of methyl-2-hydroxy-3-napthoate (MHN23) have been obtained by monitoring fluorescence separately in the short (˜410 nm) and long (˜650 nm) wavelength emission bands. The short wavelength fluorescence is assigned to two MHN23 conformers which do not undergo excited state intramolecular proton transfer (ESIPT). Analysis of the 'long wavelength' fluorescence excitation spectrum, which arises from the proton transfer tautomer of MHN23 indicates an average lifetime of τ ⩾ 18 ± 2 fs for the initially excited states. Invoking the results of Catalan et al. [J. Phys. Chem. A, 1999, 103, 10921], who determined the N tautomer to decay predominantly via a fast non-radiative process, the limit of the rate of intramolecular excited proton transfer in MHN23 is calculated as, kpt ⩽ 1 × 1012 s-1.

Non-resonant excitation of rare-earth ions via virtual Auger process

NASA Astrophysics Data System (ADS)

Yassievich, I. N.

2011-05-01

The luminescence of rare-earth ions (REI) is often intensified by defects associated with REIs or excitons bound to these defects. In this paper we show that the presence of such a state opens the possibility of non-resonance optical pumping via the process involving virtual Auger transition. It is the second order perturbation process when an electron arrives in an virtual intermediate state due to the optical transition (the first step) and the Auger transition is the second one. We have calculated the cross-section of such an excitation process when the optical transition is accompanied by creation of the exciton bound to the defect associated with REI and obtained a simple analytical expression for the cross-section. The excess energy of the excitation quanta is taken away by multiphonon emission. The electron-phonon interaction with local phonon vibrations of the bound exciton is assumed to determine the multiphonon process. It is shown that the probability of the process under study exceeds considerably the probability of direct optical 4f-4f absorption even in the case when the energy distance between the excitation quantum energy and the exciton energy is about 0.1 of the exciton energy. The excitation mechanism considered leads to the appearance of a broad unsymmetrical band in the excitation spectrum with the red side much wider and flatter than the blue one.

Relaxation times measurement in single and multiply excited xenon clusters

NASA Astrophysics Data System (ADS)

Serdobintsev, P. Yu.; Melnikov, A. S.; Pastor, A. A.; Timofeev, N. A.; Khodorkovskiy, M. A.

2018-05-01

Direct measurement of the rates of nonradiative relaxation processes in electronically excited xenon clusters was carried out. The clusters were created in a pulsed supersonic beam and two-photon excited by femtosecond laser pulses with a wavelength of 263 nm. The measurements were performed using the pump-probe method and electron spectroscopy. It is shown that relaxation of light clusters XeN (N < 15) predominantly occurs by desorption of excited xenon atoms with a characteristic time constant of 3 ps. Heavier electronically excited clusters (N > 10) vibrationally relax to the lowest electronically excited state at a rate of about 0.075 eV/ps. Multiply excited clusters are deactivated via energy exchange between excited centers with the ionization of one of them. The production of electrons in this process occurs with a delay of ˜4 ps from the pump pulse, and the process is completed in 10 ps.

Gradual collapse of nuclear wave functions regulated by frequency tuned X-ray scattering.

PubMed

Ignatova, Nina; Cruz, Vinícius V; Couto, Rafael C; Ertan, Emelie; Zimin, Andrey; Guimarães, Freddy F; Polyutov, Sergey; Ågren, Hans; Kimberg, Victor; Odelius, Michael; Gel'mukhanov, Faris

2017-03-07

As is well established, the symmetry breaking by isotope substitution in the water molecule results in localisation of the vibrations along one of the two bonds in the ground state. In this study we find that this localisation may be broken in excited electronic states. Contrary to the ground state, the stretching vibrations of HDO are delocalised in the bound core-excited state in spite of the mass difference between hydrogen and deuterium. The reason for this effect can be traced to the narrow "canyon-like" shape of the potential of the state along the symmetric stretching mode, which dominates over the localisation mass-difference effect. In contrast, the localisation of nuclear motion to one of the HDO bonds is preserved in the dissociative core-excited state . The dynamics of the delocalisation of nuclear motion in these core-excited states is studied using resonant inelastic X-ray scattering of the vibrationally excited HDO molecule. The results shed light on the process of a wave function collapse. After core-excitation into the state of HDO the initial wave packet collapses gradually, rather than instantaneously, to a single vibrational eigenstate.

Relaxed structure of typical nitro explosives in the excited state: Observation, implication and application

NASA Astrophysics Data System (ADS)

Chu, Genbai; Yang, Zuhua; Xi, Tao; Xin, Jianting; Zhao, Yongqiang; He, Weihua; Shui, Min; Gu, Yuqiu; Xiong, Ying; Xu, Tao

2018-04-01

Understanding the structural, geometrical, and chemical changes that occur after an electronic excitation is essential to elucidate the inherent mechanism of nitro explosives. Herein, relaxed structures of typical nitro explosives in the lowest singlet excited state are investigated using time-dependent density functional theory. During the excitation process, the nitro group is activated and relaxes via geometrical change. The five explosives RDX, HMX, CL-20, PETN, and LLM-105 exhibit similar relaxed structures, and the impact sensitivity is related to their excitation energy. High-sensitivity δ-HMX has a lower excitation energy for relaxed structure than β-HMX. This study offers novel insight into energetic materials.

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

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

Models of charge pair generation in organic solar cells.

PubMed

Few, Sheridan; Frost, Jarvist M; Nelson, Jenny

2015-01-28

Efficient charge pair generation is observed in many organic photovoltaic (OPV) heterojunctions, despite nominal electron-hole binding energies which greatly exceed the average thermal energy. Empirically, the efficiency of this process appears to be related to the choice of donor and acceptor materials, the resulting sequence of excited state energy levels and the structure of the interface. In order to establish a suitable physical model for the process, a range of different theoretical studies have addressed the nature and energies of the interfacial states, the energetic profile close to the heterojunction and the dynamics of excited state transitions. In this paper, we review recent developments underpinning the theory of charge pair generation and phenomena, focussing on electronic structure calculations, electrostatic models and approaches to excited state dynamics. We discuss the remaining challenges in achieving a predictive approach to charge generation efficiency.

Monte Carlo wave-packet approach to trace nuclear dynamics in molecular excited states by XUV-pump-IR-probe spectroscopy

NASA Astrophysics Data System (ADS)

Jing, Qingli; Bello, Roger Y.; Martín, Fernando; Palacios, Alicia; Madsen, Lars Bojer

2018-04-01

Recent research interests have been raised in uncovering and controlling ultrafast dynamics in excited neutral molecules. In this work we generalize the Monte Carlo wave packet (MCWP) approach to XUV-pump-IR-probe schemes to simulate the process of dissociative double ionization of H2 where singly excited states in H2 are involved. The XUV pulse is chosen to resonantly excite the initial ground state of H2 to the lowest excited electronic state of 1Σu + symmetry in H2 within the Franck-Condon region. The delayed intense IR pulse couples the excited states of 1Σu + symmetry with the nearby excited states of 1Σg + symmetry. It also induces the first ionization from H2 to H2 + and the second ionization from H2 + to H++H+. To reduce the computational costs in the MCWP approach, a sampling method is proposed to determine in time the dominant ionization events from H2 to H2+. By conducting a trajectory analysis, which is a unique possibility within the MCWP approach, the origins of the characteristic features in the nuclear kinetic energy release spectra are identified for delays ranging from 0 to 140 fs and the nuclear dynamics in the singly excited states in H2 is mapped out.

Dynamic study of excited state hydrogen-bonded complexes of harmane in cyclohexane-toluene mixtures.

PubMed

Carmona, Carmen; Balón, Manuel; Galán, Manuel; Guardado, Pilar; Muñoz, María A

2002-09-01

Photoinduced proton transfer reactions of harmane or 1-methyl-9H-pyrido[3,4-b]indole (HN) in the presence of the proton donor hexafluoroisopropanol (HFIP) in cyclohexane-toluene mixtures (CY-TL; 10% vol/vol of TL) have been studied. Three excited state species have been identified: a 1:2 hydrogen-bonded proton transfer complex (PTC), between the pyridinic nitrogen of the substrate and the proton donor, a hydrogen-bonded cation-like exciplex (CL*) with a stoichiometry of at least 1:3 and a zwitterionic exciplex (Z*). Time-resolved fluorescence measurements evidence that upon excitation of ground state PTC, an excited state equilibrium is established between PTC* and the cationlike exciplex, CL*, lambdaem approximately/= 390 nm. This excited state reaction is assisted by another proton donor molecule. Further reaction of CL* with an additional HFIP molecule produces the zwitterionic species, Z*, lambda(em) approximately/= 500 nm. From the analysis of the multiexponential decays, measured at different emission wavelengths and as a function of HFIP concentration, the mechanism of these excited state reactions has been established. Thus, three rate constants and three reciprocal lifetimes have been determined. The simultaneous study of 1,9-dimethyl-9H-pyrido[3,4-b]indole (MHN) under the same experimental conditions has helped to understand the excited state kinetics of these processes.

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

PubMed

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

2002-03-20

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

Excited-State Complexes of Conjugated Polymers: Novel Photophysical Processes and Optoelectronic Materials.

DTIC Science & Technology

1995-03-20

corresponding excited-state complexes were only recently discovered. The results of our extensive studies of intermolecular excimers and exciplexes of many...the luminescence of conjugated polymers. The luminescence and charge photogeneration in exciplexes of conjugated polymers with donor triarylamines will also be presented. jg

Disposal of Energy by UV-B Sunscreens

NASA Astrophysics Data System (ADS)

Nordlund, Thomas; Krishnan, Rajagopal

2008-03-01

Ideal sunscreens absorb dangerous UV light and dispose of the energy safely. ``Safe disposal'' usually means conversion to heat. However, efficient absorption entails a high radiative rate, which implies high energy-transfer and other rates, unless some process intervenes to ``defuse'' the excited state. We studied the excited-state kinetics of three UV-B (290-320 nm) sunscreens by absorption, steady-state and time-resolved fluorescence. Excited-state rate analysis suggests that some sunscreens have low radiative-rate ``dark'' states, in addition to normal excited states.* We deduce dark states when sunscreens of high extinction coefficient do not show lifetimes and total emission consistent with such high radiative rates. A high radiative rate, accompanied by efficient fluorescence emission and/or transfer, may be unfavorable for a sunscreen. In spite of its dark excited state, padimate O shows significant re-emission of light in the UV-A (320-400 nm) and energy transfer to a natural component of excised skin, probably collagen. * Krishnan, R. and T.M. Nordlund (2007) J. Fluoresc. DOI 10.1007/s10895-007-0264-3.

Sensitivity tests on the rates of the excited states of positron decays during the rapid proton capture process of the one-zone X-ray burst model

NASA Astrophysics Data System (ADS)

Lau, Rita

2018-02-01

In this paper, we investigate the sensitivities of positron decays on a one-zone model of type-I X-ray bursts. Most existing studies have multiplied or divided entire beta decay rates (electron captures and beta decay rates) by 10. Instead of using the standard Fuller & Fowler (FFNU) rates, we used the most recently developed weak library rates [1], which include rates from Langanke et al.'s table (the LMP table) (2000) [2], Langanke et al.'s table (the LMSH table) (2003) [3], and Oda et al.'s table (1994) [4] (all shell model rates). We then compared these table rates with the old FFNU rates [5] to study differences within the final abundances. Both positron decays and electron capture rates were included in the tables. We also used pn-QRPA rates [6,7] to study the differences within the final abundances. Many of the positron rates from the nuclei's ground states and initial excited energy states along the rapid proton capture (rp) process have been measured in existing studies. However, because temperature affects the rates of excited states, these studies should have also acknowledged the half-lives of the nuclei's excited states. Thus, instead of multiplying or dividing entire rates by 10, we studied how the half-lives of sensitive nuclei in excited states affected the abundances by dividing the half-lives of the ground states by 10, which allowed us to set the half-lives of the excited states. Interestingly, we found that the peak of the final abundance shifted when we modified the rates from the excited states of the 105Sn positron decay rates. Furthermore, the abundance of 80Zr also changed due to usage of pn-QRPA rates instead of weak library rates (the shell model rates).

Selective ultrafast probing of transient hot chemisorbed and precursor states of CO on Ru(0001).

PubMed

Beye, M; Anniyev, T; Coffee, R; Dell'Angela, M; Föhlisch, A; Gladh, J; Katayama, T; Kaya, S; Krupin, O; Møgelhøj, A; Nilsson, A; Nordlund, D; Nørskov, J K; Öberg, H; Ogasawara, H; Pettersson, L G M; Schlotter, W F; Sellberg, J A; Sorgenfrei, F; Turner, J J; Wolf, M; Wurth, W; Oström, H

2013-05-03

We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process.

Precise Design of Phosphorescent Molecular Butterflies with Tunable Photoinduced Structural Change and Dual Emission.

PubMed

Zhou, Chenkun; Tian, Yu; Yuan, Zhao; Han, Mingu; Wang, Jamie; Zhu, Lei; Tameh, Maliheh Shaban; Huang, Chen; Ma, Biwu

2015-08-10

Photoinduced structural change (PSC) is a fundamental excited-state dynamic process in chemical and biological systems. However, precise control of PSC processes is very challenging, owing to the lack of guidelines for designing excited-state potential energy surfaces (PESs). A series of rationally designed butterfly-like phosphorescent binuclear platinum complexes that undergo controlled PSC by Pt-Pt distance shortening and exhibit tunable dual (greenish-blue and red) emission are herein reported. Based on the Bell-Evans-Polanyi principle, it is demonstrated how the energy barrier of the PSC, which can be described as a chemical-reaction-like process between the two energy minima on the first triplet excited-state PES, can be controlled by synthetic means. These results reveal a simple method to engineer the dual emission of molecular systems by manipulating PES to control PSC. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT) of calix[4]arene: A TDDFT study

NASA Astrophysics Data System (ADS)

Wang, Se; Wang, Zhuang; Hao, Ce

2016-01-01

The time-dependent density functional theory (TDDFT) method was performed to investigate the excited-state intramolecular double proton transfer (ESIDPT) reaction of calix[4] arene (C4A) and the role of the intramolecular hydrogen bonds in the ESIDPT process. The geometries of C4A in the ground state and excited states (S1, S2 and T1) were optimized. Four intramolecular hydrogen bonds formed in the C4A are strengthened or weakened in the S2 and T1 states compared to those in the ground state. Interestingly, upon excitation to the S1 state of C4A, two protons H1 and H2 transfer along the two intramolecular hydrogen bonds O1-H1···O2 and O2-H2···O3, while the other two protons do not transfer. The ESIDPT reaction breaks the primary symmetry of C4A in the ground state. The potential energy curves of proton transfer demonstrate that the ESIDPT process follows the stepwise mechanism but not the concerted mechanism. Findings indicate that intramolecular hydrogen bonding is critical to the ESIDPT reactions in intramolecular hydrogen-bonded systems.

State-specific enhancement of Cl+ and Cl- desorption for SiCl4 adsorbed on a Si(100) surface following Cl 2 p and Si 2 p core-level excitations.

PubMed

Chen, J M; Lu, K T

2001-04-02

State-specific desorption for SiCl4 adsorbed on a Si(100) surface at approximately 90 K with variable coverage following the Cl 2p and Si 2p core-level excitations has been investigated using synchrotron radiation. The Cl+ yields show a significant enhancement following the Cl 2p-->8a*1 excitation. The Cl- yields are notably enhanced at the 8a*1 resonance at both Cl 2p and Si 2p edges. The enhancement of the Cl- yield occurs through the formation of highly excited states of the adsorbed molecules. These results provide some new dissociation processes from adsorbates on surfaces via core-level excitation.

Nonclassical features of trimodal excited coherent Greenberger - Horne - Zeilinger(GHZ) - type state

NASA Astrophysics Data System (ADS)

Merlin, J.; Ahmed, A. B. M.; Mohammed, S. Naina

2017-06-01

We examine the influence of photon excitation on each mode of the Glauber coherent GHZ type tripartite state. Concurrence is adopted as entanglement measure between bipartite entangled state. The pairwise concurrence is calculated and used as a quantifier of intermodal entanglement. The entanglement distribution among three modes is investigated using tangle as a measure and the residual entanglement is also calculated. The effect of the photon addition process on the quadrature squeezing is investigated. The higher order squeezing capacity of the photon addition process is also shown.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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. Suchmore » 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.« less

Electronic-structure and quantum dynamical study of the photochromism of the aromatic Schiff base salicylideneaniline

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ortiz-Sanchez, Juan Manuel; Gelabert, Ricard; Moreno, Miquel

2008-12-07

The ultrafast proton transfer dynamics of salicylideneaniline has been theoretically analyzed in the ground and first singlet excited electronic states using density functional theory (DFT) and time-dependent DFT calculations, which predict a ({pi},{pi}*) barrierless excited state intramolecular proton transfer (ESIPT). In addition to this, the photochemistry of salicylideneaniline is experimentally known to present fast depopulation processes of the photoexcited species before and after the proton transfer reaction. Such processes are explained by means of conical intersections between the ground and first singlet ({pi},{pi}*) excited electronic states. The electronic energies obtained by the time-dependent density functional theory formalism have been fittedmore » to a monodimensional potential energy surface in order to perform quantum dynamics study of the processes. Our results show that the proton transfer and deactivation of the photoexcited species before the ESIPT processes are completed within 49.6 and 37.7 fs, respectively, which is in remarkable good agreement with experiments.« less

Low-energy d-d excitations in MnO studied by resonant x-ray fluorescence spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Butorin, S.M.; Guo, J.; Magnuson, M.

1997-04-01

Resonant soft X-ray emission spectroscopy has been demonstrated to possess interesting abilities for studies of electronic structure in various systems, such as symmetry probing, alignment and polarization dependence, sensitivity to channel interference, etc. In the present abstract the authors focus on the feasibility of resonant soft X-ray emission to probe low energy excitations by means of resonant electronic X-ray Raman scattering. Resonant X-ray emission can be regarded as an inelastic scattering process where a system in the ground state is transferred to a low excited state via a virtual core excitation. The energy closeness to a core excitation of themore » exciting radiation enhances the (generally) low probability for inelastic scattering at these wavelengths. Therefore soft X-ray emission spectroscopy (in resonant electronic Raman mode) can be used to study low energy d-d excitations in transition metal systems. The involvement of the intermediate core state allows one to use the selection rules of X-ray emission, and the appearance of the elastically scattered line in the spectra provides the reference to the ground state.« less

Nonadiabatic excited-state molecular dynamics: modeling photophysics in organic conjugated materials.

PubMed

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

2014-04-15

To design functional photoactive materials for a variety of technological applications, researchers need to understand their electronic properties in detail and have ways to control their photoinduced pathways. When excited by photons of light, organic conjugated materials (OCMs) show dynamics that are often characterized by large nonadiabatic (NA) couplings between multiple excited states through a breakdown of the Born-Oppenheimer (BO) approximation. Following photoexcitation, various nonradiative intraband relaxation pathways can lead to a number of complex processes. Therefore, computational simulation of nonadiabatic molecular dynamics is an indispensable tool for understanding complex photoinduced processes such as internal conversion, energy transfer, charge separation, and spatial localization of excitons. Over the years, we have developed a nonadiabatic excited-state molecular dynamics (NA-ESMD) framework that efficiently and accurately describes photoinduced phenomena in extended conjugated molecular systems. We use the fewest-switches surface hopping (FSSH) algorithm to treat quantum transitions among multiple adiabatic excited state potential energy surfaces (PESs). Extended molecular systems often contain hundreds of atoms and involve large densities of excited states that participate in the photoinduced dynamics. We can achieve an accurate description of the multiple excited states using the configuration interaction single (CIS) formalism with a semiempirical model Hamiltonian. Analytical techniques allow the trajectory to be propagated "on the fly" using the complete set of NA coupling terms and remove computational bottlenecks in the evaluation of excited-state gradients and NA couplings. Furthermore, the use of state-specific gradients for propagation of nuclei on the native excited-state PES eliminates the need for simplifications such as the classical path approximation (CPA), which only uses ground-state gradients. Thus, the NA-ESMD methodology offers a computationally tractable route for simulating hundreds of atoms on ~10 ps time scales where multiple coupled excited states are involved. In this Account, we review recent developments in the NA-ESMD modeling of photoinduced dynamics in extended conjugated molecules involving multiple coupled electronic states. We have successfully applied the outlined NA-ESMD framework to study ultrafast conformational planarization in polyfluorenes where the rate of torsional relaxation can be controlled based on the initial excitation. With the addition of the state reassignment algorithm to identify instances of unavoided crossings between noninteracting PESs, NA-ESMD can now be used to study systems in which these so-called trivial unavoided crossings are expected to predominate. We employ this technique to analyze the energy transfer between poly(phenylene vinylene) (PPV) segments where conformational fluctuations give rise to numerous instances of unavoided crossings leading to multiple pathways and complex energy transfer dynamics that cannot be described using a simple Förster model. In addition, we have investigated the mechanism of ultrafast unidirectional energy transfer in dendrimers composed of poly(phenylene ethynylene) (PPE) chromophores and have demonstrated that differential nuclear motion favors downhill energy transfer in dendrimers. The use of native excited-state gradients allows us to observe this feature.

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

DOE PAGES

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

2017-03-17

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Optical signature of Mg-doped GaN: Transfer processes

NASA Astrophysics Data System (ADS)

Callsen, G.; Wagner, M. R.; Kure, T.; Reparaz, J. S.; Bügler, M.; Brunnmeier, J.; Nenstiel, C.; Hoffmann, A.; Hoffmann, M.; Tweedie, J.; Bryan, Z.; Aygun, S.; Kirste, R.; Collazo, R.; Sitar, Z.

2012-08-01

Mg doping of high quality, metal organic chemical vapor deposition grown GaN films results in distinct traces in their photoluminescence and photoluminescence excitation spectra. We analyze GaN:Mg grown on sapphire substrates and identify two Mg related acceptor states, one additional acceptor state and three donor states that are involved in the donor-acceptor pair band transitions situated at 3.26-3.29 eV in GaN:Mg. The presented determination of the donor-acceptor pair band excitation channels by photoluminescence excitation spectroscopy in conjunction with temperature-dependent photoluminescence measurements results in a direct determination of the donor and acceptor binding, localization, and activation energies, which is put into a broader context based on Haynes's rule. Furthermore, we analyze the biexponential decay dynamics of the photoluminescence signal of the acceptor and donor bound excitons. As all observed lifetimes scale with the localization energy of the donor and acceptor related bound excitons, defect and complex bound excitons can be excluded as their origin. Detailed analysis of the exciton transfer processes in the close energetic vicinity of the GaN band edge reveals excitation via free and bound excitonic channels but also via an excited state as resolved for the deepest localized Mg related acceptor bound exciton. For the two Mg acceptor states, we determine binding energies of 164 ± 5 and 195 ± 5 meV, which is in good agreement with recent density functional theory results. This observation confirms and quantifies the general dual nature of acceptor states in GaN based on the presented analysis of the photoluminescence and photoluminescence excitation spectra.

Investigation of excited-state relaxation processes of organic dyes by time-resolved spectroscopy

NASA Astrophysics Data System (ADS)

Przhonska, O.; Slominsky, Yu.; Kachkovsky, A.; Stahl, U.; Senoner, M.; Dähne, S.

1996-04-01

The results of the measurements of the fluorescence decay kinetics of the new series of polymethine dyes in liquid and solid polymeric media are reported. The effects of polymeric media on absorption-relaxation-emission processes are studied at wide excitation, emission and temperature regions.

Direct Visualization of Exciton Reequilibration in the LH1 and LH2 Complexes of Rhodobacter sphaeroides by Multipulse Spectroscopy

PubMed Central

Cohen Stuart, Thomas A.; Vengris, Mikas; Novoderezhkin, Vladimir I.; Cogdell, Richard J.; Hunter, C. Neil; van Grondelle, Rienk

2011-01-01

The dynamics of the excited states of the light-harvesting complexes LH1 and LH2 of Rhodobacter sphaeroides are governed, mainly, by the excitonic nature of these ring-systems. In a pump-dump-probe experiment, the first pulse promotes LH1 or LH2 to its excited state and the second pulse dumps a portion of the excited state. By selective dumping, we can disentangle the dynamics normally hidden in the excited-state manifold. We find that by using this multiple-excitation technique we can visualize a 400-fs reequilibration reflecting relaxation between the two lowest exciton states that cannot be directly explored by conventional pump-probe. An oscillatory feature is observed within the exciton reequilibration, which is attributed to a coherent motion of a vibrational wavepacket with a period of ∼150 fs. Our disordered exciton model allows a quantitative interpretation of the observed reequilibration processes occurring in these antennas. PMID:21539791

Direct visualization of exciton reequilibration in the LH1 and LH2 complexes of Rhodobacter sphaeroides by multipulse spectroscopy.

PubMed

Cohen Stuart, Thomas A; Vengris, Mikas; Novoderezhkin, Vladimir I; Cogdell, Richard J; Hunter, C Neil; van Grondelle, Rienk

2011-05-04

The dynamics of the excited states of the light-harvesting complexes LH1 and LH2 of Rhodobacter sphaeroides are governed, mainly, by the excitonic nature of these ring-systems. In a pump-dump-probe experiment, the first pulse promotes LH1 or LH2 to its excited state and the second pulse dumps a portion of the excited state. By selective dumping, we can disentangle the dynamics normally hidden in the excited-state manifold. We find that by using this multiple-excitation technique we can visualize a 400-fs reequilibration reflecting relaxation between the two lowest exciton states that cannot be directly explored by conventional pump-probe. An oscillatory feature is observed within the exciton reequilibration, which is attributed to a coherent motion of a vibrational wavepacket with a period of ∼150 fs. Our disordered exciton model allows a quantitative interpretation of the observed reequilibration processes occurring in these antennas. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Excited-state decay processes of binuclear rhodium(I) isocyanide complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miskowski, V.M.; Rice, S.F.; Gray, H.B.

1993-04-29

Emission lifetimes, quantum yields, and polarized excitation spectra of Rh[sub 2]b[sub 4][sup 2+] and Rh[sub 2](TMB)[sub 4][sup 2+] (b = 1,3-diisocyanopropane; TMB = 2,5-diisocyano-2,5-dimethylhexane) have been determined. The singlet and triplet d[sigma]* [yields] p[sigma]([sup 1,3]A[sub 2u]) excited states are luminescent with radiative rates of ca. 10[sup 8] and 10[sup 4] s[sup [minus

QM/MM studies on the excited-state relaxation mechanism of a semisynthetic dTPT3 base.

PubMed

Guo, Wei-Wei; Zhang, Teng-Shuo; Fang, Wei-Hai; Cui, Ganglong

2018-02-14

Semisynthetic alphabets can potentially increase the genetic information stored in DNA through the formation of unusual base pairs. Recent experiments have shown that near-visible-light irradiation of the dTPT3 chromophore could lead to the formation of a reactive triplet state and of singlet oxygen in high quantum yields. However, the detailed excited-state relaxation paths that populate the lowest triplet state are unclear. Herein, we have for the first time employed the QM(MS-CASPT2//CASSCF)/MM method to explore the spectroscopic properties and excited-state relaxation mechanism of the aqueous dTPT3 chromophore. On the basis of the results, we have found that (1) the S 2 ( 1 ππ*) state of dTPT3 is the initially populated excited singlet state upon near-visible light irradiation; and (2) there are two efficient relaxation pathways to populate the lowest triplet state, i.e. T 1 ( 3 ππ*). In the first one, the S 2 ( 1 ππ*) system first decays to the S 1 ( 1 nπ*) state near the S 2 /S 1 conical intersection, which is followed by an efficient S 1 → T 1 intersystem crossing process at the S 1 /T 1 crossing point; in the second one, an efficient S 2 → T 2 intersystem crossing takes place first, and then, the T 2 ( 3 nπ*) system hops to the T 1 ( 3 ππ*) state through an internal conversion process at the T 2 /T 1 conical intersection. Moreover, an S 2 /S 1 /T 2 intersection region is found to play a vital role in the excited-state relaxation. These new mechanistic insights help in understanding the photophysics and photochemistry of unusual base pairs.

Photoinduced electron transfer at the tetrapyrrole-TiO2 interface: Effect of the energy alignment

NASA Astrophysics Data System (ADS)

Nieto-Pescador, Jesus S.

Photoinduced electron transfer is a ubiquitous process behind several physical, chemical, and biological processes. Its potential applications, ranging from solar cell technologies to photodynamic cancer therapy, require a thorough understanding of the basics of the reaction. This dissertation addresses open questions for a particular case of electron transfer processes: Heterogeneous Electron Transfer (HET). In this process, an electron is transferred between a localized donor and a multitude of delocalized acceptor states. HET between photoexcited tetrapyrroles and colloidal TiO2 has been investigated using femtosecond transient absorption spectroscopy. Specifically, this work explores the not well-understood influence of the availability of states on the HET reaction. This problem is addressed by measuring electron injection times as a function of the energy difference between the LUMO and the conduction band of TiO2. The change in the energy alignment was done using two experimental strategies. The first one employs a recently synthesized phlorin with two different excited states above the conduction band of TiO2. This molecule allows comparing HET rates from two different excited states. The second strategy measures the electron injection rates after exciting the same electronic state of a set of specially designed porphyrins. The novelty of the approach is that the difference in energy alignment is attained by the introduction of dipole groups within the bridge group of the molecule. This strategy generates a difference in energy alignment of up to 200 meV. The reported measurements were carried in a high vacuum environment with an apparatus capable of resolving sub 30 fs processes. Disentanglement of the electron transfer processes was done, after careful study of the relaxation dynamics of the molecules in solution, by monitoring the decay of the excited state absorption and the rise of the cation spectral signatures. Within our time resolution, our results show that the increase in the availability of acceptor states does not influence the electron injection dynamics. The results suggest that the injection process takes place into a spectrum of states different from those obtained by steady state calculations.

Mobile bound states of Rydberg excitations in a lattice

NASA Astrophysics Data System (ADS)

Letscher, Fabian; Petrosyan, David

2018-04-01

Spin-lattice models play a central role in the studies of quantum magnetism and nonequilibrium dynamics of spin excitations—-magnons. We show that a spin lattice with strong nearest-neighbor interactions and tunable long-range hopping of excitations can be realized by a regular array of laser-driven atoms, with an excited Rydberg state representing the spin-up state and a Rydberg-dressed ground state corresponding to the spin-down state. We find exotic interaction-bound states of magnons that propagate in the lattice via the combination of resonant two-site hopping and nonresonant second-order hopping processes. Arrays of trapped Rydberg-dressed atoms can thus serve as a flexible platform to simulate and study fundamental few-body dynamics in spin lattices.

Photophysical and photochemical insights into the photodegradation of sulfapyridine in water: A joint experimental and theoretical study.

PubMed

Zhang, Heming; Wei, Xiaoxuan; Song, Xuedan; Shah, Shaheen; Chen, Jingwen; Liu, Jianhui; Hao, Ce; Chen, Zhongfang

2018-01-01

For organic pollutants, photodegradation, as a major abiotic elimination process and of great importance to the environmental fate and risk, involves rather complicated physical and chemical processes of excited molecules. Herein, we systematically studied the photophysical and photochemical processes of a widely used antibiotic, namely sulfapyridine. By means of density functional theory (DFT) computations, we examined the rate constants and the competition of both photophysical and photochemical processes, elucidated the photochemical reaction mechanism, calculated reaction quantum yield (Φ) based on both photophysical and photochemical processes, and subsequently estimated the photodegradation rate constant. We further conducted photolysis experiments to measure the photodegradation rate constant of sulfapyridine. Our computations showed that sulfapyridine at the lowest excited singlet state (S 1 ) mainly undergoes internal conversion to its ground state, and is difficult to transfer to the lowest excited triplet states (T 1 ) via intersystem crossing (ISC) and emit fluorescence. In T 1 state, compared with phosphorescence emission and ISC, chemical reaction is much easier to initiate. Encouragingly, the theoretically predicted photodegradation rate constant is close to the experimentally observed value, indicating that quantum chemistry computation is powerful enough to study photodegradation involving ultra-fast photophysical and photochemical processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Photochemical transformations of diazocarbonyl compounds: expected and novel reactions

NASA Astrophysics Data System (ADS)

Galkina, O. S.; Rodina, L. L.

2016-05-01

Photochemical reactions of diazocarbonyl compounds are well positioned in synthetic practice as an efficient method for ring contraction and homologation of carboxylic acids and as a carbene generation method. However, interpretation of the observed transformations of diazo compounds in electronically excited states is incomplete and requires a careful study of the fine mechanisms of these processes specific to different excited states of diazo compounds resorting to modern methods of investigation, including laser technology. The review is devoted to analysis of new data in the chemistry of excited states of diazocarbonyl compounds. The bibliography includes 155 references.

Influence of Wall Material on VUV Emission from Hydrogen Plasma in H- Source

NASA Astrophysics Data System (ADS)

Bacal, M.; Glass-Maujean, M.; Ivanov, A. A., Jr; Nishiura, M.; Sasao, M.; Wada, M.

2002-11-01

The study of VUV emission from a hydrogen plasma produced in a filament discharge in a magnetic multicusp device showed that the use of tantalum and tungsten filaments leads to significant differences in the spectra. The effect of the filament material is interpreted in terms of the fresh film of this material, deposited on the wall. The synthetic spectrum convoluted with our apparatus function for the conditions of this experiment (gas temperature 500 K, electron energy 100 eV) agrees roughly well with the spectrum obtained with tungsten covered walls, but not with the spectrum obtained with tantalum covered walls. We show that in the case of tungsten covered walls the E-V singlet excitation is indeed a two-step Franck-Condon transition, going through either B or C state from an initial H2 molecule with v"=0, added to a Franck-Condon transition to highly excited states cascading to the B or C states. The excitation process to high v" states in the case of tantalum covered walls is a three step process, in which the first step is the formation by recombinative desorption on the wall of a vibrationally excited molecule with v"=1 or 2, which serves as the initial molecule in the subsequent E-V excitation through the B state. The results indicate a larger recombination coefficient of atoms on the tantalum covered wall.

Investigation of the 6 p 2(3 P 0) n p Rydberg series of bismuth by multiphoton excitation

NASA Astrophysics Data System (ADS)

Bühler, B.; Cremer, C.; Gerber, G.

1985-03-01

Rydberg states of the odd-parity series 6 p 2(3 p 0) n p of BiI are excited by a three-photon process. A two-photon dissociation of Bi2 into excited atomic states followed by a one-photon absorption leads to highly excited atomic Rydberg states up to n = 32. States of the even-parity Rydberg series 6 p 2(3 p 0) nsJ=1/2, ndJ=3/2 and ndJ=5/2 are also observed. In order to avoid the background caused by ionization of the bismuth molecules we performed a two-color excitation with pulsed dye lasers. With this experiment the 6 p 2(3 p 0) npJ=3/2 Rydberg series could be resolved up to n=75. The increasing quantum defect of this series is due to a perturbing state close to the first ionization limit. By a MQDT analysis we obtain the energy of the perturbing state and a value of 58,761.68±0.1 cm-1 for the first ionization limit of atomic bismuth.

Multiple quantum coherence spectroscopy.

PubMed

Mathew, Nathan A; Yurs, Lena A; Block, Stephen B; Pakoulev, Andrei V; Kornau, Kathryn M; Wright, John C

2009-08-20

Multiple quantum coherences provide a powerful approach for studies of complex systems because increasing the number of quantum states in a quantum mechanical superposition state increases the selectivity of a spectroscopic measurement. We show that frequency domain multiple quantum coherence multidimensional spectroscopy can create these superposition states using different frequency excitation pulses. The superposition state is created using two excitation frequencies to excite the symmetric and asymmetric stretch modes in a rhodium dicarbonyl chelate and the dynamic Stark effect to climb the vibrational ladders involving different overtone and combination band states. A monochromator resolves the free induction decay of different coherences comprising the superposition state. The three spectral dimensions provide the selectivity required to observe 19 different spectral features associated with fully coherent nonlinear processes involving up to 11 interactions with the excitation fields. The different features act as spectroscopic probes of the diagonal and off-diagonal parts of the molecular potential energy hypersurface. This approach can be considered as a coherent pump-probe spectroscopy where the pump is a series of excitation pulses that prepares a multiple quantum coherence and the probe is another series of pulses that creates the output coherence.

Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission.

PubMed

Hart, Stephanie M; Silva, W Ruchira; Frontiera, Renee R

2018-02-07

Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes.

Transient photocurrent responses in amorphous Zn-Sn-O thin films

NASA Astrophysics Data System (ADS)

Kim, Ju-Yeon; Oh, Sang-A.; Yu, Kyeong Min; Bae, Byung Seong; Yun, Eui-Jung

2015-04-01

In this study we characterized the transient photocurrent responses in solution-processed amorphous zinc-tin-oxide (a-ZTO) thin films measured under light illumination with a wavelength of 400 nm at different temperatures. By using the temperature-dependent photoconductivities of a-ZTO thin films, we extracted the activation energies (E ac ) of photo-excitation and dark relaxation through an extended stretched exponential analysis (SEA). The SEA was found to describe well the dark relaxation characteristics as well as the photo-excitation processes. The SEA also indicates that the dark relaxation process reveals a dispersive transient photoconductivity with a broader distribution of the E ac while the photo-excitation process shows non-dispersive characteristics. Samples exposed by light at temperatures less than 373 K possess the fast processes of photo-excitation and dark relaxation. This suggests that a fast process, for example, a generation/recombination of charged carriers related to a band-to-band transition and/or shallow/deep oxygen-vacancy (V o ) sub-gap donor states, is dominant in the case of light illumination at low temperatures of less than 373 K. The SEA indicates, however, that a much slower process due mainly to the delay of the onset of ionization/neutralization of the deep V o states by multiple-trapping is dominant for samples under light illumination at a high temperature of 373 K. Based on the experimental results, for the dark relaxation process, we conclude that the process transitions from a fast recombination of electrons through band-to-band transitions and/or shallow/deep V o donor states to a slow neutralization of the ionized V o states occurs due to enhanced carrier multiple-trapping by relatively deep V o trap states when the temperature becomes greater than 363 K. An energy band diagram of a-ZTO thin films was proposed in terms of the temperature and the E ac distribution to explain these observed results.

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

PubMed

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

2017-04-06

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

The effect of structural changes on charge transfer states in a light-harvesting carotenoid-diaryl-porphyrin-C{sub 60} molecular triad

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olguin, Marco; Basurto, Luis; Zope, Rajendra R.

We present a detailed study of charge transfer (CT) excited states for a large number of configurations in a light-harvesting Carotenoid-diaryl-Porphyrin-C{sub 60} (CPC{sub 60}) molecular triad. The chain-like molecular triad undergoes photoinduced charge transfer process exhibiting a large excited state dipole moment, making it suitable for application to molecular-scale opto-electronic devices. An important consideration is that the structural flexibility of the CPC{sub 60} triad impacts its dynamics in solvents. Since experimentally measured dipole moments for the triad of ∼110 D and ∼160 D strongly indicate a range in structural variability in the excited state, studying the effect of structural changesmore » on the CT excited state energetics furthers the understanding of its charge transfer states. We have calculated the variation in the lowest CT excited state energies by performing a scan of possible variation in the structure of the triad. Some of these configurations were generated by incrementally scanning a 360° torsional (dihedral) twist at the C{sub 60}-porhyrin linkage and the porphyrin-carotenoid linkage. Additionally, five different CPC{sub 60} conformations were studied to determine the effect of pi-conjugation and particle-hole Coulombic attraction on the CT excitation energies. Our calculations show that configurational changes in the triad induces a variation of ∼0.6 eV in CT excited state energies in the gas-phase. The corresponding calculated excited state dipoles show a range of 47 D–188 D. The absorption spectra and density of states of these structures show little variation except for the structures where the porphyrin and aryl conjugation is changed.« less

Water-chromophore electron transfer determines the photochemistry of cytosine and cytidine.

PubMed

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

2017-07-21

Many of the UV-induced phenomena observed experimentally for aqueous cytidine were lacking the mechanistic interpretation for decades. These processes include the substantial population of the puzzling long-lived dark state, photohydration, cytidine to uridine conversion and oxazolidinone formation. Here, we present quantum-chemical simulations of excited-state spectra and potential energy surfaces of N1-methylcytosine clustered with two water molecules using the second-order approximate coupled cluster (CC2), complete active space with second-order perturbation theory (CASPT2), and multireference configuration interaction with single and double excitation (MR-CISD) methods. We argue that the assignment of the long-lived dark state to a singlet nπ* excitation involving water-chromophore electron transfer might serve as an explanation for the numerous experimental observations. While our simulated spectra for the state are in excellent agreement with experimentally acquired data, the electron-driven proton transfer process occurring on the surface may initiate the subsequent damage in the vibrationally hot ground state of the chromophore.

Improved efficiency of selective photoionization of palladium isotopes via autoionizing Rydberg states

NASA Astrophysics Data System (ADS)

Locke, Clayton R.; Kobayashi, Tohru; Midorikawa, Katsumi

2017-01-01

Odd-mass-selective ionization of palladium for purposes of resource recycling and management of long-lived fission products can be achieved by exploiting transition selection rules in a well-established three-step excitation process. In this conventional scheme, circularly polarized lasers of the same handedness excite isotopes via two intermediate 2D5/2 core states, and a third laser is then used for ionization via autoionizing Rydberg states. We propose an alternative excitation scheme via intermediate 2D3/2 core states before the autoionizing Rydberg state, improving ionization efficiency by over 130 times. We confirm high selectivity and measure odd-mass isotopes of >99.7(3)% of the total ionized product. We have identified and measured the relative ionization efficiency of the series of Rydberg states that converge to upper ionization limit of the 4 d 9(2D3/2) level, and identify the most efficient excitation is via the Rydberg state at 67668.18(10) cm-1.

Low-lying excited states by constrained DFT

NASA Astrophysics Data System (ADS)

Ramos, Pablo; Pavanello, Michele

2018-04-01

Exploiting the machinery of Constrained Density Functional Theory (CDFT), we propose a variational method for calculating low-lying excited states of molecular systems. We dub this method eXcited CDFT (XCDFT). Excited states are obtained by self-consistently constraining a user-defined population of electrons, Nc, in the virtual space of a reference set of occupied orbitals. By imposing this population to be Nc = 1.0, we computed the first excited state of 15 molecules from a test set. Our results show that XCDFT achieves an accuracy in the predicted excitation energy only slightly worse than linear-response time-dependent DFT (TDDFT), but without incurring into problems of variational collapse typical of the more commonly adopted ΔSCF method. In addition, we selected a few challenging processes to test the limits of applicability of XCDFT. We find that in contrast to TDDFT, XCDFT is capable of reproducing energy surfaces featuring conical intersections (azobenzene and H3) with correct topology and correct overall energetics also away from the intersection. Venturing to condensed-phase systems, XCDFT reproduces the TDDFT solvatochromic shift of benzaldehyde when it is embedded by a cluster of water molecules. Thus, we find XCDFT to be a competitive method among single-reference methods for computations of excited states in terms of time to solution, rate of convergence, and accuracy of the result.

On the strong and selective isotope effect in the UV excitation of N2 with implications toward the nebula and Martian atmosphere.

PubMed

Muskatel, B H; Remacle, F; Thiemens, Mark H; Levine, R D

2011-04-12

Isotopic effects associated with molecular absorption are discussed with reference to natural phenomena including early solar system processes, Titan and terrestrial atmospheric chemistry, and Martian atmospheric evolution. Quantification of the physicochemical aspects of the excitation and dissociation processes may lead to enhanced understanding of these environments. Here we examine a physical basis for an additional isotope effect during photolysis of molecular nitrogen due to the coupling of valence and Rydberg excited states. The origin of this isotope effect is shown to be the coupling of diabatic electronic states of different bonding nature that occurs after the excitation of these states. This coupling is characteristic of energy regimes where two or more excited states are nearly crossing or osculating. A signature of the resultant isotope effect is a window of rapid variation in the otherwise smooth distribution of oscillator strengths vs. frequency. The reference for the discussion is the numerical solution of the time dependent Schrödinger equation for both the electronic and nuclear modes with the light field included as part of the Hamiltonian. Pumping is to all extreme UV dipole-allowed, valence and Rydberg, excited states of N(2). The computed absorption spectra are convoluted with the solar spectrum to demonstrate the importance of including this isotope effect in planetary, interstellar molecular cloud, and nebular photochemical models. It is suggested that accidental resonance with strong discrete lines in the solar spectrum such as the CIII line at 97.703 nm can also have a marked effect.

The Spectroscopy and Photophysics of Aniline, 2-AMINOPYRIDINE, and 3-AMINOPYRIDINE

NASA Astrophysics Data System (ADS)

Kim, Byungjoo

1995-01-01

Two-photon ionization photoelectron spectroscopic techniques have been employed in concert with a picosecond laser system and molecular beam machine to study the vibrational structure of molecular ions and the intramolecular dynamics of optically prepared intermediate states. From photoelectron spectra of 2-aminopyridine via various S_1 vibronic resonances, the frequencies of several vibrations in the ionic state are assigned. The ionization potential of the molecule is found to be 8.099 +/- 0.003 eV. Using two-color ionization techniques, the electronic overlap effects in the photoionization of excited molecules have been studied, on the example of 2-aminopyridine, 3-aminopyridine, and aniline. The molecules are excited to their S_1 states, and ionized by a 200 nm laser pulse within 50 ps. The spectra of the aminopyridines show a striking absence of transitions to excited electronic states of the ions, indicating small electronic overlap factors in the ionization transitions and very little configuration interaction in the S _1 states. The spectra of aniline show the vibrationally resolved first excited electronic state band of the ion, which is very weak compared to the ground electronic state band, indicating a small amount of orbital mixing in the S_1 state. The vibrational peaks in the band were assigned by comparison of the spectra via two different vibronic resonances. The observations demonstrate that electronic overlap effects play a very general role in the ionization of polyatomic molecules in electronically excited states, and that orbital mixing patterns of the excited electronic states may become observable by projecting molecular electronic wavefunctions onto the ion states. In the time-delayed experiments for these molecules, all spectra reveal only one product of the nonradiative relaxation process. Careful considerations of electronic and vibrational overlap propensity rules for the ionization step lead to the conclusion that the dominant nonradiative decay mechanism in these molecules is the intersystem crossing to excited vibrational states of the T_1 state. This technique has been applied to study the predissociation process of CS_2 in the S_3 vibronic levels near 200 nm. The spectra show extensive vibrational structure, with unusual activity in the antisymmetric vibrations, indicating the possibility of level mixing in the intermediate state by the IVR couplings.

N2 state population in Titan's atmosphere

NASA Astrophysics Data System (ADS)

Lavvas, P.; Yelle, R. V.; Heays, A. N.; Campbell, L.; Brunger, M. J.; Galand, M.; Vuitton, V.

2015-11-01

We present a detailed model for the vibrational population of all non pre-dissociating excited electronic states of N2, as well as for the ground and ionic states, in Titan's atmosphere. Our model includes the detailed energy deposition calculations presented in the past (Lavvas, P. et al. [2011]. Icarus 213(1), 233-251) as well as the more recent developments in the high resolution N2 photo-absorption cross sections that allow us to calculate photo-excitation rates for different vibrational levels of singlet nitrogen states, and provide information for their pre-dissociation yields. In addition, we consider the effect of collisions and chemical reactions in the population of the different states. Our results demonstrate that above 600 km altitude, collisional processes are efficient only for a small sub-set of the excited states limited to the A and W(ν = 0) triplet states, and to a smaller degree to the a‧ singlet state. In addition, we find that a significant population of vibrationally excited ground state N2 survives in Titan's upper atmosphere. Our calculations demonstrate that this hot N2 population can improve the agreement between models and observations for the emission of the c4‧ state that is significantly affected by resonant scattering. Moreover we discuss the potential implications of the vibrationally excited population on the ionospheric densities.

Photodynamics of oxybenzone sunscreen: Nonadiabatic dynamics simulations.

PubMed

Li, Chun-Xiang; Guo, Wei-Wei; Xie, Bin-Bin; Cui, Ganglong

2016-08-21

Herein we have used combined static electronic structure calculations and "on-the-fly" global-switching trajectory surface-hopping dynamics simulations to explore the photochemical mechanism of oxybenzone sunscreen. We have first employed the multi-configurational CASSCF method to optimize minima, conical intersections, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decays in the (1)ππ(∗), (1)nπ(∗), and S0 states (energies are refined at the higher MS-CASPT2 level). According to the mapped potential energy profiles, we have identified two ultrafast excited-state deactivation pathways for the initially populated (1)ππ(∗) system. The first is the diabatic ESIPT process along the (1)ππ(∗) potential energy profile. The generated (1)ππ(∗) keto species then decays to the S0 state via the keto (1)ππ(∗)/gs conical intersection. The second is internal conversion to the dark (1)nπ(∗) state near the (1)ππ(∗) /(1)nπ(∗) crossing point in the course of the diabatic (1)ππ(∗) ESIPT process. Our following dynamics simulations have shown that the ESIPT and (1)ππ(∗) → S0 internal conversion times are 104 and 286 fs, respectively. Finally, our present work demonstrates that in addition to the ESIPT process and the (1)ππ(∗) → S0 internal conversion in the keto region, the (1)ππ(∗) → (1)nπ(∗) internal conversion in the enol region plays as well an important role for the excited-state relaxation dynamics of oxybenzone.

Photodynamics of oxybenzone sunscreen: Nonadiabatic dynamics simulations

NASA Astrophysics Data System (ADS)

Li, Chun-Xiang; Guo, Wei-Wei; Xie, Bin-Bin; Cui, Ganglong

2016-08-01

Herein we have used combined static electronic structure calculations and "on-the-fly" global-switching trajectory surface-hopping dynamics simulations to explore the photochemical mechanism of oxybenzone sunscreen. We have first employed the multi-configurational CASSCF method to optimize minima, conical intersections, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decays in the 1ππ∗, 1nπ∗, and S0 states (energies are refined at the higher MS-CASPT2 level). According to the mapped potential energy profiles, we have identified two ultrafast excited-state deactivation pathways for the initially populated 1ππ∗ system. The first is the diabatic ESIPT process along the 1ππ∗ potential energy profile. The generated 1ππ∗ keto species then decays to the S0 state via the keto 1ππ∗/gs conical intersection. The second is internal conversion to the dark 1nπ∗ state near the 1ππ∗ /1nπ∗ crossing point in the course of the diabatic 1ππ∗ ESIPT process. Our following dynamics simulations have shown that the ESIPT and 1ππ∗ → S0 internal conversion times are 104 and 286 fs, respectively. Finally, our present work demonstrates that in addition to the ESIPT process and the 1ππ∗ → S0 internal conversion in the keto region, the 1ππ∗ → 1nπ∗ internal conversion in the enol region plays as well an important role for the excited-state relaxation dynamics of oxybenzone.

Search for excited states of light and heavy flavor quarks in the $$\\gamma$$+jet final state in proton-proton collisions at $$\\sqrt{s} =$$ 13 TeV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sirunyan, Albert M; et al.

A search is presented for excited quarks of light and heavy flavor that decay tomore » $$\\gamma$$+jet final states. The analysis is based on data corresponding to an integrated luminosity of 35.9 fb$$^{-1}$$ collected by the CMS experiment in proton-proton collisions at $$\\sqrt{s}=$$ 13 TeV at the LHC. A signal would appear as a resonant contribution to the invariant mass spectrum of the $$\\gamma$$+jet system, above the background expected from standard model processes. No resonant excess is found, and upper limits are set on the product of the excited quark cross section and its branching fraction as a function of its mass. These are the most stringent limits to date in the $$\\gamma$$+jet final state, and exclude excited light quarks with masses below 5.5 TeV and excited b quarks with masses below 1.8 TeV, assuming standard model couplings.« less

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

NASA Astrophysics Data System (ADS)

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; Schirò, Giorgio; Adam, Virgile; Aquila, Andrew; Barends, Thomas R. M.; Boutet, Sébastien; Byrdin, Martin; Carbajo, Sergio; de La Mora, Eugenio; Doak, R. Bruce; Feliks, Mikolaj; Fieschi, Franck; Foucar, Lutz; Guillon, Virginia; Hilpert, Mario; Hunter, Mark S.; Jakobs, Stefan; Koglin, Jason E.; Kovacsova, Gabriela; Lane, Thomas J.; Lévy, Bernard; Liang, Mengning; Nass, Karol; Ridard, Jacqueline; Robinson, Joseph S.; Roome, Christopher M.; Ruckebusch, Cyril; Seaberg, Matthew; Thepaut, Michel; Cammarata, Marco; Demachy, Isabelle; Field, Martin; Shoeman, Robert L.; Bourgeois, Dominique; Colletier, Jacques-Philippe; Schlichting, Ilme; Weik, Martin

2018-01-01

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecond timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

DOE PAGES

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; ...

2017-09-11

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Comparison of Vibrational Relaxation Modeling for Strongly Non-Equilibrium Flows

DTIC Science & Technology

2014-01-01

prediction of radiative emission spectra. I. Introduction Excitation and quenching of vibrational energy modes through collision relaxation is an...restrict the VEDF to the first two excited states. For the combined excitation/ quenching cases (v i = 4), there is a greater probability of a... quenching process than a vibrationally excited collision. This is expected because the initial vibrational energy exceeds 60% of the total collisional energy

Resolving shocked and UV excited components of H2 emission in planetary nebulae with high-resolution near-infrared spectroscopy

NASA Astrophysics Data System (ADS)

Kaplan, Kyle; Dinerstein, Harriet L.; Jaffe, Daniel Thomas

2016-06-01

Planetary nebulae (PNe) form when low and intermediate-mass stars eject their outer layers into the ISM at the end of the AGB phase. Many PNe exhibit near-infrared (NIR) emission from molecular hydrogen (H2). This NIR emission arises from radiative decay out of excited rotation-vibration (rovibrational) states. The rovibrational states can be populated by excitation to higher electronic states through absorption of a far-UV photon followed by a radiative cascade to the electronic ground state, or by collisions (e.g., in a hot gas). The two processes populate the rovibrational levels of H2 differently, so the observed emergent emission spectrum provides an effective probe of the mechanisms that excite the H2. Many PNe display line intensity ratios that are intermediate between these two processes (Otsuka et al. 2013). With the advantages of the high spectral resolution (R~40000), broad wavelength coverage (1.45-2.45 μm), and high spatial resolution of the Immersion GRating Infrared Spectrometer (IGRINS, Park et al. 2014), we are able to differentiate components in position-velocity space: we see a slowly expanding UV-excited H2 shell in the PN M 1-11 and two faster moving “bullets” of thermalized H2 that we interpret as shocked gas from a bipolar outflow. We also present observations of several other PNe that exhibit similar morphologies of thermalized and UV-excited H2 components.

Mechanisms of optical losses in the 5D4 and 5D3 levels in Tb3+ doped low silica calcium aluminosilicate glasses

NASA Astrophysics Data System (ADS)

dos Santos, J. F. M.; Terra, I. A. A.; Astrath, N. G. C.; Guimarães, F. B.; Baesso, M. L.; Nunes, L. A. O.; Catunda, T.

2015-02-01

Trivalent Tb-doped materials exhibit strong emission in the green and weak emission in the UV-blue levels. Usually, this behavior is attributed to the cross relaxation (CR) process. In this paper, the luminescence properties of Tb3+-doped low silica calcium aluminosilicate glasses are analyzed for UV (λexc = 325 nm) and visible (488 nm) excitations. Under 325 nm excitation, the intensity of green luminescence increases proportionally to Tb3+ concentration. However, the blue luminescence intensity is strongly reduced with the increase of concentration from 0.5-15.0 wt. %. In the case of 488 nm excitation, a saturation behavior of the green emission is observed at intensities two orders of magnitude smaller than expected for bleaching of the ground state population. Using a rate equation model, we showed that this behavior can be explained by an excited state absorption cross section two orders of magnitude larger than the ground state absorption. The blue emission is much weaker than expected from our rate equations (325 nm and 488 nm excitation). We concluded that only the CR process cannot explain the overall feature of measured luminescence quenching in the wide range of Tb3+ concentrations. Cooperative upconversion from a pair of excited ions (5D3:5D3 or 5D3:5D4) and other mechanisms involving upper lying states (4f5d, charge transfer, host matrix, defects, etc.) may play a significant role.

Inter- and intraconfigurational luminescence of Er3+ ions in BaY2F8 under VUV excitation

NASA Astrophysics Data System (ADS)

Kirm, M.; Lichtenberg, H.; Makhov, V. N.; Negodin, E.; Ouvarova, T. V.; Suljoti, E.; True, M.; Zimmerer, G.

Using energy- and time-resolved spectroscopy the luminescence properties of Er3+ doped BaY2F8 crystals were investigated at 10 K under VUV synchrotron radiation excitation. Radiative intraconfigurational f - f and interconfigurational d - f transitions in Er3+ ions were observed under f - d excitation. Whereas the onset of S-4(3/2) population via f - d excitation starts at 59 900 cm(-1) , efficient excitation of emissions arising from the P-2(3/2) state begins only above 67 000 cm(-1) in VUV region. Such behaviour can be explained by a cross-relaxation process of the type (F-2(2)(5/2) , I-4(15/2))-->(P-2(3/2) , P-2(3/2)) taking place within f -states of Er3+ ions finally populating the emitting P-2(3/2) state.

Interatomic Coulombic decay cascades in multiply excited neon clusters

PubMed Central

Nagaya, K.; Iablonskyi, D.; Golubev, N. V.; Matsunami, K.; Fukuzawa, H.; Motomura, K.; Nishiyama, T.; Sakai, T.; Tachibana, T.; Mondal, S.; Wada, S.; Prince, K. C.; Callegari, C.; Miron, C.; Saito, N.; Yabashi, M.; Demekhin, Ph. V.; Cederbaum, L. S.; Kuleff, A. I.; Yao, M.; Ueda, K.

2016-01-01

In high-intensity laser light, matter can be ionized by direct multiphoton absorption even at photon energies below the ionization threshold. However on tuning the laser to the lowest resonant transition, the system becomes multiply excited, and more efficient, indirect ionization pathways become operative. These mechanisms are known as interatomic Coulombic decay (ICD), where one of the species de-excites to its ground state, transferring its energy to ionize another excited species. Here we show that on tuning to a higher resonant transition, a previously unknown type of interatomic Coulombic decay, intra-Rydberg ICD occurs. In it, de-excitation of an atom to a close-lying Rydberg state leads to electron emission from another neighbouring Rydberg atom. Moreover, systems multiply excited to higher Rydberg states will decay by a cascade of such processes, producing even more ions. The intra-Rydberg ICD and cascades are expected to be ubiquitous in weakly-bound systems exposed to high-intensity resonant radiation. PMID:27917867

Resonance-enhanced two-photon excitation of CaI

NASA Astrophysics Data System (ADS)

Casero-Junquera, Elena; Lawruszczuk, Rafal; Rostas, Joëlle; Taieb, Guy

1994-07-01

Induced fluorescence following visible (620-655 nm) laser excitation of the CaI radical has been detected not only in the same region (B, A-X transitions), but also in the UV (315-330 nm). The UV two-photon excitation spectrum consists of narrow bands appearing at laser frequencies located within certain bands of the Δ v = 1, 0 sequences of the B 2Σ +-X 2Σ + and A 2Π 1/2-X 2Σ + systems. The main peaks are tentatively assigned to resonance-enhanced excitation of a single vibrational level of the lowest Rydberg D 2Σ + state from successive vibrational levels of the ground state. The excitation process is a one-color two-photon optical—optical-double-resonance via B 2Σ + and A 2Π 1/2 intermediate levels. This analysis is supported by the absorption spectrum observed long ago by Walters and Barratt. The absorption and laser excitation complementary data have been used to derive approximate molecular constants for the D state.

Theory of spin-conserving excitation of the N-V(-) center in diamond.

PubMed

Gali, Adam; Janzén, Erik; Deák, Péter; Kresse, Georg; Kaxiras, Efthimios

2009-10-30

The negatively charged nitrogen-vacancy defect in diamond is an important atomic-scale structure that can be used as a qubit in quantum computing and as a marker in biomedical applications. Its usefulness relies on the ability to optically excite electrons between well-defined gap states, which requires a clear and detailed understanding of the relevant states and excitation processes. Here we show that by using hybrid density-functional-theory calculations in a large supercell we can reproduce the zero-phonon line and the Stokes and anti-Stokes shifts, yielding a complete picture of the spin-conserving excitation of this defect.

Multiconfiguration Pair-Density Functional Theory Is as Accurate as CASPT2 for Electronic Excitation.

PubMed

Hoyer, Chad E; Ghosh, Soumen; Truhlar, Donald G; Gagliardi, Laura

2016-02-04

A correct description of electronically excited states is critical to the interpretation of visible-ultraviolet spectra, photochemical reactions, and excited-state charge-transfer processes in chemical systems. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory and a new kind of density functional called an on-top density functional. Here, we show that MC-PDFT with a first-generation on-top density functional performs as well as CASPT2 for an organic chemistry database including valence, Rydberg, and charge-transfer excitations. The results are very encouraging for practical applications.

Importance of considering helium excited states in He+ scattering by an aluminum surface

NASA Astrophysics Data System (ADS)

Iglesias-García, A.; García, Evelina A.; Goldberg, E. C.

2014-11-01

The He+/Al system is a very interesting projectile-surface combination which was thought initially as an example of a pure Auger neutralization mechanism. Then, because of the measured reionization explained by the antibonding interaction of the projectile state with the core target states, the resonant charge exchange with the band states was considered as another important contribution to the neutralization. Nevertheless, by only considering the neutralization to the ground state of helium, the measured ion survival probability is still overestimated. On the other hand, measurements of electron emission from an Al surface bombarded by He positive ions suggested the possibility of occupied excited states of helium due to the ion-surface collision. In this work, we also include the excited states of He within the time-dependent scattering process in which both neutralization mechanisms, resonant and Auger, are simultaneously contemplated. Our starting point is a multiorbital Anderson Hamiltonian projected over the selected space of ground and excited atomic configurations. An extra term related to the Auger mechanism is added to this Hamiltonian. A difference with previous works is that this approach includes the electron spin and, therefore, the spin fluctuation statistics in the charge-exchange process is correctly taken into account. We find a notable improvement in the agreement with the experiments and also that the interference between both mechanisms is not dramatic.

Determination of differential cross sections for electron-impact excitation of electronic states of molecular oxygen

NASA Astrophysics Data System (ADS)

Campbell, L.; Green, M. A.; Brunger, M. J.; Teubner, P. J.; Cartwright, D. C.

2000-02-01

The development and initial results of a method for the determination of differential cross sections for electron scattering by molecular oxygen are described. The method has been incorporated into an existing package of computer programs which, given spectroscopic factors, dissociation energies and an energy-loss spectrum for electron-impact excitation, determine the differential cross sections for each electronic state relative to that of the elastic peak. Enhancements of the original code were made to deal with particular aspects of electron scattering from O2, such as the overlap of vibrational levels of the ground state with transitions to excited states, and transitions to levels close to and above the dissocation energy in the Herzberg and Schumann-Runge continua. The utility of the code is specifically demonstrated for the ``6-eV states'' of O2, where we report absolute differential cross sections for their excitation by 15-eV electrons. In addition an integral cross section, derived from the differential cross section measurements, is also reported for this excitation process and compared against available theoretical results. The present differential and integral cross sections for excitation of the ``6-eV states'' of O2 are the first to be reported in the literature for electron-impact energies below 20 eV.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Esboui, Mounir, E-mail: mounir.esboui@fst.rnu.tn; Technical and Vocational Training Corporation, Hail College of Technology, P.O. Box 1960, Hail 81441

The stepwise and concerted excited state intermolecular proton transfer (PT) and hydrogen transfer (HT) reactions in 2-hydroxypyridine-(NH{sub 3}){sub 2} complex in the gas phase under Cs symmetry constraint and without any symmetry constraints were performed using quantum chemical calculations. It shows that upon excitation, the hydrogen bonded in 2HP-(NH{sub 3}){sub 2} cluster facilitates the releasing of both hydrogen and proton transfer reactions along ammonia wire leading to the formation of the 2-pyridone tautomer. For the stepwise mechanism, it has been found that the proton and the hydrogen may transfer consecutively. These processes are distinguished from each other through charge translocationmore » analysis and the coupling between the motion of the proton and the electron density distribution along ammonia wire. For the complex under Cs symmetry, the excited state HT occurs on the A″({sup 1}πσ{sup ∗}) and A′({sup 1}nσ{sup ∗}) states over two accessible energy barriers along reaction coordinates, and excited state PT proceeds mainly through the A′({sup 1}ππ{sup ∗}) and A″({sup 1}nπ{sup ∗}) potential energy surfaces. For the unconstrained complex, potential energy profiles show two {sup 1}ππ{sup ∗}-{sup 1}πσ{sup ∗} conical intersections along enol → keto reaction path indicating that proton and H atom are localized, respectively, on the first and second ammonia of the wire. Moreover, the concerted excited state PT is competitive to take place with the stepwise process, because it proceeds over low barriers of 0.14 eV and 0.11 eV with respect to the Franck-Condon excitation of enol tautomer, respectively, under Cs symmetry and without any symmetry constraints. These barriers can be probably overcome through tunneling effect.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Limphirat, Ayut; Thailand Center of Excellence in Physics; Department of Applied Physics, Faculty of Sciences and Liberal Arts, Rajamangala University of Technology Isan, Nakhon Ratchasima 30000

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

Excited-State Charge Separation in the Photochemical Mechanism of the Light-Driven Enzyme Protochlorophyllide Oxidoreductase**

PubMed Central

Heyes, Derren J; Hardman, Samantha J O; Hedison, Tobias M; Hoeven, Robin; Greetham, Greg M; Towrie, Michael; Scrutton, Nigel S

2015-01-01

The unique light-driven enzyme protochlorophyllide oxidoreductase (POR) is an important model system for understanding how light energy can be harnessed to power enzyme reactions. The ultrafast photochemical processes, essential for capturing the excitation energy to drive the subsequent hydride- and proton-transfer chemistry, have so far proven difficult to detect. We have used a combination of time-resolved visible and IR spectroscopy, providing complete temporal resolution over the picosecond–microsecond time range, to propose a new mechanism for the photochemistry. Excited-state interactions between active site residues and a carboxyl group on the Pchlide molecule result in a polarized and highly reactive double bond. This so-called “reactive” intramolecular charge-transfer state creates an electron-deficient site across the double bond to trigger the subsequent nucleophilic attack of NADPH, by the negatively charged hydride from nicotinamide adenine dinucleotide phosphate. This work provides the crucial, missing link between excited-state processes and chemistry in POR. Moreover, it provides important insight into how light energy can be harnessed to drive enzyme catalysis with implications for the design of light-activated chemical and biological catalysts. PMID:25488797

Excited-state charge separation in the photochemical mechanism of the light-driven enzyme protochlorophyllide oxidoreductase.

PubMed

Heyes, Derren J; Hardman, Samantha J O; Hedison, Tobias M; Hoeven, Robin; Greetham, Greg M; Towrie, Michael; Scrutton, Nigel S

2015-01-26

The unique light-driven enzyme protochlorophyllide oxidoreductase (POR) is an important model system for understanding how light energy can be harnessed to power enzyme reactions. The ultrafast photochemical processes, essential for capturing the excitation energy to drive the subsequent hydride- and proton-transfer chemistry, have so far proven difficult to detect. We have used a combination of time-resolved visible and IR spectroscopy, providing complete temporal resolution over the picosecond-microsecond time range, to propose a new mechanism for the photochemistry. Excited-state interactions between active site residues and a carboxyl group on the Pchlide molecule result in a polarized and highly reactive double bond. This so-called "reactive" intramolecular charge-transfer state creates an electron-deficient site across the double bond to trigger the subsequent nucleophilic attack of NADPH, by the negatively charged hydride from nicotinamide adenine dinucleotide phosphate. This work provides the crucial, missing link between excited-state processes and chemistry in POR. Moreover, it provides important insight into how light energy can be harnessed to drive enzyme catalysis with implications for the design of light-activated chemical and biological catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Excited state intramolecular proton transfer reaction of 4'-N,N-diethylamino-3-hydroxyflavone and solvation dynamics in room temperature ionic liquids studied by optical Kerr gate fluorescence measurement.

PubMed

Kimura, Yoshifumi; Fukuda, Masanori; Suda, Kayo; Terazima, Masahide

2010-09-16

Fluorescence dynamics of 4'-N,N-diethylamino-3-hydroxyflavone (DEAHF) and its methoxy derivative (DEAMF) in various room temperature ionic liquids (RTILs) have been studied mainly by an optical Kerr gate method. DEAMF showed a single band fluorescence whose peak shifted with time by the solvation dynamics. The averaged solvation time determined by the fluorescence peak shift was proportional to the viscosity of the solvent except for tetradecyltrihexylphosphonium bis(trifluoromethanesulfonyl)amide. The solvation times were consistent with reported values determined with different probe molecules. DEAHF showed dual fluorescence due to the normal and tautomer forms produced by the excited state intramolecular proton transfer (ESIPT), and the relative intensities were dependent on the time and the solvent cation or anion species. By using the information of the fluorescence spectrum of DEAMF, the fluorescence spectrum of DEAHF at each delay time after the photoexcitation was decomposed into the normal and the tautomer fluorescence components, respectively. The normal component showed a very fast decay simulated by a biexponential function (2-3 and 20-30 ps) with an additional slower decay component. The tautomer component showed a rise with the time constants corresponding to the faster decay of the normal form with an additional instantaneous rise. The faster dynamics of the normal and tautomer population changes were assigned to the ESIPT process, while the slower decay of the fluorescence was attributed to the population decay from the excited state through the radiative and nonradiative processes. The average ESIPT time was much faster than the averaged solvation time of RTILs. Basically, the ESIPT kinetics in RTILs is similar to those in conventional liquid solvents like acetonitrile (Chou et al. J. Phys. Chem. A 2005, 109, 3777). The faster ESIPT is interpreted in terms of the activation barrierless process from the Franck-Condon state before the solvation of the normal state in the electronic excited state. With the advance of the solvation in the excited state, the normal form becomes relatively more stable than the tautomer form, which makes the ESIPT become an activation process.

Atomic vapor laser isotope separation of lead-210 isotope

DOEpatents

Scheibner, K.F.; Haynam, C.A.; Johnson, M.A.; Worden, E.F.

1999-08-31

An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207. 5 figs.

Atomic vapor laser isotope separation of lead-210 isotope

DOEpatents

Scheibner, Karl F.; Haynam, Christopher A.; Johnson, Michael A.; Worden, Earl F.

1999-01-01

An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207.

Direct measurements of nonlinear absorption and refraction in solutions of phthalocyanines

NASA Technical Reports Server (NTRS)

Wei, T. H.; Hagan, D. J.; Sence, M. J.; Van Stryland, E. W.; Perry, J. W.; Coulter, D. R.

1992-01-01

Direct measurements are reported of the excited singlet-state absorption cross section and the associated nonlinear refractive cross section using picosecond pulses at 532 nm in solutions of phthalocyanine and naphthalocyanine dyes. By monitoring the transmittance and far-field spatial beam distortion for different pulsewidths in the picosecond regime, it is shown that both the nonlinear absorption and refraction are fluence (energy-per-unit-area) rather than irradiance dependent. Thus, excited-state absorption is the dominant nonlinear absorption process, and the observed nonlinear refraction is also due to real population excitation.

Fluoride anion sensing mechanism of 2-ureido-4[1H]-pyrimidinone quadruple hydrogen-bonded supramolecular assembly: photoinduced electron transfer and partial configuration change.

PubMed

Chen, Jun-Sheng; Zhou, Pan-Wang; Li, Guang-Yue; Chu, Tian-Shu; He, Guo-Zhong

2013-05-02

The fluoride anion sensing mechanism of 6-methyl-5-(9-methylene-anthracene)-(2-butylureido-4[1H]-pyrimidinone) (AnUP) has been investigated using the DFT/TDDFT method. The theoretical results indicate that the proton of the N3-H3 group in pyrimidine moiety is captured by the added fluoride anion and then deprotonated. The calculated vertical excitation energies of AnUP-dimer and its deprotonated form agree well with the experimental results. The molecular orbital analysis demonstrates that the first excited state (S1) of AnUP-dimer is a local excited state with a π-π* transition, whereas for the deprotonated form, S1 is a completely charge-separation state and is responsible for the photoinduced electron transfer (PET) process. The PET process from anthracene to the pyrimidine moiety leads to the fluorescence quenching.

Photoinduced Ultrafast Intramolecular Excited-State Energy Transfer in the Silylene-Bridged Biphenyl and Stilbene (SBS) System: A Nonadiabatic Dynamics Point of View.

PubMed

Wang, Jun; Huang, Jing; Du, Likai; Lan, Zhenggang

2015-07-09

The photoinduced intramolecular excited-state energy-transfer (EET) process in conjugated polymers has received a great deal of research interest because of its important role in the light harvesting and energy transport of organic photovoltaic materials in photoelectric devices. In this work, the silylene-bridged biphenyl and stilbene (SBS) system was chosen as a simplified model system to obtain physical insight into the photoinduced intramolecular energy transfer between the different building units of the SBS copolymer. In the SBS system, the vinylbiphenyl and vinylstilbene moieties serve as the donor (D) unit and the acceptor (A) unit, respectively. The ultrafast excited-state dynamics of the SBS system was investigated from the point of view of nonadiabatic dynamics with the surface-hopping method at the TDDFT level. The first two excited states (S1 and S2) are characterized by local excitations at the acceptor (vinylstilbene) and donor (vinylbiphenyl) units, respectively. Ultrafast S2-S1 decay is responsible for the intramolecular D-A excitonic energy transfer. The geometric distortion of the D moiety play an essential role in this EET process, whereas the A moiety remains unchanged during the nonadiabatic dynamics simulation. The present work provides a direct dynamical approach to understand the ultrafast intramolecular energy-transfer dynamics in SBS copolymers and other similar organic photovoltaic copolymers.

Conformational relaxation dynamics in the excited electronic states of benzil in solution

NASA Astrophysics Data System (ADS)

Singh, Ajay K.; Palit, Dipak K.; Mittal, Jai P.

2002-07-01

Relaxation dynamics in the excited singlet (S1) state of benzil have been studied in solution using pico and subpicosecond transient absorption spectroscopic techniques. The triple exponential decay dynamics of the S1 state indicates that the process of conformational change from the cis-skewed to the trans-planar form takes place via the formation of a meta-stable intermediate conformer resulting the involvement of two consequent barrier crossing processes. The barrier crossing dynamics is governed by both the polarity of the solvent, which alters the barrier heights by `static' interactions, as well as the viscosity of the solvent via `dynamical' interactions.

Non-radiative decay paths in rhodamines: new theoretical insights.

PubMed

Savarese, Marika; Raucci, Umberto; Adamo, Carlo; Netti, Paolo A; Ciofini, Ilaria; Rega, Nadia

2014-10-14

We individuate a photoinduced electron transfer (PeT) as a quenching mechanism affecting rhodamine B photophysics in solvent. The PeT involves an electron transfer from the carboxylate group to the xanthene ring of rhodamine B. This is finely modulated by the subtle balance of coulombic and non-classical interactions between the carboxyphenyl and xanthene rings, also mediated by the solvent. We propose the use of an electronic density based index, the so called DCT index, as a new tool to assess and quantify the nature of the excited states involved in non-radiative decays near the region of their intersection. In the present case, this analysis allows us to gain insight on the interconversion process from the bright state to the dark state responsible for the quenching of rhodamine B fluorescence. Our findings encourage the use of density based indices to study the processes affecting excited state reactions that are characterized by a drastic change in the excitation nature, in order to rationalize the photophysical behavior of complex molecular systems.

Manipulation of resonant Auger processes with strong optical fields

NASA Astrophysics Data System (ADS)

Picón, Antonio; Buth, Christian; Doumy, Gilles; Krässig, Bertold; Young, Linda; Southworth, Stephen

2013-05-01

We recently reported on the optical control of core-excited states of a resonant Auger process in neon. We have focused on the resonant excitation 1 s --> 1s-1 3 p , while a strong optical field may resonantly couple two core-excited states (1s-1 3 p and 1s-1 3 s) in the Rydberg manifold as well as dressing the continuum. There is a clear signature in the Auger electron spectrum of the inner-shell dynamics induced by the strong optical field: i) the Auger electron spectrum is modified by the rapid optical-induced population transfer from the 1s-1 3 p state to the 1s-1 3 s state during their decay. ii) The angular anisotropy parameter, defining the angular distribution of the Auger electron, is manifested in the envelope of the (angle-integrated) sidebands. This work is funded by the Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy, under Contract No. DE-AC02-06CH11357.

Vibronic transitions in the alkali-metal (Li, Na, K, Rb) - alkaline-earth-metal (Ca, Sr) series: A systematic analysis of de-excitation mechanisms based on the graphical mapping of Frank-Condon integrals

NASA Astrophysics Data System (ADS)

Pototschnig, Johann V.; Meyer, Ralf; Hauser, Andreas W.; Ernst, Wolfgang E.

2017-02-01

Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. After forming weakly bound molecules from atoms in cold collisions, the preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. Accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. This paper is dedicated to the vibrational analysis of potentially relevant electronically excited states in the alkali-metal (Li, Na, K, Rb)- alkaline-earth metal (Ca,Sr) diatomic series. Graphical maps of Frank-Condon overlap integrals are presented for all molecules of the group. By comparison to overlap graphics produced for idealized potential surfaces, we judge the usability of the selected states for future experiments on laser-enhanced molecular formation from mixtures of quantum degenerate gases.

Molecular level energy and electron transfer processes at nanocrystalline titanium dioxide interfaces

NASA Astrophysics Data System (ADS)

Farzad, Fereshteh

This thesis describes photo-induced molecular electron and energy transfer processes occurring at nanocrystalline semiconductor interfaces. The Introductory Chapter provides background and describes how these materials may be useful for solar energy conversion. In Chapter 2, results describing excitation of Ru(deeb)(bpy)2 2+, bis(2,2'-bipyridine)(2,2'-bipyridine-4,4 '-diethylester)ruthenium(II) hexafluorophosphate, bound to nanocrystalline TiO2 thin films, immersed in an acetonitrile bath are presented. The data indicates that light excitation forms predominately long-lived metal-to-ligand charge-transfer, MLCT, excited states under these conditions. Modeling of the data as a function of irradiance has been accomplished assuming parallel unimolecular and bimolecular excited state deactivation processes. The quantum yield for excited state formation depends on the excitation irradiance, consistent with triplet-triplet annihilation processes that occur with k > 1 x 108 s-1. Chapter 3 extends the work described in Chapter 2 to LiClO4 acetonitrile solutions. Li+ addition results in a red shift in the MLCT absorption and photoluminescence, PL, and a concentration dependent quenching of the PL intensity on TiO2. The Li+ induced spectroscopic changes were found to be reversible by varying the electrolyte composition. A second-order kinetic model quantified charge recombination transients. A model is proposed wherein Li+ ion adsorption stabilizes TiO2 acceptor states resulting in energetically more favorable interfacial electron transfer. The photophysical and photoelectrochemical properties of porous nanocrystalline anatase TiO2 electrodes modified with Ru(deeb)(bpy)2 2+, Os(deeb)(bpy)22+, and mixtures of both are described in Chapters 4 and 5. In regenerative solar cells with 0.5 M LiI/0.05 M I2 acetonitrile electrolyte, both compounds efficiently inject electrons into TiO2 producing monochromatic incident photon-to-current efficiencies (IPCE), IPCE (460 nm) = 0.70 + 0.05 for Ru(dcb)(bpy)2 2+/TiO2 and 0. 10 + 0.05 for Os(dcb)(bpy)2 2+/TiO2. Os(dcb)(bpy)22+ extends the spectral sensitivity of the TiO2 material beyond 700 rim. Application of a negative bias to the derivatized TiO2 surfaces results in inefficient interfacial electron transfer and no significant photocurrent. Instead, lateral energy transfer cross the nanocrystalline TiO2 surface from Ru(dcb)(bpy)22+* to Os(dcb)(bpy) 22+ is observed. The energy transfer process can be switched off with a positive applied bias ten times with no significant deterioration. The results demonstrate control of molecular excited states at nanostructured interfaces.

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

PubMed Central

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

2005-01-01

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

Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission.

PubMed

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 (360 ns), whereas those of PcD-4Ph were quite similar in both solvent.

Decay, excitation, and ionization of lithium Rydberg states by blackbody radiation

NASA Astrophysics Data System (ADS)

Ovsiannikov, V. D.; Glukhov, I. L.

2010-09-01

Details of interaction between the blackbody radiation and neutral lithium atoms were studied in the temperature ranges T = 100-2000 K. The rates of thermally induced decays, excitations and ionization were calculated for S-, P- and D-series of Rydberg states in the Fues' model potential approach. The quantitative regularities for the states of the maximal rates of blackbody-radiation-induced processes were determined. Approximation formulas were proposed for analytical representation of the depopulation rates.

Isomer depletion as experimental evidence of nuclear excitation by electron capture

NASA Astrophysics Data System (ADS)

Chiara, C. J.; Carroll, J. J.; Carpenter, M. P.; Greene, J. P.; Hartley, D. J.; Janssens, R. V. F.; Lane, G. J.; Marsh, J. C.; Matters, D. A.; Polasik, M.; Rzadkiewicz, J.; Seweryniak, D.; Zhu, S.; Bottoni, S.; Hayes, A. B.; Karamian, S. A.

2018-02-01

The atomic nucleus and its electrons are often thought of as independent systems that are held together in the atom by their mutual attraction. Their interaction, however, leads to other important effects, such as providing an additional decay mode for excited nuclear states, whereby the nucleus releases energy by ejecting an atomic electron instead of by emitting a γ-ray. This ‘internal conversion’ has been known for about a hundred years and can be used to study nuclei and their interaction with their electrons. In the inverse process—nuclear excitation by electron capture (NEEC)—a free electron is captured into an atomic vacancy and can excite the nucleus to a higher-energy state, provided that the kinetic energy of the free electron plus the magnitude of its binding energy once captured matches the nuclear energy difference between the two states. NEEC was predicted in 1976 and has not hitherto been observed. Here we report evidence of NEEC in molybdenum-93 and determine the probability and cross-section for the process in a beam-based experimental scenario. Our results provide a standard for the assessment of theoretical models relevant to NEEC, which predict cross-sections that span many orders of magnitude. The greatest practical effect of the NEEC process may be on the survival of nuclei in stellar environments, in which it could excite isomers (that is, long-lived nuclear states) to shorter-lived states. Such excitations may reduce the abundance of the isotope after its production. This is an example of ‘isomer depletion’, which has been investigated previously through other reactions, but is used here to obtain evidence for NEEC.

Low-lying excited states by constrained DFT.

PubMed

Ramos, Pablo; Pavanello, Michele

2018-04-14

Exploiting the machinery of Constrained Density Functional Theory (CDFT), we propose a variational method for calculating low-lying excited states of molecular systems. We dub this method eXcited CDFT (XCDFT). Excited states are obtained by self-consistently constraining a user-defined population of electrons, N c , in the virtual space of a reference set of occupied orbitals. By imposing this population to be N c = 1.0, we computed the first excited state of 15 molecules from a test set. Our results show that XCDFT achieves an accuracy in the predicted excitation energy only slightly worse than linear-response time-dependent DFT (TDDFT), but without incurring into problems of variational collapse typical of the more commonly adopted ΔSCF method. In addition, we selected a few challenging processes to test the limits of applicability of XCDFT. We find that in contrast to TDDFT, XCDFT is capable of reproducing energy surfaces featuring conical intersections (azobenzene and H 3 ) with correct topology and correct overall energetics also away from the intersection. Venturing to condensed-phase systems, XCDFT reproduces the TDDFT solvatochromic shift of benzaldehyde when it is embedded by a cluster of water molecules. Thus, we find XCDFT to be a competitive method among single-reference methods for computations of excited states in terms of time to solution, rate of convergence, and accuracy of the result.

Behavior of Excited Argon Atoms in Inductively Driven Plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

HEBNER,GREGORY A.; MILLER,PAUL A.

1999-12-07

Laser induced fluorescence has been used to measure the spatial distribution of the two lowest energy argon excited states, 1s{sub 5} and 1s{sub 4}, in inductively driven plasmas containing argon, chlorine and boron trichloride. The behavior of the two energy levels with plasma conditions was significantly different, probably because the 1s{sub 5} level is metastable and the 1s{sub 4} level is radiatively coupled to the ground state but is radiation trapped. The argon data is compared with a global model to identify the relative importance of processes such as electron collisional mixing and radiation trapping. The trends in the datamore » suggest that both processes play a major role in determining the excited state density. At lower rfpower and pressure, excited state spatial distributions in pure argon were peaked in the center of the discharge, with an approximately Gaussian profile. However, for the highest rfpowers and pressures investigated, the spatial distributions tended to flatten in the center of the discharge while the density at the edge of the discharge was unaffected. The spatially resolved excited state density measurements were combined with previous line integrated measurements in the same discharge geometry to derive spatially resolved, absolute densities of the 1s{sub 5} and 1s{sub 4} argon excited states and gas temperature spatial distributions. Fluorescence lifetime was a strong fi.mction of the rf power, pressure, argon fraction and spatial location. Increasing the power or pressure resulted in a factor of two decrease in the fluorescence lifetime while adding Cl{sub 2} or BCl{sub 3} increased the fluorescence lifetime. Excited state quenching rates are derived from the data. When Cl{sub 2} or BCl{sub 3} was added to the plasma, the maximum argon metastable density depended on the gas and ratio. When chlorine was added to the argon plasma, the spatial density profiles were independent of chlorine fraction. While it is energetically possible for argon excited states to dissociate some of the molecular species present in this discharge, it does not appear to be a significant source of dissociation. The major source of interaction between the argon and the molecular species BCl{sub 3} and Cl{sub 2} appears to be through modification of the electron density.« less

TDDFT study on the sensing mechanism of a fluorescent sensor for fluoride anion: Inhibition of the ESPT process.

PubMed

Li, Guang-Yue; Liu, Dong; Zhang, Hang; Li, Wei-Wei; Wang, Feng; Liang, Ying-Hua

2015-01-01

The fluoride-sensing mechanism of a reported salicylaldehyde-based sensor (J. Photochem. Photobiol. B 2014, 138, 75) has been investigated by the TDDFT method. The present theoretical study indicates that there is an excited-state proton transfer (ESPT) process from the phenolic O-H moiety to the neighbor N atom in the sensor. The added fluoride anion could capture the proton in the O-H moiety and the corresponding phenolic anion is formed, which could inhibit the ESPT process. The experimental UV/Vis and fluorescence spectra are well reproduced by the calculated vertical excitation energies. Frontier molecular orbital analysis indicates that the local excited state of phenolic anion is responsible for its enhanced fluorescence. Due to this reason, the sensor can be used to sense fluoride anion by monitoring the fluorescent change. Copyright © 2015 Elsevier B.V. All rights reserved.

Acceptor number-dependent ultrafast photo-physical properties of push-pull chromophores using time-resolved methods

NASA Astrophysics Data System (ADS)

Chi, Xiao-Chun; Wang, Ying-Hui; Gao, Yu; Sui, Ning; Zhang, Li-Quan; Wang, Wen-Yan; Lu, Ran; Ji, Wen-Yu; Yang, Yan-Qiang; Zhang, Han-Zhuang

2018-04-01

Three push-pull chromophores comprising a triphenylamine (TPA) as electron-donating moiety and functionalized β-diketones as electron acceptor units are studied by various spectroscopic techniques. The time-correlated single-photon counting data shows that increasing the number of electron acceptor units accelerates photoluminescence relaxation rate of compounds. Transient spectra data shows that intramolecular charge transfer (ICT) takes place from TPA units to β-diketones units after photo-excitation. Increasing the number of electron acceptor units would prolong the generation process of ICT state, and accelerate the excited molecule reorganization process and the relaxation process of ICT state.

Investigation of electronically excited indole relaxation dynamics via photoionization and fragmentation pump-probe spectroscopy.

PubMed

Godfrey, T J; Yu, Hui; Ullrich, Susanne

2014-07-28

The studies herein investigate the involvement of the low-lying (1)La and (1)Lb states with (1)ππ(*) character and the (1)πσ(*) state in the deactivation process of indole following photoexcitation at 201 nm. Three gas-phase, pump-probe spectroscopic techniques are employed: (1) Time-resolved photoelectron spectroscopy (TR-PES), (2) hydrogen atom (H-atom) time-resolved kinetic energy release (TR-KER), and (3) time-resolved ion yield (TR-IY). Each technique provides complementary information specific to the photophysical processes in the indole molecule. In conjunction, a thorough examination of the electronically excited states in the relaxation process, with particular focus on the involvement of the (1)πσ(*) state, is afforded. Through an extensive analysis of the TR-PES data presented here, it is deduced that the initial excitation of the (1)Bb state decays to the (1)La state on a timescale beyond the resolution of the current experimental setup. Relaxation proceeds on the (1)La state with an ultrafast decay constant (<100 femtoseconds (fs)) to the lower-lying (1)Lb state, which is found to possess a relatively long lifetime of 23 ± 5 picoseconds (ps) before regressing to the ground state. These studies also manifest an additional component with a relaxation time of 405 ± 76 fs, which is correlated with activity along the (1)πσ(*) state. TR-KER and TR-IY experiments, both specifically probing (1)πσ(*) dynamics, exhibit similar decay constants, further validating these observations.

On-demand generation of background-free single photons from a solid-state source

NASA Astrophysics Data System (ADS)

Schweickert, Lucas; Jöns, Klaus D.; Zeuner, Katharina D.; Covre da Silva, Saimon Filipe; Huang, Huiying; Lettner, Thomas; Reindl, Marcus; Zichi, Julien; Trotta, Rinaldo; Rastelli, Armando; Zwiller, Val

2018-02-01

True on-demand high-repetition-rate single-photon sources are highly sought after for quantum information processing applications. However, any coherently driven two-level quantum system suffers from a finite re-excitation probability under pulsed excitation, causing undesirable multi-photon emission. Here, we present a solid-state source of on-demand single photons yielding a raw second-order coherence of g(2 )(0 )=(7.5 ±1.6 )×10-5 without any background subtraction or data processing. To this date, this is the lowest value of g(2 )(0 ) reported for any single-photon source even compared to the previously reported best background subtracted values. We achieve this result on GaAs/AlGaAs quantum dots embedded in a low-Q planar cavity by employing (i) a two-photon excitation process and (ii) a filtering and detection setup featuring two superconducting single-photon detectors with ultralow dark-count rates of (0.0056 ±0.0007 ) s-1 and (0.017 ±0.001 ) s-1, respectively. Re-excitation processes are dramatically suppressed by (i), while (ii) removes false coincidences resulting in a negligibly low noise floor.

UV-visible-NIR light generation through frequency upconversion in Tm3+-doped low silica calcium aluminosilicate glasses using multiple excitation around 1.2 μm

NASA Astrophysics Data System (ADS)

Trindade, C. M.; Rego-Filho, F. G.; Astrath, N. G. C.; Jacinto, C.; Gouveia-Neto, A. S.

2018-04-01

Intense ultraviolet upconversion emission was produced in single Tm3+-doped OH--free low silica calcium aluminosilicate glasses. A new excitation route based upon multi-Stokes Raman emissions generated in an optical fiber pumped at 1.064 μm, and exploiting the absorption band around 1.2 μm by means of the 3H5 thulium excited state, was used. Furthermore, the other bands of the stimulated Raman scattering spectrum resonantly enhances all the upconversion processes, resulting in efficient ultraviolet (295 nm, 360 nm), blue (456 nm, 480 nm), red (650 nm, 667 nm), and near-infrared (800 nm) emissions. The population of the 1P0, 1D2, 1G4, 3F2 and 3H4 excited-state emitting levels was accomplished through stepwise multi-photon absorption. Results indicate competing cross-relaxation processes involving Tm3+ ion-pairs producing UV emission population quenching Simplified energy-level diagram of Tm3+- doped sample excited using multi-stokes emissions. The λp indication describes all excitation wavelengths, represented by a single arrow for the sake of simplicity.

Application of spectroscopy and super-resolution microscopy: Excited state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharjee, Ujjal

Photophysics of inorganic materials and organic molecules in complex systems have been extensively studied with absorption and emission spectroscopy.1-4 Steady-state and time-resolved fluorescence studies are commonly carried out to characterize excited-state properties of fluorophores. Although steady-state fluorescence measurements are widely used for analytical applications, time-resolved fluorescence measurements provide more detailed information about excited-state properties and the environment in the vicinity of the fluorophore. Many photophysical processes, such as photoinduced electron transfer (PET), rotational reorientation, solvent relaxation, and energy transfer, occur on a nanosecond (10 -9 s) timescale, thus affecting the lifetime of the fluorophores. Moreover, time-resolved microscopy methods, such asmore » lifetimeimaging, combine the benefits of the microscopic measurement and information-rich, timeresolved data. Thus, time-resolved fluorescence spectroscopy combined with microscopy can be used to quantify these processes and to obtain a deeper understanding of the chemical surroundings of the fluorophore in a small area under investigation. This thesis discusses various photophysical and super-resolution microscopic studies of organic and inorganic materials, which have been outlined below.« less

Calculation of singlet oxygen formation from one photon absorbing photosensitizers used in PDT

NASA Astrophysics Data System (ADS)

Potasek, M.; Parilov, Evgueni; Beeson, K.

2013-03-01

Advances in biophotonic medicine require new information on photodynamic mechanisms. In photodynamic therapy (PDT), a photosensitizer (PS) is injected into the body and accumulates at higher concentrations in diseased tissue compared to normal tissue. The PS absorbs light from a light source and generates excited-state triplet states of the PS. The excited triplet states of the PS can then react with ground state molecular oxygen to form excited singlet - state oxygen or form other highly reactive species. The reactive species react with living cells, resulting in cel l death. This treatment is used in many forms of cancer including those in the prostrate, head and neck, lungs, bladder, esophagus and certain skin cancers. We developed a novel numerical method to model the photophysical and photochemical processes in the PS and the subsequent energy transfer to O2, improving the understanding of these processes at a molecular level. Our numerical method simulates light propagation and photo-physics in PS using methods that build on techniques previously developed for optical communications and nonlinear optics applications.

Infrared Auroral Emissions Driven by Resonant Electron Impact Excitation of NO Molecules

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.; Petrovic, Z. Lj.; Jelisavcic, M.; Panajotovic, R.; Buckman, S. J.

2004-05-01

Although only a minor constituent of the earth's upper atmosphere, nitric oxide (NO) plays a major role in infrared auroral emissions due to radiation from vibrationally excited (NO*) states. The main process leading to the production of these excited molecules was thought to be chemiluminescence, whereby excited nitrogen atoms interact with oxygen molecules to form vibrationally excited nitric oxide (NO*) and atomic oxygen. Here we show evidence that a different production mechanism for NO*, due to low energy electron impact excitation of NO molecules, is responsible for more than 30% of the NO auroral emission near 5 μm.

Electronically excited and ionized states in condensed phase: Theory and applications

NASA Astrophysics Data System (ADS)

Sadybekov, Arman

Predictive modeling of chemical processes in silico is a goal of XXI century. While robust and accurate methods exist for ground-state properties, reliable methods for excited states are still lacking and require further development. Electronically exited states are formed by interactions of matter with light and are responsible for key processes in solar energy harvesting, vision, artificial sensors, and photovoltaic applications. The greatest challenge to overcome on our way to a quantitative description of light-induced processes is accurate inclusion of the effect of the environment on excited states. All above mentioned processes occur in solution or solid state. Yet, there are few methodologies to study excited states in condensed phase. Application of highly accurate and robust methods, such as equation-of-motion coupled-cluster theory EOM-CC, is limited by a high computational cost and scaling precluding full quantum mechanical treatment of the entire system. In this thesis we present successful application of the EOM-CC family of methods to studies of excited states in liquid phase and build hierarchy of models for inclusion of the solvent effects. In the first part of the thesis we show that a simple gasphase model is sufficient to quantitatively analyze excited states in liquid benzene, while the latter part emphasizes the importance of explicit treatment of the solvent molecules in the case of glycine in water solution. In chapter 2, we use a simple dimer model to describe exciton formation in liquid and solid benzene. We show that sampling of dimer structures extracted from the liquid benzene is sufficient to correctly predict exited-state properties of the liquid. Our calculations explain experimentally observed features, which helped to understand the mechanism of the excimer formation in liquid benzene. Furthermore, we shed light on the difference between dimer configurations in the first solvation shell of liquid benzene and in unit cell of solid benzene and discussed the impact of these differences on the formation of the excimer state. In chapter 3, we present a theoretical approach for calculating core-level states in condensed phase. The approach is based on EOM-CC and effective fragment potential (EFP) method. By introducing an approximate treatment of double excitations in the EOM-CCSD (EOM-CC with single and double substitutions) ansatz, we addressed poor convergence issues that are encountered for the core-level states and significantly reduced computational costs. While the approximations introduce relatively large errors in the absolute values of transition energies, the errors are systematic. Consequently, chemical shifts, changes in ionization energies relative to the reference systems, are reproduced reasonably well. By using different protonation forms of solvated glycine as a benchmark system, we showed that our protocol is capable of reproducing the experimental chemical shifts with a quantitative accuracy. The results demonstrate that chemical shifts are very sensitive to the solvent interactions and that explicit treatment of solvent, such as EFP, is essential for achieving quantitative accuracy. In chapter 4, we outline future directions and discuss possible applications of the developed computational protocol for prediction of core chemical shifts in larger systems.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santos, J. F. M. dos; Terra, I. A. A.; Nunes, L. A. O.

Trivalent Tb-doped materials exhibit strong emission in the green and weak emission in the UV-blue levels. Usually, this behavior is attributed to the cross relaxation (CR) process. In this paper, the luminescence properties of Tb{sup 3+}-doped low silica calcium aluminosilicate glasses are analyzed for UV (λ{sub exc} = 325 nm) and visible (488 nm) excitations. Under 325 nm excitation, the intensity of green luminescence increases proportionally to Tb{sup 3+} concentration. However, the blue luminescence intensity is strongly reduced with the increase of concentration from 0.5–15.0 wt. %. In the case of 488 nm excitation, a saturation behavior of the green emission is observed at intensities two ordersmore » of magnitude smaller than expected for bleaching of the ground state population. Using a rate equation model, we showed that this behavior can be explained by an excited state absorption cross section two orders of magnitude larger than the ground state absorption. The blue emission is much weaker than expected from our rate equations (325 nm and 488 nm excitation). We concluded that only the CR process cannot explain the overall feature of measured luminescence quenching in the wide range of Tb{sup 3+} concentrations. Cooperative upconversion from a pair of excited ions ({sup 5}D{sub 3}:{sup 5}D{sub 3} or {sup 5}D{sub 3}:{sup 5}D{sub 4}) and other mechanisms involving upper lying states (4f5d, charge transfer, host matrix, defects, etc.) may play a significant role.« less

Real-time observation of cascaded electronic relaxation processes in p-Fluorotoluene

NASA Astrophysics Data System (ADS)

Hao, Qiaoli; Deng, Xulan; Long, Jinyou; Wang, Yanmei; Abulimiti, Bumaliya; Zhang, Bing

2017-08-01

Ultrafast electronic relaxation processes following two photoexcitation of 400 nm in p-Fluorotoluene (pFT) have been investigated utilizing time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Cascaded electronic relaxation processes started from the electronically excited S2 state are directly imaged in real time and well characterized by two distinct time constants of 85 ± 10 fs and 2.4 ± 0.3 ps. The rapid component corresponds to the lifetime of the initially excited S2 state, including the structure relaxation from the Franck-Condon region to the conical intersection of S2/S1 and the subsequent internal conversion to the highly excited S1 state. While, the slower relaxation constant is attributed to the further internal conversion to the high levels of S0 from the secondarily populated S1 locating in the channel three region. Moreover, dynamical differences with benzene and toluene of analogous structures, including, specifically, the slightly slower relaxation rate of S2 and the evidently faster decay of S1, are also presented and tentatively interpreted as the substituent effects. In addition, photoelectron kinetic energy and angular distributions reveal the feature of accidental resonances with low-lying Rydberg states (the 3p, 4s and 4p states) during the multi-photon ionization process, providing totally unexpected but very interesting information for pFT.

Numerical and analytical investigation of the chimera state excitation conditions in the Kuramoto-Sakaguchi oscillator network

NASA Astrophysics Data System (ADS)

Frolov, Nikita S.; Goremyko, Mikhail V.; Makarov, Vladimir V.; Maksimenko, Vladimir A.; Hramov, Alexander E.

2017-03-01

In this paper we study the conditions of chimera states excitation in ensemble of non-locally coupled Kuramoto-Sakaguchi (KS) oscillators. In the framework of current research we analyze the dynamics of the homogeneous network containing identical oscillators. We show the chimera state formation process is sensitive to the parameters of coupling kernel and to the KS network initial state. To perform the analysis we have used the Ott-Antonsen (OA) ansatz to consider the behavior of infinitely large KS network.

The production of CO(+) (B2Sigma +) from dissociative photoionization excitation of CO2

NASA Technical Reports Server (NTRS)

Wu, C. Y. R.; Judge, D. L.

1986-01-01

The dissociative photoionization excitation process in CO2 is studied. In contrast to previous studies, attention is focused on the vibrational and rotational levels produced in fragment ions, partial cross-section measurements for producing such fragment ions in a specific quantum state, and the mechanisms that govern the dissociative ionization excitation processes. The partial fluorescence cross section for the production of CO(+) (B2Sigma +) from CO2 over a wide wavelength range was measured. It is concluded that the production of the CO(+) (B2Sigma +) fragment near the threshold is through a direct dissociative photoionization process.

Fluorescence Spectroscopic Properties of Normal and Abnormal Biomedical Materials

NASA Astrophysics Data System (ADS)

Pradhan, Asima

Steady state and time-resolved optical spectroscopy and native fluorescence is used to study the physical and optical properties occurring in diseased and non-diseased biological human tissue, in particular, cancer of the human breast, artery and the dynamics of a photosensitizer useful in photodynamic therapy. The main focus of the research is on the optical properties of cancer and atherosclerotic tissues as compared to their normal counterparts using the different luminescence based spectroscopic techniques such as steady state fluorescence, time-resolved fluorescence, excitation spectroscopy and phosphorescence. The excitation and steady-state spectroscopic fluorescence using visible excitation wavelength displays a difference between normal and malignant tissues. This difference is attributed to absorption of the emission by hemoglobin in normal tissues. This method using 488nm fails to distinguish neoplastic tissue such as benign tissues and tumors from malignant tumors. The time-resolved fluorescence at visible, near -uv and uv excitation wavelengths display non-exponential profiles which are significantly different for malignant tumors as compared to non-malignant tissues only with uv excitation. The differences observed with visible and near-uv excitation wavelengths are not as significant. The non-exponential profiles are interpreted as due to a combination of fluorophores along with the action of non-radiative processes. Low temperature luminescence studies confirm the occurrence of non-radiative decay processes while temporal studies of various relevant biomolecules indicate the probable fluorophores responsible for the observed signal in tissues. Phosphorescence from human tissues have been observed for the first time and lifetimes of a few hundred nanoseconds are measured for malignant and benign tissues. Time-resolved fluorescence studies of normal artery and atherosclerotic plaque have shown that a combination of two excitation wavelengths can distinguish fibrous and calcified atherosclerotic plaque from normal artery. A minor effort of the study involves the high intensity effects on the optical properties of the dye, doxycycline (a particular photosensitizer of the tetracycline group) occurring during relaxation when excited at different laser intensities. This study has been performed by observing the fluorescence lifetimes and quantum yields of DOTC at different excitation intensities. The results obtained support the sequential excited state absorption model.

X-ray spectroscopy studies of nonradiative energy transfer processes in luminescent lanthanide materials

NASA Astrophysics Data System (ADS)

Pacold, Joseph I.

Luminescent materials play important roles in energy sciences, through solid state lighting and possible applications in solar energy utilization, and in biomedical research and applications, such as in immunoassays and fluorescence microscopy. The initial excitation of a luminescent material leads to a sequence of transitions between excited states, ideally ending with the emission of one or more optical-wavelength photons. It is essential to understand the microscopic physics of this excited state cascade in order to rationally design materials with high quantum efficiencies or with other fine-tuning of materials response. While optical-wavelength spectroscopies have unraveled many details of the energy transfer pathways in luminescent materials, significant questions remain open for many lanthanide-based luminescent materials. For organometallic dyes in particular, quantum yields remain limited in comparison with inorganic phosphors. This dissertation reports on a research program of synchrotron x-ray studies of the excited state electronic structure and energy-relaxation cascade in trivalent lanthanide phosphors and dyes. To this end, one of the primary results presented here is the first time-resolved x-ray absorption near edge spectroscopy studies of the transient 4f excited states in lanthanide-activated luminescent dyes and phosphors. This is a new application of time-resolved x-ray absorption spectroscopy that makes it possible to directly observe and, to some extent, quantify intramolecular nonradiative energy transfer processes. We find a transient increase in 4f spectral weight associated with an excited state confined to the 4f shell of trivalent Eu. This result implies that it is necessary to revise the current theoretical understanding of 4f excitation in trivalent lanthanide activators: either transient 4f-5d mixing effects are much stronger than previously considered, or else the lanthanide 4f excited state has an unexpectedly large contribution having a strong charge-transfer character. A second primary result comes from an an x-ray excited optical luminescence (XEOL) study that demonstrates, for the first time, that the high flux of modern synchrotron light sources can induce high fractional populations of excited states in trivalent lanthanide phosphors. In this work we have identified the leading-order nonlinear-response mechanism by drawing on strong similarities between XEOL and cathodoluminescence. These results establish the groundwork for studies that would allow deeper inquiry into energy-transfer mechanisms through time-resolved x-ray pump/optical-probe spectroscopies, through time-resolved x-ray emission spectroscopy, or through quantifying of higher-order nonlinear effects at further-enhanced fractional excitation levels. The above scientific results are augmented by a supporting effort in instrumental methodology. This includes the development of high-efficiency x-ray emission spectrometers and their use in collaborations to study pressure-induced changes in f-electron physics and to characterize the intermediate states that occur after photoexcitation of the photosystem-II protein.

Photophysical properties and photoisomerization processes of Methyl Red embedded in rigid polymer

NASA Astrophysics Data System (ADS)

Lee, Geon Joon; Kim, Dongho; Lee, Minyung

1995-01-01

The photophysical properties of Methyl Red molecules embedded in a poly(methyl methacrylate) (PMMA) matrix were investigated with photoinduced absorption, absorption kinetics, steady-state, and time-resolved luminescence spectroscopy. The excited singlet (S1) state lifetimes for trans and cis isomers of Methyl Red in PMMA at room temperature have been measured as 35 and 420 ps, respectively. The excited triplet (T1) state energy level and its lifetime at 77 K were also obtained. A slow trans-cis isomerization process having a time constant of a few hundred seconds was observed for the illuminated Methyl Red in rigid polymer. Based on measured photophysical properties and dynamic processes, an energy-level diagram for Methyl Red molecules in rigid polymer is introduced to explain these observations.

Spectroscopic investigation on the energy transfer process in photosynthetic apparatus of cyanobacteria

NASA Astrophysics Data System (ADS)

Li, Ye; Wang, Bei; Ai, Xi-Cheng; Zhang, Xing-Kang; Zhao, Jing-Quan; Jiang, Li-Jin

2004-06-01

In this work, we employ cyanobacteria, Spirulina platensis, and separate their photosynthetic apparatus, phycobilisome (PBS), thylakoid membrane and phycobilisome-thylakoid membrane complex. The steady state absorption spectra, fluorescence spectra and corresponding deconvoluted spectra and picosecond time-resolved spectra are used to investigate the energy transfer process in phycobilisome-thylakoid membrane complex. The results on steady state spectra show chlorophylls of the photosystem II are able to transfer excitation energy to phycobilisome with Chl a molecules selectively excited. The decomposition of the steady state spectra further suggest the uphill energy transfer originate from chlorophylls of photosystem II to cores of phycobilisome, while rods and cores of phycobilisome cannot receive energy from the chlorophylls of photosystem I. The time constant for the back energy transfer process is 18 ps.

Synthetic Control of Exciton Behavior in Colloidal Quantum Dots.

PubMed

Pu, Chaodan; Qin, Haiyan; Gao, Yuan; Zhou, Jianhai; Wang, Peng; Peng, Xiaogang

2017-03-08

Colloidal quantum dots are promising optical and optoelectronic materials for various applications, whose performance is dominated by their excited-state properties. This article illustrates synthetic control of their excited states. Description of the excited states of quantum-dot emitters can be centered around exciton. We shall discuss that, different from conventional molecular emitters, ground-state structures of quantum dots are not necessarily correlated with their excited states. Synthetic control of exciton behavior heavily relies on convenient and affordable monitoring tools. For synthetic development of ideal optical and optoelectronic emitters, the key process is decay of band-edge excitons, which renders transient photoluminescence as important monitoring tool. On the basis of extensive synthetic developments in the past 20-30 years, synthetic control of exciton behavior implies surface engineering of quantum dots, including surface cation/anion stoichiometry, organic ligands, inorganic epitaxial shells, etc. For phosphors based on quantum dots doped with transition metal ions, concentration and location of the dopant ions within a nanocrystal lattice are found to be as important as control of the surface states in order to obtain bright dopant emission with monoexponential yet tunable photoluminescence decay dynamics.

Search for excited quarks of light and heavy flavor in γ + jet final states in proton-proton collisions at √{ s } = 13TeV

NASA Astrophysics Data System (ADS)

Sirunyan, A. M.; Tumasyan, A.; Adam, W.; Ambrogi, F.; Asilar, E.; Bergauer, T.; Brandstetter, J.; Brondolin, E.; Dragicevic, M.; Erö, J.; Flechl, M.; Friedl, M.; Frühwirth, R.; Ghete, V. M.; Grossmann, J.; Hrubec, J.; Jeitler, M.; König, A.; Krammer, N.; Krätschmer, I.; Liko, D.; Madlener, T.; Mikulec, I.; Pree, E.; Rad, N.; Rohringer, H.; Schieck, J.; Schöfbeck, R.; Spanring, M.; Spitzbart, D.; Waltenberger, W.; Wittmann, J.; Wulz, C.-E.; Zarucki, M.; Chekhovsky, V.; Mossolov, V.; Suarez Gonzalez, J.; De Wolf, E. A.; Di Croce, D.; Janssen, X.; Lauwers, J.; Van De Klundert, M.; Van Haevermaet, H.; Van Mechelen, P.; Van Remortel, N.; Abu Zeid, S.; Blekman, F.; D'Hondt, J.; De Bruyn, I.; De Clercq, J.; Deroover, K.; Flouris, G.; Lontkovskyi, D.; Lowette, S.; Marchesini, I.; Moortgat, S.; Moreels, L.; Python, Q.; Skovpen, K.; Tavernier, S.; Van Doninck, W.; Van Mulders, P.; Van Parijs, I.; Beghin, D.; Brun, H.; Clerbaux, B.; De Lentdecker, G.; Delannoy, H.; Dorney, B.; Fasanella, G.; Favart, L.; Goldouzian, R.; Grebenyuk, A.; Lenzi, T.; Luetic, J.; Maerschalk, T.; Marinov, A.; Seva, T.; Starling, E.; Vander Velde, C.; Vanlaer, P.; Vannerom, D.; Yonamine, R.; Zenoni, F.; Zhang, F.; Cimmino, A.; Cornelis, T.; Dobur, D.; Fagot, A.; Gul, M.; Khvastunov, I.; Poyraz, D.; Roskas, C.; Salva, S.; Tytgat, M.; Verbeke, W.; Zaganidis, N.; Bakhshiansohi, H.; Bondu, O.; Brochet, S.; Bruno, G.; Caputo, C.; Caudron, A.; David, P.; De Visscher, S.; Delaere, C.; Delcourt, M.; Francois, B.; Giammanco, A.; Komm, M.; Krintiras, G.; Lemaitre, V.; Magitteri, A.; Mertens, A.; Musich, M.; Piotrzkowski, K.; Quertenmont, L.; Saggio, A.; Vidal Marono, M.; Wertz, S.; Zobec, J.; Aldá Júnior, W. L.; Alves, F. L.; Alves, G. A.; Brito, L.; Correa Martins Junior, M.; Hensel, C.; Moraes, A.; Pol, M. E.; Rebello Teles, P.; Belchior Batista Das Chagas, E.; Carvalho, W.; Chinellato, J.; Coelho, E.; Da Costa, E. M.; Da Silveira, G. G.; De Jesus Damiao, D.; Fonseca De Souza, S.; Huertas Guativa, L. M.; Malbouisson, H.; Melo De Almeida, M.; Mora Herrera, C.; Mundim, L.; Nogima, H.; Sanchez Rosas, L. J.; Santoro, A.; Sznajder, A.; Thiel, M.; Tonelli Manganote, E. J.; Torres Da Silva De Araujo, F.; Vilela Pereira, A.; Ahuja, S.; Bernardes, C. A.; Fernandez Perez Tomei, T. R.; Gregores, E. M.; Mercadante, P. G.; Novaes, S. F.; Padula, Sandra S.; Romero Abad, D.; Ruiz Vargas, J. C.; Aleksandrov, A.; Hadjiiska, R.; Iaydjiev, P.; Misheva, M.; Rodozov, M.; Shopova, M.; Sultanov, G.; Dimitrov, A.; Litov, L.; Pavlov, B.; Petkov, P.; Fang, W.; Gao, X.; Yuan, L.; Ahmad, M.; Bian, J. G.; Chen, G. M.; Chen, H. S.; Chen, M.; Chen, Y.; Jiang, C. H.; Leggat, D.; Liao, H.; Liu, Z.; Romeo, F.; Shaheen, S. M.; Spiezia, A.; Tao, J.; Wang, C.; Wang, Z.; Yazgan, E.; Zhang, H.; Zhang, S.; Zhao, J.; Ban, Y.; Chen, G.; Li, J.; Li, Q.; Liu, S.; Mao, Y.; Qian, S. J.; Wang, D.; Xu, Z.; Avila, C.; Cabrera, A.; Chaparro Sierra, L. F.; Florez, C.; González Hernández, C. F.; Ruiz Alvarez, J. D.; Segura Delgado, M. A.; Courbon, B.; Godinovic, N.; Lelas, D.; Puljak, I.; Ribeiro Cipriano, P. M.; Sculac, T.; Antunovic, Z.; Kovac, M.; Brigljevic, V.; Ferencek, D.; Kadija, K.; Mesic, B.; Starodumov, A.; Susa, T.; Ather, M. W.; Attikis, A.; Mavromanolakis, G.; Mousa, J.; Nicolaou, C.; Ptochos, F.; Razis, P. A.; Rykaczewski, H.; Finger, M.; Finger, M.; Carrera Jarrin, E.; El-khateeb, E.; Elgammal, S.; Ellithi Kamel, A.; Dewanjee, R. K.; Kadastik, M.; Perrini, L.; Raidal, M.; Tiko, A.; Veelken, C.; Eerola, P.; Kirschenmann, H.; Pekkanen, J.; Voutilainen, M.; Havukainen, J.; Heikkilä, J. K.; Järvinen, T.; Karimäki, V.; Kinnunen, R.; Lampén, T.; Lassila-Perini, K.; Laurila, S.; Lehti, S.; Lindén, T.; Luukka, P.; Siikonen, H.; Tuominen, E.; Tuominiemi, J.; Tuuva, T.; Besancon, M.; Couderc, F.; Dejardin, M.; Denegri, D.; Faure, J. L.; Ferri, F.; Ganjour, S.; Ghosh, S.; Gras, P.; Hamel de Monchenault, G.; Jarry, P.; Kucher, I.; Leloup, C.; Locci, E.; Machet, M.; Malcles, J.; Negro, G.; Rander, J.; Rosowsky, A.; Sahin, M. Ö.; Titov, M.; Abdulsalam, A.; Amendola, C.; Antropov, I.; Baffioni, S.; Beaudette, F.; Busson, P.; Cadamuro, L.; Charlot, C.; Granier de Cassagnac, R.; Jo, M.; Lisniak, S.; Lobanov, A.; Martin Blanco, J.; Nguyen, M.; Ochando, C.; Ortona, G.; Paganini, P.; Pigard, P.; Salerno, R.; Sauvan, J. B.; Sirois, Y.; Stahl Leiton, A. G.; Strebler, T.; Yilmaz, Y.; Zabi, A.; Zghiche, A.; Agram, J.-L.; Andrea, J.; Bloch, D.; Brom, J.-M.; Buttignol, M.; Chabert, E. C.; Chanon, N.; Collard, C.; Conte, E.; Coubez, X.; Fontaine, J.-C.; Gelé, D.; Goerlach, U.; Jansová, M.; Le Bihan, A.-C.; Tonon, N.; Van Hove, P.; Gadrat, S.; Beauceron, S.; Bernet, C.; Boudoul, G.; Chierici, R.; Contardo, D.; Depasse, P.; El Mamouni, H.; Fay, J.; Finco, L.; Gascon, S.; Gouzevitch, M.; Grenier, G.; Ille, B.; Lagarde, F.; Laktineh, I. B.; Lethuillier, M.; Mirabito, L.; Pequegnot, A. L.; Perries, S.; Popov, A.; Sordini, V.; Vander Donckt, M.; Viret, S.; Khvedelidze, A.; Tsamalaidze, Z.; Autermann, C.; Feld, L.; Kiesel, M. K.; Klein, K.; Lipinski, M.; Preuten, M.; Schomakers, C.; Schulz, J.; Zhukov, V.; Albert, A.; Dietz-Laursonn, E.; Duchardt, D.; Endres, M.; Erdmann, M.; Erdweg, S.; Esch, T.; Fischer, R.; Güth, A.; Hamer, M.; Hebbeker, T.; Heidemann, C.; Hoepfner, K.; Knutzen, S.; Merschmeyer, M.; Meyer, A.; Millet, P.; Mukherjee, S.; Pook, T.; Radziej, M.; Reithler, H.; Rieger, M.; Scheuch, F.; Teyssier, D.; Thüer, S.; Flügge, G.; Kargoll, B.; Kress, T.; Künsken, A.; Müller, T.; Nehrkorn, A.; Nowack, A.; Pistone, C.; Pooth, O.; Stahl, A.; Aldaya Martin, M.; Arndt, T.; Asawatangtrakuldee, C.; Beernaert, K.; Behnke, O.; Behrens, U.; Bermúdez Martínez, A.; Bin Anuar, A. A.; Borras, K.; Botta, V.; Campbell, A.; Connor, P.; Contreras-Campana, C.; Costanza, F.; Diez Pardos, C.; Eckerlin, G.; Eckstein, D.; Eichhorn, T.; Eren, E.; Gallo, E.; Garay Garcia, J.; Geiser, A.; Grados Luyando, J. M.; Grohsjean, A.; Gunnellini, P.; Guthoff, M.; Harb, A.; Hauk, J.; Hempel, M.; Jung, H.; Kasemann, M.; Keaveney, J.; Kleinwort, C.; Korol, I.; Krücker, D.; Lange, W.; Lelek, A.; Lenz, T.; Leonard, J.; Lipka, K.; Lohmann, W.; Mankel, R.; Melzer-Pellmann, I.-A.; Meyer, A. B.; Mittag, G.; Mnich, J.; Mussgiller, A.; Ntomari, E.; Pitzl, D.; Raspereza, A.; Savitskyi, M.; Saxena, P.; Shevchenko, R.; Spannagel, S.; Stefaniuk, N.; Van Onsem, G. P.; Walsh, R.; Wen, Y.; Wichmann, K.; Wissing, C.; Zenaiev, O.; Aggleton, R.; Bein, S.; Blobel, V.; Centis Vignali, M.; Dreyer, T.; Garutti, E.; Gonzalez, D.; Haller, J.; Hinzmann, A.; Hoffmann, M.; Karavdina, A.; Klanner, R.; Kogler, R.; Kovalchuk, N.; Kurz, S.; Lapsien, T.; Marconi, D.; Meyer, M.; Niedziela, M.; Nowatschin, D.; Pantaleo, F.; Peiffer, T.; Perieanu, A.; Scharf, C.; Schleper, P.; Schmidt, A.; Schumann, S.; Schwandt, J.; Sonneveld, J.; Stadie, H.; Steinbrück, G.; Stober, F. M.; Stöver, M.; Tholen, H.; Troendle, D.; Usai, E.; Vanhoefer, A.; Vormwald, B.; Akbiyik, M.; Barth, C.; Baselga, M.; Baur, S.; Butz, E.; Caspart, R.; Chwalek, T.; Colombo, F.; De Boer, W.; Dierlamm, A.; Faltermann, N.; Freund, B.; Friese, R.; Giffels, M.; Harrendorf, M. A.; Hartmann, F.; Heindl, S. M.; Husemann, U.; Kassel, F.; Kudella, S.; Mildner, H.; Mozer, M. U.; Müller, Th.; Plagge, M.; Quast, G.; Rabbertz, K.; Schröder, M.; Shvetsov, I.; Sieber, G.; Simonis, H. J.; Ulrich, R.; Wayand, S.; Weber, M.; Weiler, T.; Williamson, S.; Wöhrmann, C.; Wolf, R.; Anagnostou, G.; Daskalakis, G.; Geralis, T.; Kyriakis, A.; Loukas, D.; Topsis-Giotis, I.; Karathanasis, G.; Kesisoglou, S.; Panagiotou, A.; Saoulidou, N.; Kousouris, K.; Evangelou, I.; Foudas, C.; Gianneios, P.; Katsoulis, P.; Kokkas, P.; Mallios, S.; Manthos, N.; Papadopoulos, I.; Paradas, E.; Strologas, J.; Triantis, F. A.; Tsitsonis, D.; Csanad, M.; Filipovic, N.; Pasztor, G.; Surányi, O.; Veres, G. I.; Bencze, G.; Hajdu, C.; Horvath, D.; Hunyadi, Á.; Sikler, F.; Veszpremi, V.; Beni, N.; Czellar, S.; Karancsi, J.; Makovec, A.; Molnar, J.; Szillasi, Z.; Bartók, M.; Raics, P.; Trocsanyi, Z. L.; Ujvari, B.; Choudhury, S.; Komaragiri, J. R.; Bahinipati, S.; Bhowmik, S.; Mal, P.; Mandal, K.; Nayak, A.; Sahoo, D. K.; Sahoo, N.; Swain, S. K.; Bansal, S.; Beri, S. B.; Bhatnagar, V.; Chawla, R.; Dhingra, N.; Kalsi, A. K.; Kaur, A.; Kaur, M.; Kaur, S.; Kumar, R.; Kumari, P.; Mehta, A.; Singh, J. B.; Walia, G.; Kumar, Ashok; Shah, Aashaq; Bhardwaj, A.; Chauhan, S.; Choudhary, B. C.; Garg, R. B.; Keshri, S.; Kumar, A.; Malhotra, S.; Naimuddin, M.; Ranjan, K.; Sharma, R.; Bhardwaj, R.; Bhattacharya, R.; Bhattacharya, S.; Bhawandeep, U.; Dey, S.; Dutt, S.; Dutta, S.; Ghosh, S.; Majumdar, N.; Modak, A.; Mondal, K.; Mukhopadhyay, S.; Nandan, S.; Purohit, A.; Roy, A.; Roy Chowdhury, S.; Sarkar, S.; Sharan, M.; Thakur, S.; Behera, P. K.; Chudasama, R.; Dutta, D.; Jha, V.; Kumar, V.; Mohanty, A. K.; Netrakanti, P. K.; Pant, L. M.; Shukla, P.; Topkar, A.; Aziz, T.; Dugad, S.; Mahakud, B.; Mitra, S.; Mohanty, G. B.; Sur, N.; Sutar, B.; Banerjee, S.; Bhattacharya, S.; Chatterjee, S.; Das, P.; Guchait, M.; Jain, Sa.; Kumar, S.; Maity, M.; Majumder, G.; Mazumdar, K.; Sarkar, T.; Wickramage, N.; Chauhan, S.; Dube, S.; Hegde, V.; Kapoor, A.; Kothekar, K.; Pandey, S.; Rane, A.; Sharma, S.; Chenarani, S.; Eskandari Tadavani, E.; Etesami, S. M.; Khakzad, M.; Mohammadi Najafabadi, M.; Naseri, M.; Paktinat Mehdiabadi, S.; Rezaei Hosseinabadi, F.; Safarzadeh, B.; Zeinali, M.; Felcini, M.; Grunewald, M.; Abbrescia, M.; Calabria, C.; Colaleo, A.; Creanza, D.; Cristella, L.; De Filippis, N.; De Palma, M.; Errico, F.; Fiore, L.; Iaselli, G.; Lezki, S.; Maggi, G.; Maggi, M.; Miniello, G.; My, S.; Nuzzo, S.; Pompili, A.; Pugliese, G.; Radogna, R.; Ranieri, A.; Selvaggi, G.; Sharma, A.; Silvestris, L.; Venditti, R.; Verwilligen, P.; Abbiendi, G.; Battilana, C.; Bonacorsi, D.; Borgonovi, L.; Braibant-Giacomelli, S.; Campanini, R.; Capiluppi, P.; Castro, A.; Cavallo, F. R.; Chhibra, S. S.; Codispoti, G.; Cuffiani, M.; Dallavalle, G. M.; Fabbri, F.; Fanfani, A.; Fasanella, D.; Giacomelli, P.; Grandi, C.; Guiducci, L.; Marcellini, S.; Masetti, G.; Montanari, A.; Navarria, F. L.; Perrotta, A.; Rossi, A. M.; Rovelli, T.; Siroli, G. P.; Tosi, N.; Albergo, S.; Costa, S.; Di Mattia, A.; Giordano, F.; Potenza, R.; Tricomi, A.; Tuve, C.; Barbagli, G.; Chatterjee, K.; Ciulli, V.; Civinini, C.; D'Alessandro, R.; Focardi, E.; Lenzi, P.; Meschini, M.; Paoletti, S.; Russo, L.; Sguazzoni, G.; Strom, D.; Viliani, L.; Benussi, L.; Bianco, S.; Fabbri, F.; Piccolo, D.; Primavera, F.; Calvelli, V.; Ferro, F.; Ravera, F.; Robutti, E.; Tosi, S.; Benaglia, A.; Beschi, A.; Brianza, L.; Brivio, F.; Ciriolo, V.; Dinardo, M. E.; Fiorendi, S.; Gennai, S.; Ghezzi, A.; Govoni, P.; Malberti, M.; Malvezzi, S.; Manzoni, R. A.; Menasce, D.; Moroni, L.; Paganoni, M.; Pauwels, K.; Pedrini, D.; Pigazzini, S.; Ragazzi, S.; Tabarelli de Fatis, T.; Buontempo, S.; Cavallo, N.; Di Guida, S.; Fabozzi, F.; Fienga, F.; Iorio, A. O. M.; Khan, W. A.; Lista, L.; Meola, S.; Paolucci, P.; Sciacca, C.; Thyssen, F.; Azzi, P.; Bacchetta, N.; Benato, L.; Bisello, D.; Boletti, A.; Carlin, R.; Carvalho Antunes De Oliveira, A.; Checchia, P.; De Castro Manzano, P.; Dorigo, T.; Dosselli, U.; Gasparini, F.; Lacaprara, S.; Lujan, P.; Margoni, M.; Maron, G.; Meneguzzo, A. T.; Pozzobon, N.; Ronchese, P.; Rossin, R.; Torassa, E.; Ventura, S.; Zanetti, M.; Zotto, P.; Zumerle, G.; Braghieri, A.; Magnani, A.; Montagna, P.; Ratti, S. P.; Re, V.; Ressegotti, M.; Riccardi, C.; Salvini, P.; Vai, I.; Vitulo, P.; Alunni Solestizi, L.; Biasini, M.; Bilei, G. M.; Cecchi, C.; Ciangottini, D.; Fanò, L.; Leonardi, R.; Manoni, E.; Mantovani, G.; Mariani, V.; Menichelli, M.; Rossi, A.; Santocchia, A.; Spiga, D.; Androsov, K.; Azzurri, P.; Bagliesi, G.; Boccali, T.; Borrello, L.; Castaldi, R.; Ciocci, M. A.; Dell'Orso, R.; Fedi, G.; Giannini, L.; Giassi, A.; Grippo, M. T.; Ligabue, F.; Lomtadze, T.; Manca, E.; Mandorli, G.; Messineo, A.; Palla, F.; Rizzi, A.; Savoy-Navarro, A.; Spagnolo, P.; Tenchini, R.; Tonelli, G.; Venturi, A.; Verdini, P. G.; Barone, L.; Cavallari, F.; Cipriani, M.; Daci, N.; Del Re, D.; Di Marco, E.; Diemoz, M.; Gelli, S.; Longo, E.; Margaroli, F.; Marzocchi, B.; Meridiani, P.; Organtini, G.; Paramatti, R.; Preiato, F.; Rahatlou, S.; Rovelli, C.; Santanastasio, F.; Amapane, N.; Arcidiacono, R.; Argiro, S.; Arneodo, M.; Bartosik, N.; Bellan, R.; Biino, C.; Cartiglia, N.; Cenna, F.; Costa, M.; Covarelli, R.; Degano, A.; Demaria, N.; Kiani, B.; Mariotti, C.; Maselli, S.; Migliore, E.; Monaco, V.; Monteil, E.; Monteno, M.; Obertino, M. M.; Pacher, L.; Pastrone, N.; Pelliccioni, M.; Pinna Angioni, G. L.; Romero, A.; Ruspa, M.; Sacchi, R.; Shchelina, K.; Sola, V.; Solano, A.; Staiano, A.; Traczyk, P.; Belforte, S.; Casarsa, M.; Cossutti, F.; Della Ricca, G.; Zanetti, A.; Kim, D. H.; Kim, G. N.; Kim, M. S.; Lee, J.; Lee, S.; Lee, S. W.; Moon, C. S.; Oh, Y. D.; Sekmen, S.; Son, D. C.; Yang, Y. C.; Lee, A.; Kim, H.; Moon, D. H.; Oh, G.; Brochero Cifuentes, J. A.; Goh, J.; Kim, T. J.; Cho, S.; Choi, S.; Go, Y.; Gyun, D.; Ha, S.; Hong, B.; Jo, Y.; Kim, Y.; Lee, K.; Lee, K. S.; Lee, S.; Lim, J.; Park, S. K.; Roh, Y.; Almond, J.; Kim, J.; Kim, J. S.; Lee, H.; Lee, K.; Nam, K.; Oh, S. B.; Radburn-Smith, B. C.; Seo, S. h.; Yang, U. K.; Yoo, H. D.; Yu, G. B.; Kim, H.; Kim, J. H.; Lee, J. S. H.; Park, I. C.; Choi, Y.; Hwang, C.; Lee, J.; Yu, I.; Dudenas, V.; Juodagalvis, A.; Vaitkus, J.; Ahmed, I.; Ibrahim, Z. A.; Md Ali, M. A. B.; Mohamad Idris, F.; Wan Abdullah, W. A. T.; Yusli, M. N.; Zolkapli, Z.; Reyes-Almanza, R.; Ramirez-Sanchez, G.; Duran-Osuna, M. C.; Castilla-Valdez, H.; De La Cruz-Burelo, E.; Heredia-De La Cruz, I.; Rabadan-Trejo, R. I.; Lopez-Fernandez, R.; Mejia Guisao, J.; Sanchez-Hernandez, A.; Carrillo Moreno, S.; Oropeza Barrera, C.; Vazquez Valencia, F.; Eysermans, J.; Pedraza, I.; Salazar Ibarguen, H. A.; Uribe Estrada, C.; Morelos Pineda, A.; Krofcheck, D.; Butler, P. H.; Ahmad, A.; Ahmad, M.; Hassan, Q.; Hoorani, H. R.; Saddique, A.; Shah, M. A.; Shoaib, M.; Waqas, M.; Bialkowska, H.; Bluj, M.; Boimska, B.; Frueboes, T.; Górski, M.; Kazana, M.; Nawrocki, K.; Szleper, M.; Zalewski, P.; Bunkowski, K.; Byszuk, A.; Doroba, K.; Kalinowski, A.; Konecki, M.; Krolikowski, J.; Misiura, M.; Olszewski, M.; Pyskir, A.; Walczak, M.; Bargassa, P.; Beirão Da Cruz E Silva, C.; Di Francesco, A.; Faccioli, P.; Galinhas, B.; Gallinaro, M.; Hollar, J.; Leonardo, N.; Lloret Iglesias, L.; Nemallapudi, M. V.; Seixas, J.; Strong, G.; Toldaiev, O.; Vadruccio, D.; Varela, J.; Alexakhin, V.; Bunin, P.; Golunov, A.; Golutvin, I.; Gorbounov, N.; Kamenev, A.; Karjavin, V.; Lanev, A.; Malakhov, A.; Matveev, V.; Palichik, V.; Perelygin, V.; Savina, M.; Shmatov, S.; Shulha, S.; Skatchkov, N.; Smirnov, V.; Zarubin, A.; Ivanov, Y.; Kim, V.; Kuznetsova, E.; Levchenko, P.; Murzin, V.; Oreshkin, V.; Smirnov, I.; Sosnov, D.; Sulimov, V.; Uvarov, L.; Vavilov, S.; Vorobyev, A.; Andreev, Yu.; Dermenev, A.; Gninenko, S.; Golubev, N.; Karneyeu, A.; Kirsanov, M.; Krasnikov, N.; Pashenkov, A.; Tlisov, D.; Toropin, A.; Epshteyn, V.; Gavrilov, V.; Lychkovskaya, N.; Popov, V.; Pozdnyakov, I.; Safronov, G.; Spiridonov, A.; Stepennov, A.; Toms, M.; Vlasov, E.; Zhokin, A.; Aushev, T.; Bylinkin, A.; Chistov, R.; Danilov, M.; Parygin, P.; Philippov, D.; Polikarpov, S.; Tarkovskii, E.; Andreev, V.; Azarkin, M.; Dremin, I.; Kirakosyan, M.; Terkulov, A.; Baskakov, A.; Belyaev, A.; Boos, E.; Bunichev, V.; Dubinin, M.; Dudko, L.; Ershov, A.; Gribushin, A.; Klyukhin, V.; Kodolova, O.; Lokhtin, I.; Miagkov, I.; Obraztsov, S.; Petrushanko, S.; Savrin, V.; Blinov, V.; Skovpen, Y.; Shtol, D.; Azhgirey, I.; Bayshev, I.; Bitioukov, S.; Elumakhov, D.; Godizov, A.; Kachanov, V.; Kalinin, A.; Konstantinov, D.; Mandrik, P.; Petrov, V.; Ryutin, R.; Sobol, A.; Troshin, S.; Tyurin, N.; Uzunian, A.; Volkov, A.; Adzic, P.; Cirkovic, P.; Devetak, D.; Dordevic, M.; Milosevic, J.; Rekovic, V.; Alcaraz Maestre, J.; Bachiller, I.; Barrio Luna, M.; Cerrada, M.; Colino, N.; De La Cruz, B.; Delgado Peris, A.; Escalante Del Valle, A.; Fernandez Bedoya, C.; Fernández Ramos, J. P.; Flix, J.; Fouz, M. C.; Gonzalez Lopez, O.; Goy Lopez, S.; Hernandez, J. M.; Josa, M. I.; Moran, D.; Pérez-Calero Yzquierdo, A.; Puerta Pelayo, J.; Quintario Olmeda, A.; Redondo, I.; Romero, L.; Soares, M. S.; Álvarez Fernández, A.; Albajar, C.; de Trocóniz, J. F.; Missiroli, M.; Cuevas, J.; Erice, C.; Fernandez Menendez, J.; Gonzalez Caballero, I.; González Fernández, J. R.; Palencia Cortezon, E.; Sanchez Cruz, S.; Vischia, P.; Vizan Garcia, J. M.; Cabrillo, I. J.; Calderon, A.; Chazin Quero, B.; Curras, E.; Duarte Campderros, J.; Fernandez, M.; Garcia-Ferrero, J.; Gomez, G.; Lopez Virto, A.; Marco, J.; Martinez Rivero, C.; Martinez Ruiz del Arbol, P.; Matorras, F.; Piedra Gomez, J.; Rodrigo, T.; Ruiz-Jimeno, A.; Scodellaro, L.; Trevisani, N.; Vila, I.; Vilar Cortabitarte, R.; Abbaneo, D.; Akgun, B.; Auffray, E.; Baillon, P.; Ball, A. H.; Barney, D.; Bendavid, J.; Bianco, M.; Bloch, P.; Bocci, A.; Botta, C.; Camporesi, T.; Castello, R.; Cepeda, M.; Cerminara, G.; Chapon, E.; Chen, Y.; d'Enterria, D.; Dabrowski, A.; Daponte, V.; David, A.; De Gruttola, M.; De Roeck, A.; Deelen, N.; Dobson, M.; du Pree, T.; Dünser, M.; Dupont, N.; Elliott-Peisert, A.; Everaerts, P.; Fallavollita, F.; Franzoni, G.; Fulcher, J.; Funk, W.; Gigi, D.; Gilbert, A.; Gill, K.; Glege, F.; Gulhan, D.; Harris, P.; Hegeman, J.; Innocente, V.; Jafari, A.; Janot, P.; Karacheban, O.; Kieseler, J.; Knünz, V.; Kornmayer, A.; Kortelainen, M. J.; Krammer, M.; Lange, C.; Lecoq, P.; Lourenço, C.; Lucchini, M. T.; Malgeri, L.; Mannelli, M.; Martelli, A.; Meijers, F.; Merlin, J. A.; Mersi, S.; Meschi, E.; Milenovic, P.; Moortgat, F.; Mulders, M.; Neugebauer, H.; Ngadiuba, J.; Orfanelli, S.; Orsini, L.; Pape, L.; Perez, E.; Peruzzi, M.; Petrilli, A.; Petrucciani, G.; Pfeiffer, A.; Pierini, M.; Rabady, D.; Racz, A.; Reis, T.; Rolandi, G.; Rovere, M.; Sakulin, H.; Schäfer, C.; Schwick, C.; Seidel, M.; Selvaggi, M.; Sharma, A.; Silva, P.; Sphicas, P.; Stakia, A.; Steggemann, J.; Stoye, M.; Tosi, M.; Treille, D.; Triossi, A.; Tsirou, A.; Veckalns, V.; Verweij, M.; Zeuner, W. D.; Bertl, W.; Caminada, L.; Deiters, K.; Erdmann, W.; Horisberger, R.; Ingram, Q.; Kaestli, H. C.; Kotlinski, D.; Langenegger, U.; Rohe, T.; Wiederkehr, S. A.; Backhaus, M.; Bäni, L.; Berger, P.; Bianchini, L.; Casal, B.; Dissertori, G.; Dittmar, M.; Donegà, M.; Dorfer, C.; Grab, C.; Heidegger, C.; Hits, D.; Hoss, J.; Kasieczka, G.; Klijnsma, T.; Lustermann, W.; Mangano, B.; Marionneau, M.; Meinhard, M. T.; Meister, D.; Micheli, F.; Musella, P.; Nessi-Tedaldi, F.; Pandolfi, F.; Pata, J.; Pauss, F.; Perrin, G.; Perrozzi, L.; Quittnat, M.; Reichmann, M.; Sanz Becerra, D. A.; Schönenberger, M.; Shchutska, L.; Tavolaro, V. R.; Theofilatos, K.; Vesterbacka Olsson, M. L.; Wallny, R.; Zhu, D. H.; Aarrestad, T. K.; Amsler, C.; Canelli, M. F.; De Cosa, A.; Del Burgo, R.; Donato, S.; Galloni, C.; Hreus, T.; Kilminster, B.; Pinna, D.; Rauco, G.; Robmann, P.; Salerno, D.; Schweiger, K.; Seitz, C.; Takahashi, Y.; Zucchetta, A.; Candelise, V.; Chang, Y. H.; Cheng, K. y.; Doan, T. H.; Jain, Sh.; Khurana, R.; Kuo, C. M.; Lin, W.; Pozdnyakov, A.; Yu, S. S.; Kumar, Arun; Chang, P.; Chao, Y.; Chen, K. F.; Chen, P. H.; Fiori, F.; Hou, W.-S.; Hsiung, Y.; Liu, Y. F.; Lu, R.-S.; Paganis, E.; Psallidas, A.; Steen, A.; Tsai, J. f.; Asavapibhop, B.; Kovitanggoon, K.; Singh, G.; Srimanobhas, N.; Bakirci, M. N.; Bat, A.; Boran, F.; Cerci, S.; Damarseckin, S.; Demiroglu, Z. S.; Dozen, C.; Eskut, E.; Girgis, S.; Gokbulut, G.; Guler, Y.; Hos, I.; Kangal, E. E.; Kara, O.; Kiminsu, U.; Oglakci, M.; Onengut, G.; Ozdemir, K.; Ozturk, S.; Polatoz, A.; Tok, U. G.; Turkcapar, S.; Zorbakir, I. S.; Zorbilmez, C.; Bilin, B.; Karapinar, G.; Ocalan, K.; Yalvac, M.; Zeyrek, M.; Gülmez, E.; Kaya, M.; Kaya, O.; Tekten, S.; Yetkin, E. A.; Agaras, M. N.; Atay, S.; Cakir, A.; Cankocak, K.; Köseoglu, I.; Grynyov, B.; Levchuk, L.; Ball, F.; Beck, L.; Brooke, J. J.; Burns, D.; Clement, E.; Cussans, D.; Davignon, O.; Flacher, H.; Goldstein, J.; Heath, G. P.; Heath, H. F.; Kreczko, L.; Newbold, D. M.; Paramesvaran, S.; Sakuma, T.; Seif El Nasr-storey, S.; Smith, D.; Smith, V. J.; Bell, K. W.; Belyaev, A.; Brew, C.; Brown, R. M.; Calligaris, L.; Cieri, D.; Cockerill, D. J. A.; Coughlan, J. A.; Harder, K.; Harper, S.; Linacre, J.; Olaiya, E.; Petyt, D.; Shepherd-Themistocleous, C. H.; Thea, A.; Tomalin, I. R.; Williams, T.; Auzinger, G.; Bainbridge, R.; Borg, J.; Breeze, S.; Buchmuller, O.; Bundock, A.; Casasso, S.; Citron, M.; Colling, D.; Corpe, L.; Dauncey, P.; Davies, G.; De Wit, A.; Della Negra, M.; Di Maria, R.; Elwood, A.; Haddad, Y.; Hall, G.; Iles, G.; James, T.; Lane, R.; Laner, C.; Lyons, L.; Magnan, A.-M.; Malik, S.; Mastrolorenzo, L.; Matsushita, T.; Nash, J.; Nikitenko, A.; Palladino, V.; Pesaresi, M.; Raymond, D. M.; Richards, A.; Rose, A.; Scott, E.; Seez, C.; Shtipliyski, A.; Summers, S.; Tapper, A.; Uchida, K.; Vazquez Acosta, M.; Virdee, T.; Wardle, N.; Winterbottom, D.; Wright, J.; Zenz, S. C.; Cole, J. E.; Hobson, P. R.; Khan, A.; Kyberd, P.; Reid, I. D.; Teodorescu, L.; Zahid, S.; Borzou, A.; Call, K.; Dittmann, J.; Hatakeyama, K.; Liu, H.; Pastika, N.; Smith, C.; Bartek, R.; Dominguez, A.; Buccilli, A.; Cooper, S. I.; Henderson, C.; Rumerio, P.; West, C.; Arcaro, D.; Avetisyan, A.; Bose, T.; Gastler, D.; Rankin, D.; Richardson, C.; Rohlf, J.; Sulak, L.; Zou, D.; Benelli, G.; Cutts, D.; Garabedian, A.; Hadley, M.; Hakala, J.; Heintz, U.; Hogan, J. M.; Kwok, K. H. M.; Laird, E.; Landsberg, G.; Lee, J.; Mao, Z.; Narain, M.; Pazzini, J.; Piperov, S.; Sagir, S.; Syarif, R.; Yu, D.; Band, R.; Brainerd, C.; Breedon, R.; Burns, D.; Calderon De La Barca Sanchez, M.; Chertok, M.; Conway, J.; Conway, R.; Cox, P. T.; Erbacher, R.; Flores, C.; Funk, G.; Ko, W.; Lander, R.; Mclean, C.; Mulhearn, M.; Pellett, D.; Pilot, J.; Shalhout, S.; Shi, M.; Smith, J.; Stolp, D.; Tos, K.; Tripathi, M.; Wang, Z.; Bachtis, M.; Bravo, C.; Cousins, R.; Dasgupta, A.; Florent, A.; Hauser, J.; Ignatenko, M.; Mccoll, N.; Regnard, S.; Saltzberg, D.; Schnaible, C.; Valuev, V.; Bouvier, E.; Burt, K.; Clare, R.; Ellison, J.; Gary, J. W.; Ghiasi Shirazi, S. M. A.; Hanson, G.; Heilman, J.; Karapostoli, G.; Kennedy, E.; Lacroix, F.; Long, O. R.; Olmedo Negrete, M.; Paneva, M. I.; Si, W.; Wang, L.; Wei, H.; Wimpenny, S.; Yates, B. R.; Branson, J. G.; Cittolin, S.; Derdzinski, M.; Gerosa, R.; Gilbert, D.; Hashemi, B.; Holzner, A.; Klein, D.; Kole, G.; Krutelyov, V.; Letts, J.; Macneill, I.; Masciovecchio, M.; Olivito, D.; Padhi, S.; Pieri, M.; Sani, M.; Sharma, V.; Simon, S.; Tadel, M.; Vartak, A.; Wasserbaech, S.; Wood, J.; Würthwein, F.; Yagil, A.; Zevi Della Porta, G.; Amin, N.; Bhandari, R.; Bradmiller-Feld, J.; Campagnari, C.; Dishaw, A.; Dutta, V.; Franco Sevilla, M.; Golf, F.; Gouskos, L.; Heller, R.; Incandela, J.; Ovcharova, A.; Qu, H.; Richman, J.; Stuart, D.; Suarez, I.; Yoo, J.; Anderson, D.; Bornheim, A.; Lawhorn, J. M.; Newman, H. B.; Nguyen, T.; Pena, C.; Spiropulu, M.; Vlimant, J. R.; Xie, S.; Zhang, Z.; Zhu, R. Y.; Andrews, M. B.; Ferguson, T.; Mudholkar, T.; Paulini, M.; Russ, J.; Sun, M.; Vogel, H.; Vorobiev, I.; Weinberg, M.; Cumalat, J. P.; Ford, W. T.; Jensen, F.; Johnson, A.; Krohn, M.; Leontsinis, S.; Mulholland, T.; Stenson, K.; Wagner, S. R.; Alexander, J.; Chaves, J.; Chu, J.; Dittmer, S.; Mcdermott, K.; Mirman, N.; Patterson, J. R.; Quach, D.; Rinkevicius, A.; Ryd, A.; Skinnari, L.; Soffi, L.; Tan, S. M.; Tao, Z.; Thom, J.; Tucker, J.; Wittich, P.; Zientek, M.; Abdullin, S.; Albrow, M.; Alyari, M.; Apollinari, G.; Apresyan, A.; Apyan, A.; Banerjee, S.; Bauerdick, L. A. T.; Beretvas, A.; Berryhill, J.; Bhat, P. C.; Bolla, G.; Burkett, K.; Butler, J. N.; Canepa, A.; Cerati, G. B.; Cheung, H. W. K.; Chlebana, F.; Cremonesi, M.; Duarte, J.; Elvira, V. D.; Freeman, J.; Gecse, Z.; Gottschalk, E.; Gray, L.; Green, D.; Grünendahl, S.; Gutsche, O.; Harris, R. M.; Hasegawa, S.; Hirschauer, J.; Hu, Z.; Jayatilaka, B.; Jindariani, S.; Johnson, M.; Joshi, U.; Klima, B.; Kreis, B.; Lammel, S.; Lincoln, D.; Lipton, R.; Liu, M.; Liu, T.; Lopes De Sá, R.; Lykken, J.; Maeshima, K.; Magini, N.; Marraffino, J. M.; Mason, D.; McBride, P.; Merkel, P.; Mrenna, S.; Nahn, S.; O'Dell, V.; Pedro, K.; Prokofyev, O.; Rakness, G.; Ristori, L.; Schneider, B.; Sexton-Kennedy, E.; Soha, A.; Spalding, W. J.; Spiegel, L.; Stoynev, S.; Strait, J.; Strobbe, N.; Taylor, L.; Tkaczyk, S.; Tran, N. V.; Uplegger, L.; Vaandering, E. W.; Vernieri, C.; Verzocchi, M.; Vidal, R.; Wang, M.; Weber, H. A.; Whitbeck, A.; Acosta, D.; Avery, P.; Bortignon, P.; Bourilkov, D.; Brinkerhoff, A.; Carnes, A.; Carver, M.; Curry, D.; Field, R. D.; Furic, I. K.; Gleyzer, S. V.; Joshi, B. M.; Konigsberg, J.; Korytov, A.; Kotov, K.; Ma, P.; Matchev, K.; Mei, H.; Mitselmakher, G.; Shi, K.; Sperka, D.; Terentyev, N.; Thomas, L.; Wang, J.; Wang, S.; Yelton, J.; Joshi, Y. R.; Linn, S.; Markowitz, P.; Rodriguez, J. L.; Ackert, A.; Adams, T.; Askew, A.; Hagopian, S.; Hagopian, V.; Johnson, K. F.; Kolberg, T.; Martinez, G.; Perry, T.; Prosper, H.; Saha, A.; Santra, A.; Sharma, V.; Yohay, R.; Baarmand, M. M.; Bhopatkar, V.; Colafranceschi, S.; Hohlmann, M.; Noonan, D.; Roy, T.; Yumiceva, F.; Adams, M. R.; Apanasevich, L.; Berry, D.; Betts, R. R.; Cavanaugh, R.; Chen, X.; Evdokimov, O.; Gerber, C. E.; Hangal, D. A.; Hofman, D. J.; Jung, K.; Kamin, J.; Sandoval Gonzalez, I. D.; Tonjes, M. B.; Trauger, H.; Varelas, N.; Wang, H.; Wu, Z.; Zhang, J.; Bilki, B.; Clarida, W.; Dilsiz, K.; Durgut, S.; Gandrajula, R. P.; Haytmyradov, M.; Khristenko, V.; Merlo, J.-P.; Mermerkaya, H.; Mestvirishvili, A.; Moeller, A.; Nachtman, J.; Ogul, H.; Onel, Y.; Ozok, F.; Penzo, A.; Snyder, C.; Tiras, E.; Wetzel, J.; Yi, K.; Blumenfeld, B.; Cocoros, A.; Eminizer, N.; Fehling, D.; Feng, L.; Gritsan, A. V.; Maksimovic, P.; Roskes, J.; Sarica, U.; Swartz, M.; Xiao, M.; You, C.; Al-bataineh, A.; Baringer, P.; Bean, A.; Boren, S.; Bowen, J.; Castle, J.; Khalil, S.; Kropivnitskaya, A.; Majumder, D.; Mcbrayer, W.; Murray, M.; Royon, C.; Sanders, S.; Schmitz, E.; Tapia Takaki, J. D.; Wang, Q.; Ivanov, A.; Kaadze, K.; Maravin, Y.; Mohammadi, A.; Saini, L. K.; Skhirtladze, N.; Toda, S.; Rebassoo, F.; Wright, D.; Anelli, C.; Baden, A.; Baron, O.; Belloni, A.; Eno, S. C.; Feng, Y.; Ferraioli, C.; Hadley, N. J.; Jabeen, S.; Jeng, G. Y.; Kellogg, R. G.; Kunkle, J.; Mignerey, A. C.; Ricci-Tam, F.; Shin, Y. H.; Skuja, A.; Tonwar, S. C.; Abercrombie, D.; Allen, B.; Azzolini, V.; Barbieri, R.; Baty, A.; Bi, R.; Brandt, S.; Busza, W.; Cali, I. A.; D'Alfonso, M.; Demiragli, Z.; Gomez Ceballos, G.; Goncharov, M.; Hsu, D.; Hu, M.; Iiyama, Y.; Innocenti, G. M.; Klute, M.; Kovalskyi, D.; Lai, Y. S.; Lee, Y.-J.; Levin, A.; Luckey, P. D.; Maier, B.; Marini, A. C.; Mcginn, C.; Mironov, C.; Narayanan, S.; Niu, X.; Paus, C.; Roland, C.; Roland, G.; Salfeld-Nebgen, J.; Stephans, G. S. F.; Tatar, K.; Velicanu, D.; Wang, J.; Wang, T. W.; Wyslouch, B.; Benvenuti, A. C.; Chatterjee, R. M.; Evans, A.; Hansen, P.; Hiltbrand, J.; Kalafut, S.; Kubota, Y.; Lesko, Z.; Mans, J.; Nourbakhsh, S.; Ruckstuhl, N.; Rusack, R.; Turkewitz, J.; Wadud, M. A.; Acosta, J. G.; Oliveros, S.; Avdeeva, E.; Bloom, K.; Claes, D. R.; Fangmeier, C.; Gonzalez Suarez, R.; Kamalieddin, R.; Kravchenko, I.; Monroy, J.; Siado, J. E.; Snow, G. R.; Stieger, B.; Dolen, J.; Godshalk, A.; Harrington, C.; Iashvili, I.; Nguyen, D.; Parker, A.; Rappoccio, S.; Roozbahani, B.; Alverson, G.; Barberis, E.; Freer, C.; Hortiangtham, A.; Massironi, A.; Morse, D. M.; Orimoto, T.; Teixeira De Lima, R.; Trocino, D.; Wamorkar, T.; Wang, B.; Wisecarver, A.; Wood, D.; Bhattacharya, S.; Charaf, O.; Hahn, K. A.; Mucia, N.; Odell, N.; Schmitt, M. H.; Sung, K.; Trovato, M.; Velasco, M.; Bucci, R.; Dev, N.; Hildreth, M.; Hurtado Anampa, K.; Jessop, C.; Karmgard, D. J.; Kellams, N.; Lannon, K.; Li, W.; Loukas, N.; Marinelli, N.; Meng, F.; Mueller, C.; Musienko, Y.; Planer, M.; Reinsvold, A.; Ruchti, R.; Siddireddy, P.; Smith, G.; Taroni, S.; Wayne, M.; Wightman, A.; Wolf, M.; Woodard, A.; Alimena, J.; Antonelli, L.; Bylsma, B.; Durkin, L. S.; Flowers, S.; Francis, B.; Hart, A.; Hill, C.; Ji, W.; Liu, B.; Luo, W.; Winer, B. L.; Wulsin, H. W.; Cooperstein, S.; Driga, O.; Elmer, P.; Hardenbrook, J.; Hebda, P.; Higginbotham, S.; Kalogeropoulos, A.; Lange, D.; Luo, J.; Marlow, D.; Mei, K.; Ojalvo, I.; Olsen, J.; Palmer, C.; Piroué, P.; Stickland, D.; Tully, C.; Malik, S.; Norberg, S.; Barker, A.; Barnes, V. E.; Das, S.; Folgueras, S.; Gutay, L.; Jha, M. K.; Jones, M.; Jung, A. W.; Khatiwada, A.; Miller, D. H.; Neumeister, N.; Peng, C. C.; Qiu, H.; Schulte, J. F.; Sun, J.; Wang, F.; Xiao, R.; Xie, W.; Cheng, T.; Parashar, N.; Stupak, J.; Chen, Z.; Ecklund, K. M.; Freed, S.; Geurts, F. J. M.; Guilbaud, M.; Kilpatrick, M.; Li, W.; Michlin, B.; Padley, B. P.; Roberts, J.; Rorie, J.; Shi, W.; Tu, Z.; Zabel, J.; Zhang, A.; Bodek, A.; de Barbaro, P.; Demina, R.; Duh, Y. t.; Ferbel, T.; Galanti, M.; Garcia-Bellido, A.; Han, J.; Hindrichs, O.; Khukhunaishvili, A.; Lo, K. H.; Tan, P.; Verzetti, M.; Ciesielski, R.; Goulianos, K.; Mesropian, C.; Agapitos, A.; Chou, J. P.; Gershtein, Y.; Gómez Espinosa, T. A.; Halkiadakis, E.; Heindl, M.; Hughes, E.; Kaplan, S.; Kunnawalkam Elayavalli, R.; Kyriacou, S.; Lath, A.; Montalvo, R.; Nash, K.; Osherson, M.; Saka, H.; Salur, S.; Schnetzer, S.; Sheffield, D.; Somalwar, S.; Stone, R.; Thomas, S.; Thomassen, P.; Walker, M.; Delannoy, A. G.; Foerster, M.; Heideman, J.; Riley, G.; Rose, K.; Spanier, S.; Thapa, K.; Bouhali, O.; Castaneda Hernandez, A.; Celik, A.; Dalchenko, M.; De Mattia, M.; Delgado, A.; Dildick, S.; Eusebi, R.; Gilmore, J.; Huang, T.; Kamon, T.; Mueller, R.; Pakhotin, Y.; Patel, R.; Perloff, A.; Perniè, L.; Rathjens, D.; Safonov, A.; Tatarinov, A.; Ulmer, K. A.; Akchurin, N.; Damgov, J.; De Guio, F.; Dudero, P. R.; Faulkner, J.; Gurpinar, E.; Kunori, S.; Lamichhane, K.; Lee, S. W.; Libeiro, T.; Mengke, T.; Muthumuni, S.; Peltola, T.; Undleeb, S.; Volobouev, I.; Wang, Z.; Greene, S.; Gurrola, A.; Janjam, R.; Johns, W.; Maguire, C.; Melo, A.; Ni, H.; Padeken, K.; Sheldon, P.; Tuo, S.; Velkovska, J.; Xu, Q.; Arenton, M. W.; Barria, P.; Cox, B.; Hirosky, R.; Joyce, M.; Ledovskoy, A.; Li, H.; Neu, C.; Sinthuprasith, T.; Wang, Y.; Wolfe, E.; Xia, F.; Harr, R.; Karchin, P. E.; Poudyal, N.; Sturdy, J.; Thapa, P.; Zaleski, S.; Brodski, M.; Buchanan, J.; Caillol, C.; Dasu, S.; Dodd, L.; Duric, S.; Gomber, B.; Grothe, M.; Herndon, M.; Hervé, A.; Hussain, U.; Klabbers, P.; Lanaro, A.; Levine, A.; Long, K.; Loveless, R.; Ruggles, T.; Savin, A.; Smith, N.; Smith, W. H.; Taylor, D.; Woods, N.; CMS Collaboration

2018-06-01

A search is presented for excited quarks of light and heavy flavor that decay to γ +jet final states. The analysis is based on data corresponding to an integrated luminosity of 35.9fb-1 collected by the CMS experiment in proton-proton collisions at √{ s } = 13TeV at the LHC. A signal would appear as a resonant contribution to the invariant mass spectrum of the γ +jet system, above the background expected from standard model processes. No resonant excess is found, and upper limits are set on the product of the excited quark cross section and its branching fraction as a function of its mass. These are the most stringent limits to date in the γ + jet final state, and exclude excited light quarks with masses below 5.5 TeV and excited b quarks with masses below 1.8 TeV, assuming standard model like coupling strengths.

Efficient Multiphoton Generation in Waveguide Quantum Electrodynamics.

PubMed

González-Tudela, A; Paulisch, V; Kimble, H J; Cirac, J I

2017-05-26

Engineering quantum states of light is at the basis of many quantum technologies such as quantum cryptography, teleportation, or metrology among others. Though, single photons can be generated in many scenarios, the efficient and reliable generation of complex single-mode multiphoton states is still a long-standing goal in the field, as current methods either suffer from low fidelities or small probabilities. Here we discuss several protocols which harness the strong and long-range atomic interactions induced by waveguide QED to efficiently load excitations in a collection of atoms, which can then be triggered to produce the desired multiphoton state. In order to boost the success probability and fidelity of each excitation process, atoms are used to both generate the excitations in the rest, as well as to herald the successful generation. Furthermore, to overcome the exponential scaling of the probability of success with the number of excitations, we design a protocol to merge excitations that are present in different internal atomic levels with a polynomial scaling.

Multicomponent Time-Dependent Density Functional Theory: Proton and Electron Excitation Energies.

PubMed

Yang, Yang; Culpitt, Tanner; Hammes-Schiffer, Sharon

2018-04-05

The quantum mechanical treatment of both electrons and protons in the calculation of excited state properties is critical for describing nonadiabatic processes such as photoinduced proton-coupled electron transfer. Multicomponent density functional theory enables the consistent quantum mechanical treatment of more than one type of particle and has been implemented previously for studying ground state molecular properties within the nuclear-electronic orbital (NEO) framework, where all electrons and specified protons are treated quantum mechanically. To enable the study of excited state molecular properties, herein the linear response multicomponent time-dependent density functional theory (TDDFT) is derived and implemented within the NEO framework. Initial applications to FHF - and HCN illustrate that NEO-TDDFT provides accurate proton and electron excitation energies within a single calculation. As its computational cost is similar to that of conventional electronic TDDFT, the NEO-TDDFT approach is promising for diverse applications, particularly nonadiabatic proton transfer reactions, which may exhibit mixed electron-proton vibronic excitations.

Photoisomerization and photoionization of the photoactive yellow protein chromophore in solution.

PubMed

Larsen, Delmar S; Vengris, Mikas; van Stokkum, Ivo H M; van der Horst, Michael A; de Weerd, Frank L; Hellingwerf, Klaas J; van Grondelle, Rienk

2004-04-01

Dispersed pump-dump-probe spectroscopy has the ability to characterize and identify the underlying ultrafast dynamical processes in complicated chemical and biological systems. This technique builds on traditional pump-probe techniques by exploring both ground- and excited-state dynamics and characterizing the connectivity between constituent transient states. We have used the dispersed pump-dump-probe technique to investigate the ground-state dynamics and competing excited-state processes in the excitation-induced ultrafast dynamics of thiomethyl p-coumaric acid, a model chromophore for the photoreceptor photoactive yellow protein. Our results demonstrate the parallel formation of two relaxation pathways (with multiple transient states) that jointly lead to two different types of photochemistry: cis-trans isomerization and detachment of a hydrated electron. The relative transition rates and quantum yields of both pathways have been determined. We find that the relaxation of the photoexcited chromophores involves multiple, transient ground-state intermediates and the chromophore in solution does not generate persistent photoisomerized products, but instead undergoes photoionization resulting in the generation of detached electrons and radicals. These results are of great value in interpreting the more complex dynamical changes in the optical properties of the photoactive yellow protein.

Photoisomerization and Photoionization of the Photoactive Yellow Protein Chromophore in Solution

PubMed Central

Larsen, Delmar S.; Vengris, Mikas; van Stokkum, Ivo H. M.; van der Horst, Michael A.; de Weerd, Frank L.; Hellingwerf, Klaas J.; van Grondelle, Rienk

2004-01-01

Dispersed pump-dump-probe spectroscopy has the ability to characterize and identify the underlying ultrafast dynamical processes in complicated chemical and biological systems. This technique builds on traditional pump-probe techniques by exploring both ground- and excited-state dynamics and characterizing the connectivity between constituent transient states. We have used the dispersed pump-dump-probe technique to investigate the ground-state dynamics and competing excited-state processes in the excitation-induced ultrafast dynamics of thiomethyl p-coumaric acid, a model chromophore for the photoreceptor photoactive yellow protein. Our results demonstrate the parallel formation of two relaxation pathways (with multiple transient states) that jointly lead to two different types of photochemistry: cis-trans isomerization and detachment of a hydrated electron. The relative transition rates and quantum yields of both pathways have been determined. We find that the relaxation of the photoexcited chromophores involves multiple, transient ground-state intermediates and the chromophore in solution does not generate persistent photoisomerized products, but instead undergoes photoionization resulting in the generation of detached electrons and radicals. These results are of great value in interpreting the more complex dynamical changes in the optical properties of the photoactive yellow protein. PMID:15041690

Vibrational motions associated with primary processes in bacteriorhodopsin studied by coherent infrared emission spectroscopy.

PubMed

Groma, Géza I; Colonna, Anne; Martin, Jean-Louis; Vos, Marten H

2011-03-16

The primary energetic processes driving the functional proton pump of bacteriorhodopsin take place in the form of complex molecular dynamic events after excitation of the retinal chromophore into the Franck-Condon state. These early events include a strong electronic polarization, skeletal stretching, and all-trans-to-13-cis isomerization upon formation of the J intermediate. The effectiveness of the photoreaction is ensured by a conical intersection between the electronic excited and ground states, providing highly nonadiabatic coupling to nuclear motions. Here, we study real-time vibrational coherences associated with these motions by analyzing light-induced infrared emission from oriented purple membranes in the 750-1400 cm(-)(1) region. The experimental technique applied is based on second-order femtosecond difference frequency generation on macroscopically ordered samples that also yield information on phase and direction of the underlying motions. Concerted use of several analysis methods resulted in the isolation and characterization of seven different vibrational modes, assigned as C-C stretches, out-of-plane methyl rocks, and hydrogen out-of-plane wags, whereas no in-plane H rock was found. Based on their lifetimes and several other criteria, we deduce that the majority of the observed modes take place on the potential energy surface of the excited electronic state. In particular, the direction sensitivity provides experimental evidence for large intermediate distortions of the retinal plane during the excited-state isomerization process. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

In-vivo multi-nonlinear optical imaging of a living cell using a supercontinuum light source generated from a photonic crystal fiber

NASA Astrophysics Data System (ADS)

Kano, Hideaki; Hamaguchi, Hiro-O.

2006-04-01

A supercontinuum light source generated with a femtosecond Ti:Sapphire oscillator has been used to obtain both vibrational and two-photon excitation fluorescence (TPEF) images of a living cell simultaneously at different wavelengths. Owing to an ultrabroadband spectral profile of the supercontinuum, multiple vibrational resonances have been detected through coherent anti-Stokes Raman scattering (CARS) process. In addition to the multiplex CARS process, multiple electronic states can be excited due to the broadband electronic two-photon excitation using the supercontinuum, giving rise to a two-photon excitation fluorescence (TPEF) signal. Using a living yeast cell whose nucleus is labeled by green fluorescent protein (GFP), we have succeeded in visualizing organelles such as mitochondria, septum, and nucleus through the CARS and the TPEF processes. The supercontinuum enables us to perform unique multi-nonlinear optical imaging through two different nonlinear optical processes.

The electronically excited states of LH2 complexes from Rhodopseudomonas acidophila strain 10050 studied by time-resolved spectroscopy and dynamic Monte Carlo simulations. II. Homo-arrays of LH2 complexes reconstituted into phospholipid model membranes.

PubMed

Pflock, Tobias J; Oellerich, Silke; Krapf, Lisa; Southall, June; Cogdell, Richard J; Ullmann, G Matthias; Köhler, Jürgen

2011-07-21

We performed time-resolved spectroscopy on homoarrays of LH2 complexes from the photosynthetic purple bacterium Rhodopseudomonas acidophila. Variations of the fluorescence transients were monitored as a function of the excitation fluence and the repetition rate of the excitation. These parameters are directly related to the excitation density within the array and to the number of LH2 complexes that still carry a triplet state prior to the next excitation. Comparison of the experimental observations with results from dynamic Monte Carlo simulations for a model cluster of LH2 complexes yields qualitative agreement without the need for any free parameter and reveals the mutual relationship between energy transfer and annihilation processes.

Ultrafast Nonradiative Decay and Excitation Energy Transfer by Carotenoids in Photosynthetic Light-Harvesting Proteins

NASA Astrophysics Data System (ADS)

Ghosh, Soumen

This dissertation investigates the photophysical and structural dynamics that allow carotenoids to serve as efficient excitation energy transfer donor to chlorophyll acceptors in photosynthetic light harvesting proteins. Femtosecond transient grating spectroscopy with optical heterodyne detection has been employed to follow the nonradiative decay pathways of carotenoids and excitation energy transfer to chlorophylls. It was found that the optically prepared S2 (11Bu+) state of beta-carotene decays in 12 fs fs to populate an intermediate electronic state, Sx, which then decays nonradiatively to the S 1 state. The ultrafast rise of the dispersion component of the heterodyne transient grating signal reports the formation of Sx intermediate since the rise of the dispersion signal is controlled by the loss of stimulated emission from the S2 state. These findings were extended to studies of peridinin, a carbonyl substituted carotenoid that serves as a photosynthetic light-harvesting chromophore in dinoflagellates. Numerical simulations using nonlinear response formalism and the multimode Brownian oscillator model assigned the Sx intermediate to a torsionally distorted structure evolving on the S2 potential surface. The decay of the Sx state is promoted by large amplitude out-of-plane torsional motions and is significantly retarded by solvent friction owing to the development of an intramolecular charge transfer character in peridinin. The slowing of the nonradiative decay allows the Sx state to transfer significant portion of the excitation energy to chlorophyll a acceptors in the peridinin-chlorophyll a protein. The results of heterodyne transient grating study on peridinin-chlorophyll a protein suggests two distinct energy transfer channels from peridinin to chlorophyll a: a 30 fs process involving quantum coherence and delocalized peridinin-Chl states and an incoherent, 2.5 ps process involving the distorted S2 state of peridinin. The torsional evolution on the S2 state is accompanied by the formation of an ICT character and dynamic exciton localization, which controls the mechanism of excitation energy transfer to chlorophyll a acceptors in the peridinin-chlorophyll a protein.

Studies of Ionospheric Processes in the Atmosphere and the Laboratory

DTIC Science & Technology

2006-06-01

relevance to HAARP observations, and on vibrationally-excited levels of the O2 ground state [2] and the b1Σ +g excited state [3]. Synergy with the...UT [20] 29.4 (33) 260 0.94 .077 3/24/95 1737 UT 43.4 (44) 278 0.54 0.53 HAARP 62N, 145W 3/20/04 0617 UT [21] 54 (44) 290 0.33 0.54... HAARP 0.62 5.0E8 1.09E8 4.6 Studies of Ionospheric Processes in the Atmosphere and the Laboratory RTO-MP-IST-056 1 - 9 UNCLASSIFIED/UNLIMITED

An efficient implementation of semiempirical quantum-chemical orthogonalization-corrected methods for excited-state dynamics

NASA Astrophysics Data System (ADS)

Liu, Jie; Thiel, Walter

2018-04-01

We present an efficient implementation of configuration interaction with single excitations (CIS) for semiempirical orthogonalization-corrected OMx methods and standard modified neglect of diatomic overlap (MNDO)-type methods for the computation of vertical excitation energies as well as analytical gradients and nonadiabatic couplings. This CIS implementation is combined with Tully's fewest switches algorithm to enable surface hopping simulations of excited-state nonadiabatic dynamics. We introduce an accurate and efficient expression for the semiempirical evaluation of nonadiabatic couplings, which offers a significant speedup for medium-size molecules and is suitable for use in long nonadiabatic dynamics runs. As a pilot application, the semiempirical CIS implementation is employed to investigate ultrafast energy transfer processes in a phenylene ethynylene dendrimer model.

An efficient implementation of semiempirical quantum-chemical orthogonalization-corrected methods for excited-state dynamics.

PubMed

Liu, Jie; Thiel, Walter

2018-04-21

We present an efficient implementation of configuration interaction with single excitations (CIS) for semiempirical orthogonalization-corrected OMx methods and standard modified neglect of diatomic overlap (MNDO)-type methods for the computation of vertical excitation energies as well as analytical gradients and nonadiabatic couplings. This CIS implementation is combined with Tully's fewest switches algorithm to enable surface hopping simulations of excited-state nonadiabatic dynamics. We introduce an accurate and efficient expression for the semiempirical evaluation of nonadiabatic couplings, which offers a significant speedup for medium-size molecules and is suitable for use in long nonadiabatic dynamics runs. As a pilot application, the semiempirical CIS implementation is employed to investigate ultrafast energy transfer processes in a phenylene ethynylene dendrimer model.

Electron Attachment to Radicals and Highly-Excited States in Laser-Irradiated CCl_2F_2*

NASA Astrophysics Data System (ADS)

Pinnaduwage, Lal; Datskos, Panos

1997-10-01

We have measured electron attachment rate constants for two species produced via ArF-excimer- laser irradiated CF_2Cl_2, i.e., the CF_2Cl radical and the highly-excited electronically-excited states of CF_2Cl_2. These measurements show that while electron attachment to the fragment radical has a rate constants about an order of magnitude higher compared to the ground states of CF_2Cl_2, electron attachment to the highly- excited states have many orders of magnitude larger rate constants. To our knowledge, only one other electron attachment measurement has been conducted on molecular fragments up to now. Implications of these measurements for plasma processing discharges will be discussed. Research supported by the National Science Foundation under contract No. ECS-9626217 with the University of Tennessee, Knoxville. The Oak Ridge National Laboratory is managed by Lockheed Martin Energy Research Corp. for the U. S. DOE under contract No. DE-AC05- 96OR22464.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Generation of Antibunched Light by Excited Molecules in a Microcavity Trap

NASA Technical Reports Server (NTRS)

DeMartini, F.; DiGiuseppe, G.; Marrocco, M.

1996-01-01

The active microcavity is adopted as an efficient source of non-classical light. By this device, excited by a mode-locked laser at a rate of 100 MHz, single-photons are generated over a single field mode with a nonclassical sub-poissonian distribution. The process of adiabatic recycling within a multi-step Franck-Condon molecular optical-pumping mechanism, characterized in our case by a quantum efficiency very close to one, implies a pump self-regularization process leading to a striking n-squeezing effect. By a replication of the basic single-atom excitation process a beam of quantum photon (Fock states) can be created. The new process represents a significant advance in the modern fields of basic quantum-mechanical investigation, quantum communication and quantum cryptography.

Transport coefficients and heat fluxes in non-equilibrium high-temperature flows with electronic excitation

NASA Astrophysics Data System (ADS)

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

2017-02-01

The influence of electronic excitation on transport processes in non-equilibrium high-temperature ionized mixture flows is studied. Two five-component mixtures, N 2 / N2 + / N / N + / e - and O 2 / O2 + / O / O + / e - , are considered taking into account the electronic degrees of freedom for atomic species as well as the rotational-vibrational-electronic degrees of freedom for molecular species, both neutral and ionized. Using the modified Chapman-Enskog method, the transport coefficients (thermal conductivity, shear viscosity and bulk viscosity, diffusion and thermal diffusion) are calculated in the temperature range 500-50 000 K. Thermal conductivity and bulk viscosity coefficients are strongly affected by electronic states, especially for neutral atomic species. Shear viscosity, diffusion, and thermal diffusion coefficients are not sensible to electronic excitation if the size of excited states is assumed to be constant. The limits of applicability for the Stokes relation are discussed; at high temperatures, this relation is violated not only for molecular species but also for electronically excited atomic gases. Two test cases of strongly non-equilibrium flows behind plane shock waves corresponding to the spacecraft re-entry (Hermes and Fire II) are simulated numerically. Fluid-dynamic variables and heat fluxes are evaluated in gases with electronic excitation. In inviscid flows without chemical-radiative coupling, the flow-field is weakly affected by electronic states; however, in viscous flows, their influence can be more important, in particular, on the convective heat flux. The contribution of different dissipative processes to the heat transfer is evaluated as well as the effect of reaction rate coefficients. The competition of diffusion and heat conduction processes reduces the overall effect of electronic excitation on the convective heating, especially for the Fire II test case. It is shown that reliable models of chemical reaction rates are of great importance for accurate predictions of the fluid dynamic variables and heat fluxes.

Lifetime-vibrational interference effects in resonantly excited x-ray emission spectra of CO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skytt, P.; Glans, P.; Gunnelin, K.

1997-04-01

The parity selection rule for resonant X-ray emission as demonstrated for O{sub 2} and N{sub 2} can be seen as an effect of interference between coherently excited degenerate localized core states. One system where the core state degeneracy is not exact but somewhat lifted was previously studied at ALS, namely the resonant X-ray emission of amino-substituted benzene (aniline). It was shown that the X-ray fluorescence spectrum resulting from excitation of the C1s at the site of the {open_quotes}aminocarbon{close_quotes} could be described in a picture separating the excitation and the emission processes, whereas the spectrum corresponding to the quasi-degenerate carbons couldmore » not. Thus, in this case it was necessary to take interference effects between the quasi-degenerate intermediate core excited states into account in order to obtain agreement between calculations and experiment. The different vibrational levels of core excited states in molecules have energy splittings which are of the same order of magnitude as the natural lifetime broadening of core excitations in the soft X-ray range. Therefore, lifetime-vibrational interference effects are likely to appear and influence the band shapes in resonant X-ray emission spectra. Lifetime-vibrational interference has been studied in non-resonant X-ray emission, and in Auger spectra. In this report the authors discuss results of selectively excited soft X-ray fluorescence spectra of molecules, where they focus on lifetime-interference effects appearing in the band shapes.« less

Electron-driven excitation of O 2 under night-time auroral conditions: Excited state densities and band emissions

NASA Astrophysics Data System (ADS)

Jones, D. B.; Campbell, L.; Bottema, M. J.; Teubner, P. J. O.; Cartwright, D. C.; Newell, W. R.; Brunger, M. J.

2006-01-01

Electron impact excitation of vibrational levels in the ground electronic state and seven excited electronic states in O 2 have been simulated for an International Brightness Coefficient-Category 2+ (IBC II+) night-time aurora, in order to predict O 2 excited state number densities and volume emission rates (VERs). These number densities and VERs are determined as a function of altitude (in the range 80-350 km) in the present study. Recent electron impact excitation cross-sections for O 2 were combined with appropriate altitude dependent IBC II+ auroral secondary electron distributions and the vibrational populations of the eight O 2 electronic states were determined under conditions of statistical equilibrium. Pre-dissociation, atmospheric chemistry involving atomic and molecular oxygen, radiative decay and quenching of excited states were included in this study. This model predicts relatively high number densities for the X3Σg-(v'⩽4),a1Δandb1Σg+ metastable electronic states and could represent a significant source of stored energy in O 2* for subsequent thermospheric chemical reactions. Particular attention is directed towards the emission intensities of the infrared (IR) atmospheric (1.27 μm), Atmospheric (0.76 μm) and the atomic oxygen 1S→ 1D transition (5577 Å) lines and the role of electron-driven processes in their origin. Aircraft, rocket and satellite observations have shown both the IR atmospheric and Atmospheric lines are dramatically enhanced under auroral conditions and, where possible, we compare our results to these measurements. Our calculated 5577 Å intensity is found to be in good agreement with values independently measured for a medium strength IBC II+ aurora.

Laser pulse control of ultrafast heterogeneous electron transfer: a computational study.

PubMed

Wang, Luxia; May, Volkhard

2004-10-22

Laser pulse control of the photoinduced 90 fs charge injection from perylene into the conduction band of TiO2 is studied theoretically. The approach accounts for the electronic-ground state of the dye, the first excited state, the ionized state formed after charge injection, and the continuum of the electronic states in the conduction band, all defined vs a single reaction coordinate. To address different control tasks optimal control theory is combined with a full quantum dynamical description of the electron-vibrational motion accompanying the charge injection process. First it is proved in which way the charge injection time can be changed by tailored laser pulses. In a second step a pump-dump scheme from the perylene ground state to the first excited electronic state and back to the ground state is discussed. Because of the strong coupling of the excited perylene state to the band continuum of TiO2 this control task is more suited to an experimental test than the direct control of the charge injection.

Guest concentration, bias current, and temperature-dependent sign inversion of magneto-electroluminescence in thermally activated delayed fluorescence devices

NASA Astrophysics Data System (ADS)

Deng, Junquan; Jia, Weiyao; Chen, Yingbing; Liu, Dongyu; Hu, Yeqian; Xiong, Zuhong

2017-03-01

Non-emissive triplet excited states in devices that undergo thermally activated delayed fluorescence (TADF) can be up-converted to singlet excited states via reverse intersystem crossing (RISC), which leads to an enhanced electroluminescence efficiency. Exciton-based fluorescence devices always exhibit a positive magneto-electroluminescence (MEL) because intersystem crossing (ISC) can be suppressed effectively by an external magnetic field. Conversely, TADF devices should exhibit a negative MEL because RISC is suppressed by the external magnetic field. Intriguingly, we observed a positive MEL in TADF devices. Moreover, the sign of the MEL was either positive or negative, and depended on experimental conditions, including doping concentration, current density and temperature. The MEL observed from our TADF devices demonstrated that ISC in the host material and RISC in the guest material coexisted. These competing processes were affected by the experimental conditions, which led to the sign change of the MEL. This work gives important insight into the energy transfer processes and the evolution of excited states in TADF devices.

Multiphoton Rydberg and valence dynamics of CH3Br probed by mass spectrometry and slice imaging.

PubMed

Hafliðason, Arnar; Glodic, Pavle; Koumarianou, Greta; Samartzis, Peter C; Kvaran, Ágúst

2018-06-18

The multiphoton dynamics of CH3Br were probed by Mass Resolved MultiPhoton Ionization (MR-MPI), Slice Imaging and Photoelectron Imaging in the two-photon excitation region of 66 000 to 80 000 cm-1. Slice images of the CH3+ and Br+ photoproducts of ten two-photon resonant transitions to np and nd Rydberg states of the parent molecule were recorded. CH3+ ions dominate the mass spectra. Kinetic energy release spectra (KERs) were derived from slice and photoelectron images and anisotropy parameters were extracted from the angular distributions of the ions to identify the processes and the dynamics involved. At all wavelengths we observe three-photon excitations, via the two-photon resonant transitions to molecular Rydberg states, forming metastable, superexcited (CH3Br#) states which dissociate to form CH3 Rydberg states (CH3**) along with Br/Br*. A correlation between the parent Rydberg states excited and CH3** formed is evident. For the three highest excitation energies used, the CH3Br# metastable states also generate high kinetic energy fragments of CH3(X) and Br/Br*. In addition for two out of these three wavelengths we also measure one-photon photolysis of CH3Br in the A band forming CH3(X) in various vibrational modes and bromine atoms in the ground (Br) and spin-orbit excited (Br*) states.

Theoretical Insights Into the Excited State Double Proton Transfer Mechanism of Deep Red Pigment Alkannin.

PubMed

Zhao, Jinfeng; Dong, Hao; Zheng, Yujun

2018-02-08

As the most important component of deep red pigments, alkannin is investigated theoretically in detail based on time-dependent density functional theory (TDDFT) method. Exploring the dual intramolecular hydrogen bonds (O1-H2···O3 and O4-H5···O6) of alkannin, we confirm the O1-H2···O3 may play a more important role in the first excited state than the O4-H5···O6 one. Infrared (IR) vibrational analyses and subsequent charge redistribution also support this viewpoint. Via constructing the S 1 -state potential energy surface (PES) and searching transition state (TS) structures, we illuminate the excited state double proton transfer (ESDPT) mechanism of alkannin is the stepwise process that can be first launched by the O1-H2···O3 hydrogen bond wire in gas state, acetonitrile (CH 3 CN) and cyclohexane (CYH) solvents. We present a novel mechanism that polar aprotic solvents can contribute to the first-step proton transfer (PT) process in the S 1 state, and nonpolar solvents play important roles in lowering the potential energy barrier of the second-step PT reaction.

The Dynamics of the Photofragmentation of Ketene 3-Cyclopentenone, 3,5-Cycloheptadienone, and Tropone.

DTIC Science & Technology

1985-01-01

suggested that the concerted reaction should be allowed photochemically and the conrotatory mode should be favored. The data were in accord with this...crossing), or (4) reaction to form products, e.g., isomers or fragments, directly from the excited state. Further radiative, non-radiative, and photochemical ...processes can occur from intermediate excited states. Typical photochemical reactions observed in simple ketones in the gas phase are: (1) Norrish

Photoelectron imaging of autoionizing states of xenon: Effect of external electric fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shubert, V. Alvin; Pratt, Stephen T.

Velocity map photoelectron imaging was used to study the photoelectron angular distributions of autoionizing Stark states of atomic xenon excited just below the Xe{sup +} {sup 2} P{sub 1/2}{sup o} threshold at fields ranging from 50 to 700 V/cm. Two-color, two-photon resonant, three-photon excitation via the 6p{sup '}[1/2]{sub 0} level was used to probe the region of interest. The wavelength scans show a similar evolution of structure to that observed in single-photon excitation [Ernst et al., Phys. Rev. A 37, 4172 (1988)]. The photoelectron angular distributions following autoionization of the Stark states provide information on the decay of excited statesmore » in electron fields. In the present experiments, the large autoionization width of the ({sup 2} P{sub 1/2}{sup o})nd[3/2]{sub 1}{sup o} series dominates the decay processes, and thus controls the angular distributions. However, the angular distributions of the Stark states also indicate the presence of other decay channels contributing to the decay of these states.« less

Collisional Processes Probed by using Resonant Four-Wave Mixing Spectroscopy

NASA Astrophysics Data System (ADS)

McCormack, E. F.; Stampanoni, A.; Hemmerling, B.

2000-06-01

Collisionally-induced decay processes in excited-state nitric oxide (NO) have been measured by using time-resolved two-color, resonant four-wave mixing (TC-RFWM) spectroscopy and polarization spectroscopy (PS). Markedly different time dependencies were observed in the data obtained by using TC-RFWM when compared to PS. Oscillations in the PS signal as a function of delay between the pump and probe laser pulses were observed and it was determined that their characteristics depend very sensitively on laser polarization. Analysis reveals that the oscillations in the decay curves are due to coherent excitation of unresolved hyperfine structure in the A state of NO. A comparison of beat frequencies obtained by taking Fourier transforms of the time data to the predicted hyperfine structure of the A state support this explanation. Further, based on a time-dependent model of PS as a FWM process, the signal’s dependence as a function of time on polarization configuration and excitation scheme can be predicted. By using the beat frequency values, fits of the model results to experimental decay curves for different pressures allows a study of the quenching rate in the A state due to collisional processes. A comparison of the PS data to laser-induced fluorescence decay measurements reveals different decay rates which suggests that the PS signal decay depends on the orientation and alignment of the excited molecules. The different behavior of the decay curves obtained by using TC-RFWM and PS can be understood in terms of the various contributions to the decay as described by the model and this has a direct bearing on which technique is preferable for a given set of experimental parameters.

Measuring upconversion nanoparticles photoluminescence lifetime with FastFLIM and phasor plots

NASA Astrophysics Data System (ADS)

Sun, Yuansheng; Lee, Hsien-Ming; Qiu, Hailin; Liao, Shih-Chu Jeff; Coskun, Ulas; Barbieri, Beniamino

2018-02-01

Photon upconversion is a nonlinear process in which the sequential of absorption of two or more photons leads to the anti-stoke emission. Different than the conventional multiphoton excitation process, upconversion can be efficiently performed at low excitation densities. Recent developments in lanthanide-doped upconversion nanoparticles (UCNPs) have led to a diversity of applications, including detecting and sensing of biomolecules, imaging of live cells, tissues and animals, cancer diagnostic and therapy, etc. Measuring the upconversion lifetime provides a new dimension of its imaging and opens a new window for its applications. Due to the long metastable intermediate excited state, UCNP typically has a long excited state lifetime ranging from sub-microseconds to milliseconds. Here, we present a novel development using the FastFLIM technique to measure UCNP lifetime by laser scanning confocal microscopy. FastFLIM is capable of measuring lifetime from 100 ps to 100 ms and features the high data collection efficiency (up to 140-million counts per second). Other than the traditional nonlinear least-square fitting analysis, the raw data acquired by FastFLIM can be directly processed by the model-free phasor plots approach for instant and unbiased lifetime results, providing the ideal routine for the UCNP photoluminescence lifetime microscopy imaging.

The role of secondary processes in kinetics of triplet states of a hydrogen molecule in an ECR discharge

NASA Astrophysics Data System (ADS)

Shakhatov, V. A.; Lebedev, Yu A.; Lacoste, A.; Bechu, S.

2017-11-01

An electronic state sensitive semiempirical collision-radiative model of hydrogen plasma of ECR-discharge is used to analyze the applicability of emission of triplet states of molecular hydrogen for plasma diagnostics. It is shown that secondary processes make the greatest contribution to the kinetics of population-depopulation of triplet states {a}3{{Σ }}}g+,{c}3{{{\\Pi }}}u,{d}3{{{\\Pi }}}u,{e}3{{{Σ }}}u+,{g}3{{{Σ }}}g+,{h}3{{{Σ }}}g+, i 3Πg and r 3Πg. The secondary processes give the smallest contribution to the excitation and deactivation of triplet states {f}3{{{Σ }}}u+ {\\unicode{x00438;} {k}3{{{\\Pi }}}u. Thus a simplified coronal model (electron impact excitation followed by radiative decay) can be used to process the intensities of the dipole allowed {f}3{{{Σ }}}u+ \\to {a}3{{{Σ }}}g+,{g}3{{{Σ }}}g+ and {k}3{{{\\Pi }}}u \\to {a}3{{{Σ }}}g+ transitions. The complicated collision-radiative model should be used for other transitions.

Enhanced eumelanin emission by stepwise three-photon excitation

NASA Astrophysics Data System (ADS)

Kerimo, Josef; Rajadhyaksha, Milind; DiMarzio, Charles A.

2011-03-01

Eumelanin fluorescence from Sepia officinalis and black human hair was activated with near-infrared radiation and multiphoton excitation. A third order multiphoton absorption by a step-wise process appears to be the underlying mechanism. The activation was caused by a photochemical process since it could not be reproduced by simple heating. Both fluorescence and brightfield imaging indicate the near-infrared irradiation caused photodamage to the eumelanin and the activated emission originated from the photodamaged region. At least two different components with about thousand-fold enhanced fluorescence were activated and could be distinguished by their excitation properties. One component was excited with wavelengths in the visible region and exhibited linear absorption dependence. The second component could be excited with near-infrared wavelengths and had a third order dependence on the laser power. The third order dependence is explained by a step-wise excited state absorption (ESA) process since it could be observed equally with the CW and femtosecond lasers. The new method for photoactivating the eumelanin fluorescence was used to map the melanin content in human hair.

Probing ground-state hole transfer between equivalent, electrochemically inaccessible states in multiporphyrin arrays using time-resolved optical spectroscopy.

PubMed

Song, Hee-eun; Taniguchi, Masahiko; Kirmaier, Christine; Bocian, David F; Lindsey, Jonathan S; Holten, Dewey

2009-01-01

A new strategy is described and implemented for determining the rates of hole-transfer between equivalent porphyrins in multiporphyrin architectures. The approach allows access to these rates between sites that are not the most easily oxidized components of the array. The specific architectures investigated with this new strategy are triads consisting of one zinc porphyrin (Zn) and two free base porphyrins (Fb). The triads employ a diphenylethyne linker (ZnFbFbU) and a phenylene linker (ZnFbFbPhi). The zinc porphyrin is selectively oxidized to produce Zn(+)FbFb, the free base porphyrins are excited to produce the excited-state mixture Zn(+)Fb*Fb and Zn(+)FbFb*, and the subsequent dynamics are monitored by ultrafast absorption spectroscopy. The system evolves by a combination of energy- and hole-transfer processes involving (adjacent and nonadjacent) zinc and free base porphyrin constituents that are complete within 100 ps of excitation; the rate constants of many of these processes are derived from prior studies of the oxidized forms of the benchmark dyads (ZnFbU and ZnFbPhi). One of the excited-state decay channels produces the metastable state ZnFbFb(+) that decays to a second metastable state ZnFb(+)Fb by the target hole-transfer process, followed by rapid hole transfer to produce the Zn(+)FbFb thermodynamic ground state of the system. The rate constant for hole transfer between the free base porphyrins in the oxidized ZnFbFb triads is found to be (0.5 ns)(-1) and (0.6 ns)(-1) across phenylene and diphenylethyne linkers, respectively. These rate constants are comparable to those recently measured, using a related but distinct strategy, for ground-state hole transfer between zinc porphyrins in oxidized ZnZnFb triads. The two complementary strategies provide unique approaches for probing hole transfer between equivalent sites in multiporphyrin arrays, with the choice of method being guided by the particular target process and the ease of synthesis of the necessary architectures.

Dissociative excitation of the N(+)(5S) state by electron impact on N2 - Excitation function and quenching

NASA Technical Reports Server (NTRS)

Erdman, P. W.; Zipf, E. C.

1986-01-01

Metastable N(+)(5S) ions were produced in the laboratory by dissociative excitation of N2 with energetic electrons. The resulting radiative decay of the N(+)(5S) state was observed with sufficient resolution to completely resolve the doublet from the nearby N2 molecular radiation. The excitation function was measured from threshold to 500 eV. The cross section peaks at a high electron energy and also exhibits a high threshold energy both of which are typical of dissociative excitation-ionization processes. This finding complicates the explanation of electron impact on N2 as the mechanism for the source of the 2145 A 'auroral mystery feature' by further increasing the required peak cross section. It is suggested that the apparent N(+)(5S) quenching in auroras may be an artifact due to the softening of the electron energy spectrum in the auroral E region.

Electron-helium S-wave model benchmark calculations. II. Double ionization, single ionization with excitation, and double excitation

NASA Astrophysics Data System (ADS)

Bartlett, Philip L.; Stelbovics, Andris T.

2010-02-01

The propagating exterior complex scaling (PECS) method is extended to all four-body processes in electron impact on helium in an S-wave model. Total and energy-differential cross sections are presented with benchmark accuracy for double ionization, single ionization with excitation, and double excitation (to autoionizing states) for incident-electron energies from threshold to 500 eV. While the PECS three-body cross sections for this model given in the preceding article [Phys. Rev. A 81, 022715 (2010)] are in good agreement with other methods, there are considerable discrepancies for these four-body processes. With this model we demonstrate the suitability of the PECS method for the complete solution of the electron-helium system.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Tanping, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu; Kumar, Revati, E-mail: tanping@lsu.edu, E-mail: revatik@lsu.edu

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 breaksmore » 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.« less

Laser-induced dispersive fluorescence spectrum and the detection of NO II

NASA Astrophysics Data System (ADS)

Zhang, Guiyin; Jin, Yidong

2008-03-01

Laser-induced dispersive fluorescence (LIDF) spectrum of NO II molecule in the spectral region of 508.3-708.3nm is obtained with the 508.0nm excitation wavelength. It is found that at low sample pressure the spectrum is composed of a banded structure superimposed on a continuous one. While the spectrum show itself as a continuous envelope centered at 630.0nm when the pressure with a higher value. NO II molecules are excited to the first excited state A2B II by absorbing laser photons. Owing to the strong interaction between X2A I~A2B II and A2B II ~ B2B Istates, some excited molecules redistribute to X2A I and B2B I states by the process of internal energy conversion or quenching. This induces the fluorescence come from different excited states. Based on the experimental data, the vibration frequencies of the ground electronic state of NO II molecule are obtained. They are ω I=(1319+/-12)cm -1, ω II=(759.8+/-0.7)cm -1,and ω 3=(1635+/-29)cm -1. The optimum-receiving wavelength for detecting NO II gas with the technique of LIDF is proposed.

Evolution of Excited-State Dynamics in Periodic Au 28, Au 36, Au 44, and Au 52 Nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Meng; Zeng, Chenjie; Sfeir, Matthew Y.

An understanding of the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au 28, Au 36, Au 44, and Au 52), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast S n → S 1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO–LUMO gap excitation lacksmore » ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core–shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blom, Alex Jason

2009-01-01

Excited state charge transfer processes are studied using the fs/ps-CARS probe technique. This probe allows for multiplexed detection of Raman active vibrational modes. Systems studied include Michler's Ketone, Coumarin 120, 4-dimethylamino-4'-nitrostilbene, and several others. The vibrational spectrum of the para di-substituted benzophenone Michler's Ketone in the first excited singlet state is studied for the first time. It is found that there are several vibrational modes indicative of structural changes of the excited molecule. A combined experimental and theoretical approach is used to study the simplest 7-amino-4-methylcoumarin, Coumarin 120. Vibrations observed in FTIR and spontaneous Raman spectra are assigned using densitymore » 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.« less

Evolution of Excited-State Dynamics in Periodic Au 28, Au 36, Au 44, and Au 52 Nanoclusters

DOE PAGES

Zhou, Meng; Zeng, Chenjie; Sfeir, Matthew Y.; ...

2017-08-10

An understanding of the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au 28, Au 36, Au 44, and Au 52), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast S n → S 1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO–LUMO gap excitation lacksmore » ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core–shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.« less

Double-Resonance Facilitated Decomposion of Emission Spectra

NASA Astrophysics Data System (ADS)

Kato, Ryota; Ishikawa, Haruki

2016-06-01

Emission spectra provide us with rich information about the excited-state processes such as proton-transfer, charge-transfer and so on. In the cases that more than one excited states are involved, emission spectra from different excited states sometimes overlap and a decomposition of the overlapped spectra is desired. One of the methods to perform a decomposition is a time-resolved fluorescence technique. It uses a difference in time evolutions of components involved. However, in the gas-phase, a concentration of the sample is frequently too small to carry out this method. On the other hand, double-resonance technique is a very powerful tool to discriminate or identify a common species in the spectra in the gas-phase. Thus, in the present study, we applied the double-resonance technique to resolve the overlapped emission spectra. When transient IR absorption spectra of the excited state are available, we can label the population of the certain species by the IR excitation with a proper selection of the IR wavenumbers. Thus, we can obtain the emission spectra of labeled species by subtracting the emission spectra with IR labeling from that without IR. In the present study, we chose the charge-transfer emission spectra of cyanophenyldisilane (CPDS) as a test system. One of us reported that two charge-transfer (CT) states are involved in the intramolecular charge-transfer (ICT) process of CPDS-water cluster and recorded the transient IR spectra. As expected, we have succeeded in resolving the CT emission spectra of CPDS-water cluster by the double resonance facilitated decomposion technique. In the present paper, we will report the details of the experimental scheme and the results of the decomposition of the emission spectra. H. Ishikawa, et al., Chem. Phys. Phys. Chem., 9, 117 (2007).

Ultrafast photo-initiated molecular quantum dynamics in the DNA dinucleotide d(ApG) revealed by broadband transient absorption spectroscopy.

PubMed

Stuhldreier, Mayra C; Temps, Friedrich

2013-01-01

The ultrafast photo-initiated quantum dynamics of the adenine-guanine dinucleotide d(ApG) in aqueous solution (pH 7) has been studied by femtosecond time-resolved spectroscopy after excitation at lambda = 260 nm. The results reveal a hierarchy of processes on time scales from tau < 100 fs to tau > 100 ps. Characteristic spectro-temporal signatures are observed indicating the transformation of the molecules in the electronic relaxation from the photo-excited state to a long-lived exciplex. In particular, broadband UV/VIS excited-state absorption (ESA) measurements detected a distinctive absorption by the excited dinucleotide around lambda = 335 nm, approximately 0.5 eV to the blue compared to the maximum of the broad and unstructured ESA spectrum after excitation of an equimolar mixture of the mononucleotides dAMP and dGMP. A similar feature has been identified as signature of the excimer in the dynamics of the adenine dinucleotide d(ApA). The lifetime of the d(ApG) exciplex was found to be tau = 124 +/- 4 ps both from the ESA decay time and from the ground-state recovery time, far longer than the sub-picosecond lifetimes of excited dAMP or dGMP. Fluorescence-time profiles measured by the up-conversion technique indicate that the exciplex state is reached around approximately 6 ps after excitation. Very weak residual fluorescence at longer times red-shifted to the emission from the photo-excited state shows that the exciplex is almost optically dark, but still has enough oscillator strength to give rise to the dual fluorescence of the dinucleotide in the static fluorescence spectrum.

The observation of ultrafast excited-state dynamical evolution in B800- partially or completely released LH2 of Rhodobacter sphaeroides 601 at room temperature.

PubMed

Liu, Weimin; Liu, Yuan; Yan, Yongli; Liu, Kangjun; Guo, Lijun; Xu, Chunhe; Qian, Shixiong

2006-04-01

Photodynamics of two kinds of peripheral antenna complexes (LH2 of Rhodobacter sphaeroides, native LH2 (RS601) and B800-released LH2 where B800-BChls were partially or completely removed with different pH treatments), were studied using femtosecond pump-probe technique at different laser wavelengths. The obtained results for these samples with different B800/B850 ratios demonstrated that under the excitation around B800 nm, the photoabsorption and photobleaching dynamics were caused by the direct excitation of upper excitonic levels of B850 and excited state of B800 pigments, respectively. Furthermore, the removal of B800 pigments had little effect on the energy transfer processes of B850 interband/intraband transfer.

Sequential and direct ionic excitation in the strong-field ionization of 1-butene molecules.

PubMed

Schell, Felix; Boguslavskiy, Andrey E; Schulz, Claus Peter; Patchkovskii, Serguei; Vrakking, Marc J J; Stolow, Albert; Mikosch, Jochen

2018-05-18

We study the Strong-Field Ionization (SFI) of the hydrocarbon 1-butene as a function of wavelength using photoion-photoelectron covariance and coincidence spectroscopy. We observe a striking transition in the fragment-associated photoelectron spectra: from a single Above Threshold Ionization (ATI) progression for photon energies less than the cation D0-D1 gap to two ATI progressions for a photon energy greater than this gap. For the first case, electronically excited cations are created by SFI populating the ground cationic state D0, followed by sequential post-ionization excitation. For the second case, direct sub-cycle SFI to the D1 excited cation state contributes significantly. Our experiments access ionization dynamics in a regime where strong-field and resonance-enhanced processes can interplay.

Photophysics of self-assembled zinc porphyrin-bidentate diamine ligand complexes.

PubMed

Danger, Brook R; Bedient, Krysta; Maiti, Manisankar; Burgess, Ian J; Steer, Ronald P

2010-10-21

The effects of complexation--by bidentate nitrogen-containing ligands such as pyrazine and 4,4'-bipyridine commonly used for porphyrin self-assembly--on the photophysics of the model metalloporphyrin, ZnTPP, are reported. Ligation to form the 5-coordinate species introduces an intramolecular charge transfer (ITC) state that, depending on the oxidation and reduction potentials of the electron donor and acceptor, can become involved in the excited state relaxation processes. For ZnTPP, ligation with pyridine has little effect on excited state relaxation following either Q-band or Soret band excitation. However, coordination of ZnTPP with pyrazine and bipyridine causes the S(2) (Soret) state of the ligated species to decay almost exclusively via an S(2)-ICT-S(1) pathway, while affecting the S(1) decay route only slightly. In these 5-coordinate species the S(2)-ICT-S(1) decay route is ultrafast and nearly quantitative. Literature redox data for other bidentate ligands such as DABCO and multidentate ligands commonly used for pophyrin assembly suggest that the ITC states introduced by them could also modify the excited state relaxation dynamics of a wide variety of multiporphyrin arrays.

Resonant recombination and autoionization in electron-ion collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mueller, A.

1990-06-01

The occurence of resonances in elastic and inelastic electron-ion collisions is discussed. Resonant processes involve excitation of the ion with simultaneous capture of the initially free electron. The decay mechanism subsequent to the formation of the intermediate multiply excited state determines whether a resonance is found in recombination, excitation, elastic scattering, in single or even in multiple ionization. This review concentrates on resonances in the ionization channel. Correlated two-electron transitions are considered.

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

NASA Astrophysics Data System (ADS)

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

1992-04-01

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

Ultrafast Photodissociation Dynamics of Nitromethane.

PubMed

Nelson, Tammie; Bjorgaard, Josiah; Greenfield, Margo; Bolme, Cindy; Brown, Katie; McGrane, Shawn; Scharff, R Jason; Tretiak, Sergei

2016-02-04

Nitromethane (NM), a high explosive (HE) with low sensitivity, is known to undergo photolysis upon ultraviolet (UV) irradiation. The optical transparency, homogeneity, and extensive study of NM make it an ideal system for studying photodissociation mechanisms in conventional HE materials. The photochemical processes involved in the decomposition of NM could be applied to the future design of controllable photoactive HE materials. In this study, the photodecomposition of NM from the nπ* state excited at 266 nm is being investigated on the femtosecond time scale. UV femtosecond transient absorption (TA) spectroscopy and excited state femtosecond stimulated Raman spectroscopy (FSRS) are combined with nonadiabatic excited state molecular dynamics (NA-ESMD) simulations to provide a unified picture of NM photodecomposition. The FSRS spectrum of the photoproduct exhibits peaks in the NO2 region and slightly shifted C-N vibrational peaks pointing to methyl nitrite formation as the dominant photoproduct. A total photolysis quantum yield of 0.27 and an nπ* state lifetime of ∼20 fs were predicted from NA-ESMD simulations. Predicted time scales revealed that NO2 dissociation occurs in 81 ± 4 fs and methyl nitrite formation is much slower having a time scale of 452 ± 9 fs corresponding to the excited state absorption feature with a decay of 480 ± 17 fs observed in the TA spectrum. Although simulations predict C-N bond cleavage as the primary photochemical process, the relative time scales are consistent with isomerization occurring via NO2 dissociation and subsequent rebinding of the methyl radical and nitrogen dioxide.

Ultrafast time-resolved pump-probe spectroscopy of PYP by a sub-8 fs pulse laser at 400 nm.

PubMed

Liu, Jun; Yabushita, Atsushi; Taniguchi, Seiji; Chosrowjan, Haik; Imamoto, Yasushi; Sueda, Keiichi; Miyanaga, Noriaki; Kobayashi, Takayoshi

2013-05-02

Impulsive excitation of molecular vibration is known to induce wave packets in both the ground state and excited state. Here, the ultrafast dynamics of PYP was studied by pump-probe spectroscopy using a sub-8 fs pulse laser at 400 nm. The broadband spectrum of the UV pulse allowed us to detect the pump-probe signal covering 360-440 nm. The dependence of the vibrational phase of the vibrational mode around 1155 cm(-1) on the probe photon energy was observed for the first time to our knowledge. The vibrational mode coupled to the electronic transition observed in the probe spectral ranges of 2.95-3.05 and 3.15-3.35 eV was attributed to the wave packets in the ground state and the excited state, respectively. The frequencies in the ground state and excited state were determined to be 1155 ± 1 and 1149 ± 1 cm(-1), respectively. The frequency difference is due to change after photoexcitation. This means a reduction of the bond strength associated with π-π* excitation, which is related to the molecular structure change associated with the primary isomerization process in the photocycle in PYP. Real-time vibrational modes at low frequency around 138, 179, 203, 260, and 317 cm(-1) were also observed and compared with the Raman spectrum for the assignment of the vibrational wave packet.

Photodynamics of oxybenzone sunscreen: Nonadiabatic dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Chun-Xiang; Guo, Wei-Wei; Xie, Bin-Bin

Herein we have used combined static electronic structure calculations and “on-the-fly” global-switching trajectory surface-hopping dynamics simulations to explore the photochemical mechanism of oxybenzone sunscreen. We have first employed the multi-configurational CASSCF method to optimize minima, conical intersections, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decays in the {sup 1}ππ{sup ∗}, {sup 1}nπ{sup ∗}, and S{sub 0} states (energies are refined at the higher MS-CASPT2 level). According to the mapped potential energy profiles, we have identified two ultrafast excited-state deactivation pathways for the initially populated {sup 1}ππ{sup ∗} system. The first is the diabatic ESIPTmore » process along the {sup 1}ππ{sup ∗} potential energy profile. The generated {sup 1}ππ{sup ∗} keto species then decays to the S{sub 0} state via the keto {sup 1}ππ{sup ∗}/gs conical intersection. The second is internal conversion to the dark {sup 1}nπ{sup ∗} state near the {sup 1}ππ{sup ∗} /{sup 1}nπ{sup ∗} crossing point in the course of the diabatic {sup 1}ππ{sup ∗} ESIPT process. Our following dynamics simulations have shown that the ESIPT and {sup 1}ππ{sup ∗} → S{sub 0} internal conversion times are 104 and 286 fs, respectively. Finally, our present work demonstrates that in addition to the ESIPT process and the {sup 1}ππ{sup ∗} → S{sub 0} internal conversion in the keto region, the {sup 1}ππ{sup ∗} → {sup 1}nπ{sup ∗} internal conversion in the enol region plays as well an important role for the excited-state relaxation dynamics of oxybenzone.« less

ESIPT and photodissociation of 3-hydroxychromone in solution: photoinduced processes studied by static and time-resolved UV/Vis, fluorescence, and IR spectroscopy.

PubMed

Chevalier, Katharina; Grün, Anneken; Stamm, Anke; Schmitt, Yvonne; Gerhards, Markus; Diller, Rolf

2013-11-07

The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC.

Excited nuclei, resonances and reactions in neutron star crusts

NASA Astrophysics Data System (ADS)

Takibayev, N.; Nasirova, D.; Katō, K.; Kurmangaliyeva, V.

2018-01-01

The short review of research results concerning the study of reactions and processes that occur in the neutron star crusts is given. The peculiarities of electron capture reactions by a nucleus in overdense crystalline structures have been demonstrated for various nuclei, in particular some even-even nuclei at electron capture reactions give daughter nuclei in excited states. Excited nuclei due to nonlinear interactions lead to a high-order harmonic generation. High energy gammas interact with charged particles, give a neutrino radiation and also knock out nucleons from neighbour nuclei. It is also shown that interactions of neutrons with two and more nuclei in an overdence lattice give a large number of new resonance states. These resonances result in a formation of specific local oscillations in the corresponding layers of the lattice. The periodic enhancement of these processes in the dependence on the elemental composition of the primary neutron star matter is considered.

Linking photochemistry in the gas and solution phase: S-H bond fission in p-methylthiophenol following UV photoexcitation.

PubMed

Oliver, Thomas A A; Zhang, Yuyuan; Ashfold, Michael N R; Bradforth, Stephen E

2011-01-01

Gas-phase H (Rydberg) atom photofragment translational spectroscopy and solution-phase femtosecond-pump dispersed-probe transient absorption techniques are applied to explore the excited state dynamics of p-methylthiophenol connecting the short time reactive dynamics in the two phases. The molecule is excited at a range of UV wavelengths from 286 to 193 nm. The experiments clearly demonstrate that photoexcitation results in S-H bond fission--both in the gas phase and in ethanol solution-and that the resulting p-methythiophenoxyl radical fragments are formed with significant vibrational excitation. In the gas phase, the recoil anisotropy of the H atom and the vibrational energy disposal in the p-MePhS radical products formed at the longer excitation wavelengths reveal the operation of two excited state dissociation mechanisms. The prompt excited state dissociation motif appears to map into the condensed phase also. In both phases, radicals are produced in both their ground and first excited electronic states; characteristic signatures for both sets of radical products are already apparent in the condensed phase studies after 50 fs. No evidence is seen for either solute ionisation or proton coupled electron transfer--two alternate mechanisms that have been proposed for similar heteroaromatics in solution. Therefore, at least for prompt S-H bond fissions, the direct observation of the dissociation process in solution confirms that the gas phase photofragmentation studies indeed provide important insights into the early time dynamics that transfer to the condensed phase.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2016-01-01

This report will describe our recent studies of transition metal complex structural dynamics on the fs and ps time scales using an X-ray free electron laser source, Linac Coherent Light Source (LCLS). Ultrafast XANES spectra at the Ni K-edge of nickel(II) tetramesitylporphyrin (NiTMP) were successfully measured for optically excited state at a timescale from 100 fs to 50 ps, providing insight into its sub-ps electronic and structural relaxation processes. Importantly, a transient reduced state Ni(I) (π, 3dx2-y2) electronic state is captured through the interpretation of a short-lived excited state absorption on the low-energy shoulder of the edge, which is aidedmore » by the computation of X-ray transitions for postulated excited electronic states. The observed and computed inner shell to valence orbital transition energies demonstrate and quantify the influence of electronic configuration on specific metal orbital energies. A strong influence of the valence orbital occupation on the inner shell orbital energies indicates that one should not use the transition energy from 1s to other orbitals to draw conclusions about the d-orbital energies. For photocatalysis, a transient electronic configuration could influence d-orbital energies up to a few eV and any attempt to steer the reaction pathway should account for this to ensure that external energies can be used optimally in driving desirable processes. NiTMP structural evolution and the influence of the porphyrin macrocycle conformation on relaxation kinetics can be likewise inferred from this study.« less

Coulomb scattering rates of excited states in monolayer electron-doped germanene

NASA Astrophysics Data System (ADS)

Shih, Po-Hsin; Chiu, Chih-Wei; Wu, Jhao-Ying; Do, Thi-Nga; Lin, Ming-Fa

2018-05-01

Excited conduction electrons, conduction holes, and valence holes in monolayer electron-doped germanene exhibit unusual Coulomb decay rates. The deexcitation processes are studied using the screened exchange energy. They might utilize the intraband single-particle excitations (SPEs), the interband SPEs, and the plasmon modes, depending on the quasiparticle states and the Fermi energies. The low-lying valence holes can decay through the undamped acoustic plasmon, so that they present very fast Coulomb deexcitations, nonmonotonous energy dependence, and anisotropic behavior. However, the low-energy conduction electrons and holes are similar to those in a two-dimensional electron gas. The higher-energy conduction states and the deeper-energy valence ones behave similarly in the available deexcitation channels and have a similar dependence of decay rate on the wave vector k .

A wavelength dependent investigation of the indole photophysics via ionization and fragmentation pump-probe spectroscopies.

PubMed

Godfrey, T J; Yu, Hui; Biddle, Michael S; Ullrich, Susanne

2015-10-14

A wavelength dependent study investigating the low-lying (1)La and (1)Lb states, both possessing (1)ππ* character, and the (1)πσ* state in the deactivation process of indole is presented here. Relaxation dynamics following excitation at 241, 250, 260, 270, 273, and 282 nm are examined using three gas-phase, pump-probe spectroscopic techniques: (1) hydrogen atom (H-atom) time-resolved kinetic energy release (TR-KER), (2) time-resolved photoelectron spectroscopy (TR-PES), and (3) time-resolved ion yield (TR-IY). Applied in combination, a more complete picture of the indole relaxation dynamics may be gleaned. For instance, TR-PES experiments directly observe all relaxation pathways by probing the evolution of the excited states following photoexcitation; whereas, TR-KER measurements indirectly, yet specifically, probe for (1)πσ*-state activity through the detection of H-atoms eliminated along the indole nitrogen-hydrogen (N-H) stretch coordinate-a possible outcome of (1)πσ*-state relaxation in indole. In addition, mass information obtained via TR-IY monitors fragmentation dynamics that may occur within the neutral electronically excited and/or cationic states. The work herein assesses the onset and importance of the (1)πσ* state at various pump wavelengths by systematically tuning across the ultraviolet absorption spectrum of indole with a particular focus on those pump wavelengths longer than 263 nm, where the involvement of the (1)πσ* state is under current debate. As far as this experimental work is concerned, there does not appear to be any significant involvement by the (1)πσ* state in the indole relaxation processes following excitation at 270, 273, or 282 nm. This investigation also evaluates the primary orbital promotions contributing to the (1)La, (1)Lb, and (1)πσ* transitions based on ionization preferences observed in TR-PES spectra. Relaxation time constants associated with dynamics along these states are also reported for excitation at all of the aforementioned pump wavelengths and are used to pinpoint the origin of the discrepancies found in the literature. In this context, advantages and disadvantages of the three experimental techniques are discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guldi, D.M.; Torres-Garcia, G.; Mattay, J.

Excited-state properties of three different pyrazine derivatives 4--6 were probed by emission and transient absorption spectroscopy. They display emission maxima at 464 (4), 417 (5), and 515 nm (6) that are red-shifted with respect to their strong UV ground-state absorption and formed with overall quantum yields ({Phi}) of 0.156, 0.22, and 0.13, respectively. Once photoexcited, these triplet excited pyrazines undergo rapid intermolecular energy transfer to a monofunctionalized fullerene derivative (7) with bimolecular rate constants ranging from 3.64 {times} 10{sup 9} M{sup {minus}1} s{sup {minus}1} (6) to 1.1 {times} 10{sup 10} M{sup {minus}1} s{sup {minus}1} (4). The product of these bimolecularmore » energy-transfer reactions is in all cases the fullerene triplet excited state. Functionalization of pristine C{sub 60} with the investigated pyrazine derivatives promotes the UV-vis absorption characteristics and, in turn, improves the light-harvesting efficiency of the resulting dyads 1--3 relative to pristine C{sub 60}. Photoexcitation of the pyrazine moieties in dyads 1--3 leads to the formation of their singlet excited states. In contrast to the pyrazine models, photoexcitation of dyad 1--3 is followed by rapid intramolecular deactivation processes of the latter via energy transfer to the fullerene ground state with half-lives between 37 and 100 ps. In turn, energy transfer transforms the short-lived and moderately redox-active singlet excited states of pyrazine into the highly reactive fullerene triplet excited state. The latter is found to produce effectively singlet oxygen ({sup 1}O{sub 2}) with quenching rate constants for 1--3 of (1--1.5) {times} 10{sup 9} M{sup {minus}1} s{sup {minus}1}. Similarly, reductive quenching of the triplet excited states in dyads 1--3 via electron transfer with diazabicyclooctane (DABCO) occurs with rate constants of 5.2--9.4 {times} 10{sup 7} M{sup {minus}1} s{sup {minus}1}.« less

Fine-structure-resolution for Rovibrational Excitation of CN Due to H2

NASA Astrophysics Data System (ADS)

Byrd, Nat; Yang, Benhui H.; Stancil, Phillip C.

2018-06-01

Diatomic molecules can be readily excited in interstellar environments exposed to intense UV radiation, such as the inner rim of a protoplanetary disk. Non-thermal populations of excited rovibrational levels can result, for example, following decay from electronically excited states to the electronic ground state. Competition between radiative decay and collisional processes, mostly due to H2, determine the resulting rovibrational emission spectrum. For CN, and other open-shell molecules, the resulting spectrum will be complicated due to fine-structure splitting of the rotational levels. In some cases, fine-structure resolution has been previously computed for rotational transitions in atom- or diatom-diatom collisional processes. Here we present the first fine-structure resolution for vibrational deexcitation for CN colliding with H2. The collisional cross sections were computed using a 6D potential energy surface with a full close-coupling approach. Fine-structure resolution is obtained by adopting an angular momentum recoupling scheme to transform the scattering matrices to a recoupled basis. Here we present low-energy calculations for the v=1 to 0 transition.This work was supported by NASA Grant NNX16AF09G.

Application of novel low-intensity nonscanning fluorescence lifetime imaging microscopy for monitoring excited state dynamics in individual chloroplasts and living cells of photosynthetic organisms

NASA Astrophysics Data System (ADS)

Eckert, Hann-Jörg; Petrášek, Zdeněk; Kemnitz, Klaus

2006-10-01

Picosecond fluorescence lifetime imaging microscopy (FLIM) provides a most valuable tool to analyze the primary processes of photosynthesis in individual cells and chloroplasts of living cells. In order to obtain correct lifetimes of the excited states, the peak intensity of the exciting laser pulses as well as the average intensity has to be sufficiently low to avoid distortions of the kinetics by processes such as singlet-singlet annihilation, closing of the reaction centers or photoinhibition. In the present study this requirement is achieved by non-scanning wide-field FLIM based on time- and space-correlated single-photon counting (TSCSPC) using a novel microchannel plate photomultiplier with quadrant anode (QA-MCP) that allows parallel acquisition of time-resolved images under minimally invasive low-excitation conditions. The potential of the wide-field TCSPC method is demonstrated by presenting results obtained from measurements of the fluorescence dynamics in individual chloroplasts of moss leaves and living cells of the chlorophyll d-containing cyanobacterium Acaryochloris marina.

Surface-Enhanced Impulsive Coherent Vibrational Spectroscopy

PubMed Central

Du, Juan; Harra, Juha; Virkki, Matti; Mäkelä, Jyrki M.; Leng, Yuxin; Kauranen, Martti; Kobayashi, Takayoshi

2016-01-01

Surface-enhanced Raman spectroscopy (SERS) has attracted a lot of attention in molecular sensing because of the remarkable ability of plasmonic metal nanostructures to enhance the weak Raman scattering process. On the other hand, coherent vibrational spectroscopy triggered by impulsive excitation using ultrafast laser pulses provides complete information about the temporal evolution of molecular vibrations, allowing dynamical processes in molecular systems to be followed in “real time”. Here, we combine these two concepts and demonstrate surface-enhanced impulsive vibrational spectroscopy. The vibrational modes of the ground and excited states of poly[2-methoxy-5-(2-ethylhexyloxy)−1,4-phenylenevinylene] (MEH-PPV), spin-coated on a substrate covered with monodisperse silver nanoparticles, are impulsively excited with a sub-10 fs pump pulse and characterized with a delayed broad-band probe pulse. The maximum enhancement in the spectrally and temporally resolved vibrational signatures averaged over the whole sample is about 4.6, while the real-time information about the instantaneous vibrational amplitude together with the initial vibrational phase is preserved. The phase is essential to determine the vibrational contributions from the ground and excited states. PMID:27812020

The molecular mechanism of excitation in visual transduction and bacteriorhodopsin

PubMed Central

Lewis, Aaron

1978-01-01

An electronic theory of excitation is proposed and described in terms of a three-dimensional excited/ground-state energy surface which elucidates the photochemical and excited-state dynamics of rhodopsins. In this theory the primary action of light is to produce significant electron redistribution in the retinal, thereby generating new interactions that vibrationally excite and perturb the ground-state protein conformation. Thus, light energy causes charge redistribution in the retinal and induces transient charge-density assisted bond rearrangements (such as proton translocation) in the protein structure which is stabilized by subsequent retinal structural alteration. In this theory the isoprenoid chain of the retinal is considered a structurally pliable molecular entity that can generate charge redistributions and can be subsequently achieve intermediate conformations or various isomeric states to minimize the energy of the new protein structure generated by light. Thus, the 11-cis to all trans isomerization of the retinylidene chromophore is not considered a primary mechanism of excitation. An alternate biological role for this molecular process (which is eventually completed in all photoreceptors but not in bacterial rhodopsins) is to provide the irreversibility needed for effective quantum detection on the time scale of a neural response. Finally, it will be demonstrated that this mechanism, which readily accounts for the photophysical and photochemical data, can also be restated in terms of the Monod, Wyman, and Changeux terminology suggesting that aggregates of these pigments may function allosterically. PMID:273216

Very slow decay of a defect related emission band at 2.4 eV in AlN: Signatures of the Si related shallow DX state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lamprecht, M., E-mail: matthias.lamprecht@uni-ulm.de; Grund, C.; Neuschl, B.

2016-04-21

We report on a defect related luminescence band at 2.4 eV in aluminum nitride bulk crystals, for which we find strong indications to be related to silicon DX centers. Time resolved photoluminescence spectroscopy using a sub-bandgap excitation reveals two different recombination processes with very long decay times of 13 ms and 153 ms at low temperature. Based on the results of temperature and excitation dependent photoluminescence experiments, the process with the shorter lifetime is assigned to a donor-acceptor pair transition involving the shallow silicon donor state, which can be emptied with a thermal dissociation energy of 65 meV. The slower process with a thermalmore » quenching energy of 15 meV is assigned to the slightly deeper Si DX state known from electron paramagnetic resonance experiments, which is transferred back to the shallow donor state.« less

Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission† †Electronic supplementary information (ESI) available: Actinic pump spectrum, discussion on ground state addition process, peak fitting procedure, transient absorption data, power dependence measurements, etalon pulse shaping, TIPS-pentacene FSRS data, and optimized geometry and frequency calculation results. See DOI: 10.1039/c7sc03496b

PubMed Central

Hart, Stephanie M.; Silva, W. Ruchira

2017-01-01

Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes. PMID:29675170

Excited-state solvation and proton transfer dynamics of DAPI in biomimetics and genomic DNA.

PubMed

Banerjee, Debapriya; Pal, Samir Kumar

2008-08-14

The fluorescent probe DAPI (4',6-diamidino-2-phenylindole) is an efficient DNA binder. Studies on the DAPI-DNA complexes show that the probe exhibits a wide variety of interactions of different strengths and specificities with DNA. Recently the probe has been used to report the environmental dynamics of a DNA minor groove. However, the use of the probe as a solvation reporter in restricted environments is not straightforward. This is due to the presence of two competing relaxation processes (intramolecular proton transfer and solvation stabilization) in the excited state, which can lead to erroneous interpretation of the observed excited-state dynamics. In this study, the possibility of using DAPI to unambiguously report the environmental dynamics in restricted environments including DNA is explored. The dynamics of the probe is studied in bulk solvents, biomimetics like micelles and reverse micelles, and genomic DNA using steady-state and picosecond-resolved fluorescence spectroscopies.

Optical properties of an inhomogeneously broadened ΛV-system with multiple excited states

NASA Astrophysics Data System (ADS)

Kaur, Paramjit; Bharti, Vineet; Wasan, Ajay

2014-09-01

We present a theoretical model using a density matrix approach to show the influence of multiple excited states on the optical properties of an inhomogeneously broadened ?V-system of the ?Rb D2 line. These closely spaced multiple excited states cause asymmetry in absorption and dispersion profiles. We observe the reduced absorption profiles, due to dressed state interactions of the applied electromagnetic fields, which results the Mollow sideband-like transparency windows. In a room temperature vapor, we obtain a narrow enhanced absorption and steep positive dispersion at the line center when the strengths of control and pump fields are equal. Here, we show how the probe transmittance varies when it passes through the atomic medium. We also discuss the transient behavior of our system which agrees well with the corresponding absorption and dispersion profiles. This study has potential applications in controllability of group velocity, and for optical and quantum information processing.

Ultrafast Spin Crossover in [FeII (bpy)3 ]2+ : Revealing Two Competing Mechanisms by Extreme Ultraviolet Photoemission Spectroscopy.

PubMed

Moguilevski, Alexandre; Wilke, Martin; Grell, Gilbert; Bokarev, Sergey I; Aziz, Saadullah G; Engel, Nicholas; Raheem, Azhr A; Kühn, Oliver; Kiyan, Igor Yu; Aziz, Emad F

2017-03-03

Photoinduced spin-flip in Fe II complexes is an ultrafast phenomenon that has the potential to become an alternative to conventional processing and magnetic storage of information. Following the initial excitation by visible light into the singlet metal-to-ligand charge-transfer state, the electronic transition to the high-spin quintet state may undergo different pathways. Here we apply ultrafast XUV (extreme ultraviolet) photoemission spectroscopy to track the low-to-high spin dynamics in the aqueous iron tris-bipyridine complex, [Fe(bpy) 3 ] 2+ , by monitoring the transient electron density distribution among excited states with femtosecond time resolution. Aided by first-principles calculations, this approach enables us to reveal unambiguously both the sequential and direct de-excitation pathways from singlet to quintet state, with a branching ratio of 4.5:1. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical modulation of electronic structure at the excited state

NASA Astrophysics Data System (ADS)

Li, F.; Song, C.; Gu, Y. D.; Saleem, M. S.; Pan, F.

2017-12-01

Spin-polarized electronic structures are the cornerstone of spintronics, and have thus attracted a significant amount of interest; in particular, researchers are looking into how to modulate the electronic structure to enable multifunctional spintronics applications, especially in half-metallic systems. However, the control of the spin polarization has only been predicted in limited two-dimensional systems with spin-polarized Dirac structures and is difficult to achieve experimentally. Here, we report the modulation of the electronic structure in the light-induced excited state in a typical half-metal, L a1 /2S r1 /2Mn O3 -δ . According to the spin-transport measurements, there appears a light-induced increase in magnetoresistance due to the enhanced spin scattering, which is closely associated with the excited spin polarization. Strikingly, the light-induced variation can be enhanced via alcohol processing and reduced by oxygen annealing. X-ray photoelectron spectroscopy measurements show that in the chemical process, a redox reaction occurs with a change in the valence of Mn. Furthermore, first-principles calculations reveal that the change in the valence of Mn alters the electronic structure and consequently modulates the spin polarization in the excited state. Our findings thus report a chemically tunable electronic structure, demonstrating interesting physics and the potential for multifunctional applications and ultrafast spintronics.

A Multireference Configuration Interaction Study of the Photodynamics of Nitroethylene

PubMed Central

2014-01-01

Extended multireference configuration interaction with singles and doubles (MR-CISD) calculations of nitroethylene (H2C=CHNO2) were carried out to investigate the photodynamical deactivation paths to the ground state. The ground (S0) and the first five valence excited electronic states (S1–S5) were investigated. In the first step, vertical excitations and potential energy curves for CH2 and NO2 torsions and CH2 out-of-plane bending starting from the ground state geometry were computed. Afterward, five conical intersections, one between each pair of adjacent states, were located. The vertical calculations mostly confirm the previous assignment of experimental spectrum and theoretical results using lower-level calculations. The conical intersections have as main features the torsion of the CH2 moiety, different distortions of the NO2 group and CC, CN, and NO bond stretchings. In these conical intersections, the NO2 group plays an important role, also seen in excited state investigations of other nitro molecules. Based on the conical intersections found, a photochemical nonradiative deactivation process after a π–π* excitation to the bright S5 state is proposed. In particular, the possibility of NO2 release in the ground state, an important property in nitro explosives, was found to be possible. PMID:25158277

The Impact of Emotional States on Cognitive Control Circuitry and Function.

PubMed

Cohen, Alexandra O; Dellarco, Danielle V; Breiner, Kaitlyn; Helion, Chelsea; Heller, Aaron S; Rahdar, Ahrareh; Pedersen, Gloria; Chein, Jason; Dyke, Jonathan P; Galvan, Adriana; Casey, B J

2016-03-01

Typically in the laboratory, cognitive and emotional processes are studied separately or as a stream of fleeting emotional stimuli embedded within a cognitive task. Yet in life, thoughts and actions often occur in more lasting emotional states of arousal. The current study examines the impact of emotions on actions using a novel behavioral paradigm and functional neuroimaging to assess cognitive control under sustained states of threat (anticipation of an aversive noise) and excitement (anticipation of winning money). Thirty-eight healthy adult participants were scanned while performing an emotional go/no-go task with positive (happy faces), negative (fearful faces), and neutral (calm faces) emotional cues, under threat or excitement. Cognitive control performance was enhanced during the excited state relative to a nonarousing control condition. This enhanced performance was paralleled by heightened activity of frontoparietal and frontostriatal circuitry. In contrast, under persistent threat, cognitive control was diminished when the valence of the emotional cue conflicted with the emotional state. Successful task performance in this conflicting emotional condition was associated with increased activity in the posterior cingulate cortex, a default mode network region implicated in complex processes such as processing emotions in the context of self and monitoring performance. This region showed positive coupling with frontoparietal circuitry implicated in cognitive control, providing support for a role of the posterior cingulate cortex in mobilizing cognitive resources to improve performance. These findings suggest that emotional states of arousal differentially modulate cognitive control and point to the potential utility of this paradigm for understanding effects of situational and pathological states of arousal on behavior.

Relaxation pathways of photoexcited iodide-methanol clusters: a computational investigation.

PubMed

Mak, Chun C; Peslherbe, Gilles H

2014-06-26

Upon photoexcitation of iodide-methanol clusters, I(-)(CH3OH)n, to a charge-transfer-to-solvent (CTTS) excited state, extensive relaxation was found to occur, accompanied by a convoluted modulation of the stability of the excited electron, which ultimately decreases substantially. In order to develop a molecular-level understanding of the relaxation processes of CTTS excited I(-)(CH3OH)n, high-level quantum chemical calculations are first used to investigate the ground, excited, and ionized states of I(-)(CH3OH)n (n = 2). Because of the relatively small size of I(-)(CH3OH)2, it was possible to characterize the contributions of solvent-solvent interactions to the stability of the CTTS excited cluster relative to dissociation into methanol, iodine, and a free electron, which exhibits a substantial dependence on the cluster geometric configuration. Ab initio molecular dynamics simulations of CTTS excited I(-)(CH3OH)3 are then performed to shed some light onto the nature of the relaxation pathways involved in the modulation of the stability of the excited electron in larger clusters. Simulation results suggest that separation of I and (CH3OH)3(-) accompanied by solvent reorganization in the latter can initially stabilize the excited electron, while gradual cluster fragmentation to I, (CH3OH)2(-), and CH3OH ultimately destabilizes it. This work shows, for the first time, that the inability of small CTTS excited I(-)(CH3OH)n to retain a solvated electron may be attributed to the limited hydrogen-bonding capacity of CH3OH, which increases the propensity for fragmentation to smaller clusters with lower excess-electron binding energies, and highlights the critical role of intricate molecular interactions in the electron solvation process.

Nonequilibrium spin crossover in copper phthalocyanine

NASA Astrophysics Data System (ADS)

Siegert, Benjamin; Donarini, Andrea; Grifoni, Milena

2016-03-01

We demonstrate the nonequilibrium tip induced control of the spin state of copper phthalocyanine on an insulator coated substrate. We find that, under the condition of energetic proximity of many-body neutral excited states to the anionic ground state, the system can undergo a population inversion towards these excited states. The resulting state of the system is accompanied by a change in the total spin quantum number. Experimental signatures of the crossover are the appearance of additional nodal planes in the topographical scanning tunneling microscopy images as well as a strong suppression of the current near the center of the molecule. The robustness of the effect against moderate charge conserving relaxation processes has also been tested.

Dewar Lesion Formation in Single- and Double-Stranded DNA is Quenched by Neighboring Bases.

PubMed

Bucher, Dominik B; Pilles, Bert M; Carell, Thomas; Zinth, Wolfgang

2015-07-16

UV-induced Dewar lesion formation is investigated in single- and double-stranded oligonucleotides with ultrafast vibrational spectroscopy. The quantum yield for the conversion of the (6-4) lesion to the Dewar isomer in DNA strands is reduced by a factor of 4 in comparison to model dinucleotides. Time resolved spectroscopy reveals a fast process in the excited state with spectral characteristics of bases which are adjacent to the excited (6-4) lesion. These kinetic components have large amplitudes and indicate that an additional quenching channel acts in the stranded DNA systems and reduces the Dewar formation yield. Presumably relaxation evolves via a charge transfer to the neighboring guanine and the paired cytosine participates in a double-stranded oligomer. Changes in the decay of the relaxed excited electronic state of the (6-4) chromophore point to modifications in the excited state energy landscape which may lead to an additional reduction of the Dewar formation yield.

REVIEW: Excited states in the active media of oxygen — iodine lasers

NASA Astrophysics Data System (ADS)

Azyazov, V. N.

2009-11-01

A review of investigations of kinetic processes in active media oxygen — iodine lasers (OILs) performed in the last decade is presented. The mechanisms of pumping and quenching of electronically and vibrationally excited O2 and I2 molecules are considered, and dissociation mechanisms of I2 in the active medium of the OIL are analysed. The values of kinetic constants of processes proceeding in the active media of OILs are recommended.

Time Crystal Behavior of Excited Eigenstates

NASA Astrophysics Data System (ADS)

Syrwid, Andrzej; Zakrzewski, Jakub; Sacha, Krzysztof

2017-12-01

In analogy to spontaneous breaking of continuous space translation symmetry in the process of space crystal formation, it was proposed that spontaneous breaking of continuous time translation symmetry could lead to time crystal formation. In other words, a time-independent system prepared in the energy ground state is expected to reveal periodic motion under infinitely weak perturbation. In the case of the system proposed originally by Wilczek, spontaneous breaking of time translation symmetry cannot be observed if one starts with the ground state. We point out that the symmetry breaking can take place if the system is prepared in an excited eigenstate. The latter can be realized experimentally in ultracold atomic gases. We simulate the process of the spontaneous symmetry breaking due to measurements of particle positions and analyze the lifetime of the resulting symmetry broken state.

Time Crystal Behavior of Excited Eigenstates.

PubMed

Syrwid, Andrzej; Zakrzewski, Jakub; Sacha, Krzysztof

2017-12-22

In analogy to spontaneous breaking of continuous space translation symmetry in the process of space crystal formation, it was proposed that spontaneous breaking of continuous time translation symmetry could lead to time crystal formation. In other words, a time-independent system prepared in the energy ground state is expected to reveal periodic motion under infinitely weak perturbation. In the case of the system proposed originally by Wilczek, spontaneous breaking of time translation symmetry cannot be observed if one starts with the ground state. We point out that the symmetry breaking can take place if the system is prepared in an excited eigenstate. The latter can be realized experimentally in ultracold atomic gases. We simulate the process of the spontaneous symmetry breaking due to measurements of particle positions and analyze the lifetime of the resulting symmetry broken state.

Dynamics of a single-atom electron pump.

PubMed

van der Heijden, J; Tettamanzi, G C; Rogge, S

2017-03-15

Single-electron pumps based on isolated impurity atoms have recently been experimentally demonstrated. In these devices the Coulomb potential of an atom creates a localised electron state with a large charging energy and considerable orbital level spacings, enabling robust charge capturing processes. In contrast to the frequently used gate-defined quantum dot pumps, which experience a strongly time-dependent potential, the confinement potential in these single-atom pumps is hardly affected by the periodic driving of the system. Here we describe the behaviour and performance of an atomic, single parameter, electron pump. This is done by considering the loading, isolating and unloading of one electron at the time, on a phosphorous atom embedded in a silicon double gate transistor. The most important feature of the atom pump is its very isolated ground state, which is populated through the fast loading of much higher lying excited states and a subsequent fast relaxation process. This leads to a substantial increase in pumping accuracy, and is opposed to the adverse role of excited states observed for quantum dot pumps due to non-adiabatic excitations. The pumping performance is investigated as a function of dopant position, revealing a pumping behaviour robust against the expected variability in atomic position.

Dynamics of a single-atom electron pump

PubMed Central

van der Heijden, J.; Tettamanzi, G. C.; Rogge, S.

2017-01-01

Single-electron pumps based on isolated impurity atoms have recently been experimentally demonstrated. In these devices the Coulomb potential of an atom creates a localised electron state with a large charging energy and considerable orbital level spacings, enabling robust charge capturing processes. In contrast to the frequently used gate-defined quantum dot pumps, which experience a strongly time-dependent potential, the confinement potential in these single-atom pumps is hardly affected by the periodic driving of the system. Here we describe the behaviour and performance of an atomic, single parameter, electron pump. This is done by considering the loading, isolating and unloading of one electron at the time, on a phosphorous atom embedded in a silicon double gate transistor. The most important feature of the atom pump is its very isolated ground state, which is populated through the fast loading of much higher lying excited states and a subsequent fast relaxation process. This leads to a substantial increase in pumping accuracy, and is opposed to the adverse role of excited states observed for quantum dot pumps due to non-adiabatic excitations. The pumping performance is investigated as a function of dopant position, revealing a pumping behaviour robust against the expected variability in atomic position. PMID:28295055

Collisional and radiative processes in high-pressure discharge plasmas

NASA Astrophysics Data System (ADS)

Becker, Kurt H.; Kurunczi, Peter F.; Schoenbach, Karl H.

2002-05-01

Discharge plasmas at high pressures (up to and exceeding atmospheric pressure), where single collision conditions no longer prevail, provide a fertile environment for the experimental study of collisions and radiative processes dominated by (i) step-wise processes, i.e., the excitation of an already excited atomic/molecular state and by (ii) three-body collisions leading, for instance, to the formation of excimers. The dominance of collisional and radiative processes beyond binary collisions involving ground-state atoms and molecules in such environments allows for many interesting applications of high-pressure plasmas such as high power lasers, opening switches, novel plasma processing applications and sputtering, absorbers and reflectors for electromagnetic waves, remediation of pollutants and waste streams, and excimer lamps and other noncoherent vacuum-ultraviolet light sources. Here recent progress is summarized in the use of hollow cathode discharge devices with hole dimensions in the range 0.1-0.5 mm for the generation of vacuum-ultraviolet light.

Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

DOE PAGES

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

2016-08-02

Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups.more » Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S 2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.« less

Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups.more » Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S 2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.« less

Metastable Oxygen Production by Electron-Impact of Oxygen

NASA Astrophysics Data System (ADS)

Hein, J. D.; Malone, C. P.; Kanik, I.; Johnson, P. V.

2013-12-01

Electron-impact excitation processes involving atomic and molecular oxygen are important in atmospheric interactions. The production of long-lived metastable O(1S) and O(1D) through electron impact of atomic O and molecular O2 play a significant role in the dynamics of oxygen-containing atmospheres (Earth, Europa, Io). Emissions from metastable O (1S → 1D) produce the well-recognized green light from terrestrial aurora. Electron-impact excitation to 1S and 1D are sensitive channels for determining energy partitioning and dynamics from space weather. Electron-impact excitation cross sections determined through fundamental experimental studies are necessary for modeling of natural phenomena and observation data. The detection of metastable states in laboratory experiments requires a novel approach, since typical detection techniques (e.g., fluorescence by radiative de-excitation) cannot be performed due to the long-lived nature of the excited species. In this work, metastable O is incident on a cryogenically cooled rare gas matrix, where excimer production and subsequent rapid radiative de-excitation provides measurable signal that is directly related to the originating electron-impact excitation process.

Metastable Oxygen Production by Electron-Impact of Oxygen

NASA Astrophysics Data System (ADS)

Hein, Jeffrey; Johnson, Paul; Kanik, Isik; Malone, Charles

2014-05-01

Electron-impact excitation processes involving atomic and molecular oxygen are important in atmospheric interactions. The production of long-lived metastable O(1S) and O(1D) through electron impact of atomic O and molecular O2 play a significant role in the dynamics of oxygen-containing atmospheres (Earth, Europa, Io). Emissions from metastable O (1S --> 1D) produce the well-recognized green light from terrestrial aurora. Electron-impact excitation to 1S and 1D are sensitive channels for determining energy partitioning and dynamics from space weather. Electron-impact excitation cross sections determined through fundamental experimental studies are necessary for modeling of natural phenomena and observation data. The detection of metastable states in laboratory experiments requires a novel approach, since typical detection techniques (e.g., fluorescence by radiative de-excitation) cannot be performed due to the long-lived nature of the excited species. In this work, metastable O is produced through electron impact, and is incident on a cryogenically cooled rare gas matrix. The excimer production and subsequent rapid radiative de-excitation provides measurable signal that is directly related to the originating electron-impact excitation process.

Laser-induced fluorescence fiber optic probe measurement of oil dilution by fuel

DOEpatents

Parks, II, James E [Knoxville, TN; Partridge, Jr., William P [Oak Ridge, TN

2010-11-23

Apparatus for detecting fuel in oil includes an excitation light source in optical communication with an oil sample for exposing the oil sample to excitation light in order to excite the oil sample from a non-excited state to an excited state and a spectrally selective device in optical communication with the oil sample for detecting light emitted from the oil sample as the oil sample returns from the excited state to a non-excited state to produce spectral indicia that can be analyzed to determine the presence of fuel in the oil sample. A method of detecting fuel in oil includes the steps of exposing a oil sample to excitation light in order to excite the oil sample from a non-excited state to an excited state, as the oil sample returns from the excited state to a non-excited state, detecting light emitted from the oil sample to produce spectral indicia; and analyzing the spectral indicia to determine the presence of fuel in the oil sample.

Laboratory Kinetic Studies of OH and CO2 Relevant to Upper Atmospheric Radiation Balance

NASA Technical Reports Server (NTRS)

Nelson, David D.; Villalta, Peter; Zahniser, Mark S.; Kolb, Charles E.

1997-01-01

The purpose of this project was to quantify the rates of two processes which are crucial to our understanding of radiative energy balance in the upper atmosphere. The first process is radiative emission from vibrationally hot OH radicals following the H + O3 reaction in the upper mesosphere. The importance of this process depends strongly on the OH radiative emission coefficients. Our goal was to measure the OH permanent dipole moment in excited vibrational states and to use these measurements to construct an improved OH dipole moment function and improved radiative emission coefficients. Significant progress was made on these experiments including the construction of a supersonic jet source for vibrationally excited OH radicals. Unfortunately, our efforts to transport the OH radicals into a second lower pressure vacuum chamber were not successful, and we were unable to make improved dipole moment measurements for OH. The second key kinetic process which we attempted to quantify during this project is the rate of relaxation of bend-excited CO2 by oxygen atoms. Since excitation of the bending vibrational mode of CO2 is the major cooling mechanism in the upper mesosphere/lower thermosphere, the cooling rate of this region depends crucially on the rate of energy transfer out of this state. It is believed that the most efficient transfer mechanism is via atomic oxygen but the rate for this process has not been directly measured in the laboratory at appropriate temperatures and even the room temperature rate remains controversial. We attempted to directly measure the relaxation rate Of CO2 (010) by oxygen atoms using the discharge flow technique. This experiment was set up at Aerodyne Research. Again, significant progress was achieved in this experiment. A hot CO2 source was set up, bend excited CO2 was detected and the rate of relaxation of bend excited CO2 by He atoms was measured. Unfortunately, the project ran out of time before the oxygen atom kinetic studies could be implemented.

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

NASA Technical Reports Server (NTRS)

Hansen, C. Frederick

1993-01-01

Most of the important chemical reactions which occur in the very high temperature air produced around space vehicles as they enter the atmosphere were investigated both experimentally and theoretically, to some extent at least. One remaining reaction about which little is known, and which could be quite important at the extremely high temperatures that will be produced by the class of space vehicles now contemplated - such as the AOTV - is the excitation of bound electron states due to collisions between heavy gas particles. Rates of electronic excitation due to free electron collisions are known to be very rapid, but because these collisions quickly equilibrate the free and bound electron energy, the approach to full equilibrium with the heavy particle kinetic energy will depend primarily on the much slower process of bound electron excitation in heavy particle collisions and the subsequent rapid transfer to free electron energy. This may be the dominant mechanism leading to full equilibrium in the gas once the dissociation process has depleted the molecular states so the transfer between molecular vibrational energy and free electron energy is no longer available as a channel for equilibration of free electron and heavy particle kinetic energies. Two mechanisms seem probable in electronic excitation by heavy particle impact. One of these is the collision excitation and deexcitation of higher electronic states which are Rydberg like. A report, entitled 'Semi-Classical Theory of Electronic Excitation Rates', was submitted previously. This presented analytic expressions for the transition probabilities, assuming that the interaction potential is an exponential repulsion with a perturbation ripple due to the dipole-induced dipole effect in the case of neutral-neutral collisions, and to the ion-dipole interaction in the case of ion-neutral collisions. However the above may be, there is little doubt that excitation of ground state species by collision occurs at the point where the initial and final potentials cross, or at least come very close. Therefore, this mechanism would be applicable to the case where a gas is initially at very low temperature suddenly subjected to high energy heavy particle bombardment. This situation would model the measurement of excitation cross section by molecular beam techniques, for example. The purpose is to report values of cross sections and rate coefficients for collision excitation of ground state atoms estimated with the Landau-Zener transition theory and to compare results with measurement of excitation cross sections for a beam of Hydrogen atoms impacting Argon atom targets. Some very dubious approximations are used, and the comparison with measurement is found less than ideal, but results are at least consistent within order of magnitude. The same model is then applied to the case of N-N atom collisions, even though the approximations then become even more doubtful. Still the rate coefficients obtained are at least plausible in both magnitude and functional form, and as far as I am aware these are the only estimates available for such rate coefficients.

Laminar-specific Scaling Down of Balanced Excitation and Inhibition in Auditory Cortex by Active Behavioral States

PubMed Central

Zhou, Mu; Liang, Feixue; Xiong, Xiaorui R.; Li, Lu; Li, Haifu; Xiao, Zhongju; Tao, Huizhong W.; Zhang, Li I.

2014-01-01

Cortical sensory processing is modulated by behavioral and cognitive states. How the modulation is achieved through impacting synaptic circuits remains largely unknown. In awake mouse auditory cortex, we reported that sensory-evoked spike responses of layer 2/3 (L2/3) excitatory cells were scaled down with preserved sensory tuning when animals transitioned from quiescence to active behaviors, while L4 and thalamic responses were unchanged. Whole-cell voltage-clamp recordings further revealed that tone-evoked synaptic excitation and inhibition exhibited a robust functional balance. Changes of behavioral state caused scaling down of excitation and inhibition at an approximately equal level in L2/3 cells, but no synaptic changes in L4 cells. This laminar-specific gain control could be attributed to an enhancement of L1–mediated inhibitory tone, with L2/3 parvalbumin inhibitory neurons suppressed as well. Thus, L2/3 circuits can adjust the salience of output in accordance with momentary behavioral demands while maintaining the sensitivity and quality of sensory processing. PMID:24747575

Atomic Processes for XUV Lasers: Alkali Atoms and Ions

NASA Astrophysics Data System (ADS)

Dimiduk, David Paul

The development of extreme ultraviolet (XUV) lasers is dependent upon knowledge of processes in highly excited atoms. Described here are spectroscopy experiments which have identified and characterized certain autoionizing energy levels in core-excited alkali atoms and ions. Such levels, termed quasi-metastable, have desirable characteristics as upper levels for efficient, powerful XUV lasers. Quasi -metastable levels are among the most intense emission lines in the XUV spectra of core-excited alkalis. Laser experiments utilizing these levels have proved to be useful in characterizing other core-excited levels. Three experiments to study quasi-metastable levels are reported. The first experiment is vacuum ultraviolet (VUV) absorption spectroscopy on the Cs 109 nm transitions using high-resolution laser techniques. This experiment confirms the identification of transitions to a quasi-metastable level, estimates transition oscillator strengths, and estimates the hyperfine splitting of the quasi-metastable level. The second experiment, XUV emission spectroscopy of Ca II and Sr II in a microwave-heated plasma, identifies transitions from quasi-metastable levels in these ions, and provides confirming evidence of their radiative, rather than autoionizing, character. In the third experiment, core-excited Ca II ions are produced by inner-shell photoionization of Ca with soft x-rays from a laser-produced plasma. This preliminary experiment demonstrated a method of creating large numbers of these highly-excited ions for future spectroscopic experiments. Experimental and theoretical evidence suggests the CA II 3{ rm p}^5 3d4s ^4 {rm F}^circ_{3/2 } quasi-metastable level may be directly pumped via a dipole ionization process from the Ca I ground state. The direct process is permitted by J conservation, and occurs due to configuration mixing in the final state and possibly the initial state as well. The experiments identifying and characterizing quasi-metastable levels are compared to calculations using the Hartree-Fock code RCN/RCG. Calculated parameters include energy levels, wavefunctions, and transition rates. Based on an extension of this code, earlier unexplained experiments showing strong two-electron radiative transitions from quasi-metastable levels are now understood.

Photodissociation of OCS: deviations between theory and experiment, and the importance of higher order correlation effects.

PubMed

Schmidt, J A; Olsen, J M H

2014-11-14

The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 136, 131101 (2012); J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 2(1)A' (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 1(1)A″ (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO.

Polymethine and squarylium molecules with large excited-state absorption

NASA Astrophysics Data System (ADS)

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

1999-07-01

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

Circular polarization of X-ray radiation emitted by longitudinally polarized electron impact excitation: Under a screened Coulomb interaction

NASA Astrophysics Data System (ADS)

Chen, Zhan-Bin

2017-12-01

Longitudinally polarized electron impact excitation from the ground state 1s2 to the excited state 1s2l (l =s,p) levels of highly charged He-like Fe24+ ions in weakly coupled hot-dense plasmas is investigated using a fully relativistic distorted-wave method. The Debye-Hückel potential is used to describe the plasma screening. Benchmark results such as the total cross sections, the magnetic sublevels cross sections, and the circular polarizations of corresponding X-ray radiations are presented. For the excitation process, results show that the plasma screening has an effect in reducing both the total and magnetic sublevels cross sections. For the de-excitation process, it is found that while the plasma screening as a slightly effect on the circular polarizations of radiations for the 1 s 2 s 3S1 → 1 s21S0,1 s 2 p 3P2 → 1 s21S0 , and 1 s 2 p 1P1 → 1 s21S0 transition lines, it gives a substantial contribution for the same properties of the 1 s 2 p 3P1 → 1 s21S0 line.

Photoinduced Charge Shifts and Electron Transfer in Viologen-Tetraphenylborate Complexes: Push-Pull Character of the Exciplex.

PubMed

Santos, Willy G; Budkina, Darya S; Deflon, Victor M; Tarnovsky, Alexander N; Cardoso, Daniel R; Forbes, Malcolm D E

2017-06-14

Viologen-tetraarylborate ion-pair complexes were prepared and investigated by steady-state and time-resolved spectroscopic techniques such as fluorescence and femtosecond transient absorption. The results highlight a charge transfer transition that leads to changes in the viologen structure in the excited singlet state. Femtosecond transient absorption reveals the formation of excited-state absorption and stimulated emission bands assigned to the planar (k obs < 10 12 s -1 ) and twisted (k obs ∼ 10 10 s -1 ) structures between two pyridinium groups in the viologen ion. An efficient photoinduced electron transfer from the tetraphenylborate anionic moiety to the viologen dication was observed less than 1 μs after excitation. This is a consequence of the push-pull character of the electron donor twisted viologen structure, which helps formation of the borate triplet state. The borate triplet state is deactivated further via a second electron transfer process, generating viologen cation radical (V •+ ).

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nelson, Tammie Renee; Tretiak, Sergei

2017-01-06

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

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

PubMed

Maurer, Reinhard J; Reuter, Karsten

2013-07-07

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

Even-parity resonances with synchrotron radiation from Laser Excited Lithium at 1s^22p State

NASA Astrophysics Data System (ADS)

Huang, Ming-Tie; Wehlitz, Ralf

2010-03-01

Correlated many-body dynamics is still one of the unsolved fundamental problems in physics. Such correlation effects can be most clearly studied in processes involving single atoms for their simplicity.Lithium, being the simplest open shell atom, has been under a lot of study. Most of the studies focused on ground state lithium. However, only odd parity resonances can be populated through single photon (synchrotron radiation) absorption from ground state lithium (1s^22s). Lithium atoms, after being laser excited to the 1s^22p state, allow the study of even parity resonances. We have measured some of the even parity resonances of lithium for resonant energies below 64 eV. A single-mode diode laser is used to excite lithium from 1s^22s ground state to 1s^22p (^2P3/2) state. Photoions resulting from the interaction between the excited lithium and synchrotron radiation were analyzed and collected by an ion time-of-flight (TOF) spectrometer with a Z- stack channel plate detector. The Li^+ ion yield was recorded while scanning the undulator along with the monochromator. The energy scans have been analyzed regarding resonance energies and parameters of the Fano profiles. Our results for the observed resonances will be presented.

Transition rate diagrams and excitation of titanium in a glow discharge in argon and neon

NASA Astrophysics Data System (ADS)

Weiss, Zdeněk; Steers, Edward B. M.; Pickering, Juliet C.

2018-06-01

Emission spectra of titanium in a Grimm-type glow discharge in argon and neon were studied using the formalism of transition rate diagrams. Ti I spectra in argon and neon discharges are similar, without signs of selective excitation, and populations of Ti I levels exhibit a decreasing trend as function of energy, except for some scatter. A major excitation process of Ti II in argon discharge is charge transfer from argon ions to neutral titanium. In neon discharge, a strong selective excitation was observed of Ti II levels at ≈13.3-13.4 eV relative to the Ti I ground state. It was attributed to charge transfer from doubly charged titanium ions to neutral titanium, while the Ti++ ions are produced by charge transfer and ionization of neutral titanium by neon ions. Cascade excitation is important for Ti II levels up to an energy of ≈13 eV relative to the Ti I ground state, both in argon and neon discharges.

Charge transfer excitations from exact and approximate ensemble Kohn-Sham theory

NASA Astrophysics Data System (ADS)

Gould, Tim; Kronik, Leeor; Pittalis, Stefano

2018-05-01

By studying the lowest excitations of an exactly solvable one-dimensional soft-Coulomb molecular model, we show that components of Kohn-Sham ensembles can be used to describe charge transfer processes. Furthermore, we compute the approximate excitation energies obtained by using the exact ensemble densities in the recently formulated ensemble Hartree-exchange theory [T. Gould and S. Pittalis, Phys. Rev. Lett. 119, 243001 (2017)]. Remarkably, our results show that triplet excitations are accurately reproduced across a dissociation curve in all cases tested, even in systems where ground state energies are poor due to strong static correlations. Singlet excitations exhibit larger deviations from exact results but are still reproduced semi-quantitatively.

Nonadiabatic Molecular Dynamics and Orthogonality Constrained Density Functional Theory

NASA Astrophysics Data System (ADS)

Shushkov, Philip Georgiev

The exact quantum dynamics of realistic, multidimensional systems remains a formidable computational challenge. In many chemical processes, however, quantum effects such as tunneling, zero-point energy quantization, and nonadiabatic transitions play an important role. Therefore, approximate approaches that improve on the classical mechanical framework are of special practical interest. We propose a novel ring polymer surface hopping method for the calculation of chemical rate constants. The method blends two approaches, namely ring polymer molecular dynamics that accounts for tunneling and zero-point energy quantization, and surface hopping that incorporates nonadiabatic transitions. We test the method against exact quantum mechanical calculations for a one-dimensional, two-state model system. The method reproduces quite accurately the tunneling contribution to the rate and the distribution of reactants between the electronic states for this model system. Semiclassical instanton theory, an approach related to ring polymer molecular dynamics, accounts for tunneling by the use of periodic classical trajectories on the inverted potential energy surface. We study a model of electron transfer in solution, a chemical process where nonadiabatic events are prominent. By representing the tunneling electron with a ring polymer, we derive Marcus theory of electron transfer from semiclassical instanton theory after a careful analysis of the tunneling mode. We demonstrate that semiclassical instanton theory can recover the limit of Fermi's Golden Rule rate in a low-temperature, deep-tunneling regime. Mixed quantum-classical dynamics treats a few important degrees of freedom quantum mechanically, while classical mechanics describes affordably the rest of the system. But the interface of quantum and classical description is a challenging theoretical problem, especially for low-energy chemical processes. We therefore focus on the semiclassical limit of the coupled nuclear-electronic dynamics. We show that the time-dependent Schrodinger equation for the electrons employed in the widely used fewest switches surface hopping method is applicable only in the limit of nearly identical classical trajectories on the different potential energy surfaces. We propose a short-time decoupling algorithm that restricts the use of the Schrodinger equation only to the interaction regions. We test the short-time approximation on three model systems against exact quantum-mechanical calculations. The approximation improves the performance of the surface hopping approach. Nonadiabatic molecular dynamics simulations require the efficient and accurate computation of ground and excited state potential energy surfaces. Unlike the ground state calculations where standard methods exist, the computation of excited state properties is a challenging task. We employ time-independent density functional theory, in which the excited state energy is represented as a functional of the total density. We suggest an adiabatic-like approximation that simplifies the excited state exchange-correlation functional. We also derive a set of minimal conditions to impose exactly the orthogonality of the excited state Kohn-Sham determinant to the ground state determinant. This leads to an efficient, variational algorithm for the self-consistent optimization of the excited state energy. Finally, we assess the quality of the excitation energies obtained by the new method on a set of 28 organic molecules. The new approach provides results of similar accuracy to time-dependent density functional theory.

Electron scattering measurements from molecules of technological relevance

NASA Astrophysics Data System (ADS)

Jones, Darryl

2014-10-01

Biomass represents a significant opportunity to provide renewable and sustainable biofuels. Non-thermal atmospheric pressure plasmas provide an opportunity to efficiently breakdown the naturally-resilient biomass into its useful subunits. Free electrons produced in the plasma may assist in this process by inducing fragmentation though dissociative excitation, ionization or attachment processes. To assist in understanding and refining this process, we have performed electron energy loss experiments from phenol (C6H5OH), a key structural building block of biomass. This enables a quantitative assessment of the excited electronic states of phenol. Differential cross sections for the electron-driven excitation of phenol have also been obtained for incident electron energies in the 20--250 eV range and over 3--90° scattering angles. DBJ acknowledges financial support provided by an Australian Research Council DECRA.

Electron kinetics dependence on gas pressure in laser-induced oxygen plasma experiment: Theoretical analysis

NASA Astrophysics Data System (ADS)

Gamal, Yosr E. E.-D.; Abdellatif, Galila

2017-08-01

A study is performed to investigate the dependency of threshold intensity on gas pressure observed in the measurements of the breakdown of molecular oxygen that carried out by Phuoc (2000) [1]. In this experiment, the breakdown was induced by 532 nm laser radiation of pulse width 5.5 ns and spot size of 8.5 μm, in oxygen over a wide pressure range (190-3000 Torr). The analysis aimed to explore the electron kinetic reliance on gas pressure for the separate contribution of each of the gain and loss processes encountered in this study. The investigation is based on an electron cascade model applied previously in Gamal and Omar (2001) [2] and Gaabour et al. (2013) [3]. This model solves numerically a differential equation designates the time evolution of the electron energy distribution, and a set of rate equations that describe the change of excited states population. The numerical examination of the electron energy distribution function and its parameters revealed that photo-ionization of the excited molecules plays a significant role in enhancing the electron density growth rate over the whole tested gas pressure range. This process is off set by diffusion of electrons out of the focal volume in the low-pressure regime. At atmospheric pressure electron, collisional processes dominate and act mainly to populate the excited states. Hence photo-ionization becomes efficient and compete with the encountered loss processes (electron diffusion, vibrational excitation of the ground state molecules as well as two body attachments). At high pressures ( 3000 Torr) three body attachments are found to be the primary cause of losses which deplete the electron density and hence results in the slow decrease of the threshold intensity.

Photoisomerization and photodissociation dynamics of reactive free radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bise, Ryan T.

2000-08-01

The photofragmentation pathways of chemically reactive free radicals have been examined using the technique of fast beam photofragment translational spectroscopy. Measurements of the photodissociation cross-sections, product branching ratios, product state energy distributions, and angular distributions provide insight into the excited state potential energy surfaces and nonadiabatic processes involved in the dissociation mechanisms. Photodissociation spectroscopy and dynamics of the predissociativemore » $$\\tilde{A}$$ 2A 1 and $$\\tilde{B}$$ 2A 2 states of CH 3S have been investigated. At all photon energies, CH 3 + S( 3P j), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH 3 umbrella mode and the S( 3P j) fine-structure distribution from which the nature of the coupled repulsive surfaces is inferred. Dissociation rates are deduced from the photofragment angular distributions, which depend intimately on the degree of vibrational excitation in the C-S stretch. Nitrogen combustion radicals, NCN, CNN and HNCN have also been studied. For all three radicals, the elimination of molecular nitrogen is the primary reaction channel. Excitation to linear excited triplet and singlet electronic states of the NCN radical generates resolved vibrational structure of the N 2 photofragment. The relatively low fragment rotational excitation suggests dissociation via a symmetric C 2V transition state. Resolved vibrational structure of the N 2 photofragment is also observed in the photodissociation of the HNCN radical. The fragment vibrational and rotational distributions broaden with increased excitation energy. Simple dissociation models suggest that the HNCN radical isomerizes to a cyclic intermediate (c-HCNN) which then dissociates via a tight cyclic transition state. In contrast to the radicals mentioned above, resolved vibrational structure was not observed for the ICNN radical due to extensive fragment rotational excitation, suggesting that intermediate bent states are strongly coupled along the dissociation pathway. The measurements performed in this Thesis have additionally refined the heats of formation and bond dissociation energies of these radicals and have unambiguously confirmed and added to the known electronic spectroscopy.« less

Collectivity in the light radon nuclei measured directly via Coulomb excitation

NASA Astrophysics Data System (ADS)

Gaffney, L. P.; Robinson, A. P.; Jenkins, D. G.; Andreyev, A. N.; Bender, M.; Blazhev, A.; Bree, N.; Bruyneel, B.; Butler, P. A.; Cocolios, T. E.; Davinson, T.; Deacon, A. N.; De Witte, H.; DiJulio, D.; Diriken, J.; Ekström, A.; Fransen, Ch.; Freeman, S. J.; Geibel, K.; Grahn, T.; Hadinia, B.; Hass, M.; Heenen, P.-H.; Hess, H.; Huyse, M.; Jakobsson, U.; Kesteloot, N.; Konki, J.; Kröll, Th.; Kumar, V.; Ivanov, O.; Martin-Haugh, S.; Mücher, D.; Orlandi, R.; Pakarinen, J.; Petts, A.; Peura, P.; Rahkila, P.; Reiter, P.; Scheck, M.; Seidlitz, M.; Singh, K.; Smith, J. F.; Van de Walle, J.; Van Duppen, P.; Voulot, D.; Wadsworth, R.; Warr, N.; Wenander, F.; Wimmer, K.; Wrzosek-Lipska, K.; Zielińska, M.

2015-06-01

Background: Shape coexistence in heavy nuclei poses a strong challenge to state-of-the-art nuclear models, where several competing shape minima are found close to the ground state. A classic region for investigating this phenomenon is in the region around Z =82 and the neutron midshell at N =104 . Purpose: Evidence for shape coexistence has been inferred from α -decay measurements, laser spectroscopy, and in-beam measurements. While the latter allow the pattern of excited states and rotational band structures to be mapped out, a detailed understanding of shape coexistence can only come from measurements of electromagnetic matrix elements. Method: Secondary, radioactive ion beams of 202Rn and 204Rn were studied by means of low-energy Coulomb excitation at the REX-ISOLDE in CERN. Results: The electric-quadrupole (E 2 ) matrix element connecting the ground state and first excited 21+ state was extracted for both 202Rn and 204Rn, corresponding to B (E 2 ;21+→01+) =29-8+8 and 43-12+17 W.u., respectively. Additionally, E 2 matrix elements connecting the 21+ state with the 41+ and 22+ states were determined in 202Rn. No excited 0+ states were observed in the current data set, possibly owing to a limited population of second-order processes at the currently available beam energies. Conclusions: The results are discussed in terms of collectivity and the deformation of both nuclei studied is deduced to be weak, as expected from the low-lying level-energy schemes. Comparisons are also made to state-of-the-art beyond-mean-field model calculations and the magnitude of the transitional quadrupole moments are well reproduced.

Origin of Broad Visible Emission from Branched Polysilane and Polygermane Chains

NASA Astrophysics Data System (ADS)

Watanabe, Akira; Sato, Takaaki; Matsuda, Minoru

2001-11-01

The emission properties of branched polysilane and polygermane are studied using time-resolved emission spectroscopy. As branched polymers, the organosilicon cluster (OSI) and organogermanium cluster (OGE) are investigated, which are prepared from tetrachlorosilane and tetrachlorogermane, respectively, and have a hyperbranched structure. The broad visible emissions of OSI and OGE are explained by the energy diagram based on a configuration coordinate model, and the excited states are attributed to a localized state around the branching point. The molecular orbital (MO) calculation suggested the formation of a localized state by the distortion around the branching point in the excited state. The potential barrier for the nonradiative relaxation process was determined from the temperature dependence of the emission lifetime.

Localized Magnetic Moments with Tunable Spin Exchange in a Gas of Ultracold Fermions

NASA Astrophysics Data System (ADS)

Riegger, L.; Darkwah Oppong, N.; Höfer, M.; Fernandes, D. R.; Bloch, I.; Fölling, S.

2018-04-01

We report on the experimental realization of a state-dependent lattice for a two-orbital fermionic quantum gas with strong interorbital spin exchange. In our state-dependent lattice, the ground and metastable excited electronic states of 173Yb take the roles of itinerant and localized magnetic moments, respectively. Repulsive on-site interactions in conjunction with the tunnel mobility lead to spin exchange between mobile and localized particles, modeling the coupling term in the well-known Kondo Hamiltonian. In addition, we find that this exchange process can be tuned resonantly by varying the on-site confinement. We attribute this to a resonant coupling to center-of-mass excited bound states of one interorbital scattering channel.

Intramolecular, Exciplex-Mediated, Proton-Coupled, Charge-Transfer Processes in N,N-Dimethyl-3-(1-pyrenyl)propan-1-ammonium Cations: Influence of Anion, Solvent Polarity, and Temperature.

PubMed

Safko, Trevor M; Faleiros, Marcelo M; Atvars, Teresa D Z; Weiss, Richard G

2016-06-16

An intramolecular exciplex-mediated, proton-coupled, charge-transfer (PCCT) process has been investigated for a series of N,N-dimethyl-3-(1-pyrenyl)propan-1-ammonium cations with different anions (PyS) in solvents of low to intermediate polarity over a wide temperature range. Solvent mediates both the equilibrium between conformations of the cation that place the pyrenyl and ammonium groups in proximity (conformation C) or far from each other (conformation O) and the ability of the ammonium group to transfer a proton adiabatically in the PyS excited singlet state. Thus, exciplex emission, concurrent with the PCCT process, was observed only in hydrogen-bond accepting solvents of relatively low polarity (tetrahydrofuran, ethyl acetate, and 1,4-dioxane) and not in dichloromethane. From the exciplex emission and other spectroscopic and thermodynamic data, the acidity of the ammonium group in conformation C of the excited singlet state of PyS (pKa*) has been estimated to be ca. -3.4 in tetrahydrofuran. The ratios between the intensities of emission from the exciplex and the locally excited state (IEx/ILE) appear to be much more dependent on the nature of the anion than are the rates of exciplex formation and decay, although the excited state data do not provide a quantitative measure of the anion effect on the C-O equilibrium. The activation energies associated with exciplex formation in THF are calculated to be 0.08 to 0.15 eV lower than for the neutral amine, N,N-dimethyl-3-(1-pyrenyl)propan-1-amine. Decay of the exciplexes formed from the deprotonation of PyS is hypothesized to occur through charge-recombination processes. To our knowledge, this is the first example in which photoacidity and intramolecular exciplex formation (i.e., a PCCT reaction) are coupled.

Dynamic evolution of light-induced orientation of dye-doped liquid crystals in liquid phase studied by time-resolved optically heterodyned optical Kerr effect technique.

PubMed

Yang, Pei; Liu, Liying; Xu, Lei

2008-02-28

Transient evolution of light-induced molecular reorientation both in 1-amino-anthraquinone (1AAQ) dye and azobenzene doped isotropic liquid crystals (LCs) were studied by time-resolved optically heterodyned optical Kerr effect method. The results give clear direct experimental proof that under short pulse (30 ps) excitation, LC molecules orientate toward the excitation light polarization direction in the 1AAQ/LC system. However, LC molecular orientation becomes orthogonal to the light polarization in azobenzene/LC system. Time-resolved excited-state absorption of 1AAQ and wavelength dependent excited-state absorption of azobenzene were also observed and their contributions to the early dynamics of the third order optical responses of the two systems were confirmed. A simplified two-level mean-field theory was derived to reveal the intensity dependence of orientation enhancement factor in azobenzene/LC system considering the photoisomerization process.

Acceleration of a ground-state reaction by selective femtosecond-infrared-laser-pulse excitation

NASA Astrophysics Data System (ADS)

Stensitzki, Till; Yang, Yang; Kozich, Valeri; Ahmed, Ashour A.; Kössl, Florian; Kühn, Oliver; Heyne, Karsten

2018-02-01

Infrared (IR) excitation of vibrations that participate in the reaction coordinate of an otherwise thermally driven chemical reaction are believed to lead to its acceleration. Attempts at the practical realization of this concept have been hampered so far by competing processes leading to sample heating. Here we demonstrate, using femtosecond IR-pump IR-probe experiments, the acceleration of urethane and polyurethane formation due to vibrational excitation of the reactants for 1:1 mixtures of phenylisocyanate and cyclohexanol, and toluene-2,4-diisocyanate and 2,2,2-trichloroethane-1,1-diol, respectively. We measured reaction rate changes upon selective vibrational excitation with negligible heating of the sample and observed an increase of the reaction rate up to 24%. The observation is rationalized using reactant and transition-state structures obtained from quantum chemical calculations. We subsequently used IR-driven reaction acceleration to write a polyurethane square on sample windows using a femtosecond IR pulse.

Magnetic vortex core reversal by excitation of spin waves.

PubMed

Kammerer, Matthias; Weigand, Markus; Curcic, Michael; Noske, Matthias; Sproll, Markus; Vansteenkiste, Arne; Van Waeyenberge, Bartel; Stoll, Hermann; Woltersdorf, Georg; Back, Christian H; Schuetz, Gisela

2011-01-01

Micron-sized magnetic platelets in the flux-closed vortex state are characterized by an in-plane curling magnetization and a nanometer-sized perpendicularly magnetized vortex core. Having the simplest non-trivial configuration, these objects are of general interest to micromagnetics and may offer new routes for spintronics applications. Essential progress in the understanding of nonlinear vortex dynamics was achieved when low-field core toggling by excitation of the gyrotropic eigenmode at sub-GHz frequencies was established. At frequencies more than an order of magnitude higher vortex state structures possess spin wave eigenmodes arising from the magneto-static interaction. Here we demonstrate experimentally that the unidirectional vortex core reversal process also occurs when such azimuthal modes are excited. These results are confirmed by micromagnetic simulations, which clearly show the selection rules for this novel reversal mechanism. Our analysis reveals that for spin-wave excitation the concept of a critical velocity as the switching condition has to be modified.

Dissociative recombination of HCl+

NASA Astrophysics Data System (ADS)

Larson, Åsa; Fonseca dos Santos, Samantha; E. Orel, Ann

2017-08-01

The dissociative recombination of HCl+, including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0 , to the first three excited vibrational states, v = 1 , v = 2 , and v = 3 , are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.

Dissociative recombination of HCl.

PubMed

Larson, Åsa; Fonseca Dos Santos, Samantha; E Orel, Ann

2017-08-28

The dissociative recombination of HCl + , including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0, to the first three excited vibrational states, v = 1, v = 2, and  v = 3, are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.

An investigation of proton pair correlations relevant to the neutrinoless double beta decay of 76Ge

NASA Astrophysics Data System (ADS)

Ticehurst, David R.

The observation of neutrinoless double beta decay (0nubetabeta ) would demonstrate that the neutrino is a Majorana particle and allow determination of its mass by comparing the measured decay rate to the calculated rate. The main uncertainty in the calculation of the 0 nubetabeta rate is due to uncertainties in the nuclear structure models used in the computation of the nuclear matrix elements for the decay process. This project tested the validity of using wavefunctions for the nuclear states involved in the 0nubetabeta process that are based on a first-order application of the Bardeen-Cooper-Schrieffer (BCS) theory of superconductivity. In the BCS approximation, most of the strength for two-nucleon transfer reactions should be for transitions to the 0 + ground state of the final nucleus (i.e., little strength should go to the 0+ excited states). This experiment measured the strength to the first 0+ excited state for the 74Ge( 3He,n)76Se and 76Ge( 3He,n)78Se reactions relative to the strength for transition to the 0+ ground state in selenium. For both nuclei, and at 3He beam energies of 15 and 21 MeV, the observed relative strength for transfer to the first 0+ excited state was less than 13%. This result supports the validity of using the BCS approximation to describe the ground state of both 76Se and 78Se and is consistent with the results of recent ( 3He,n) cross section measurements on 74Ge and 76Ge. In addition, the magnitude and shape of the measured angular distributions suggest that contribution of the sequential two-nucleon transfer process, which is an indicator of long-range nucleon-nucleon correlations, is over-predicted by the DWBA code FRESCO.

Wave-front propagation in a discrete model of excitable media

NASA Astrophysics Data System (ADS)

Feldman, A. B.; Chernyak, Y. B.; Cohen, R. J.

1998-06-01

We generalize our recent discrete cellular automata (CA) model of excitable media [Y. B. Chernyak, A. B. Feldman, and R. J. Cohen, Phys. Rev. E 55, 3215 (1997)] to incorporate the effects of inhibitory processes on the propagation of the excitation wave front. In the common two variable reaction-diffusion (RD) models of excitable media, the inhibitory process is described by the v ``controller'' variable responsible for the restoration of the equilibrium state following excitation. In myocardial tissue, the inhibitory effects are mainly due to the inactivation of the fast sodium current. We represent inhibition using a physical model in which the ``source'' contribution of excited elements to the excitation of their neighbors decreases with time as a simple function with a single adjustable parameter (a rate constant). We sought specific solutions of the CA state transition equations and obtained (both analytically and numerically) the dependence of the wave-front speed c on the four model parameters and the wave-front curvature κ. By requiring that the major characteristics of c(κ) in our CA model coincide with those obtained from solutions of a specific RD model, we find a unique set of CA parameter values for a given excitable medium. The basic structure of our CA solutions is remarkably similar to that found in typical RD systems (similar behavior is observed when the analogous model parameters are varied). Most notably, the ``turn-on'' of the inhibitory process is accompanied by the appearance of a solution branch of slow speed, unstable waves. Additionally, when κ is small, we obtain a family of ``eikonal'' relations c(κ) that are suitable for the kinematic analysis of traveling waves in the CA medium. We compared the solutions of the CA equations to CA simulations for the case of plane waves and circular (target) waves and found excellent agreement. We then studied a spiral wave using the CA model adjusted to a specific RD system and found good correspondence between the shapes of the RD and CA spiral arms in the region away from the tip where kinematic theory applies. Our analysis suggests that only four physical parameters control the behavior of wave fronts in excitable media.

Efficient near-infrared up-conversion photoluminescence in carbon nanotubes

PubMed Central

Akizuki, Naoto; Aota, Shun; Mouri, Shinichiro; Matsuda, Kazunari; Miyauchi, Yuhei

2015-01-01

Photoluminescence phenomena normally obey Stokes' law of luminescence according to which the emitted photon energy is typically lower than its excitation counterparts. Here we show that carbon nanotubes break this rule under one-photon excitation conditions. We found that the carbon nanotubes exhibit efficient near-infrared photoluminescence upon photoexcitation even at an energy lying >100–200 meV below that of the emission at room temperature. This apparently anomalous phenomenon is attributed to efficient one-phonon-assisted up-conversion processes resulting from unique excited-state dynamics emerging in an individual carbon nanotube with accidentally or intentionally embedded localized states. These findings may open new doors for energy harvesting, optoelectronics and deep-tissue photoluminescence imaging in the near-infrared optical range. PMID:26568250

A meta-analysis and review examining a possible role for oxidative stress and singlet oxygen in diverse diseases.

PubMed

Petrou, Athinoula L; Terzidaki, Athina

2017-08-02

From kinetic data (k, T) we calculated the thermodynamic parameters for various processes (nucleation, elongation, fibrillization, etc.) of proteinaceous diseases that are related to the β-amyloid protein (Alzheimer's), to tau protein (Alzheimer's, Pick's), to α-synuclein (Parkinson's), prion, amylin (type II diabetes), and to α-crystallin (cataract). Our calculations led to ΔG ≠ values that vary in the range 92.8-127 kJ mol -1 at 310 K. A value of ∼10-30 kJ mol -1 is the activation energy for the diffusion of reactants, depending on the reaction and the medium. The energy needed for the excitation of O 2 from the ground to the first excited state ( 1 Δ g , singlet oxygen) is equal to 92 kJ mol -1 So, the ΔG ≠ is equal to the energy needed for the excitation of ground state oxygen to the singlet oxygen ( 1 Δ g first excited) state. The similarity of the ΔG ≠ values is an indication that a common mechanism in the above disorders may be taking place. We attribute this common mechanism to the (same) role of the oxidative stress and specifically of singlet oxygen, ( 1 Δ g ), to the above-mentioned processes: excitation of ground state oxygen to the singlet oxygen, 1 Δ g , state (92 kJ mol -1 ), and reaction of the empty π* orbital with high electron density regions of biomolecules (∼10-30 kJ mol -1 for their diffusion). The ΔG ≠ for cases of heat-induced cell killing (cancer) lie also in the above range at 310 K. The present paper is a review and meta-analysis of literature data referring to neurodegenerative and other disorders. © 2017 The Author(s); published by Portland Press Limited on behalf of the Biochemical Society.

Ping-Pong Energy Transfer in a Boron Dipyrromethane Containing Pt(II)-Schiff Base Complex: Synthesis, Photophysical Studies, and Anti-Stokes Shift Increase in Triplet-Triplet Annihilation Upconversion.

PubMed

Razi, Syed S; Koo, Yun Hee; Kim, Woojae; Yang, Wenbo; Wang, Zhijia; Gobeze, Habtom; D'Souza, Francis; Zhao, Jianzhang; Kim, Dongho

2018-05-07

A boron dipyrromethane (BDP)-containing Pt(II)-Schiff base complex (Pt-BDP), showing ping-pong singlet-triplet energy transfer, was synthesized, and the detailed photophysical properties were investigated using various steady-state and time-resolved transient spectroscopies. Femtosecond/nanosecond transient absorption spectroscopies demonstrated that, upon selective excitation of the BDP unit in Pt-BDP at 490 nm, Förster resonance energy transfer from the BDP unit to the Pt(II) coordination center occurred (6.7 ps), accompanied by an ultrafast intersystem crossing at the Pt(II) coordination center (<1 ps) and triplet-triplet energy transfer back to the BDP moiety (148 ps). These processes generated a triplet state localized at BDP, and the lifetime was 103.2 μs, much longer than the triplet-state lifetime of Pt-Ph (3.5 μs), a complex without the BDP moiety. Finally, Pt-BDP was used as a triplet photosensitizer for triplet-triplet annihilation (TTA) upconversion through selective excitation of the BDP unit or the Pt(II) coordination center at lower excitation energy. An upconversion quantum yield of up to 10% was observed with selective excitation of the BDP moiety, and a large anti-Stokes shift of 0.65 eV was observed upon excitation of the lower-energy band of the Pt(II) coordination center. We propose that using triplet photosensitizers with the ping-pong energy-transfer process may become a useful method for increasing the anti-Stokes shift of TTA upconversion.

Exciplex formation and energy transfer in a self-assembled metal-organic hybrid system.

PubMed

Haldar, Ritesh; Rao, K Venkata; George, Subi J; Maji, Tapas Kumar

2012-05-07

Exciting assemblies: A metal-organic self-assembly of pyrenebutyric acid (PBA), 1,10-phenanthroline (o-phen), and Mg(II) shows solid-state fluorescence originating from a 1:1 PBA-o-phen exciplex. This exciplex fluorescence is sensitized by another residual PBA chromophore through an excited-state energy-transfer process. The solvent polarity modulates the self-assembly and the corresponding exciplex as well as the energy transfer, resulting in tunable emission of the hybrid (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct optical state preparation of the dark exciton in a quantum dot

NASA Astrophysics Data System (ADS)

Lüker, S.; Kuhn, T.; Reiter, D. E.

2015-11-01

Because of their weak coupling to the electromagnetic field, dark excitons in semiconductor quantum dots possess extremely long lifetimes, which makes them attractive candidates for quantum information processing. On the other hand, the preparation and manipulation of dark states is challenging, because commonly used optical excitation mechanisms are not applicable. We propose an efficient mechanism for the deterministic preparation of the dark exciton exploiting the application of a tilted magnetic field and the optical excitation with a chirped, i.e., frequency modulated, laser pulse.

General features of the dissociative recombination of polyatomic molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pratt, S. T.; Jungen, Ch.; Schneider, I. F.

We discuss some aspects of a simple expression for the low-energy dissociative recombination cross section that applies when the recombination process is dominated by the indirect mechanism. In most previous applications, this expression has been applied to capture into vibrationally excited Rydberg states with the assumption that capture is always followed by prompt dissociation. Here we consider the dissociative recombination of larger polyatomic ions and electrons. More specifically, we consider capture into electronically core-excited Rydberg states, and begin to assess its potential importance for larger systems.

General features of the dissociative recombination of polyatomic molecules

DOE PAGES

Pratt, S. T.; Jungen, Ch.; Schneider, I. F.; ...

2015-01-29

We discuss some aspects of a simple expression for the low-energy dissociative recombination cross section that applies when the recombination process is dominated by the indirect mechanism. In most previous applications, this expression has been applied to capture into vibrationally excited Rydberg states with the assumption that capture is always followed by prompt dissociation. Here we consider the dissociative recombination of larger polyatomic ions and electrons. More specifically, we consider capture into electronically core-excited Rydberg states, and begin to assess its potential importance for larger systems.

Ultrafast non-adiabatic dynamics of methyl substituted ethylenes: the π3s Rydberg state.

PubMed

Wu, Guorong; Boguslavskiy, Andrey E; Schalk, Oliver; Schuurman, Michael S; Stolow, Albert

2011-10-28

Excited state unimolecular reactions of some polyenes exhibit localization of their dynamics at a single ethylenic double bond. Here we present studies of the fundamental photophysical processes in the ethylene unit itself. Combined femtosecond time-resolved photoelectron spectroscopy (TRPES) and ab initio quantum chemical calculations was applied to the study of excited state dynamics in cis-butene, trans-butene, trimethylethylene, and tetramethylethylene, following initial excitation to their respective π3s Rydberg states. The wavelength dependence of the π3s Rydberg state dynamics of tetramethylethylene was investigated in more detail. The π3s Rydberg to ππ(∗) valence state decay rate varies greatly with substituent: the 1,2-di- and tri-methyl substituted ethylenes (cis-butene, trans-butene, and trimethylethylene) show an ultrafast decay (∼20 fs), whereas the fully methylated tetramethylethylene shows a decay rate of 2 to 4 orders of magnitude slower. These observations are rationalized in terms of topographical trends in the relevant potential energy surfaces, as found from ab initio calculations: (1) the barrier between the π3s state and the ππ∗ state increases with increasing methylation, and (2) the π3s∕ππ∗ minimum energy conical intersection displaces monotonically away from the π3s Franck-Condon region with increasing methylation. The use of systematic methylation in combination with TRPES and ab initio computation is emerging as an important tool in discerning the excited state dynamics of unsaturated hydrocarbons.

Ultrafast non-adiabatic dynamics of methyl substituted ethylenes: The π3s Rydberg state

NASA Astrophysics Data System (ADS)

Wu, Guorong; Boguslavskiy, Andrey E.; Schalk, Oliver; Schuurman, Michael S.; Stolow, Albert

2011-10-01

Excited state unimolecular reactions of some polyenes exhibit localization of their dynamics at a single ethylenic double bond. Here we present studies of the fundamental photophysical processes in the ethylene unit itself. Combined femtosecond time-resolved photoelectron spectroscopy (TRPES) and ab initio quantum chemical calculations was applied to the study of excited state dynamics in cis-butene, trans-butene, trimethylethylene, and tetramethylethylene, following initial excitation to their respective π3s Rydberg states. The wavelength dependence of the π3s Rydberg state dynamics of tetramethylethylene was investigated in more detail. The π3s Rydberg to ππ* valence state decay rate varies greatly with substituent: the 1,2-di- and tri-methyl substituted ethylenes (cis-butene, trans-butene, and trimethylethylene) show an ultrafast decay (˜20 fs), whereas the fully methylated tetramethylethylene shows a decay rate of 2 to 4 orders of magnitude slower. These observations are rationalized in terms of topographical trends in the relevant potential energy surfaces, as found from ab initio calculations: (1) the barrier between the π3s state and the ππ* state increases with increasing methylation, and (2) the π3s/ππ* minimum energy conical intersection displaces monotonically away from the π3s Franck-Condon region with increasing methylation. The use of systematic methylation in combination with TRPES and ab initio computation is emerging as an important tool in discerning the excited state dynamics of unsaturated hydrocarbons.

Flame Chemiluminescence Rate Constants for Quantitative Microgravity Combustion Diagnostics

NASA Technical Reports Server (NTRS)

Luque, Jorge; Smith, Gregory P.; Jeffries, Jay B.; Crosley, David R.; Weiland, Karen (Technical Monitor)

2001-01-01

Absolute excited state concentrations of OH(A), CH(A), and C2(d) were determined in three low pressure premixed methane-air flames. Two dimensional images of chemiluminescence from these states were recorded by a filtered CCD camera, processed by Abel inversion, and calibrated against Rayleigh scattering, Using a previously validated 1-D flame model with known chemistry and excited state quenching rate constants, rate constants are extracted for the reactions CH + O2 (goes to) OH(A) + CO and C2H + O (goes to) CH(A) + CO at flame temperatures. Variations of flame emission intensities with stoichiometry agree well with model predictions.

Thickness-dependent electron–lattice equilibration in laser-excited thin bismuth films

DOE PAGES

Sokolowski-Tinten, K.; Li, R. K.; Reid, A. H.; ...

2015-11-19

Electron–phonon coupling processes determine electronic transport properties of materials and are responsible for the transfer of electronic excess energy to the lattice. With decreasing device dimensions an understanding of these processes in nanoscale materials is becoming increasingly important. We use time-resolved electron diffraction to directly study energy relaxation in thin bismuth films after optical excitation. Precise measurements of the transient Debye–Waller-effect for various film thicknesses and over an extended range of excitation fluences allow to separate different contributions to the incoherent lattice response. While phonon softening in the electronically excited state is responsible for an immediate increase of the r.m.s.more » atomic displacement within a few hundred fs, 'ordinary' electron–phonon coupling leads to subsequent heating of the material on a few ps time-scale. Moreover, the data reveal distinct changes in the energy transfer dynamics which becomes faster for stronger excitation and smaller film thickness, respectively. The latter effect is attributed to a cross-interfacial coupling of excited electrons to phonons in the substrate.« less

Complete Mechanism of Hemithioindigo Motor Rotation.

PubMed

Wilcken, Roland; Schildhauer, Monika; Rott, Florian; Huber, Ludwig Alexander; Guentner, Manuel; Thumser, Stefan; Hoffmann, Kerstin; Oesterling, Sven; de Vivie-Riedle, Regina; Riedle, Eberhard; Dube, Henry

2018-04-18

Hemithioindigo-based molecular motors are powered by nondamaging visible light and provide very fast directional rotations at ambient conditions. Their ground state energy profile has been probed in detail, but the crucial excited state processes are completely unknown so far. In addition, very fast processes in the ground state are also still elusive to date and thus knowledge of the whole operational mechanism remains to a large extent in the dark. In this work we elucidate the complete light-driven rotation mechanism by a combination of multiscale broadband transient absorption measurements covering a time scale from fs to ms in conjunction with a high level theoretical description of the excited state. In addition to a full description of the excited state dynamics in the various time regimes, we also provide the first experimental evidence for the elusive fourth intermediate ground state of the original HTI motor. The fate of this intermediate also is followed directly proving complete unidirectionality for both 180° rotation steps. At the same time, we uncover the hitherto unknown involvement of an unproductive triplet state pathway, which slightly diminishes the quantum yield of the E to Z photoisomerization. A rate model analysis shows that increasing the speed of motor rotation is most effectively done by increasing the photoisomerization quantum yields instead of barrier reduction for the thermal ratcheting steps. Our findings are of crucial importance for improved future designs of any light-driven molecular motor in general to yield better efficiencies and applicability.

Infrared vibrational spectroscopy of [Ru(bpy)2(bpm)]2+ and [Ru(bpy)3]2+ in the excited triplet state.

PubMed

Mukuta, Tatsuhiko; Fukazawa, Naoto; Murata, Kei; Inagaki, Akiko; Akita, Munetaka; Tanaka, Sei'ichi; Koshihara, Shin-ya; Onda, Ken

2014-03-03

This work involved a detailed investigation into the infrared vibrational spectra of ruthenium polypyridyl complexes, specifically heteroleptic [Ru(bpy)2(bpm)](2+) (bpy = 2,2'-bipyridine and bpm = 2,2'-bipyrimidine) and homoleptic [Ru(bpy)3](2+), in the excited triplet state. Transient spectra were acquired 500 ps after photoexcitation, corresponding to the vibrational ground state of the excited triplet state, using time-resolved infrared spectroscopy. We assigned the observed bands to specific ligands in [Ru(bpy)2(bpm)](2+) based on the results of deuterium substitution and identified the corresponding normal vibrational modes using quantum-chemical calculations. Through this process, the more complex vibrational bands of [Ru(bpy)3](2+) were assigned to normal vibrational modes. The results are in good agreement with the model in which excited electrons are localized on a single ligand. We also found that the vibrational bands of both complexes associated with the ligands on which electrons are little localized appear at approximately 1317 and 1608 cm(-1). These assignments should allow the study of the reaction dynamics of various photofunctional systems including ruthenium polypyridyl complexes.

Electron Impact Ionization Cross Sections in Rb and Cs.

NASA Astrophysics Data System (ADS)

Reddish, T. J.; Lukomski, M.; Sutton, S.; Kedzierski, W.; McConkey, J. W.; Bartschat, K.; Bartlett, P. L.; Stelbovics, A. T.; Bray, I.

2006-05-01

We present a new atom trapping technique for determining absolute, total ionisation cross sections (TICS) out of an excited atom. The novel feature of this method is in utilizing Doppler cooling of neutral atoms to determine ionisation cross sections. This fluorescence-monitoring experiment, which is a variant of the `trap loss' technique, has enabled us to obtain the experimental electron impact ionisation cross sections out of the Cs 6^2P3/2 excited state between 7 - 400 eV. New CCC, R-Matrix with Pseudo-States (RMPS), and Born approximation single ionisation cross sections (SICS) are also presented for both the ground and excited states of Cs and Rb, and compared with the available experimental data. The comparison of the results reveals the importance of the autoionisation and multiple ionisation contributions to the TICS. The autoionisation contribution appears to be substantial for ionisation out of the Cs 6^2P and Rb 5^2P excited states; ˜ 3-4 larger than the direct ionisation contribution predicted by CCC at ˜ 30-50 eV. This surprising result shows the importance of multi-electron processes in determining the ionisation cross sections of heavy alkali atoms.

Modeling Photochemical Dynamics in Optically Active Energetic Materials

NASA Astrophysics Data System (ADS)

Nelson, Tammie; Bjorgaard, Josiah; Greenfield, Margo; Bolme, Cindy; Brown, Katie; McGrane, Shawn; Scharff, R. Jason; Tretiak, Sergei

Most high explosives (HEs) absorb in the UV range, making it difficult to develop HEs that can be excited with standard lasers. The conventional optical initiation mechanisms require high laser intensity and occur via indirect thermal or shock processes. A photochemical initiation mechanism could allow control over the chemistry contributing to decomposition leading to initiation. We combine UV femtosecond transient absorption (TA) spectroscopy and excited state femtosecond stimulated Raman spectroscopy (FSRS) with Nonadiabatic Excited State Molecular Dynamics (NA-ESMD) to model the photochemical pathways in nitromethane (NM), a low sensitivity HE known to undergo UV photolysis. We investigate the ultrafast photodecomposition of NM from the nπ* state excited at 266 nm. The FSRS photoproduct spectrum points to methyl nitrite formation as the dominant photoproduct. A total photolysis quantum yield of 0.27 and an nπ* state lifetime of 20 fs were predicted from simulations. Predicted time scales reveal that NO2 dissociation occurs in 81 +/-4 fs and methyl nitrite formation is much slower at 452 +/-9 fs corresponding to the absorption feature in the TA spectrum. The relative time scales are consistent with isomerization by NO2 dissociation and ONO rebinding.

Optical excitations dynamics at hetero-interfaces fullerene/quantum dots

NASA Astrophysics Data System (ADS)

Righetto, Marcello; Privitera, Alberto; Franco, Lorenzo; Bozio, Renato

2017-08-01

Embedding Semiconductor Quantum Dots (QDs) into hybrid organic-inorganic solar cell holds promises for improving photovoltaic performances. Thanks to their strong coupling with electro-magnetic radiation field, QDs represent paradigmatic photon absorbers. Nevertheless, the quest for suitable charge separating hetero-interfaces is still an open challenge. Within this framework, the excited state interactions between QDs and fullerene derivatives are of great interest for ternary solar cells (polymer:QDs:fullerene). In this work, we investigated the exciton dynamics of core/shell CdSe/CdS QDs both in solution and in blends with fullerene derivative (PCBM). By means of transient optical techniques, we aimed to unveil the dynamics of the QDs-PCBM interaction. Indeed, the observed excited state depopulation of QDs in blends is compatible with an excited state interaction living on picosecond timescale. Through electron paramagnetic resonance, we delved into the nature of this interaction, identifying the presence of charge separated states. The concurrence of these observations suggest a fast electron transfer process, where QDs act as donors and PCBM molecules as acceptors, followed by effective charge separation. Therefore, our experimental results indicate the QDs-PCBM heterointerface as suitable exciton separating interface, paving the way for possible applications in photovoltaics.

Transient excitation and data processing techniques employing the fast fourier transform for aeroelastic testing

NASA Technical Reports Server (NTRS)

Jennings, W. P.; Olsen, N. L.; Walter, M. J.

1976-01-01

The development of testing techniques useful in airplane ground resonance testing, wind tunnel aeroelastic model testing, and airplane flight flutter testing is presented. Included is the consideration of impulsive excitation, steady-state sinusoidal excitation, and random and pseudorandom excitation. Reasons for the selection of fast sine sweeps for transient excitation are given. The use of the fast fourier transform dynamic analyzer (HP-5451B) is presented, together with a curve fitting data process in the Laplace domain to experimentally evaluate values of generalized mass, model frequencies, dampings, and mode shapes. The effects of poor signal to noise ratios due to turbulence creating data variance are discussed. Data manipulation techniques used to overcome variance problems are also included. The experience is described that was gained by using these techniques since the early stages of the SST program. Data measured during 747 flight flutter tests, and SST, YC-14, and 727 empennage flutter model tests are included.

Bonded exciplex formation: electronic and stereoelectronic effects.

PubMed

Wang, Yingsheng; Haze, Olesya; Dinnocenzo, Joseph P; Farid, Samir; Farid, Ramy S; Gould, Ian R

2008-12-18

As recently proposed, the singlet-excited states of several cyanoaromatics react with pyridine via bonded-exciplex formation, a novel concept in photochemical charge transfer reactions. Presented here are electronic and steric effects on the quenching rate constants, which provide valuable support for the model. Additionally, excited-state quenching in poly(vinylpyridine) is strongly inhibited both relative to that in neat pyridine and also to conventional exciplex formation in polymers, consistent with a restrictive orientational requirement for the formation of bonded exciplexes. Examples of competing reactions to form both conventional and bonded exciplexes are presented, which illustrate the delicate balance between these two processes when their reaction energetics are similar. Experimental and computational evidence is provided for the formation of a bonded exciplex in the reaction of the singlet excited state of 2,6,9,10-tetracyanoanthracene (TCA) with an oxygen-substituted donor, dioxane, thus expanding the scope of bonded exciplexes.

Spectroscopy of Isolated Prebiotic Nucleobases

NASA Technical Reports Server (NTRS)

Svadlenak, Nathan; Callahan, Michael P.; Ligare, Marshall; Gulian, Lisa; Gengeliczki, Zsolt; Nachtigallova, Dana; Hobza, Pavel; deVries, Mattanjah

2011-01-01

We use multiphoton ionization and double resonance spectroscopy to study the excited state dynamics of biologically relevant molecules as well as prebiotic nucleobases, isolated in the gas phase. Molecules that are biologically relevant to life today tend to exhibit short excited state lifetimes compared to similar but non-biologically relevant analogs. The mechanism is internal conversion, which may help protect the biologically active molecules from UV damage. This process is governed by conical intersections that depend very strongly on molecular structure. Therefore we have studied purines and pyrimidines with systematic variations of structure, including substitutions, tautomeric forms, and cluster structures that represent different base pair binding motifs. These structural variations also include possible alternate base pairs that may shed light on prebiotic chemistry. With this in mind we have begun to probe the ultrafast dynamics of molecules that exhibit very short excited states and search for evidence of internal conversions.

Threshold kinetics of a solar-simulator-pumped iodine laser

NASA Technical Reports Server (NTRS)

Wilson, J. W.; Lee, Y.; Weaver, W. R.; Humes, D. H.; Lee, J. H.

1984-01-01

A model of the chemical kinetics of the n-C3F7I solar-simulator-pumped iodine laser is utilized to study the major kinetic processes associated with the threshold behavior of this experimental system. Excited-state diffusion to the cell wall is the dominant limiting factor below 5 torr. Excited-state diffusion to the cell wall is the dominant limiting factor below 5 torr. Excited-state recombination with the alkyl radical and quenching by the parent gas control threshold at higher pressures. Treatment of the hyperfine splitting and uncertainty in the pressure broadening are important factors in fixing the threshold level. In spite of scatter in the experimental data caused by instabilities in the simulator high-pressure high-pressure arc, reasonable agreement is achieved between the model and experiment. Model parameters arrived at are within the uncertainty range of values found in the literature.

Dynamics of the quantum phase transition in the one-dimensional Bose-Hubbard model: Excitations and correlations induced by a quench

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gardas, Bartłomiej; Dziarmaga, Jacek; Zurek, Wojciech H.

The ground state of the one-dimensional Bose-Hubbard model at unit filling undergoes the Mott-superfluid quantum phase transition. It belongs to the Kosterlitz-Thouless universality class with an exponential divergence of the correlation length in place of the usual power law. Here, we present numerical simulations of a linear quench both from the Mott insulator to superfluid and back. The results satisfy the scaling hypothesis that follows from the Kibble-Zurek mechanism (KZM). In the superfluid-to-Mott quenches there is no significant excitation in the superfluid phase despite its gaplessness. And since all critical superfluid ground states are qualitatively similar, the excitation begins tomore » build up only after crossing the critical point when the ground state begins to change fundamentally. The last process falls into the KZM framework.« less

Exploring methods to expedite the recording of CEST datasets using selective pulse excitation

NASA Astrophysics Data System (ADS)

Yuwen, Tairan; Bouvignies, Guillaume; Kay, Lewis E.

2018-07-01

Chemical Exchange Saturation Transfer (CEST) has emerged as a powerful tool for studies of biomolecular conformational exchange involving the interconversion between a major, visible conformer and one or more minor, invisible states. Applications typically entail recording a large number of 2D datasets, each of which differs in the position of a weak radio frequency field, so as to generate a CEST profile for each nucleus from which the chemical shifts of spins in the invisible state(s) are obtained. Here we compare a number of band-selective CEST schemes for speeding up the process using either DANTE or cosine-modulated excitation approaches. We show that while both are essentially identical for applications such as 15N CEST, in cases where the probed spins are dipolar or scalar coupled to other like spins there can be advantages for the cosine-excitation scheme.

Electron impact ionization-excitation of Helium

NASA Astrophysics Data System (ADS)

Ancarani, Lorenzo Ugo; Gomez, A. I.; Gasaneo, G.; Mitnik, D. M.; Ambrosio, M. J.

2016-09-01

We calculate triple differential cross sections (TDCS) for the process of ionization-excitation of Helium by fast electron impact in which the residual ion is left in the n =2 excited state. We chose the strongly asymmetric kinematics used in the experiment performed by Dupré et al.. In a perturbative scheme, for high projectile energies the four-body problem reduces to a three-body one and, within that framework, we solve the time- independent Schrödinger equation with a Sturmian approach. The method, based on Generalized Sturmian Functions (GSF), is employed to obtain the initial ground state of Helium, the single-continuum state and the scattering wave function; for each of them, the GSF basis is constructed with the corresponding adequate asymptotic conditions. Besides, the method presents the following advantage: the scattering amplitudes can be extracted directly in the asymptotic region of the scattering solution, and thus the TDCS can be obtained without requiring a matrix element evaluation.

Coherent Spin Control at the Quantum Level in an Ensemble-Based Optical Memory.

PubMed

Jobez, Pierre; Laplane, Cyril; Timoney, Nuala; Gisin, Nicolas; Ferrier, Alban; Goldner, Philippe; Afzelius, Mikael

2015-06-12

Long-lived quantum memories are essential components of a long-standing goal of remote distribution of entanglement in quantum networks. These can be realized by storing the quantum states of light as single-spin excitations in atomic ensembles. However, spin states are often subjected to different dephasing processes that limit the storage time, which in principle could be overcome using spin-echo techniques. Theoretical studies suggest this to be challenging due to unavoidable spontaneous emission noise in ensemble-based quantum memories. Here, we demonstrate spin-echo manipulation of a mean spin excitation of 1 in a large solid-state ensemble, generated through storage of a weak optical pulse. After a storage time of about 1 ms we optically read-out the spin excitation with a high signal-to-noise ratio. Our results pave the way for long-duration optical quantum storage using spin-echo techniques for any ensemble-based memory.

Dynamics of the quantum phase transition in the one-dimensional Bose-Hubbard model: Excitations and correlations induced by a quench

DOE PAGES

Gardas, Bartłomiej; Dziarmaga, Jacek; Zurek, Wojciech H.

2017-03-24

The ground state of the one-dimensional Bose-Hubbard model at unit filling undergoes the Mott-superfluid quantum phase transition. It belongs to the Kosterlitz-Thouless universality class with an exponential divergence of the correlation length in place of the usual power law. Here, we present numerical simulations of a linear quench both from the Mott insulator to superfluid and back. The results satisfy the scaling hypothesis that follows from the Kibble-Zurek mechanism (KZM). In the superfluid-to-Mott quenches there is no significant excitation in the superfluid phase despite its gaplessness. And since all critical superfluid ground states are qualitatively similar, the excitation begins tomore » build up only after crossing the critical point when the ground state begins to change fundamentally. The last process falls into the KZM framework.« less

Parallel multireference configuration interaction calculations on mini-β-carotenes and β-carotene

NASA Astrophysics Data System (ADS)

Kleinschmidt, Martin; Marian, Christel M.; Waletzke, Mirko; Grimme, Stefan

2009-01-01

We present a parallelized version of a direct selecting multireference configuration interaction (MRCI) code [S. Grimme and M. Waletzke, J. Chem. Phys. 111, 5645 (1999)]. The program can be run either in ab initio mode or as semiempirical procedure combined with density functional theory (DFT/MRCI). We have investigated the efficiency of the parallelization in case studies on carotenoids and porphyrins. The performance is found to depend heavily on the cluster architecture. While the speed-up on the older Intel Netburst technology is close to linear for up to 12-16 processes, our results indicate that it is not favorable to use all cores of modern Intel Dual Core or Quad Core processors simultaneously for memory intensive tasks. Due to saturation of the memory bandwidth, we recommend to run less demanding tasks on the latter architectures in parallel to two (Dual Core) or four (Quad Core) MRCI processes per node. The DFT/MRCI branch has been employed to study the low-lying singlet and triplet states of mini-n-β-carotenes (n =3, 5, 7, 9) and β-carotene (n =11) at the geometries of the ground state, the first excited triplet state, and the optically bright singlet state. The order of states depends heavily on the conjugation length and the nuclear geometry. The B1u+ state constitutes the S1 state in the vertical absorption spectrum of mini-3-β-carotene but switches order with the 2 A1g- state upon excited state relaxation. In the longer carotenes, near degeneracy or even root flipping between the B1u+ and B1u- states is observed whereas the 3 A1g- state is found to remain energetically above the optically bright B1u+ state at all nuclear geometries investigated here. The DFT/MRCI method is seen to underestimate the absolute excitation energies of the longer mini-β-carotenes but the energy gaps between the excited states are reproduced well. In addition to singlet data, triplet-triplet absorption energies are presented. For β-carotene, where these transition energies are known from experiment, excellent agreement with our calculations is observed.

Parallel multireference configuration interaction calculations on mini-beta-carotenes and beta-carotene.

PubMed

Kleinschmidt, Martin; Marian, Christel M; Waletzke, Mirko; Grimme, Stefan

2009-01-28

We present a parallelized version of a direct selecting multireference configuration interaction (MRCI) code [S. Grimme and M. Waletzke, J. Chem. Phys. 111, 5645 (1999)]. The program can be run either in ab initio mode or as semiempirical procedure combined with density functional theory (DFT/MRCI). We have investigated the efficiency of the parallelization in case studies on carotenoids and porphyrins. The performance is found to depend heavily on the cluster architecture. While the speed-up on the older Intel Netburst technology is close to linear for up to 12-16 processes, our results indicate that it is not favorable to use all cores of modern Intel Dual Core or Quad Core processors simultaneously for memory intensive tasks. Due to saturation of the memory bandwidth, we recommend to run less demanding tasks on the latter architectures in parallel to two (Dual Core) or four (Quad Core) MRCI processes per node. The DFT/MRCI branch has been employed to study the low-lying singlet and triplet states of mini-n-beta-carotenes (n=3, 5, 7, 9) and beta-carotene (n=11) at the geometries of the ground state, the first excited triplet state, and the optically bright singlet state. The order of states depends heavily on the conjugation length and the nuclear geometry. The (1)B(u) (+) state constitutes the S(1) state in the vertical absorption spectrum of mini-3-beta-carotene but switches order with the 2 (1)A(g) (-) state upon excited state relaxation. In the longer carotenes, near degeneracy or even root flipping between the (1)B(u) (+) and (1)B(u) (-) states is observed whereas the 3 (1)A(g) (-) state is found to remain energetically above the optically bright (1)B(u) (+) state at all nuclear geometries investigated here. The DFT/MRCI method is seen to underestimate the absolute excitation energies of the longer mini-beta-carotenes but the energy gaps between the excited states are reproduced well. In addition to singlet data, triplet-triplet absorption energies are presented. For beta-carotene, where these transition energies are known from experiment, excellent agreement with our calculations is observed.

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

NASA Astrophysics Data System (ADS)

Closser, Kristina Danielle

This thesis presents new developments in excited state electronic structure theory. Contrasted with the ground state, the electronically excited states of atoms and molecules often are unstable and have short lifetimes, exhibit a greater diversity of character and are generally less well understood. The very unusual excited states of helium clusters motivated much of this work. These clusters consist of large numbers of atoms (experimentally 103--109 atoms) and bands of nearly degenerate excited states. For an isolated atom the lowest energy excitation energies are from 1s → 2s and 1s → 2 p transitions, and in clusters describing the lowest energy band minimally requires four states per atom. In the ground state the clusters are weakly bound by van der Waals interactions, however in the excited state they can form well-defined covalent bonds. The computational cost of quantum chemical calculations rapidly becomes prohibitive as the size of the systems increase. Standard excited-state methods such as configuration interaction singles (CIS) and time-dependent density functional theory (TD-DFT) can be used with ≈100 atoms, and are optimized to treat only a few states. Thus, one of our primary aims is to develop a method which can treat these large systems with large numbers of nearly degenerate excited states. Additionally, excited states are generally formed far from their equilibrium structures. Vertical excitations from the ground state induce dynamics in the excited states. Thus, another focus of this work is to explore the results of these forces and the fate of the excited states. Very little was known about helium cluster excited states when this work began, thus we first investigated the excitations in small helium clusters consisting of 7 or 25 atoms using CIS. The character of these excited states was determined using attachment/detachment density analysis and we found that in the n = 2 manifold the excitations could generally be interpreted as superpositions of atomic states with surface states appearing close to the atomic excitation energies and interior states being blue shifted by up to ≈2 eV. The dynamics resulting from excitation of He_7 were subsequently explored using ab initio molecular dynamics (AIMD). These simulations were performed with classical adiabatic dynamics coupled to a new state-following algorithm on CIS potential energy surfaces. Most clusters were found to completely dissociate and resulted in a single excited atomic state (90%), however, some trajectories formed bound, He*2 (3%), and a few yielded excited trimers (<0.5%). Comparisons were made with available experimental information on much larger clusters. Various applications of this state following algorithm are also presented. In addition to AIMD, these include excited-state geometry optimization and minimal energy path finding via the growing string method. When using state following we demonstrate that more physical results can be obtained with AIMD calculations. Also, the optimized geometries of three excited states of cytosine, two of which were not found without state following, and the minimal energy path between the lowest two singlet excited states of protonated formaldimine are offered as example applications. Finally, to address large clusters, a local variation of CIS was developed. This method exploits the properties of absolutely localized molecular orbitals (ALMOs) to limit the total number of excitations to scaling only linearly with cluster size, which results in formal scaling with the third power of the system size. The derivation of the equations and design of the algorithm are discussed in detail, and computational timings as well as a pilot application to the size dependence of the helium cluster spectrum are presented.

The energy structure and decay channels of the 4p6-shell excited states in Sr

NASA Astrophysics Data System (ADS)

Kupliauskienė, A.; Kerevičius, G.; Borovik, V.; Shafranyosh, I.; Borovik, A.

2017-11-01

The ejected-electron spectra arising from the decay of the 4p{}5{{nln}}{\\prime }{l}{\\prime }{n}{\\prime\\prime }{l}{\\prime\\prime } autoionizing states in Sr atoms have been studied precisely at the incident-electron energies close to excitation and ionization thresholds of the 4{{{p}}}6 subshell. The excitation behaviors for 58 lines observed between 12 and 21 eV ejected-electron kinetic energy have been investigated. Also, the ab initio calculations of excitation energies, autoionization probabilities and electron-impact excitation cross sections of the states 4p{}5{{nln}}{\\prime }{l}{\\prime }{n}{\\prime\\prime }{l}{\\prime\\prime } (nl = 4d, 5s, 5p; {n}{\\prime }{l}{\\prime } = 4d, 5s, 5p; {n}{\\prime\\prime }{l}{\\prime\\prime } = 5s, 6s, 7s, 8s, 9s, 5p, 6p, 5d, 6d, 7d, 8d, 4f, 5g) have been performed by employing the large-scale configuration-interaction method in the basis of the solutions of Dirac-Fock-Slater equations. The obtained experimental and theoretical data have been used for the accurate identification of the 60 lines in ejected-electron spectra and the 68 lines observed earlier in photoabsorption spectra. The excitation and decay processes for 105 classified states in the 4p55s{}2{nl}, 4p54d{}2{nl} and 4p55s{{nln}}{\\prime }{l}{\\prime } configurations have been considered in detail. In particular, most of the states lying below the ionization threshold of the 4p6 subshell at 26.92 eV possess up to four decay channels with formation of Sr+ in 5s{}1/2, 4d{}3/{2,5/2} and 5p{}1/{2,3/2} states. Two-step autoionization and two-electron Auger transitions with formation of Sr2+ in the 4p6 {}1{{{S}}}0 ground state are the main decay paths for high-lying autoionizing states. The excitation threshold of the 4{{{p}}}6 subshell in Sr has been established at 20.98 ± 0.05 eV.

Time-dependent view of an isotope effect in electron-nuclear nonequilibrium dynamics with applications to N2.

PubMed

Ajay, Jayanth S; Komarova, Ksenia G; Remacle, Francoise; Levine, R D

2018-06-05

Isotopic fractionation in the photodissociation of N 2 could explain the considerable variation in the 14 N/ 15 N ratio in different regions of our galaxy. We previously proposed that such an isotope effect is due to coupling of photoexcited bound valence and Rydberg electronic states in the frequency range where there is strong state mixing. We here identify features of the role of the mass in the dynamics through a time-dependent quantum-mechanical simulation. The photoexcitation of N 2 is by an ultrashort pulse so that the process has a sharply defined origin in time and so that we can monitor the isolated molecule dynamics in time. An ultrafast pulse is necessarily broad in frequency and spans several excited electronic states. Each excited molecule is therefore not in a given electronic state but in a superposition state. A short time after excitation, there is a fairly sharp onset of a mass-dependent large population transfer when wave packets on two different electronic states in the same molecule overlap. This coherent overlap of the wave packets on different electronic states in the region of strong coupling allows an effective transfer of population that is very mass dependent. The extent of the transfer depends on the product of the populations on the two different electronic states and on their relative phase. It is as if two molecules collide but the process occurs within one molecule, a molecule that is simultaneously in both states. An analytical toy model recovers the (strong) mass and energy dependence.

Unraveling the electronic relaxation dynamics in photoexcited 2,4-difluoroaniline via femtosecond time-resolved photoelectron imaging

NASA Astrophysics Data System (ADS)

Ling, Fengzi; Li, Shuai; Wei, Jie; Liu, Kai; Wang, Yanmei; Zhang, Bing

2018-04-01

Time-resolved photoelectron imaging is employed to investigate the relaxation dynamics of the lowest two excited electronic states S1(ππ*) and S2(π3s/πσ*) in 2,4-difluoroaniline (24DFA). As the S1(ππ*) state is populated directly following 289 nm excitation, the population undergoes ultrafast intramolecular vibrational redistribution on a 540 fs time scale, followed by efficient intersystem crossing from S1(ππ*) to the triplet state within 379 ps, and the subsequent slower deactivation process of the triplet state. For excitation to the S2(π3s/πσ*) state at 238 nm, the population probably bifurcates into two decay channels. The dominant channel with 84 fs involves ultrafast internal conversion to the S1(ππ*) state, from which it relaxes to the electronic ground state on a 116 ps time scale. The other appears to involve motion along the S2(π3s/πσ*) potential energy surface. Our data also determine experimentally the electronic energies of S2(π3s/πσ*), S3(ππ*), and several Rydberg states in 24DFA.

Temporal resistance variation of the second generation HTS tape during superconducting-to-normal state transition.

PubMed

Malginov, Vladimir A; Malginov, Andrey V; Fleishman, Leonid S

2013-01-01

The quench process in high-temperature superconducting (HTS) wires plays an important role in superconducting power devices, such as fault current limiters, magnets, cables, etc. The superconducting device should survive after the overheating due to quench. We studied the evolution of the resistance of the YBCO tape wire during the quench process with 1 ms time resolution for various excitation voltages. The resistive normal zone was found to be located in a domain of about 1-4 cm long. The normal state nucleation begins in 40-60 ms after voltage is applied across the HTS tape. In subsequent 200-300 ms other normal state regions appear. The normal domain heating continues in the following 5-10s that results in a factor of 2-3 increase of its resistance. Formation of the normal domain during the quench process follows the same stages for different excitation voltages. Characteristic domain sizes, lifetimes and temperatures are determined for all stages.

Femtosecond two-photon Rabi oscillations in excited He driven by ultrashort intense laser fields

NASA Astrophysics Data System (ADS)

Fushitani, M.; Liu, C.-N.; Matsuda, A.; Endo, T.; Toida, Y.; Nagasono, M.; Togashi, T.; Yabashi, M.; Ishikawa, T.; Hikosaka, Y.; Morishita, T.; Hishikawa, A.

2016-02-01

Coherent light-matter interaction provides powerful methods for manipulating quantum systems. Rabi oscillation is one such process. As it enables complete population transfer to a target state, it is thus routinely exploited in a variety of applications in photonics, notably quantum information processing. The extension of coherent control techniques to the multiphoton regime offers wider applicability, and access to highly excited or dipole-forbidden transition states. However, the multiphoton Rabi process is often disrupted by other competing nonlinear effects such as the a.c. Stark shift, especially at the high laser-field intensities necessary to achieve ultrafast Rabi oscillations. Here we demonstrate a new route to drive two-photon Rabi oscillations on timescales as short as tens of femtoseconds, by utilizing the strong-field phenomenon known as Freeman resonance. The scenario is not specific to atomic helium as investigated in the present study, but broadly applicable to other systems, thus opening new prospects for the ultrafast manipulation of Rydberg states.

Ultrafast re-structuring of the electronic landscape of transparent dielectrics: new material states (Die-Met)

NASA Astrophysics Data System (ADS)

Gamaly, E. G.; Rode, A. V.

2018-03-01

Swift excitation of transparent dielectrics by ultrashort and highly intense laser pulse leads to ultra-fast re-structuring of the electronic landscape and generates many transient material states, which are continuously reshaped in accord with the changing pulse intensity. These unconventional transient material states, which exhibit simultaneously both dielectric and metallic properties, we termed here as the `Die-Met' states. The excited material is transparent and conductive at the same time. The real part of permittivity of the excited material changes from positive to negative values with the increase of excitation, which affects strongly the interaction process during the laser pulse. When the incident field has a component along the permittivity gradient, the amplitude of the field increases resonantly near the point of zero permittivity, which dramatically changes the interaction mode and increases absorption in a way that is similar to the resonant absorption in plasma. The complex 3D structure of the permittivity makes a transparent part of the excited dielectric (at ɛ 0 > ɛ re > 0) optically active. The electro-magnetic wave gets a twisted trajectory and accrues the geometric phase while passing through such a medium. Both the phase and the rotation of the polarisation plane depend on the 3D permittivity structure. Measuring the transmission, polarisation and the phase of the probe beam allows one to quantitatively identify these new transient states. We discuss the revelations of this effect in different experimental situations and their possible applications.

Neutron Fission of 235,237,239U and 241,243Pu: Cross Sections, Integral Cross Sections and Cross Sections on Excited States

DOE Office of Scientific and Technical Information (OSTI.GOV)

Younes, W; Britt, H C

In a recent paper submitted to Phys. Rev. C they have presented estimates for (n,f) cross sections on a series of Thorium, Uranium and Plutonium isotopes over the range E{sub n} = 0.1-2.5 MeV. The (n,f) cross sections for many of these isotopes are difficult or impossible to measure in the laboratory. The cross sections were obtained from previous (t,pf) reaction data invoking a model which takes into account the differences between (t,pf) and (n,f) reaction processes, and which includes improved estimates for the neutron compound formation process. The purpose of this note is: (1) to compare the estimated crossmore » sections to current data files in both ENDF and ENDL databases; (2) to estimate ratios of cross sections relatively to {sup 235}U integrated over the ''tamped flattop'' critical assembly spectrum that was used in the earlier {sup 237}U report; and (3) to show the effect on the integral cross sections when the neutron capturing state is an excited rotational state or an isomer. The isomer and excited state results are shown for {sup 235}U and {sup 237}U.« less

An excited state underlies gene regulation of a transcriptional riboswitch

PubMed Central

Zhao, Bo; Guffy, Sharon L.; Williams, Benfeard; Zhang, Qi

2017-01-01

Riboswitches control gene expression through ligand-dependent structural rearrangements of the sensing aptamer domain. However, we found that the Bacillus cereus fluoride riboswitch aptamer adopts identical tertiary structures in solution with and without ligand. Using chemical exchange saturation transfer (CEST) NMR spectroscopy, we revealed that the structured ligand-free aptamer transiently accesses a low-populated (~1%) and short-lived (~3 ms) excited conformational state that unravels a conserved ‘linchpin’ base pair to signal transcription termination. Upon fluoride binding, this highly localized fleeting process is allosterically suppressed to activate transcription. We demonstrated that this mechanism confers effective fluoride-dependent gene activation over a wide range of transcription rates, which is essential for robust toxicity response across diverse cellular conditions. These results unveil a novel switching mechanism that employs ligand-dependent suppression of an aptamer excited state to coordinate regulatory conformational transitions rather than adopting distinct aptamer ground-state tertiary architectures, exemplifying a new mode of ligand-dependent RNA regulation. PMID:28719589

Observation of correlated excitations in bimolecular collisions

NASA Astrophysics Data System (ADS)

Gao, Zhi; Karman, Tijs; Vogels, Sjoerd N.; Besemer, Matthieu; van der Avoird, Ad; Groenenboom, Gerrit C.; van de Meerakker, Sebastiaan Y. T.

2018-02-01

Although collisions between atoms and molecules are largely understood, collisions between two molecules have proven much harder to study. In both experiment and theory, our ability to determine quantum-state-resolved bimolecular cross-sections lags behind their atom-molecule counterparts by decades. For many bimolecular systems, even rules of thumb—much less intuitive understanding—of scattering cross sections are lacking. Here, we report the measurement of state-to-state differential cross sections on the collision of state-selected and velocity-controlled nitric oxide (NO) radicals and oxygen (O2) molecules. Using velocity map imaging of the scattered NO radicals, the full product-pair correlations of rotational excitation that occurs in both collision partners from individual encounters are revealed. The correlated cross sections show surprisingly good agreement with quantum scattering calculations using ab initio NO-O2 potential energy surfaces. The observations show that the well-known energy-gap law that governs atom-molecule collisions does not generally apply to bimolecular excitation processes, and reveal a propensity rule for the vector correlation of product angular momenta.

Vibrational excitation in O2and Cl2inductively-coupled plasmas and DC discharges

NASA Astrophysics Data System (ADS)

Booth, Jean-Paul; Marinov, Daniil; Foucher, Mickael; Annusova, Adriana; Guerra, Vasco

2016-09-01

Low-energy electrons can interact with molecules via resonances to cause vibrational excitation with large cross-sections. Such processes can absorb significant energy from the plasma electrons, affecting the electron energy distribution and potentially (via vibration-translation (VT) energy transfer) causing substantial gas heating. The presence of vibrationally excited molecules may significant increase the rates of collisional processes, including electron dissociative attachment and electron impact dissociation into neutral atoms. However, the cross-sections of these processes are often poorly known since they are extremely difficult to measure directly, and reliable theoretical calculations are only now appearing for simple diatomic molecules. We have measured the vibrational distributions in discharges in pure O2 and pure Cl2, using high-sensitivity ultra-broadband ultraviolet absorption spectroscopy. In O2 plasmas significant vibrational excitation is observed, up to v'' =18, with a tail temperature of around 8000K. In Cl2 excitation is only observed up to v'' =3, and the distribution appears to be in local equilibrium with the gas translational temperature (up to 1500K). We are developing a detailed self-consistent 0D global model of these systems including vibrational excitation. Work performed in the LABEX Plas@par project, with financial state aid (ANR-11-IDEX-0004-02 and ANR-13-BS09-0019).

Influence of different environments on the excited-state proton transfer and dual fluorescence of fisetin

NASA Astrophysics Data System (ADS)

Guharay, Jayanti; Dennison, S. Moses; Sengupta, Pradeep K.

1999-05-01

The influence of different protic and aprotic solvent environments on the excited-state intramolecular proton transfer (ESIPT) leading to a dual fluorescence behaviour of a biologically important, naturally occurring, polyhydroxyflavone, fisetin (3,3',4',7-tetrahydroxyflavone), has been investigated. The normal fluorescence band, in particular, is extremely sensitive to solvent polarity with νmax shifting from 24 510 cm -1 in dioxane ( ET(30)=36.0) to 20 790 cm -1 in methanol ( ET(30)=55.5). This is rationalized in terms of solvent dipolar relaxation process, which also accounts for the red edge excitation shifts (REES) observed in viscous environments such as glycerol at low temperatures. Significant solvent dependence of the tautomer fluorescence properties ( νmax, yield and decay kinetics) reveals the influence of external hydrogen bonding perturbation on the internal hydrogen bond of the molecule. These excited-state relaxation phenomena and their relevant parameters have been used to probe the microenvironment of fisetin in a membrane mimetic system, namely AOT reverse micelles in n-heptane at different water/surfactant molar ratio ( w0).

Photoinduced ICT vs. excited rotamer intercoversion in two quadrupolar polyaromatic N-methylpyridinium cations.

PubMed

Cesaretti, A; Carlotti, B; Elisei, F; Fortuna, C G; Spalletti, A

2018-01-24

The excited state dynamics of two quadrupolar polyaromatic N-methylpyridinium cations have been fully investigated in order to acquire detailed information on their photo-induced behavior. The two molecules are symmetric push-pull compounds having a D-π-A + -π-D motif, with the same electron-acceptor central unit (A = N-methylpyridinium) and two distinctive electron-donor polyaromatic side groups (D), namely naphthyl and pyrenyl substituents. Both molecules undergo charge transfer during the absorption, as revealed by a significant solvatochromism exhibited with solvent polarity, but the fate of their excited state was found to be markedly different. The careful analysis of the data gathered from femtosecond-resolved fluorescence up-conversion and transient absorption experiments, supported by DFT quantum mechanical calculations and temperature-dependent stationary measurements, shows the leading role of intramolecular charge transfer, assisted by symmetry breaking, in the pyrenyl derivative and that of rotamer interconversion in the naphthtyl one. Both excited state processes are controlled by the viscosity rather than polarity of the solvent, and they occur during inertial solvation in low-viscous media and lengthening up to tens of picoseconds in highly viscous solvents.

Electron capture and excitation processes in H+-H collisions in dense quantum plasmas

NASA Astrophysics Data System (ADS)

Jakimovski, D.; Markovska, N.; Janev, R. K.

2016-10-01

Electron capture and excitation processes in proton-hydrogen atom collisions taking place in dense quantum plasmas are studied by employing the two-centre atomic orbital close-coupling (TC-AOCC) method. The Debye-Hückel cosine (DHC) potential is used to describe the plasma screening effects on the Coulomb interaction between charged particles. The properties of a hydrogen atom with DHC potential are investigated as a function of the screening strength of the potential. It is found that the decrease in binding energy of nl levels with increasing screening strength is considerably faster than in the case of the Debye-Hückel (DH) screening potential, appropriate for description of charged particle interactions in weakly coupled classical plasmas. This results in a reduction in the number of bound states in the DHC potential with respect to that in the DH potential for the same plasma screening strength, and is reflected in the dynamics of excitation and electron capture processes for the two screened potentials. The TC-AOCC cross sections for total and state-selective electron capture and excitation cross sections with the DHC potential are calculated for a number of representative screening strengths in the 1-300 keV energy range and compared with those for the DH and pure Coulomb potential. The total capture cross sections for a selected number of screening strengths are compared with the available results from classical trajectory Monte Carlo calculations.

Electron transfer in silicon-bridged adjacent chromophores: the source for blue-green emission.

PubMed

Bayda, Malgorzata; Angulo, Gonzalo; Hug, Gordon L; Ludwiczak, Monika; Karolczak, Jerzy; Koput, Jacek; Dobkowski, Jacek; Marciniak, Bronislaw

2017-05-10

Si-Bridged chromophores have been proposed as sources for blue-green emission in several technological applications. The origin of this dual emission is to be found in an internal charge transfer reaction. The current work is an attempt to describe the details of these processes in these kinds of substances, and to design a molecular architecture to improve their performance. Nuclear motions essential for intramolecular charge transfer (ICT) can involve processes from twisted internal moieties to dielectric relaxation of the solvent. To address these issues, we studied ICT between adjacent chromophores in a molecular compound containing N-isopropylcarbazole (CBL) and 1,4-divinylbenzene (DVB) linked by a dimethylsilylene bridge. In nonpolar solvents emission arises from the local excited state (LE) of carbazole whereas in solvents of higher polarity dual emission was detected (LE + ICT). The CT character of the additional emission band was concluded from the linear dependence of the fluorescence maxima on solvent polarity. Electron transfer from CBL to DVB resulted in a large excited-state dipole moment (37.3 D) as determined from a solvatochromic plot and DFT calculations. Steady-state and picosecond time-resolved fluorescence experiments in butyronitrile (293-173 K) showed that the ICT excited state arises from the LE state of carbazole. These results were analyzed and found to be in accordance with an adiabatic version of Marcus theory including solvent relaxation.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. I. General formalism and application to open-shell states.

PubMed

Miranda, R P; Fisher, A J; Stella, L; Horsfield, A P

2011-06-28

The solution of the time-dependent Schrödinger equation for systems of interacting electrons is generally a prohibitive task, for which approximate methods are necessary. Popular approaches, such as the time-dependent Hartree-Fock (TDHF) approximation and time-dependent density functional theory (TDDFT), are essentially single-configurational schemes. TDHF is by construction incapable of fully accounting for the excited character of the electronic states involved in many physical processes of interest; TDDFT, although exact in principle, is limited by the currently available exchange-correlation functionals. On the other hand, multiconfigurational methods, such as the multiconfigurational time-dependent Hartree-Fock (MCTDHF) approach, provide an accurate description of the excited states and can be systematically improved. However, the computational cost becomes prohibitive as the number of degrees of freedom increases, and thus, at present, the MCTDHF method is only practical for few-electron systems. In this work, we propose an alternative approach which effectively establishes a compromise between efficiency and accuracy, by retaining the smallest possible number of configurations that catches the essential features of the electronic wavefunction. Based on a time-dependent variational principle, we derive the MCTDHF working equation for a multiconfigurational expansion with fixed coefficients and specialise to the case of general open-shell states, which are relevant for many physical processes of interest.

Two-neutrino double-β decay of 150Nd to excited final states in 150Sm

NASA Astrophysics Data System (ADS)

Kidd, M. F.; Esterline, J. H.; Finch, S. W.; Tornow, W.

2014-11-01

Background: Double-β decay is a rare nuclear process in which two neutrons in the nucleus are converted to two protons with the emission of two electrons and two electron antineutrinos. Purpose: We measured the half-life of the two-neutrino double-β decay of 150Nd to excited final states of 150Sm by detecting the deexcitation γ rays of the daughter nucleus. Method: This study yields the first detection of the coincidence γ rays from the 0 1+ excited state of 150Sm. These γ rays have energies of 333.97 and 406.52 keV and are emitted in coincidence through a 01+→21+→0gs+ transition. Results: The enriched Nd2O3 sample consisted of 40.13 g 150Nd and was observed for 642.8 days at the Kimballton Underground Research Facility, producing 21.6 net events in the region of interest. This count rate gives a half-life of T1 /2=[1 .07-0.25+0.45(stat ) ±0.07 (syst ) ] ×1020 yr. The effective nuclear matrix element was found to be 0.0465 -0.0054+0.0098. Finally, lower limits were obtained for decays to higher excited final states. Conclusions: Our half-life measurement agrees within uncertainties with another recent measurement in which no coincidence was employed. Our nuclear matrix element calculation may have an impact on a recent neutrinoless double-β decay nuclear matrix element calculation which implies that the decay to the first excited state in 150Sm is favored over that to the ground state.

Transfer of a weakly bound electron in collisions of Rydberg atoms with neutral particles. II. Ion-pair formation and resonant quenching of the Rb(nl) and Ne(nl) States by Ca, Sr, and Ba atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Narits, A. A.; Mironchuk, E. S.; Lebedev, V. S., E-mail: vlebedev@sci.lebedev.ru

2013-10-15

Electron-transfer processes are studied in thermal collisions of Rydberg atoms with alkaline-earth Ca(4s{sup 2}), Sr(5s{sup 2}), and Ba(6s{sup 2}) atoms capable of forming negative ions with a weakly bound outermost p-electron. We consider the ion-pair formation and resonant quenching of highly excited atomic states caused by transitions between Rydberg covalent and ionic terms of a quasi-molecule produced in collisions of particles. The contributions of these reaction channels to the total depopulation cross section of Rydberg states of Rb(nl) and Ne(nl) atoms as functions of the principal quantum number n are compared for selectively excited nl-levels with l Much-Less-Than n andmore » for states with large orbital quantum numbers l = n - 1, n - 2. It is shown that the contribution from resonant quenching dominates at small values of n, and the ion-pair formation process begins to dominate with increasing n. The values and positions of the maxima of cross sections for both processes strongly depend on the electron affinity of an alkaline-earth atom and on the orbital angular momentum l of a highly excited atom. It is shown that in the case of Rydberg atoms in states with large l {approx} n - 1, the rate constants of ion-pair formation and collisional quenching are considerably lower than those for nl-levels with l Much-Less-Than n.« less

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

NASA Astrophysics Data System (ADS)

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

2010-07-01

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

Resolving biomolecular motion and interactions by R2 and R1ρ relaxation dispersion NMR.

PubMed

Walinda, Erik; Morimoto, Daichi; Sugase, Kenji

2018-04-26

Among the tools of structural biology, NMR spectroscopy is unique in that it not only derives a static three-dimensional structure, but also provides an atomic-level description of the local fluctuations and global dynamics around this static structure. A battery of NMR experiments is now available to probe the motions of proteins and nucleic acids over the whole biologically relevant timescale from picoseconds to hours. Here we focus on one of these methods, relaxation dispersion, which resolves dynamics on the micro- to millisecond timescale. Key biological processes that occur on this timescale include enzymatic catalysis, ligand binding, and local folding. In other words, relaxation-dispersion-resolved dynamics are often closely related to the function of the molecule and therefore highly interesting to the structural biochemist. With an astounding sensitivity of ∼0.5%, the method detects low-population excited states that are invisible to any other biophysical method. The kinetics of the exchange between the ground state and excited states are quantified in the form of the underlying exchange rate, while structural information about the invisible excited state is obtained in the form of its chemical shift. Lastly, the population of the excited state can be derived. This diversity in the information that can be obtained makes relaxation dispersion an excellent method to study the detailed mechanisms of conformational transitions and molecular interactions. Here we describe the two branches of relaxation dispersion, R 2 and R 1ρ , discussing their applicability, similarities, and differences, as well as recent developments in pulse sequence design and data processing. Copyright © 2018 Elsevier Inc. All rights reserved.

Coherent blue emission generated by Rb two-photon excitation using diode and femtosecond lasers

NASA Astrophysics Data System (ADS)

Lopez, Jesus P.; Moreno, Marco P.; de Miranda, Marcio H. G.; Vianna, Sandra S.

2017-04-01

The coherent blue light generated in rubidium vapor due to the combined action of an ultrashort pulse train and a continuous wave diode laser is investigated. Each step of the two-photon transition 5S-5P{}3/2-5D is excited by one of the lasers, and the induced coherence between the 5S and 6P{}3/2 states is responsible for generating the blue beam. Measurements of the excitation spectrum reveal the frequency comb structure and allow us to identify the resonant modes responsible for inducing the nonlinear process. Further, each resonant mode excites a different group of atoms, making the process selective in atomic velocity. The signal dependency on the atomic density is characterized by a sharp growth and a rapid saturation. We also show that for high intensity of the diode laser, the Stark shift at resonance causes the signal suppression observed at low atomic density.

Spatial Imaging of Strongly Interacting Rydberg Atoms

NASA Astrophysics Data System (ADS)

Thaicharoen, Nithiwadee

The strong interactions between Rydberg excitations can result in spatial correlations between the excitations. The ability to control the interaction strength and the correlations between Rydberg atoms is applicable in future technological implementations of quantum computation. In this thesis, I investigates how both the character of the Rydberg-Rydberg interactions and the details of the excitation process affect the nature of the spatial correlations and the evolution of those correlations in time. I first describes the experimental apparatus and methods used to perform high-magnification Rydberg-atom imaging, as well as three experiments in which these methods play an important role. The obtained Rydberg-atom positions reveal the correlations in the many-body Rydberg-atom system and their time dependence with sub-micron spatial resolution. In the first experiment, atoms are excited to a Rydberg state that experiences a repulsive van der Waals interaction. The Rydberg excitations are prepared with a well-defined initial separation, and the effect of van der Waals forces is observed by tracking the interatomic distance between the Rydberg atoms. The atom trajectories and thereby the interaction coefficient C6 are extracted from the pair correlation functions of the Rydberg atom positions. In the second experiment, the Rydberg atoms are prepared in a highly dipolar state by using adiabatic state transformation. The atom-pair kinetics that follow from the strong dipole-dipole interactions are observed. The pair correlation results provide the first direct visualization of the electric-dipole interaction and clearly exhibit its anisotropic nature. In both the first and the second experiment, results of semi-classical simulations of the atom-pair trajectories agree well with the experimental data. In the analysis, I use energy conservation and measurements of the initial positions and the terminal velocities of the atom pairs to extract the C6 and C 3 interaction coefficients. The final experiment demonstrates the ability to enhance or suppress the degree of spatial correlation in a system of Rydberg excitations, using a rotary-echo excitation process in concert with particular excitation laser detunings. The work in this thesis demonstrates an ability to control long-range interactions between Rydberg atoms, which paves the way towards preparing and studying increasingly complex many-body systems.

DFT/TDDFT study on the photodissociation mechanism of the original monascus red and orange pigments

NASA Astrophysics Data System (ADS)

Liu, Yi; Wu, Li; Lv, Qingzhang

2015-06-01

The weak photostability has to some extent restricted the wide utilization of monascus pigments in food industries, and their photobleaching mechanism is unclear yet. Density functional theory and time-dependent density functional theory at B3LYP/6-311+G(d,p) level have been performed to optimize the geometries of ground states, single and triplet excited-states of the original monascus red and orange pigments, the possible photodissociation mechanism of which is analyzed according to the calculated data. It is the break of the chromophores, conjugated π bonds which has induced their decoloration. The photodissociation of these pigments involves three steps, excitation of the large conjugated π system, water addition to the singlet or triplet excited-state, and Norrish type I photochemical cleavage reactions of the side chains. The former two steps are much more important steps which have led to the destruction of the chromophores and the fading of the four original monascus red and orange pigments. According to the photobleaching mechanism obtained, one could find some solutions to enhance the photostability of these monascus colorants during the food processing process and extend the shelf life of the foods added with monascus pigments.

Dipole-resonance assisted isomerization in the electronic ground state using few-cycle infrared pulses.

PubMed

Skocek, Oliver; Uiberacker, Christoph; Jakubetz, Werner

2011-06-30

A computational investigation of HCN → HNC isomerization in the electronic ground state by one- and few-cycle infrared pulses is presented. Starting from a vibrationally pre-excited reagent state, isomerization yields of more than 50% are obtained using single one- to five-cycle pulses. The principal mechanism includes two steps of population transfer by dipole-resonance (DR), and hence, the success of the method is closely linked to the polarity of the system and, in particular, the stepwise change of the dipole moment from reactant to transition state and on to products. The yield drops massively if the diagonal dipole matrix elements are artificially set to zero. In detail, the mechanism includes DR-induced preparation of a delocalized vibrational wavepacket, which traverses the barrier region and is finally trapped in the product well by DR-dominated de-excitation. The excitation and de-excitation steps are triggered by pulse lobes of opposite field direction. As the number of optical cycles is increased, the leading field lobes prepare a vibrational superposition state by off-resonant ladder climbing, which is then subjected to the three steps of the principal isomerization mechanism. DR excitation is more efficient from a preformed vibrational wavepacket than from a molecular eigenstate. The entire process can be loosely described as Tannor-Kosloff-Rice type transfer mechanism on a single potential surface effected by a single pulse, individual field lobes assuming the roles of pump- and dump-pulses. Pre-excitation to a transient wavepacket can be enhanced by applying a separate, comparatively weak few-cycle prepulse, in which the prepulse prepares a vibrational wavepacket. The two-pulse setup corresponds to a double Tannor-Kosloff-Rice control scheme on a single potential surface.

Challenges in Optical Emission Spectroscopy

NASA Astrophysics Data System (ADS)

Siepa, Sarah; Berger, Birk; Schulze, Julian; Schuengel, Edmund; von Keudell, Achim

2016-09-01

Collisional-radiative models (CRMs) are widely used to investigate plasma properties such as electron density, electron temperature and the form of the electron energy distribution function. In this work an extensive CRM for argon is presented, which models 30 excited states and various kinds of processes including electron impact excitation/de-excitation, radiation and radiation trapping. The CRM is evaluated in several test cases, i.e. inductively and capacitively coupled plasmas at various pressures, powers/voltages and gas admixtures. Deviations are found between modelled and measured spectra. The escape factor as a means of describing radiation trapping is discussed as well as the cross section data for electron impact processes. This work was supported by the Ruhr University Research School PLUS, funded by Germany's Excellence Initiative [DFG GSC 98/3].

Ultrafast quantum control of ionization dynamics in krypton.

PubMed

Hütten, Konrad; Mittermair, Michael; Stock, Sebastian O; Beerwerth, Randolf; Shirvanyan, Vahe; Riemensberger, Johann; Duensing, Andreas; Heider, Rupert; Wagner, Martin S; Guggenmos, Alexander; Fritzsche, Stephan; Kabachnik, Nikolay M; Kienberger, Reinhard; Bernhardt, Birgitta

2018-02-19

Ultrafast spectroscopy with attosecond resolution has enabled the real time observation of ultrafast electron dynamics in atoms, molecules and solids. These experiments employ attosecond pulses or pulse trains and explore dynamical processes in a pump-probe scheme that is selectively sensitive to electronic state of matter via photoelectron or XUV absorption spectroscopy or that includes changes of the ionic state detected via photo-ion mass spectrometry. Here, we demonstrate how the implementation of combined photo-ion and absorption spectroscopy with attosecond resolution enables tracking the complex multidimensional excitation and decay cascade of an Auger auto-ionization process of a few femtoseconds in highly excited krypton. In tandem with theory, our study reveals the role of intermediate electronic states in the formation of multiply charged ions. Amplitude tuning of a dressing laser field addresses different groups of decay channels and allows exerting temporal and quantitative control over the ionization dynamics in rare gas atoms.

Python-Based Tool for Universal Nuclear Data Extraction

NASA Astrophysics Data System (ADS)

McDonald, William; Blair, Hayden; Consalvi, Peter; Garbiso, Markus; Grover, Hannah; Harget, Alex; Martin, Matthew; Natzke, Connor; Leach, Kyle

2017-09-01

Over the past 70 years, nuclear physics experiments have provided a vast wealth of experimental data on both ground and excited state properties across the nuclear chart. In many cases, searching for and parsing the relevant nuclear structure data from previous work can be tedious and difficult. Although the compilation, evaluation, and digitization of this data by multiple groups around the world over the past several decades has helped dramatically in this respect, the process of performing systematic studies using this data can still be cumbersome and limited. We are in the process of creating a python-based program to extract, sort, and manipulate nuclear and atomic data efficiently. In its current state, the program is able to extract all atomic-shell ionization energies, excited- and ground-state nuclear properties, and all beta-decay rates and ratios. As a part of this ongoing project, we plan to use this tool to examine beta-decay rates in extreme astrophysical environments.

Optimal superadiabatic population transfer and gates by dynamical phase corrections

NASA Astrophysics Data System (ADS)

Vepsäläinen, A.; Danilin, S.; Paraoanu, G. S.

2018-04-01

In many quantum technologies adiabatic processes are used for coherent quantum state operations, offering inherent robustness to errors in the control parameters. The main limitation is the long operation time resulting from the requirement of adiabaticity. The superadiabatic method allows for faster operation, by applying counterdiabatic driving that corrects for excitations resulting from the violation of the adiabatic condition. In this article we show how to construct the counterdiabatic Hamiltonian in a system with forbidden transitions by using two-photon processes and how to correct for the resulting time-dependent ac-Stark shifts in order to enable population transfer with unit fidelity. We further demonstrate that superadiabatic stimulated Raman passage can realize a robust unitary NOT-gate between the ground state and the second excited state of a three-level system. The results can be readily applied to a three-level transmon with the ladder energy level structure.

Three-dimensional infinite order sudden quantum theory for indirect photodissociation processes. Application to the photofragment yield spectrum of NOCl in the region of the T1(13A″) ←S0(11A') transition. Fragment rotational distributions and thermal averages

NASA Astrophysics Data System (ADS)

Grinberg, Horacio; Freed, Karl F.; Williams, Carl J.

1997-08-01

The analytical infinite order sudden (IOS) quantum theory of triatomic photodissociation, developed in paper I, is applied to study the indirect photodissociation of NOCl through a real or virtual intermediate state. The theory uses the IOS approximation for the dynamics in the final dissociative channels and an Airy function approximation for the continuum functions. The transition is taken as polarized in the plane of the molecule; symmetric top wave functions are used for both the initial and intermediate bound states; and simple semiempirical model potentials are employed for each state. The theory provides analytical expressions for the photofragment yield spectrum for producing particular final fragment ro-vibrational states as a function of the photon excitation energy. Computations are made of the photofragment excitation spectrum of NOCl in the region of the T1(13A″)←S0(11A') transition for producing the NO fragment in the vibrational states nNO=0, 1, and 2. The computed spectra for the unexcited nNO==0 and excited nNO=2 states are in reasonable agreement with experiment. However, some discrepancies are observed for the singly excited nNO=1 vibrational state, indicating deficiencies in the semiempirical potential energy surface. Computations for two different orientations of the in-plane transition dipole moment produce very similar excitation spectra. Calculations of fragment rotational distributions are performed for high values of the total angular momentum J, a feature that would be very difficult to perform with close-coupled methods. Computations are also made of the thermally averaged rotational energy distributions to simulate the conditions in actual supersonic jet experiments.

Role of Electron-Driven Proton-Transfer Processes in the Ultrafast Deactivation of Photoexcited Anionic 8-oxoGuanine-Adenine and 8-oxoGuanine-Cytosine Base Pairs.

PubMed

Wu, Xiuxiu; Karsili, Tolga N V; Domcke, Wolfgang

2017-01-14

It has been reported that 8-oxo-7,8-dihydro-guanosine (8-oxo-G), which is the main product of oxidative damage of DNA, can repair cyclobutane pyrimidine dimer (CPD) lesions when incorporated into DNA or RNA strands in proximity to such lesions. It has therefore been suggested that the 8-oxo-G nucleoside may have been a primordial precursor of present-day flavins in DNA or RNA repair. Because the electron transfer leading to the splitting of a thymine-thymine pair in a CPD lesion occurs in the photoexcited state, a reasonably long excited-state lifetime of 8-oxo-G is required. The neutral (protonated) form of 8-oxo-G exhibits a very short (sub-picosecond) intrinsic excited-state lifetime which is unfavorable for repair. It has therefore been argued that the anionic (deprotonated) form of 8-oxo-G, which exhibits a much longer excited-state lifetime, is more likely to be a suitable cofactor for DNA repair. Herein, we have investigated the exited-state quenching mechanisms in the hydrogen-bonded complexes of deprotonated 8-oxo-G - with adenine (A) and cytosine (C) using ab initio wave-function-based electronic-structure calculations. The calculated reaction paths and potential-energy profiles reveal the existence of barrierless electron-driven inter-base proton-transfer reactions which lead to low-lying S₁/S₀ conical intersections. The latter can promote ultrafast excited-state deactivation of the anionic base pairs. While the isolated deprotonated 8-oxo-G - nucleoside may have been an efficient primordial repair cofactor, the excited states of the 8-oxo-G - -A and 8-oxo-G - -C base pairs are likely too short-lived to be efficient electron-transfer repair agents.

Dynamics of solvation and desolvation of rubidium attached to He nanodroplets

NASA Astrophysics Data System (ADS)

von Vangerow, J.; John, O.; Stienkemeier, F.; Mudrich, M.

2015-07-01

The real-time dynamics of photoexcited and photoionized rubidium (Rb) atoms attached to helium (He) nanodroplets is studied by femtosecond pump-probe mass spectrometry. While excited Rb atoms in the perturbed 6p-state (Rb*) desorb off the He droplets, Rb+ photoions tend to sink into the droplet interior when created near the droplet surface. The transition from Rb+ solvation to full Rb* desorption is found to occur at a delay time τ ˜ 600 fs for Rb* in the 6pΣ-state and τ ˜ 1200 fs for the 6pΠ-state. Rb+He ions are found to be created by directly exciting bound Rb*He exciplex states as well as by populating bound Rb+He-states in a photoassociative ionization process.

Photophysical and Photochemical Properties of Some Fluorescent Derivatives of Vitamin B1

NASA Astrophysics Data System (ADS)

Marciniak, B.

1987-05-01

Absorption and emission spectra, depopulation kinetics of the lowest excited singlet and triplet states and acid-base equilibria of two fluorescent vitamin B, derivatives, the products I and II of the reaction of N-methylated vitamine B, with cytidine and adenosine, respectively, were investigated. Analysis of the lifetime and quantum yield data indicate that at 77 K emissions are the main processes of deactivation of the S1 and T1 states for the free ion and protonated forms. The pKa values indicate a much higher acidity in the excited singlet and triplet states than in the ground state. I and II undergo very slow photochemical reactions in solution in the presence of oxygen (Φ ~ 10-4).

Non-equilibrium plasma kinetics of reacting CO: an improved state to state approach

NASA Astrophysics Data System (ADS)

Pietanza, L. D.; Colonna, G.; Capitelli, M.

2017-12-01

Non-equilibrium plasma kinetics of reacting CO for conditions typically met in microwave discharges have been developed based on the coupling of excited state kinetics and the Boltzmann equation for the electron energy distribution function (EEDF). Particular attention is given to the insertion in the vibrational kinetics of a complete set of electron molecule resonant processes linking the whole vibrational ladder of the CO molecule, as well as to the role of Boudouard reaction, i.e. the process of forming CO2 by two vibrationally excited CO molecules, in shaping the vibrational distribution of CO and promoting reaction channels assisted by vibrational excitation (pure vibrational mechanisms, PVM). PVM mechanisms can become competitive with electron impact dissociation processes (DEM) in the activation of CO. A case study reproducing the conditions of a microwave discharge has been considered following the coupled kinetics also in the post discharge conditions. Results include the evolution of EEDF in discharge and post discharge conditions highlighting the role of superelastic vibrational and electronic collisions in shaping the EEDF. Moreover, PVM rate coefficients and DEM ones are studied as a function of gas temperature, showing a non-Arrhenius behavior, i.e. the rate coefficients increase with decreasing gas temperature as a result of a vibrational-vibrational (V-V) pumping up mechanism able to form plateaux in the vibrational distribution function. The accuracy of the results is discussed in particular in connection to the present knowledge of the activation energy of the Boudouard process.

Processes of ionization of atoms in nonstationary states by the field of an attosecond pulse

NASA Astrophysics Data System (ADS)

Makarov, D. N.; Matveev, V. I.

2015-02-01

Processes of ionization at the interaction of attosecond pulses of an electromagnetic field with atoms in nonstationary states have been considered. The probabilities and ionization cross section at the radiative relaxation of an excited state of a single-electron atom and at the Auger decay of the autoionization state of a two-electron atom have been calculated. The developed method allows the expansion to the case of more complex targets, including those in the collision state, and to various chemical reactions.

Simulating superradiance from higher-order-intensity-correlation measurements: Single atoms

NASA Astrophysics Data System (ADS)

Wiegner, R.; Oppel, S.; Bhatti, D.; von Zanthier, J.; Agarwal, G. S.

2015-09-01

Superradiance typically requires preparation of atoms in highly entangled multiparticle states, the so-called Dicke states. In this paper we discuss an alternative route where we prepare such states from initially uncorrelated atoms by a measurement process. By measuring higher-order intensity-intensity correlations we demonstrate that we can simulate the emission characteristics of Dicke superradiance by starting with atoms in the fully excited state. We describe the essence of the scheme by first investigating two excited atoms. Here we demonstrate how via Hanbury Brown and Twiss type of measurements we can produce Dicke superradiance and subradiance displayed commonly with two atoms in the single excited symmetric and antisymmetric Dicke states, respectively. We thereafter generalize the scheme to arbitrary numbers of atoms and detectors, and explain in detail the mechanism which leads to this result. The approach shows that the Hanbury Brown and Twiss type of intensity interference and the phenomenon of Dicke superradiance can be regarded as two sides of the same coin. We also present a compact result for the characteristic functional which generates all order intensity-intensity correlations.

On the properties of microsolvated molecules in the ground (S0) and excited (S1) states: The anisole-ammonia 1:1 complex

NASA Astrophysics Data System (ADS)

Biczysko, Malgorzata; Piani, Giovanni; Pasquini, Massimiliano; Schiccheri, Nicola; Pietraperzia, Giangaetano; Becucci, Maurizio; Pavone, Michele; Barone, Vincenzo

2007-10-01

State-of-the-art spectroscopic and theoretical methods have been exploited in a joint effort to elucidate the subtle features of the structure and the energetics of the anisole-ammonia 1:1 complex, a prototype of microsolvation processes. Resonance enhanced multiphoton ionization and laser-induced fluorescence spectra are discussed and compared to high-level first-principles theoretical models, based on density functional, many body second order perturbation, and coupled cluster theories. In the most stable nonplanar structure of the complex, the ammonia interacts with the delocalized π electron density of the anisole ring: hydrogen bonding and dispersive forces provide a comparable stabilization energy in the ground state, whereas in the excited state the dispersion term is negligible because of electron density transfer from the oxygen to the aromatic ring. Ground and excited state geometrical parameters deduced from experimental data and computed by quantum mechanical methods are in very good agreement and allow us to unambiguously determine the molecular structure of the anisole-ammonia complex.

Multinucleon transfer in O,1816,19F+208Pb reactions at energies near the fusion barrier

NASA Astrophysics Data System (ADS)

Rafferty, D. C.; Dasgupta, M.; Hinde, D. J.; Simenel, C.; Simpson, E. C.; Williams, E.; Carter, I. P.; Cook, K. J.; Luong, D. H.; McNeil, S. D.; Ramachandran, K.; Vo-Phuoc, K.; Wakhle, A.

2016-08-01

Background: Nuclear reactions are complex, involving collisions between composite systems where many-body dynamics determines outcomes. Successful models have been developed to explain particular reaction outcomes in distinct energy and mass regimes, but a unifying picture remains elusive. The irreversible transfer of kinetic energy from the relative motion of the collision partners to their internal states, as is known to occur in deep inelastic collisions, has yet to be successfully incorporated explicitly into fully quantal reaction models. The influence of these processes on fusion is not yet quantitatively understood. Purpose: To investigate the population of high excitation energies in transfer reactions at sub-barrier energies, which are precursors to deep inelastic processes, and their dependence on the internuclear separation. Methods: Transfer probabilities and excitation energy spectra have been measured in collisions of O,1816,19F+208Pb , at various energies below and around the fusion barrier, by detecting the backscattered projectile-like fragments in a Δ E -E telescope. Results: The relative yields of different transfer outcomes are strongly driven by Q values, but change with the internuclear separation. In 16O+208Pb , single nucleon transfer dominates, with a strong contribution from -2 p transfer close to the Coulomb barrier, though this channel becomes less significant in relation to the -2 p 2 n transfer channel at larger separations. For 18O+208Pb , the -2 p 2 n channel is the dominant charge transfer mode at all separations. In the reactions with 19F,-3 p 2 n transfer is significant close to the barrier, but falls off rapidly with energy. Multinucleon transfer processes are shown to lead to high excitation energies (up to ˜15 MeV), which is distinct from single nucleon transfer modes which predominantly populate states at low excitation energy. Conclusions: Kinetic energy is transferred into internal excitations following transfer, with this energy being distributed over a larger number of states and to higher excitations with increasing numbers of transferred nucleons. Multinucleon transfer is thus a mechanism by which energy can be dissipated from the relative motion before reaching the fusion barrier radius.

Vibrational population of the A super 3 sigma sub u/+/ and B super 3 pi sub g states of N2 in normal auroras.

NASA Technical Reports Server (NTRS)

Cartwright, D. C.; Trajmar, S.; Williams, W.

1971-01-01

Use of new electron impact excitation cross sections for the six lowest triplet states (A, B, W, C, E, D) of N2, and solution of the coupled equations of statistical equilibrium to obtain the vibrational population of each electronic state. The results show that cascade from high levels of the A super 3 sigma sub u(+) state and from the W super 3 delta sub u state is significant in populating the lower vibrational levels of the B state and hence the character of its ?apparent' excitation cross sections. For the B state excited under auroral conditions, the fraction of the total population due to cascade processes exceeds 25% for all levels lower than 7 and is greater than 80% for B(v' = 0). For the A state under similar conditions, cascade from the B state contributes 50% or more of the total vibrational population for levels lower than 7, and 80% or more for levels below 4. For levels of the A state greater than 7, the A yields B transitions depopulate the levels rapidly and indicate that the Vegard-Kaplan emissions from these higher levels will be weak or totally absent in normal auroras.

Surface hopping investigation of the relaxation dynamics in radical cations

DOE PAGES

Assmann, Mariana; Weinacht, Thomas; Matsika, Spiridoula

2016-01-19

Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in thesemore » systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Furthermore, examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.« less

Spin-orbit-coupled Bose-Einstein condensates of rotating polar molecules

NASA Astrophysics Data System (ADS)

Deng, Y.; You, L.; Yi, S.

2018-05-01

An experimental proposal for realizing spin-orbit (SO) coupling of pseudospin 1 in the ground manifold 1Σ (υ =0 ) of (bosonic) bialkali polar molecules is presented. The three spin components are composed of the ground rotational state and two substates from the first excited rotational level. Using hyperfine resolved Raman processes through two select excited states resonantly coupled by a microwave, an effective coupling between the spin tensor and linear momentum is realized. The properties of Bose-Einstein condensates for such SO-coupled molecules exhibiting dipolar interactions are further explored. In addition to the SO-coupling-induced stripe structures, the singly and doubly quantized vortex phases are found to appear, implicating exciting opportunities for exploring novel quantum physics using SO-coupled rotating polar molecules with dipolar interactions.

Charge-transfer state excitation as the main mechanism of the photodarkening process in ytterbium-doped aluminosilicate fibres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bobkov, K K; Rybaltovsky, A A; Vel'miskin, V V

2014-12-31

We have studied photodarkening in ytterbium-doped fibre preforms with an aluminosilicate glass core. Analysis of their absorption and luminescence spectra indicates the formation of stable Yb{sup 2+} ions in the glass network under IR laser pumping at a wavelength λ = 915 nm and under UV irradiation with an excimer laser (λ = 193 nm). We have performed comparative studies of the luminescence spectra of the preforms and crystals under excitation at a wavelength of 193 nm. The mechanism behind the formation of Yb{sup 2+} ions and aluminium – oxygen hole centres (Al-OHCs), common to ytterbium-doped YAG crystals and aluminosilicatemore » glass, has been identified: photoinduced Yb{sup 3+} charge-transfer state excitation. (optical fibres)« less

Excitation Energy Transfer by Coherent and Incoherent Mechanisms in the Peridinin-Chlorophyll a Protein.

PubMed

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

2017-01-19

Excitation energy transfer from peridinin to chlorophyll (Chl) a is unusually efficient in the peridinin-chlorophyll a protein (PCP) from dinoflagellates. This enhanced performance is derived from the long intrinsic lifetime of 4.4 ps for the S 2 (1 1 B u + ) state of peridinin in PCP, which arises from the electron-withdrawing properties of its carbonyl substituent. Results from heterodyne transient grating spectroscopy indicate that S 2 serves as the donor for two channels of energy transfer: a 30 fs process involving quantum coherence and delocalized peridinin-Chl states and an incoherent, 2.5 ps process initiated by dynamic exciton localization, which accompanies the formation of a conformationally distorted intermediate in 45 fs. The lifetime of the S 2 state is lengthened in PCP by its intramolecular charge-transfer character, which increases the system-bath coupling and slows the torsional motions that promote nonradiative decay to the S 1 (2 1 A g - ) state.

Density matrix-based time-dependent configuration interaction approach to ultrafast spin-flip dynamics

NASA Astrophysics Data System (ADS)

Wang, Huihui; Bokarev, Sergey I.; Aziz, Saadullah G.; Kühn, Oliver

2017-08-01

Recent developments in attosecond spectroscopy yield access to the correlated motion of electrons on their intrinsic timescales. Spin-flip dynamics is usually considered in the context of valence electronic states, where spin-orbit coupling is weak and processes related to the electron spin are usually driven by nuclear motion. However, for core-excited states, where the core-hole has a nonzero angular momentum, spin-orbit coupling is strong enough to drive spin-flips on a much shorter timescale. Using density matrix-based time-dependent restricted active space configuration interaction including spin-orbit coupling, we address an unprecedentedly short spin-crossover for the example of L-edge (2p→3d) excited states of a prototypical Fe(II) complex. This process occurs on a timescale, which is faster than that of Auger decay (∼4 fs) treated here explicitly. Modest variations of carrier frequency and pulse duration can lead to substantial changes in the spin-state yield, suggesting its control by soft X-ray light.

Quantum dynamics of charge state in silicon field evaporation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silaeva, Elena P.; Uchida, Kazuki; Watanabe, Kazuyuki, E-mail: kazuyuki@rs.kagu.tus.ac.jp

2016-08-15

The charge state of an ion field-evaporating from a silicon-atom cluster is analyzed using time-dependent density functional theory coupled to molecular dynamics. The final charge state of the ion is shown to increase gradually with increasing external electrostatic field in agreement with the average charge state of silicon ions detected experimentally. When field evaporation is triggered by laser-induced electronic excitations the charge state also increases with increasing intensity of the laser pulse. At the evaporation threshold, the charge state of the evaporating ion does not depend on the electrostatic field due to the strong contribution of laser excitations to themore » ionization process both at low and high laser energies. A neutral silicon atom escaping the cluster due to its high initial kinetic energy is shown to be eventually ionized by external electrostatic field.« less

Transfer of entangled state, entanglement swapping and quantum information processing via the Rydberg blockade

NASA Astrophysics Data System (ADS)

Deng, Li; Chen, Ai-Xi; Zhang, Jian-Song

2011-11-01

We provide a scheme with which the transfer of the entangled state and the entanglement swapping can be realized in a system of neutral atoms via the Rydberg blockade. Our idea can be extended to teleport an unknown atomic state. According to the latest theoretical research of the Rydberg excitation and experimental reports of the Rydberg blockade effect in quantum information processing, we discuss the experimental feasibility of our scheme.

Burst-mode manipulation of magnonic vortex crystals

NASA Astrophysics Data System (ADS)

Hänze, Max; Adolff, Christian F.; Weigand, Markus; Meier, Guido

2015-03-01

The manipulation of polarization states in 4 ×4 vortex crystals using sinusoidal magnetic field bursts is investigated by means of a broadband ferromagnetic-resonance setup. Magnetic field excitation with the proper amplitude and frequency allows tuning different polarization states, which are observed in the measured absorption spectra. The variation of the sinusoidal burst width consecutively identifies the time scale of the underlying process. A memorylike polarization state writing process is demonstrated on the submicrosecond time scale.

Enantioselective Photochemical Organocascade Catalysis.

PubMed

Woźniak, Łukasz; Magagnano, Giandomenico; Melchiorre, Paolo

2018-01-22

Reported herein is a photochemical cascade process that combines the excited-state and ground-state reactivity of chiral organocatalytic intermediates. This strategy directly converts racemic cyclopropanols and α,β-unsaturated aldehydes into stereochemically dense cyclopentanols with exquisite stereoselectivity. Mechanistic investigations have enabled elucidating the origin of the stereoconvergence, which is governed by a kinetic resolution process. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Absolute vacuum ultraviolet photoabsorption cross section studies of atomic and molecular species: Techniques and observational data

NASA Technical Reports Server (NTRS)

Judge, D. L.; Wu, C. Y. R.

1990-01-01

Absorption of a high energy photon (greater than 6 eV) by an isolated molecule results in the formation of highly excited quasi-discrete or continuum states which evolve through a wide range of direct and indirect photochemical processes. These are: photoionization and autoionization, photodissociation and predissociation, and fluorescence. The ultimate goal is to understand the dynamics of the excitation and decay processes and to quantitatively measure the absolute partial cross sections for all processes which occur in photoabsorption. Typical experimental techniques and the status of observational results of particular interest to solar system observations are presented.

Spectroscopic properties of the S1 state of linear carotenoids after excess energy excitation

NASA Astrophysics Data System (ADS)

Kuznetsova, Valentyna; Southall, June; Cogdell, Richard J.; Fuciman, Marcel; Polívka, Tomáš

2017-09-01

Properties of the S1 state of neurosporene, spheroidene and lycopene were studied after excess energy excitation in the S2 state. Excitation of carotenoids into higher vibronic levels of the S2 state generates excess vibrational energy in the S1 state. The vibrationally hot S1 state relaxes faster when carotenoid is excited into the S2 state with excess energy, but the S1 lifetime remains constant regardless of which vibronic level of the S2 state is excited. The S∗ signal depends on excitation energy only for spheroidene, which is likely due to asymmetry of the molecule, facilitating conformations responsible for the S∗ signal.

Theoretical studies of electronically excited states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Besley, Nicholas A.

2014-10-06

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

Spectral line intensity irreversibility in circulatory plasma magnetization processes

NASA Astrophysics Data System (ADS)

Qu, Z. Q.; Dun, G. T.

2012-01-01

Spectral line intensity variation is found to be irreversible in circulatory plasma magnetization process by experiments described in this paper, i.e., the curves illustrating spectral line photon fluxes irradiated from a light source immerged in a magnetic field by increasing the magnetic induction cannot be reproduced by decreasing the magnetic induction within the errors. There are two plasma magnetization patterns found. One shows that the intensities are greater at the same magnetic inductions during the magnetic induction decreasing process after the increasing, and the other gives the opposite effect. This reveals that the magneto-induced excitation and de-excitation process is irreversible like ferromagnetic magnetization. But the two irreversible processes are very different in many aspects stated in the text.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jiayue; Zhang, Dong; Chen, Zhen

The vibrationally excited reaction of F + CHD{sub 3}(ν{sub 1} = 1) → DF + CHD{sub 2} at a collision energy of 9.0 kcal/mol is investigated using the crossed-beams and time-sliced velocity map imaging techniques. Detailed and quantitative information of the CH stretching excitation effects on the reactivity and dynamics of the title reaction is extracted with the help of an accurate determination of the fraction of the excited CHD{sub 3} reagent in the crossed-beam region. It is found that all vibrational states of the CHD{sub 2} products observed in the ground-state reaction, which mainly involve the excitation of themore » umbrella mode of the CHD{sub 2} products, are severely suppressed by the CH stretching excitation. However, there are four additional vibrational states of the CHD{sub 2} products appearing in the excited-state reaction which are not presented in the ground-state reaction. These vibrational states either have the CH stretching excitation retained or involve one quantum excitation in the CH stretching and the excitation of the umbrella mode. Including all observed vibrational states, the overall cross section of the excited-state reaction is estimated to be 66.6% of that of the ground-state one. Experimental results also show that when the energy of CH stretching excitation is released during the reaction, it is deposited almost exclusively as the rovibrational energy of the DF products, with little portion in the translational degree of freedom. For vibrational states of the CHD{sub 2} products observed in both ground- and excited-state reactions, the CH stretching excitation greatly suppresses the forward scattered products, causing a noticeable change in the product angular distributions.« less

Experimental evaluation of analyte excitation mechanisms in the inductively coupled plasma

NASA Astrophysics Data System (ADS)

Lehn, Scott A.; Hieftje, Gary M.

2003-10-01

The inductively coupled plasma (ICP) is a justifiably popular source for atomic emission spectrometry. However, despite its popularity, the ICP is still only partially understood. Even the mechanisms of analyte excitation remain unclear; some energy levels are quite clearly populated by charge transfer while others might be populated by electron-ion recombination, by electron impact, or by Penning processes. Distinguishing among these alternatives is possible by means of a steady-state kinetics approach that examines correlations between the emission of a selected atom, ion, or level and the local number densities of species assumed to produce the excitation. In an earlier investigation, strong correlations were found between either calcium atom or ion emission and selected combinations of calcium atom or ion number densities and electron number densities in the plasma. However, all radially resolved data employed in the earlier study were produced from Abel inversion and from measurements that were crude by today's standards. Now, by means of tomographic imaging, laser-saturated atomic fluorescence, and Thomson and Rayleigh scattering, it is possible to measure the required radially resolved data without Abel inversion and with far greater fidelity. The correlations previously studied for calcium have been investigated with these more reliable data. Ion-electron recombination, either radiative or with argon as a third body, was determined to be the most likely excitation mechanism for calcium atom, while electron impact appeared to be the most important process to produce excite-state calcium ions. These results were consistent with the previous study. However, the present study suggests that collisional deactivation, rather than radiative decay, is the most likely mode of returning both calcium atoms and ions to the ground state.

Energy conversion of X-ray, ultraviolet and infrared radiation in Gd2O3 crystals doped with Er3+ ions

NASA Astrophysics Data System (ADS)

Trofimova, E. S.; Pustovarov, V. A.; Kuznetsova, Yu. A.; Zatsepin, A. F.

2017-09-01

Spectra of photoluminescence (PL) and X-ray excited luminescence (XRL) in region of 1.5-5.0 eV, PL excitation spectra (2.8-5.8 eV), PL decay kinetics were measured in Gd2O3 crystals doped both with Er3+ and Zn2+ ions. Synchrotron radiation (VEPP-3 storage ring, Novosibirsk, Russia) were used for XRL measurements. PL spectra were studied at room temperature and T= 88 K under excitation with energy Eexc: a) in fundamental absorption region (Eexc≥Eg); b) in intracenter excitation region (Eexc

Luminescence of Radachlorin Photosensitizer in Aqueous Solution under Excitation at 405 and 660 nm

NASA Astrophysics Data System (ADS)

Beltukova, D. M.; Belik, V. P.; Vasyutinskii, O. S.; Gadzhiev, I. M.; Goncharov, S. E.; Semenova, I. V.

2018-01-01

Entire luminescence spectrum of a commercial photosensitizer Radachlorin in aqueous solution has been recorded under laser excitation at 660 nm and analyzed. The peak of singlet oxygen phosphorescence at 1274 nm has been observed. The results obtained were compared with those recorded with laser excitation at 405 nm and reported earlier. The comparison showed the similarity of relaxation and luminescence processes occurring in both cases. Effective absorption cross sections were determined at each excitation wavelength, it was also shown that the singlet oxygen quantum yield is independent of photosensitizer concentration. The lifetime of the first excited triplet state in Radachlorin was determined. The results obtained can be used for optimization of the conditions of singlet oxygen generation and detection in solutions and biological samples.

Ultrafast dynamics of photoactive yellow protein via the photoexcitation and emission processes.

PubMed

Nakamura, Ryosuke; Hamada, Norio; Ichida, Hideki; Tokunaga, Fumio; Kanematsu, Yasuo

2007-01-01

Pump-dump fluorescence spectroscopy was performed for photoactive yellow protein (PYP) at room temperature. The effect of the dump pulse on the population of the potential energy surface of the electronic excited state was examined as depletion in the stationary fluorescence intensity. The dynamic behavior of the population in the electronic excited state was successfully probed in the various combinations of the pump-dump delay, the dump-pulse wavelength, the dump-pulse energy and the observation wavelength. The experimental results were compared with the results obtained by the femtosecond time-resolved fluorescence spectroscopy.

Vibrational autoionization of state-selective jet-cooled methanethiol (CH 3SH) investigated with infrared + vacuum-ultraviolet photoionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Min; Shen, Zhitao; Pratt, S. T.

Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. In this work, we employed time-of-flight mass detection of CH 3SH + to record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH 3SH) on exciting CH 3SH to a specific vibrationally excited state with an infrared (IR) laser, followed by excitation with a tunable laser in the vacuum-ultraviolet (VUV) region for ionization. Autoionizing Rydberg states assigned to the ns, np, nd and nf series are identified. When IR light at 2601 (ν 3, SH stretching mode) and 2948 cm -1 (ν 2, CHmore » 3 symmetric stretching mode) was employed, the Rydberg series converged to the respective vibrationally excited (ν 3 and ν 2) states of CH 3SH +. When IR light at 3014 cm -1 (overlapped ν 1/ν 9, CH 3 antisymmetric stretching and CH 2 antisymmetric stretching modes) was employed, Rydberg series converging to two vibrationally excited states (ν 1 and ν 9) of CH 3SH + were observed. When IR light at 2867 cm -1 (2ν 10, overtone of CH 3 deformation mode) and 2892 cm -1 (2ν 4, overtone of CH 2 scissoring mode) was employed, both Δν = -1 and Δν = -2 ionization transitions were observed; there is evidence for direct ionization from the initial state into the CH 3SH + (ν 4 + = 1) continuum. In all observed IR-VUV-PIE spectra, the ns and nd series show intensity greater than the other Rydberg series, which is consistent with the fact that the highest-occupied molecular orbital of CH 3SH is a p-like lone pair orbital on the S atom. Finally, the quantum yields for autoionization of various vibrational excited states are discussed. Values of ν 1 = 3035, ν 2 = 2884, ν 3 = 2514, and ν 9 = 2936 cm -1 for CH 3SH + derived from the converged limits agree satisfactorily with values observed for Ar-tagged CH 3SH + at 3026, 2879, 2502, and 2933 cm -1.« less

Vibrational autoionization of state-selective jet-cooled methanethiol (CH 3SH) investigated with infrared + vacuum-ultraviolet photoionization

DOE PAGES

Xie, Min; Shen, Zhitao; Pratt, S. T.; ...

2017-10-24

Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. In this work, we employed time-of-flight mass detection of CH 3SH + to record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH 3SH) on exciting CH 3SH to a specific vibrationally excited state with an infrared (IR) laser, followed by excitation with a tunable laser in the vacuum-ultraviolet (VUV) region for ionization. Autoionizing Rydberg states assigned to the ns, np, nd and nf series are identified. When IR light at 2601 (ν 3, SH stretching mode) and 2948 cm -1 (ν 2, CHmore » 3 symmetric stretching mode) was employed, the Rydberg series converged to the respective vibrationally excited (ν 3 and ν 2) states of CH 3SH +. When IR light at 3014 cm -1 (overlapped ν 1/ν 9, CH 3 antisymmetric stretching and CH 2 antisymmetric stretching modes) was employed, Rydberg series converging to two vibrationally excited states (ν 1 and ν 9) of CH 3SH + were observed. When IR light at 2867 cm -1 (2ν 10, overtone of CH 3 deformation mode) and 2892 cm -1 (2ν 4, overtone of CH 2 scissoring mode) was employed, both Δν = -1 and Δν = -2 ionization transitions were observed; there is evidence for direct ionization from the initial state into the CH 3SH + (ν 4 + = 1) continuum. In all observed IR-VUV-PIE spectra, the ns and nd series show intensity greater than the other Rydberg series, which is consistent with the fact that the highest-occupied molecular orbital of CH 3SH is a p-like lone pair orbital on the S atom. Finally, the quantum yields for autoionization of various vibrational excited states are discussed. Values of ν 1 = 3035, ν 2 = 2884, ν 3 = 2514, and ν 9 = 2936 cm -1 for CH 3SH + derived from the converged limits agree satisfactorily with values observed for Ar-tagged CH 3SH + at 3026, 2879, 2502, and 2933 cm -1.« less

Micromanipulation and physiological monitoring of cells using two-photon excited fluorescence in cw laser tweezers

NASA Astrophysics Data System (ADS)

Sonek, Gregory J.; Liu, Yagang; Berns, Michael W.; Tromberg, Bruce J.

1996-05-01

We report the observation of two-photon fluorescence excitation and cell confinement, simultaneously, in a continuous-wave (cw) single-beam gradient force optical trap, and demonstrate its use as an in-situ probe to study the physiological state of an optically confined cell sample. At the wavelength of 1064 nm, a single focused gaussian laser beam is used to simultaneously confine, and excite visible fluorescence from, a human sperm cell that has been tagged with propidium iodide, a exogenous fluorescent dye that functions as a viability assay of cellular physiological state. The intensity at the dye peak emission wavelength of 620 nm exhibits a near-square-law dependence on incident trapping beam photon laser power, a behavior consistent with a two-photon absorption process. In addition, for a sperm cell held stationary in the optical tweezers for a period of several minutes at a constant trapping power, red fluorescence emission was observed to increase the time, indicating that the cell has gradually transitioned between a live and dead state. Two-photon excited fluorescence was also observed in chinese hamster ovary cells that were confined by cw laser tweezers and stained with either propidium iodide or Snarf, a pH-sensitive dye probe. These results suggest that, for samples suitably tagged with fluorescent probes and vital stains, optical tweezers can be used to generate their own in-situ diagnostic optical probes of cellular viability or induced photodamage, via two-photon processes.

Homeostatic Scaling of Excitability in Recurrent Neural Networks

PubMed Central

Remme, Michiel W. H.; Wadman, Wytse J.

2012-01-01

Neurons adjust their intrinsic excitability when experiencing a persistent change in synaptic drive. This process can prevent neural activity from moving into either a quiescent state or a saturated state in the face of ongoing plasticity, and is thought to promote stability of the network in which neurons reside. However, most neurons are embedded in recurrent networks, which require a delicate balance between excitation and inhibition to maintain network stability. This balance could be disrupted when neurons independently adjust their intrinsic excitability. Here, we study the functioning of activity-dependent homeostatic scaling of intrinsic excitability (HSE) in a recurrent neural network. Using both simulations of a recurrent network consisting of excitatory and inhibitory neurons that implement HSE, and a mean-field description of adapting excitatory and inhibitory populations, we show that the stability of such adapting networks critically depends on the relationship between the adaptation time scales of both neuron populations. In a stable adapting network, HSE can keep all neurons functioning within their dynamic range, while the network is undergoing several (patho)physiologically relevant types of plasticity, such as persistent changes in external drive, changes in connection strengths, or the loss of inhibitory cells from the network. However, HSE cannot prevent the unstable network dynamics that result when, due to such plasticity, recurrent excitation in the network becomes too strong compared to feedback inhibition. This suggests that keeping a neural network in a stable and functional state requires the coordination of distinct homeostatic mechanisms that operate not only by adjusting neural excitability, but also by controlling network connectivity. PMID:22570604

Vibrational relaxation of hot carriers in C60 molecule

NASA Astrophysics Data System (ADS)

Madjet, Mohamed; Chakraborty, Himadri

2017-04-01

Electron-phonon coupling in molecular systems is at the heart of several important physical phenomena, including the mobility of carriers in organic electronic devices. Following the optical absorption, the vibrational relaxation of excited (hot) electrons and holes to the fullerene band-edges driven by electron-phonon coupling, known as the hot carrier thermalization process, is of particular fundamental interest. Using the non-adiabatic molecular dynamical methodology (PYXAID + Quantum Espresso) based on density functional approach, we have performed a simulation of vibrionic relaxations of hot carriers in C60. Time-dependent population decays and transfers in the femtosecond scale from various excited states to the states at the band-edge are calculated to study the details of this relaxation process. This work was supported by the U.S. National Science Foundation.

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

DOE PAGES

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

2016-08-25

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

Electronic Relaxation Processes of Transition Metal Atoms in Helium Nanodroplets

NASA Astrophysics Data System (ADS)

Kautsch, Andreas; Lindebner, Friedrich; Koch, Markus; Ernst, Wolfgang E.

2014-06-01

Spectroscopy of doped superfluid helium nanodroplets (He_N) gives information about the influence of this cold, chemically inert, and least interacting matrix environment on the excitation and relaxation dynamics of dopant atoms and molecules. We present the results from laser induced fluorescence (LIF), photoionization (PI), and mass spectroscopy of Cr and Cu doped He_N. From these results, we can draw a comprehensive picture of the complex behavior of such transition metal atoms in He_N upon photo-excitation. The strong Cr and Cu ground state transitions show an excitation blueshift and broadening with respect to the bare atom transitions which can be taken as indication for the solvation inside the droplet. From the originally excited states the atoms relax to energetically lower states and are ejected from the He_N. The relaxation processes include bare atom spin-forbidden transitions, which clearly bears the signature of the He_N influence. Two-color resonant two-photon ionization (2CR2PI) also shows the formation of bare atoms and small Cr-He_n and Cu-He_n clusters in their ground and metastable states ^c. Currently, Cr dimer excitation studies are in progress and a brief outlook on the available results will be given. C. Callegari and W. E. Ernst, Helium Droplets as Nanocryostats for Molecular Spectroscopy - from the Vacuum Ultraviolet to the Microwave Regime, in Handbook of High-Resolution Spectroscopy, eds. M. Quack and F. Merkt, John Wiley & Sons, Chichester, 2011. A. Kautsch, M. Koch, and W. E. Ernst, J. Phys. Chem. A, 117 (2013) 9621-9625, DOI: 10.1021/jp312336m F. Lindebner, A. Kautsch, M. Koch, and W. E. Ernst, Int. J. Mass Spectrom. (2014) in press, DOI: 10.1016/j.ijms.2013.12.022 M. Koch, A. Kautsch, F. Lackner, and W. E. Ernst, submitted to J. Phys. Chem. A

Creation of Excitons Excited by Light with a Spatial Mode

NASA Astrophysics Data System (ADS)

Syouji, Atsushi; Saito, Shingo; Otomo, Akira

2017-12-01

When light is absorbed into matter, its degrees of freedom (i.e., energy, polarization, and phase) are transferred to the matter and conserved. In this study, we demonstrate that elementary excitations in matter, which are one-photon-forbidden transition states, become allowed states because of the phase conservation across the entire cross section of excitation light. In particular, when 1S orthoexcitons of the yellow series in the semiconductor cuprous oxide (Cu2O) were resonantly excited by light with a spatial mode, an increase in the Γ 3 - -phonon-emission peak intensity of the excitons was detected depending on the spatial mode. Using group-theory-based analysis, we show that the irreducible representation of a one-photon-forbidden exciton, which is one of the orthoexcitons, can be transmuted to an allowed state by taking the direct product with the polar vector produced from the spatial mode of the light. Although the transition process of the exciton is locally characterized by the usual quadrupole interaction, the phase conservation at each position at which the sample is irradiated causes the exciton to be in the same spatial-mode state. That causes a change in the transition selection rule. The selection rule relaxation due to the spatial mode of the light was also applied for paraexciton creation.

Electron impact excitation of higher energy states of molecular oxygen in the atmosphere of Europa

NASA Astrophysics Data System (ADS)

Campbell, L.; Tanaka, H.; Kato, H.; Jayaraman, S.; Brunger, M. J.

2012-01-01

Recent measurements of integral cross sections for electron impact excitation of the Schumann-Runge continuum, longest band and second band of molecular oxygen are applied to calculations of emissions from the atmosphere of Europa. Molecules excited to these bands predissociate, producing O(1D) (excited oxygen) atoms which subsequently decay to produce 630.0-nm radiation. Radiation of this wavelength is also produced by direct excitation of O atoms and by the recombination of O _2^+ + 2 with electrons, but these two processes also produce O(1S) atoms which then emit at 557.7 nm. It is shown by modeling that the ratio of 630.0-nm to 557.7-nm is sensitive to the relative importance of the three processes, suggesting that the ratio would be a useful remote sensing probe in the atmosphere of Europa. In particular, the excitation of the Schumann-Runge continuum, longest band and second band is produced by magnetospheric electrons while the recombination is produced by secondary electrons produced in the atmosphere. This difference raises the possibility of determination of the secondary electron spectrum by measurement of light emissions.

Investigation of polar and stereoelectronic effects on pure excited-state hydrogen atom abstractions from phenols and alkylbenzenes.

PubMed

Pischel, Uwe; Patra, Digambara; Koner, Apurba L; Nau, Werner M

2006-01-01

The fluorescence quenching of singlet-excited 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by 22 phenols and 12 alkylbenzenes has been investigated. Quenching rate constants in acetonitrile are in the range of 10(8)-10(9) M(-1)s(-1) for phenols and 10(5)-10(6) M(-1)s(-1) for alkylbenzenes. In contrast to the quenching of triplet-excited benzophenone, no exciplexes are involved, so that a pure hydrogen atom transfer is proposed as quenching mechanism. This is supported by (1) pronounced deuterium isotope effects (kH/kD ca 4-6), which were observed for phenols and alkylbenzenes, and (2) a strongly endergonic thermodynamics for charge transfer processes (electron transfer, exciplex formation). In the case of phenols, linear free energy relationships applied, which led to a reaction constant of rho = -0.40, suggesting a lower electrophilicity of singlet-excited DBO than that of triplet-excited ketones and alkoxyl radicals. The reactivity of singlet-excited DBO exposes statistical, steric, polar and stereoelectronic effects on the hydrogen atom abstraction process in the absence of complications because of competitive exciplex formation.

Polaron effects on the performance of light-harvesting systems: a quantum heat engine perspective

NASA Astrophysics Data System (ADS)

Xu, Dazhi; Wang, Chen; Zhao, Yang; Cao, Jianshu

2016-02-01

We explore energy transfer in a generic three-level system, which is coupled to three non-equilibrium baths. Built on the concept of quantum heat engine, our three-level model describes non-equilibrium quantum processes including light-harvesting energy transfer, nano-scale heat transfer, photo-induced isomerization, and photovoltaics in double quantum-dots. In the context of light-harvesting, the excitation energy is first pumped up by sunlight, then is transferred via two excited states which are coupled to a phonon bath, and finally decays to the reaction center. The efficiency of this process is evaluated by steady state analysis via a polaron-transformed master equation; thus the entire range of the system-phonon coupling strength can be covered. We show that the coupling with the phonon bath not only modifies the steady state, resulting in population inversion, but also introduces a finite steady state coherence which optimizes the energy transfer flux and efficiency. In the strong coupling limit, the steady state coherence disappears and the efficiency recovers the heat engine limit given by Scovil and Schultz-Dubois (1959 Phys. Rev. Lett. 2 262).

Photoemission into water adsorbed on metals: Probing dissociative electron transfer using theory

NASA Astrophysics Data System (ADS)

Zhang, Yu; Whitten, J. L.

The photoinduced dissociation of water adsorbed on a silver nanoparticle is explored using theory to probe reaction pathways that produce hydrogen. Ab initio configuration theory is used to describe the systems. A formulation that allows excited electronic states embedded in a near continuum of lower energy states to be calculated accurately is described. Electron attachment of a photoemitted electron to adsorbed water can lead to the formation of H2 at a very low energy barrier with oxygen remaining on the Ag surface. A large energy barrier to form H2 plus adsorbed O is found for the ground state. The excited state has a much smaller barrier to OH stretch; however, to dissociate, the system must cross over from the excited state to the ground state potential energy surface. The cross over point is near the transition state for a ground state process. A characteristic feature of the excited state potential curve is an increase in energy in the early stages of OH stretch as the charge transfer state evolves from a state with considerable Rydberg character to one that has a typical OH antibonding molecular orbital. Another pathway releases a H atom leaving OH on the surface. Effects due to doping of a Ag nanoparticle with a K electron donor atom are compared with those caused by a Fermi level shift due to an applied potential. Results are also reported for electron transfer to a solvated lithium ion, Li(H2O) 6+, near the surface of a silver particle. A steering mechanism is found that involves the interaction of a hydridic hydrogen formed after electron transfer with an acidic hydrogen of a second solvated water molecule.

Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2 and the implications to the early earth’s atmosphere

PubMed Central

Whitehill, Andrew R.; Xie, Changjian; Hu, Xixi; Xie, Daiqian; Guo, Hua; Ono, Shuhei

2013-01-01

Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen (16O,17O,18O) and sulfur (32S, 33S, 34S, 36S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ33S up to 78‰ and Δ36S up to 110‰, from the broadband excitation of SO2 in the 250–350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO2 (3B1), which results from intersystem crossing from the excited singlet (1A2/1B1) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO2 and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO2 to the singlet states but from an isotope selective spin–orbit interaction between the singlet (1A2/1B1) and triplet (3B1) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for 33SO2 and 36SO2 for the low vibrational levels of the 1A2 state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems. PMID:23836655

Inelastic rate coefficients for collisions of C6H- with H2 and He

NASA Astrophysics Data System (ADS)

Walker, Kyle M.; Lique, François; Dumouchel, Fabien; Dawes, Richard

2017-04-01

The recent detection of anions in the interstellar medium has shown that they exist in a variety of astrophysical environments - circumstellar envelopes, cold dense molecular clouds and star-forming regions. Both radiative and collisional processes contribute to molecular excitation and de-excitation in these regions so that the 'local thermodynamic equilibrium' approximation, where collisions cause the gas to behave thermally, is not generally valid. Therefore, along with radiative coefficients, collisional excitation rate coefficients are needed to accurately model the anionic emission from these environments. We focus on the calculation of state-to-state rate coefficients of the C6H- molecule in its ground vibrational state in collisions with para-H2, ortho-H2 and He using new potential energy surfaces. Dynamical calculations for the pure rotational excitation of C6H- were performed for the first 11 rotational levels (up to j1 = 10) using the close-coupling method, while the coupled-states approximation was used to extend the H2 rate coefficients to j1 = 30, where j1 is the angular momentum quantum number of C6H-. State-to-state rate coefficients were obtained for temperatures ranging from 2 to 100 K. The rate coefficients for H2 collisions for Δj1 = -1 transitions are of the order of 10-10 cm3 s-1, a factor of 2 to 3 greater than those of He. Propensity rules are discussed. The collisional excitation rate coefficients produced here impact astrophysical modelling since they are required for obtaining accurate C6H- level populations and line emission for regions that contain anions.

Mechanism of Ethane Destruction in Dielectric Barrier Discharge in Air: Detailed Elementary Reaction Model and Experiment

NASA Astrophysics Data System (ADS)

Krasnoperov, Lev; Modenese, Camila; Krishtopa, Larisa

2006-10-01

Free radical destruction mechanism was extended by inclusion of reactions of excited and ionic species. The mechanism consists of 935 reactions of 85 neutral species, 9 excited states and 38 ions. The reactions include 9 initiation processes in streamers, 66 processes involving excited states and 83 reactions involving ions. The reactant, the final products as well as the major intermediates of the destruction of ethane in air in corona discharge were identified and quantified Carbon dioxide (CO2), water (H2O), formaldehyde (H2CO), acetaldehyde (CH3CHO), methanol (CH3OH), ethanol (C2H5OH), formic acid (HCOOH), acetic acid (CH3COOH), methyl nitrate (CH3ONO2) and ethyl nitrate (C2H5ONO2) were identified among the major destruction products. The destruction efficiency predicted by the mechanism is in good agreement with the experiment, the major contribution is being due to the ionization transfer reactions. Reactions of excited species play but only a minor role. The product spectrum is consistent with the subsequent low temperature free radical reactions complicated by the presence of ozone and nitrogen oxides. The generic reaction mechanism for other organic as well as inorganic compounds is discussed.

Quantum chemical methods for the investigation of photoinitiated processes in biological systems: theory and applications.

PubMed

Dreuw, Andreas

2006-11-13

With the advent of modern computers and advances in the development of efficient quantum chemical computer codes, the meaningful computation of large molecular systems at a quantum mechanical level became feasible. Recent experimental effort to understand photoinitiated processes in biological systems, for instance photosynthesis or vision, at a molecular level also triggered theoretical investigations in this field. In this Minireview, standard quantum chemical methods are presented that are applicable and recently used for the calculation of excited states of photoinitiated processes in biological molecular systems. These methods comprise configuration interaction singles, the complete active space self-consistent field method, and time-dependent density functional theory and its variants. Semiempirical approaches are also covered. Their basic theoretical concepts and mathematical equations are briefly outlined, and their properties and limitations are discussed. Recent successful applications of the methods to photoinitiated processes in biological systems are described and theoretical tools for the analysis of excited states are presented.

Survival of nature's rarest isotope {sup 180}Ta under stellar conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohr, P.; Kaeppeler, F.; Gallino, R.

2007-01-15

The nucleosynthesis of nature's rarest isotope {sup 180}Ta depends sensitively on the temperature of the astrophysical environment because of depopulation of the long-living isomeric state via intermediate states to the short-living ground state by thermal photons. Reaction rates for this transition have been measured in the laboratory. These ground state rates underestimate the stellar rates dramatically because under stellar conditions intermediate states are mainly populated by excitations from thermally excited states in {sup 180m}Ta. Full thermalization of {sup 180}Ta is already achieved for typical s-process temperatures around kT=25 keV. Consequently, for the survival of {sup 180}Ta in the s-process fastmore » convective mixing is required which has to transport freshly synthesized {sup 180}Ta to cooler regions. In supernova explosions {sup 180}Ta is synthesized by photon- or neutrino-induced reactions at temperatures above T{sub 9}=1 in thermal equilibrium; independent of the production mechanism, freeze-out from thermal equilibrium occurs at kT{approx_equal}40 keV, and only 35{+-}4% of the synthesized {sup 180}Ta survive in the isomeric state.« less

Study of inelastic processes in Li+-Ar, K+-Ar, and Na+-He collisions in the energy range 0.5-10 keV

NASA Astrophysics Data System (ADS)

Lomsadze, Ramaz A.; Gochitashvili, Malkhaz R.; Kezerashvili, Roman Ya; Schulz, Michael

2017-11-01

Absolute cross sections are measured for charge-exchange, ionization, and excitation processes within the same experimental setup for the Li{}+-Ar, K{}+-Ar, and Na{}+-He collisions in the ion energy range of 0.5-10 keV. The results of the measurements and schematic correlation diagrams are used to analyze and determine the mechanisms for these processes. The experimental results show that the charge-exchange processes occur with high probabilities and electrons are predominantly captured in ground states. The contributions of various partial inelastic channels to the total ionization cross section are estimated, and a primary mechanism for the process is identified. In addition, the energy-loss spectrum is applied in order to estimate the relative contribution of different inelastic channels, and to determine the mechanisms for the ionization and for some excitation processes of Ar resonance lines for the {{{K}}}+-Ar collision system. The excitation cross sections for the helium and for the sodium doublet lines for the Na{}+-He collision system both reveal some unexpected features. A mechanism to explain this observation is suggested.

Cross-section and rate formulas for electron-impact ionization, excitation, deexcitation, and total depopulation of excited atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vriens, L.; Smeets, A.H.M.

1980-09-01

For electron-induced ionization, excitation, and de-excitation, mainly from excited atomic states, a detailed analysis is presented of the dependence of the cross sections and rate coefficients on electron energy and temperature, and on atomic parameters. A wide energy range is covered, including sudden as well as adiabatic collisions. By combining the available experimental and theoretical information, a set of simple analytical formulas is constructed for the cross sections and rate coefficients of the processes mentioned, for the total depopulation, and for three-body recombination. The formulas account for large deviations from classical and semiclassical scaling, as found for excitation. They agreemore » with experimental data and with the theories in their respective ranges of validity, but have a wider range of validity than the separate theories. The simple analytical form further facilitates the application in plasma modeling.« less

Quantum coherence effects in natural light-induced processes: cis-trans photoisomerization of model retinal under incoherent excitation.

PubMed

Tscherbul, Timur V; Brumer, Paul

2015-12-14

We present a theoretical study of quantum coherence effects in the primary cis-trans photoisomerization of retinal in rhodopsin induced by incoherent solar light. Using the partial secular Bloch-Redfield quantum master equation approach based on a two-state two-mode linear vibronic coupling model of the retinal chromophore [S. Hahn and G. Stock, J. Phys. Chem. B, 2000, 104, 1146-1149], we show that a sudden turn-on of incoherent pumping can generate substantial Fano coherences among the excited states of retinal. These coherences are the most pronounced in the regime where the matrix elements of the transition dipole moment between the ground and excited eigenstates are parallel to one another. We show that even when the transition dipole moments are perpendicular (implying the absence of light-induced Fano coherence) a small amount of excited-state coherence is still generated due to the coupling to intramolecular vibrational modes and the protein environment, causing depopulation of the excited eigenstates. The overall effect of the coherences on the steady-state population and on the photoproduct quantum yield is shown to be small; however we observe a significant transient effect on the formation of the trans photoproduct, enhancing the photoreaction quantum yield by ∼11% at 200 fs. These calculations suggest that coupling to intramolecular vibrational modes and the protein environment play an important role in photoreaction dynamics, suppressing oscillations in the quantum yield associated with Fano interference.

Excited-State Dynamics of Biological Molecules in Solution: Photoinduced Charge Transfer in Oxidatively Damaged DNA and Deactivation of Violacein in Viscous Solvents

NASA Astrophysics Data System (ADS)

Beckstead, Ashley Ann

UV radiation from the sun is strongly absorbed by DNA, and the resulting electronic excited states can lead to the formation of mutagenic photoproducts. Decades of research have brought to light the excited-state dynamics of single RNA and DNA nucleobases, but questions remain about the nature of excited states accessed in DNA strands. In this thesis, I present ultrafast spectroscopic observations of photoinduced electron transfer from the oxidatively damaged bases, 8-oxo-7,8-dihydro-2'-deoxyguanosine, 5-hydroxy-2'-deoxycytidine and 5-hydroxy-2'-deoxyuridine, to adenine in three dinucleotides. The results reveal that charge transfer states are formed on a timescale faster than our instrumental resolution (<0.5 ps), and back electron transfer efficiently returns the excited-state population to the ground state on timescales from tens to hundreds of ps. In addition to recent spectroscopic observations of charge transfer state species in DNA by other groups, our results have augmented understanding of the long-lived transient signals observed in DNA strands. The observation of photoinduced electron transfer in these oxidatively damaged nucleobases also supports a recent proposal regarding the role of oxidative products in pre-RNA catalysis. I discuss these observations in the contexts of fundamental DNA excited-state dynamics and prebiotic chemical evolution. In this thesis, I also present the first ultrafast spectroscopic investigation of violacein, a pigment isolated from Antarctic bacteria. Despite claims for the photoprotective role of this pigment, there has never been a spectroscopic analysis of excited-state deactivation in violacein. Emission spectra, fluorescence quantum yields and excited-state lifetimes of violacein in various solvents were measured for the first time. Both the fluorescence quantum yield and excited-state lifetime of violacein increase in increasingly viscous solvents, suggesting a large-scale motion mediates excited-state deactivation. I compare these results to similar observations of viscosity-dependent excited-state decay rates in other molecules. I also consider the relevance of violacein's excited-state properties to the hypothesized sunscreening role of violacein. Overall, the studies presented in this dissertation illustrate how ultrafast spectroscopic techniques can be used to unravel complex biomolecular excited-state dynamics in solution.

σ-SCF: A direct energy-targeting method to mean-field excited states.

PubMed

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

2017-12-07

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 Δ-SCF (self-consistent field), 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, σ-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 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 Δ-SCF solutions that are otherwise hardly accessible by the usual non-aufbau configuration initial guess. We present results for this new method for small atoms (He, Be) and molecules (H 2 , HF). We find that σ-SCF is very effective at locating excited states, including individual, high energy excitations within a dense manifold of excited states. Like all single determinant methods, σ-SCF shows prominent spin-symmetry breaking for open shell states and our results suggest that this method could be further improved with spin projection.

Atomic data on inelastic processes in low-energy manganese-hydrogen collisions

NASA Astrophysics Data System (ADS)

Belyaev, Andrey K.; Voronov, Yaroslav V.

2017-10-01

Aims: The aim of this paper is to calculate cross sections and rate coefficients for inelastic processes in low-energy Mn + H and Mn+ + H- collisions, especially, for processes with high and moderate rate coefficients. These processes are required for non-local thermodynamic equilibrium (non-LTE) modeling of manganese spectra in cool stellar atmospheres, and in particular, for metal-poor stars. Methods: The calculations of the cross sections and the rate coefficients were performed by means of the quantum model approach within the framework of the Born-Oppenheimer formalism, that is, the asymptotic semi-empirical method for the electronic MnH molecular structure calculation followed by the nonadiabatic nuclear dynamical calculation by means of the multichannel analytic formulas. Results: The cross sections and the rate coefficients for low-energy inelastic processes in manganese-hydrogen collisions are calculated for all transitions between 21 low-lying covalent states and one ionic state. We show that the highest values of the cross sections and the rate coefficients correspond to the mutual neutralization processes into the final atomic states Mn(3d54s(7S)5s e 6S), Mn(3d54s(7S)5p y 8P°), Mn(3d54s(7S)5s e 8S), Mn(3d54s(7S)4d e 8D) [the first group], the processes with the rate coefficients (at temperature T = 6000 K) of the values 4.38 × 10-8, 2.72 × 10-8, 1.98 × 10-8, and 1.59 × 10-8 cm3/ s, respectively, that is, with the rate coefficients exceeding 10-8 cm3/ s. The processes with moderate rate coefficients, that is, with values between 10-10 and 10-8 cm3/ s include many excitation, de-excitation, mutual neutralization and ion-pair formation processes. In addition to other processes involving the atomic states from the first group, the processes from the second group include those involving the following atomic states: Mn(3d5(6S)4s4p (1P°) y 6P°), Mn(3d54s(7S)4d e 6D), Mn(3d54s(7S)5p w 6P°), Mn(3d5(4P)4s4p (3P°) y 6D°), Mn(3d5(4G)4s4p (3P°) y 6F°). The processes with the highest and moderate rate coefficients are expected to be important for non-LTE modeling of manganese spectra in stellar atmospheres. Rate coefficients Kif(T) for the excitation, de-excitation, mutual neutralization, and ion-pair formation processes in manganese-hydrogen collisions are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/606/A106

Non-equilibrium calculations of atmospheric processes initiated by electron impact.

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.

2007-05-01

Electron impact in the atmosphere produces ionisation, dissociation, electronic excitation and vibrational excitation of atoms and molecules. The products can then take part in chemical reactions, recombination with electrons, or radiative or collisional deactivation. While most such processes are fast, some longer--lived species do not reach equilibrium. The electron source (photoelectrons or auroral electrons) also varies over time and longer-lived species can move substantially in altitude by molecular, ambipolar or eddy diffusion. Hence non-equilibrium calculations are required in some circumstances. Such time-step calculations need to have sufficiently short steps so that the fastest processes are still calculated correctly, but this can lead to computation times that are too large. Hence techniques to allow for longer time steps by incorporating equilibrium calculations are described. Examples are given for results of atmospheric non-equilibrium calculations, including the populations of the vibrational levels of ground state N2, the electron density and its dependence on vibrationally excited N2, predictions of nitric oxide density, and detailed processes during short duration auroral events.

Convergent Synthesis and Photoinduced Processes in Multi-Chromophoric Rotaxanes1

PubMed Central

Megiatto, Jackson D.; Li, Ke; Schuster, David I.; Palkar, Amit; Herranz, M. Ángeles; Echegoyen, Luis; Abwandner, Silke; de Miguel, Gustavo; Guldi, Dirk M.

2010-01-01

A series of [2]rotaxane materials, in which [60]fullerene is linked to a macrocycle and ferrocene (Fc) moieties are placed at the termini of a thread, both of which possess a central Cu(I)-1,10-phenanthroline [Cu(phen)2]+ complex, were synthesized by self-assembly using Sauvage metal template methodology. Two types of threads were constructed, one with terminal ester linkages, and a second with terminal 1,2,3-triazole linkages derived from Cu(I)-catalyzed “click” 1,3-cycloaddition reactions. Model compounds lacking the fullerene moiety were prepared in an analogous manner. The ability of the interlocked Fc-[Cu(phen)2]+-C60 hybrids to undergo electron transfer upon photoexcitation was investigated by means of time-resolved fluorescence and transient absorption spectroscopy, using excitation wavelengths directed at the fullerene and [Cu(phen)2]+ subunits. The energies of the electronic excited states and charge separated (CS) states that might be formed upon photoexcitation were determined from spectroscopic and electrochemical data. These studies showed that MLCT excited states of the copper complex in the fullerenerotaxanes were quenched by electron transfer to the fullerene, resulting in charge separated states with oxidized copper and reduced fullerene moieties, (Fc)2-[Cu(phen)2]2+-C60•−. Even though electron transfer from Fc to the oxidized copper complex is predicted to be exergonic by 0.18 eV, no unequivocal evidence in support of such a process was obtained. The conclusion that Fc plays no role in the photoinduced processes in our systems rests on the lack of enhancement of the lifetime of the charge separated state as measured by decay of C60•− at ~ 1000 nm, since one-electron oxidized Fc is very difficult to detect spectroscopically in the 500–800 nm spectral region. PMID:20518479

Selfconsistent vibrational and free electron kinetics for CO2 dissociation in cold plasmas

NASA Astrophysics Data System (ADS)

Capitelli, Mario

2016-09-01

The activation of CO2 by cold plasmas is receiving new theoretical interest thanks to two European groups. The Bogaerts group developed a global model for the activation of CO2 trying to reproduce the experimental values for DBD and microwave discharges. The approach of Pietanza et al was devoted to understand the dependence of electron energy distribution function (eedf) of pure CO2 on the presence of concentrations of electronically and vibrationally excited states taken as parameter. To understand the importance of the vibrational excitation in the dissociation process Pietanza et al compared an upper limit to the dissociation process from a pure vibrational mechanism (PVM) with the corresponding electron impact dissociation rate, the prevalence of the two models depending on the reduced electric field and on the choice of the electron molecule cross section database. Improvement of the Pietanza et al model is being considered by coupling the time dependent Boltzmann solver with the non equilibrium vibrational kinetics of asymmetric mode and with simplified plasma chemistry kinetics describing the ionization/recombination process and the excitation-deexcitation of a metastable level at 10.5eV. A new PVM mechanism is also considered. Preliminary results, for both discharge and post discharge conditions, emphasize the action of superelastic collisions involving both vibrationally and electronically excited states in affecting the eedf. The new results can be used to plan a road map for future developments of numerical codes for rationalizing existing experimental values, as well as, for indicating new experimental situations.

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

PubMed

Li, Xin; Parrish, Robert M; Liu, Fang; Kokkila Schumacher, Sara I L; Martínez, Todd J

2017-08-08

The Frenkel exciton model is a useful tool for theoretical studies of multichromophore systems. We recently showed that the exciton model could be used to coarse-grain electronic structure in multichromophoric systems, focusing on singly excited exciton states [ Acc. Chem. Res. 2014 , 47 , 2857 - 2866 ]. However, our previous implementation excluded charge-transfer excited states, which can play an important role in light-harvesting systems and near-infrared optoelectronic materials. Recent studies have also emphasized the significance of charge-transfer in singlet fission, which mediates the coupling between the locally excited states and the multiexcitonic states. In this work, we report on an ab initio exciton model that incorporates charge-transfer excited states and demonstrate that the model provides correct charge-transfer excitation energies and asymptotic behavior. Comparison with TDDFT and EOM-CC2 calculations shows that our exciton model is robust with respect to system size, screening parameter, and different density functionals. Inclusion of charge-transfer excited states makes the exciton model more useful for studies of singly excited states and provides a starting point for future construction of a model that also includes double-exciton states.

Spectroscopic and TDDFT investigation on highly selective fluorogenic chemosensor and construction of molecular logic gates.

PubMed

Basheer, Sabeel M; Kumar, Saravana Loganathan Ashok; Kumar, Moorthy Saravana; Sreekanth, Anandaram

2017-03-01

1,5-Bis(2-fluorene)thiocarbohydrazone (FBTC) was designed and synthesized for selective sensing of fluoride and copper ions. The binding constants of FBTC towards fluoride and copper ions have been calculated using the Benesi-Hildebrand equation, and FBTC has more binding affinity towards copper ion than fluoride ion. The 1 H NMR and 13 C NMR titration studies strongly support the deprotonation was taken from the N-H protons followed by the formation of hydrogen bond via N-H … F. To understand the fluoride ion sensing mechanism, theoretical investigation had been carried out using the density functional theory and time-dependent density functional theory. The theoretical data well reproduced the experimental results. The deprotonation process has a moderate transition barrier (481.55kcal/mol). The calculated ΔE and ΔG values (-253.92 and -192.41kcal/mol respectively) suggest the feasibility of sensing process. The potential energy curves give the optimized structures of FBTC-F complex in the ground state and excited state, which states the proton transition occurs at the excited state. The excited state proton transition mechanism was further confirmed with natural bond orbital analysis. The reversibility of the sensor was monitored by the alternate addition of F - and Cu 2+ ions, which was explained with "Read-Erase-Write-Read" behaviour. The multi-ion detection of sensor used to construct the molecular logic gate, such as AND, OR, NOR and INHIBITION logic gates. Copyright © 2016 Elsevier B.V. All rights reserved.

Nested variant of the method of moments of coupled cluster equations for vertical excitation energies and excited-state potential energy surfaces.

PubMed

Kowalski, Karol

2009-05-21

In this article we discuss the problem of proper balancing of the noniterative corrections to the ground- and excited-state energies obtained with approximate coupled cluster (CC) and equation-of-motion CC (EOMCC) approaches. It is demonstrated that for a class of excited states dominated by single excitations and for states with medium doubly excited component, the newly introduced nested variant of the method of moments of CC equations provides mathematically rigorous way of balancing the ground- and excited-state correlation effects. The resulting noniterative methodology accounting for the effect of triples is tested using its parallel implementation on the systems, for which iterative CC/EOMCC calculations with full inclusion of triply excited configurations or their most important subset are numerically feasible.

Rare isotopes and the sound of dilute nuclear matter

NASA Astrophysics Data System (ADS)

Papakonstantinou, P.

2018-04-01

Dilute baryonic matter, at densities below the normal saturation density of symmetric matter, is found on the crust of neutron stars and in collapsing supernova matter, its properties determining the evolution of those stellar objects. It is also readily found on the surface of ordinary and exotic atomic nuclei and lives fleetingly in the form of space-extended resonances of excited nucleons. Liminal states of nuclear matter, between saturation and full evaporation or clusterization, are manifest in the structure of symmetric nuclei through clustering and of very asymmetric rare species in haloes and the neutron skin; they stand literally at the threshold of a nucleus's response to hadronic probes, including processes which hinder or enable fusion. In this contribution I focus on excited states, and in particular exotic or not-so-exotic dipole excitation modes of N = Z nuclei and neutron-rich species, including new theoretical results on threshold strength. Modes of special interest are vibrations of and within diffuse surface layers and alpha-cluster oscillations. The modeling of such processes is relevant, directly or indirectly, for the description of reactions at astrophysical energies.

Energy transfer and radiative recombination processes in (Gd, Lu)3Ga3Al2O12:Pr3+ scintillators

NASA Astrophysics Data System (ADS)

Wu, Yuntao; Ren, Guohao

2013-10-01

(GdxLu3-x)Ga3Al2O12:0.3 at.%Pr (x = 0.025, 0.05, 0.1, 0.2, 0.4, 0.6) (GLGAG:Pr) polycrystalline powders are prepared by solid-state reaction method. To better understand the luminescence mechanism, the optical diffuse reflectance, photoluminescence emission and excitation, X-ray excited luminescence spectra and decay kinetics of GLGAG:Pr were investigated in detailed, allowing the determination of energy transfer from 5d state of Pr3+ to 4f state of Gd3+, and the non-radiative relaxation from 5d to 4f state of Pr3+. Besides, the former process plays more negative role in the emission quenching of GLGAG:Pr than later one. Pr3+ ion is regarded as an ineffective activation ion in Gd-based multicomponent aluminate garnets. In addition, the wavelength-resolved thermoluminescence spectra of GLGAG:Pr were studied after UV and X-ray irradiation. It is revealed that the localized recombination processes from electron traps to lower lying 4f levels of Pr3+ occurs without populating the higher 5d levels of Pr3+.

Semiempirical modeling of Ag nanoclusters: New parameters for optical property studies enable determination of double excitation contributions to plasmonic excitation

DOE PAGES

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

2016-06-03

Quantum mechanical studies of Ag nanoclusters have shown that plasmonic behavior can be modeled in terms of excited states where collectivity among single excitations leads to strong absorption. However, new computational approaches are needed to provide understanding of plasmonic excitations beyond the single-excitation level. We show that semiempirical INDO/CI approaches with appropriately selected parameters reproduce the TD-DFT optical spectra of various closed-shell Ag clusters. The plasmon-like states with strong optical absorption comprise linear combinations of many singly excited configurations that contribute additively to the transition dipole moment, whereas all other excited states show significant cancellation among the contributions to themore » transition dipole moment. The computational efficiency of this approach allows us to investigate the role of double excitations at the INDO/SDCI level. The Ag cluster ground states are stabilized by slight mixing with doubly excited configurations, but the plasmonic states generally retain largely singly excited character. The consideration of double excitations in all cases improves the agreement of the INDO/CI absorption spectra with TD-DFT, suggesting that the SDCI calculation effectively captures some of the ground-state correlation implicit in DFT. Furthermore, these results provide the first evidence to support the commonly used assumption that single excitations are in many cases sufficient to describe the optical spectra of plasmonic excitations quantum mechanically.« less

Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(I) chromophore and a fullerene electron acceptor unit.

PubMed

Nastasi, Francesco; Puntoriero, Fausto; Natali, Mirco; Mba, Miriam; Maggini, Michele; Mussini, Patrizia; Panigati, Monica; Campagna, Sebastiano

2015-05-01

A novel molecular dyad, 1, made of a dinuclear {[Re2(μ-X)2(CO)6(μ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

Excitations of single-beauty hadrons

NASA Astrophysics Data System (ADS)

Burch, Tommy; Hagen, Christian; Lang, Christian B.; Limmer, Markus; Schäfer, Andreas

2009-01-01

In this work we study the predominantly orbital and radial excitations of hadrons containing a single heavy quark. We present meson and baryon mass splittings and ratios of meson decay constants (e.g., fBs/fB and fBs'/fBs) resulting from quenched and dynamical two-flavor configurations. Light quarks are simulated using the chirally improved lattice Dirac operator at valence masses as light as Mπ≈350MeV. The heavy quark is approximated by a static propagator, appropriate for the b quark on our lattices (1/ã1-2GeV). We also include some preliminary calculations of the O(1/mQ) kinetic corrections to the states, showing, in the process, a viable way of applying the variational method to three-point functions involving excited states. We compare our results with recent experimental findings.

An examination of energy transfers and kinetic mechanisms in argon and in an argon-hydrogen medium excited by an electron beam Application in research on new lasers

NASA Astrophysics Data System (ADS)

Puech, V.

Experimental results on a Ar-H laser pumped by an electron gun are presented, along with a kinetic model of the evolution of states in Ar lasers with additives. Data from trials with the Ar-H laser are provided to confirm model predictions of the electron energy transfer. The electron densities and temperatures evolving on a nanosecond scale in the laser are quantified. A solution is found for the Boltzmann equation for the collisional processes characterizing the electron distribution of interactions between the pumping electrons and the various excited molecular states. The electron distribution function is assumed to be Maxwellian, and the distribution is shown to converge within a few picoseconds when the excitation is above the ionization energy.

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

Revisiting the relaxation dynamics of isolated pyrrole

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montero, Raúl; Ovejas, Virginia; Fernández-Fernández, Marta

Herein, the interpretation of the femtosecond-scale temporal evolution of the pyrrole ion signal, after excitation in the 267–217 nm interval, recently published by our group [R. Montero, A. Peralta Conde, V. Ovejas, M. Fernández-Fernández, F. Castaño, J. R. Vázquez de Aldana, and A. Longarte, J. Chem. Phys.137, 064317 (2012)] is re-visited. The observation of a shift in the pyrrole{sup +} transient respect to zero delay reference, initially attributed to ultrafast dynamics on the πσ{sup *} type state (3s a{sub 1} ← π 1a{sub 2}), is demonstrated to be caused by the existence of pump + probe populated states, along themore » ionization process. The influence of these resonances in pump-prone ionization experiments, when multi-photon probes are used, and the significance of a proper zero-time reference, is discussed. The possibility of preparing the πσ{sup *} state by direct excitation is investigated by collecting 1 + 1 photoelectron spectra, at excitation wavelengths ranging from 255 to 219 nm. No conclusive evidences of ionization through this state are found.« less

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

DOE PAGES

Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.; ...

2017-06-22

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

Rovibrational transitions of H2 by collision with H+ at high temperature

NASA Astrophysics Data System (ADS)

González-Lezana, T.; Honvault, P.

2017-05-01

The H+ + H2 reaction is studied by means of both exact and statistical quantum methods. Integral cross-sections for processes initiated with rotationally excited H2(v, j = 1) to produce molecular hydrogen in its rotational ground state are reported up to a value of the collision energy of 3 eV. Rate constants for state-to-state transitions between different H2 rovibrational states are calculated up to 3000 K. Special emphasis is made on ortho/para conversion processes in which the parity j of the H2(j) states changes.

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

PubMed

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

2014-05-14

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruberti, M.; Yun, R.; Averbukh, V.

2014-05-14

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

Scattering of 42 MeV alpha particles from copper-65

NASA Technical Reports Server (NTRS)

Stewart, W. M.; Seth, K. K.

1973-01-01

Beams of 42-MeV alpha particles were elastically and inelastically scattered from Cu-65 in an attempt to excite states which may be described in terms of an excited core model. Angular distributions were measured for 17 excited states. Seven of the excited states had angular distributions similar to a core quadrupole excitation and eight of the excited states had angular distributions similar to a core octupole excitation. The excited state at 2.858 MeV had an angular distribution which suggests that it may have results from the particle coupling to a two-phonon core state. An extended particle-core coupling calculation was performed and the predicted energy levels and reduced transition probabilities compared to the experimental data. The low lying levels are described quite well and the wavefunctions of these states explain the large spectroscopic factors measured in stripping reactions. For Cu-65 the coupling of the particle to the core is no larger weak as in the simpler model, and configuration mixing results.

On the importance of electron impact processes in excimer-pumped alkali laser-induced plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Markosyan, Aram H.

We present that the excimer-pumped alkali laser (XPAL) system has recently been demonstrated in several different mixtures of alkali vapor and rare gas. Without special preventive measures, plasma formation during operation of XPAL is unavoidable. Some recent advancements in the availability of reliable data for electron impact collisions with atoms and molecules have enabled development of a complete reaction mechanism to investigate XPAL-induced plasmas. Here, we report on pathways leading to plasma formation in an Ar/C 2H 6/CsAr/C2H6/Cs XPAL sustained at different cell temperatures. We find that depending on the operating conditions, the contribution of electron impact processes can bemore » as little as bringing the excitation of Cs(P 2) states to higher level Cs** states, and can be as high as bringing Cs(P 2) excited states to a full ionization. Increasing the input pumping power or cell temperature, or decreasing the C 2H 6 mole fraction leads to electron impact processes dominating in plasma formation over the energy pooling mechanisms previously reported in literature.« less

On the importance of electron impact processes in excimer-pumped alkali laser-induced plasmas

DOE PAGES

Markosyan, Aram H.

2017-10-18

We present that the excimer-pumped alkali laser (XPAL) system has recently been demonstrated in several different mixtures of alkali vapor and rare gas. Without special preventive measures, plasma formation during operation of XPAL is unavoidable. Some recent advancements in the availability of reliable data for electron impact collisions with atoms and molecules have enabled development of a complete reaction mechanism to investigate XPAL-induced plasmas. Here, we report on pathways leading to plasma formation in an Ar/C 2H 6/CsAr/C2H6/Cs XPAL sustained at different cell temperatures. We find that depending on the operating conditions, the contribution of electron impact processes can bemore » as little as bringing the excitation of Cs(P 2) states to higher level Cs** states, and can be as high as bringing Cs(P 2) excited states to a full ionization. Increasing the input pumping power or cell temperature, or decreasing the C 2H 6 mole fraction leads to electron impact processes dominating in plasma formation over the energy pooling mechanisms previously reported in literature.« less

Inner-shell excitation and ionic fragmentation of molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1997-04-01

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

Solar Gamma Rays Above 8 MeV

NASA Technical Reports Server (NTRS)

Crannell, C. J.; Crannell, H.; Ramaty, R.

1978-01-01

Processes which lead to the production of gamma rays with energy greater than 8 MeV in solar flares are reviewed and evaluated. Excited states produced by inelastic scattering, charge exchange, and spallation reactions in the abundant nuclear species are considered in order to identify nuclear lines which may contribute to the Gamma ray spectrum of solar flares. The flux of 15.11 MeV Gamma rays relative to the flux of 4.44 MeV Gamma rays from the de-excitation of the corresponding states in C12 is calculated for a number of assumed distributions of exciting particles. This flux ratio is a sensitive diagnostic of accelerated particle spectra. Other high energy nuclear levels are not so isolated as the 15.11 MeV state and are not expected to be so strong. The spectrum of Gamma rays from the decay of Pi dey is sensitive to the energy distribution of particles accelerated to energies greater than 100 MeV.

A roaming wavepacket in the dynamics of electronically excited 2-hydroxypyridine.

PubMed

Poisson, Lionel; Nandi, Dhananjay; Soep, Benoît; Hochlaf, Majdi; Boggio-Pasqua, Martial; Mestdagh, Jean-Michel

2014-01-14

How much time does it take for a wavepacket to roam on a multidimensional potential energy surface? This combined theoretical and pump-probe femtosecond time experiment on 2-hydroxypyridine proposes an answer. Bypassing the well-established transition state and conical intersection relaxation pathways, this molecular system undergoes relaxation into the S1 excited state: the central ring is destabilized by the electronic excitation, within ~100 fs after absorption of the pump photon, then the H-atom bound to oxygen undergoes a roaming behavior when it couples to other degrees of freedom of the molecule. The timescale of the latter process is measured to be ~1.3 ps. Further evolution of the wavepacket is either an oscillation onto the S1 potential or a conversion into the triplet state for timescale larger than ~110 ps. Our work introduces a new tool for the understanding of time-resolved relaxation dynamics applied to large molecules through the roaming dynamics characterized by its strongly delocalized wavepacket on flat molecular potential energy surfaces.

Vibrational and Nonadiabatic Coherence in 2D Electronic Spectroscopy, the Jahn-Teller Effect, and Energy Transfer

NASA Astrophysics Data System (ADS)

Jonas, David M.

2018-04-01

Femtosecond two-dimensional (2D) Fourier transform spectroscopy generates and probes several types of coherence that characterize the couplings between vibrational and electronic motions. These couplings have been studied in molecules with Jahn-Teller conical intersections, pseudo-Jahn-Teller funnels, dimers, molecular aggregates, photosynthetic light harvesting complexes, and photosynthetic reaction centers. All have closely related Hamiltonians and at least two types of vibrations, including one that is decoupled from the electronic dynamics and one that is nonadiabatically coupled. Polarized pulse sequences can often be used to distinguish these types of vibrations. Electronic coherences are rapidly obscured by inhomogeneous dephasing. The longest-lived coherences in these systems arise from delocalized vibrations on the ground electronic state that are enhanced by a nonadiabatic Raman excitation process. These characterize the initial excited-state dynamics. 2D oscillation maps are beginning to isolate the medium lifetime vibronic coherences that report on subsequent stages of the excited-state dynamics.

Solvent effects on the ultrafast nonradiative deactivation mechanisms of thymine in aqueous solution: Excited-state QM/MM molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Nakayama, Akira; Arai, Gaku; Yamazaki, Shohei; Taketsugu, Tetsuya

2013-12-01

On-the-fly excited-state quantum mechanics/molecular mechanics molecular dynamics (QM/MM-MD) simulations of thymine in aqueous solution are performed to investigate the role of solvent water molecules on the nonradiative deactivation process. The complete active space second-order perturbation theory (CASPT2) method is employed for a thymine molecule as the QM part in order to provide a reliable description of the excited-state potential energies. It is found that, in addition to the previously reported deactivation pathway involving the twisting of the C-C double bond in the pyrimidine ring, another efficient deactivation pathway leading to conical intersections that accompanies the out-of-plane displacement of the carbonyl group is observed in aqueous solution. Decay through this pathway is not observed in the gas phase simulations, and our analysis indicates that the hydrogen bonds with solvent water molecules play a key role in stabilizing the potential energies of thymine in this additional decay pathway.

Electronic properties of Al xGa 1- xAs surface passivated by ultrathin silicon interface control layer

NASA Astrophysics Data System (ADS)

Adamowicz, B.; Miczek, M.; Ikeya, K.; Mutoh, M.; Saitoh, T.; Fujikura, H.; Hasegawa, H.

1999-03-01

The photoluminescence surface state spectroscopy (PLS 3) method was applied to a study of the surface state distribution ( NSS), effective surface recombination velocity ( Seff), electron ( EFn) and hole ( EFp) quasi-Fermi levels and band bending ( VS) on the Al 0.33Ga 0.67As surface air-exposed and passivated by the Si interface control layer (ICL) technique. Using the detailed measurements of the PL quantum efficiency for different excitation intensities, combined with the rigorous computer simulations of the bulk and surface recombination processes, the behavior and correlation among the surface characteristics under photo-excitation was determined. The present analysis indicated that forming of a Si 3N 4/Si ICL double layer (with a monolayer level control) on AlGaAs surface reduces the minimum interface state density down to 10 10 cm -2 eV -1 and surface recombination velocity to the range of 10 4 cm/s under low excitations.

Relaxation of Vibrationally Excited States in Solid Binary Carbonate-Sulfate Systems

NASA Astrophysics Data System (ADS)

Aliev, A. R.; Akhmedov, I. R.; Kakagasanov, M. G.; Aliev, Z. A.; Gafurov, M. M.; Rabadanov, K. Sh.; Amirov, A. M.

2018-02-01

The processes of molecular relaxation in solid binary carbonate-sulfate systems, such as Li2CO3-Li2SO4, Na2CO3-Na2SO4, K2CO3-K2SO4, have been studied by Raman spectroscopy. It has been revealed that the relaxation time of CO 3 2- anion vibration ν1(A) in a binary system is higher than in an individual carbonate. It is shown that an increase in the relaxation rate may be explained by the existence of an additional mechanism of the relaxation of vibrationally excited states of a carbonate anion. This mechanism is associated with the excitation of the vibration of another anion (SO 4 2- ) and the "birth" of a lattice phonon. It has been established that the condition for the implementation of such a relaxation mechanism is that the difference between the frequencies of these vibrations must correspond to the region of a rather high density of phonon spectrum states.

Nonadiabatic Photo-Process Involving the πσ* State in Intramolecular Charge Transfer: a Concerted Spectroscopic and Computational Study 4-(DIMETHYLAMINO)BENZETHYNE and 4-(DIMETHYLAMINO)BENZONITRILE.

NASA Astrophysics Data System (ADS)

Fujiwara, Takashige; Segarra-Martí, Javier; Coto, Pedro B.

2014-06-01

The ubiquitous nature of the low-lying πσ* state in the photo-excited aromatic molecules or biomolecules is widely recognized to play an important role in nonadiabatic photo-process such as photodissociation or intramolecular charge transfer (ICT). For instance, the O--H elimination channel in phenol is attributed to the state-cross of the repulsive πσ* state that exhibits a conical intersection with the lowest bright ππ* state and with the ground state, leading to ultrafast electronic deactivation. A similar decay pathway has been found in the ICT formation of 4-(dialkylamino)benzonitriles in a polar environment, where an initially photoexcited Frank-Condon state bifurcates in the presence of a dark intermediate πσ* state that crosses the fluorescent ππ* state, followed by a conical intersection with the twisted intramolecular charge transfer (TICT) state. We proposed such a two-fold decay mechanism that πσ*-state highly mediates intramolecular charge transfer in 4-(dialkylamino)benzonitriles, which is supported from both our high-level ab initio calculations and ultrafast laser spectroscopies in the previous study. 4-(Dimethylamino)benzethyne (DMABE) is isoelectronic with 4-(dimethylamino)benzonitrile (DMABN), and the electronic structures and electronic spectra of the two molecules bear very close resemblance. However, DMABN does show the ICT formation in a polar environment, whereas DMABE does not. To probe the photophysical differences among the low-lying excited-state configurations, we performed concerted time-resolved laser spectroscopies and high level ab initio multireference perturbation theory quantum-chemical (CASPT2//CASSCF) computations on the two molecules. In this paper we demonstrate the importance of the bound excited-state of a πσ* configuration that induce highly πσ*-state mediated intramolecular charge transfer in 4-(dialkylamino)benzonitriles.

Electron-Driven Processes: From Single Collision Experiments to High-Pressure Discharge Plasmas

NASA Astrophysics Data System (ADS)

Becker, Kurt

2001-10-01

Plasmas are complex systems which consist of various groups of interacting particles (neutral atoms and molecules in their ground states and in excite states, electrons, and positive and negative ions). In principle, one needs to understand and describe all interactions between these particles in order to model the properties of the plasma and to predict its behavior. However, two-body interactions are often the only processes of relevance and only a subset of all possible collisional interactions are important. The focus of this talk is on collisional and radiative processes in low-temperature plasmas, both at low and high pressures. We will limit the discussion (i) to ionization and dissociation processes in molecular low-pressure plasmas and (ii) to collisional and radiative processes in high-pressure plasmas in rare gases and mixtures of rare gases and N2, O2, and H2. Electron-impact dissociation processes can be divided into dissociative excitation and dissociation into neutral ground-state fragments. Neutral molecular dissociation has only recently received attention from experimentalists and theorists because of the serious difficulties associated with the investigation of these processes. Collisional and radiative processes in high-pressure plasmas provide a fertile environment to the study of interactions that go beyond binary collisions involving ground-state species. Step-wise processes and three-body collisions begin to dominate the behavior of such plasmas. We will discuss examples of such processes as they relate to high-pressure rare gas discharge plasmas. Work supported by NSF, DOE, DARPA, NASA, and ABA Inc.

Excitation of lowest electronic states of thymine by slow electrons

NASA Astrophysics Data System (ADS)

Chernyshova, I. V.; Kontros, E. J.; Markush, P. P.; Shpenik, O. B.

2013-11-01

Excitation of lowest electronic states of the thymine molecules in the gas phase is studied by elec- tron energy loss spectroscopy. In addition to dipole-allowed transitions to singlet states, transitions to the lowest triplet states were observed. The low-energy features of the spectrum at 3.66 and 4.61 eV are identified with the excitation of the first triplet states 13 A' (π → π*) and 13 A″ ( n → π*). The higher-lying features at 4.96, 5.75, 6.17, and 7.35 eV are assigned mainly to the excitation of the π → π* transitions to the singlet states of the molecule. The excitation dynamics of the lowest states is studied. It is found that the first triplet state 13 A'(π → π*) is most efficiently excited at a residual energy close to zero, while the singlet 21 A'(π → π*) state is excited with almost identical efficiency at different residual energies.

Defects Enable Dark Exciton Photoluminescence in Single-Walled Carbon Nanotubes

DOE PAGES

Amori, Amanda R.; Rossi, Jamie E.; Landi, Brian J.; ...

2018-01-24

Variable temperature photoluminescence excitation spectroscopy of three (n,m) species of single-walled carbon nanotubes revealed that at resonant S 22 excitation, in addition to allowed excitonic optical transitions, several sidebands that should be forbidden based on selection rules were observed and appeared to have a strong temperature dependence. In particular, we found that a sideband located approximately 130 meV away from the bright S 11 exciton peak relating to the K-momentum dark exciton state, called X 1, decreased in intensity five-fold as the samples were cooled. Direct optical excitation of this dark state is nominally forbidden, thus calling into question howmore » the state is populated, and why it is so prominent in the photoluminescence spectrum. Interestingly, the ratio of the integrated photoluminescence intensities of X 1 to S 11 scales with a Boltzmann factor unrelated to the phonon that is thought to be responsible for depopulating the K-momentum dark exciton state: an in-plane transverse optical phonon, A 1’. Furthermore, photoluminescence spectra from individual (7,5) nanotubes show that only a small fraction exhibit the X 1 feature, with varying oscillator strength, thus suggesting that intrinsic processes such as phonon scattering are not responsible for populating the dark state. Alternatively, we suggest that populating the K-momentum dark exciton state requires scattering from defects, which is consistent with the increased magnitude of the X 1 feature for samples with increased sample purification and processing. Thus, the presence of an X 1 peak in photoluminescence is an extremely sensitive spectroscopic indicator of defects on single-walled carbon nanotubes.« less

Defects Enable Dark Exciton Photoluminescence in Single-Walled Carbon Nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amori, Amanda R.; Rossi, Jamie E.; Landi, Brian J.

Variable temperature photoluminescence excitation spectroscopy of three (n,m) species of single-walled carbon nanotubes revealed that at resonant S 22 excitation, in addition to allowed excitonic optical transitions, several sidebands that should be forbidden based on selection rules were observed and appeared to have a strong temperature dependence. In particular, we found that a sideband located approximately 130 meV away from the bright S 11 exciton peak relating to the K-momentum dark exciton state, called X 1, decreased in intensity five-fold as the samples were cooled. Direct optical excitation of this dark state is nominally forbidden, thus calling into question howmore » the state is populated, and why it is so prominent in the photoluminescence spectrum. Interestingly, the ratio of the integrated photoluminescence intensities of X 1 to S 11 scales with a Boltzmann factor unrelated to the phonon that is thought to be responsible for depopulating the K-momentum dark exciton state: an in-plane transverse optical phonon, A 1’. Furthermore, photoluminescence spectra from individual (7,5) nanotubes show that only a small fraction exhibit the X 1 feature, with varying oscillator strength, thus suggesting that intrinsic processes such as phonon scattering are not responsible for populating the dark state. Alternatively, we suggest that populating the K-momentum dark exciton state requires scattering from defects, which is consistent with the increased magnitude of the X 1 feature for samples with increased sample purification and processing. Thus, the presence of an X 1 peak in photoluminescence is an extremely sensitive spectroscopic indicator of defects on single-walled carbon nanotubes.« less

Nonlinearities of polymethine and squarylium molecules for optical limiting

NASA Astrophysics Data System (ADS)

Lim, Jin Hong

Optical limiting, a process that reduces transmittance at high laser input energies (irradiance, fluence), is of interest in applications where sensitive optical components, e.g. detectors, are vulnerable to damage by the laser beam. Polymethine and squarylium dyes show strong reverse saturable absorption (RSA) at 532 nm. RSA is a process by which weak linear absorption populates excited states which subsequently absorb strongly. Thus, low inputs are transmitted while high inputs are absorbed. This nonlinear absorption is determined by the ground and excited-state absorption cross sections as well as excited state lifetimes of the molecular system. We characterized a series of polymethine and squarine molecules in ethanol and polyurethane acrylate polymeric host (PUA) using Z-scan and pump-probe techniques at the second harmonic of the Nd:YAG laser system. A comparison of the properties in these two hosts is made. Some of these dyes show a large ratio of excited to ground state absorption cross section, ~200, which is larger than any previously reported values. In order to determine the wavelength dependence of the nonlinearities of these molecules, we also performed Z-scan and pump-probe experiments at wavelengths from 440 to 650 nm using a picosecond optical parametric oscillator (OPO) which is synchronously pumped by the third-harmonic of a modelocked train of Nd:YAG laser pulses. The OPO is continuously tunable from 400 to 700 nm using two critically phase-matched BBO crystals mounted for walkoff compensation. A polymethine dye in PUA (PD #3), which is one of the best polymethine dyes at 532 nm, shows strong RSA over a broad spectral range from 480 to 620 nm. while a squarylium dye shows RSA over a relatively narrow spectral range from 500 to 560 nm. However, the excited state lifetimes (~2.5 ns in PUA) are shorter than desirable for good nanosecond optical limiting (10 ns) and at high inputs (>=0.36 J/cm2) the limiting properties are reduced. Extensive measurements of these molecules along with computer modeling indicate that the reduced limiting at high inputs is due to molecular degradation induced after a trans-cis conformational change. Evidence for this and possible methods to eliminate this problem are presented.

Nanoscale steady-state temperature gradients within polymer nanocomposites undergoing continuous-wave photothermal heating from gold nanorods.

PubMed

Maity, Somsubhra; Wu, Wei-Chen; Tracy, Joseph B; Clarke, Laura I; Bochinski, Jason R

2017-08-17

Anisotropically-shaped metal nanoparticles act as nanoscale heaters via excitation of a localized surface plasmon resonance, utilizing a photothermal effect which converts the optical energy into local heat. Steady-state temperatures within a polymer matrix embedded with gold nanorods undergoing photothermal heating using continuous-wave excitation are measured in the immediate spatial vicinity of the nanoparticle (referred to as the local temperature) from observing the rate of physical rotation of the asymmetric nanoparticles within the locally created polymer melt. Average temperatures across the entire (mostly solid) sample (referred to as the global temperature) are simultaneously observed using a fluorescence method from randomly dispersed molecular emitters. Comparing these two independent measurements in films having varying concentrations of nanorods reveals the interplay between the local and global temperatures, clearly demonstrating the capability of these material samples to sustain large steady-state spatial temperature gradients when experiencing continuous-wave excitation photothermal heating. These results are discussed quantitatively. Illustrative imaging studies of nanofibers under photothermal heating also support the presence of a large temperature gradient. Photothermal heating in this manner has potential utility in creating unique thermal processing conditions for outcomes such as driving chemical reactions, inducing crystallinity changes, or enhancing degradation processes in a manner unachievable by conventional heating methods.

Two-Centre Convergent Close-Coupling Approach to Ion-Atom Collisions: Current Progress

NASA Astrophysics Data System (ADS)

Kadyrov, Alisher; Abdurakhmanov, Ilkhom; Bailey, Jackson; Bray, Igor

2016-09-01

There are two versions of the convergent close-coupling (CCC) approach to ion-atom collisions: quantum-mechanical (QM-CCC) and semi-classical (SC-CCC). Recently, both implementations have been extended to include electron-transfer channels. The SC-CCC approach has been applied to study the excitation and the electron-capture processes in proton-hydrogen collisions. The integral alignment parameter A20 for polarization of Lyman- α emission and the cross sections for excitation and electron-capture into the lowest excited states have been calculated for a wide range of the proton impact energies. It has been established that for convergence of the results a very wide range of impact parameters (typically, 0-50 a.u.) is required due to extremely long tails of transition probabilities for transitions into the 2 p states at high energies. The QM-CCC approach allowed to obtain an accurate solution of proton-hydrogen scattering problem including all underlying processes, namely, direct scattering and ionisation, and electron capture into bound and continuum states of the projectile. In this presentation we give a general overview of current progress in applications of the two-centre CCC approach to ion-atom and atom-atom collisions. The work is supported by the Australian Research Council.

Nitric oxide excited under auroral conditions: Excited state densities and band emissions

NASA Astrophysics Data System (ADS)

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

2000-09-01

Electron impact excitation of vibrational levels in the ground electronic state and nine excited electronic states in NO has been simulated for an IBC II aurora (i.e., ˜10 kR in 3914 Å radiation) in order to predict NO excited state number densities and band emission intensities. New integral electron impact excitation cross sections for NO were combined with a measured IBC II auroral secondary electron distribution, and the vibrational populations of 10 NO electronic states were determined under conditions of statistical equilibrium. This model predicts an extended vibrational distribution in the NO ground electronic state produced by radiative cascade from the seven higher-lying doublet excited electronic states populated by electron impact. In addition to significant energy storage in vibrational excitation of the ground electronic state, both the a 4Π and L2 Φ excited electronic states are predicted to have relatively high number densities because they are only weakly connected to lower electronic states by radiative decay. Fundamental mode radiative transitions involving the lowest nine excited vibrational levels in the ground electronic state are predicted to produce infrared (IR) radiation from 5.33 to 6.05 μm with greater intensity than any single NO electronic emission band. Fundamental mode radiative transitions within the a 4Π electronic state, in the 10.08-11.37 μm region, are predicted to have IR intensities comparable to individual electronic emission bands in the Heath and ɛ band systems. Results from this model quantitatively predict the vibrational quantum number dependence of the NO IR measurements of Espy et al. [1988].

Direct evidence for the participation of band-tails and excited-state tunnelling in the luminescence of irradiated feldspars

NASA Astrophysics Data System (ADS)

Poolton, N. R. J.; Kars, R. H.; Wallinga, J.; Bos, A. J. J.

2009-12-01

The significance and extent of band-tail states in the luminescence and dosimetry properties of natural aluminosilicates (feldspars) is investigated by means of studies using low temperature (10 K) irradiation and optically stimulated luminescence (OSL) stimulation spectroscopy, and thermoluminescence (TL) in the range 10-200 K, made in comparison with high temperature (300 K) irradiation and photo-transferred OSL and TL investigations undertaken at low temperature. These measurements allow mappings of the band-tails to be made; they are found to be ~0.4 eV in extent in the typical materials studied. Furthermore, by populating charge trapping centres at high temperature (300 K) and monitoring the OSL stimulation spectra at temperatures in the range 10-300 K, clear evidence is presented for the presence of both thermally activated and non-thermally activated OSL processes; it is argued that the former result from thermally activated hopping through the band-tail states, whilst the latter are due to tunnelling processes, either from the excited state of the OSL centres or through the tail states. The spectral measurements are supported by analysis of the temporal dependence of the OSL signals, which correspond to either tunnelling or general order kinetic decay processes.

An Ab Initio Exciton Model Including Charge-Transfer Excited States

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

An Ab Initio Exciton Model Including Charge-Transfer Excited States

DOE PAGES

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

2017-06-15

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

Line Profile of H Lyman (alpha) from Dissociative Excitation of H2 with Application to Jupiter

NASA Technical Reports Server (NTRS)

Ajello, Joseph M.; Kasnik, Isik; Ahmed, Syed M.; Clarke, John T.

1995-01-01

Observations of the H Lyman(alpha) (Ly-alpha) emission from Jupiter have shown pronounced emissions, exceeding solar fluorescence, in the polar aurora and equatorial "bulge" regions. The H Ly-alpha line profiles from these regions are broader than expected, indicating high-energy processes producing fast atoms as determined from the observed Doppler broadening. Toward understanding that process a high-resolution ultraviolet (UV) spectrometer was employed for the first measurement of the H Ly-alpha emission Doppler profile from dissociative excitation of H2 by electron impact. Analysis of the deconvolved line profile reveals the existence of a narrow central peak of 40 +/- 4 mA full width at half maximum and a broad pedestal base about 240 mA wide. Two distinct dissociation mechanisms account for this Doppler structure. Slow H(2p) atoms characterized by a distribution function with peak energy near 80 meV produce the peak profile, which is nearly independent of the electron impact energy. Slow H(2p) atoms arise from direct dissociation and predissociation of singly excited states which have a dissociation limit of 14.68 eV. The wings of H Ly-alpha arise from dissociative excitation of a series of doubly excited states which cross the Franck-Condon region between 23 and 40 eV. The profile of the wings is dependent on the electron impact energy, and the distribution function of fast H(2p) atoms is therefore dependent on the electron impact energy. The fast atom kinetic energy distribution at 100 eV electron impact energy spans the energy range from 1 to 10 eV with a peak near 4 eV. For impact energies above 23 eV the fast atoms contribute to a slightly asymmetric structure of the line profile. The absolute cross sections of the H Ly-alpha line peak and wings were measured over the range from 0 to 200 eV. Analytic model coefficients are given for the measured cross sections which can be applied to planetary atmosphere auroral and dayglow calculations. The dissociative excitation process, while one contributing process, appears insufficient by itself to explain the line broadening observed at Jupiter.

Three-dimensional spectroscopy of vibrational energy in liquids: nitromethane and acetonitrile.

PubMed

Sun, Yuxiao; Pein, Brandt C; Dlott, Dana D

2013-12-12

We introduce a novel type of three-dimensional (3D) spectroscopy to study vibrational energy transfer, where an IR pulse tunable through the CH-stretching and CD-stretching regions was used to create parent vibrational excitations in liquids and a visible probe pulse was used to generate both Stokes and anti-Stokes Raman spectra as a function of delay time. The Raman spectra determine how much vibrational excitation was present in each probed state. The three dimensions are the wavenumber of the pumped state, the wavenumber of the probed state, and the time interval. The technique was used to study nitromethane (NM) and acetonitrile (ACN) and their deuterated analogues at ambient temperature. The 3D spectra were quite complicated. Three types of artifacts due to nonlinear light scattering were observed. Along the diagonal were two fundamental CH-stretch (or CD-stretch) transitions and several weaker combination bands or overtone transitions. Because Raman spectroscopy allows us to simultaneously probe a wide wavenumber region, for every diagonal peak, there were ∼10 off-diagonal peaks. The cross-peaks at shorter delay times reveal the nature of the initial excitation by showing which lower-wavenumber excitations were produced along with the pumped CH-stretch or CD-stretch. The longer-time spectra characterized vibrational energy relaxation processes, and showed how daughter vibrations were generated by different parent excitations.

Existence of a new emitting singlet state of proflavine: femtosecond dynamics of the excited state processes and quantum chemical studies in different solvents.

PubMed

Kumar, Karuppannan Senthil; Selvaraju, Chellappan; Malar, Ezekiel Joy Padma; Natarajan, Paramasivam

2012-01-12

Proflavine (3,6-diaminoacridine) shows fluorescence emission with lifetime, 4.6 ± 0.2 ns, in all the solvents irrespective of the solvent polarity. To understand this unusual photophysical property, investigations were carried out using steady state and time-resolved fluorescence spectroscopy in the pico- and femtosecond time domain. Molecular geometries in the ground and low-lying excited states of proflavine were examined by complete structural optimization using ab initio quantum chemical computations at HF/6-311++G** and CIS/6-311++G** levels. Time dependent density functional theory (TDDFT) calculations were performed to study the excitation energies in the low-lying excited states. The steady state absorption and emission spectral details of proflavine are found to be influenced by solvents. The femtosecond fluorescence decay of the proflavine in all the solvents follows triexponential function with two ultrafast decay components (τ(1) and τ(2)) in addition to the nanosecond component. The ultrafast decay component, τ(1), is attributed to the solvation dynamics of the particular solvent used. The second ultrafast decay component, τ(2), is found to vary from 50 to 215 ps depending upon the solvent. The amplitudes of the ultrafast decay components vary with the wavelength and show time dependent spectral shift in the emission maximum. The observation is interpreted that the time dependent spectral shift is not only due to solvation dynamics but also due to the existence of more than one emitting state of proflavine in the solvent used. Time resolved area normalized emission spectral (TRANES) analysis shows an isoemissive point, indicating the presence of two emitting states in homogeneous solution. Detailed femtosecond fluorescence decay analysis allows us to isolate the two independent emitting components of the close lying singlet states. The CIS and TDDFT calculations also support the existence of the close lying emitting states. The near constant lifetime observed for proflavine in different solvents is suggested to be due to the similar dipole moments of the ground and the evolved emitting singlet state of the dye from the Franck-Condon excited state.

(π−1) → (π−1), (π−1) emission spectra of chlorofluorobenzene cations in the gaseous phase and their lifetimes in the (0o) states

USGS Publications Warehouse

Maier, John Paul; Marthaler, O.; Mohraz, Manijeh; Shiley, R.H.

1980-01-01

The radiative decay of seventeen electronically excited chlorofluorobenzene cations in the gaseous phase has been detected. The reported emission spectra, which have been obtained using low energy electron beam excitation, are assigned to the B(??-1 ??? X(??-1 electronic transitions of these cations on the basis of their Ne(I) photoelectron spectra. In another sixteen chloroflourobenzene cations, the B ??? X radiative decay could not be detected, from which is inferred that the B states are now associated with Cl 3p(??-1 ionisation processes. The lifetimes of the studied cations in the lowest vibrational levels of the B(??-1 state have been measured. ?? 1980.

Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Enriquez, Miriam M.; Zhang, Cheng; Tan, Howe-Siang, E-mail: howesiang@ntu.edu.sg

2015-06-07

The pathways and dynamics of excitation energy transfer between the chlorophyll (Chl) domains in solubilized trimeric and aggregated light-harvesting complex II (LHCII) are examined using two-dimensional electronic spectroscopy (2DES). The LHCII trimers and aggregates exhibit the unquenched and quenched excitonic states of Chl a, respectively. 2DES allows direct correlation of excitation and emission energies of coupled states over population time delays, hence enabling mapping of the energy flow between Chls. By the excitation of the entire Chl b Q{sub y} band, energy transfer from Chl b to Chl a states is monitored in the LHCII trimers and aggregates. Global analysismore » of the two-dimensional (2D) spectra reveals that energy transfer from Chl b to Chl a occurs on fast and slow time scales of 240–270 fs and 2.8 ps for both forms of LHCII. 2D decay-associated spectra resulting from the global analysis identify the correlation between Chl states involved in the energy transfer and decay at a given lifetime. The contribution of singlet–singlet annihilation on the kinetics of Chl energy transfer and decay is also modelled and discussed. The results show a marked change in the energy transfer kinetics in the time range of a few picoseconds. Owing to slow energy equilibration processes, long-lived intermediate Chl a states are present in solubilized trimers, while in aggregates, the population decay of these excited states is significantly accelerated, suggesting that, overall, the energy transfer within the LHCII complexes is faster in the aggregated state.« less

Simultaneous manipulation and observation of multiple ro-vibrational eigenstates in solid para-hydrogen.

PubMed

Katsuki, Hiroyuki; Ohmori, Kenji

2016-09-28

We have experimentally performed the coherent control of delocalized ro-vibrational wave packets (RVWs) of solid para-hydrogen (p-H 2 ) by the wave packet interferometry (WPI) combined with coherent anti-Stokes Raman scattering (CARS). RVWs of solid p-H 2 are delocalized in the crystal, and the wave function with wave vector k ∼ 0 is selectively excited via the stimulated Raman process. We have excited the RVW twice by a pair of femtosecond laser pulses with delay controlled by a stabilized Michelson interferometer. Using a broad-band laser pulse, multiple ro-vibrational states can be excited simultaneously. We have observed the time-dependent Ramsey fringe spectra as a function of the inter-pulse delay by a spectrally resolved CARS technique using a narrow-band probe pulse, resolving the different intermediate states. Due to the different fringe oscillation periods among those intermediate states, we can manipulate their amplitude ratio by tuning the inter-pulse delay on the sub-femtosecond time scale. The state-selective manipulation and detection of the CARS signal combined with the WPI is a general and efficient protocol for the control of the interference of multiple quantum states in various quantum systems.

Probabilistic solutions of nonlinear oscillators excited by combined colored and white noise excitations

NASA Astrophysics Data System (ADS)

Siu-Siu, Guo; Qingxuan, Shi

2017-03-01

In this paper, single-degree-of-freedom (SDOF) systems combined to Gaussian white noise and Gaussian/non-Gaussian colored noise excitations are investigated. By expressing colored noise excitation as a second-order filtered white noise process and introducing colored noise as an additional state variable, the equation of motion for SDOF system under colored noise is then transferred artificially to multi-degree-of-freedom (MDOF) system under white noise excitations with four-coupled first-order differential equations. As a consequence, corresponding Fokker-Planck-Kolmogorov (FPK) equation governing the joint probabilistic density function (PDF) of state variables increases to 4-dimension (4-D). Solution procedure and computer programme become much more sophisticated. The exponential-polynomial closure (EPC) method, widely applied for cases of SDOF systems under white noise excitations, is developed and improved for cases of systems under colored noise excitations and for solving the complex 4-D FPK equation. On the other hand, Monte Carlo simulation (MCS) method is performed to test the approximate EPC solutions. Two examples associated with Gaussian and non-Gaussian colored noise excitations are considered. Corresponding band-limited power spectral densities (PSDs) for colored noise excitations are separately given. Numerical studies show that the developed EPC method provides relatively accurate estimates of the stationary probabilistic solutions, especially the ones in the tail regions of the PDFs. Moreover, statistical parameter of mean-up crossing rate (MCR) is taken into account, which is important for reliability and failure analysis. Hopefully, our present work could provide insights into the investigation of structures under random loadings.

Atomic Data on Inelastic Processes in Calcium–Hydrogen Collisions

NASA Astrophysics Data System (ADS)

Belyaev, A. K.; Voronov, Y. V.; Yakovleva, S. A.; Mitrushchenkov, A.; Guitou, M.; Feautrier, N.

2017-12-01

Inelastic cross sections and rate coefficients in Ca + H and Ca+ + H‑ collisions for all transitions between the 17 lowest covalent states plus one ionic molecular state are calculated based on the most recent ab initio adiabatic potentials for the 11 lowest molecular states, as well as on the model asymptotic potentials for higher-lying states, including the ground ionic molecular state. Nuclear dynamics is treated by the probability-current method and the multichannel formulas for the collision energy range 0.01–100 eV. The rates are computed for mutual neutralization, ion-pair formation, and (de-)excitation processes for the temperature range T = 1000–10,000 K. The calculations single out the partial processes with large and moderate rate coefficients. The largest rates correspond to the mutual neutralization into the {Ca}(4s5s{}3S), {Ca}(4s5p{}3P^\\circ ), {Ca}(4s5s{}1S), and {Ca}(4s5p{}{1}P^\\circ ) final states; at T = 6000 K the largest value is 5.50 × 10‑8 cm3 s‑1 for {Ca}(4s5s{}3S). Among the (de-)excitation processes, the largest rate coefficient corresponds to the {Ca}(4s5s{}1S)\\to {Ca}(4s5s{}3S) transition; at T = 6000 K, the largest rate has the value of 8.46 × 10‑9 cm3 s‑1.

The triplet excited state of Bodipy: formation, modulation and application.

PubMed

Zhao, Jianzhang; Xu, Kejing; Yang, Wenbo; Wang, Zhijia; Zhong, Fangfang

2015-12-21

Boron dipyrromethene (Bodipy) is one of the most extensively investigated organic chromophores. Most of the investigations are focused on the singlet excited state of Bodipy, such as fluorescence. In stark contrast, the study of the triplet excited state of Bodipy is limited, but it is an emerging area, since the triplet state of Bodipy is tremendously important for several areas, such as the fundamental photochemistry study, photodynamic therapy (PDT), photocatalysis and triplet-triplet annihilation (TTA) upconversion. The recent developments in the study of the production, modulation and application of the triplet excited state of Bodipy are discussed in this review article. The formation of the triplet state of Bodipy upon photoexcitation, via the well known approach such as the heavy atom effect (including I, Br, Ru, Ir, etc.), and the new methods, such as using a spin converter (e.g. C60), charge recombination, exciton coupling and the doubly substituted excited state, are summarized. All the Bodipy-based triplet photosensitizers show strong absorption of visible or near IR light and the long-lived triplet excited state, which are important for the application of the triplet excited state in PDT or photocatalysis. Moreover, the methods for switching (or modulation) of the triplet excited state of Bodipy were discussed, such as those based on the photo-induced electron transfer (PET), by controlling the competing Förster-resonance-energy-transfer (FRET), or the intermolecular charge transfer (ICT). Controlling the triplet excited state will give functional molecules such as activatable PDT reagents or molecular devices. It is worth noting that switching of the singlet excited state and the triplet state of Bodipy may follow different principles. Application of the triplet excited state of Bodipy in PDT, hydrogen (H2) production, photoredox catalytic organic reactions and TTA upconversion were discussed. The challenges and the opportunities in these areas were briefly discussed.

Bound state and localization of excitation in many-body open systems

NASA Astrophysics Data System (ADS)

Cui, H. T.; Shen, H. Z.; Hou, S. C.; Yi, X. X.

2018-04-01

We study the exact bound state and time evolution for single excitations in one-dimensional X X Z spin chains within a non-Markovian reservoir. For the bound state, a common feature is the localization of single excitations, which means the spontaneous emission of excitations into the reservoir is prohibited. Exceptionally, the pseudo-bound state can be found, for which the single excitation has a finite probability of emission into the reservoir. In addition, a critical energy scale for bound states is also identified, below which only one bound state exists, and it is also the pseudo-bound state. The effect of quasirandom disorder in the spin chain is also discussed; such disorder induces the single excitation to locate at some spin sites. Furthermore, to display the effect of bound state and disorder on the preservation of quantum information, the time evolution of single excitations in spin chains is studied exactly. An interesting observation is that the excitation can stay at its initial location with high probability only when the bound state and disorder coexist. In contrast, when either one of them is absent, the information of the initial state can be erased completely or becomes mixed. This finding shows that the combination of bound state and disorder can provide an ideal mechanism for quantum memory.

Excited State Processes in Electronic and Bio Nanomaterials (ESP-2016)

Science.gov Websites

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Shining light on the antenna chromophore in lanthanide based dyes.

PubMed

Junker, Anne Kathrine R; Hill, Leila R; Thompson, Amber L; Faulkner, Stephen; Sørensen, Thomas Just

2018-04-03

Lanthanide based dyes and assays exploit the antenna effect, where a sensitiser-chromophore is used as a light harvesting antenna and subsequent excited state energy transfer populates the emitting lanthanide centred excited state. A rudimentary understanding of the design criteria for designing efficient dyes and assays based on the antenna effect is in place. By preparing kinetically inert lanthanide complexes based on the DO3A scaffold, we are able to study the excited state energy transfer from a 7-methoxy-coumarin antenna chromophore to europium(iii) and terbium(iii) centred excited states. By contrasting the photophysical properties of complexes of metal centres with and without accessible excited states, we are able to separate the contributions from the heavy atom effect, photoinduced electron transfer quenching, excited state energy transfer and molecular conformations. Furthermore, by studying the photophysical properties of the antenna chromophore, we can directly monitor the solution structure and are able to conclude that excited state energy transfer from the chromophore singlet state to the lanthanide centre does occur.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Excited state and charge-carrier dynamics in perovskite solar cell materials

NASA Astrophysics Data System (ADS)

Ponseca, Carlito S., Jr.; Tian, Yuxi; Sundström, Villy; Scheblykin, Ivan G.

2016-02-01

Organo-metal halide perovskites (OMHPs) have attracted enormous interest in recent years as materials for application in optoelectronics and solar energy conversion. These hybrid semiconductors seem to have the potential to challenge traditional silicon technology. In this review we will give an account of the recent development in the understanding of the fundamental light-induced processes in OMHPs from charge-photo generation, migration of charge carries through the materials and finally their recombination. Our and other literature reports on time-resolved conductivity, transient absorption and photoluminescence properties are used to paint a picture of how we currently see the fundamental excited state and charge-carrier dynamics. We will also show that there is still no fully coherent picture of the processes in OMHPs and we will indicate the problems to be solved by future research.

The impact of photon flight path on S1 pulse shape analysis in liquid xenon two-phase detectors

NASA Astrophysics Data System (ADS)

Moongweluwan, M.

2016-02-01

The LUX dark matter search experiment is a 350 kg dual-phase xenon time projection chamber located at the 4850 ft level of the Sanford Underground Research Facility in Lead, SD. The success of two-phase xenon detectors for dark matter searches relies on their ability to distinguish electron recoil (ER) background events from nuclear recoil (NR) signal events. Typically, the NR-ER discrimination is obtained from the ratio of the electroluminescence light (S2) to the prompt scintillation light (S1). Analysis of the S1 pulse shape is an additional discrimination technique that can be used to distinguish NR from ER. Pulse-shape NR-ER discrimination can be achieved based on the ratio of the de-excitation processes from singlet and triplet states that generate the S1. The NR S1 is dominated by the de-excitation process from singlet states with a time constant of about 3 ns while the ER S1 is dominated by the de-excitation process from triplet states with a time constant of about 24 ns. As the size of the detectors increases, the variation in the S1 photon flight path can become comparable to these decay constants, reducing the utility of pulse-shape analysis to separate NR from ER. The effect of path length variations in the LUX detector has been studied using the results of simulations and the impact on the S1 pulse shape analysis is discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Argondizzo, Adam; Cui, Xuefeng; Wang, Cong

We investigate the spectroscopy and photoinduced electron dynamics within the conduction band of reduced rutile TiO2(110) surface by multiphoton photoemission (mPP) spectroscopy with wavelength tunable ultrafast (!20 fs) laser pulse excitation. Tuning the mPP photon excitation energy between 2.9 and 4.6 eV reveals a nearly degenerate pair of new unoccupied states located at 2.73 ± 0.05 and 2.85 ± 0.05 eV above the Fermi level, which can be analyzed through the polarization and sample azimuthal orientation dependence of the mPP spectra. Based on the calculated electronic structure and optical transition moments, as well as related spectroscopic evidence, we assign thesemore » resonances to transitions between Ti 3d bands of nominally t2g and eg symmetry, which are split by crystal field. The initial states for the optical transition are the reduced Ti3+ states of t2g symmetry populated by formation oxygen vacancy defects, which exist within the band gap of TiO2. Furthermore,we studied the electron dynamics within the conduction band of TiO2 by three-dimensional time-resolved pump-probe interferometric mPP measurements. The spectroscopic and time-resolved studies reveal competition between 2PP and 3PP processes where the t2g-eg transitions in the 2PP process saturate, and are overtaken by the 3PP process initiated by the band-gap excitation from the valence band of TiO2.« less

Excitation of nucleobases from a computational perspective I: reaction paths.

PubMed

Giussani, Angelo; Segarra-Martí, Javier; Roca-Sanjuán, Daniel; Merchán, Manuela

2015-01-01

The main intrinsic photochemical events in nucleobases can be described on theoretical grounds within the realm of non-adiabatic computational photochemistry. From a static standpoint, the photochemical reaction path approach (PRPA), through the computation of the respective minimum energy path (MEP), can be regarded as the most suitable strategy in order to explore the electronically excited isolated nucleobases. Unfortunately, the PRPA does not appear widely in the studies reported in the last decade. The main ultrafast decay observed experimentally for the gas-phase excited nucleobases is related to the computed barrierless MEPs from the bright excited state connecting the initial Franck-Condon region and a conical intersection involving the ground state. At the highest level of theory currently available (CASPT2//CASPT2), the lowest excited (1)(ππ*) hypersurface for cytosine has a shallow minimum along the MEP deactivation pathway. In any case, the internal conversion processes in all the natural nucleobases are attained by means of interstate crossings, a self-protection mechanism that prevents the occurrence of photoinduced damage of nucleobases by ultraviolet radiation. Many alternative and secondary paths have been proposed in the literature, which ultimately provide a rich and constructive interplay between experimentally and theoretically oriented research.

Excitation and charge transfer in low-energy hydrogen atom collisions with neutral oxygen

NASA Astrophysics Data System (ADS)

Barklem, P. S.

2018-02-01

Excitation and charge transfer in low-energy O+H collisions is studied; it is a problem of importance for modelling stellar spectra and obtaining accurate oxygen abundances in late-type stars including the Sun. The collisions have been studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals (LCAO) model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multichannel Landau-Zener model. The method has been extended to include configurations involving excited states of hydrogen using an estimate for the two-electron transition coupling, but this extension was found to not lead to any remarkably high rates. Rate coefficients are calculated for temperatures in the range 1000-20 000 K, and charge transfer and (de)excitation processes involving the first excited S-states, 4s.5So and 4s.3So, are found to have the highest rates. Data are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/vizbin/qcat?J/A+A/610/A57. The data are also available at http://https://github.com/barklem/public-data

Removal of Default-State Associated Inhibition During Repetition Priming Improves Response Articulation

PubMed Central

Dacks, Andrew M.; Siniscalchi, Michael J.; Weiss, Klaudiusz R.

2012-01-01

Behavior is a product of both the stimuli encountered and the current internal state. At the level of the nervous system, the internal state alters the biophysical properties of, and connections between, neurons establishing a “network state”. To establish a network state, the nervous system must be altered from an initial default/resting state, but what remains unclear is the extent to which this process represents induction from a passive default state or the removal of suppression by an active default state. We use repetition priming (a history-dependent improvement of behavioral responses to repeatedly encountered stimuli) to determine the cellular mechanisms underlying the transition from the default to the primed network state. We demonstrate that both removal of active suppression and induction of neuron excitability changes each contribute separately to the production of a primed state. The feeding system of Aplysia californica displays repetition priming via an increase in the activity of the radula closure neuron B8, which results in increased bite strength with each motor program. We found that during priming, B8 received progressively less inhibitory input from the multi-functional neurons B4/5. Additionally, priming enhanced the excitability of B8, but the rate at which B8 activity increased as a result of these changes was regulated by the progressive removal of inhibitory input. Thus, the establishment of the network state involves the induction of processes from a rested state, yet the consequences of these processes are conditional upon critical gating mechanisms actively enforced by the default state. PMID:23223294

Pyrimidinone: versatile Trojan horse in DNA photodamage?

PubMed

Micheel, Mathias; Torres Ziegenbein, Christian; Gilch, Peter; Ryseck, Gerald

2015-09-26

(6-4) Photolesions between adjacent pyrimidine DNA bases are prone to secondary photochemistry. It has been shown that singlet excited (6-4) moieties form Dewar valence isomers as well as triplet excitations. We here report on the triplet state of a minimal model for the (6-4) photolesion, 1-methyl-2(1H)-pyrimidinone. Emphasis is laid on its ability to abstract hydrogen atoms from alcohols and carbohydrates. Steady-state and time-resolved experiments consistently yield bimolecular rate constants of ∼10(4) M(-1) s(-1) for the hydrogen abstraction. The process also occurs intramolecularly as experiments on zebularine (1-(β-d-ribofuranosyl)-2(1H)-pyrimidinone) show.

An amorphous silicon photodiode with 2 THz gain-bandwidth product based on cycling excitation process

NASA Astrophysics Data System (ADS)

Yan, Lujiang; Yu, Yugang; Zhang, Alex Ce; Hall, David; Niaz, Iftikhar Ahmad; Raihan Miah, Mohammad Abu; Liu, Yu-Hsin; Lo, Yu-Hwa

2017-09-01

Since impact ionization was observed in semiconductors over half a century ago, avalanche photodiodes (APDs) using impact ionization in a fashion of chain reaction have been the most sensitive semiconductor photodetectors. However, APDs have relatively high excess noise, a limited gain-bandwidth product, and high operation voltage, presenting a need for alternative signal amplification mechanisms of superior properties. As an amplification mechanism, the cycling excitation process (CEP) was recently reported in a silicon p-n junction with subtle control and balance of the impurity levels and profiles. Realizing that CEP effect depends on Auger excitation involving localized states, we made the counter intuitive hypothesis that disordered materials, such as amorphous silicon, with their abundant localized states, can produce strong CEP effects with high gain and speed at low noise, despite their extremely low mobility and large number of defects. Here, we demonstrate an amorphous silicon low noise photodiode with gain-bandwidth product of over 2 THz, based on a very simple structure. This work will impact a wide range of applications involving optical detection because amorphous silicon, as the primary gain medium, is a low-cost, easy-to-process material that can be formed on many kinds of rigid or flexible substrates.

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

PubMed

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.

Excitation of lowest electronic states of the uracil molecule by slow electrons

NASA Astrophysics Data System (ADS)

Chernyshova, I. V.; Kontros, J. E.; Markush, P. P.; Shpenik, O. B.

2012-07-01

The excitation of lowest electronic states of the uracil molecule in the gas phase has been studied by electron energy loss spectroscopy. Along with excitation of lowest singlet states, excitation of two lowest triplet states at 3.75 and 4.76 eV (±0.05 eV) and vibrational excitation of the molecule in two resonant ranges (1-2 and 3-4 eV) have been observed for the first time. The peak of the excitation band related to the lowest singlet state (5.50 eV) is found to be blueshifted by 0.4 eV in comparison with the optical absorption spectroscopy data. The threshold excitation spectra have been measured for the first time, with detection of electrons inelastically scattered by an angle of 180°. These spectra exhibit clear separation of the 5.50-eV-wide band into two bands, which are due to the excitation of the triplet 13 A″ and singlet 11 A' states.

Using resonant x-ray scattering to determine how structure controls the charge generation process in PCPDTBT:PC70BM solar cells

NASA Astrophysics Data System (ADS)

Pope, Michael; Waldrip, Matthew; Ferron, Thomas; Collins, Brian

Increased solar power conversion efficiencies to 12% in bulk heterojunction organic photovoltaics (OPVs) continue to brighten their prospects as an economically viable source of solar energy. It is known that OPV performance can be enhanced through processing additives that change the nanostructure. We track these critical structure-property relationships in the OPV system PCPDTBT:PC70BM while varying the amount of DIO additive. Resonant Soft X-ray Scattering reveals domain purity, domain size, and molecular orientation to highlight the system's complex dependence on DIO concentration. We will show the effect the resulting structure has on charge generation and recombination via in-situ transient and steady state optoelectronic measurements. By measuring structure, excited state dynamics and device performance all on the same sample enables direct relationships to be measured. We show that the appropriate balance of crystallinity, domain size and domain purity are important for optimized excited state dynamics and device performance.

Benzothiazole-Based AIEgen with Tunable Excited-State Intramolecular Proton Transfer and Restricted Intramolecular Rotation Processes for Highly Sensitive Physiological pH Sensing.

PubMed

Li, Kai; Feng, Qi; Niu, Guangle; Zhang, Weijie; Li, Yuanyuan; Kang, Miaomiao; Xu, Kui; He, Juan; Hou, Hongwei; Tang, Ben Zhong

2018-04-23

In this work, a benzothiazole-based aggregation-induced emission luminogen (AIEgen) of 2-(5-(4-carboxyphenyl)-2-hydroxyphenyl)benzothiazole (3) was designed and synthesized, which exhibited multifluorescence emissions in different dispersed or aggregated states based on tunable excited-state intramolecular proton transfer (ESIPT) and restricted intramolecular rotation (RIR) processes. 3 was successfully used as a ratiometric fluorescent chemosensor for the detection of pH, which exhibited reversible acid/base-switched yellow/cyan emission transition. More importantly, the pH jump of 3 was very precipitous from 7.0 to 8.0 with a midpoint of 7.5, which was well matched with the physiological pH. This feature makes 3 very suitable for the highly sensitive detection of pH fluctuation in biosamples and neutral water samples. 3 was also successfully used as a ratiometric fluorescence chemosensor for the detection of acidic and basic organic vapors in test papers.

The interaction of the excited states of safranine-O with low generation carboxyl terminated PAMAM dendrimers in an aqueous medium.

PubMed

Militello, M Paula; Altamirano, Marcela S; Bertolotti, Sonia G; Previtali, Carlos M

2018-05-16

The interaction of the singlet and triplet excited states of the synthetic dye safranine-O with carboxyl-terminated poly(amidoamine) (PAMAM) dendrimers was investigated in a buffer solution at pH 8. Low half-generation PAMAM dendrimers (G -0.5; G +0.5: G 1.5) were employed. The UV-vis absorption spectrum of the dye presents only a very small red shift in the presence of dendrimers. Fluorescence quenching was detected and it was interpreted by a static mechanism in terms of the association of the dye with the dendrimer. Laser flash photolysis experiments were carried out and transient absorption spectra of the triplet and radicals were obtained. The triplet state is quenched by the dendrimers with rate constants well below the diffusional limit. The quenching process was characterized as an electron transfer process and the quantum yield of radicals was estimated. It was found that radicals are formed with a high efficiency in the triplet quenching reaction.

Theoretical Studies of Dissociative Recombination of Electrons with SH+ Ions

NASA Astrophysics Data System (ADS)

Kashinski, D. O.; di Nallo, O. E.; Hickman, A. P.; Mezei, J. Zs.; Schneider, I. F.; Talbi, D.

2015-05-01

We are investigating the dissociative recombination (DR) of electrons with the molecular ion SH+. (The process is e- +SH+ --> S + H .) SH+ is found in the interstellar medium (ISM), and little is known concerning its interstellar chemistry. The abundance of SH+ in the ISM suggests that destruction processes, like DR, are inefficient. Understanding the role of DR as a destruction pathway for SH+ will lead to more accurate astrophysical models. Large active-space multi-reference configuration interaction (MRCI) electronic structure calculations were performed to obtain excited-state potential energy curves (PECs) for several values of SH separation. Excited Rydberg states have proven to be of importance. The block diagonalization method was used to disentangle interacting states, forming a diabatic representation of the PECs. Currently we are performing Multichannel Quantum Defect Theory (MQDT) dynamics calculations to obtain DR rates. The status of the work will be presented at the conference. Work supported by the French CNRS, the NSF, the XSEDE, and USMA.

Molecular photoionization processes of astrophysical and aeronomical interest

NASA Technical Reports Server (NTRS)

Langhoff, P. W.

1985-01-01

An account is given of aspects of photoionization processes in molecules, with particular reference to recent theoretical and experimental studies of partial cross sections for production of specific final electronic states and of parent and fragment ions. Such cross sections help provide a basis for specifying the state of excitation of the ionized medium, are useful for estimating the kinetic energy distributions of photoejected electrons and fragment ions, provide parent-and fragment-ion yields, and clarify the possible origins of neutral fragments in highly excited rovibronic states. A descriptive account is given of photoionization phenomena, including tabulation of valence- and inner-shell potentials for some molecules of astrophysical and aeronomical interest. Cross sectional expressions are given. Various approximations currently employed in computational studies are described briefly, threshold laws and high-energy limits are indicated, and distinction is drawn between resonant and direct photoionization phenomena. Recent experimental and theoretical studies of partial photoionization cross sections in selected compounds of astrophysical and aeronomical relevance are described and discussed.

Persistent optical hole-burning spectroscopy of nano-confined dye molecules in liquid at room temperature: Spectral narrowing due to a glassy state and extraordinary relaxation in a nano-cage

NASA Astrophysics Data System (ADS)

Murakami, Hiroshi

2018-04-01

Persistent optical hole-burning spectroscopy has been conducted for a dye molecule within a very small (˜1 nm) reverse micelle at room temperature. The spectra show a spectral narrowing due to site-selective excitation. This definitely demonstrates that the surroundings of the dye molecule are in a glassy state regardless of a solution at room temperature. On the other hand, the hole-burning spectra exhibit large shifts from excitation frequencies, and their positions are almost independent of excitation frequencies. The hole-burning spectra have been theoretically calculated by taking account of a vibronic absorption band of the dye molecule under the assumption that the surroundings of the dye molecule are in a glassy state. The calculated results agree with the experimental ones that were obtained for the dye molecule in a polymer glass for comparison, where it has been found that the ratio of hole-burning efficiencies of vibronic- to electronic-band excitations is quite high. On the other hand, the theoretical results do not explain the large spectral shift from the excitation frequency and small spectral narrowing observed in the hole-burning spectra measured for the dye-containing reverse micelle. It is thought that the spectral shift and broadening occur within the measurement time owing to the relaxation process of the surroundings that are hot with the thermal energy deposited by the dye molecule optically excited. Furthermore, the relaxation should be temporary because the cooling of the inside of the reverse micelle takes place with the dissipation of the excess thermal energy to the outer oil solvent, and so the surroundings of the dye molecule return to the glassy state and do not attain the thermal equilibrium. These results suggest that a very small reverse micelle provides a unique reaction field in which the diffusional motion can be controlled by light in a glassy state.

σ-SCF: A direct energy-targeting method to mean-field excited states

NASA Astrophysics Data System (ADS)

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

2017-12-01

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 Δ-SCF (self-consistent field), 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, σ-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 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 Δ-SCF solutions that are otherwise hardly accessible by the usual non-aufbau configuration initial guess. We present results for this new method for small atoms (He, Be) and molecules (H2, HF). We find that σ-SCF is very effective at locating excited states, including individual, high energy excitations within a dense manifold of excited states. Like all single determinant methods, σ-SCF shows prominent spin-symmetry breaking for open shell states and our results suggest that this method could be further improved with spin projection.

Pink splash of active nitrogen in the discharge afterglow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akishev, Yu. S.; Grushin, M. E.; Karal'nik, V. B.

2007-09-15

Results are presented from experimental studies of the glow dynamics of active nitrogen in the stage of its excitation by a current pulse and during the discharge afterglow. The mechanism is proposed for the generation of a light splash in a highly activated nitrogen after the end of its pulsed excitation. The key role in the generation of this splash is played by the D-V processes, by which the dissociation energy is transferred to the vibrational degrees of freedom in the course of recombination of nitrogen atoms, and the V-E processes, by which the vibrational energy of highly excited moleculesmore » N{sub 2}(X, v {>=} 25-27) is transferred to the emitting electronic states N{sub 2}(B, v) after the V-V delay. Results of simulations based on the mechanism proposed are also presented.« less

Pulsed radiolysis of model aromatic polymers and epoxy based matrix materials

NASA Technical Reports Server (NTRS)

Gupta, A.; Moacanin, J.; Liang, R.; Coulter, D.

1982-01-01

Models of primary processes leading to deactivation of energy deposited by a pulse of high energy electrons were derived for epoxy matrix materials and polyl-vinyl naphthalene. The basic conclusion is that recombination of initially formed charged states is complete within 1 nanosecond, and subsequent degradation chemistry is controlled by the reactivity of these excited states. Excited states in both systems form complexes with ground state molecules. These excimers or exciplexes have their characteristics emissive and absorptive properties and may decay to form separated pairs of ground state molecules, cross over to the triplet manifold or emit fluorescence. ESR studies and chemical analyses subsequent to pulse radiolysis were performed in order to estimate bond cleavage probabilities and net reaction rates. The energy deactivation models which were proposed to interpret these data have led to the development of radiation stabilization criteria for these systems.

Data on inelastic processes in low-energy potassium-hydrogen and rubidium-hydrogen collisions

NASA Astrophysics Data System (ADS)

Yakovleva, S. A.; Barklem, P. S.; Belyaev, A. K.

2018-01-01

Two sets of rate coefficients for low-energy inelastic potassium-hydrogen and rubidium-hydrogen collisions were computed for each collisional system based on two model electronic structure calculations, performed by the quantum asymptotic semi-empirical and the quantum asymptotic linear combinations of atomic orbitals (LCAO) approaches, followed by quantum multichannel calculations for the non-adiabatic nuclear dynamics. The rate coefficients for the charge transfer (mutual neutralization, ion-pair formation), excitation and de-excitation processes are calculated for all transitions between the five lowest lying covalent states and the ionic states for each collisional system for the temperature range 1000-10 000 K. The processes involving higher lying states have extremely low rate coefficients and, hence, are neglected. The two model calculations both single out the same partial processes as having large and moderate rate coefficients. The largest rate coefficients correspond to the mutual neutralization processes into the K(5s 2S) and Rb(4d 2D) final states and at temperature 6000 K have values exceeding 3 × 10-8 cm3 s-1 and 4 × 10-8 cm3 s-1, respectively. It is shown that both the semi-empirical and the LCAO approaches perform equally well on average and that both sets of atomic data have roughly the same accuracy. The processes with large and moderate rate coefficients are likely to be important for non-LTE modelling in atmospheres of F, G and K-stars, especially metal-poor stars.

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

DOE PAGES

Kowalski, Karol; Valiev, Marat

2007-01-01

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

Hybrid lead halide perovskites for light energy conversion: Excited state properties and photovoltaic applications

NASA Astrophysics Data System (ADS)

Manser, Joseph S.

The burgeoning class of metal halide perovskites constitutes a paradigm shift in the study and application of solution-processed semiconductors. Advancements in thin film processing and our understanding of the underlying structural, photophysical, and electronic properties of these materials over the past five years have led to development of perovskite solar cells with power conversion efficiencies that rival much more mature first and second-generation commercial technologies. It seems only a matter of time before the real-world impact of these compounds is put to the test. Like oxide perovskites, metal halide perovskites have ABX3 stoichiometry, where typically A is a monovalent cation, B a bivalent post-transition metal, and X a halide anion. Characterizing the behavior of photogenerated charges in metal halide perovskites is integral for understanding the operating principles and fundamental limitations of perovskite optoelectronics. The majority of studies outlined in this dissertation involve fundamental study of the prototypical organic-inorganic compound methylammonium lead iodide (CH3NH3PbI 3). Time-resolved pump-probe spectroscopy serves as a principle tool in these investigations. Excitation of a semiconductor can lead to formation of a number different excited state species and electronic complexes. Through analysis of excited state decay kinetics and optical nonlinearities in perovskite thin films, we identify spontaneous formation of a large fraction of free electrons and holes, whose presence is requisite for efficient photovoltaic operation. Following photogeneration of charge carriers in a semiconductor absorber, these species must travel large distances across the thickness of the material to realize large external quantum efficiencies and efficient carrier extraction. Using a powerful technique known as transient absorption microscopy, we directly image long-range carrier diffusion in a CH3NH3PbI 3 thin film. Charges are unambiguously shown to travel 220 nm over the course of 2 ns after photoexcitation, with an extrapolated diffusion length greater than one micrometer over the full excited state lifetime. The solution-processability of metal halide perovskites necessarily raises questions as to the properties of the solvated precursors and their connection to the final solid-state perovskite phase. Through structural and steady-state and time-resolved absorption studies, the important link between the excited state properties of the precursor components, composed of solvated and solid-state halometallate complexes, and CH3NH3PbI3 is evinced. This connection provides insight into optical nonlinearities and electronic properties of the perovskite phase. Fundamental studies of CH 3NH3PbI3 ultimately serve as a foundation for application of this and other related materials in high-performance devices. In the final chapter, the operation of CH3NH3PbI 3 solar cells in a tandem architecture is presented. The quest for economic, large scale hydrogen production has motivated the search for new materials and device designs capable of splitting water using only energy from the sun. In light of this, we introduce an all solution-processed tandem water splitting assembly composed of a BiVO4 photoanode and a single-junction CH3NH3PbI3 hybrid perovskite solar cell. This unique configuration allows efficient solar photon management, with the metal oxide photoanode selectively harvesting high energy visible photons and the underlying perovskite solar cell capturing lower energy visible-near IR wavelengths in a single-pass excitation. Operating without external bias under standard terrestrial one sun illumination, the photoanode-photovoltaic architecture, in conjunction with an earthabundant cobalt phosphate catalyst, exhibits a solar-to-hydrogen conversion efficiency of 2.5% at neutral pH. The design of low-cost tandem water splitting assemblies employing single-junction hybrid perovskite materials establishes a potentially promising new frontier for solar water splitting research.

Microwave-optical two-photon excitation of Rydberg states

NASA Astrophysics Data System (ADS)

Tate, D. A.; Gallagher, T. F.

2018-03-01

We report efficient microwave-optical two photon excitation of Rb Rydberg atoms in a magneto-optical trap. This approach allows the excitation of normally inaccessible states and provides a path toward excitation of high-angular-momentum states. The efficiency stems from the elimination of the Doppler width, the use of a narrow-band pulsed laser, and the enormous electric-dipole matrix element connecting the intermediate and final states of the transition. The excitation is efficient in spite of the low optical and microwave powers, of order 1 kW and 1 mW, respectively. This is an application of the large dipole coupling strengths between Rydberg states to achieve two-photon excitation of Rydberg atoms.

Laser-induced transitions between triply excited hollow states

NASA Astrophysics Data System (ADS)

Madsen, L. B.; Schlagheck, P.; Lambropoulos, P.

2000-12-01

Using complex scaling and a correlated basis constructed in terms of B splines, we calculate the Li+ photoion yield in the presence of a laser-induced coupling between the triply excited 2s22p(2Po) and 2s2p2(2De) resonances in lithium, the first of which is assumed to be excited by synchrotron radiation from the ground state. The laser coupling between the triply excited states is shown to lead to a significant and readily measurable modification of the line profile which provides a unique probe of the dipole strength between highly correlated triply excited states. We also present results for some higher-lying triply excited states of 2Po symmetry.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Nonlinear absorption dynamics using field-induced surface hopping: zinc porphyrin in water.

PubMed

Röhr, Merle I S; Petersen, Jens; Wohlgemuth, Matthias; Bonačić-Koutecký, Vlasta; Mitrić, Roland

2013-05-10

We wish to present the application of our field-induced surface-hopping (FISH) method to simulate nonlinear absorption dynamics induced by strong nonresonant laser fields. We provide a systematic comparison of the FISH approach with exact quantum dynamics simulations on a multistate model system and demonstrate that FISH allows for accurate simulations of nonlinear excitation processes including multiphoton electronic transitions. In particular, two different approaches for simulating two-photon transitions are compared. The first approach is essentially exact and involves the solution of the time-dependent Schrödinger equation in an extended manifold of excited states, while in the second one only transiently populated nonessential states are replaced by an effective quadratic coupling term, and dynamics is performed in a considerably smaller manifold of states. We illustrate the applicability of our method to complex molecular systems by simulating the linear and nonlinear laser-driven dynamics in zinc (Zn) porphyrin in the gas phase and in water. For this purpose, the FISH approach is connected with the quantum mechanical-molecular mechanical approach (QM/MM) which is generally applicable to large classes of complex systems. Our findings that multiphoton absorption and dynamics increase the population of higher excited states of Zn porphyrin in the nonlinear regime, in particular in solution, provides a means for manipulating excited-state properties, such as transient absorption dynamics and electronic relaxation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-photon interband absorption coefficients in tungstate and molybdate crystals

NASA Astrophysics Data System (ADS)

Lukanin, V. I.; Karasik, A. Ya.

2015-02-01

Two-photon absorption (TPA) coefficients were measured in tungstate and molybdate crystals - BaWO4, KGW, CaMoO4, BaMoO4, CaWO4, PbWO4 and ZnWO4 upon different orientations of excitation polarization with respect to the crystallographic axes. Trains of 25 ps pulses with variable radiation intensities of third (349 nm) harmonics of passively mode-locked 1047 nm Nd:YLF laser were used for interband two-photon excitation of the crystals. It was suggested that in the case, when 349 nm radiation pumping energy exceeds the bandgap width (hν>Eg), the nonlinear excitation process can be considered as two-step absorption. The interband two-photon absorption in all the studied crystals induces the following one-photon absorption from the exited states, which affects the nonlinear process dynamics and leads to a hysteresis in the dependence of the transmission on the excitation intensity. This fact was taken into account under analysis of the experimental dependences of the reciprocal transmission on the excitation intensity. Laser excitation in the transparency region of the crystals caused stimulated Raman scattering (SRS) not for all the crystals studied. The measured nonlinear coefficients allowed us to explain the suppression of SRS in crystals as a result of competition between the SRS and TPA.

Tunable ultraviolet and blue light generation from Nd:YAB random laser bolstered by second-order nonlinear processes

NASA Astrophysics Data System (ADS)

Moura, André L.; Carreño, Sandra J. M.; Pincheira, Pablo I. R.; Fabris, Zanine V.; Maia, Lauro J. Q.; Gomes, Anderson S. L.; de Araújo, Cid B.

2016-06-01

Ultraviolet and blue light were obtained by nonlinear frequency conversion in a random laser (RL) based on Nd0.10Y0.90Al3(BO3)4 nanocrystalline powder. RL operation at 1062 nm, due to the 4F3/2 → 4I11/2 transition of neodymium ions (Nd3+), was achieved by exciting the Nd3+ with a tunable beam from 680 to 920 nm covering the ground state absorption transitions to the 4F9/2, (4F7/2,4S3/2), (4F5/2,2H9/2), and 4F3/2 states. Light from 340 to 460 nm was obtained via the second-harmonic generation of the excitation beam while tunable blue light, from 417 to 486 nm, was generated by self-sum-frequency mixing between the excitation beam and the RL emission.

Development and Applications of Orthogonality Constrained Density Functional Theory for the Accurate Simulation of X-Ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Derricotte, Wallace D.

The aim of this dissertation is to address the theoretical challenges of calculating core-excited states within the framework of orthogonality constrained density functional theory (OCDFT). OCDFT is a well-established variational, time independent formulation of DFT for the computation of electronic excited states. In this work, the theory is first extended to compute core-excited states and generalized to calculate multiple excited state solutions. An initial benchmark is performed on a set of 40 unique core-excitations, highlighting that OCDFT excitation energies have a mean absolute error of 1.0 eV. Next, a novel implementation of the spin-free exact-two-component (X2C) one-electron treatment of scalar relativistic effects is presented and combined with OCDFT in an effort to calculate core excited states of transition metal complexes. The X2C-OCDFT spectra of three organotitanium complexes (TiCl4, TiCpCl3, and TiCp2Cl2) are shown to be in good agreement with experimental results and show a maximum absolute error of 5-6 eV. Next the issue of assigning core excited states is addressed by introducing an automated approach to analyzing the excited state MO by quantifying its local contributions using a unique orbital basis known as localized intrinsic valence virtual orbitals (LIVVOs). The utility of this approach is highlighted by studying sulfur core-excitations in ethanethiol and benzenethiol, as well as the hydrogen bonding in the water dimer. Finally, an approach to selectively target specic core-excited states in OCDFT based on atomic orbital subspace projection is presented in an effort to target core excited states of chemisorbed organic molecules. The core excitation spectrum of pyrazine chemisorbed on Si(100) is calculated using OCDFT and further characterized using the LIVVO approach.

Nuclear Excitation by Electronic Transition of U-235

NASA Astrophysics Data System (ADS)

Chodash, Perry

2017-01-01

Nuclear excitation by electronic transition (NEET) is a rare nuclear excitation that is theorized to exist in numerous isotopes. NEET is the inverse of bound internal conversion and occurs when an electronic transition couples to a nuclear transition causing the nucleus to enter an excited state. This process can only occur for isotopes with low-lying nuclear levels due to the requirement that the electronic and nuclear transitions have similar energies. One of the candidate isotopes for NEET, 235U, has been studied several times over the past 40 years and NEET of 235U has never been conclusively observed. These past experiments generated conflicting results with some experiments claiming to observe NEET of 235U and others setting limits for the NEET rate. If NEET of 235U were to occur, the uranium would be excited to its first excited nuclear state. The first excited nuclear state in 235U is only 76 eV, the second lowest known nuclear state. Additionally, the 76 eV state is a nuclear isomer that decays by internal conversion with a half-life of 26 minutes. In order to measure whether NEET occurs in 235U and at what rate, a uranium plasma was required. The plasma was generated using a Q-switched Nd:YAG laser outputting 789 mJ pulses of 1064 nm light. The laser light was focused onto uranium targets generating an intensity on target of order 1012 W/cm2. The resulting plasma was captured on a catcher plate and electrons emitted from the catcher plate were accelerated and focused onto a microchannel plate detector. Measurements performed using a variety of uranium targets spanning depleted uranium up to 99.4% enriched uranium did not observe a 26 minute decay. An upper limit for the NEET rate of 235U was determined. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. The U.S. DHS, UC Berkeley, the NNIS fellowship and the NSSC further supported this work.

Neuronal excitability level transition induced by electrical stimulation

NASA Astrophysics Data System (ADS)

Florence, G.; Kurths, J.; Machado, B. S.; Fonoff, E. T.; Cerdeira, H. A.; Teixeira, M. J.; Sameshima, K.

2014-12-01

In experimental studies, electrical stimulation (ES) has been applied to induce neuronal activity or to disrupt pathological patterns. Nevertheless, the underlying mechanisms of these activity pattern transitions are not clear. To study these phenomena, we simulated a model of the hippocampal region CA1. The computational simulations using different amplitude levels and duration of ES revealed three states of neuronal excitability: burst-firing mode, depolarization block and spreading depression wave. We used the bifurcation theory to analyse the interference of ES in the cellular excitability and the neuronal dynamics. Understanding this process would help to improve the ES techniques to control some neurological disorders.

Density of states and dynamical crossover in a dense fluid revealed by exponential mode analysis of the velocity autocorrelation function

NASA Astrophysics Data System (ADS)

Bellissima, S.; Neumann, M.; Guarini, E.; Bafile, U.; Barocchi, F.

2017-01-01

Extending a preceding study of the velocity autocorrelation function (VAF) in a simulated Lennard-Jones fluid [Phys. Rev. E 92, 042166 (2015), 10.1103/PhysRevE.92.042166] to cover higher-density and lower-temperature states, we show that the recently demonstrated multiexponential expansion method allows for a full account and understanding of the basic dynamical processes encompassed by a fundamental quantity as the VAF. In particular, besides obtaining evidence of a persisting long-time tail, we assign specific and unambiguous physical meanings to groups of exponential modes related to the longitudinal and transverse collective dynamics, respectively. We have made this possible by consistently introducing the interpretation of the VAF frequency spectrum as a global density of states in fluids, generalizing a solid-state concept, and by giving to specific spectral components, obtained through the VAF exponential expansion, the corresponding meaning of partial densities of states relative to specific dynamical processes. The clear identification of a high-frequency oscillation of the VAF with the near-top excitation frequency in the dispersion curve of acoustic waves is a neat example of the power of the method. As for the transverse mode contribution, its analysis turns out to be particularly important, because the multiexponential expansion reveals a transition marking the onset of propagating excitations when the density is increased beyond a threshold value. While this finding agrees with the recent literature debating the issue of dynamical crossover boundaries, such as the one identified with the Frenkel line, we can add detailed information on the modes involved in this specific process in the domains of both time and frequency. This will help obtain a still missing full account of transverse dynamics, in both its nonpropagating and propagating aspects which are linked through dynamical transitions depending on both the thermodynamic states and the excitation wave vectors.

Pump-probe photoelectron velocity-map imaging of autoionizing singly excited 4s{sup 1}4p{sup 6}np{sup 1}(n=7,8) and doubly excited 4s{sup 2}4p{sup 4}5s{sup 1}6p{sup 1} resonances in atomic krypton

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doughty, Benjamin; Haber, Louis H.; Leone, Stephen R.

2011-10-15

Pump-probe photoelectron velocity-map imaging, using 27-eV high-harmonic excitation and 786-nm ionization, is used to resolve overlapping autoionizing resonances in atomic krypton, obtaining two-photon photoelectron angular distributions (PADs) for singly and doubly excited states. Two features in the photoelectron spectrum are assigned to singly excited 4s{sup 1}4p{sup 6}np{sup 1} (n = 7,8) configurations and four features provide information about double excitation configurations. The anisotropy parameters for the singly excited 7p configuration are measured to be {beta}{sub 2} = 1.61 {+-} 0.06 and {beta}{sub 4} = 1.54 {+-} 0.16 while the 8p configuration gives {beta}{sub 2} = 1.23 {+-} 0.19 and {beta}{submore » 4} = 0.60 {+-} 0.15. These anisotropies most likely represent the sum of overlapping PADs from states of singlet and triplet spin multiplicities. Of the four bands corresponding to ionization of doubly excited states, two are assigned to 4s{sup 2}4p{sup 4}5s{sup 1}6p{sup 1} configurations that are probed to different J-split ion states. The two remaining doubly excited states are attributed to a previously observed, but unassigned, resonance in the vacuum-ultraviolet photoabsorption spectrum. The PADs from each of the double excitation states are also influenced by overlap from neighboring states that are not completely spectrally resolved. The anisotropies of the observed double excitation states are reported, anticipating future theoretical and experimental work to separate the overlapping PADs into the state resolved PADs. The results can be used to test theories of excited state ionization.« less

Excited-state dynamics of pentacene derivatives with stable radical substituents.

PubMed

Ito, Akitaka; Shimizu, Akihiro; Kishida, Noriaki; Kawanaka, Yusuke; Kosumi, Daisuke; Hashimoto, Hideki; Teki, Yoshio

2014-06-23

The excited-state dynamics of pentacene derivatives with stable radical substituents were evaluated in detail through transient absorption measurements. The derivatives showed ultrafast formation of triplet excited state(s) in the pentacene moiety from a photoexcited singlet state through the contributions of enhanced intersystem crossing and singlet fission. Detailed kinetic analyses for the transient absorption data were conducted to quantify the excited-state characteristics of the derivatives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observation of correlated electronic decay in expanding clusters triggered by near-infrared fields

PubMed Central

Schütte, B.; Arbeiter, M.; Fennel, T.; Jabbari, G.; Kuleff, A.I.; Vrakking, M.J.J.; Rouzée, A.

2015-01-01

When an excited atom is embedded into an environment, novel relaxation pathways can emerge that are absent for isolated atoms. A well-known example is interatomic Coulombic decay, where an excited atom relaxes by transferring its excess energy to another atom in the environment, leading to its ionization. Such processes have been observed in clusters ionized by extreme-ultraviolet and X-ray lasers. Here, we report on a correlated electronic decay process that occurs following nanoplasma formation and Rydberg atom generation in the ionization of clusters by intense, non-resonant infrared laser fields. Relaxation of the Rydberg states and transfer of the available electronic energy to adjacent electrons in Rydberg states or quasifree electrons in the expanding nanoplasma leaves a distinct signature in the electron kinetic energy spectrum. These so far unobserved electron-correlation-driven energy transfer processes may play a significant role in the response of any nano-scale system to intense laser light. PMID:26469997

Role of ion-pair states in the predissociation dynamics of Rydberg states of molecular iodine.

PubMed

von Vangerow, J; Bogomolov, A S; Dozmorov, N V; Schomas, D; Stienkemeier, F; Baklanov, A V; Mudrich, M

2016-07-28

Using femtosecond pump-probe ion imaging spectroscopy, we establish the key role of I(+) + I(-) ion-pair (IP) states in the predissociation dynamics of molecular iodine I2 excited to Rydberg states. Two-photon excitation of Rydberg states lying above the lowest IP state dissociation threshold (1st tier) is found to be followed by direct parallel transitions into IP states of the 1st tier asymptotically correlating to a pair of I ions in their lowest states I(+)((3)P2) + I(-)((1)S0), of the 2nd tier correlating to I(+)((3)P0) + I(-)((1)S0), and of the 3rd tier correlating to I(+)((1)D2) + I(-)((1)S0). Predissociation via the 1st tier proceeds presumably with a delay of 1.6-1.7 ps which is close to the vibrational period in the 3rd tier state (3rd tier-mediated process). The 2nd tier IP state is concluded to be the main precursor for predissociation via lower lying Rydberg states proceeding with a characteristic time of 7-8 ps and giving rise to Rydberg atoms I(5s(2)5p(4)6s(1)). The channel generating I((2)P3/2) + I((2)P1/2) atoms with total kinetic energy corresponding to one-photon excitation is found to proceed via a pump - dump mechanism with dramatic change of angular anisotropy of this channel as compared with earlier nanosecond experiments.

Observation and control of coherent torsional dynamics in a quinquethiophene molecule.

PubMed

Cirmi, Giovanni; Brida, Daniele; Gambetta, Alessio; Piacenza, Manuel; Della Sala, Fabio; Favaretto, Laura; Cerullo, Giulio; Lanzani, Guglielmo

2010-07-28

By applying femtosecond pump-probe spectroscopy to a substituted quinquethiophene molecule in solution, we observe in the time domain the coherent torsional dynamics that drives planarization of the excited state. Our interpretation is based on numerical modeling of the ground and excited state potential energy surfaces and simulation of wavepacket dynamics, which reveals two symmetric excited state deactivation pathways per oscillation period. We use the acquired knowledge on torsional dynamics to coherently control the excited state population with a pump-dump scheme, exploiting the non-stationary Franck-Condon overlap between ground and excited states.

Excited-State Effective Masses in Lattice QCD

DOE Office of Scientific and Technical Information (OSTI.GOV)

George Fleming, Saul Cohen, Huey-Wen Lin

2009-10-01

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

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

NASA Astrophysics Data System (ADS)

Szczepanik, Beata

2015-11-01

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

Effects of bias and temperature on the intersubband absorption in very long wavelength GaAs/AlGaAs quantum well infrared photodetectors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, X. H.; Zhou, X. H., E-mail: xhzhou@mail.sitp.ac.cn; Li, N.

2014-03-28

The temperature- and bias-dependent photocurrent spectra of very long wavelength GaAs/AlGaAs quantum well infrared photodetectors (QWIPs) are studied using spectroscopic measurements and corresponding theoretical calculations. It is found that the peak response wavelength will shift as the bias and temperature change. Aided by band structure calculations, we propose a model of the double excited states and explain the experimental observations very well. In addition, the working mechanisms of the quasi-bound state confined in the quantum well, including the processes of tunneling and thermionic emission, are also investigated in detail. We confirm that the first excited state, which belongs to themore » quasi-bound state, can be converted into a quasi-continuum state induced by bias and temperature. These obtained results provide a full understanding of the bound-to-quasi-bound state and the bound-to-quasi-continuum state transition, and thus allow for a better optimization of QWIPs performance.« less

Measurements of Excitation Functions and Line Polarizations for Electron Impact Excitation of the n = 2, 3 States of Atomic Hydrogen in the Energy Range 11 - 2000 eV

NASA Technical Reports Server (NTRS)

James, G. K.; Ajello, J. M.; Kanik, I.; Slevin, J.; Franklin, B.; Shemansky, D.

1993-01-01

The electron-atomic hydrogen scattering system is an important testing ground for theoretical models and has received a great deal of attention from experimentalists and theoreticians alike over the years. A complete description of the excitation process requires a knowledge of many different parameters, and experimental measurements of these parameters have been performed in various laboratories around the world. As far as total cross section data are concerned it has been noted that the discrepancy between the data of Long et al. and Williams for n = 2 excitations needs to be resolved in the interests of any further refinement of theory. We report new measurements of total cross sections and atomic line polarizations for both n=2 and n=3 excitations at energies from threshold to 2000 eV...

Realization of reliable solid-state quantum memory for photonic polarization qubit.

PubMed

Zhou, Zong-Quan; Lin, Wei-Bin; Yang, Ming; Li, Chuan-Feng; Guo, Guang-Can

2012-05-11

Faithfully storing an unknown quantum light state is essential to advanced quantum communication and distributed quantum computation applications. The required quantum memory must have high fidelity to improve the performance of a quantum network. Here we report the reversible transfer of photonic polarization states into collective atomic excitation in a compact solid-state device. The quantum memory is based on an atomic frequency comb (AFC) in rare-earth ion-doped crystals. We obtain up to 0.999 process fidelity for the storage and retrieval process of single-photon-level coherent pulse. This reliable quantum memory is a crucial step toward quantum networks based on solid-state devices.

Double-pulse dichromatic photolysis of fac-CIRe(CO){sub 3}L{sub 2} (L=4-phenylpyridine or 4-cyanopyridine): Photohomolysis of Re-L bonds insuced by irradiation of photochemically unreactive charge transfer states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feliz, M.; Ferraudi, G.

1992-04-02

Photochemical reactions of fac-ClRe(CO){sub 3}L{sub 2} (L=4-phenylpyridine or 4-cyanopyridine), were investigated by sequential biphotonic excitations: one laser flash was used for the preparation of the compounds in the lowest lying MLCT (Re{r_arrow}) state and another flash for the irradiation of the compounds in such excited states. These photolyses led to photodecompostions into CIRe(CO){sub 3}L{sup +} and L{sup .} in a charge transfer state placed 40 Kk above ground state. Quantum yields determined or various excitation energies show that not all the excited state populated in monophotonic excitations can be reached under the sequential biphotonic regime. Therefore, photogeneration of the biradicalmore » intermediate, ClRe(CO){sub 3}L{sup +} and L{sup .}, from ligand-centered states has not been detected in these experiments. Results from monophotonic and biphotonic excitations have been used for a semiquantitative mapping of the excited-state potential surfaces. 41 refs., 6 figs.« less

Theoretical description of the 2A/double prime/ and 2A/prime/ states of the peroxyformyl radical. [for air pollution and Mars atmospheric studies

NASA Technical Reports Server (NTRS)

Winter, N. W.; Goddard, W. A., III; Bender, C. F.

1975-01-01

Simple orbital ideas are used to describe the lowest two states of the peroxyformyl radical, and ab initio Hartree-Fock calculations in these states are reported. It is found that both states may be formed exothermically by association of O2 and HCO in their ground states; however, the excited state may decompose readily to OH and CO2. The possible role of such processes in oxidation of aldelydes is discussed.

Computational Photophysics in the Presence of an Environment

NASA Astrophysics Data System (ADS)

Nogueira, Juan J.; González, Leticia

2018-04-01

Most processes triggered by ultraviolet (UV) or visible (vis) light in nature take place in complex biological environments. The first step in these photophysical events is the excitation of the absorbing system or chromophore to an electronically excited state. Such an excitation can be monitored by the UV-vis absorption spectrum. A precise calculation of the UV-vis spectrum of a chromophore embedded in an environment is a challenging task that requires the consideration of several ingredients, besides an accurate electronic-structure method for the excited states. Two of the most important are an appropriate description of the interactions between the chromophore and the environment and accounting for the vibrational motion of the whole system. In this contribution, we review the most common theoretical methodologies to describe the environment (including quantum mechanics/continuum and quantum mechanics/molecular mechanics models) and to account for vibrational sampling (including Wigner sampling and molecular dynamics). Further, we illustrate in a series of examples how the lack of these ingredients can lead to a wrong interpretation of the electronic features behind the UV-vis absorption spectrum.

Vibrational energy flow in photoactive yellow protein revealed by infrared pump-visible probe spectroscopy.

PubMed

Nakamura, Ryosuke; Hamada, Norio

2015-05-14

Vibrational energy flow in the electronic ground state of photoactive yellow protein (PYP) is studied by ultrafast infrared (IR) pump-visible probe spectroscopy. Vibrational modes of the chromophore and the surrounding protein are excited with a femtosecond IR pump pulse, and the subsequent vibrational dynamics in the chromophore are selectively probed with a visible probe pulse through changes in the absorption spectrum of the chromophore. We thus obtain the vibrational energy flow with four characteristic time constants. The vibrational excitation with an IR pulse at 1340, 1420, 1500, or 1670 cm(-1) results in ultrafast intramolecular vibrational redistribution (IVR) with a time constant of 0.2 ps. The vibrational modes excited through the IVR process relax to the initial ground state with a time constant of 6-8 ps in parallel with vibrational cooling with a time constant of 14 ps. In addition, upon excitation with an IR pulse at 1670 cm(-1), we observe the energy flow from the protein backbone to the chromophore that occurs with a time constant of 4.2 ps.

Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN) 4] 2-

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.

The excited state dynamics of solvated [Fe(bpy)(CN) 4] 2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN) 4] 2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile. Here, in the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN) 4] 2-more » in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet ( 3MC) character, unlike other reported six-coordinate Fe(II)-centered coordination compounds, which form MC quintet ( 5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN) 4] 2- allows us to infer the influence of the solvent on the electronic structure of the complex. Lastly, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.« less

Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN) 4] 2-

DOE PAGES

Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.; ...

2018-01-19

The excited state dynamics of solvated [Fe(bpy)(CN) 4] 2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN) 4] 2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile. Here, in the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN) 4] 2-more » in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet ( 3MC) character, unlike other reported six-coordinate Fe(II)-centered coordination compounds, which form MC quintet ( 5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN) 4] 2- allows us to infer the influence of the solvent on the electronic structure of the complex. Lastly, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.« less

Solvent effects in time-dependent self-consistent field methods. II. Variational formulations and analytical gradients

DOE PAGES

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

2015-08-06

This study describes variational energy expressions and analytical excited state energy gradients for time-dependent self-consistent field methods with polarizable solvent effects. Linear response, vertical excitation, and state-specific solventmodels are examined. Enforcing a variational ground stateenergy expression in the state-specific model is found to reduce it to the vertical excitation model. Variational excited state energy expressions are then provided for the linear response and vertical excitation models and analytical gradients are formulated. Using semiempiricalmodel chemistry, the variational expressions are verified by numerical and analytical differentiation with respect to a static external electric field. Lastly, analytical gradients are further tested by performingmore » microcanonical excited state molecular dynamics with p-nitroaniline.« less

Laser-Induced-Emission Spectroscopy In Hg/Ar Discharge

NASA Technical Reports Server (NTRS)

Maleki, Lutfollah; Blasenheim, Barry J.; Janik, Gary R.

1992-01-01

Laser-induced-emission (LIE) spectroscopy used to probe low-pressure mercury/argon discharge to determine influence of mercury atoms in metastable 6(Sup3)P(Sub2) state on emission of light from discharge. LIE used to study all excitation processes affected by metastable population, including possible effects on excitation of atoms, ions, and buffer gas. Technique applied to emissions of other plasmas. Provides data used to make more-accurate models of such emissions, exploited by lighting and laser industries and by laboratories studying discharges. Also useful in making quantitative measurements of relative rates and cross sections of direct and two-step collisional processes involving metastable level.

Fluorescence anisotropy of indole molecules under two-photon excitation in the spectral range of 485-510 nm

NASA Astrophysics Data System (ADS)

Sasin, M. E.; Tushkanov, V. I.; Smolin, A. G.; Vasyutinskii, O. S.

2017-10-01

Decay of polarized fluorescence in indole dissolved in propylene glycol under two-photon excitation by femtosecond laser pulses in the wavelength range of 485-510 nm has been studied. It is shown that under the experimental conditions used the fluorescence decay signal can be well described by a single excited state lifetime τf and a single rotation diffusion time τrot. By processing the data obtained, the times τf and τrot as well as anisotropy parameter r 0 characterizing the symmetry of two-photon excitation of indole molecules have been determined. Decreasing of the anisotropy parameter r0 down to zero under two-photon excitation energy higher than 5.1 eV has been observed. Interpretation of the obtained results have been done on the basis of ab initio quantum-mechanical computations. A model of energy relaxation under the condition of twophoton excitation of indole in a polar solvent has been discussed.

Coulomb Excitation of 78,80Se and the radioactive 84Se (N = 50) isotopes

NASA Astrophysics Data System (ADS)

Galindo-Uribarri, A.; Padilla-Rodal, E.; Garcia-Ruiz, R. F.; Allmond, J. M.; Batchelder, J. C.; Beene, J. R.; Lagergren, K. B.; Mueller, P. E.; Radford, D. C.; Stracener, D. W.; Urrego-Blanco, J. P.; Varner, R. L.; Yu, C.-H.

2011-10-01

Coulomb excitation is a purely electromagnetic excitation process of nuclear states due to the Coulomb field of two colliding nuclei. It is a very precise tool to measure excitation probabilities and provide insight on the collectivity of nuclear excitations and in particular on nuclear shapes. We have measured the B(E2) value of various nuclei in the mass A ~ 80 region using particle-gamma coincidences with the HyBall and Clarion arrays at HRIBF. The Coulomb excitation of various projectile-target combinations (ASe on 12C, 24Mg, 27Al and 50Ti) allow the use of consistency cross checks and the systematic study of isotopic and isotonic chains using both stable and radioactive nuclei under almost identical experimental conditions.We present new results for 78Se, 80Se and the radioactive nucleus 84Se (N = 50). Research sponsored by the Office of Nuclear Physics, U.S. Department of Energy and CONACyT Grant 103366.

OPTOELECTRONICS, FIBER OPTICS, AND OTHER ASPECTS OF QUANTUM ELECTRONICS: Influence of the Rayleigh backscattering on the mode composition of radiation in multimode graded-index waveguides with a quadratic refractive-index profile

NASA Astrophysics Data System (ADS)

Esayan, G. L.; Krivoshlykov, S. G.

1989-08-01

A method of coherent states is used to describe the process of Rayleigh scattering in a multimode graded-index waveguide with a quadratic refractive-index profile. Explicit expressions are obtained for the coefficients representing excitation of Gaussian-Hermite backscattering modes in two cases of practical importance: excitation of a waveguide by an extended noncoherent light source and selective excitation of different modes at the entry to a waveguide. An analysis is also made of the coefficients of coupling between forward and backward modes. Explicit expressions for the coefficients representing capture of backscattered radiation by a waveguide are obtained for two special cases of excitation (extended light source and zeroth mode).

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Efficiency of passage of highly vibrationally excited CF3I molecules in a beam through a cooled converging hollow truncated cone

NASA Astrophysics Data System (ADS)

Makarov, Grigorii N.; Petin, A. N.

2006-09-01

The passage of CF3I molecules excited by high-intensity IR laser radiation to high vibrational states (with energy Ev >= 0.3-1.5 eV) and unexcited molecules in a pulsed beam through a converging truncated hollow metal cone cooled to Ts approx 80-85 K and mounted at an angle to the beam axis is studied. It is found that the excited molecules pass much more readily through the cone than the unexcited (vibrationally cold) molecules. This opens the possibility for studying the processes of energy transfer and redistribution over a cold surface covered by molecular (cluster) layers, and for separating excited and unexcited molecules in a beam.

Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

PubMed

Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

2017-12-21

Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

Stationary spectroscopy of biotissues in vivo: Fluorescent studies of some pathological states

NASA Astrophysics Data System (ADS)

Giraev, K. M.; Ashurbekov, N. A.; Medzhidov, R. T.

2003-11-01

The stationary spectra of autofluorescence, along with the reflection coefficient at the wavelength of excitation, are measured in vivo for some stomach tissues in the case of different pathological states (dysplasia, superficial gastritis, and cancer) using a nitrogen laser as the source of excitation (λrad=337.1 nm). The fluorescence spectra obtained are decomposed into Gaussian-Lorentzian components. It is found that, in development of dysplasia and tumor processes, at least seven groups of fluorophores can be distinguished that form the entire emission spectrum. The ratio between the fluorescence intensities of flavins and NAD(P)H is determined and the degree of respiratory activity of cells estimated for the states considered. The quantum yields of fluorescence of the biotissues under investigation are estimated.

Local CC2 response method based on the Laplace transform: analytic energy gradients for ground and excited states.

PubMed

Ledermüller, Katrin; Schütz, Martin

2014-04-28

A multistate local CC2 response method for the calculation of analytic energy gradients with respect to nuclear displacements is presented for ground and electronically excited states. The gradient enables the search for equilibrium geometries of extended molecular systems. Laplace transform is used to partition the eigenvalue problem in order to obtain an effective singles eigenvalue problem and adaptive, state-specific local approximations. This leads to an approximation in the energy Lagrangian, which however is shown (by comparison with the corresponding gradient method without Laplace transform) to be of no concern for geometry optimizations. The accuracy of the local approximation is tested and the efficiency of the new code is demonstrated by application calculations devoted to a photocatalytic decarboxylation process of present interest.

Theory of raman scattering from molecules adsorbed at semiconductor surfaces

NASA Astrophysics Data System (ADS)

Ueba, H.

1983-09-01

A theory is presented to calculate the Raman polarizability of an adsorbed molecule at a semiconductor surface, where the electronic excitation in the molecular site interacts with excitons (elementary excitations in the semiconductor) through non-radiative energy transfer between them, in an intermediate state in the Raman scattering process. The Raman polarizability thus calculated is found to exhibit a peak at the energy corresponding to a resonant excitation of excitons, thereby suggesting the possibility of surface enhanced Raman scattering on semiconductor surfaces. The mechanism studied here can also give an explanation of a recent observation of the Raman excitation profiles of p-NDMA and p-DMAAB adsorbed on ZnO or TiO 2, where those profiles were best described by assuming a resonant intermediate state of the exciton transition in the semiconductors. It is also demonstrated that in addition to vibrational Raman scattering, excitonic Raman scattering of adsorbed molecules will occur in the coupled molecule-semiconductor system, where the molecular returns to its ground electronic state by leaving an exciton in the semiconductor. A spectrum of the excitonic Raman scattering is expected to appear in the background of the vibrational Raman band and to be characterized by the electronic structure of excitons. A desirable experiment is suggested for an examination of the theory.

Vibronic coupling in the excited-states of carotenoids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miki, Takeshi; Buckup, Tiago; Krause, Marie S.

2016-01-01

The ultrafast femtochemistry of carotenoids is governed by the interaction between electronic excited states, which has been explained by the relaxation dynamics within a few hundred femtoseconds from the lowest optically allowed excited state S 2to the optically dark state S 1.

Vibronic coupling in the excited-states of carotenoids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miki, Takeshi; Buckup, Tiago; Krause, Marie S.

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 S 2to the optically dark state S 1.

σ -SCF: A Direct Energy-targeting Method To Mean-field Excited States

NASA Astrophysics Data System (ADS)

Ye, Hongzhou; Welborn, Matthew; Ricke, Nathan; van Voorhis, Troy

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 Δ-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, σ-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 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 Δ-SCF solutions that are otherwise hardly accessible by the usual non-aufbau configuration initial guess. We present results for this new method for small atoms (He, Be) and molecules (H2, HF). This work was funded by a Grant from NSF (CHE-1464804).

Initial decomposition mechanism for the energy release from electronically excited energetic materials: FOX-7 (1,1-diamino-2,2-dinitroethene, C{sub 2}H{sub 4}N{sub 4}O{sub 4})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

Decomposition of the energetic material FOX-7 (1,1-diamino-2,2-dinitroethylene, C{sub 2}H{sub 4}N{sub 4}O{sub 4}) is investigated both theoretically and experimentally. The NO molecule is observed as an initial decomposition product subsequent to electronic excitation. The observed NO product is rotationally cold (<35 K) and vibrationally hot (2800 K). The initial decomposition mechanism is explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. Electronically excited S{sub 2} FOX-7 can radiationlessly relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{submore » 1}/S{sub 0}){sub CI} conical intersections and undergo a nitro-nitrite isomerization to generate NO product on the S{sub 0} state. The theoretically predicted mechanism is consistent with the experimental results. As FOX-7 decomposes on the ground electronic state, thus, the vibrational energy of the NO product from FOX-7 is high. The observed rotational energy distribution for NO is consistent with the final transition state structure on the S{sub 0} state. Ground state FOX-7 decomposition agrees with previous work: the nitro-nitrite isomerization has the lowest average energy barrier, the C–NH{sub 2} bond cleavage is unlikely under the given excitation conditions, and HONO formation on the ground state surface is energy accessible but not the main process.« less

Coherent quantum depletion of an interacting atom condensate

PubMed Central

Kira, M.

2015-01-01

Sufficiently strong interactions promote coherent quantum transitions in spite of thermalization and losses, which are the adversaries of delicate effects such as reversibility and correlations. In atomic Bose–Einstein condensates (BECs), strong atom–atom interactions can eject atoms from the BEC to the normal component, yielding quantum depletion instead of temperature depletion. A recent experiment has already been verified to overcome losses. Here I show that it also achieves coherent quantum-depletion dynamics in a BEC swept fast enough from weak to strong atom–atom interactions. The elementary coherent process first excites the normal component into a liquid state that evolves into a spherical shell state, where the atom occupation peaks at a finite momentum to shield 50% of the BEC atoms from annihilation. The identified coherent processes resemble ultrafast semiconductor excitations expanding the scope of BEC explorations to many-body non-equilibrium studies. PMID:25767044

Energy-transfer processes in neon-hydrogen mixtures excited by electron beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morozov, A.; Kruecken, R.; Ulrich, A.

2005-12-15

Energy- and charge-transfer processes in neon-hydrogen mixtures (500-1400 hPa neon and 0.001-3 hPa hydrogen partial pressures) excited by a pulsed low-energy ({approx}10 keV) electron beam were investigated using time-resolved spectroscopy. Time spectra of the hydrogen Lyman-{alpha} line, neon excimer emission (second continuum), and neon atomic lines (3p-3s transitions) were recorded. The time-integrated intensity of the Lyman-{alpha} emission was measured for the same range of gas mixtures. It is shown that direct energy transfer from Ne{sub 2}* excimers and neon atoms in the four lowest excited states as well as recombination of H{sub 3}{sup +} ions are the main channels populatingmore » atomic hydrogen in the n=2 state. A rate constant of (4.2{+-}1.4)x10{sup -11} cm{sup 3} s{sup -1} was obtained for the charge transfer from Ne{sub 2}{sup +} ions to molecular hydrogen. A lower limit for the depopulation rate constant of Ne{sub 2}* excimers by molecular hydrogen (combination of energy transfer and ionization) was found to be 1.0x10{sup -10} cm{sup 3} s{sup -1}.« less

Correlated electronic decay in expanding clusters triggered by intense XUV pulses from a Free-Electron-Laser

PubMed Central

Oelze, Tim; Schütte, Bernd; Müller, Maria; Müller, Jan P.; Wieland, Marek; Frühling, Ulrike; Drescher, Markus; Al-Shemmary, Alaa; Golz, Torsten; Stojanovic, Nikola; Krikunova, Maria

2017-01-01

Irradiation of nanoscale clusters and large molecules with intense laser pulses transforms them into highly-excited non- equilibrium states. The dynamics of intense laser-cluster interaction is encoded in electron kinetic energy spectra, which contain signatures of direct photoelectron emission as well as emission of thermalized nanoplasma electrons. In this work we report on a so far not observed spectrally narrow bound state signature in the electron kinetic energy spectra from mixed Xe core - Ar shell clusters ionized by intense extreme-ultraviolet (XUV) pulses from a free-electron-laser. This signature is attributed to the correlated electronic decay (CED) process, in which an excited atom relaxes and the excess energy is used to ionize the same or another excited atom or a nanoplasma electron. By applying the terahertz field streaking principle we demonstrate that CED-electrons are emitted at least a few picoseconds after the ionizing XUV pulse has ended. Following the recent finding of CED in clusters ionized by intense near-infrared laser pulses, our observation of CED in the XUV range suggests that this process is of general relevance for the relaxation dynamics in laser produced nanoplasmas. PMID:28098175

Surface states in the photoionization of high-quality CdSe core/shell nanocrystals.

PubMed

Li, Shu; Steigerwald, Michael L; Brus, Louis E

2009-05-26

We use electric force microscopy (EFM) to study single nanocrystal photoionization in two classes of high-quality nanocrystals whose exciton luminescence quantum yields approach unity in solution. The CdSe/CdS/ZnS core/shell nanocrystals do not photoionize, while the CdSe/CdS nanocrystals do show substantial photoionization. This verifies the theoretical prediction that the ZnS shell confines the excited electron within the nanocrystal. Despite the high luminescence quantum yield, photoionization varies substantially among the CdSe/CdS nanocrystals. We have studied the nanocrystal photoionization with both UV (396 nm) and green (532 nm) light, and we have found that the magnitude of the charge due to photoionization per absorbed photon is greater for UV excitation than for green excitation. A fraction of the photoionization occurs directly via a "hot electron" process, using trap states that are either on the particle surface, within the ligand sphere, or within the silicon oxide layer. This must occur without relaxation to the thermalized, lowest-energy, emitting exciton. We discuss the occurrence of hot carrier processes that are common to photoionization, luminescence blinking, and the fast transient optical absorption that is associated with multiple exciton generation MEG studies.