WorldWideScience

Sample records for excited state charge

  1. Charge-displacement analysis for excited states

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-02-07

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

  2. Excited state intramolecular charge transfer reaction in 4-(1 ...

    Indian Academy of Sciences (India)

    Administrator

    Abstract. Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several.

  3. Excited state intramolecular charge transfer reaction in 4-(1 ...

    Indian Academy of Sciences (India)

    Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several other ...

  4. Excited State Atom-Ion Charge-Exchange

    Science.gov (United States)

    Li, Ming; Makrides, Constantinos; Petrov, Alexander; Kotochigova, Svetlana

    2017-04-01

    We theoretically investigate the exothermic charge-exchange reaction between an excited atom and a ground-state positive ion. In particular, we focus on MOT-excited Ca*(4s4p 1P) atoms colliding with ground-state Yb+ ions, which are under active study by the experimental group of E. Hudson at UCLA. Collisions between an excited atom and an ion are guided by two major contributions to the long-range interaction potentials, the induction C4 /R4 and charge-quadrupole C3 /R3 potentials, and their coupling by the electron-exchange interaction. Our model of these forces leads to close-coupling equations for multiple reaction channels. We find several avoided crossings between the potentials that couple to the nearby asymptotic limits of Yb*+Ca+, some of which can possibly provide large charge exchange rate coefficients above 10-10 cm3 / s. We acknowledge support from the US Army Research Office, MURI Grants W911NF-14-1-0378 and the US National Science Foundation, Grant PHY-1619788.

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

    DEFF Research Database (Denmark)

    Bohr, Henrik; Malik, F. Bary

    2013-01-01

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

  6. Excited state intramolecular charge transfer reaction of 4 ...

    Indian Academy of Sciences (India)

    Administrator

    We will use the twisted intramolecular charge transfer (TICT) model to explain the photo-induced charge transfer ..... full width at half maxima (Γ) are expressed in 103 cm–1. –ΔGr are in kJ mol–1 units. PFH: per- ..... incorrect values of thermodynamic and kinetic parameters calculated using these reaction times, leading to ...

  7. Excited-state dynamics of hybrid multichromophoric systems: toward an excitation wavelength control of the charge separation pathways.

    Science.gov (United States)

    Banerji, Natalie; Duvanel, Guillaume; Perez-Velasco, Alejandro; Maity, Santanu; Sakai, Naomi; Matile, Stefan; Vauthey, Eric

    2009-07-23

    The photophysical properties of two hybrid multichromophoric systems consisting of an oligophenylethynyl (OPE) scaffold decorated by 10 red or blue naphthalene diimides (NDIs) have been investigated using femtosecond spectroscopy. Ultrafast charge separation was observed with both red and blue systems. However, the nature of the charge-separated state and its lifetime were found to differ substantially. For the red system, electron transfer occurs from the OPE scaffold to an NDI unit, independently of whether the OPE or an NDI is initially excited. However, charge separation upon OPE excitation is about 10 times faster, and takes place with a 100 fs time constant. The average lifetime of the ensuing charge-separated state amounts to about 650 ps. Charge separation in the blue system depends on which of the OPE scaffold or an NDI is excited. In the first case, an electron is transferred from the OPE to an NDI and the hole subsequently shifts to another NDI unit, whereas in the second case symmetry-breaking charge separation between two NDI units occurs. Although the charges are located on two NDIs in both cases, different recombination dynamics are observed. This is explained by the location of the ionic NDI moieties that depends on the charge separation pathway, hence on the excitation wavelength. The very different dynamics observed with red and blue systems can be accounted for by the oxidation potentials of the respective NDIs that are higher and lower than that of the OPE scaffold. Because of this, the relative energies of the two charge-separated states (hole on the OPE or an NDI) are inverted.

  8. Excited state intramolecular charge transfer reaction in non-aqueous ...

    Indian Academy of Sciences (India)

    concentration dependent reaction rate constant of a. TICT reaction already measured in bulk electrolyte solutions.44–46 Here, we report such a study where photo-induced intramolecular charge transfer reaction has been investigated in AOT/heptane non-aqueous reverse micelles at different Ws values, and also in.

  9. Excited state charge transfer reaction in (mixed solvent + electrolyte ...

    Indian Academy of Sciences (India)

    charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) in two sets of mixed solvents, (1-propanol + ethyl acetate) and (propylene ...... Harun Al Rasid Gazi and Ranjit Biswas. PrOH+EA. Normalized F.I.. 0. 1. Normalized F.I.. 0. 1. -3. 0. 3. 3000. 4000. 5000. 6000. Residual. -3. 0. 3. Residual. -3. 0. 3. Time(ps). 3000. 4000.

  10. Supporting Information for the article entitled, “Excited State Charge ...

    Indian Academy of Sciences (India)

    Supporting Information for the article entitled, “Excited State Charge Transfer Reaction in (Mixed Solvent + Electrolyte) Systems: Role of Reactant-Solvent and ... S2: Composition dependence of the reaction time (, upper panels) and long time ( , lower panels) constants obtained from bi-exponential fit of the collected LE ...

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

    KAUST Repository

    Whited, Matthew T.

    2012-01-01

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

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

    DEFF Research Database (Denmark)

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

    2014-01-01

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

  13. Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

    Energy Technology Data Exchange (ETDEWEB)

    Van Tassle, Aaron Justin [Univ. of California, Berkeley, CA (United States)

    2006-01-01

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

  14. Dynamics of charge-transfer excited states relevant to photochemical energy conversion

    Energy Technology Data Exchange (ETDEWEB)

    Lim, E.C.

    1991-11-01

    The primary objective of the research program is to gain a fundamental understanding of the factors governing the efficiency of excited-state charge transfer CT interactions between two chromophores that are brought together in close proximity, either by a very short covalent linkage or by ground-state complex formation. CT and van der Walls (vdW), interactions in covalently bonded bichromophoric compounds in condensed phase, as well as those in vdW complexes in supersonic jets, are being investigated using laser-based techniques under a variety of experimental conditions. This progress report is divided into three parts, according to the class of molecular systems and the phase (liquid vs. gas) in which the excited-state interactions are probed. The first is concerned with the excited states of bridged diaryl compounds in the condensed phase. The second involves the excited states of vdW complexes in supersonic jets. Finally, the third, is concerned with the excited states of electron donor-acceptor (EDA) systems in both the condensed phase and supersonic jets. In each of these studies, we are concerned with the interchromophore interactions ranging from weak vdW forces to strong CT forces, and the factors determining whether the interaction forces are weak or strong in related molecules.

  15. Charge-transfer excited states in aqueous DNA: Insights from many-body Green's function theory.

    Science.gov (United States)

    Yin, Huabing; Ma, Yuchen; Mu, Jinglin; Liu, Chengbu; Rohlfing, Michael

    2014-06-06

    Charge-transfer (CT) excited states play an important role in the excited-state dynamics of DNA in aqueous solution. However, there is still much controversy on their energies. By ab initio many-body Green's function theory, together with classical molecular dynamics simulations, we confirm the existence of CT states at the lower energy side of the optical absorption maximum in aqueous DNA as observed in experiments. We find that the hydration shell can exert strong effects (∼1  eV) on both the electronic structure and CT states of DNA molecules through dipole electric fields. In this case, the solvent cannot be simply regarded as a macroscopic screening medium as usual. The influence of base stacking and base pairing on the CT states is also discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-01-01

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

  17. Dynamics of charge-transfer excited states relevant to photochemical energy conversion

    Energy Technology Data Exchange (ETDEWEB)

    Lim, E.C.

    1993-01-01

    A systematic study of intramolecular photoassociation and photoinduced charge transfer (CT) was initiated in bichromophoric systems of M-X-M, where two identical aromatic hydrocarbons M are joined by X=CH[sub 2], O, NH, etc. Dinaphthylamines, dinaphthylethers, and dinaphthylmethanes in nonpolar solvents form triplet excimers, following inter system crossing of singlets to the triplet manifold; in polar solvents, the molecule forms an intramolecular CT state. The interchromophore interaction study was extended to N-phenyl-2-naphthylamine. The lowest excited singlet states of the dinaphthylamines were studied by semiempirical quantum chemical methods. Exciplex formation was studied in excited states of jet-cooled van der Waals complexes, such as fluorene/substituted benzenes and 1-cyanonaphthalene-aliphatic amines.

  18. Tracking the charge and spin dynamics of electronic excited states in inorganic complexes

    Science.gov (United States)

    Gaffney, Kelly

    2015-03-01

    Inorganic complexes have many advantageous properties for solar energy applications, including strong visible absorption and photocatalytic activity. Whether used as a photocatalyst or a photosensitizer, the lifetime of electronic excited states and the earth abundance of the molecular components represent a key property for solar energy applications. These dual needs have undermined the usefulness of many coordination compounds. Isoelectronic iron and ruthenium based complexes represent a clear example. Ru-polypyridal based molecules have been the workhorse of solar energy related research and dye sensitized solar cells for decades, but the replacement of low abundance Ru with Fe leads to million-fold reductions in metal to ligand charge transfer (MLCT) excited state lifetimes. Understanding the origin of this million-fold reduction in lifetime and how to control excited state relaxation in 3d-metal complexes motivates the work I will discuss. We have used the spin sensitivity of hard x-ray fluorescence spectroscopy and the intense femtosecond duration pulses generated by the LCLS x-ray laser to probe the spin dynamics in a series of electronically excited [Fe(CN)6-2N(2,2'-bipyridine)N]2 N - 4 complexes, with N = 1-3. These femtosecond resolution measurements demonstrate that modification of the solvent and ligand environment can lengthen the MLCT excited state lifetime by more than two orders of magnitude. They also verify the role of triplet ligand field excited states in the spin crossover dynamics from singlet to quintet spin configurations. Work supported by the AMOS program within the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy.

  19. Excited states

    CERN Document Server

    Lim, Edward C

    1974-01-01

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

  20. Assignment of the Charge-Transfer Excited States of Bis(N-Heterocyclic) Complexes of Copper(I)

    Science.gov (United States)

    1989-03-21

    Excited States of Bis (N-Heterocyclic) Complexes of Copper ( I) 12 PERSONAL AUTHOR(S( W. L. Parker and G. A. Crosby 3a 7YPE OF REPORT i b ’!ME COVERED ~ aDATE...Assignment of the Charge-Transfer Excited States of Bis (N-Heterocyclic) Complexes of Copper (I) by W. L. Parker and G. A. Crosby Prepared for Publication in...IHmited. Assignment of the Charge-Transfer Excited States of Bis (N-Heterocycl ic) Complexes of Copper (I) W. L. Parker and G. A. Crosby* Chemical

  1. Generation of excited coherent states for a charged particle in a uniform magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Mojaveri, B., E-mail: bmojaveri@azaruniv.ac.ir [Department of Physics, Azarbaijan Shahid Madani University, P.O. Box 51745-406, Tabriz (Iran, Islamic Republic of); Dehghani, A., E-mail: a-dehghani@tabrizu.ac.ir, E-mail: alireza.dehghani@gmail.com [Department of Physics, Payame Noor University, P.O. Box 19395-3697, Tehran (Iran, Islamic Republic of)

    2015-04-15

    We introduce excited coherent states, |β,α;nгЂ‰≔a{sup †n}|β,αгЂ‰, where n is an integer and states |β,αгЂ‰ denote the coherent states of a charged particle in a uniform magnetic field. States |β,αгЂ‰ minimize the Schrödinger-Robertson uncertainty relation while having the nonclassical properties. It has been shown that the resolution of identity condition is realized with respect to an appropriate measure on the complex plane. Some of the nonclassical features such as sub-Poissonian statistics and quadrature squeezing of these states are investigated. Our results are compared with similar Agarwal’s type photon added coherent states (PACSs) and it is shown that, while photon-counting statistics of |β,α,nгЂ‰ are the same as PACSs, their squeezing properties are different. It is also shown that for large values of |β|, while they are squeezed, they minimize the uncertainty condition. Additionally, it has been demonstrated that by changing the magnitude of the external magnetic field, B{sub ext}, the squeezing effect is transferred from one component to another. Finally, a new scheme is proposed to generate states |β,α;nгЂ‰ in cavities. .

  2. Charge-Transfer Dynamics in the Lowest Excited State of a Pentacene–Fullerene Complex: Implications for Organic Solar Cells

    KAUST Repository

    Joseph, Saju

    2017-10-02

    We characterize the dynamic nature of the lowest excited state in a pentacene/C60 complex on the femtosecond time scale, via a combination of ab initio molecular dynamics and time-dependent density functional theory. We analyze the correlations between the molecular vibrations of the complex and the oscillations in the electron-transfer character of its lowest excited state, which point to vibration-induced coherences between the (pentacene-based) local-excitation (LE) state and the complex charge-transfer (CT) state. We discuss the implications of our results on this model system for the exciton-dissociation process in organic solar cells.

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

    DEFF Research Database (Denmark)

    Zhang, Wenkai; Kjær, Kasper Skov; Alonso-Mori, Roberto

    2017-01-01

    state lifetime of iron based complexes due to spin crossover-the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand...... iron complexes with four cyanide (CN-;) ligands and one 2,2′-bipyridine (bpy) ligand. This enables MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL......) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN)4(bpy)]2-. The two experimental techniques are highly complementary; the time-resolved UV...

  4. Dual fluorescent polyaniline model compounds: steric and temperature effects on excited state charge separation.

    Science.gov (United States)

    Kapelle, Sabine; Rettig, Wolfgang; Lapouyade, René

    2002-07-01

    Low temperature dual fluorescence of several derivatives of 4-aminodiphenylamine is investigated quantitatively. A strong thermochromic and solvatochromic redshift is indicative of the high dipole moment of the CT state emitting at long wavelength. The combination of steady state and time-resolved data allowed the calculation of the excited-state equilibrium. The absence of CT-risetimes in diethyl ether and their presence in butyronitrile points to the complication by additional ground state conformational equilibria. Both ground and excited state equilibria depend on solvent polarity and temperature. High solvent polarity favours one of the ground state conformers.

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

    Science.gov (United States)

    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.

  6. Dynamics of charge-transfer excited states relevant to photochemical energy conversion. Progress report, June 1, 1991--November 15, 1991

    Energy Technology Data Exchange (ETDEWEB)

    Lim, E.C.

    1991-11-01

    The primary objective of the research program is to gain a fundamental understanding of the factors governing the efficiency of excited-state charge transfer CT interactions between two chromophores that are brought together in close proximity, either by a very short covalent linkage or by ground-state complex formation. CT and van der Walls (vdW), interactions in covalently bonded bichromophoric compounds in condensed phase, as well as those in vdW complexes in supersonic jets, are being investigated using laser-based techniques under a variety of experimental conditions. This progress report is divided into three parts, according to the class of molecular systems and the phase (liquid vs. gas) in which the excited-state interactions are probed. The first is concerned with the excited states of bridged diaryl compounds in the condensed phase. The second involves the excited states of vdW complexes in supersonic jets. Finally, the third, is concerned with the excited states of electron donor-acceptor (EDA) systems in both the condensed phase and supersonic jets. In each of these studies, we are concerned with the interchromophore interactions ranging from weak vdW forces to strong CT forces, and the factors determining whether the interaction forces are weak or strong in related molecules.

  7. Molecular approaches to solar energy conversion: the energetic cost of charge separation from molecular-excited states.

    Science.gov (United States)

    Durrant, James R

    2013-08-13

    This review starts with a brief overview of the technological potential of molecular-based solar cell technologies. It then goes on to focus on the core scientific challenge associated with using molecular light-absorbing materials for solar energy conversion, namely the separation of short-lived, molecular-excited states into sufficiently long-lived, energetic, separated charges capable of generating an external photocurrent. Comparisons are made between different molecular-based solar cell technologies, with particular focus on the function of dye-sensitized photoelectrochemical solar cells as well as parallels with the function of photosynthetic reaction centres. The core theme of this review is that generating charge carriers with sufficient lifetime and a high quantum yield from molecular-excited states comes at a significant energetic cost-such that the energy stored in these charge-separated states is typically substantially less than the energy of the initially generated excited state. The role of this energetic loss in limiting the efficiency of solar energy conversion by such devices is emphasized, and strategies to minimize this energy loss are compared and contrasted.

  8. Dynamics of charge-transfer excited states relevant to photochemical energy conversion. Technical report, June 1, 1992--March 30, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Lim, E.C.

    1993-06-01

    A systematic study of intramolecular photoassociation and photoinduced charge transfer (CT) was initiated in bichromophoric systems of M-X-M, where two identical aromatic hydrocarbons M are joined by X=CH{sub 2}, O, NH, etc. Dinaphthylamines, dinaphthylethers, and dinaphthylmethanes in nonpolar solvents form triplet excimers, following inter system crossing of singlets to the triplet manifold; in polar solvents, the molecule forms an intramolecular CT state. The interchromophore interaction study was extended to N-phenyl-2-naphthylamine. The lowest excited singlet states of the dinaphthylamines were studied by semiempirical quantum chemical methods. Exciplex formation was studied in excited states of jet-cooled van der Waals complexes, such as fluorene/substituted benzenes and 1-cyanonaphthalene-aliphatic amines.

  9. Evidence for coherent mixing of excited and charge-transfer states in the major plant light-harvesting antenna, LHCII.

    Science.gov (United States)

    Ramanan, Charusheela; Ferretti, Marco; van Roon, Henny; Novoderezhkin, Vladimir I; van Grondelle, Rienk

    2017-08-30

    LHCII, the major light harvesting antenna from plants, plays a dual role in photosynthesis. In low light it is a light-harvester, while in high light it is a quencher that protects the organism from photodamage. The switching mechanism between these two orthogonal conditions is mediated by protein dynamic disorder and photoprotective energy dissipation. The latter in particular is thought to occur in part via spectroscopically 'dark' states. We searched for such states in LHCII trimers from spinach, at both room temperature and at 77 K. Using 2D electronic spectroscopy, we explored coherent interactions between chlorophylls absorbing on the low-energy side of LHCII, which is the region that is responsible for both light-harvesting and photoprotection. 2D beating frequency maps allow us to identify four frequencies with strong excitonic character. In particular, our results show the presence of a low-lying state that is coupled to a low-energy excitonic state. We assign this to a mixed excitonic-charge transfer state involving the state with charge separation within the Chl a603-b609 heterodimer, borrowing some dipole strength from the Chl a602-a603 excited states. Such a state may play a role in photoprotection, in conjunction with specific and environmentally controlled realizations of protein dynamic disorder. Our identification and assignment of the coherences observed in the 2D frequency maps suggests that the structure of exciton states as well as a mixing of the excited and charge-transfer states is affected by coupling of these states to resonant vibrations in LHCII.

  10. Attosecond angular flux of partial charges on the carbon atoms of benzene in non-aromatic excited state

    Science.gov (United States)

    Hermann, Gunter; Liu, ChunMei; Manz, Jörn; Paulus, Beate; Pohl, Vincent; Tremblay, Jean Christophe

    2017-09-01

    Recently, it was discovered that excitation of the oriented model benzene from its aromatic electronic ground state S0 (1A1g) to the non-aromatic S0 +S2 (1B1u) superposition state generates negative and positive partial charges on alternating carbon atoms. Subsequently, they vary periodically, due to adiabatic attosecond charge migration AACM. Here, we determine the angular electronic flux that mediates this new type of AACM, by means of quantum dynamics simulations. It is found to be periodic, with period τ bar = 590as , and with a pincer motion type pattern such that a total of 1.2 valence electrons flow concertedly between alternating sources and sinks at the carbon nuclei.

  11. Observation of Ground- and Excited-State Charge Transfer at the C60/Graphene Interface.

    Science.gov (United States)

    Jnawali, Giriraj; Rao, Yi; Beck, Jonathan H; Petrone, Nicholas; Kymissis, Ioannis; Hone, James; Heinz, Tony F

    2015-07-28

    We examine charge transfer interactions in the hybrid system of a film of C60 molecules deposited on single-layer graphene using Raman spectroscopy and Terahertz (THz) time-domain spectroscopy. In the absence of photoexcitation, we find that the C60 molecules in the deposited film act as electron acceptors for graphene, yielding increased hole doping in the graphene layer. Hole doping of the graphene film by a uniform C60 film at a level of 5.6 × 10(12)/cm(2) or 0.04 holes per interfacial C60 molecule was determined by the use of both Raman and THz spectroscopy. We also investigate transient charge transfer occurring upon photoexcitation by femtosecond laser pulses with a photon energy of 3.1 eV. The C60/graphene hybrid exhibits a short-lived (ps) decrease in THz conductivity, followed by a long-lived increase in conductivity. The initial negative photoconductivity transient, which decays within 2 ps, reflects the intrinsic photoresponse of graphene. The longer-lived positive conductivity transient, with a lifetime on the order of 100 ps, is attributed to photoinduced hole doping of graphene by interfacial charge transfer. We discuss possible microscopic pathways for hot carrier processes in the hybrid system.

  12. Deactivation of 6-Aminocoumarin Intramolecular Charge Transfer Excited State through Hydrogen Bonding

    Science.gov (United States)

    Krystkowiak, Ewa; Dobek, Krzysztof; Maciejewski, Andrzej

    2014-01-01

    This paper presents results of the spectral (absorption and emission) and photophysical study of 6-aminocoumarin (6AC) in various aprotic hydrogen-bond forming solvents. It was established that solvent polarity as well as hydrogen-bonding ability influence solute properties. The hydrogen-bonding interactions between S1-electronic excited solute and solvent molecules were found to facilitate the nonradiative deactivation processes. The energy-gap dependence on radiationless deactivation in aprotic solvents was found to be similar to that in protic solvents. PMID:25244014

  13. Cold neutral atoms via charge exchange from excited state positronium: a proposal

    CERN Document Server

    Bertsche, W A; Eriksson, S

    2016-01-01

    We present a method for generating cold neutral atoms via charge exchange reactions between trapped ions and Rydberg positronium. The high charge exchange reaction cross section leads to efficient neutralisation of the ions and since the positronium-ion mass ratio is small, the neutrals do not gain appreciable kinetic energy in the process. When the original ions are cold the reaction produces neutrals that can be trapped or further manipulated with electromagnetic fields. Because a wide range of species can be targeted we envisage that our scheme may enable experiments at low temperature that have been hitherto intractable due to a lack of cooling methods. We present an estimate for achievable temperatures, neutral number and density in an experiment where the neutrals are formed at a milli-Kelvin temperature from either directly or sympathetically cooled ions confined on an ion chip. The neutrals may then be confined by their magnetic moment in a co-located magnetic minimum well also formed on the chip. We ...

  14. Cold neutral atoms via charge exchange from excited state positronium: a proposal

    Science.gov (United States)

    Bertsche, W. A.; Charlton, M.; Eriksson, S.

    2017-05-01

    We present a method for generating cold neutral atoms via charge exchange reactions between trapped ions and Rydberg positronium. The high charge exchange reaction cross section leads to efficient neutralisation of the ions and since the positronium-ion mass ratio is small, the neutrals do not gain appreciable kinetic energy in the process. When the original ions are cold the reaction produces neutrals that can be trapped or further manipulated with electromagnetic fields. Because a wide range of species can be targeted we envisage that our scheme may enable experiments at low temperature that have been hitherto intractable due to a lack of cooling methods. We present an estimate for achievable temperatures, neutral number and density in an experiment where the neutrals are formed at a milli-Kelvin temperature from either directly or sympathetically cooled ions confined on an ion chip. The neutrals may then be confined by their magnetic moment in a co-located magnetic minimum well also formed on the chip. We discuss general experimental requirements.

  15. Excited-State Dynamics of Biological Molecules in Solution: Photoinduced Charge Transfer in Oxidatively Damaged DNA and Deactivation of Violacein in Viscous Solvents

    Science.gov (United States)

    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 (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

  16. Intramolecular photoassociation and photoinduced charge transfer in bridged diaryl compounds. 2. Charge-transfer interactions in the lowest excited singlet state of dinaphthylamines

    Energy Technology Data Exchange (ETDEWEB)

    Dresner, J.; Modiano, S.H.; Lim, E.C. [Univ. of Akron, OH (United States)

    1992-05-28

    The formation of an intramolecular charge-transfer (CT) exciplex is demonstrated for 1,1{prime}-dinaphthylamine (1,1{prime}-DNA) and 2,2{prime}-dinaphthylamine (2,2{prime}-DNA) in the lowest excited singlet state using steady-state and picosecond time-resolved fluorescence spectroscopy. The exciplex is formed through a mutual reorientation of the two naphthalene rings. Differences in the rate of formation and relaxation of the CT state for 1,1{prime}-DNA and 2,2{prime}-DNA indicate the importance of the bridge position in this process. The comparison of the steady-state fluorescence of 2,2{prime}-DNA with that of its protonated form, as well as the fluorescence of 2,2{prime}-dinaphthyl ether and 2,2{prime}-dinaphthylmethane, show the role of the lone-pair electrons of the nitrogen atom in the exciplex formation. 18 refs., 20 figs., 5 tabs.

  17. Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine2(CN2

    Directory of Open Access Journals (Sweden)

    Kasper S. Kjær

    2017-07-01

    Full Text Available We have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy2(CN2], where bpy=2,2′-bipyridine, initiated by metal-to-ligand charge transfer (MLCT excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2′-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy2(CN2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a short lived metal-centered triplet transient species. These measurements of [Fe(bpy2(CN2] complement prior measurement performed on [Fe(bpy3]2+ and [Fe(bpy(CN4]2− in dimethylsulfoxide solution and help complete the chemical series [Fe(bpyN(CN6–2N]2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3d transition metal complexes.

  18. Excited states 2

    CERN Document Server

    Lim, Edward C

    2013-01-01

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

  19. Excited states 4

    CERN Document Server

    Lim, Edward C

    2013-01-01

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

  20. Improved film morphology reduces charge carrier recombination into the triplet excited state in a small bandgap polymer-fullerene photovoltaic cell

    Energy Technology Data Exchange (ETDEWEB)

    Di Nuzzo, Daniele; Shahid, Munazza; Gevaerts, Veronique S. [Molecular Materials and Nanosystems, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands); Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven (Netherlands); Aguirre, Aranzazu; Meskers, Stefan C.J.; Janssen, Rene A.J. [Molecular Materials and Nanosystems, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven (Netherlands)

    2010-10-08

    The use of diiodooctane as processing additive for construction of PCPDTBT:PCBM solar cells results in a profound change in photophysical behavior of this blend. In the improved morphology obtained with the additive, recombination of charge carriers to the lowest triplet excited state is suppressed. This contributes to the boost in solar power conversion efficiency induced by the use of the processing agent. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  1. Search for excited charged leptons in electron positron collisions

    CERN Document Server

    Vachon, Brigitte Marie Christine; Sobie, Randall

    2002-01-01

    A search for evidence that fundamental particles are made of smaller subconstituents is performed. The existence of excited states of fundamental particles would be an unambiguous indication of their composite nature. Experimental signatures compatible with the production of excited states of charged leptons in electron-positron collisions are studied. The data analysed were collected by the OPAL detector at the LEP collider. No evidence for the existence of excited states of charged leptons was found. Upper limits on the product of the cross-section and the electromagnetic branching fraction are inferred. Using results from the search for singly produced excited leptons, upper limits on the ratio of the excited lepton coupling constant to the compositeness scale are calculated. From pair production searches, 95% confidence level lower limits on the masses of excited electrons, muons and taus are determined to be 103.2 GeV.

  2. A novel chalcone-analogue as an optical sensor based on ground and excited states intramolecular charge transfer: A combined experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Fayed, Tarek A. [Chemistry Department, Faculty of Science, Tanta University, 31527-Tanta (Egypt)], E-mail: tfayed2003@yahoo.co.uk

    2006-05-31

    Steady-state absorption and emission spectroscopic techniques as well as semiempirical quantum calculations at the AM1 and ZINDO/S levels have been used to investigate the intramolecular charge transfer (ICT) behaviour of a novel chalcone namely; 1-(2-pyridyl)-5-(4-dimethylaminophenyl)-penta-2,4-diene-1-one, DMAC. The ground state DMAC has a significant ICT character and a great sensitivity to the hydrogen bond donating ability of the medium as reflected from the change of the absorption spectra in pure and mixed organic solvents. On the other hand, its excited singlet state exhibits high ICT characters as manifested by the drastic solvatochromic effects. These results are consistent with the data of charge density calculations in both the ground and excited state, which indicates enhancement of the charge transfer from the dimethyl-amino group to the carbonyl oxygen upon excitation. Also, the dipole moment calculations indicates a highly dipolar excited singlet state ({delta}{mu} {sub eg} = 15.5 D). The solvent dependence of the fluorescence quantum yield of DMAC was interpreted on the basis of positive and negative solvatokinetic as well as the hydrogen bonding effects. Incorporation of the 2-pyridyl group in the chemical structure of the present DMAC led to design of a potential optical sensor for probing acidity of the medium and metal cations such as Zn{sup 2+}, Cd{sup 2+} and Hg{sup 2+}. This was concluded from the high acidochromic and metallochromic behaviour of DMAC on adding such cations to its acetonitrile solutions.

  3. Correlating excited state and charge carrier dynamics with photovoltaic parameters of perylene dye sensitized solar cells: influences of an alkylated carbazole ancillary electron-donor.

    Science.gov (United States)

    Li, Yang; Wang, Junting; Yuan, Yi; Zhang, Min; Dong, Xiandui; Wang, Peng

    2017-01-18

    Two perylene dyes characteristic of electron-donors phenanthrocarbazole (PC) and carbazyl functionalized PC are selected to study the complicated dynamics of excited states and charge carriers, which underlie the photovoltaic parameters of dye-sensitized solar cells (DSCs). We have combined femtosecond fluorescence up-conversion and time-resolved single-photon counting techniques to probe the wavelength-dependent photoluminescence dynamics of dye molecules not only dissolved in THF but also grafted on the surface of oxide nanoparticles. Excited state relaxation and electron injection both occur on a similar timescale, resulting in a very distributive kinetics of electron injection. It is also found that the carbazyl ancillary electron-donor causes a faster electron injection, which over-compensates the adverse impact of a slightly shorter lifetime of the equilibrium excited state. Nanosecond transient absorption and transient photovoltage decay measurements have shown that conjugating carbazyl to PC can effectively slow down the kinetics of charge recombination of electrons in titania with both photo-oxidized dye molecules and triiodide anions, improving the cell photovoltage.

  4. Self-excitation of space charge waves

    DEFF Research Database (Denmark)

    Lyuksyutov, Sergei; Buchhave, Preben; Vasnetsov, Mikhail

    1997-01-01

    We report a direct observation of space charge waves in photorefractive crystals with point group 23 (sillenites) based on their penetration into an area with uniform light illumination. It is shown experimentally that the quality factor of the waves increases substantially with respect to what...... current theory predicts [B. Sturman el al., Appl. Phys. A 55, 235 (1992)]. This results in the appearance of strong spontaneous beams caused by space charge wave self-excitation....

  5. Excited states of muonium in atomic hydrogen

    Indian Academy of Sciences (India)

    Muonium formation in excited states in muon-hydrogen charge-exchange collision is investigated using a method developed in a previous paper. Differential cross-section results are found to resemble positronium formation cross-section results of positron-hydrogen charge-exchange problem. Forward differential and ...

  6. Charges and Electromagnetic Radiation as Topological Excitations

    Directory of Open Access Journals (Sweden)

    Manfried Faber

    2017-01-01

    Full Text Available We discuss a model with stable topological solitons in Minkowski space with only three degrees of freedom, the rotational angles of a spatial Dreibein. This model has four types of solitons differing in two topological quantum numbers which we identify with electric charge and spin. The vacuum has a two-dimensional degeneracy leading to two types of massless excitations, characterised by a topological quantum number which could have a physical equivalent in the photon number.

  7. State-selective electron transfer and ionization in collisions of highly charged ions with ground-state Na(3s) and laser-excited Na*(3p)

    NARCIS (Netherlands)

    Blank, I.; Otranto, S.; Meinema, C.; Olson, R. E.; Hoekstra, R.

    2012-01-01

    Single electron transfer and ionization in collisions of N5+ and Ne8+ with ground state Na(3s) and laser excited Na*(3p) are investigated both experimentally and theoretically at collision energies from 1 to 10 keV/amu, which includes the classical orbital velocity of the valence electron.

  8. Synthesis, spectral behaviour and photophysics of donor-acceptor kind of chalcones: Excited state intramolecular charge transfer and fluorescence quenching studies

    Science.gov (United States)

    Pannipara, Mehboobali; Asiri, Abdullah M.; Alamry, Khalid A.; Arshad, Muhammad N.; El-Daly, Samy A.

    2015-02-01

    The spectral and photophysical properties of two chalcones containing electron donating and accepting groups with intramolecular charge transfer characteristics were synthesized and characterized by 1H NMR, 13C NMR and X-ray crystallography. Both compounds show very strong solvent polarity dependent changes in their photophysical characteristics, namely, remarkable red shift in the emission spectra with increasing solvent polarity, large change in Stokes shift, significant reduction in the fluorescence quantum yield; indicating that the fluorescence states of these compounds are of intramolecular charge transfer (ICT) character. The solvent effect on the photophysical parameters such as singlet absorption, molar absorptivity, oscillator strength, dipole moment, fluorescence spectra, and fluorescence quantum yield of both compounds have been investigated comprehensively. For both dyes, Lippert-Mataga and Reichardt's correlations were used to estimate the difference between the excited and ground state dipole moments (Δμ). The interactions of dyes with colloidal silver nanoparticles (Ag NPs) were also studied in ethanol using steady state fluorescence quenching measurements. The fluorescence quenching data reveal that dynamic quenching and energy transfer play a major role in the fluorescence quenching of dyes by Ag NPs.

  9. Resonance Raman examination of the electronic excited states of glycylglycine and other dipeptides: Observation of a carboxylate{yields}amide charge transfer transition

    Energy Technology Data Exchange (ETDEWEB)

    Chen, X.G.; Li, P.; Holtz, J.S.W.; Chi, Z.; Pajcini, V.; Asher, S.A. [Univ. of Pittsburgh, PA (United States); Kelly, L.A. [Brookhaven National Lab., Upton, NY (United States)

    1996-10-09

    We have examined the UV resonance Raman and the VUV absorption spectra of aqueous glycylglycine and other dipeptides. We observe strong resonance Raman enhancement of the amide I, II, and III bands and the amide C{sub {alpha}}H bending mode in a manner similar to that we observed previously with excitation within the {pi}{yields}{pi}{sup *} transition of N-methylacetamide. However, in addition, we observe strong resonance Raman enhancement of the ca. 1400 cm{sup -1} symmetric COO{sup -} stretching vibration, whose 206.5 nm Raman cross section is increased 20-fold compared to that of the carboxylate in sodium acetate, for example. Addition of a methylene spacer between the amide and carboxylate groups causes the resonance Raman enhancement of this symmetric COO{sup -} stretch to disappear. The UV resonance Raman excitation profiles, the Raman depolarization ratio dispersion, and the VUV absorption spectra of glycylglycine and other dipeptides demonstrate the existence of a new 197 nm charge transfer band which involves electron transfer from a nonbonding carboxylate orbital to the amide-like {pi}{sup *} orbital. This transition occurs at the penultimate carboxylate end of all peptides and proteins. 18 refs., 9 figs., 3 tabs.

  10. Excited B states at LEP

    CERN Document Server

    Kluit, Peter M

    2005-01-01

    The first orbitally excited B states were discovered at LEP in 1995. In subsequent years evidence was put forward for the existence of several excited B hadron states. Now, ten years later it is time to review the situation. New analyses have been performed in DELPHI using the full LEP data set with improved and high performance analysis tools. Measurements for the production rate and masses of narrow and broad B/sub u, d//sup **/ mesons will be presented as well as results for the search for B/sub s//sup **/ mesons and Sigma /sub b//sup (*)/ baryons. The results will be compared to earlier measurements, predictions from HQET and measurements in the charm sector.

  11. Relaxation dynamics in the excited states of a ketocyanine dye ...

    Indian Academy of Sciences (India)

    WINTEC

    Pramanik et al proposed the twisted intramolecular charge transfer (TICT) process in the S1 state, which .... trile clearly suggests that a photon of 400 nm light excites the molecule to its S2 state, the higher energy emission .... 400 nm photon as well as the dynamics of the re- laxation processes taking place in the S1 state. At.

  12. Using RIXS to Uncover Elementary Charge and Spin Excitations

    Directory of Open Access Journals (Sweden)

    Chunjing Jia

    2016-05-01

    Full Text Available Despite significant progress in resonant inelastic x-ray scattering (RIXS experiments on cuprates at the Cu L-edge, a theoretical understanding of the cross section remains incomplete in terms of elementary excitations and the connection to both charge and spin structure factors. Here, we use state-of-the-art, unbiased numerical calculations to study the low-energy excitations probed by RIXS in the Hubbard model, relevant to the cuprates. The results highlight the importance of scattering geometry, in particular, both the incident and scattered x-ray photon polarization, and they demonstrate that on a qualitative level the RIXS spectral shape in the cross-polarized channel approximates that of the spin dynamical structure factor. However, in the parallel-polarized channel, the complexity of the RIXS process beyond a simple two-particle response complicates the analysis and demonstrates that approximations and expansions that attempt to relate RIXS to less complex correlation functions cannot reproduce the full diversity of RIXS spectral features.

  13. Low-charge-state linac

    Energy Technology Data Exchange (ETDEWEB)

    Shepard, K.W.; Kim, J.W.

    1995-08-01

    A design is being developed for a low-charge-state linac suitable for injecting ATLAS with a low-charge-state, radioactive beam. Initial work indicates that the existing ATLAS interdigital superconducting accelerating structures, together with the superconducting quadrupole transverse focussing element discussed above, provides a basis for a high-performance low-charge-state linac. The initial 2 or 3 MV of such a linac could be based on a normally-conducting, low-frequency RFQ, possibly combined with 24-MHz superconducting interdigital structures. Beam dynamics studies of the whole low-charge-state post-accelerator section were carried out in early FY 1995.

  14. Quantum dynamics of vibrational excitations and vibrational charge ...

    Indian Academy of Sciences (India)

    Quantum dynamics of vibrational excitations and vibrational charge transfer processes in H+ + O2 collisions at collision energy 23 eV ... The Fritz Haber Research Centre and The Department of Physical Chemisry, Hebrew University of Jerusalem, Jerusalem, Israel 91904; Department of Chemistry, Indian Institute of ...

  15. Excited State Properties of Hybrid Perovskites.

    Science.gov (United States)

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

    2016-01-19

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

  16. Excited-state Wigner crystals

    Science.gov (United States)

    Rogers, Fergus J. M.; Loos, Pierre-François

    2017-01-01

    Wigner crystals (WCs) are electronic phases peculiar to low-density systems, particularly in the uniform electron gas. Since its introduction in the early twentieth century, this model has remained essential to many aspects of electronic structure theory and condensed-matter physics. Although the (lowest-energy) ground-state WC (GSWC) has been thoroughly studied, the properties of excited-state WCs (ESWCs) are basically unknown. To bridge this gap, we present a well-defined procedure to obtain an entire family of ESWCs in a one-dimensional electron gas using a symmetry-broken mean-field approach. While the GSWC is a commensurate crystal (i.e., the number of density maxima equals the number of electrons), these ESWCs are incommensurate crystals exhibiting more or less maxima. Interestingly, they are lower in energy than the (uniform) Fermi fluid state. For some of these ESWCs, we have found asymmetrical band gaps, which would lead to anisotropic conductivity. These properties are associated with unusual characteristics in their electronic structure.

  17. Excited state Intramolecular Proton Transfer in Anthralin

    DEFF Research Database (Denmark)

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

    1998-01-01

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

  18. The mechanisms of Excited states in enzymes

    DEFF Research Database (Denmark)

    Petersen, Frederic Nicolas Rønne; Bohr, Henrik

    2010-01-01

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

  19. Scientific Computation Application Partnerships in Materials and Chemical Sciences, Charge Transfer and Charge Transport in Photoactivated Systems, Developing Electron-Correlated Methods for Excited State Structure and Dynamics in the NWChem Software Suite

    Energy Technology Data Exchange (ETDEWEB)

    Cramer, Christopher J. [Univ. of Minnesota, Minneapolis, MN (United States)

    2017-11-12

    Charge transfer and charge transport in photoactivated systems are fundamental processes that underlie solar energy capture, solar energy conversion, and photoactivated catalysis, both organometallic and enzymatic. We developed methods, algorithms, and software tools needed for reliable treatment of the underlying physics for charge transfer and charge transport, an undertaking with broad applicability to the goals of the fundamental-interaction component of the Department of Energy Office of Basic Energy Sciences and the exascale initiative of the Office of Advanced Scientific Computing Research.

  20. Quantum dynamics of charge state in silicon field evaporation

    Directory of Open Access Journals (Sweden)

    Elena P. Silaeva

    2016-08-01

    Full Text Available 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 the 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.

  1. Quantum dynamics of charge state in silicon field evaporation

    Energy Technology Data Exchange (ETDEWEB)

    Silaeva, Elena P.; Uchida, Kazuki; Watanabe, Kazuyuki, E-mail: kazuyuki@rs.kagu.tus.ac.jp [Department of Physics, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601 (Japan)

    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 the 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.

  2. Exciting baryon resonances in isobar charge-exchange reactions

    Science.gov (United States)

    Benlliure, J.; Rodriguez-Sanchez, J. L.; Vargas, J.; Alavarez-Pol, H.; Aumann, T.; Atkinson, J.; Ayyad, Y.; Beceiro, S.; Boretzky, K.; Chatillon, A.; Cortina, D.; Diaz, P.; Estrade, A.; Geissel, H.; Lenske, H.; Litvinov, Y.; Mostazo, M.; Paradela, C.; Pietri, S.; Prochazka, A.; Takechi, M.; Vidaña, I.; Weick, H.; Winfield, J.

    2017-11-01

    Isobaric charge-exchange reactions induced by different tin isotopes have been investigated at GSI. The high-resolving power of the FRS spectrometer made it possible to separate elastic and inelastic components in the missing-energy spectra of the ejectiles. The inelastic component was associated to the in-medium excitation of nucleon resonances such as the Delta and Roper resonances. These data are expected to contribute to better understand the in-medium properties of baryon resonances but also to investigate the abundance of protons and neutrons at the nuclear periphery.

  3. Electron impact excitation of highly charged sodium-like ions

    Science.gov (United States)

    Blaha, M.; Davis, J.

    1978-01-01

    Optical transition probabilities and electron collision strengths for Ca X, Fe XVI, Zn XX, Kr XXVI and Mo XXXII are calculated for transitions between n equal to 3 and n equal to 4 levels. The calculations neglect relativistic effects on the radial functions. A semi-empirical approach provides wave functions of the excited states; a distorted wave function without exchange is employed to obtain the excitation cross sections. The density dependence of the relative intensities of certain emission lines in the sodium isoelectronic sequence is also discussed.

  4. The Role of Charge Balance and Excited State Levels on Device Performance of Exciplex-based Phosphorescent Organic Light Emitting Diodes.

    Science.gov (United States)

    Lee, Sangyeob; Koo, Hyun; Kwon, Ohyun; Jae Park, Young; Choi, Hyeonho; Lee, Kwan; Ahn, Byungmin; Min Park, Young

    2017-09-20

    The design of novel exciplex-forming co-host materials provides new opportunities to achieve high device performance of organic light emitting diodes (OLEDs), including high efficiency, low driving voltage and low efficiency roll-off. Here, we report a comprehensive study of exciplex-forming co-host system in OLEDs including the change of co-host materials, mixing composition of exciplex in the device to improve the performance. We investigate various exciplex systems using 5-(3-4,6-diphenyl-1,3,5-triazin-2-yl)phenyl-3,9-diphenyl-9H-carbazole, 5-(3-4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9-phenyl-9H-3,9'-bicarbazole, and 2-(3-(6,9-diphenyl-9H-carbazol-4-yl)phenyl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine, as electron transporting (ET: electron acceptor) hosts and 9,9'-dipenyl-9H, 9'H-3,3'-bicarbazole and 9-([1,1'-biphenyl]-4-yl)-9'-phenyl-9H,9'H-3,3'-bicarbazole as hole transporting (HT: electron donor) hosts. As a result, a very high current efficiency of 105.1 cd/A at 10(3) cd/m(2) and an extremely long device lifetime of 739 hrs (t95: time after 5% decrease of luminance) are achieved which is one of the best performance in OLEDs. Systematic approach, controlling mixing ratio of HT to ET host materials is suggested to select the component of two host system using energy band matching and charge balance optimization method. Furthermore, our analysis on exciton stability also reveal that lifetime of OLEDs have close relationship with two parameters; singlet energy level difference of HT and ET host and difference of singlet and triplet energy level in exciplex.

  5. Rearrangements in ground and excited states

    CERN Document Server

    de Mayo, Paul

    1980-01-01

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

  6. Charmonium excited state spectrum in lattice QCD

    Energy Technology Data Exchange (ETDEWEB)

    Jozef Dudek; Robert Edwards; Nilmani Mathur; David Richards

    2008-02-01

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

  7. Search for excited states in 25O

    Science.gov (United States)

    Jones, M. D.; Fossez, K.; Baumann, T.; DeYoung, P. A.; Finck, J. E.; Frank, N.; Kuchera, A. N.; Michel, N.; Nazarewicz, W.; Rotureau, J.; Smith, J. K.; Stephenson, S. L.; Stiefel, K.; Thoennessen, M.; Zegers, R. G. T.

    2017-11-01

    Background: Theoretical calculations suggest the presence of low-lying excited states in 25O. Previous experimental searches by means of proton knockout on 26F produced no evidence for such excitations. Purpose: We search for excited states in 25O using the 24O(d ,p ) 25O reaction. The theoretical analysis of excited states in unbound O,2725 is based on the configuration interaction approach that accounts for couplings to the scattering continuum. Method: We use invariant-mass spectroscopy to measure neutron-unbound states in 25O. For the theoretical approach, we use the complex-energy Gamow Shell Model and Density Matrix Renormalization Group method with a finite-range two-body interaction optimized to the bound states and resonances of O-2623, assuming a core of 22O. We predict energies, decay widths, and asymptotic normalization coefficients. Results: Our calculations in a large s p d f space predict several low-lying excited states in 25O of positive and negative parity, and we obtain an experimental limit on the relative cross section of a possible Jπ=1/2 + state with respect to the ground state of 25O at σ1 /2 +/σg .s .=0 .25-0.25+1.0 . We also discuss how the observation of negative parity states in 25O could guide the search for the low-lying negative parity states in 27O. Conclusion: Previous experiments based on the proton knockout of 26F suffered from the low cross sections for the population of excited states in 25O because of low spectroscopic factors. In this respect, neutron transfer reactions carry more promise.

  8. Zp-graded charge coherent states

    Science.gov (United States)

    Chung, Won Sang

    2014-06-01

    A new kind of charge coherent state called a Zp-graded charge coherent state is constructed by using the complex solution of the equation qp = 1. The p-1 charge operators are also explicitly constructed. We explicitly investigate some nonclassical properties for the Z3-graded charge coherent state.

  9. Excitation of Terahertz Charge Transfer Plasmons in Metallic Fractal Structures

    Science.gov (United States)

    Ahmadivand, Arash; Gerislioglu, Burak; Sinha, Raju; Vabbina, Phani Kiran; Karabiyik, Mustafa; Pala, Nezih

    2017-08-01

    There have been extensive researches on terahertz (THz) plasmonic structures supporting resonant modes to demonstrate nano and microscale devices with high efficiency and responsivity as well as frequency selectivity. Here, using antisymmetric plasmonic fractal Y-shaped (FYS) structures as building blocks, we introduce a highly tunable four-member fractal assembly to support charge transfer plasmons (CTPs) and classical dipolar resonant modes with significant absorption cross section in the THz domain. We first present that the unique geometrical nature of the FYS system and corresponding spectral response allow for supporting intensified dipolar plasmonic modes under polarised light exposure in a standalone structure. In addition to classical dipolar mode, for the very first time, we demonstrated CTPs in the THz domain due to the direct shuttling of the charges across the metallic fractal microantenna which led to sharp resonant absorption peaks. Using both numerical and experimental studies, we have investigated and confirmed the excitation of the CTP modes and highly tunable spectral response of the proposed plasmonic fractal structure. This understanding opens new and promising horizons for tightly integrated THz devices with high efficiency and functionality.

  10. Peculiarity of the charge-exchange quadrupole excitation in nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Leonardi, R.; Lipparini, E.; Stringari, S.

    1987-04-01

    The experimental isovector quadrupole strength in the charge exchange channels is smaller than predicted by random phase approximation calculations using conventional nuclear interactions. The introduction of nonlocal components in the interaction combined with the existence of a low-lying 0h-dash-bar..omega.. rotational 2/sup +/ quadrupole state in the daughter nucleus can explain this behavior. These nonlocal interactions do not play a role in the properties of the isovector monopole and dipole resonance.

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

    Science.gov (United States)

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

    2015-04-15

    A consideration of the excited state potential energy surfaces of carotenoids develops a new hypothesis for the nature of the conformational motions that follow optical preparation of the S2 (1(1)Bu(+)) state. After an initial displacement from the Franck-Condon geometry along bond length alternation coordinates, it is suggested that carotenoids pass over a transition-state barrier leading to twisted conformations. This hypothesis leads to assignments for several dark intermediate states encountered in femtosecond spectroscopic studies. The Sx state is assigned to the structure reached upon the onset of torsional motions near the transition state barrier that divides planar and twisted structures on the S2 state potential energy surface. The X state, detected recently in two-dimensional electronic spectra, corresponds to a twisted structure well past the barrier and approaching the S2 state torsional minimum. Lastly, the S(∗) state is assigned to a low lying S1 state structure with intramolecular charge transfer character (ICT) and a pyramidal conformation. It follows that the bent and twisted structures of carotenoids that are found in photosynthetic light-harvesting proteins yield excited-state structures that favor the development of an ICT character and optimized energy transfer yields to (bacterio)chlorophyll acceptors. Copyright © 2015 Elsevier Inc. All rights reserved.

  12. Computing correct truncated excited state wavefunctions

    Science.gov (United States)

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

    2016-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-14

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

  14. Electronic excited states at ultrathin dielectric-metal interfaces

    Science.gov (United States)

    Sementa, L.; Marini, A.; Barcaro, G.; Negreiros, F. R.; Fortunelli, A.

    2013-09-01

    Electronic excited states at a bcc(110) lithium surface, both bare and covered by ionic ultrathin (1-2 monolayers) LiF epitaxial films, are investigated via many-body perturbation theory calculations achieving an atomistic level of detail. The full self-consistent solution of the GW equations is used to account for correlation effects and to properly describe the screened potential in the vacuum. In addition to the correct prediction of image-potential states, we find that the mixing between resonances and image states and the charge compression due to the dielectric ultrathin overlayer give rise to excitations with a hybrid localized but low-lying character whose accurate description cannot intrinsically be achieved via simple models or low-level calculations, but which are expected to play a crucial role in determining the electronic response and transport properties of these systems.

  15. Acute excited states and sudden death

    National Research Council Canada - National Science Library

    Farnham, Frank R; Kennedy, Henry G

    1997-01-01

    ... mortality. 2 Such deaths, often in police custody or other highly charged situations, commonly give rise to high profile coroner's hearings and inquiries. 3 In the era before neuroleptics death in such agitated states was attributed to exhaustion, though neuroleptic malignant syndrome and the cardiac effects of neuroleptics now often enter into considerat...

  16. Excited states of muonium in atomic hydrogen

    Indian Academy of Sciences (India)

    Differential cross-section results are found to resemble positronium formation cross-section results of positron–hydrogen charge-exchange problem. Forward ... using velocity scaling are compared with the results of the present calculation. .... to carry out calculations for e− capture by muon into n = 2 and n = 3 states.

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

    Science.gov (United States)

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

    2013-10-31

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

  18. Excited states of {sup 4}He droplets

    Energy Technology Data Exchange (ETDEWEB)

    Guardiola, R.; Navarro, J.; Portesi, M.

    2001-06-01

    We study low-lying excited states of {sup 4}He clusters up to a cluster size of 40 atoms in a variational framework. The ansatz wave function combines two- and three-body correlations, coming from a translationally invariant configuration interaction description, and Jastrow-type short-range correlation. We have previously used this scheme to determine the ground-state energies of {sup 4}He and {sup 3}He clusters. Here we present an extension of this ansatz wave function having a good quantum angular momentum L. The variational procedure is applied independently to the cases with L=0,2,4, and upper bounds for the corresponding energies are thus obtained. Moreover, centroid energies for L excitations are calculated through the use of sum rules. A comparison with previous calculations is also made.

  19. Controlling excited-state contamination in nucleon matrix elements

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-06-01

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

  20. Rearrangements in ground and excited states

    CERN Document Server

    de Mayo, Paul

    1980-01-01

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

  1. Measurement of light charged particles in the decay channels of medium-mass excited compound nuclei

    Directory of Open Access Journals (Sweden)

    Valdré S.

    2014-03-01

    Indeed, in this mass region (A ~ 100 models predict that shape transitions can occur at high spin values and relatively scarce data exist in the literature about coincidence measurements between evaporation residues and light charged particles. Signals of shape transitions can be found in the variations of the lineshape of high energy gamma rays emitted from the de-excitation of GDR states gated on different region of angular momenta. For this purpose it is important to keep under control the FE and FF processes, to regulate the statistical model parameters and to control the onset of possible pre-equilibrium emissions from 300 to 600 MeV bombarding energy.

  2. Excited state electron affinity calculations for aluminum

    Science.gov (United States)

    Hussein, Adnan Yousif

    2017-08-01

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

  3. Excited States in Solution through Polarizable Embedding

    DEFF Research Database (Denmark)

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

    2010-01-01

    We present theory and implementation of an advanced quantum mechanics/molecular mechanics (QM/MM) approach using a fully self-consistent polarizable embedding (PE) scheme. It is a polarizable layered model designed for effective yet accurate inclusion of an anisotropic medium in a quantum...... mechanical calculation. The polarizable embedding potential is described by an atomistic representation including terms up to localized octupoles and anisotropic polarizabilities. It is generally applicable to any quantum chemical description but is here implemented for the case of Kohn−Sham density...... functional theory which we denote the PE-DFT method. It has been implemented in combination with time-dependent quantum mechanical linear and nonlinear response techniques, thus allowing for assessment of electronic excitation processes and dynamic ground- and excited-state molecular properties using...

  4. Excited state kinetics of anthracene-bridge-aniline intramolecular exciplexes

    DEFF Research Database (Denmark)

    Thyrhaug, Erling; Hammershøj, Peter; Kjær, Kasper Skov

    2014-01-01

    excited anthracene state (LE) and an excited state complex (exciplex, EP) in non-polar solvents. The kinetics of the excited state processes were established in decalin from the time-resolved emission, and was shown to be strongly influenced by an electron-transfer state (ET). For quantitative studies...

  5. Holographic construction of excited CFT states

    Energy Technology Data Exchange (ETDEWEB)

    Christodoulou, Ariana; Skenderis, Kostas [STAG Research Centre and Mathematical Sciences, University of Southampton,High-field, Southampton SO17 1BJ (United Kingdom)

    2016-04-15

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

  6. Identification of excited states in conjugated polymers

    CERN Document Server

    Hartwell, L J

    2003-01-01

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

  7. First 3- excited state of Fe56

    Science.gov (United States)

    Fotiades, N.; Nelson, R. O.; Devlin, M.

    2010-03-01

    There is no reliable evidence for the existence of the 3.076 MeV (3-) level adopted in the ENSDF evaluation for Fe56 although it has been reported in a few experiments. Previous reports of the observation of this level appear to be based on an incorrect assignment in early (e,e') work. Recent neutron inelastic scattering measurements by Demidov [Phys. At. Nucl. 67, 1884, (2004)] show that the assigned γ-ray decay of this state does not occur at a level consistent with known properties of inelastic scattering. In the present work the Fe56(n,n'γ) reaction was used to populate excited states in Fe56. Neutrons in the energy range from 1 to 250 MeV were provided by the pulsed neutron source of the Los Alamos Neutron Science Center’s WNR facility. Deexciting γ rays were detected with the GEANIE spectrometer, a Compton suppressed array of 26 Ge detectors. The γ-γ data obtained with GEANIE were used to establish coincidence relations between transitions. All previously reported levels up to Ex=3.6 MeV excitation energy were observed except for the 3.076 MeV (3-) level. The 991- and 2229-keV transitions, previously reported to deexcite this level, were not observed in the γ-γ coincidence data obtained in the present experiment. The present work supports the assignment of the 4509.6 keV level as the first 3- excited state in Fe56 by observation of two previously known transitions deexciting this state.

  8. Effect of collective response on electron capture and excitation in collisions of highly charged ions with fullerenes.

    Science.gov (United States)

    Kadhane, U; Misra, D; Singh, Y P; Tribedi, Lokesh C

    2003-03-07

    Projectile deexcitation Lyman x-ray emission following electron capture and K excitation has been studied in collisions of bare and Li-like sulphur ions (of energy 110 MeV) with fullerenes (C(60)/C(70)) and different gaseous targets. The intensity ratios of different Lyman x-ray lines in collisions with fullerenes are found to be substantially lower than those for the gas targets, both for capture and excitation. This has been explained in terms of a model based on "solidlike" effect, namely, wakefield induced stark mixing of the excited states populated via electron capture or K excitation: a collective phenomenon of plasmon excitation in the fullerenes under the influence of heavy, highly charged ions.

  9. Efficient charge generation by relaxed charge-transfer states at organic interfaces

    KAUST Repository

    Vandewal, Koen

    2013-11-17

    Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy. © 2014 Macmillan Publishers Limited.

  10. Semiclassical quantization of highly excited scar states

    Science.gov (United States)

    Vergini, Eduardo G.

    2017-04-01

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

  11. Excited state dynamics of DNA bases

    Czech Academy of Sciences Publication Activity Database

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

    2013-01-01

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

  12. Photoinduced charge-transfer electronic excitation of tetracyanoethylene/tetramethylethylene complex in dichloromethane

    Science.gov (United States)

    Xu, Long-Kun; Bi, Ting-Jun; Ming, Mei-Jun; Wang, Jing-Bo; Li, Xiang-Yuan

    2017-07-01

    Based on the previous work on nonequilibrium solvation model by the authors, Intermolecular charge-transfer electronic excitation of tetracyanoethylene (TCE)/tetramethylethylene (TME) π -stacked complex in dichloromethane (DCM) has been investigated. For weak interaction correction, dispersion corrected functional DFT-D3 is adopted for geometry optimization. In order to identify the excitation metric, dipole moment components of each Cartesian direction, atomic charge, charge separation and Δr index are analyzed for TCE/TME complex. Calculation shows that the calculated excitation energy is dependent on the functional choice, when conjuncted with suitable time-dependent density functional, the modified nonequilibrium expression gives satisfied results for intermolecular charge-transfer electronic excitation.

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

    Science.gov (United States)

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

    2016-01-01

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

  14. Calculations on the electronic excited states of ureas and oligoureas.

    Science.gov (United States)

    Oakley, Mark T; Guichard, Gilles; Hirst, Jonathan D

    2007-03-29

    We report CASPT2 calculations on the electronic excited states of several ureas. For monoureas, we find an electric dipole forbidden n --> pi* transition between 180 and 210 nm, dependent on the geometry and substituents of the urea. We find two intense pinb --> pi* transitions between 150 and 210 nm, which account for the absorptions seen in the experimental spectra. The n' --> pi* and pib --> pi* transitions are at wavelengths below 125 nm, which is below the lower limit of the experimental spectra. Parameter sets modeling the charge densities of the electronic transitions have been derived and permit calculations on larger oligoureas, using the exciton matrix method. For glycouril, a urea dimer, both the CASPT2 method and the matrix method yield similar results. Calculations of the electronic circular dichroism spectrum of an oligourea containing eight urea groups indicate that the experimental spectrum cannot be reproduced without the inclusion of electronic excitations involving the side chains. These calculations are one of the first attempts to understand the relationship between the structure and excited states of this class of macromolecule.

  15. Neutral excitations in the Gaffnian state

    Science.gov (United States)

    Kang, Byungmin; Moore, Joel E.

    2017-06-01

    We study a model fractional quantum Hall (FQH) wave function called the Gaffnian state, which is believed to represent a gapless, strongly correlated state that is very different from conventional metals. To understand this exotic gapless state better, we provide a representation based on work of Halperin in which the pairing structure of the Gaffnian state becomes more explicit. We employ the single-mode approximation introduced by Girvin, MacDonald, and Platzman, here extended to three-body interactions, in order to treat a neutral collective excitation mode in order to clarify the physical origin of the gaplessness of the Gaffnian state. We discuss approaches to extract systematically the relevant physics in the long-distance, large-electron-number limit of FQH states using numerical calculations with relatively few electrons. In Appendices, we provide second-quantized expressions for many-body Haldane pseudopotentials in various geometries including the plane, sphere, cylinder, and torus based on the proper definition of the relative angular momentum.

  16. Do Charge State Signatures Guarantee Protein Conformations?

    Science.gov (United States)

    Hall, Zoe; Robinson, Carol V.

    2012-07-01

    The extent to which proteins in the gas phase retain their condensed-phase structure is a hotly debated issue. Closely related to this is the degree to which the observed charge state reflects protein conformation. Evidence from electron capture dissociation, hydrogen/deuterium exchange, ion mobility, and molecular dynamics shows clearly that there is often a strong correlation between the degree of folding and charge state, with the most compact conformations observed for the lowest charge states. In this article, we address recent controversies surrounding the relationship between charge states and folding, focussing also on the manipulation of charge in solution and its effect on conformation. `Supercharging' reagents that have been used to effect change in charge state can promote unfolding in the electrospray droplet. However for several protein complexes, supercharging does not appear to perturb the structure in that unfolding is not detected. Consequently, a higher charge state does not necessarily imply unfolding. Whilst the effect of charge manipulation on conformation remains controversial, there is strong evidence that a folded, compact state of a protein can survive in the gas phase, at least on a millisecond timescale. The exact nature of the side-chain packing and secondary structural elements in these compact states, however, remains elusive and prompts further research.

  17. Radiative and Excited State Charmonium Physics

    Energy Technology Data Exchange (ETDEWEB)

    Jozef Dudek

    2007-07-30

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

  18. A treatment of excited states in nucleosynthesis

    Science.gov (United States)

    Gupta, Sanjib Shankar

    2002-10-01

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

  19. Aerosol charge state characterisation using an ELPI

    Science.gov (United States)

    Matthews, J. C.; Wright, M. D.; Biddiscombe, M. F.; Usmani, O. S.; Henshaw, D. L.

    2011-06-01

    A new technique has been developed to measure the size distribution and charge state of highly charged aerosols using an Electrical Low Pressure Impactor (ELPI). The internal charger was switched alternately on and off and the time between stable charge states found to be ~ 10 s. The size distribution of aerosols was found when the charger was on, from which the charge distribution can be estimated when the charger is off using the current at each impactor stage. This method was tested in background conditions, when a candle was burning and when a negative air ioniser was used. The ELPI electrometers were not sensitive enough to accurately measure the charge state on background and candle air, but gave a value for air charged by an ioniser. Comparing results from the ELPI with other techniques showed inaccuracies in this method that need to be addressed before further use of this technique.

  20. Aerosol charge state characterisation using an ELPI

    Energy Technology Data Exchange (ETDEWEB)

    Matthews, J C; Wright, M D; Henshaw, D L [University of Bristol (United Kingdom); Biddiscombe, M F; Usmani, O S, E-mail: j.c.matthews@bristol.ac.uk [NHLI, Imperial College London and Royal Brompton Hospital (United Kingdom)

    2011-06-23

    A new technique has been developed to measure the size distribution and charge state of highly charged aerosols using an Electrical Low Pressure Impactor (ELPI). The internal charger was switched alternately on and off and the time between stable charge states found to be {approx} 10 s. The size distribution of aerosols was found when the charger was on, from which the charge distribution can be estimated when the charger is off using the current at each impactor stage. This method was tested in background conditions, when a candle was burning and when a negative air ioniser was used. The ELPI electrometers were not sensitive enough to accurately measure the charge state on background and candle air, but gave a value for air charged by an ioniser. Comparing results from the ELPI with other techniques showed inaccuracies in this method that need to be addressed before further use of this technique.

  1. Electron affinity and excited states of methylglyoxal

    Science.gov (United States)

    Dauletyarov, Yerbolat; Dixon, Andrew R.; Wallace, Adam A.; Sanov, Andrei

    2017-07-01

    Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A'), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A') = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A' state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A' ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

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

    DEFF Research Database (Denmark)

    Shelby, Megan L.; Lestrange, Patrick J.; Jackson, Nicholas E.

    2016-01-01

    and nuclear structure for critical excited electronic states in the relaxation pathway characterize the dependence of the complex's geometry on the electron occupation of the 3d orbitals. Calculated XANES transitions for these excited states assign a short-lived transient signal to the spectroscopic signature...... of the Ni(I) species, resulting from intramolecular charge transfer on a time scale that has eluded previous synchrotron studies. These combined results enable us to examine the excited state structural dynamics of NiTMP prior to thermal relaxation and to capture intermediates of potential photocatalytic...

  3. Charge-exchange, ionization and excitation in low-energy Li$^{+}-$ Ar, K$^{+}-$ Ar, and Na$^{+}-$He collisions

    CERN Document Server

    Lomsadze, Ramaz A; Kezerashvili, RomanYa; Schulz, Michael

    2016-01-01

    Absolute cross sections are measured for charge-exchange, ionization, and excitation within the same experimental setup for the Li$^{+}-$Ar, K$^{+}-$ Ar, and Na$^{+}-$ He collisions in the ion energy range $0.5-10$ keV. Results of our measurements along with existing experimental data and the schematic correlation diagrams are used to analyze and determine the mechanisms for these processes. The experimental results show that the charge-exchange processes are realized with high probabilities and electrons are predominately captured in ground states. The cross section ratio for charge exchange, ionization and excitation processes roughly attains the value $10:2:1$, respectively. The contributions of various partial inelastic channels to the total ionization cross sections are estimated and a primary mechanism for the process is defined. The energy-loss spectrum, in addition, is applied to estimate the relative contribution of different inelastic channels and to determine the mechanisms for the ionization and f...

  4. Search for excited $B_c^{+}$ states

    CERN Document Server

    Aaij, Roel; LHCb Collaboration; Adinolfi, Marco; Ajaltouni, Ziad; Akar, Simon; Albrecht, Johannes; Alessio, Federico; Alexander, Michael; Alfonso Albero, Alejandro; Ali, Suvayu; Alkhazov, Georgy; Alvarez Cartelle, Paula; Alves Jr, Antonio Augusto; Amato, Sandra; Amerio, Silvia; Amhis, Yasmine; An, Liupan; Anderlini, Lucio; Andreassi, Guido; Andreotti, Mirco; Andrews, Jason; Appleby, Robert; Archilli, Flavio; d'Argent, Philippe; Arnau Romeu, Joan; Artamonov, Alexander; Artuso, Marina; Aslanides, Elie; Atzeni, Michele; Auriemma, Giulio; Baalouch, Marouen; Babuschkin, Igor; Bachmann, Sebastian; Back, John; Badalov, Alexey; Baesso, Clarissa; Baker, Sophie; Balagura, Vladislav; Baldini, Wander; Baranov, Alexander; Barlow, Roger; Barschel, Colin; Barsuk, Sergey; Barter, William; Baryshnikov, Fedor; Batozskaya, Varvara; Battista, Vincenzo; Bay, Aurelio; Beaucourt, Leo; Beddow, John; Bedeschi, Franco; Bediaga, Ignacio; Beiter, Andrew; Bel, Lennaert; Beliy, Nikita; Bellee, Violaine; Belloli, Nicoletta; Belous, Konstantin; Belyaev, Ivan; Ben-Haim, Eli; Bencivenni, Giovanni; Benson, Sean; Beranek, Sarah; Berezhnoy, Alexander; Bernet, Roland; Berninghoff, Daniel; Bertholet, Emilie; Bertolin, Alessandro; Betancourt, Christopher; Betti, Federico; Bettler, Marc-Olivier; van Beuzekom, Martinus; Bezshyiko, Iaroslava; Bifani, Simone; Billoir, Pierre; Birnkraut, Alex; Bizzeti, Andrea; Bjørn, Mikkel; Blake, Thomas; Blanc, Frederic; Blusk, Steven; Bocci, Valerio; Boettcher, Thomas; Bondar, Alexander; Bondar, Nikolay; Bordyuzhin, Igor; Borghi, Silvia; Borisyak, Maxim; Borsato, Martino; Bossu, Francesco; Boubdir, Meriem; Bowcock, Themistocles; Bowen, Espen Eie; Bozzi, Concezio; Braun, Svende; Brodzicka, Jolanta; Brundu, Davide; Buchanan, Emma; Burr, Christopher; Bursche, Albert; Buytaert, Jan; Byczynski, Wiktor; Cadeddu, Sandro; Cai, Hao; Calabrese, Roberto; Calladine, Ryan; Calvi, Marta; Calvo Gomez, Miriam; Camboni, Alessandro; Campana, Pierluigi; Campora Perez, Daniel Hugo; Capriotti, Lorenzo; Carbone, Angelo; Carboni, Giovanni; Cardinale, Roberta; Cardini, Alessandro; Carniti, Paolo; Carson, Laurence; Carvalho Akiba, Kazuyoshi; Casse, Gianluigi; Cassina, Lorenzo; Cattaneo, Marco; Cavallero, Giovanni; Cenci, Riccardo; Chamont, David; Chapman, Matthew George; Charles, Matthew; Charpentier, Philippe; Chatzikonstantinidis, Georgios; Chefdeville, Maximilien; Chen, Shanzhen; Cheung, Shu Faye; Chitic, Stefan-Gabriel; Chobanova, Veronika; Chrzaszcz, Marcin; Chubykin, Alexsei; Ciambrone, Paolo; Cid Vidal, Xabier; Ciezarek, Gregory; Clarke, Peter; Clemencic, Marco; Cliff, Harry; Closier, Joel; Coco, Victor; Cogan, Julien; Cogneras, Eric; Cogoni, Violetta; Cojocariu, Lucian; Collins, Paula; Colombo, Tommaso; Comerma-Montells, Albert; Contu, Andrea; Coombs, George; Coquereau, Samuel; Corti, Gloria; Corvo, Marco; Costa Sobral, Cayo Mar; Couturier, Benjamin; Cowan, Greig; Craik, Daniel Charles; Crocombe, Andrew; Cruz Torres, Melissa Maria; Currie, Robert; D'Ambrosio, Carmelo; Da Cunha Marinho, Franciole; Da Silva, Cesar Luiz; Dall'Occo, Elena; Dalseno, Jeremy; Davis, Adam; De Aguiar Francisco, Oscar; De Bruyn, Kristof; De Capua, Stefano; De Cian, Michel; De Miranda, Jussara; De Paula, Leandro; De Serio, Marilisa; De Simone, Patrizia; Dean, Cameron Thomas; Decamp, Daniel; Del Buono, Luigi; Dembinski, Hans Peter; Demmer, Moritz; Dendek, Adam; Derkach, Denis; Deschamps, Olivier; Dettori, Francesco; Dey, Biplab; Di Canto, Angelo; Di Nezza, Pasquale; Dijkstra, Hans; Dordei, Francesca; Dorigo, Mirco; Dosil Suárez, Alvaro; Douglas, Lauren; Dovbnya, Anatoliy; Dreimanis, Karlis; Dufour, Laurent; Dujany, Giulio; Durante, Paolo; Durham, John Matthew; Dutta, Deepanwita; Dzhelyadin, Rustem; Dziewiecki, Michal; Dziurda, Agnieszka; Dzyuba, Alexey; Easo, Sajan; Ebert, Marcus; Egede, Ulrik; Egorychev, Victor; Eidelman, Semen; Eisenhardt, Stephan; Eitschberger, Ulrich; Ekelhof, Robert; Eklund, Lars; Ely, Scott; Esen, Sevda; Evans, Hannah Mary; Evans, Timothy; Falabella, Antonio; Farley, Nathanael; Farry, Stephen; Fazzini, Davide; Federici, Luca; Ferguson, Dianne; Fernandez, Gerard; Fernandez Declara, Placido; Fernandez Prieto, Antonio; Ferrari, Fabio; Ferreira Lopes, Lino; Ferreira Rodrigues, Fernando; Ferro-Luzzi, Massimiliano; Filippov, Sergey; Fini, Rosa Anna; Fiorini, Massimiliano; Firlej, Miroslaw; Fitzpatrick, Conor; Fiutowski, Tomasz; Fleuret, Frederic; Fontana, Marianna; Fontanelli, Flavio; Forty, Roger; Franco Lima, Vinicius; Frank, Markus; Frei, Christoph; Fu, Jinlin; Funk, Wolfgang; Furfaro, Emiliano; Färber, Christian; Gabriel, Emmy; Gallas Torreira, Abraham; Galli, Domenico; Gallorini, Stefano; Gambetta, Silvia; Gandelman, Miriam; Gandini, Paolo; Gao, Yuanning; Garcia Martin, Luis Miguel; García Pardiñas, Julián; Garra Tico, Jordi; Garrido, Lluis; Garsed, Philip John; Gascon, David; Gaspar, Clara; Gavardi, Laura; Gazzoni, Giulio; Gerick, David; Gersabeck, Evelina; Gersabeck, Marco; Gershon, Timothy; Ghez, Philippe; Gianì, Sebastiana; Gibson, Valerie; Girard, Olivier Göran; Giubega, Lavinia-Helena; Gizdov, Konstantin; Gligorov, Vladimir; Golubkov, Dmitry; Golutvin, Andrey; Gomes, Alvaro; Gorelov, Igor Vladimirovich; Gotti, Claudio; Govorkova, Ekaterina; Grabowski, Jascha Peter; Graciani Diaz, Ricardo; Granado Cardoso, Luis Alberto; Graugés, Eugeni; Graverini, Elena; Graziani, Giacomo; Grecu, Alexandru; Greim, Roman; Griffith, Peter; Grillo, Lucia; Gruber, Lukas; Gruberg Cazon, Barak Raimond; Grünberg, Oliver; Gushchin, Evgeny; Guz, Yury; Gys, Thierry; Göbel, Carla; Hadavizadeh, Thomas; Hadjivasiliou, Christos; Haefeli, Guido; Haen, Christophe; Haines, Susan; Hamilton, Brian; Han, Xiaoxue; Hancock, Thomas Henry; Hansmann-Menzemer, Stephanie; Harnew, Neville; Harnew, Samuel; Hasse, Christoph; Hatch, Mark; He, Jibo; Hecker, Malte; Heinicke, Kevin; Heister, Arno; Hennessy, Karol; Henrard, Pierre; Henry, Louis; van Herwijnen, Eric; Heß, Miriam; Hicheur, Adlène; Hill, Donal; Hopchev, Plamen Hristov; Hu, Wenhua; Huang, Wenqian; Huard, Zachary; Hulsbergen, Wouter; Humair, Thibaud; Hushchyn, Mikhail; Hutchcroft, David; Ibis, Philipp; Idzik, Marek; Ilten, Philip; Jacobsson, Richard; Jalocha, Pawel; Jans, Eddy; Jawahery, Abolhassan; Jiang, Feng; John, Malcolm; Johnson, Daniel; Jones, Christopher; Joram, Christian; Jost, Beat; Jurik, Nathan; Kandybei, Sergii; Karacson, Matthias; Kariuki, James Mwangi; Karodia, Sarah; Kazeev, Nikita; Kecke, Matthieu; Keizer, Floris; Kelsey, Matthew; Kenzie, Matthew; Ketel, Tjeerd; Khairullin, Egor; Khanji, Basem; Khurewathanakul, Chitsanu; Kirn, Thomas; Klaver, Suzanne; Klimaszewski, Konrad; Klimkovich, Tatsiana; Koliiev, Serhii; Kolpin, Michael; Kopecna, Renata; Koppenburg, Patrick; Kosmyntseva, Alena; Kotriakhova, Sofia; Kozeiha, Mohamad; Kravchuk, Leonid; Kreps, Michal; Kress, Felix Johannes; Krokovny, Pavel; Krzemien, Wojciech; Kucewicz, Wojciech; Kucharczyk, Marcin; Kudryavtsev, Vasily; Kuonen, Axel Kevin; Kvaratskheliya, Tengiz; Lacarrere, Daniel; Lafferty, George; Lai, Adriano; Lanfranchi, Gaia; Langenbruch, Christoph; Latham, Thomas; Lazzeroni, Cristina; Le Gac, Renaud; Leflat, Alexander; Lefrançois, Jacques; Lefèvre, Regis; Lemaitre, Florian; Lemos Cid, Edgar; Leroy, Olivier; Lesiak, Tadeusz; Leverington, Blake; Li, Pei-Rong; Li, Tenglin; Li, Yiming; Li, Zhuoming; Liang, Xixin; Likhomanenko, Tatiana; Lindner, Rolf; Lionetto, Federica; Lisovskyi, Vitalii; Liu, Xuesong; Loh, David; Loi, Angelo; Longstaff, Iain; Lopes, Jose; Lucchesi, Donatella; Lucio Martinez, Miriam; Luo, Haofei; Lupato, Anna; Luppi, Eleonora; Lupton, Oliver; Lusiani, Alberto; Lyu, Xiao-Rui; Machefert, Frederic; Maciuc, Florin; Macko, Vladimir; Mackowiak, Patrick; Maddrell-Mander, Samuel; Maev, Oleg; Maguire, Kevin; Maisuzenko, Dmitrii; Majewski, Maciej Witold; Malde, Sneha; Malecki, Bartosz; Malinin, Alexander; Maltsev, Timofei; Manca, Giulia; Mancinelli, Giampiero; Marangotto, Daniele; Maratas, Jan; Marchand, Jean François; Marconi, Umberto; Marin Benito, Carla; Marinangeli, Matthieu; Marino, Pietro; Marks, Jörg; Martellotti, Giuseppe; Martin, Morgan; Martinelli, Maurizio; Martinez Santos, Diego; Martinez Vidal, Fernando; Massafferri, André; Matev, Rosen; Mathad, Abhijit; Mathe, Zoltan; Matteuzzi, Clara; Mauri, Andrea; Maurice, Emilie; Maurin, Brice; Mazurov, Alexander; McCann, Michael; McNab, Andrew; McNulty, Ronan; Mead, James Vincent; Meadows, Brian; Meaux, Cedric; Meier, Frank; Meinert, Nis; Melnychuk, Dmytro; Merk, Marcel; Merli, Andrea; Michielin, Emanuele; Milanes, Diego Alejandro; Millard, Edward James; Minard, Marie-Noelle; Minzoni, Luca; Mitzel, Dominik Stefan; Mogini, Andrea; Molina Rodriguez, Josue; Mombächer, Titus; Monroy, Igancio Alberto; Monteil, Stephane; Morandin, Mauro; Morello, Michael Joseph; Morgunova, Olga; Moron, Jakub; Morris, Adam Benjamin; Mountain, Raymond; Muheim, Franz; Mulder, Mick; Müller, Dominik; Müller, Janine; Müller, Katharina; Müller, Vanessa; Naik, Paras; Nakada, Tatsuya; Nandakumar, Raja; Nandi, Anita; Nasteva, Irina; Needham, Matthew; Neri, Nicola; Neubert, Sebastian; Neufeld, Niko; Neuner, Max; Nguyen, Thi Dung; Nguyen-Mau, Chung; Nieswand, Simon; Niet, Ramon; Nikitin, Nikolay; Nikodem, Thomas; Nogay, Alla; O'Hanlon, Daniel Patrick; Oblakowska-Mucha, Agnieszka; Obraztsov, Vladimir; Ogilvy, Stephen; Oldeman, Rudolf; Onderwater, Gerco; Ossowska, Anna; Otalora Goicochea, Juan Martin; Owen, Patrick; Oyanguren, Maria Aranzazu; Pais, Preema Rennee; Palano, Antimo; Palutan, Matteo; Papanestis, Antonios; Pappagallo, Marco; Pappalardo, Luciano; Parker, William; Parkes, Christopher; Passaleva, Giovanni; Pastore, Alessandra; Patel, Mitesh; Patrignani, Claudia; Pearce, Alex; Pellegrino, Antonio; Penso, Gianni; Pepe Altarelli, Monica; Perazzini, Stefano; Pereima, Dmitrii; Perret, Pascal; Pescatore, Luca; Petridis, Konstantinos; Petrolini, Alessandro; Petrov, Aleksandr; Petruzzo, Marco; Picatoste Olloqui, Eduardo; Pietrzyk, Boleslaw; Pietrzyk, Guillaume; Pikies, Malgorzata; Pinci, Davide; Pisani, Flavio; Pistone, Alessandro; Piucci, Alessio; Placinta, Vlad-Mihai; Playfer, Stephen; Plo Casasus, Maximo; Polci, Francesco; Poli Lener, Marco; Poluektov, Anton; Polyakov, Ivan; Polycarpo, Erica; Pomery, Gabriela Johanna; Ponce, Sebastien; Popov, Alexander; Popov, Dmitry; Poslavskii, Stanislav; Potterat, Cédric; Price, Eugenia; Prisciandaro, Jessica; Prouve, Claire; Pugatch, Valery; Puig Navarro, Albert; Pullen, Hannah Louise; Punzi, Giovanni; Qian, Wenbin; Qin, Jia-Jia; Quagliani, Renato; Quintana, Boris; Rachwal, Bartlomiej; Rademacker, Jonas; Rama, Matteo; Ramos Pernas, Miguel; Rangel, Murilo; Raniuk, Iurii; Ratnikov, Fedor; Raven, Gerhard; Ravonel Salzgeber, Melody; Reboud, Meril; Redi, Federico; Reichert, Stefanie; dos Reis, Alberto; Remon Alepuz, Clara; Renaudin, Victor; Ricciardi, Stefania; Richards, Sophie; Rihl, Mariana; Rinnert, Kurt; Robbe, Patrick; Robert, Arnaud; Rodrigues, Ana Barbara; Rodrigues, Eduardo; Rodriguez Lopez, Jairo Alexis; Rogozhnikov, Alexey; Roiser, Stefan; Rollings, Alexandra Paige; Romanovskiy, Vladimir; Romero Vidal, Antonio; Rotondo, Marcello; Rudolph, Matthew Scott; Ruf, Thomas; Ruiz Valls, Pablo; Ruiz Vidal, Joan; Saborido Silva, Juan Jose; Sadykhov, Elnur; Sagidova, Naylya; Saitta, Biagio; Salustino Guimaraes, Valdir; Sanchez Mayordomo, Carlos; Sanmartin Sedes, Brais; Santacesaria, Roberta; Santamarina Rios, Cibran; Santimaria, Marco; Santovetti, Emanuele; Sarpis, Gediminas; Sarti, Alessio; Satriano, Celestina; Satta, Alessia; Saunders, Daniel Martin; Savrina, Darya; Schael, Stefan; Schellenberg, Margarete; Schiller, Manuel; Schindler, Heinrich; Schmelling, Michael; Schmelzer, Timon; Schmidt, Burkhard; Schneider, Olivier; Schopper, Andreas; Schreiner, HF; Schubiger, Maxime; Schune, Marie Helene; Schwemmer, Rainer; Sciascia, Barbara; Sciubba, Adalberto; Semennikov, Alexander; Sepulveda, Eduardo Enrique; Sergi, Antonino; Serra, Nicola; Serrano, Justine; Sestini, Lorenzo; Seyfert, Paul; Shapkin, Mikhail; Shapoval, Illya; Shcheglov, Yury; Shears, Tara; Shekhtman, Lev; Shevchenko, Vladimir; Siddi, Benedetto Gianluca; Silva Coutinho, Rafael; Silva de Oliveira, Luiz Gustavo; Simi, Gabriele; Simone, Saverio; Sirendi, Marek; Skidmore, Nicola; Skwarnicki, Tomasz; Smith, Iwan Thomas; Smith, Jackson; Smith, Mark; Soares Lavra, Lais; Sokoloff, Michael; Soler, Paul; Souza De Paula, Bruno; Spaan, Bernhard; Spradlin, Patrick; Sridharan, Srikanth; Stagni, Federico; Stahl, Marian; Stahl, Sascha; Stefko, Pavol; Stefkova, Slavomira; Steinkamp, Olaf; Stemmle, Simon; Stenyakin, Oleg; Stepanova, Margarita; Stevens, Holger; Stone, Sheldon; Storaci, Barbara; Stracka, Simone; Stramaglia, Maria Elena; Straticiuc, Mihai; Straumann, Ulrich; Sun, Jiayin; Sun, Liang; Swientek, Krzysztof; Syropoulos, Vasileios; Szumlak, Tomasz; Szymanski, Maciej Pawel; T'Jampens, Stephane; Tayduganov, Andrey; Tekampe, Tobias; Tellarini, Giulia; Teubert, Frederic; Thomas, Eric; van Tilburg, Jeroen; Tilley, Matthew James; Tisserand, Vincent; Tobin, Mark; Tolk, Siim; Tomassetti, Luca; Tonelli, Diego; Tourinho Jadallah Aoude, Rafael; Tournefier, Edwige; Traill, Murdo; Tran, Minh Tâm; Tresch, Marco; Trisovic, Ana; Tsaregorodtsev, Andrei; Tsopelas, Panagiotis; Tully, Alison; Tuning, Niels; Ukleja, Artur; Usachov, Andrii; Ustyuzhanin, Andrey; Uwer, Ulrich; Vacca, Claudia; Vagner, Alexander; Vagnoni, Vincenzo; Valassi, Andrea; Valat, Sebastien; Valenti, Giovanni; Vazquez Gomez, Ricardo; Vazquez Regueiro, Pablo; Vecchi, Stefania; van Veghel, Maarten; Velthuis, Jaap; Veltri, Michele; Veneziano, Giovanni; Venkateswaran, Aravindhan; Verlage, Tobias Anton; Vernet, Maxime; Vesterinen, Mika; Viana Barbosa, Joao Vitor; Vieira, Daniel; Vieites Diaz, Maria; Viemann, Harald; Vilasis-Cardona, Xavier; Vitti, Marcela; Volkov, Vladimir; Vollhardt, Achim; Voneki, Balazs; Vorobyev, Alexey; Vorobyev, Vitaly; Voß, Christian; de Vries, Jacco; Vázquez Sierra, Carlos; Waldi, Roland; Walsh, John; Wang, Jianchun; Wang, Yilong; Ward, David; Wark, Heather Mckenzie; Watson, Nigel; Websdale, David; Weiden, Andreas; Weisser, Constantin; Whitehead, Mark; Wicht, Jean; Wilkinson, Guy; Wilkinson, Michael; Williams, Mark Richard James; Williams, Mike; Williams, Timothy; Wilson, Fergus; Wimberley, Jack; Winn, Michael Andreas; Wishahi, Julian; Wislicki, Wojciech; Witek, Mariusz; Wormser, Guy; Wotton, Stephen; Wyllie, Kenneth; Xie, Yuehong; Xu, Menglin; Xu, Qingnian; Xu, Zehua; Xu, Zhirui; Yang, Zhenwei; Yang, Zishuo; Yao, Yuezhe; Yin, Hang; Yu, Jiesheng; Yuan, Xuhao; Yushchenko, Oleg; Zarebski, Kristian Alexander; Zavertyaev, Mikhail; Zhang, Liming; Zhang, Yanxi; Zhelezov, Alexey; Zheng, Yangheng; Zhu, Xianglei; Zhukov, Valery; Zonneveld, Jennifer Brigitta; Zucchelli, Stefano

    2017-01-01

    A search is performed in the invariant mass spectrum of the $B_c^{+}\\pi^{+}\\pi^{-}$ system for the excited $B_c^{+}$ states $B_c(2^{1}S_{0})^+$ and $B_c(2^{3}S_{1})^+$ using a data sample of $pp$ collisions collected by the LHCb experiment at the centre-of-mass energy of $\\sqrt{s} = 8 \\,{\\mathrm{TeV}}$, corresponding to an integrated luminosity of $2 \\,{\\mathrm{fb^{-1}}}$. No evidence is seen for either state. Upper limits on the ratios of the production cross-sections of the $B_c(2^{1}S_{0})^+$ and $B_c(2^{3}S_{1})^+$ states times the branching fractions of ${B_c(2^{1}S_{0})^+} \\to {B_c^{+}\\pi^{+}\\pi^{-}}$ and ${B_c(2^{3}S_{1})^+} \\to {B_c^{*+}\\pi^{+}\\pi^{-}}$ over the production cross-section of the $B_c^{+}$ state are given as a function of their masses. They are found to be between 0.02 and 0.14 at $95\\%$ confidence level for $B_c(2^{1}S_{0})^+$ and $B_c(2^{3}S_{1})^+$ in the mass ranges $[6830, 6890] \\,{\\mathrm{MeV}}/c^{2}$ and $[6795,6890] \\,{\\mathrm{MeV}}/c^{2}$, respectively.

  5. Unbound excited states in $^{19}$,$^{17}$C

    CERN Document Server

    Satou, Y; Fukuda, N; Sugimoto, T; Kondo, Y; Matsui, N; Hashimoto, Y; Nakabayashi, T; Okumura, T; Shinohara, M; Motobayashi, T; Yanagisawa, Y; Aoi, N; Takeuchi, S; Gomi, T; Togano, Y; Kawai, S; Sakuraï, H; Ong, H J; Onishi, T K; Shimoura, S; Tamaki, M; Kobayashi, T; Otsu, H; Matsuda, Y; Endo, N; Kitayama, M; Ishihara, M

    2008-01-01

    The neutron-rich carbon isotopes 19,17C have been investigated via proton inelastic scattering on a liquid hydrogen target at 70 MeV/nucleon. The invariant mass method in inverse kinematics was employed to reconstruct the energy spectrum, in which fast neutrons and charged fragments were detected in coincidence using a neutron hodoscope and a dipole magnet system. A peak has been observed with an excitation energy of 1.46(10) MeV in 19C, while three peaks with energies of 2.20(3), 3.05(3), and 6.13(9) MeV have been observed in 17C. Deduced cross sections are compared with microscopic DWBA calculations based on p-sd shell model wave functions and modern nucleon-nucleus optical potentials. Jpi assignments are made for the four observed states as well as the ground states of both nuclei.

  6. Quantum marginals from pure doubly excited states

    Science.gov (United States)

    Maciążek, Tomasz; Tsanov, Valdemar

    2017-11-01

    The possible spectra of one-particle reduced density matrices that are compatible with a pure multipartite quantum system of finite dimension form a convex polytope. We introduce a new construction of inner- and outer-bounding polytopes that constrain the polytope for the entire quantum system. The outer bound is sharp. The inner polytope stems only from doubly excited states. We find all quantum systems, where the bounds coincide giving the entire polytope. We show, that those systems are: (i) any system of two particles (ii) L qubits, (iii) three fermions on N≤slant 7 levels, (iv) any number of bosons on any number of levels and (v) fermionic Fock space on N≤slant 5 levels. The methods we use come from symplectic geometry and representation theory of compact Lie groups. In particular, we study the images of proper momentum maps, where our method describes momentum images for all representations that are spherical.

  7. Excited states in {sup 155}Yb and

    Energy Technology Data Exchange (ETDEWEB)

    Ding, K. Y.; Cizewski, J. A.; Seweryniak, D.; Amro, H.; Carpenter, M. P.; Davids, C. N.; Fotiades, N.; Janssens, R. V. F.; Lauritsen, T.; Lister, C. J. (and others)

    2001-09-01

    The 270-MeV {sup 58}Ni+{sup 102}Pd reaction was used for the first recoil-decay tagging measurement with Gammasphere coupled to the Fragment Mass Analyzer at Argonne National Laboratory. Level structures of {sup 155}Yb, {sup 156}Lu, and {sup 157}Lu, as well as the excited states associated with the 25/2{sup -} isomer in {sup 155}Lu, are identified for the first time. The systematical behavior of the energy levels is compared with that of neighboring isotones and isotopes. The attractive interaction between h{sub 11/2} protons and h{sub 9/2} neutrons plays an important role in the structure of {sup 155}Yb and {sup 155,156}Lu.

  8. Low-charge-state RFQ injector

    Energy Technology Data Exchange (ETDEWEB)

    Shepard, K.W.; Kim, J.W.

    1995-08-01

    Preliminary design work was done for a short, normally-conducting RFQ entrance section for a low-charge-state linac. Early results indicate that a low- frequency (12 MHz) RFQ, operated on a high-voltage platform, and injected with a pre-bunched beam, can provide ATLAS quality beams of ions of charge-to-mass ratio less than 1/132.

  9. Charging power optimization for nonlinear vibration energy harvesting systems subjected to arbitrary, persistent base excitations

    Science.gov (United States)

    Dai, Quanqi; Harne, Ryan L.

    2018-01-01

    The vibrations of mechanical systems and structures are often a combination of periodic and random motions. Emerging interest to exploit nonlinearities in vibration energy harvesting systems for charging microelectronics may be challenged by such reality due to the potential to transition between favorable and unfavorable dynamic regimes for DC power delivery. Therefore, a need exists to devise an optimization method whereby charging power from nonlinear energy harvesters remains maximized when excitation conditions are neither purely harmonic nor purely random, which have been the attention of past research. This study meets the need by building from an analytical approach that characterizes the dynamic response of nonlinear energy harvesting platforms subjected to combined harmonic and stochastic base accelerations. Here, analytical expressions are formulated and validated to optimize charging power while the influences of the relative proportions of excitation types are concurrently assessed. It is found that about a 2 times deviation in optimal resistive loads can reduce the charging power by 20% when the system is more prominently driven by harmonic base accelerations, whereas a greater proportion of stochastic excitation results in a 11% reduction in power for the same resistance deviation. In addition, the results reveal that when the frequency of a predominantly harmonic excitation deviates by 50% from optimal conditions the charging power reduces by 70%, whereas the same frequency deviation for a more stochastically dominated excitation reduce total DC power by only 20%. These results underscore the need for maximizing direct current power delivery for nonlinear energy harvesting systems in practical operating environments.

  10. Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications

    Energy Technology Data Exchange (ETDEWEB)

    Pattengale, Brian [Department; Yang, Sizhuo [Department; Ludwig, John [Department; Huang, Zhuangqun [Department; Zhang, Xiaoyi [X-ray; Huang, Jier [Department

    2016-06-22

    Zeolitic Imidazolate Frameworks (ZIFs) have emerged as a novel class of porous metal-organic frameworks (MOFs) for catalysis application because of their exceptional thermal and chemical stability. Inspired by the broad absorption of ZIF-67 in UV-visible-near IR region, we explored its excited state and charge separation dynamics, properties essential for photocatalytic applications, using optical (OTA) and X-ray transient absorption (XTA) spectroscopy. OTA results show that an exceptionally long-lived excited state is formed after photoexcitation. This long-lived excited state was confirmed to be the charge separated state with ligandto-metal charge transfer character using XTA. The surprisingly long-lived charge separated state, together with its intrinsic hybrid nature, all point to its potential application in heterogeneous photocatalysis and energy conversion.

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

    DEFF Research Database (Denmark)

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

    1994-01-01

    A combination of steady-state and dynamic spectral measurements are used to provide new insights into the nature of the excited-state processes of all-trans-1,4-diphenyl-1,3-butadiene and several analogs: 1,4-diphenyl- 1,3-cyclopentadiene, 1,1,4,4-tetraphenylbutadiene, 1,2,3,4-tetraphenyl-1,3-cyc...... indicate that phenyl torsional motion is not important to the excited-state dynamics and reveal alternative excited-state reaction pathways. The results demonstrate how molecular systems that are structually similar can exhibit different electronic properties and excited-state dynamics....

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

    Science.gov (United States)

    Etienne, Thibaud

    2015-04-14

    This article reports a novel theoretical approach related to the analysis of molecular excited states. The strategy introduced here involves gathering two pieces of physical information, coming from Hilbert and direct space operations, into a general, unique quantum mechanical descriptor of electronic transitions' locality. Moreover, the projection of Hilbert and direct space-derived indices in an Argand plane delivers a straightforward way to visually probe the ability of a dye to undergo a long- or short-range charge-transfer. This information can be applied, for instance, to the analysis of the electronic response of families of dyes to light absorption by unveiling the trend of a given push-pull chromophore to increase the electronic cloud polarization magnitude of its main transition with respect to the size extension of its conjugated spacer. We finally demonstrate that all the quantities reported in this article can be reliably approximated by a linear algebraic derivation, based on the contraction of detachment/attachment density matrices from canonical to atomic space. This alternative derivation has the remarkable advantage of a very low computational cost with respect to the previously used numerical integrations, making fast and accurate characterization of large molecular systems' excited states easily affordable.

  13. Vibronic coupling in the excited-states of carotenoids

    Energy Technology Data Exchange (ETDEWEB)

    Miki, Takeshi [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg, Germany; Buckup, Tiago [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg, Germany; Krause, Marie S. [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg, Germany; Southall, June [College of Medical; Veterinary, and Life Science; University of Glasgow; G12 8QQ Glasgow, UK; Cogdell, Richard J. [College of Medical; Veterinary, and Life Science; University of Glasgow; G12 8QQ Glasgow, UK; Motzkus, Marcus [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg, Germany

    2016-01-01

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

  14. Excited-State Effective Masses in Lattice QCD

    Energy Technology Data Exchange (ETDEWEB)

    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.

  15. Quantum dynamics of vibrational excitations and vibrational charge ...

    Indian Academy of Sciences (India)

    Administrator

    Present address: The Fritz Haber Research Centre and The Department of Physical Chemisry,. Hebrew University of Jerusalem, ... state of the diatom. Good amount of state-selected experimental data obtained from the molecular beam and the H+/H energy-loss spectroscopy also exists at. Ec.m. = 23 eV for both the IVE ...

  16. Spin-charge-lattice coupling through resonant multimagnon excitations in multiferroic BiFeO3

    Science.gov (United States)

    Ramirez, M. O.; Kumar, A.; Denev, S. A.; Chu, Y. H.; Seidel, J.; Martin, L. W.; Yang, S.-Y.; Rai, R. C.; Xue, X. S.; Ihlefeld, J. F.; Podraza, N. J.; Saiz, E.; Lee, S.; Klug, J.; Cheong, S. W.; Bedzyk, M. J.; Auciello, O.; Schlom, D. G.; Orenstein, J.; Ramesh, R.; Musfeldt, J. L.; Litvinchuk, A. P.; Gopalan, V.

    2009-04-01

    Spin-charge-lattice coupling mediated by multimagnon processes is demonstrated in multiferroic BiFeO3. Experimental evidence of two- and three-magnon excitations as well as multimagnon coupling at electronic energy scales and high temperatures are reported. Temperature dependent Raman experiments show up to five resonant enhancements of the two-magnon excitation below the Néel temperature. These are shown to be collective interactions between on-site Fe d-d electronic resonance, phonons, and multimagnons.

  17. Metastable charge-transfer state of californium(iii) compounds.

    Science.gov (United States)

    Liu, Guokui; Cary, Samantha K; Albrecht-Schmitt, Thomas E

    2015-06-28

    Among a series of anomalous physical and chemical properties of Cf(iii) compounds revealed by recent investigations, the present work addresses the characteristics of the optical spectra of An(HDPA)3·H2O (An = Am, Cm, and Cf), especially the broadband photoluminescence from Cf(HDPA)3·H2O induced by ligand-to-metal charge transfer (CT). As a result of strong ion-ligand interactions and the relative ease of reducing Cf(iii) to Cf(ii), a CT transition occurs at low energy (transfer state undergoes radiative and non-radiative relaxations. Broadening of the CT transition arises from strong vibronic coupling and hole-charge interactions in the valence band. The non-radiative relaxation of the metastable CT state results from a competition between phonon-relaxation and thermal tunneling that populates the excited states of Cf(iii).

  18. Femtosecond insights into direct electron injection in dye anchored ZnO QDs following charge transfer excitation.

    Science.gov (United States)

    Kumar, Pushpendra; Kumar, Sunil; Ghosh, Subrata; Pal, Suman Kalyan

    2016-07-27

    The role of the charge transfer (CT) state in interfacial electron transfer in dye-sensitized semiconductor nanocrystals is still poorly understood. To address this problem, femtosecond transient absorption (TA) spectroscopy is used as a probe to investigate the electron injection across a newly synthesized coumarin dye (8-hydroxy-2-oxo-4-phenyl-2 benzo[h]chromene-3-carbonitrile, coded BC5) and ZnO quantum dots (QDs). Steady state and time-resolved spectroscopic measurements reveal that BC5 dye interacts strongly with ZnO QDs in the ground state forming a CT complex. The BC5-ZnO QD complex absorbs more towards red compared to only the dye and QDs, and emits fluorescence due to radiative recombination of photogenerated charges. The formation of charges following the excitation of the CT complex has been demonstrated by observing the signature of dye radical cations and electrons in the conduction band (CB) of the QDs in the TA spectra. The TA signals of these charges grow sharply as a result of ultrafast direct electron injection into the QD. We have monitored the complete dynamics of photogenerated charges by measuring the TA signals of the charges up to a couple of nanoseconds. The injected electrons that are free or shallowly trapped recombine with a time constant of 625 fs, whereas deeply trapped electrons disappear slowly (526 ps) via radiative recombination. Furthermore, theoretical studies based on ab initio calculations have been carried out to complement the experimental findings.

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

    Science.gov (United States)

    Strümpfer, Johan; Schulten, Klaus

    2012-08-01

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

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

    Science.gov (United States)

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

    2014-12-21

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

  1. Photo-excited charge collection spectroscopy probing the traps in field-effect transistors

    CERN Document Server

    Im, Seongil; Kim, Jae Hoon

    2013-01-01

    Solid state field-effect devices such as organic and inorganic-channel thin-film transistors (TFTs) have been expected to promote advances in display and sensor electronics. The operational stabilities of such TFTs are thus important, strongly depending on the nature and density of charge traps present at the channel/dielectric interface or in the thin-film channel itself. This book contains how to characterize these traps, starting from the device physics of field-effect transistor (FET). Unlike conventional analysis techniques which are away from well-resolving spectral results, newly-introduced photo-excited charge-collection spectroscopy (PECCS) utilizes the photo-induced threshold voltage response from any type of working transistor devices with organic-, inorganic-, and even nano-channels, directly probing on the traps. So, our technique PECCS has been discussed through more than ten refereed-journal papers in the fields of device electronics, applied physics, applied chemistry, nano-devices and materia...

  2. Frenkel and Charge-Transfer Excitations in Donor-acceptor Complexes from Many-Body Green's Functions Theory.

    Science.gov (United States)

    Baumeier, Björn; Andrienko, Denis; Rohlfing, Michael

    2012-08-14

    Excited states of donor-acceptor dimers are studied using many-body Green's functions theory within the GW approximation and the Bethe-Salpeter equation. For a series of prototypical small-molecule based pairs, this method predicts energies of local Frenkel and intermolecular charge-transfer excitations with the accuracy of tens of meV. Application to larger systems is possible and allowed us to analyze energy levels and binding energies of excitons in representative dimers of dicyanovinyl-substituted quarterthiophene and fullerene, a donor-acceptor pair used in state of the art organic solar cells. In these dimers, the transition from Frenkel to charge transfer excitons is endothermic and the binding energy of charge transfer excitons is still of the order of 1.5-2 eV. Hence, even such an accurate dimer-based description does not yield internal energetics favorable for the generation of free charges either by thermal energy or an external electric field. These results confirm that, for qualitative predictions of solar cell functionality, accounting for the explicit molecular environment is as important as the accurate knowledge of internal dimer energies.

  3. Vibrationally excited state stectroscopy of radicals in a supersonic plasma

    NARCIS (Netherlands)

    G. Bazalgette Courreges-Lacoste, J. Bulthuis, S. Stolte, T. Motylewski; Linnartz, H.V.J.

    2001-01-01

    A plasma source based on a multilayer discharge geometry in combination with a time-of-flight REMPI experiment is used to study rotationally cold spectra of highly excited vibrational states of mass selected radicals. The rovibrational state distributions upon discharge excitation are characterised

  4. Elastic, excitation, ionization and charge transfer cross sections of current interest in fusion energy research

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, D.R.; Krstic, P.S. [Oak Ridge National Lab. TN (United States). Physics Div.

    1997-01-01

    Due to the present interest in modeling and diagnosing the edge and divertor plasma regions in magnetically confined fusion devices, we have sought to provide new calculations regarding the elastic, excitation, ionization, and charge transfer cross sections in collisions among relevant ions, neutrals, and isotopes in the low-to intermediate-energy regime. We summarize here some of our recent work. (author)

  5. Collective charge excitations and the metal-insulator transition in the square lattice Hubbard-Coulomb model

    Science.gov (United States)

    Ulybyshev, Maksim; Winterowd, Christopher; Zafeiropoulos, Savvas

    2017-11-01

    In this article, we discuss the nontrivial collective charge excitations (plasmons) of the extended square lattice Hubbard model. Using a fully nonperturbative approach, we employ the hybrid Monte Carlo algorithm to simulate the system at half-filling. A modified Backus-Gilbert method is introduced to obtain the spectral functions via numerical analytic continuation. We directly compute the single-particle density of states which demonstrates the formation of Hubbard bands in the strongly correlated phase. The momentum-resolved charge susceptibility also is computed on the basis of the Euclidean charge-density-density correlator. In agreement with previous extended dynamical mean-field theory studies, we find that, at high strength of the electron-electron interaction, the plasmon dispersion develops two branches.

  6. Excited-State Deactivation of Branched Phthalocyanine Compounds.

    Science.gov (United States)

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

    2015-12-21

    The excited-state relaxation dynamics and chromophore interactions in two phthalocyanine compounds (bis- and trisphthalocyanines) are studied by using steady-state and femtosecond transient absorption spectral measurements, where the excited-state energy-transfer mechanism is explored. By exciting phthalocyanine compounds to their second electronically excited states and probing the subsequent relaxation dynamics, a multitude of deactivation pathways are identified. The transient absorption spectra show the relaxation pathway from the exciton state to excimer state and then back to the ground state in bisphthalocyanine (bis-Pc). In trisphthalocyanine (tris-Pc), the monomeric and dimeric subunits are excited and the excitation energy transfers from the monomeric vibrationally hot S1 state to the exciton state of a pre-associated dimer, with subsequent relaxation to the ground state through the excimer state. The theoretical calculations and steady-state spectra also show a face-to-face conformation in bis-Pc, whereas in tris-Pc, two of the three phthalocyanine branches form a pre-associated face-to-face dimeric conformation with the third one acting as a monomeric unit; this is consistent with the results of the transient absorption experiments from the perspective of molecular structure. The detailed structure-property relationships in phthalocyanine compounds is useful for exploring the function of molecular aggregates in energy migration of natural photosynthesis systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Direct conversion of graphite into diamond through electronic excited states

    CERN Document Server

    Nakayama, H

    2003-01-01

    An ab initio total energy calculation has been performed for electronic excited states in diamond and rhombohedral graphite by the full-potential linearized augmented plane wave method within the framework of the local density approximation (LDA). First, calculations for the core-excited state in diamond have been performed to show that the ab initio calculations based on the LDA describe the wavefunctions in the electronic excited states as well as in the ground state quite well. Fairly good coincidence with both experimental data and theoretical prediction has been obtained for the lattice relaxation of the core exciton state. The results of the core exciton state are compared with nitrogen-doped diamond. Next, the structural stability of rhombohedral graphite has been investigated to examine the possibility of the transition into the diamond structure through electronic excited states. While maintaining the rhombohedral symmetry, rhombohedral graphite can be spontaneously transformed to cubic diamond. Tota...

  8. Environment-protected solid-state-based distributed charge qubit

    Science.gov (United States)

    Tayebi, Amin; Hoatson, Tanya Nicole; Wang, Joie; Zelevinsky, Vladimir

    2016-12-01

    A solid-state-based charge qubit is presented. The system consists of a one-dimensional wire with a pair of qubits embedded at its center. It is shown that the system supports collective states localized in the left and right sides of the wire and therefore, as a whole, performs as a single qubit. The couplings between the ground and excited states of the two central qubits are inversely proportional making them fully asynchronized and allowing for coherent manipulation and gate operations. Initialization and measurement devices, such as leads and charge detectors, connected to the edges of the wire are modeled by a continuum of energy states. The coupling to the continuum is discussed using the effective non-Hermitian Hamiltonian. At weak continuum coupling, all internal states uniformly acquire small decay widths. This changes dramatically as the coupling strength increases: the width distribution undergoes a sharp restructuring and is no longer uniformly divided among the eigenstates. Two broad resonances localized at the ends of the wire are formed. These superradiant states (analogous to Dicke states in quantum optics) effectively protect the remaining internal states from decaying into the continuum and hence increase the lifetime of the qubit. Environmental noise is introduced by considering random Gaussian fluctuations of electronic energies. The interplay between decoherence and superradiance is studied by solving the stochastic Liouville equation. In addition to increasing the lifetime, the emergence of the superradiant states increases the qubit coherence.

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

    Energy Technology Data Exchange (ETDEWEB)

    Shelby, Megan L. [Chemical; Department; Lestrange, Patrick J. [Department; Jackson, Nicholas E. [Department; Haldrup, Kristoffer [Physics; Mara, Michael W. [Chemical; Department; Stickrath, Andrew B. [Chemical; Zhu, Diling [LCLS, SLAC National Laboratory, Menlo Park, California 94025, United States; Lemke, Henrik T. [LCLS, SLAC National Laboratory, Menlo Park, California 94025, United States; Chollet, Matthieu [LCLS, SLAC National Laboratory, Menlo Park, California 94025, United States; Hoffman, Brian M. [Department; Li, Xiaosong [Department; Chen, Lin X. [Chemical; Department

    2016-07-06

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

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

    Science.gov (United States)

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

    2017-06-01

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

  11. A Simple Hubbard Model for the Excited States of Dibenzoterrylene

    CERN Document Server

    Sadeq, Z S

    2016-01-01

    We use a simple Hubbard model to characterize the electronic excited states of the dibenzoterrylene (DBT) molecule; we compute the excited state transition energies and oscillator strengths from the ground state to several singlet excited states. We consider the lowest singlet and triplet states of the molecule, examine their wavefunctions, and compute the density correlation functions that describe these states. We find that the DBT ground state is mostly a closed shell singlet with very slight radical character. We predict a relatively small singlet-triplet splitting of 0.75 eV, which is less than the mid-sized -acenes but larger than literature predictions for this state; this is because the Hubbard interaction makes a very small correction to the singlet and triplet states.

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

    DEFF Research Database (Denmark)

    Miroshnychenko, Yevhen; Gaëtan, Alpha; Evellin, Charles

    2010-01-01

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

  13. Electronically excited states of tryptamine and its microhydrated complex

    NARCIS (Netherlands)

    Schmitt, M.; Brause, R.; Marian, C.M.; Salzmann, S.; Meerts, W.L.

    2006-01-01

    The lowest electronically excited singlet states of tryptamine and the tryptamine (H2O)(1) cluster have been studied, using time dependent density functional theory for determination of the geometries and multireference configuration interaction for the vertical and adiabatic excitation energies,

  14. Excited state of {sup 7}He and its unique structure

    Energy Technology Data Exchange (ETDEWEB)

    Korsheninnikov, A.A.; Golovkov, M.S.; Ozawa, A.; Yoshida, K.; Tanihata, I.; Fulop, Z.; Kusaka, K.; Morimoto, K.; Otsu, H.; Petrascu, H.; Tokanai, F. [Institute of Physical and Chemical Research, Wako, Saitama (Japan); Kuzmin, E.A.; Nikolskii, E.Yu.; Novatskii, B.G.; Ogloblin, A.A. [Russian Research Centre Kurchatov Inst., Moscow (Russian Federation)

    2000-07-01

    The transfer reaction p({sup 8}He,d){sup 7}He with the exotic {sup 8}He-beam has been studied by correlational measurements, and an excited state of {sup 7}He was observed. Most likely, it has a structure with a neutron in an excited state coupled to the {sup 6}He-core which itself is in the excited 2{sup +}-state. The transfer reaction p({sup 8}He,{sup 2}He){sup 7}H was also studied, and manifestation on the possible existence of the resonance {sup 7}H was obtained. (orig.)

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

    Energy Technology Data Exchange (ETDEWEB)

    Gorska, M.

    1998-11-01

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

  16. Excited State Dynamics of DNA and RNA bases

    Science.gov (United States)

    Hudock, Hanneli; Levine, Benjamin; Martinez, Todd

    2007-03-01

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

  17. Negative Binomial States of the Radiation Field and their Excitations are Nonlinear Coherent States

    OpenAIRE

    Wang, Xiao-Guang; Fu, Hong-Chen

    1999-01-01

    We show that the well-known negative binomial states of the radiation field and their excitations are nonlinear coherent states. Excited nonlinear coherent state are still nonlinear coherent states with different nonlinear functions. We finally give exponential form of the nonlinear coherent states and remark that the binomial states are not nonlinear coherent states.

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

    Science.gov (United States)

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

    2017-10-04

    The cyclopropyl (cPr) group, which is a well-known probe for detecting radical character at atoms to which it is connected, is tested as an indicator for aromaticity in the first ππ* triplet and singlet excited states (T 1 and S 1 ). Baird's rule says that the π-electron counts for aromaticity and antiaromaticity in the T 1 and S 1 states are opposite to Hückel's rule in the ground state (S 0 ). Our hypothesis is that the cPr group, as a result of Baird's rule, will remain closed when attached to an excited-state aromatic ring, enabling it to be used as an indicator to distinguish excited-state aromatic rings from excited-state antiaromatic and nonaromatic rings. Quantum chemical calculations and photoreactivity experiments support our hypothesis; calculated aromaticity indices reveal that openings of cPr substituents on [4n]annulenes ruin the excited-state aromaticity in energetically unfavorable processes. Yet, polycyclic compounds influenced by excited-state aromaticity (e.g., biphenylene), as well as 4nπ-electron heterocycles with two or more heteroatoms represent limitations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Excited state dynamics of liquid water near the surface

    Directory of Open Access Journals (Sweden)

    Schultz Thomas

    2013-03-01

    Full Text Available Time resolved photoelectron spectroscopy explores the excited state dynamics of liquid water in presence of cations close to the surface. A transient hydrated electroncation complex is observed.

  20. Vibrational kinetics of electronically excited states in H2 discharges

    Science.gov (United States)

    Colonna, Gianpiero; Pietanza, Lucia D.; D'Ammando, Giuliano; Celiberto, Roberto; Capitelli, Mario; Laricchiuta, Annarita

    2017-11-01

    The evolution of atmospheric pressure hydrogen plasma under the action of repetitively ns electrical pulse has been investigated using a 0D state-to-state kinetic model that self-consistently couples the master equation of heavy particles and the Boltzmann equation for free electrons. The kinetic model includes, together with atomic hydrogen states and the vibrational kinetics of H2 ground state, vibrational levels of singlet states, accounting for the collisional quenching, having a relevant role because of the high pressure. The mechanisms of excitations, radiative decay and collisional quenching involving the excited H2 states and the corresponding cross sections, integrated over the non-equilibrium electron energy distribution function (EEDF) to obtain kinetic rates, are discussed in the light of the kinetic simulation results, i.e. the time evolution during the pulse of the plasma composition, of the EEDF and of the vibrational distributions of ground and singlet excited states.

  1. Comparative study on contribution of charge-transfer collision to excitations of iron ion between argon radio-frequency inductively-coupled plasma and nitrogen microwave induced plasma

    Energy Technology Data Exchange (ETDEWEB)

    Satoh, Kozue; Wagatsuma, Kazuaki, E-mail: wagatuma@imr.tohoku.ac.jp

    2015-06-01

    various excitation levels. • We find a non-thermal behavior of the high-lying energy levels in MIP which deviates from the normal distribution. • This non-thermal behavior would be caused by charge-transfer collisions with the ground state of nitrogen molecule ion.

  2. Self-modulated dynamics of a relativistic charged particle beam in plasma wake field excitation

    Energy Technology Data Exchange (ETDEWEB)

    Akhter, T.; Fedele, R. [Dipartimento di Fisica ‘Ettore Pancini’, Università di Napoli Federico II and INFN Sezione di Napoli, Napoli (Italy); Nicola, S. De [CNR-SPIN and INFN Sezione di Napoli, Napoli (Italy); Tanjia, F. [Dipartimento di Fisica ‘Ettore Pancini’, Università di Napoli Federico II and INFN Sezione di Napoli, Napoli (Italy); Jovanović, D. [Institute of Physics, University of Belgrade, Belgrade (Serbia); Mannan, A. [Department of Physics, Jahangirnagar University, Savar, Dhaka (Bangladesh)

    2016-09-01

    The self-modulated dynamics of a relativistic charged particle beam is provided within the context of the theory of plasma wake field excitation. The self-consistent description of the beam dynamics is provided by coupling the Vlasov equation with a Poisson-type equation relating the plasma wake potential to the beam density. An analysis of the beam envelope self-modulation is then carried out and the criteria for the occurrence of the instability are discussed thereby.

  3. Projectile charge state dependent sputtering of solid surfaces

    CERN Document Server

    Hayderer, G

    2000-01-01

    dependence on the ion kinetic energy. This new type of potential sputtering not only requires electronic excitation of the target material, but also the formation of a collision cascade within the target in order to initiate the sputtering process and has therefore been termed kinetically assisted potential sputtering. In order to study defects induced by potential sputtering on the atomic scale we performed measurements of multiply charged Ar ion irradiated HOPG (highly oriented pyrolitic graphite) samples with scanning tunneling microscopy (STM). The only surface defects found in the STM images are protrusions. The mean diameter of the defects increases with projectile charge state while the height of the protrusions stays roughly the same indicating a possible pre-equilibrium effect of the stopping of slow multiply charged projectiles in HOPG. Total sputter yields for impact of slow singly and multiply charged ions on metal- (Au), oxide- (Al2O3, MgO) and alkali-halide surfaces (LiF) have been measured as a...

  4. Metastable states of highly excited heavy ions

    Science.gov (United States)

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

    1973-01-01

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

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

    Science.gov (United States)

    Papadakis, Raffaello; Ottosson, Henrik

    2015-09-21

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-06-28

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

  7. Charge and excitation dynamics in semiconducting polymer layers doped with emitters and charge carrier traps; Ladungstraeger- und Anregungsdynamik in halbleitenden Polymerschichten mit eingemischten Emittern und Ladungstraegerfallen

    Energy Technology Data Exchange (ETDEWEB)

    Jaiser, F.

    2006-06-15

    blend, the nature of the excited states as well as the method of the charge transport through the layer are of great importance to the transfer. Again, the charge carrier balance influences the emission. To characterize the trapping of charges in trap states, a method based on the measurement of transient photocurrents is enhanced. The results show that models developed for ordered systems can not simply be transferred to polymer systems with a high degree of disorder. Finally, time-resolved measurements of the phosphorescence decay in blends of polymers with organo-metallic compounds are shown. Usually, these systems contain more components that facilitate charge transport. Thus, triplets may be transferred from the phosphorescent dye other components of the film. Knowing the underlying interactions, unwanted processes can be suppressed. (orig.)

  8. Entanglement entropy in excited states of the quantum Lifshitz model

    Science.gov (United States)

    Parker, Daniel E.; Vasseur, Romain; Moore, Joel E.

    2017-06-01

    We investigate the entanglement properties of an infinite class of excited states in the quantum Lifshitz model (QLM). The presence of a conformal quantum critical point in the QLM makes it unusually tractable for a model above one spatial dimension, enabling the ground state entanglement entropy for an arbitrary domain to be expressed in terms of geometrical and topological quantities. Here we extend this result to excited states and find that the entanglement can be naturally written in terms of quantities which we dub ‘entanglement propagator amplitudes’ (EPAs). EPAs are geometrical probabilities that we explicitly calculate and interpret. A comparison of lattice and continuum results demonstrates that EPAs are universal. This work shows that the QLM is an example of a 2  +  1d field theory where the universal behavior of excited-state entanglement may be computed analytically.

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

    Science.gov (United States)

    Smith, Jenna; MoNA Collaboration

    2013-10-01

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

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

    Indian Academy of Sciences (India)

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

  11. Femtosecond spectroscopy of the primary charge separation in reaction centers of Chloroflexus aurantiacus with selective excitation in the QY and Soret bands.

    Science.gov (United States)

    Xin, Yueyong; Lin, Su; Blankenship, Robert E

    2007-09-27

    The primary charge separation and electron-transfer processes of photosynthesis occur in the reaction center (RC). Isolated RCs of the green filamentous anoxygenic phototrophic bacterium Chloroflexus aurantiacus were studied at room temperature by using femtosecond transient absorption spectroscopy with selective excitation. Upon excitation in the Q(Y) absorbance band of the bacteriochlorophyll (BChl) dimer (P) at 865 nm, a 7.0 +/- 0.5 ps kinetic component was observed in the 538 nm region (Q(X) band of the bacteriopheophytin (BPheo)), 750 nm region (Q(Y) band of the BPheo), and 920 nm region (stimulated emission of the excited-state of P), indicating that this lifetime represents electron transfer from P to BPheo. The same time constant was also observed upon 740 nm or 800 nm excitation. A longer lifetime (300 +/- 30 ps), which was assigned to the time of reduction of the primary quinone, Q(A), was also observed. The transient absorption spectra and kinetics all indicate that only one electron-transfer branch is involved in primary charge separation under these excitation conditions. However, the transient absorption changes upon excitation in the Soret band at 390 nm reveal a more complex set of energy and electron-transfer processes. By comparison to studies on the RCs of the purple bacterium Rhodobacter sphaeroides, we discuss the possible mechanism of electron-transfer pathway dependence on excitation energy and propose a model of the Cf. aurantiacus RC that better explains the observed results.

  12. Electron transfer mechanism and photochemistry of ferrioxalate induced by excitation in the charge transfer band.

    Science.gov (United States)

    Chen, Jie; Zhang, Hua; Tomov, Ivan V; Rentzepis, Peter M

    2008-03-17

    The photoredox reaction of ferrioxalate after 266/267 nm excitation in the charge transfer band has been studied by means of ultrafast extended X-ray absorption fine structure (EXAFS) analysis, optical transient spectroscopy, and quantum chemistry calculations. The Fe-O bond length changes combined with the transient spectra and kinetics have been measured and in combination with ultrahigh frequency density functional theory (UHF/DFT) calculations are used to determine the photochemical mechanism for the Fe(III) to Fe(II) redox reaction. The present data and the results obtained with 266/267 nm excitations strongly suggest that the primary reaction is the dissociation of the Fe-O bond before intramolecular electron transfer occurs. Low quantum yield electron photodetachment from ferrioxalate has also been observed.

  13. Thermally excited multiplet states in macerals separated from bituminous coal

    Science.gov (United States)

    Wieckowski; Pilawa; Swiatkowska; Wojtowicz; Slowik; Lewandowski

    2000-07-01

    Electron paramagnetic resonance searches of thermally excited multiplet states in macerals, exinite, vitrinite, and inertinite of Polish medium-rank coal (85.6 wt% C), were performed. Numerical analysis of lineshape indicates a multicomponent structure of the EPR spectra of macerals heated at 300 degrees and 650 degrees C. EPR spectra of exinite and vitrinite are a superposition of broad Gauss, broad Lorentz (Lorentz 1), and narrow Lorentz (Lorentz 3) lines. Two narrow Lorentz (Lorentz 2 and Lorentz 3) lines were observed in the resonance absorption curves of inertinite. The influence of the measuring temperature (100-300 K) on the EPR lines of the macerals was also studied. The experimentally obtained temperature dependence of the EPR line intensities were fitted by the theoretical functions characteristic for paramagnetic centers with ground doublet state (S = 12) and paramagnetic centers with thermally excited triplet (S = 1) and quadruplet (S = 32) states. Thermally excited multiplet states were found in exinite and vitrinite. Both paramagnetic centers with doublet ground state (S = 12) and paramagnetic centers with thermally excited states, probably quadruplet states (S = 32), exist in the group of paramagnetic centers of exinite and vitrinite with the broad Lorentz 1 lines. Intensities (I) of the broad Gauss and the narrow Lorentz 3 lines of exinite and vitrinite changes with temperature according to the Curie law (I = C/T). The existence of thermally excited multiplet states was not stated for inertinite. The two groups of paramagnetic centers of inertinite with Lorentz 2 and Lorentz 3 lines obey the Curie law. Copyright 2000 Academic Press.

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

    Science.gov (United States)

    Robinson, David

    2014-12-09

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

  15. Vibronic coupling in Frenkel and charge-transfer states of oligothiophene crystals

    NARCIS (Netherlands)

    Stradomska, Anna; Kulig, Waldemar; Petelenz, Piotr

    A novel approach, recently proposed to describe exciton phonon coupling in Frenkel states of an infinite molecular crystal, is generalized to incorporate charge-transfer (CT) excitons. Both types of electronic excitations are treated on the same footing. The corresponding Hamiltonian in the Lang

  16. Excited-state dynamics of mononucleotides and DNA strands in a deep eutectic solvent.

    Science.gov (United States)

    Zhang, Yuyuan; de La Harpe, Kimberly; Hariharan, Mahesh; Kohler, Bern

    2018-01-31

    The photophysics of several mono- and oligonucleotides were investigated in a deep eutectic solvent for the first time. The solvent glyceline, prepared as a 1 : 2 mole ratio mixture of choline chloride and glycerol, was used to study excited-state deactivation in a non-aqueous solvent by the use of steady-state and time-resolved spectroscopy. DNA strands in glyceline retain the secondary structures that are present in aqueous solution to some degree, thus enabling a study of the effects of solvent properties on the excited states of stacked bases and stacked base pairs. The excited-state lifetime of the mononucleotide 5'-AMP in glyceline is 630 fs, or twice as long as in aqueous solution. Even slower relaxation is seen for 5'-TMP in glyceline, and a possible triplet state with a lifetime greater than 3 ns is observed. Circular dichroism spectra show that the single strand (dA)18 and the duplex d(AT)9·d(AT)9 adopt similar structures in glyceline and in aqueous solution. Despite having similar conformations in both solvents, femtosecond transient absorption experiments reveal striking changes in the dynamics. Excited-state decay and vibrational cooling generally take place more slowly in glyceline than in water. Additionally, the fraction of long-lived excited states in both oligonucleotide systems is lower in glyceline than in aqueous solution. For a DNA duplex, water is suggested to favor decay pathways involving intrastrand charge separation, while the deep eutectic solvent favors interstrand deactivation channels involving neutral species. Slower solvation dynamics in the viscous deep eutectic solvent may also play a role. These results demonstrate that the dynamics of excitations in stacked bases and stacked base pairs depend not only on conformation, but are also highly sensitive to the solvent.

  17. Excitation of Nucleon Resonances in Heavy-Ion Charge-Exchange Reactions

    Science.gov (United States)

    Benlliure, J.; Vargas, J.; Alvarez-Pol, H.; Aumann, T.; Atkinson, J.; Ayyad, Y.; Beceiro, S.; Borezky, K.; Chatillon, A.; Cortina, D.; Diaz, P.; Estrade, A.; Geissel, H.; Lenske, H.; Litvinov, Y.; Mostazo, M.; Paradela, C.; Pietri, S.; Prochazka, A.; Taieb, J.; Takechi, M.; Vidaña, I.; Weick, H.; Winfield, J.

    Isobaric charge-exchange reactions induced by different tin isotopes have been investigated at GSI. The high-resolving power of the FRS spectrometer made it possible to separate elastic and inelastic components in the missing-energy spectra of the ejectiles. The inelastic component was associated to the in-medium excitation of nucleon resonances such as the Delta and Roper resonances. These data are expected to contribute to better understand the role of subnuclear degrees of freedom in three body forces or the missing strength in Gamow-Teller transitions but also to investigate the abundance of protons and neutrons at the nuclear periphery.

  18. Can $\\beta$-decay probe excited state halos?

    CERN Multimedia

    2002-01-01

    In the first experiment at the newly constructed ISOLDE Facility the first-forbidden $\\beta$-decay of $^{17}$Ne into the first excited state of $^{17}$F has been measured. It is a factor two faster than the corresponding mirror decay and thus gives one of the largest recorded asymmetries for $\\beta$-decays feeding bound final states. Shell-model calculations can only reproduce the asymmetry if the halo structure of the $^{17}$F state is taken into account.

  19. Environmental photochemistry on surfaces. Charge injection from excited fulvic acid into semiconductor colloids

    Energy Technology Data Exchange (ETDEWEB)

    Vinodgopal, K. (Indiana Univ. Northwest, Gary, IN (United States)); Kamat, P.V. (Univ. of Notre Dame, Notre Dame, IN (United States))

    1992-10-01

    The ability of naturally occurring fulvic acid to sensitize a large band-gap semiconductor, colloidal ZnO, has been investigated by fluorescence emission and transient absorption measurements in a mixed alcohol-water system. The fulvic acid strongly adsorbs on the semiconductor particles, with an apparent association constant of 12000 [+-] 500 M[sup [minus]1]. The net charge-transfer efficiency as determined by the fluorescence quenching of reference Suwanee River fulvic acid (SFA) by ZnO was 73%. The laser flash photolysis experiments that elucidate the mechanistic details of the charge injection from excited fulvic acid into the conduction band of ZnO (k[sub et] = 6.8 x 10[sup 8] s[sup [minus]1]) are described. 28 refs., 5 figs.

  20. Excited state carbene formation from UV irradiated diazomethane.

    Science.gov (United States)

    Lee, Hosik; Miyamoto, Yoshiyuki; Tateyama, Yoshitaka

    2009-01-16

    The laser flash photolysis process of diazomethane has been studied by using a real time propagation time-dependent density functional theory (RTP-TDDFT) combined with molecular dynamics. The activation energy barrier for disintegrating diazomethane into nitrogen (N(2)) and carbene (CH(2)) molecules significantly decreases in the electronic excited S(1) state compared to that in the S(0) ground state. Furthermore, the produced carbene molecule can be in the electronic excited state of (1)CH(2) ((1)B(1)) instead of the lowest state among singlet states (1)CH(2) ((1)A(1)), which is evident in the wave function characteristics of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) throughout the disintegration. This is regarded as the initial stage of the rearrangement in the excited state (RIES), the evidence of which has been given by experiments in the past decade. In the RIES mechanism scheme, we suggest that the photoreaction in the S(1) state contributes considerably to the photochemistry of carbene formation. The passing near the S(1)/S(0) conical intersection, which allows the transition to ground state diazomethane producing the lowest singlet state carbene molecule, is considered a rare event from our molecular dynamics, although this has been regarded as the dominant mechanism in previous theoretical studies.

  1. A semiempirical study for the ground and excited states of free-base and zinc porphyrin-fullerene dyads

    Science.gov (United States)

    Parusel, A. B.

    2000-01-01

    The ground and excited states of a covalently linked porphyrin-fullerene dyad in both its free-base and zinc forms (D. Kuciauskas et al., J. Phys. Chem. 100 (1996) 15926) have been investigated by semiempirical methods. The excited-state properties are discussed by investigation of the character of the molecular orbitals. All frontier MOs are mainly localized on either the donor or the acceptor subunit. Thus, the absorption spectra of both systems are best described as the sum of the spectra of the single components. The experimentally observed spectra are well reproduced by the theoretical computations. Both molecules undergo efficient electron transfer in polar but not in apolar solvents. This experimental finding is explained theoretically by explicitly considering solvent effects. The tenth excited state in the gas phase is of charge-separated character where an electron is transferred from the porphyrin donor to the fullerene acceptor subunit. This state is stabilized in energy in polar solvents due to its large formal dipole moment. The stabilization energy for an apolar environment such as benzene is not sufficient to lower this state to become the first excited singlet state. Thus, no electron transfer is observed, in agreement with experiment. In a polar environment such as acetonitrile, the charge-separated state becomes the S, state and electron transfer takes place, as observed experimentally. The flexible single bond connecting both the donor and acceptor subunits allows free rotation by ca. +/- 30 degrees about the optimized ground-state conformation. For the charge-separated state this optimized geometry has a maximum dipole moment. The geometry of the charge-separated state thus does not change relatively to the ground-state conformation. The electron-donating properties of porphyrin are enhanced in the zinc derivative due to a reduced porphyrin HOMO-LUMO energy gap. This yields a lower energy for the charge-separated state compared to the free

  2. Aircraft Battery State of Charge and Charge Control System.

    Science.gov (United States)

    1987-04-01

    electrode for oxygen comsumption . This concept divides the functions of charge and discharge and eliminates prob- lems encountered in conventional two...Marathon batteries will be performed at constant low temperatures. Two more aircraft batteries-- General Electric and one to be furnished by the

  3. ANISOTROPY EFFECTS IN SINGLE-ELECTRON TRANSFER BETWEEN LASER-EXCITED ATOMS AND HIGHLY-CHARGED IONS

    NARCIS (Netherlands)

    Recent collision experiments are reviewed in which one-electron transfer between laser excited target atoms and (highly charged) keV-ions has been studied. Especially results showing a dependence of the charge exchange on the initial target orbital alignment are discussed. The question to what

  4. Failures of TDDFT in describing the lowest intramolecular charge-transfer excitation in para-nitroaniline

    DEFF Research Database (Denmark)

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

    2013-01-01

    for charge{transfer character, we furthermore conrm that the di¿erence between excitation energies calculated with TDDFT and with the Tamm-Danco¿ approximation (TDA) to TDDFT is indeed correlated with the charge-transfer character of a given electronic transition both in vacuo and in solution...

  5. Construction of Vibronic Diabatic Hamiltonian for Excited-State Electron and Energy Transfer Processes.

    Science.gov (United States)

    Xie, Yu; Jiang, Shengshi; Zheng, Jie; Lan, Zhenggang

    2017-12-21

    Photoinduced excited-state electron and energy transfer processes are crucial in biological photoharvesting systems and organic photovoltaic devices. We discuss the construction of a diabatic vibronic Hamiltonian for the proper treatment of these processes involving the projection approach acting on both electronic wave functions and vibrational modes. In the electronic part, the wave function projection approach is used to construct the diabatic Hamiltonian in which both local excited states and charge-transfer states are included on the same footing. For the vibrational degrees of freedom, the vibronic couplings in the diabatic Hamiltonian are obtained in the basis of the pseudonormal modes localized on each monomer site by applying delocalized-to-localized mode projection. This systematic approach allows us to construct the vibronic diabatic Hamiltonian in molecular aggregates.

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

    Indian Academy of Sciences (India)

    . In the present work we have used the close coupling R-matrix method [8,11] to ob- tain accurate photoionization cross-section from the first three excited 1s22s22p53s 3 1P0,. 1s22s22p53p 3Se states of Mg III, allowing for the residual ion to ...

  7. Excited electronic state decomposition mechanisms of clusters of ...

    Indian Academy of Sciences (India)

    In this report, electronically non-adiabatic decomposition pathways of clusters of dimethylnitramine and aluminum (DMNA-Al and DMNA-Al2) are discussed in comparison to isolated dimethylnitramine (DMNA). Electronically excited state processes of DMNA-Al and DMNA-Al2 are explored using the complete active space ...

  8. Size dependent deactivation of the excited state of DHICA

    DEFF Research Database (Denmark)

    Gauden, Magdalena; Pezzella, Alessandro; Panzella, Lucia

    2008-01-01

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

  9. Double, Rydberg and charge transfer excitations from pairing matrix fluctuation and particle-particle random phase approximation

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yang [Department of Chemistry, Duke University, Durham, North Carolina 27708 (United States); Aggelen, Helen van [Department of Chemistry, Duke University, Durham, North Carolina 27708 (United States); Department of Inorganic and Physical Chemistry, Ghent University, 9000 Ghent (Belgium); Yang, Weitao, E-mail: weitao.yang@duke.edu [Department of Chemistry and Department of Physics, Duke University, Durham, North Carolina 27708 (United States)

    2013-12-14

    Double, Rydberg, and charge transfer (CT) excitations have been great challenges for time-dependent density functional theory (TDDFT). Starting from an (N ± 2)-electron single-determinant reference, we investigate excitations for the N-electron system through the pairing matrix fluctuation, which contains information on two-electron addition/removal processes. We adopt the particle-particle random phase approximation (pp-RPA) and the particle-particle Tamm-Dancoff approximation (pp-TDA) to approximate the pairing matrix fluctuation and then determine excitation energies by the differences of two-electron addition/removal energies. This approach captures all types of interesting excitations: single and double excitations are described accurately, Rydberg excitations are in good agreement with experimental data and CT excitations display correct 1/R dependence. Furthermore, the pp-RPA and the pp-TDA have a computational cost similar to TDDFT and consequently are promising for practical calculations.

  10. An EBIS for charge state breeding in the SPES project

    Indian Academy of Sciences (India)

    The 'charge state breeder', BRIC (breeding ion charge) is in construction at the INFN section of Bari (Italy). It is based on EBIS scheme and it is designed to accept radioactive ion beam (RIB) with charge state +1 in a slow injection mode. This experiment can be considered as a first step towards the design and construction ...

  11. Electron Impact Excitation and Dielectronic Recombination of Highly Charged Tungsten Ions

    Directory of Open Access Journals (Sweden)

    Zhongwen Wu

    2015-11-01

    Full Text Available Electron impact excitation (EIE and dielectronic recombination (DR of tungsten ions are basic atomic processes in nuclear fusion plasmas of the International Thermonuclear Experimental Reactor (ITER tokamak. Detailed investigation of such processes is essential for modeling and diagnosing future fusion experiments performed on the ITER. In the present work, we studied total and partial electron-impact excitation (EIE and DR cross-sections of highly charged tungsten ions by using the multiconfiguration Dirac–Fock method. The degrees of linear polarization of the subsequent X-ray emissions from unequally-populated magnetic sub-levels of these ions were estimated. It is found that the degrees of linear polarization of the same transition lines, but populated respectively by the EIE and DR processes, are very different, which makes diagnosis of the formation mechanism of X-ray emissions possible. In addition, with the help of the flexible atomic code on the basis of the relativistic configuration interaction method, DR rate coefficients of highly charged W37+ to W46+ ions are also studied, because of the importance in the ionization equilibrium of tungsten plasmas under running conditions of the ITER.

  12. Lattice QCD determination of patterns of excited baryon states

    CERN Document Server

    Basak, Subhasish; Fleming, G T; Juge, K J; Lichtl, A; Morningstar, C; Richards, D G; Sato, I; Wallace, S J

    2007-01-01

    Energies for excited isospin I=1/2 and I=3/2 states that include the nucleon and Delta families of baryons are computed using quenched, anisotropic lattices. Baryon interpolating field operators that are used include nonlocal operators that provide G_2 irreducible representations of the octahedral group. The decomposition of spin 5/2 or higher spin states is realized for the first time in a lattice QCD calculation. We observe patterns of degenerate energies in the irreducible representations of the octahedral group that correspond to the subduction of the continuum spin 5/2 or higher. The overall pattern of low-lying excited states corresponds well to the pattern of physical states subduced to the irreducible representations of the octahedral group.

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

    Science.gov (United States)

    Mondal, Sayan; Puranik, Mrinalini

    2016-05-18

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

  14. Differential and total cross sections for charge transfer and transfer-excitation in ion-helium collisions

    Science.gov (United States)

    Halder, S.; Mondal, A.; Samaddar, S.; Mandal, C. R.; Purkait, M.

    2017-09-01

    Total cross sections for single charge transfer in collisions of multicharged bare ions with ground-state helium atoms at incident energy ranging from 40 to 5000 keV/amu have been calculated in the framework of a four-body model of final channel distorted-wave (FC-DW-4B) approximation. In this formalism, distortion in the final channel related to the Coulomb continuum of the target and the Coulomb interaction between the passive electron in the target with the projectile are included. In all cases, total single electron-capture cross sections have been calculated by summing over all contributions up to n =3 shells and subshells. It has been observed that the contribution of the capture cross sections into excited states have insignificant contributions for symmetric collisions. Comprehensive comparisons are made between the four body model of boundary corrected continuum intermediate-state approximations [Phys. Rev. A 83, 032706 (2011), 10.1103/PhysRevA.83.032706] and the present FC-DW-4B model. The main purpose of the present study is to investigate the relative importance of dynamic electron correlation and the role of passive electron in the target at intermediate and high impact energies. In addition, projectile angular differential cross sections (DCS) for charge transfer and transfer-excitation in p -He collisions are calculated at different impact energies. At low projectile energies, the present DCS data exhibits the typical steeply decreasing dependence on the projectile scattering angles, whereas at high impact energies, the double-scattering region centered on the Thomas angle is obtained. Detailed comparisons with the available experimental data and other theories are reported with the purpose of further assessing the relevance of the present model at different impact energies. Overall, the calculated cross sections show good agreement with the available experimental findings.

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

    Directory of Open Access Journals (Sweden)

    Z Nourbakhsh

    2009-09-01

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

  16. Twisting in the excited state of an N-methylpyridinium fluorescent dye modulated by nano-heterogeneous micellar systems.

    Science.gov (United States)

    Cesaretti, A; Carlotti, B; Gentili, P L; Germani, R; Spalletti, A; Elisei, F

    2016-04-01

    A push-pull N-methylpyridinium fluorescent dye with a pyrenyl group as the electron-donor portion was investigated within the nano-heterogeneous media provided by some micellar systems. The molecule was studied by stationary and time-resolved spectroscopic techniques in spherical micellar solutions and viscoelastic hydrogels, in order to throw light on the role played by twisting in its excited state deactivation. As proven by femtosecond fluorescence up-conversion and transient absorption experiments, the excited state dynamics of the molecule is ruled by charge transfer and twisting processes, which, from the locally excited (LE) state initially populated upon excitation, progressively lead to twisted (TICT) and planar (PICT) intramolecular charge transfer states. The inclusion within micellar aggregates was found to slow down and/or limit the rotation of the molecule with respect to what had previously been observed in water, while its confinement within the hydrophobic domains of the gel matrixes prevents any molecular torsion. The increasing viscosity of the medium, when passing from water to micellar systems, implies that the detected steady-state fluorescence comes from an excited state which is not fully relaxed, as is the case with the TICT state in micelles or the LE state in hydrogels, where the detected emission changes its usual orange colour to yellow.

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

    Science.gov (United States)

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

    2017-09-01

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

  18. Excited S-symmetry states of positronic lithium and beryllium.

    Science.gov (United States)

    Strasburger, Krzysztof

    2016-04-14

    The possibility of the existence of excited S-symmetry states of positronic lithium and beryllium, resulting from the positron attachment to high-spin P parent atomic states, is examined and confirmed with variational calculations in the basis of explicitly correlated Gaussian functions. The unexpectedly different order of the energies of the S and P states is explained by the formation of the positronium cluster structure and associated disappearance of the destabilizing centrifugal force. The annihilation properties of newly discovered states are discussed in the context of prospective experimental detection.

  19. Formation of Bonded Exciplex in the Excited States of Dicyanoanthracene-Pyridine System : Time Dependent Density Functional Theory Study

    NARCIS (Netherlands)

    Setiawan, D.; Sethio, D.; Martoprawiro, M.A.; Filatov, M.; Gaol, FL; Nguyen, QV

    2012-01-01

    Strong quenching of fluorescence was recently observed in pyridine solutions of 9,10-dicyanoanthracene chromophore. It was hypothesized that quenching may be attributed to the formation of bound charge transfer complexes in the excited states of the molecules. In this work, using time-dependent

  20. Charge Migration in Eyring, Walter and Kimball's 1944 Model of the Electronically Excited Hydrogen-Molecule Ion.

    Science.gov (United States)

    Diestler, Dennis J; Hermann, Gunter; Manz, Jörn

    2017-07-20

    In an elementary variational treatment of the electronic structure of H2(+), Eyring, Walter, and Kimball (EWK) serendipitously discovered charge migration (CM) in 1944. Using an analytic expression for the electronic probability density (EPD), they found that if the electron is initially localized on one of the protons (by taking the initial state to be a superposition of the ground and first excited electronic energy eigenstates), then it oscillates adiabatically between fixed protons with a period T inversely proportional to the energy gap between the eigenstates. At the equilibrium internuclear separation, T = 550.9 as. As shown here, the EWK model also yields an analytic formula for the electronic flux density (EFD). While the EPD indicates where the electron is at any instant, the EFD reveals the pathways the electron follows during its migration. Thus, the EFD complements the EPD, providing valuable new insight into the mechanism of CM. The formula for the EFD is a simple product of a time factor and a spatial factor. This factoring exposes a plethora of spatial-temporal symmetry relations which imply novel and surprising properties. An especially significant finding is that, in contrast to multielectron systems, where electron correlation may play a role in CM, in the EWK model of H2(+), CM is due strictly to quantum interference between the ground and first excited electronic states.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2016-09-13

    Super-atom molecular orbitals are orbitals that form diffuse hydrogenic excited electronic states of fullerenes with their electron density centred at the centre of the hollow carbon cage and a significant electron density inside the cage. This is a consequence of the high symmetry and hollow structure of the molecules and distinguishes them from typical low-lying molecular Rydberg states. This review summarizes the current experimental and theoretical studies related to these exotic excited electronic states with emphasis on femtosecond photoelectron spectroscopy experiments on gas-phase fullerenes.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'. © 2016 The Author(s).

  3. Excited state intramolecular charge transfer reaction of 4 ...

    Indian Academy of Sciences (India)

    Author Affiliations. Tuhin Pradhan1 Harun Al Rasid Gazi1 Ranjit Biswas1. Department of Chemical, Biological and Macromolecular Sciences, S.N. Bose National Centre for Basic Sciences, J.D. Block, Sector III, Salt Lake, Kolkata 700 098 ...

  4. Excited state charge transfer reaction in (mixed solvent+ electrolyte ...

    Indian Academy of Sciences (India)

    Author Affiliations. Harun Al Rasid Gazi1 Ranjit Biswas1. Department of Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences, JD Block, Sector III, Salt Lake, Kolkata, 700 098, India ...

  5. Excited-State N2 Dissociation Pathway on Fe-Functionalized Au.

    Science.gov (United States)

    Martirez, John Mark P; Carter, Emily A

    2017-03-29

    Localized surface plasmon resonances (LSPRs) offer the possibility of light-activated chemical catalysis on surfaces of strongly plasmonic metal nanoparticles. This technology relies on lower-barrier bond formation and/or dissociation routes made available through energy transfer following the eventual decay of LSPRs. The coupling between these decay processes and a chemical trajectory (nuclear motion, charge-transfer, intersystem crossing, etc.) dictates the availability of these alternative (possibly lower barrier) excited-state channels. The Haber-Bosch method of NH3 synthesis from N2 and H2 is notoriously energy intensive. This is due to the difficulty of N2 dissociation despite the overall reaction being thermodynamically favorable at ambient temperatures and pressures. LSPRs may provide means to improve the kinetics of N2 dissociation via induced resonance electronic excitation. In this work, we calculate, via embedded n-electron valence second-order perturbation theory within the density functional embedding theory, the excited-state potential energy surfaces for dissociation of N2 on an Fe-doped Au(111) surface. This metal alloy may take advantage simultaneously of the strong LSPR of Au and the catalytic activity of Fe toward N2 dissociation. We find the ground-state dissociation activation energy to be 4.74 eV/N2, with Fe as the active site on the surface. Consecutive resonance energy transfers (RETs) may be accessed due to the availability of many electronically excited states with intermediate energies arising from the metal surface that may couple to states induced by the Fe-dopant and the adsorbate molecule, and crossing between excited states may effectively lower the dissociation barrier to 1.33 eV. Our work illustrates that large energetic barriers, prohibitive toward chemical reaction, may be overcome through multiple RETs facilitating an otherwise difficult chemical process.

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

    Science.gov (United States)

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

    2014-11-13

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

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

    KAUST Repository

    Cekli, Seda

    2016-02-12

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

  8. Ground and excited states for exotic three-body atomic systems

    Directory of Open Access Journals (Sweden)

    Gasaneo G.

    2010-04-01

    Full Text Available An Angular Correlated Configuration Interaction method is extended and applied to exotic threebody atomic systems with general masses. A recently proposed angularly correlated basis set is used to construct, simultaneously and with a single diagonalization, ground and excited states wave functions which: (i satisfy exactly Kato cusp conditions at the two-body coalescence points; (ii have only linear parameters; (iii show a fast convergency rate for the energy; (iv form an orthogonal set. The efficiency of the construction is illustrated by the study a variety of three-body atomic systems [m1− m2− m3z3+ ] with two negatively charged light particles, with 123 diverse masses m1− and m2−, and a heavy positively charged nucleus m3z3+. The calculated ground 11S and several excited n1,3S state energies are compared with those given in the literature, when available. We also present a short discussion on the critical charge necessary to get a stable three-body system supporting two electrons, an electron and a muon, or two muons.

  9. Excited state potential energy surfaces of bistridentate RuII complexes - A TD-DFT study

    Science.gov (United States)

    Österman, Tomas; Persson, Petter

    2012-10-01

    Time-dependent density functional theory (TD-DFT) calculations have been used to investigate low-energy singlet and triplet excited state potential energy surfaces (PES) of two prototype RuII-bistridentate complexes: [RuII(tpy)2]2+ (tpy is 2,2':6',2''-terpyridine) and [RuII(dqp)2]2+ (dqp is 2,6-di(quinolin-8-yl)pyridine). Solvent effects were considered using a self-consistent reaction field scheme. The calculations provide information about the excited state manifold along pathways for activated decay of metal-to-ligand charge-transfer (MLCT) excited states via metal-centered (MC) states for the two complexes. Significant differences in the energy profiles of the investigated PESs are explained through characterization of the electronic properties of the involved states calculated by the TD-DFT calculations. Finally, implications of the computational results for the design of octahedral metal complexes utilizing ligand field splitting (LFS) strategies for efficient light-harvesting in photochemical applications such as artificial photosynthesis are discussed.

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

    Science.gov (United States)

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

    2014-08-07

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

  11. Sunlight-Initiated Photochemistry: Excited Vibrational States of Atmospheric Chromophores

    OpenAIRE

    Veronica Vaida; Karl J. Feierabend; Nabilah Rontu; Kaito Takahashi

    2008-01-01

    Atmospheric chemical reactions are often initiated by ultraviolet (UV) solar radiation since absorption in that wavelength range coincides to typical chemical bond energies. In this review, we present an alternative process by which chemical reactions occur with the excitation of vibrational levels in the ground electronic state by red solar photons. We focus on the O–H vibrational manifold which can be an atmospheric chromophore for driving vibrationally mediated overtone-induced chemical re...

  12. Probing excited electronic states and ionisation mechanisms of fullerenes

    OpenAIRE

    Johansson, Olof; Campbell, Eleanor E. B.

    2013-01-01

    Fullerenes are interesting model systems for probing the complex, fundamental electron dynamics and ionisation mechanisms of large molecules and nanoparticles. In this Tutorial Review we explain how recent experimental and theoretical advances are providing insight into the interesting phenomenon of thermal electron emission from molecular systems and the properties of hydrogenic, diffuse, excited electronic states, known as superatom molecular orbitals, which are responsible for relatively s...

  13. Charge State Distributions of Molecular Dissociation

    Science.gov (United States)

    Renfrow, S. N.; Potter, Rudolf H.; Duggan, J. L.; McDaniel, F. D.

    1998-05-01

    The charge state distributions (CSD) of moleculer break-up fragments is important to both Trace Element Accelerator Mass Spectrometry (TEAMS) (S.A. Datar, Z.Y. Zhao, S.N. Renfrow, B.N. Guo, J.M. Anthony, and F.D. McDaniel, Fourteenth International CAARI, Denton, TX, Nov, 1996, AIP Conf. Proc. 392, AIP Press, Ed. by J.L. Duggan and I.L. Morgan (AIP, Woodbury, NY, 1997) pp. 815) and the implantation industry. We have studied the CSD of 1.7MeV SiX^+ molecules for atoms that do not readily form negative ions, using a NEC Tandem Pelletron accelerator. After acceleration, the q=1+ molecular ion was passed through a dilute N2 gas target. The resulting breakups were analyzed using an electrostatic deflector and measured with a position sensitive detector. Equilibrium CSD were determined and a comparison was made of molecular CSD data to ion CSD data. The experimental details of these studies as well as a discussion of a model and will be given in this presentation.

  14. Lifetimes of excited states in neutron-rich Xe isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Ilieva, Stoyanka; Kroell, Thorsten [Institut fuer Kernphysik, TU Darmstadt (Germany); Collaboration: EXILL-FATIMA-Collaboration

    2016-07-01

    The EXILL and FATIMA campaign at ILL, Grenoble is the first prompt-fission γ-ray spectroscopy experiment performed with a mixed array of Ge detectors (EXILL) and fast LaBr{sub 3}(Ce) scintillators (FATIMA). The lifetimes of excited states, populated by neutron-induced fission of {sup 235}U and {sup 241}Pu targets, were directly measured. The high-resolution EXILL detector gives us the possibility to identify the nuclides of interest among the large amount of produced fission fragments. Using the generalized centroid difference method to analyse the data from FATIMA we could measure lifetimes down to ∼ 10 ps. The lifetime of an excited state is a direct measure for the strength (collectivity) of a transition. The properties of the excited states in even-even nuclei can be largely described by quadrupole and octupole degrees of freedom. This contribution will present the current status of the analysis for the neutron-rich even-even {sup 138,140,142}Xe isotopes which lie in the vicinity of the double shell closure Z=50 and N=82. Through the direct lifetime measurement we aim to study the evolution of quadrupole and octupole collectivity above {sup 132}Sn.

  15. Excited state properties of the chromophore of the asFP595 chromoprotein: 2D and 3D theoretical analyses

    Science.gov (United States)

    Sun, Mengtao

    The ground and excited state properties (e.g., the intramolecular charge and energy transfer, and electron-hole coherence) of the chromophore of the asFP595 chromoprotein from Anemonia sulcata in the neutral and anionic forms are theoretically studied with quantum chemistry methods. The ground-state properties of the asFP595 in the neutral and anionic forms, such as the alternations of the bond lengths and the Mulliken charge distributions, are compared. The calculated transition energies of the asFP595 in the neutral and anionic form are consistent with the experimental results. To study the excited state properties of the asFP595 chromophore, the energies and densities of highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs), as well as the CI main coefficients, are compared between the two forms. The intramolecular charge and energy transfer in the neutral and anionic forms are investigated and compared with the three-dimensional (3D) real-space analysis methods, including the strength and orientation of the transition dipoles with transition density, and the orientation and result of the intramolecular charge transfer with charge difference density. The electron-hole coherence and delocalization on the excitation are studied with the 2D real-space analysis method of the transition density matrix. In all, the calculated results are remain in good agreement with the experimental data, and the theoretical analysis results supported the proposed models in the experiment.

  16. Recombination dynamics of optically excited charge carriers in bulk MoS2

    Science.gov (United States)

    Völzer, Tim; Lütgens, Matthias; Fennel, Franziska; Lochbrunner, Stefan

    2017-10-01

    Transition metal dichalcogenides (TMDCs), such as MoS2, are promising candidates for optoelectronic or catalytic applications. On that account, a detailed characterization of the electronic dynamics in these materials is of pivotal importance. Here, we investigate the temporal evolution of an excited carrier population by all-optical pump-probe spectroscopy. On the sub-picosecond time scale we observe thermal relaxation of the excited carriers by electron-phonon coupling. The dynamics on the nanosecond time scale can be understood in terms of defect-assisted Auger recombination over a broad carrier density regime spanning more than one order of magnitude. Hence, our results emphasize the importance of defect states for electronic processes in TMDCs at room temperature.

  17. Dynamical and scale invariance of charged particles slipping on a rough surface with periodic excitation

    Science.gov (United States)

    Zhang, Hao; Luo, Pengcheng; Ding, Huifang

    2017-07-01

    This letter deals with the dynamical and scaling invariance of charged particles slipping on a rough surface with periodic excitation. A variant of the Fermi-Ulam model (FUM) is proposed to describe the transport behavior of the particles when the electric field force Fe is smaller or larger than the friction force Ff, i.e., A 0. For these two cases, the stability of fixed points is analyzed with the help of the eigenvalue analysis method, and further the invariant manifolds are constructed to investigate the dynamical invariance such as energy diffusion for some initial conditions in the case A > 0 and decay process in the case A law of the statistical behavior. It follows that both the FA phenomenon for A > 0 and the velocity decay process for A < 0 satisfy scaling invariance with respect to the nondimensional acceleration A. Besides, for A < 0, the transient number nx is proposed to evaluate the speed of the velocity decay process. More importantly, nx is found to possess the attribute of scaling invariance with respect to both the initial velocity V0 and the nondimensional acceleration A. These results are very useful for the in-depth understanding of the energy transport properties of charged particle systems.

  18. Rotational Spectra in 29 Vibrationally Excited States of Interstellar Aminoacetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Kolesniková, L.; Alonso, E. R.; Mata, S.; Alonso, J. L. [Grupo de Espectroscopia Molecular (GEM), Edificio Quifima, Área de Química-Física, Laboratorios de Espectroscopia y Bioespectroscopia, Parque Científico UVa, Unidad Asociada CSIC, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2017-04-01

    We report a detailed spectroscopic investigation of the interstellar aminoacetonitrile, a possible precursor molecule of glycine. Using a combination of Stark and frequency-modulation microwave and millimeter wave spectroscopies, we observed and analyzed the room-temperature rotational spectra of 29 excited states with energies up to 1000 cm{sup −1}. We also observed the {sup 13}C isotopologues in the ground vibrational state in natural abundance (1.1%). The extensive data set of more than 2000 new rotational transitions will support further identifications of aminoacetonitrile in the interstellar medium.

  19. Modular Hamiltonian for Excited States in Conformal Field Theory.

    Science.gov (United States)

    Lashkari, Nima

    2016-07-22

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

  20. Chemical modulation of electronic structure at the excited state

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2017-04-01

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

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

    Science.gov (United States)

    López-Bara, F I; López-Aguilar, F

    2017-04-20

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

  3. Excited states using semistochastic heat-bath configuration interaction

    Science.gov (United States)

    Holmes, Adam A.; Umrigar, C. J.; Sharma, Sandeep

    2017-10-01

    We extend our recently developed heat-bath configuration interaction (HCI) algorithm, and our semistochastic algorithm for performing multireference perturbation theory, to calculate excited-state wavefunctions and energies. We employ time-reversal symmetry, which reduces the memory requirements by more than a factor of two. An extrapolation technique is introduced to reliably extrapolate HCI energies to the full CI limit. The resulting algorithm is used to compute fourteen low-lying potential energy surfaces of the carbon dimer using the cc-pV5Z basis set, with an estimated error in energy of 30-50 μHa compared to full CI. The excitation energies obtained using our algorithm have a mean absolute deviation of 0.02 eV compared to experimental values.

  4. Contribution of the excited 1+ states of 100Tc to the 2ν2β-amplitude of 100Mo

    Science.gov (United States)

    Semenov, S. V.

    2017-11-01

    The total and differential intensities of the two-neutrino double beta transition in 100Mo are calculated by taking into account experimental data on the charge-exchange reactions on 100Mo. It is shown that excited 1+ states should be considered in addition to the ground state of the intermediate nucleus 100Tc, which leads to the generalization of the SSD mechanism for the two-neutrino process.

  5. Spectroscopic and excited-state properties of tri-9-anthrylborane I: Solvent polarity effects.

    Science.gov (United States)

    Kitamura, Noboru; Sakuda, Eri

    2005-08-25

    Spectroscopic and excited-state properties of tri-9-anthrylborane (TAB), showing unique absorption and fluorescence characteristics originating from p(boron)-pi(anthryl group) orbital interactions, were studied in 12 solvents. Although the absorption maximum energy (nu(a)) of TAB which appeared at around 21 x 10(3) cm(-1) (band I) was almost independent of the solvent polarity parameter, f(X) (f(X) = (D(s) - 1)/(2D(s) + 1) - (n(2) - 1)/(2n(2) + 1) where D(s) and n represent the static dielectric constant and the refractive index of a solvent, respectively), the fluorescence maximum energy (nu(f)) showed a linear correlation with f(X). The f(X) dependence of the value of nu(a) - nu(f) demonstrated that the change in the dipole moment of TAB upon light excitation was approximately 8.0 D, indicating that absorption band I was ascribed to an intramolecular charge-transfer transition in nature. The excited electron of TAB was thus concluded to localize primarily on the p orbital of the boron atom. Furthermore, it was shown that the fluorescence lifetime and quantum yield of TAB varied from 11.8 to 1.1 ns and from 0.41 to 0.02, respectively, with an increase in f(X). The present results indicated that the nonradiative decay rate constant (k(nr)) of TAB was influenced significantly by f(X). Excited-state decay of TAB was understood by intramolecular back-electron (charge) transfer from the p orbital of the boron atom to the pi orbital of the anthryl group, which was discussed in terms of the energy gap dependence of k(nr). Specific solvent interactions of TAB revealed by the present spectroscopic and photophysical studies are also discussed.

  6. Application of spectroscopy and super-resolution microscopy: Excited state

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharjee, Ujjal [Iowa State Univ., Ames, IA (United States)

    2016-02-19

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

  7. Charge-exchange dipole excitations in neutron-rich nuclei: -1 ℏ ω0 , anti-analog pygmy and anti-analog giant resonances

    Science.gov (United States)

    Yoshida, Kenichi

    2017-11-01

    The occurrence of low-lying charge-exchange non-spin-flip dipole modes below the giant resonance in neutron-rich nuclei is predicted on the basis of nuclear density functional theory. The ground and excited states are described within the framework of the self-consistent Hartree-Fock-Bogoliubov theory and the proton-neutron quasiparticle-random-phase approximation employing a Skyrme-type energy density functional. The model calculations are performed for the spherical neutron-rich Ca, Ni, and Sn isotopes. It is found that the low-lying states appear sensitive to the shell structure associated with the -1 ℏ ω0 excitation below the Gamow-Teller states. Furthermore, the pygmy resonance emerges below the giant resonance when the neutrons occupy the low-ℓ (ℓ ≤2 -3 ) orbitals analogous to the pygmy resonance seen in the electric-dipole response.

  8. Photoluminescence and excited states dynamics in PbWO4:Pr3+ crystals

    CERN Document Server

    Auffray, E; Shalapska, T; Zazubovich, S

    2014-01-01

    Luminescence and photo-thermally stimulated defects creation processes are studied for a Pr3+-doped PbWO4 crystal at 4.2-400 K under excitation in the band-to-band, exciton, and charge-transfer transitions regions, as well as in the Pr3+-related absorption bands. Emission spectra of Pr3+ centers depend on the excitation energy, indicating the presence of Pr3+ centers of two types. The origin of these centers is discussed. The 2.03-2.06 eV emission, arising from the D-1(2) -> H-3(4) transitions of Pr3+ ions, is found to be effectively excited in a broad intense absorption band peaking at 4.2 K at 3.92 eV. By analogy with some other Pe(3+)-doped compounds, this band is suggested to arise from an electron transfer from an impurity Pr3+ ion to the crystal lattice W6+ or Pb2+ ions. The dynamics of the Pr3+-related excited states is clarified. In the PbWO4:Pr crystal studied, the concentration of single oxygen and lead vacancies as traps for electrons and holes is found to be negligible.

  9. Quantum State Transmission in a Superconducting Charge Qubit-Atom Hybrid

    Science.gov (United States)

    Yu, Deshui; Valado, María Martínez; Hufnagel, Christoph; Kwek, Leong Chuan; Amico, Luigi; Dumke, Rainer

    2016-01-01

    Hybrids consisting of macroscopic superconducting circuits and microscopic components, such as atoms and spins, have the potential of transmitting an arbitrary state between different quantum species, leading to the prospective of high-speed operation and long-time storage of quantum information. Here we propose a novel hybrid structure, where a neutral-atom qubit directly interfaces with a superconducting charge qubit, to implement the qubit-state transmission. The highly-excited Rydberg atom located inside the gate capacitor strongly affects the behavior of Cooper pairs in the box while the atom in the ground state hardly interferes with the superconducting device. In addition, the DC Stark shift of the atomic states significantly depends on the charge-qubit states. By means of the standard spectroscopic techniques and sweeping the gate voltage bias, we show how to transfer an arbitrary quantum state from the superconducting device to the atom and vice versa. PMID:27922087

  10. Laguerre polynomial excited coherent state: generation and nonclassical properties

    Science.gov (United States)

    Ye, Wei; Zhou, Weidong; Zhang, Haoliang; Liu, Cunjin; Huang, Jiehui; Hu, Liyun

    2017-11-01

    We propose a theoretical protocol to generate a kind of non-Gaussian state—a Laguerre polynomial excited coherent state (LPECS) by exploiting a two-mode squeezing transformation and a conditional measurement with a coherent state input. Then we investigate the nonclassical features of the LPECS according to the Glauber-Sudarshan P(α ) function, photon number distribution, Mandel’s Q parameter, second-order correlation function, and squeezing properties as well as negative Wigner distribution. Our results show that the generated output state presents obvious nonclassical properties which can be modulated by a coherent amplitude, a squeezing parameter and a conditional measurement. In particular, the squeezing and negative Wigner function are clear.

  11. Excited state mass spectra of doubly heavy Ξ baryons

    Energy Technology Data Exchange (ETDEWEB)

    Shah, Zalak; Rai, Ajay Kumar [Sardar Vallabhbhai National Institute of Technology, Department of Applied Physics, Surat, Gujarat (India)

    2017-02-15

    In this paper, the mass spectra are obtained for doubly heavy Ξ baryons, namely, Ξ{sub cc}{sup +}, Ξ{sub cc}{sup ++}, Ξ{sub bb}{sup -}, Ξ{sub bb}{sup 0}, Ξ{sub bc}{sup 0} and Ξ{sub bc}{sup +}. These baryons consist of two heavy quarks (cc, bb, and bc) with a light (d or u) quark. The ground, radial, and orbital states are calculated in the framework of the hypercentral constituent quark model with Coulomb plus linear potential. Our results are also compared with other predictions, thus, the average possible range of excited states masses of these Ξ baryons can be determined. The study of the Regge trajectories is performed in (n, M{sup 2}) and (J, M{sup 2}) planes and their slopes and intercepts are also determined. Lastly, the ground state magnetic moments of these doubly heavy baryons are also calculated. (orig.)

  12. Excited-State Dynamics of Oxyluciferin in Firefly Luciferase.

    Science.gov (United States)

    Snellenburg, Joris J; Laptenok, Sergey P; DeSa, Richard J; Naumov, Panče; Solntsev, Kyril M

    2016-12-21

    The color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time-resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH-dependent emission to a single chemical species would be an oversimplification.

  13. Excited-State Dynamics of Oxyluciferin in Firefly Luciferase

    KAUST Repository

    Snellenburg, Joris J.

    2016-11-23

    The color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH dependent emission to a single chemical species would be an oversimplification.

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

    Science.gov (United States)

    Zhao, Jinfeng; Dong, Hao; Zheng, Yujun

    2018-01-24

    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 S1-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 (CH3CN) 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 S1 state, and nonpolar solvents play important roles in lowering the potential energy barrier of the second-step PT reaction.

  15. Probing excited electronic states and ionisation mechanisms of fullerenes.

    Science.gov (United States)

    Johansson, J Olof; Campbell, Eleanor E B

    2013-07-07

    Fullerenes are interesting model systems for probing the complex, fundamental electron dynamics and ionisation mechanisms of large molecules and nanoparticles. In this Tutorial Review we explain how recent experimental and theoretical advances are providing insight into the interesting phenomenon of thermal electron emission from molecular systems and the properties of hydrogenic, diffuse, excited electronic states, known as superatom molecular orbitals, which are responsible for relatively simple, well-resolved structure in fs laser photoelectron spectra of fullerenes. We focus on the application of velocity map imaging combined with fs laser photoionisation to study angular-resolved photoelectron emission.

  16. Triaxiality near the 110Ru ground state from Coulomb excitation

    Directory of Open Access Journals (Sweden)

    D.T. Doherty

    2017-03-01

    Full Text Available A multi-step Coulomb excitation measurement with the GRETINA and CHICO2 detector arrays was carried out with a 430-MeV beam of the neutron-rich 110Ru (t1/2=12 s isotope produced at the CARIBU facility. This represents the first successful measurement following the post-acceleration of an unstable isotope of a refractory element. The reduced transition probabilities obtained for levels near the ground state provide strong evidence for a triaxial shape; a conclusion confirmed by comparisons with the results of beyond-mean-field and triaxial rotor model calculations.

  17. Strategies to enhance the excitation energy-transfer efficiency in a light-harvesting system using the intra-molecular charge transfer character of carotenoids

    Energy Technology Data Exchange (ETDEWEB)

    Yukihira, Nao [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Sugai, Yuko [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Fujiwara, Masazumi [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Kosumi, Daisuke [Institute of Pulsed Power Science; Kumamoto University; Kumamoto; Japan; Iha, Masahiko [South Product Co. Ltd.; Uruma-shi; Japan; Sakaguchi, Kazuhiko [Department of Chemistry; Graduate School of Science; Osaka City University; Osaka 558-8585; Japan; Katsumura, Shigeo [Department of Chemistry; Graduate School of Science; Osaka City University; Osaka 558-8585; Japan; Gardiner, Alastair T. [Glasgow Biomedical Research Centre; University of Glasgow; 126 University Place; Glasgow, G12 8QQ; UK; Cogdell, Richard J. [Glasgow Biomedical Research Centre; University of Glasgow; 126 University Place; Glasgow, G12 8QQ; UK; Hashimoto, Hideki [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan

    2017-01-01

    Fucoxanthin is a carotenoid that is mainly found in light-harvesting complexes from brown algae and diatoms. Due to the presence of a carbonyl group attached to polyene chains in polar environments, excitation produces an excited intra-molecular charge transfer. This intra-molecular charge transfer state plays a key role in the highly efficient (~95%) energy-transfer from fucoxanthin to chlorophyllain the light-harvesting complexes from brown algae. In purple bacterial light-harvesting systems the efficiency of excitation energy-transfer from carotenoids to bacteriochlorophylls depends on the extent of conjugation of the carotenoids. In this study we were successful, for the first time, in incorporating fucoxanthin into a light-harvesting complex 1 from the purple photosynthetic bacterium,Rhodospirillum rubrumG9+ (a carotenoidless strain). Femtosecond pump-probe spectroscopy was applied to this reconstituted light-harvesting complex in order to determine the efficiency of excitation energy-transfer from fucoxanthin to bacteriochlorophyllawhen they are bound to the light-harvesting 1 apo-proteins.

  18. Charge state of vacancy defects in Eu-doped GaN

    Science.gov (United States)

    Mitchell, B.; Hernandez, N.; Lee, D.; Koizumi, A.; Fujiwara, Y.; Dierolf, V.

    2017-08-01

    Eu ions have been doped into GaN in order to achieve red luminescence under current injection, where coupling between the Eu ions and intrinsic defects such as vacancies are known to play an important role. However, the charge state of the vacancies and the impact it would have on the optical and magnetic properties of the Eu ions have not been explored. Through a combination of first-principle calculations and experimental results, the influence of the charge state of the defect environment surrounding the Eu ions has been investigated. We have identified two Eu centers that are related through the charge state of a local vacancy defect. These two centers were found to exhibit a mutual metastability, such that each center can be excited in one configuration and emit as the other. This metastability was found to be dependent on temperature and the wavelength of the excitation laser. Furthermore, one of these centers was found to have an effective magnetic g factor that is substantially larger than what is expected for an isolated E u3 + ion and is explained by a change in the charge state of the defect environment around the Eu. This prediction could also offer a new explanation for the saturation magnetization previously observed in GaN : Eu and other GaN:RE systems.

  19. Charge sensitive amplifies. The state of arts

    Energy Technology Data Exchange (ETDEWEB)

    Mori, Kunishiro [Clear Pulse Co., Tokyo (Japan)

    1996-07-01

    In the radiation detectors, signals are essentially brought with charges produced by radiation, then it is naturally the best way to use a charge sensitive amplifier (CSA) system to extract those signals. The CSA is thought to be the best amplifier suitable to almost all the radiation detectors, if neglecting economical points of view. The CSA has been only applied to special fields like radiation detection because the concept of `charges` is not so universal against the concepts of `voltage` and `current`. The CSA, however, is low in noise and a high speed amplifier and may be applicable not only to radiation measurement but also piezoelectric devices and also bolometers. In this article, noise in the CSA, basic circuit on the CSA, concepts of `equivalent noise charge` (ENC), a method for the ENC, and importance of the `open-loop gain` in the CSA to achieve better performance of it and how to realize in a practical CSA were described. And, characteristics on a counting rate of the CSA, various circuit used in the CSA, and CSAs which are commercially available at present and special purpose CSAs were also introduced. (G.K.)

  20. Phase Fluctuations and the Absence of Topological Defects in Photo-excited Charge Ordered Nickelate

    Energy Technology Data Exchange (ETDEWEB)

    Lee, W.S.; Chuang, Y.D.; Moore, R.G.; Zhu, Y.; Patthey, L.; Trigo, M.; Lu, D.H.; Kirchmann, P.S.; Krupin, O.; Yi, M.; Langner, M.; Huse, N.; Robinson, J.S.; Chen, Y.; Zhou, S.Y.; Coslovich, G.; Huber, B.; Reis, D.A.; Kaindl, R.A.; Schoenlein, R.W.; Doering, D.

    2012-05-15

    The dynamics of an order parameter's amplitude and phase determines the collective behaviour of novel states emerging in complex materials. Time- and momentum-resolved pump-probe spectroscopy, by virtue of measuring material properties at atomic and electronic time scales out of equilibrium, can decouple entangled degrees of freedom by visualizing their corresponding dynamics in the time domain. Here we combine time-resolved femotosecond optical and resonant X-ray diffraction measurements on charge ordered La{sub 1.75}Sr{sub 0.25}NiO{sub 4} to reveal unforeseen photoinduced phase fluctuations of the charge order parameter. Such fluctuations preserve long-range order without creating topological defects, distinct from thermal phase fluctuations near the critical temperature in equilibrium. Importantly, relaxation of the phase fluctuations is found to be an order of magnitude slower than that of the order parameter's amplitude fluctuations, and thus limits charge order recovery. This new aspect of phase fluctuations provides a more holistic view of the phase's importance in ordering phenomena of quantum matter.

  1. Ultrafast excited state dynamics of tris-(2,2'-bipyridine) Ruthenium (II)

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, Alvin T.W. [Univ. of California, Berkeley, CA (United States)

    2000-03-01

    Time resolved anisotropy measurements and time dependent transient absorption measurements are used to study the evolution of the photoexcited Franck-Condon state to the formation of the long-lived triplet metal-to-ligand charge-transfer (3MLCT) state in tris-(2,2’-bipyridine) ruthenium. [Ru(bpy)3]2+ represents a large class of inorganic compounds with interesting and potentially applicable photophysical properties. These compounds have generated much interest in the inorganic chemistry community because their photophysical properties are easily manipulated by synthetic chemistry methods. However, little remains known about the processes which govern the evolution horn initial photoexcitation to the formation of the long-lived excited state.

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

    CERN Document Server

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

    2015-01-01

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

  3. Collective charge excitations of the two-dimensional electride Ca2N

    Science.gov (United States)

    Cudazzo, Pierluigi; Gatti, Matteo

    2017-09-01

    Ca2N is a layered material that has been recently identified as a two-dimensional (2D) electride, an unusual ionic compound in which electrons serve as anions. The electronic properties of 2D electrides attract considerable interest as the anionic electrons, which form a 2D layer sandwiched between atomic planes, are highly mobile as they are not attached to any ion. Here, on the basis of first-principles time-dependent density-functional theory calculations, we investigate the collective excitations of the electrons—i.e., the plasmons—in Ca2N as a function of wave vector q . Our calculations reveal an intrinsic negative in-plane dispersion of the anionic plasmon, in striking contrast with the homogeneous electron gas. Moreover, for wave vectors q normal to the planes, we find a long-lived plasmon that continues to exist well beyond the first Brillouin zone. This is a mark of the electronic inhomogeneities in the charge response that Ca2N shares with other layered materials like transition-metal dichalcogenides and MgB2. Finally, we compare the plasmon properties of Ca2N in its bulk and monolayer forms, which shows the effect of the different electronic structures and dimensionalities.

  4. SEP ionic charge states in ESP and impulsive events

    Science.gov (United States)

    Popecki, M.; Moebius, E.; Galvin, A.; Kistler, L.; Kucharek, H.; Klecker, B.

    The SEPICA instrument on the Advanced Composition Explorer (ACE) spacecraft has measured ionic charge states of solar energetic particles (SEPs) from late 1997 through 2000. Charge state measurements provide insights about the acceleration and propa- gation history of SEPs. In impulsive events, SEP charge states provide information about the flare environment, where source heating and collisions are important. In in- terplanetary shock events, SEP charge states are diagnostics of the rigidity-dependent acceleration process and particle seed populations. For example, 3He enrichment has been observed in some events with a local shock passage (Desai et al., 2001). An en- hancement in high charge state Fe has also been observed in these events (Popecki et al., 2001). This suggests that the seed population for the interplanetary shock con- tained ions previously accelerated in flares. SEP charge states from impulsive events will be compared to those from events with a local shock passage (ESP events). In addition, the ESP events wil be separated into those with and without 3He enrichment. Results will be presented in the context of mission-integrated ionic charge state distributions for each species.

  5. Search for Charged Excited Leptons in $e^+ e^-$ Collisions at $\\sqrt{s}$ = 183-209 GeV

    CERN Document Server

    Abbiendi, G.; Akesson, P.F.; Alexander, G.; Allison, John; Amaral, P.; Anagnostou, G.; Anderson, K.J.; Arcelli, S.; Asai, S.; Axen, D.; Azuelos, G.; Bailey, I.; Barberio, E.; Barlow, R.J.; Batley, R.J.; Bechtle, P.; Behnke, T.; Bell, Kenneth Watson; Bell, P.J.; Bella, G.; Bellerive, A.; Benelli, G.; Bethke, S.; Biebel, O.; Bloodworth, I.J.; Boeriu, O.; Bock, P.; Bonacorsi, D.; Boutemeur, M.; Braibant, S.; Brigliadori, L.; Brown, Robert M.; Buesser, K.; Burckhart, H.J.; Cammin, J.; Campana, S.; Carnegie, R.K.; Caron, B.; Carter, A.A.; Carter, J.R.; Chang, C.Y.; Charlton, David G.; Cohen, I.; Csilling, A.; Cuffiani, M.; Dado, S.; Dallavalle, G.Marco; Dallison, S.; De Roeck, A.; De Wolf, E.A.; Desch, K.; Donkers, M.; Dubbert, J.; Duchovni, E.; Duckeck, G.; Duerdoth, I.P.; Elfgren, E.; Etzion, E.; Fabbri, F.; Feld, L.; Ferrari, P.; Fiedler, F.; Fleck, I.; Ford, M.; Frey, A.; Furtjes, A.; Gagnon, P.; Gary, John William; Gaycken, G.; Geich-Gimbel, C.; Giacomelli, G.; Giacomelli, P.; Giunta, Marina; Goldberg, J.; Gross, E.; Grunhaus, J.; Gruwe, M.; Gunther, P.O.; Gupta, A.; Hajdu, C.; Hamann, M.; Hanson, G.G.; Harder, K.; Harel, A.; Harin-Dirac, M.; Hauschild, M.; Hauschildt, J.; Hawkes, C.M.; Hawkings, R.; Hemingway, R.J.; Hensel, C.; Herten, G.; Heuer, R.D.; Hill, J.C.; Hoffman, Kara Dion; Homer, R.J.; Horvath, D.; Howard, R.; Huntemeyer, P.; Igo-Kemenes, P.; Ishii, K.; Jeremie, H.; Jovanovic, P.; Junk, T.R.; Kanaya, N.; Kanzaki, J.; Karapetian, G.; Karlen, D.; Kartvelishvili, V.; Kawagoe, K.; Kawamoto, T.; Keeler, R.K.; Kellogg, R.G.; Kennedy, B.W.; Kim, D.H.; Klein, K.; Klier, A.; Kluth, S.; Kobayashi, T.; Kobel, M.; Kokott, T.P.; Komamiya, S.; Kormos, Laura L.; Kowalewski, Robert V.; Kramer, T.; Kress, T.; Krieger, P.; von Krogh, J.; Krop, D.; Kupper, M.; Kyberd, P.; Lafferty, G.D.; Landsman, H.; Lanske, D.; Layter, J.G.; Leins, A.; Lellouch, D.; Letts, J.; Levinson, L.; Lillich, J.; Lloyd, S.L.; Loebinger, F.K.; Lu, J.; Ludwig, J.; Macpherson, A.; Mader, W.; Marcellini, S.; Marchant, T.E.; Martin, A.J.; Martin, J.P.; Masetti, G.; Mashimo, T.; Mattig, Peter; McDonald, W.J.; McKenna, J.; McMahon, T.J.; McPherson, R.A.; Meijers, F.; Mendez-Lorenzo, P.; Menges, W.; Merritt, F.S.; Mes, H.; Michelini, A.; Mihara, S.; Mikenberg, G.; Miller, D.J.; Moed, S.; Mohr, W.; Mori, T.; Mutter, A.; Nagai, K.; Nakamura, I.; Neal, H.A.; Nisius, R.; O'Neale, S.W.; Oh, A.; Okpara, A.; Oreglia, M.J.; Orito, S.; Pahl, C.; Pasztor, G.; Pater, J.R.; Patrick, G.N.; Pilcher, J.E.; Pinfold, J.; Plane, David E.; Poli, B.; Polok, J.; Pooth, O.; Przybycien, M.; Quadt, A.; Rabbertz, K.; Rembser, C.; Renkel, P.; Rick, H.; Roney, J.M.; Rosati, S.; Rozen, Y.; Runge, K.; Rust, D.R.; Sachs, K.; Saeki, T.; Sahr, O.; Sarkisyan, E.K.G.; Schaile, A.D.; Schaile, O.; Scharff-Hansen, P.; Schieck, J.; Schoerner-Sadenius, Thomas; Schroder, Matthias; Schumacher, M.; Schwick, C.; Scott, W.G.; Seuster, R.; Shears, T.G.; Shen, B.C.; Shepherd-Themistocleous, C.H.; Sherwood, P.; Siroli, G.; Skuja, A.; Smith, A.M.; Sobie, R.; Soldner-Rembold, S.; Spagnolo, S.; Spano, F.; Stahl, A.; Stephens, K.; Strom, David M.; Strohmer, R.; Tarem, S.; Tasevsky, M.; Taylor, R.J.; Teuscher, R.; Thomson, M.A.; Torrence, E.; Toya, D.; Tran, P.; Trefzger, T.; Tricoli, A.; Trigger, I.; Trocsanyi, Z.; Tsur, E.; Turner-Watson, M.F.; Ueda, I.; Ujvari, B.; Vachon, B.; Vollmer, C.F.; Vannerem, P.; Verzocchi, M.; Voss, H.; Vossebeld, J.; Waller, D.; Ward, C.P.; Ward, D.R.; Watkins, P.M.; Watson, A.T.; Watson, N.K.; Wells, P.S.; Wengler, T.; Wermes, N.; Wetterling, D.; Wilson, G.W.; Wilson, J.A.; Wolf, G.; Wyatt, T.R.; Yamashita, S.; Zacek, V.; Zer-Zion, D.; Zivkovic, Lidija

    2002-01-01

    A search for charged excited leptons decaying into a lepton and photon has been performed using approximately 680 pb-1 of e+e- collision data collected by the OPAL detector at LEP at centre-of-mass energies between 183 GeV and 209 GeV. No evidence for their existence was found. Upper limits on the product of the cross-section and the branching fraction are inferred. Using results from the search for singly produced excited leptons, upper limits on the ratio of the excited lepton coupling constant to the compositeness scale are calculated. From pair production searches, 95% confidence level lower limits on the masses of excited electrons, muons and taus are determined to be 103.2 GeV.

  6. The Astrophysical Weeds: Rotational Transitions in Excited Vibrational States

    Science.gov (United States)

    Alonso, José L.; Kolesniková, Lucie; Alonso, Elena R.; Mata, Santiago

    2017-06-01

    The number of unidentified lines in the millimeter and submillimeter wave surveys of the interstellar medium has grown rapidly. The major contributions are due to rotational transitions in excited vibrational states of a relatively few molecules that are called the astrophysical weeds. necessary data to deal with spectral lines from astrophysical weeds species can be obtained from detailed laboratory rotational measurements in the microwave and millimeter wave region. A general procedure is being used at Valladolid combining different time and/or frequency domain spectroscopic tools of varying importance for providing the precise set of spectroscopic constants that could be used to search for this species in the ISM. This is illustrated in the present contribution through its application to several significant examples. Fortman, S. M., Medvedev, I. R., Neese, C.F., & De Lucia, F.C. 2010, ApJ,725, 1682 Rotational Spectra in 29 Vibrationally Excited States of Interstellar Aminoacetonitrile, L. Kolesniková, E. R. Alonso, S. Mata, and J. L. Alonso, The Astrophysical Journal Supplement Series 2017, (in press).

  7. Excited state mass spectra of singly charmed baryons

    Energy Technology Data Exchange (ETDEWEB)

    Shah, Zalak; Kumar Rai, Ajay [Sardar Vallabhbhai National Institute of Technology, Department of Applied Physics, Surat, Gujarat (India); Thakkar, Kaushal [GIDC Degree Engineering College, Department of Applied Sciences and Humanities, Abrama (India); Vinodkumar, P.C. [Sardar Patel University, Department of Physics, V.V. Nagar (India)

    2016-10-15

    Mass spectra of excited states of the singly charmed baryons are calculated using the hypercentral description of the three-body system. The baryons consist of a charm quark and light quarks (u, d and s) are studied in the framework of QCD motivated constituent quark model. The form of the confinement potential is hyper-Coloumb plus power potential with potential index ν, varying from 0.5 to 2.0. The first-order correction to the confinement potential is also incorporated in this approach. The radial as well as orbital excited state masses of Σ{sub c}{sup ++}, Σ{sub c}{sup +}, Σ{sub c}{sup 0}, Ξ{sub c}{sup +}, Ξ{sub c}{sup 0}, Λ{sub c}{sup +}, Ω{sub c}{sup 0} baryons, are reported in this paper. We have incorporated spin-spin, spin-orbit and tensor interactions perturbatively in the present study. The semi-electronic decay of Ω{sub c} and Ξ{sub c} are also calculated using the spectroscopic parameters of these baryons. The computed results are compared with other theoretical predictions as well as with the available experimental observations. We also construct the Regge trajectory in (n{sub r},M{sup 2}) and (J,M{sup 2}) planes for these baryons. (orig.)

  8. Trapped electronic states in YAG crystal excited by femtosecond radiation

    Energy Technology Data Exchange (ETDEWEB)

    Zavedeev, E.V.; Kononenko, V.V.; Konov, V.I. [General Physics Institute of RAS, Moscow (Russian Federation); National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Moscow (Russian Federation)

    2017-07-15

    The excitation of an electronic subsystem of an yttrium aluminum garnet by 800 nm femtosecond radiation was studied theoretically and experimentally. The spatio-temporal dynamics of the refractive index (n) inside the beam waist was explored by means of the pump-probe interferometric technique with a submicron resolution. The observed increase in n indicated the formation of bound electronic states relaxed for ∝ 150 ps. We showed that the experimental data agreed with the computational simulation based on the numerical solution of the nonlinear Schroedinger equation only if these transient states were considered to arise from a direct light-induced process but not from the decay of radiatively generated free-electron-hole pairs. (orig.)

  9. Hybrid lead halide perovskites for light energy conversion: Excited state properties and photovoltaic applications

    Science.gov (United States)

    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

  10. Resonant coherent excitation of hydrogen-like ions planar channeled in a crystal; Transition into the first excited state

    Science.gov (United States)

    Babaev, A.; Pivovarov, Yu. L.

    2012-03-01

    in the ground state or in the first excited state, or to be ionized, the Schrödinger equation is solved for the electron of ion. The numerical solving of the Schrödinger equation is carried out taking into account the fine structure of electronic energy levels, the Stark effect due to the influence of the crystal electric field on electronic energy levels and the ionization of ion due to the collisions with crystal electrons. Solution method: The wave function of the electron of ion is the superposition of the wave functions of stationary states with time-dependent coefficients. These stationary wave functions and corresponding energies are defined from the stationary Schrödinger equation. The equation is reduced to the problem of the eigen values and vectors of Hermitian matrix. The corresponding matrix equation is considered as the linear equation system. Then the time-dependent coefficients of the electron wave function are defined from the Schrödinger equation, with a time-periodic crystal field. The time-periodic field is responsible for the transitions between the stationary states. The final time-dependent Schrödinger equation represents the matrix equation which has been solved by means of the QR-algorithm. Restrictions: As expected the program gives the correct results for relativistic hydrogen-like ions with the kinetic energies up to 1 GeV/u and at the crystal thicknesses of 1-100 μm. The restrictions are: first, the program might give inadequate results, when the ion kinetic energy is too large (>10 GeV/u); second, the unaccounted physical factors may be significant at specific conditions. For example, the spontaneous emission by exited highly charged ions, as well as both energy and angular spread of the incident beam, could lead to additional broadening of the resonance. The medium polarization by the electric field of ion can influence the electronic energy levels of the ion in the non-relativistic case. The role of these factors was discussed in

  11. Bilayer Graphene: Interaction-Induced Quantum Hall States and Unusual Excitations

    Science.gov (United States)

    Sondhi, Shivaji; Abanin, D. A.; Parameswaran, S. A.

    2010-03-01

    Recently, new interaction-induced quantum Hall (QH) states were observedfootnotetextB. Feldman et al., Nature Physics, doi:10.1038/nphys1406 (2009); Y. Zhao et al., arXiv:0910.0217 (2009). in bilayer graphene (BG). In this talk we address the nature of these QH states, as well as their propertiesfootnotetextD. Abanin et al., Phys. Rev. Lett. 103, 076802 (2009), and to be published.. We focus on the ferromagnetic (FM) states at even filling factors, which, in the leading approximation, result from the spontaneous breaking of valley/spin SU(4) symmetry. Calculating microscopic anisotropies of the QHFM, we find the order in which Landau level (LL) degeneracies are lifted. Furthermore, we discuss the phase diagram of the system as a function of perpendicular electric field and parallel magnetic field, and find that they can be used to drive transitions between different QH states. We show that, as a result of unusual LL structure of BG, some of the QHFM states support new type of excitations -- spin/valley textures (skyrmions) that carry charge two, which provides a unique example of pairing of charges in a system with purely repulsive interactions. We propose several experiments to test our findings.

  12. Accounting for highly excited states in detailed opacity calculations

    CERN Document Server

    Pain, Jean-Christophe

    2015-01-01

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

  13. Energy cascades, excited state dynamics, and photochemistry in cob(III)alamins and ferric porphyrins.

    Science.gov (United States)

    Rury, Aaron S; Wiley, Theodore E; Sension, Roseanne J

    2015-03-17

    Porphyrins and the related chlorins and corrins contain a cyclic tetrapyrrole with the ability to coordinate an active metal center and to perform a variety of functions exploiting the oxidation state, reactivity, and axial ligation of the metal center. These compounds are used in optically activated applications ranging from light harvesting and energy conversion to medical therapeutics and photodynamic therapy to molecular electronics, spintronics, optoelectronic thin films, and optomagnetics. Cobalt containing corrin rings extend the range of applications through photolytic cleavage of a unique axial carbon-cobalt bond, permitting spatiotemporal control of drug delivery. The photochemistry and photophysics of cyclic tetrapyrroles are controlled by electronic relaxation dynamics including internal conversion and intersystem crossing. Typically the electronic excitation cascades through ring centered ππ* states, ligand to metal charge transfer (LMCT) states, metal to ligand charge transfer (MLCT) states, and metal centered states. Ultrafast transient absorption spectroscopy provides a powerful tool for the investigation of the electronic state dynamics in metal containing tetrapyrroles. The UV-visible spectrum is sensitive to the oxidation state, electronic configuration, spin state, and axial ligation of the central metal atom. Ultrashort broadband white light probes spanning the range from 270 to 800 nm, combined with tunable excitation pulses, permit the detailed unravelling of the time scales involved in the electronic energy cascade. State-of-the-art theoretical calculations provide additional insight required for precise assignment of the states. In this Account, we focus on recent ultrafast transient absorption studies of ferric porphyrins and corrin containing cob(III)alamins elucidating the electronic states responsible for ultrafast energy cascades, excited state dynamics, and the resulting photoreactivity or photostability of these compounds. Iron

  14. Charge Transfer and Triplet States in High Efficiency OPV Materials and Devices

    Science.gov (United States)

    Dyakonov, Vladimir

    2013-03-01

    The advantage of using polymers and molecules in electronic devices, such as light-emitting diodes (LED), field-effect transistors (FET) and, more recently, solar cells (SC) is justified by the unique combination of high device performance and processing of the semiconductors used. Power conversion efficiency of nanostructured polymer SC is in the range of 10% on lab scale, making them ready for up-scaling. Efficient charge carrier generation and recombination in SC are strongly related to dissociation of the primary singlet excitons. The dissociation (or charge transfer) process should be very efficient in photovoltaics. The mechanisms governing charge carrier generation, recombination and transport in SC based on the so-called bulk-heterojunctions, i.e. blends of two or more semiconductors with different electron affinities, appear to be very complex, as they imply the presence of the intermediate excited states, neutral and charged ones. Charge transfer states, or polaron pairs, are the intermediate states between free electrons/holes and strongly bound excitons. Interestingly, the mostly efficient OLEDs to date are based on the so-called triplet emitters, which utilize the triplet-triplet annihilation process. In SC, recent investigations indicated that on illumination of the device active layer, not only mobile charges but also triplet states were formed. With respect to triplets, it is unclear how these excited states are generated, via inter-system crossing or via back transfer of the electron from acceptor to donor. Triplet formation may be considered as charge carrier loss channel; however, the fusion of two triplets may lead to a formation of singlet excitons instead. In such case, a generation of charges by utilizing of the so far unused photons will be possible. The fundamental understanding of the processes involving the charge transfer and triplet states and their relation to nanoscale morphology and/or energetics of blends is essential for the

  15. Real-time decay of a highly excited charge carrier in the one-dimensional Holstein model

    Science.gov (United States)

    Dorfner, F.; Vidmar, L.; Brockt, C.; Jeckelmann, E.; Heidrich-Meisner, F.

    2015-03-01

    We study the real-time dynamics of a highly excited charge carrier coupled to quantum phonons via a Holstein-type electron-phonon coupling. This is a prototypical example for the nonequilibrium dynamics in an interacting many-body system where excess energy is transferred from electronic to phononic degrees of freedom. We use diagonalization in a limited functional space (LFS) to study the nonequilibrium dynamics on a finite one-dimensional chain. This method agrees with exact diagonalization and the time-evolving block-decimation method, in both the relaxation regime and the long-time stationary state, and among these three methods it is the most efficient and versatile one for this problem. We perform a comprehensive analysis of the time evolution by calculating the electron, phonon and electron-phonon coupling energies, and the electronic momentum distribution function. The numerical results are compared to analytical solutions for short times, for a small hopping amplitude and for a weak electron-phonon coupling. In the latter case, the relaxation dynamics obtained from the Boltzmann equation agrees very well with the LFS data. We also study the time dependence of the eigenstates of the single-site reduced density matrix, which defines the so-called optimal phonon modes. We discuss their structure in nonequilibrium and the distribution of their weights. Our analysis shows that the structure of optimal phonon modes contains very useful information for the interpretation of the numerical data.

  16. Excited-state Raman spectroscopy with and without actinic excitation: S{sub 1} Raman spectra of trans-azobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Dobryakov, A. L.; Quick, M.; Ioffe, I. N.; Granovsky, A. A.; Ernsting, N. P.; Kovalenko, S. A. [Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, D-12489 Berlin (Germany)

    2014-05-14

    We show that femtosecond stimulated Raman spectroscopy can record excited-state spectra in the absence of actinic excitation, if the Raman pump is in resonance with an electronic transition. The approach is illustrated by recording S{sub 1} and S{sub 0} spectra of trans-azobenzene in n-hexane. The S{sub 1} spectra were also measured conventionally, upon nπ* (S{sub 0} → S{sub 1}) actinic excitation. The results are discussed and compared to earlier reports.

  17. Excited state mass spectra and Regge trajectories of bottom baryons

    Science.gov (United States)

    Thakkar, Kaushal; Shah, Zalak; Rai, Ajay Kumar; C. Vinodkumar, P.

    2017-09-01

    We present the mass spectra of radial and orbital excited states of singly heavy bottom baryons; Σb+, Σb-, Ξb-, Ξb0, Λb0 and Ωb-. The QCD motivated hypercentral quark model is employed for the three body description of baryons and the form of confinement potential is hyper Coulomb plus linear. The first order correction to the confinement potential is also incorporated in this work. The semi-electronic decay of Ωb and Ξb are calculated using the spectroscopic parameters of the baryons. The computed results are compared with other theoretical predictions as well as with the available experimental observations. The Regge trajectories are plotted in (n ,M2) plane.

  18. Sunlight-Initiated Photochemistry: Excited Vibrational States of Atmospheric Chromophores

    Directory of Open Access Journals (Sweden)

    Veronica Vaida

    2008-01-01

    Full Text Available Atmospheric chemical reactions are often initiated by ultraviolet (UV solar radiation since absorption in that wavelength range coincides to typical chemical bond energies. In this review, we present an alternative process by which chemical reactions occur with the excitation of vibrational levels in the ground electronic state by red solar photons. We focus on the O–H vibrational manifold which can be an atmospheric chromophore for driving vibrationally mediated overtone-induced chemical reactions. Experimental and theoretical O–H intensities of several carboxylic acids, alcohols, and peroxides are presented. The importance of combination bands in spectra at chemically relevant energies is examined in the context of atmospheric photochemistry. Candidate systems for overtone-initiated chemistry are provided, and their lowest energy barrier for reaction and the minimum quanta of O–H stretch required for reaction are calculated. We conclude with a discussion of the major pathways available for overtone-induced reactions in the atmosphere.

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

    DEFF Research Database (Denmark)

    Birkedal, Dan

    2000-01-01

    The coherent interaction of light and the electronic states of semiconductors near the fundamental bandgap has been a very active topic of research since the advent of ultrafast lasers. While many of the ultrafast nonlinear properties of semiconductors have been well explained within mean field...... to the nonlinear susceptibility. The method exploits that emission from two-exciton coherences can occur in non-specular directions, with the recoil momentum taken up by an exciton left behind in the sample. Using ultrafast spectral interferometry we demonstrate the presence of this new coherent component...... of the secondary emission from quantum wells following ultrafast resonant excitation and find that it provides information on not only the bound biexcitons but also the biexciton continuum. Due to the heterodyne nature of the experimental technique we obtain both amplitude and phase of the coherent emission...

  20. Projectile- and charge-state-dependent electron yields from ion penetration of solids as a probe of preequilibrium stopping power

    DEFF Research Database (Denmark)

    Rothard, H.; Schou, Jørgen; Groeneveld, K.-O.

    1992-01-01

    Kinetic electron-emission yields gamma from swift ion penetration of solids are proportional to the (electronic) stopping power gamma approximately Beta-S*, if the preequilibrium evolution of the charge and excitation states of the positively charged ions is taken into account. We show...... by investigating the "transport factor" beta, the energy spectrum of directly ejected recoil electrons and the evolution of ionic charge state inside solids. Estimates of the energy-loss fraction leading to electron emission and the effective charges of the ions near the surface allow a quantitative description...... that the concept of the preequilibrium near-surface stopping S* can be applied successfully to describe the dependence of the ion-induced electron yields on the projectile atomic number Z(P) and on the charge states q(i) of the incoming ions. We discuss the implementation of this concept into Schou's transport...

  1. Photochemistry and electron-transfer mechanism of transition metal oxalato complexes excited in the charge transfer band.

    Science.gov (United States)

    Chen, Jie; Zhang, Hua; Tomov, Ivan V; Ding, Xunliang; Rentzepis, Peter M

    2008-10-07

    The photoredox reaction of trisoxalato cobaltate (III) has been studied by means of ultrafast extended x-ray absorption fine structure and optical transient spectroscopy after excitation in the charge-transfer band with 267-nm femtosecond pulses. The Co-O transient bond length changes and the optical spectra and kinetics have been measured and compared with those of ferrioxalate. Data presented here strongly suggest that both of these metal oxalato complexes operate under similar photoredox reaction mechanisms where the primary reaction involves the dissociation of a metal-oxygen bond. These results also indicate that excitation in the charge-transfer band is not a sufficient condition for the intramolecular electron transfer to be the dominant photochemistry reaction mechanism.

  2. Using Diffusion Monte Carlo to Probe Rotational Excited States

    Science.gov (United States)

    Petit, Andrew S.; McCoy, Anne B.

    2009-06-01

    Since its inception in 1975 by Anderson, has been successfully applied to a wide range of electronic and vibrational problems. In the latter case, it has been shown to be a powerful method for studying highly fluxional systems exhibiting large amplitude vibrational motions. We report here our recent work developing a new DMC algorithm capable of treating rotational excited states. We first develop the appropriate coordinates, nodal structures, and re-crossing corrections for this problem. Then, using H_3O^+ and D_3O^+ as model systems, we show that our method can successfully describe a range of rotational states from mid0,0,0> to {1}/{√{2}} (mid10,10,0 > + mid 10,-10,0 >). In particular, we examine the combined effects of rotational and zero-point vibrational motion on the geometric structure of the molecules. Finally, we find the mid 10,0,0 > state to be somewhat problematic but show that the problem is straightforward to identify and has a well-defined solution. J. B. Anderson, J. Chem. Phys., 63, 1499 (1975). X. Huang, S. Carter, and J. Bowman, J. Chem. Phys., 118, 5431 (2003).

  3. Ground State and Excited State Tuning in Ferric Dipyrrin Complexes Promoted by Ancillary Ligand Exchange

    Energy Technology Data Exchange (ETDEWEB)

    Kleinlein, Claudia; Zheng, Shao-Liang; Betley, Theodore A.

    2017-04-24

    Three ferric dipyrromethene complexes featuring different ancillary ligands were synthesized by one electron oxidation of ferrous precursors. Four-coordinate iron complexes of the type (ArL)FeX2 [ArL = 1,9-(2,4,6-Ph3C6H2)2-5-mesityldipyrromethene] with X = Cl or tBuO were prepared and found to be high-spin (S = 5/2), as determined by superconducting quantum interference device magnetometry, electron paramagnetic resonance, and 57Fe Mössbauer spectroscopy. The ancillary ligand substitution was found to affect both ground state and excited properties of the ferric complexes examined. While each ferric complex displays reversible reduction and oxidation events, each alkoxide for chloride substitution results in a nearly 600 mV cathodic shift of the FeIII/II couple. The oxidation event remains largely unaffected by the ancillary ligand substitution and is likely dipyrrin-centered. While the alkoxide substituted ferric species largely retain the color of their ferrous precursors, characteristic of dipyrrin-based ligand-to-ligand charge transfer (LLCT), the dichloride ferric complex loses the prominent dipyrrin chromophore, taking on a deep green color. Time-dependent density functional theory analyses indicate the weaker-field chloride ligands allow substantial configuration mixing of ligand-to-metal charge transfer into the LLCT bands, giving rise to the color changes observed. Furthermore, the higher degree of covalency between the alkoxide ferric centers is manifest in the observed reactivity. Delocalization of spin density onto the tert-butoxide ligand in (ArL)FeCl(OtBu) is evidenced by hydrogen atom abstraction to yield (ArL)FeCl and HOtBu in the presence of substrates containing weak C–H bonds, whereas the chloride (ArL)FeCl2 analogue does not react under these conditions.

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

    Energy Technology Data Exchange (ETDEWEB)

    Pinnaduwage, L.A. [Oak Ridge National Lab., TN (United States). Health Sciences Research Div.]|[Univ. of Tennessee, Knoxville, TN (United States). Dept. of Physics

    1995-12-31

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

  5. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu

    2015-09-02

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  6. Unrestricted density functional theory based on the fragment molecular orbital method for the ground and excited state calculations of large systems

    Energy Technology Data Exchange (ETDEWEB)

    Nakata, Hiroya, E-mail: nakata.h.ab@m.titech.ac.jp [Center for Biological Resources and Informatics, Tokyo Institute of Technology, B-62 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8501 (Japan); RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Fedorov, Dmitri G. [NRI, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568 (Japan); Yokojima, Satoshi [RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Tokyo University of Pharmacy and Life Sciences, 1423-1 Horinouchi, Hachioji-shi, Tokyo 192-0392 (Japan); Kitaura, Kazuo [Graduate School of System Informatics, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501 (Japan); Sakurai, Minoru [Center for Biological Resources and Informatics, Tokyo Institute of Technology, B-62 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8501 (Japan); Nakamura, Shinichiro [RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)

    2014-04-14

    We extended the fragment molecular orbital (FMO) method interfaced with density functional theory (DFT) into spin unrestricted formalism (UDFT) and developed energy gradients for the ground state and single point excited state energies based on time-dependent DFT. The accuracy of FMO is evaluated in comparison to the full calculations without fragmentation. Electronic excitations in solvated organic radicals and in the blue copper protein, plastocyanin (PDB code: 1BXV), are reported. The contributions of solvent molecules to the electronic excitations are analyzed in terms of the fragment polarization and quantum effects such as interfragment charge transfer.

  7. Exciting hot carrier to a high energy state by impact excitation in low density nanocrystalline Si films

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Wei, E-mail: yuwei_hbu@126.com [College of Physics Science and Technology, Hebei University, Baoding 071002 (China); Wang, Xinzhan; Dai, Wanlei; Liu, Yumei; Xu, Yanmei; Lu, Wanbing; Fu, Guangsheng [College of Physics Science and Technology, Hebei University, Baoding 071002 (China)

    2013-02-15

    The carrier recombination processes in low density nanocrystalline (nc-) Si films have been studied by steady and time-resolved photoluminescence (PL) spectra, and the hot carriers have been excited to a high energy state by impact excitation. A yellow-green PL band locating at 580 nm appears when the studied film is excited by two optical beams. The yellow-green PL band results from band-to-band transition in Si nanocrystals with double-bonded oxygen atoms, which is caused by impact excitation among the carriers in the nc-Si film. The decay time of the yellow-green PL band is 230 ns, which is much longer than the hot carrier cooling. The results indicate that the lost energy in the solar cell may be collected from the new recombination center in the further structural design.

  8. Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission

    Science.gov (United States)

    Sen, Ananya; Matthews, Edward M.; Hou, Gao-Lei; Wang, Xue-Bin; Dessent, Caroline E. H.

    2015-11-01

    We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine, and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ˜1.7 eV, values that are lower than the RCB of the uncomplexed PtCl62- dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl62- ṡ thymine and PtCl62- ṡ adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)42- ṡ nucleobase complexes [A. Sen et al., J. Phys. Chem. B 119, 11626 (2015)]. The observation of delayed electron emission bands in the PtCl62- ṡ nucleobase spectra obtained in this work, as for the previously studied Pt(CN)42- ṡ nucleobase complexes, is attributed to one-photon excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a "dynamic tag" which has the propensity to emit electrons when the attached nucleobase decays over a time scale long enough to allow autodetachment.

  9. Excited states properties of organic molecules: from density functional theory to the GW and Bethe-Salpeter Green's function formalisms.

    Science.gov (United States)

    Faber, C; Boulanger, P; Attaccalite, C; Duchemin, I; Blase, X

    2014-03-13

    Many-body Green's function perturbation theories, such as the GW and Bethe-Salpeter formalisms, are starting to be routinely applied to study charged and neutral electronic excitations in molecular organic systems relevant to applications in photovoltaics, photochemistry or biology. In parallel, density functional theory and its time-dependent extensions significantly progressed along the line of range-separated hybrid functionals within the generalized Kohn-Sham formalism designed to provide correct excitation energies. We give an overview and compare these approaches with examples drawn from the study of gas phase organic systems such as fullerenes, porphyrins, bacteriochlorophylls or nucleobases molecules. The perspectives and challenges that many-body perturbation theory is facing, such as the role of self-consistency, the calculation of forces and potential energy surfaces in the excited states, or the development of embedding techniques specific to the GW and Bethe-Salpeter equation formalisms, are outlined.

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

    Science.gov (United States)

    Lan, Sheng-Cheng; Liu, Yu-Hui

    2015-03-15

    Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations have been employed to study the excited-state intramolecular proton transfer (ESIPT) reaction of 8-hydroxyquinoline (8HQ). Infrared spectra of 8HQ in both the ground and the lowest singlet excited states have been calculated, revealing a red-shift of the hydroxyl group (-OH) stretching band in the excited state. Hence, the intramolecular hydrogen bond (O-H···N) in 8HQ would be significantly strengthened upon photo-excitation to the S1 state. As the intramolecular proton-transfer reaction occurs through hydrogen bonding, the ESIPT reaction of 8HQ is effectively facilitated by strengthening of the electronic excited-state hydrogen bond (O-H···N). As a result, the intramolecular proton-transfer reaction would occur on an ultrafast timescale with a negligible barrier in the calculated potential energy curve for the ESIPT reaction. Therefore, although the intramolecular proton-transfer reaction is not favorable in the ground state, the ESIPT process is feasible in the excited state. Finally, we have identified that radiationless deactivation via internal conversion (IC) becomes the main dissipative channel for 8HQ by analyzing the energy gaps between the S1 and S0 states for the enol and keto forms. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Thermodynamical analysis of spin-state transitions in LaCo O3 : Negative energy of mixing to assist thermal excitation to the high-spin excited state

    Science.gov (United States)

    Kyômen, Tôru; Asaka, Yoshinori; Itoh, Mitsuru

    2005-01-01

    Magnetic susceptibility and heat capacity due to the spin-state transition in LaCoO3 were calculated by a molecular-field model in which the energy-level diagram of high-spin state reported by Ropka and Radwanski [Phys. Rev. B 67, 172401 (2003)] is assumed for the excited state, and the energy and entropy of mixing of high-spin Co ions and low-spin Co ions are introduced phenomenologically. The experimental data below 300K were well reproduced by this model, which proposes that the high-spin excited state can be populated even if the energy of high-spin state is much larger than that of low-spin state, because the negatively large energy of mixing reduces the net excitation energy. The stability of each spin state including the intermediate-spin state is discussed based on the present results and other reports.

  12. Production of excited beauty states in Z decays

    CERN Document Server

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

    1996-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1982-01-01

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

  14. Evaluation of excitation energy and spin from light charged particles multiplicities in heavy-ion collisions

    CERN Document Server

    Steckmeyer, J C; Grotowski, K; Pawowski, P; Aiello, S; Anzalone, A; Bini, M; Borderie, B; Bougault, R; Cardella, G; Casini, G; Cavallaro, S; Charvet, J L; Dayras, R; De Filippo, E; Durand, D; Femin, S; Frankland, J D; Galíchet, E; Geraci, M; Giustolisi, F; Guazzoni, P; Iacono-Manno, M; Lanzalone, G; Lanzan, G; Le Neindre, N; Lo Nigro, S; Lo Piano, F; Olmi, A; Pagano, A; Papa, M; Pârlog, M; Pasquali, G; Piantelli, S; Pirrone, S; Politi, G; Porto, F; Rivet, M F; Rizzo, F; Rosato, E; Roy, R; Sambataro, S; Sperduto, M L; Stefanini, A A; Sutera, C; Tamain, B; Vient, E; Volant, C; Wieleczko, J P; Zetta, L

    2005-01-01

    A simple procedure for evaluating the excitation energy and the spin transfer in heavy-ion dissipative collisions is proposed. It is based on a prediction of the GEMINI evaporation code : for a nucleus with a given excitation energy, the average number of emitted protons decreases with increasing spin, whereas the average number of alpha particles increases. Using that procedure for the reaction 107Ag+58Ni at 52 MeV/nucleon, the excitation energy and spin of quasi-projectiles have been evaluated. The results obtained in this way have been compared with the predictions of a model describing the primary dynamic stage of heavy-ion collisions.

  15. Analysis of LISA Commissioning Run Data for Study of 24O Excited State Decay Energies

    Science.gov (United States)

    Taylor, N.; Garrett, S.; Barker, A.; Rogers, W. F.

    2012-10-01

    The commissioning run for the Large-area multi-institutional Scintillator Array (LISA), located at the National Superconducting Cyclotron Laboratory at Michigan State University (and built by undergraduates from 9 primarily undergraduate institutions) was conducted over summer 2011. Used along with the Modular Neutron Array (MoNA) and the Sweeper Magnet, the purpose of this run was to study the neutron-unbound excited states of 24O by measuring the energies and trajectories of the charged fragments and the neutrons resulting from the breakup. Careful calibration of all detectors is necessary, including correction for time drifts and absolute time calibration of all charged-particle and neutron detectors. In the Sweeper chamber, the two Cathode-Readout Drift Chamber detectors experienced significant drift in the vertical direction over the course of the experiment, requiring particular care in calibration. Absolute time calibration of all detectors is also necessary before clean isotope separation and decay energies can be determined. Additionally, a variety of isotopes produced in the secondary target interactions for possible future study was made. Results will be presented.

  16. A QM/MM Approach Using the AMOEBA Polarizable Embedding: From Ground State Energies to Electronic Excitations.

    Science.gov (United States)

    Loco, Daniele; Polack, Étienne; Caprasecca, Stefano; Lagardère, Louis; Lipparini, Filippo; Piquemal, Jean-Philip; Mennucci, Benedetta

    2016-08-09

    A fully polarizable implementation of the hybrid quantum mechanics/molecular mechanics approach is presented, where the classical environment is described through the AMOEBA polarizable force field. A variational formalism, offering a self-consistent relaxation of both the MM induced dipoles and the QM electronic density, is used for ground state energies and extended to electronic excitations in the framework of time-dependent density functional theory combined with a state specific response of the classical part. An application to the calculation of the solvatochromism of the pyridinium N-phenolate betaine dye used to define the solvent ET(30) scale is presented. The results show that the QM/AMOEBA model not only properly describes specific and bulk effects in the ground state but it also correctly responds to the large change in the solute electronic charge distribution upon excitation.

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

    CERN Document Server

    Sadeq, Z S

    2015-01-01

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

  18. Interference through the resonant Auger process via multiple core-excited states

    Science.gov (United States)

    Chatterjee, Souvik; Nakajima, Takashi

    2017-12-01

    We theoretically investigate the resonant Auger process via multiple core-excited states. The presence of multiple core-excited states sets off interference into the common final continuum, and we show that the degree of interference depends on the various parameters such as the intensity of the employed x-ray pulse and the lifetimes of the core-excited states. For the specific examples we employ the double (1 s-13 p and 1 s-14 p ) core-excited states of Ne atom and numerically solve the time-dependent Schrödinger equation to demonstrate that the energy-resolved electron spectra clearly exhibit the signature of interference.

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

    Energy Technology Data Exchange (ETDEWEB)

    Esboui, Mounir, E-mail: mounir.esboui@fst.rnu.tn [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications, Département de Physique, Faculté des Sciences de Tunis, 2092 Tunis (Tunisia); Technical and Vocational Training Corporation, Hail College of Technology, P.O. Box 1960, Hail 81441 (Saudi Arabia)

    2015-07-21

    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 translocation 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.

  20. Spectroscopic and theoretical evidence for the photoinduced twisted intramolecular charge transfer state formation in N,N-dimethylaminonaphthyl-(acrylo)-nitrile

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Rupashree Balia; Mahanta, Subrata; Kar, Samiran [Department of Chemistry, University of Calcutta, 92, A. P. C. Road, Kolkata 700009 (India); Guchhait, Nikhil [Department of Chemistry, University of Calcutta, 92, A. P. C. Road, Kolkata 700009 (India)], E-mail: nikhil.guchhait@rediffmail.com

    2008-09-15

    The phenomenon of excited state twisted intramolecular charge transfer (TICT) process in N,N-dimethylaminonaphthyl-(acrylo)-nitrile (DMANAN) has been reported on the basis of steady-state absorption and fluorescence spectroscopy in combination with quantum chemical calculations. The absorption and fluorescence characteristics of DMANAN in solvents of different polarity reveal the presence of a single species in the ground state which forms the intramolecular charge transfer state upon photoexcitation. The observed dual fluorescence is assigned to a high-energy emission from the locally excited or the Franck-Condon state and the red-shifted emission from the charge transfer (CT) state. In polar protic solvents, hydrogen-bonding interaction on CT emission has been established from the linear dependency of the position of the low-energy emission maxima on hydrogen-bonding parameter ({alpha}). The experimental findings have been correlated with the theoretical results based on TICT model obtained at density functional theory (DFT) level. The theoretical potential energy surface for the first excited state along both the donor and acceptor twist coordinates in the gas phase obtained by time dependent density functional theory (TDDFT) method and in polar solvent by time dependent density functional theory-polarized continuum model (TDDFT-PCM) method predicts well the experimental spectral properties.

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

    CERN Document Server

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

    2014-01-01

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

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

    KAUST Repository

    Filatov, Mikhail A.

    2015-10-13

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

  3. Solvent effects on excitation energies obtained using the state-specific TD-DFT method with a polarizable continuum model based on constrained equilibrium thermodynamics.

    Science.gov (United States)

    Bi, Ting-Jun; Xu, Long-Kun; Wang, Fan; Ming, Mei-Jun; Li, Xiang-Yuan

    2017-12-13

    Nonequilibrium solvation effects need to be treated properly in the study of electronic absorption processes of solutes since solvent polarization is not in equilibrium with the excited-state charge density of the solute. In this work, we developed a state specific (SS) method based on the novel nonequilibrium solvation model with constrained equilibrium manipulation to account for solvation effects in electronic absorption processes. Time-dependent density functional theory (TD-DFT) is adopted to calculate electronic excitation energies and a polarizable continuum model is employed in the treatment of bulk solvent effects on both the ground and excited electronic states. The equations based on this novel nonequilibrium solvation model in the framework of TDDFT to calculate vertical excitation energy are presented and implemented in the Q-Chem package. The implementation is validated by comparing reorganization energies for charge transfer excitations between two atoms obtained from Q-Chem and those obtained using a two-sphere model. Solvent effects on electronic transitions of coumarin 153 (C153), acetone, pyridine, (2E)-3-(3,4-dimethoxyphenyl)-1-(2-hydroxyphenyl)prop-2-en-1-one (DMHP), and uracil in different solvents are investigated using the newly developed code. Our results show that the obtained vertical excitation energies as well as spectral shifts generally agree better with the available experimental values than those obtained using the traditional nonequlibrium solvation model. This new model is thus appropriate to study nonequilibrium excitation processes in solution.

  4. Influence of base stacking geometry on the nature of excited states in G-quadruplexes: a time-dependent DFT study.

    Science.gov (United States)

    Lech, Christopher J; Phan, Anh Tuân; Michel-Beyerle, Maria-Elisabeth; Voityuk, Alexander A

    2015-03-05

    G-quadruplexes are four-stranded structures of nucleic acids that are formed from the association of guanine nucleobases into cyclical arrangements known as tetrads. G-quadruplexes are involved in a host of biological processes and are of interest in nanomaterial applications. However, not much is known about their electronic properties. In this paper, we analyze electronic excited states of G-quadruplexes using a combination of time-dependent DFT calculations and molecular dynamics simulations. We systematically consider experimentally observed arrangements of stacked guanine tetrads. The effects of structural features on exciton delocalization and photoinduced charge separation are explored using a quantitative analysis of the transition electron density. It is shown that collective coherent excitations shared between two guanine nucleobases dominate in the absorption spectrum of stacked G-tetrads. These excitations may also include a significant contribution of charge transfer states. Large variation in exciton localization is also observed between different structures with a general propensity toward localization between two bases. We reveal large differences in how charge separation occurs within different nucleobase arrangements, with some geometries favoring separation within a single tetrad and others favoring separation between tetrads. We also investigate the effects of the coordinating K(+) ion located in the central cavity of G-quadruplexes on the relative excited state properties of such systems. Our results demonstrate how the nature of excited states in G-quadruplexes depends on the nucleobase stacking geometry resulting from the mutual arrangement of guanine tetrads.

  5. Photoemission spectra of charge density wave states in cuprates

    Science.gov (United States)

    Tu, Wei-Lin; Chen, Peng-Jen; Lee, Ting-Kuo

    Angle-resolved photoemission spectroscopy(ARPES) experiments have reported many exotic properties of cuprates, such as Fermi arc at normal state, two gaps at superconducting state and particle-hole asymmetry at the antinodal direction. On the other hand, a number of inhomogeneous states or so-called charge density waves(CDW) states have also been discovered in cuprates by many experimental groups. The relation between these CDW states and ARPES spectra is unclear. With the help of Gutzwiller projected mean-field theory, we can reproduce the quasiparticle spectra in momentum space. The spectra show strong correspondence to the experimental data with afore-mentioned exotic features in it.

  6. Temperature and Magnetic Field Effects on the Transport Controlled Charge State of a Single Quantum Dot

    Directory of Open Access Journals (Sweden)

    Moskalenko ES

    2010-01-01

    Full Text Available Abstract Individual InAs/GaAs quantum dots are studied by micro-photoluminescence. By varying the strength of an applied external magnetic field and/or the temperature, it is demonstrated that the charge state of a single quantum dot can be tuned. This tuning effect is shown to be related to the in-plane electron and hole transport, prior to capture into the quantum dot, since the photo-excited carriers are primarily generated in the barrier.

  7. Ab initio QM/MM excited-state molecular dynamics study of coumarin 151 in water solution

    Science.gov (United States)

    Kina, Daisuke; Arora, Pooja; Nakayama, Akira; Noro, Takeshi; Gordon, Mark S.; Taketsugu, Tetsuya

    Ab initio molecular dynamics (AIMD) simulations are performed to investigate the excited state dynamics of coumarin 151 (C151) in the gas phase and in water solution at the CASSCF level of theory with segmented DZP basis sets, where in the latter case effective fragment potentials (EFP) are used. The dipole moment of an isolated C151 molecule increases considerably upon electronic vertical excitation, from 5.0 D (S0 state) to 11.1 D (S1 state). Two equilibrium structures have been identified in the S1 state, i.e., a charge-transfer state with a planar amino group and a deformed structure of the six-membered ring with the carbonyl group, and a structure that is similar to the S0 equilibrium structure. In AIMD simulations for an isolated C151 molecule (presumably similar to dynamics in nonpolar solvents), C151 decays from S1 to S0 via a crossing point of the charge-transfer state in some trajectories, while in the AIMD simulations for C151-EFP (including solvent), the S1 and S0 energies show an almost parallel energy variation with structural changes, and no crossing point is observed. This result is in good agreement with the experimental observation.

  8. Focus: Phase-resolved nonlinear terahertz spectroscopy—From charge dynamics in solids to molecular excitations in liquids

    Energy Technology Data Exchange (ETDEWEB)

    Elsaesser, Thomas, E-mail: elsasser@mbi-berlin.de; Reimann, Klaus; Woerner, Michael, E-mail: woerner@mbi-berlin.de [Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie, 12489 Berlin (Germany)

    2015-06-07

    Intense terahertz (THz) electric field transients with amplitudes up to several megavolts/centimeter and novel multidimensional techniques are the key ingredients of nonlinear THz spectroscopy, a new area of basic research. Both nonlinear light-matter interactions including the non-perturbative regime and THz driven charge transport give new insight into the character and dynamics of low-energy excitations of condensed matter and into quantum kinetic phenomena. This article provides an overview of recent progress in this field, combining an account of technological developments with selected prototype results for liquids and solids. The potential of nonlinear THz methods for future studies of low-frequency excitations of condensed-phase molecular systems is discussed as well.

  9. Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state

    DEFF Research Database (Denmark)

    Reynisson, J.; Wilbrandt, R.; Brinck, V.

    2002-01-01

    of the long wavelength absorption band. A strong fluorescence is observed at 520 nm (tau(n) = 14.6 ns, phi(n) = 0.12 in deaerated acetonitrile). The fluorescence is quenched by 10 aromatic electron donors predominantly via a dynamic charge transfer mechanism, but ground state complexation is shown...

  10. Ultrafast spin exchange-coupling torque via photo-excited charge-transfer processes

    National Research Council Canada - National Science Library

    Ma, X; Fang, F; Li, Q; Zhu, J; Yang, Y; Wu, Y Z; Zhao, H B; Lüpke, G

    2015-01-01

    .... Recently developed optical approaches such as ultrafast demagnetization, spin-transfer and spin-orbit torques open new pathways to manipulate spin through its interaction with photon, orbit, charge or phonon...

  11. Analysis of Ion Charge States in Solar Wind and CMEs

    Indian Academy of Sciences (India)

    We discuss needs in dielectronic recombination data motivated by recent work directed at a quantitative understanding of ion charge states of various elements observed in situ in the solar wind and CMEs. The competing processes of ionization and recombination lead to departures from collision ionization equilibrium.

  12. State-of-Charge Indication in Portable Applications

    NARCIS (Netherlands)

    Pop, V.; Bergveld, H.J.; Notten, P.H.L.; Regtien, Paulus P.L.

    2005-01-01

    The known methods of state-of-charge (SoC) indication in portable applications are not accurate enough under all practical conditions. The method presented in this paper aims at designing and testing an SoC indication system capable of predicting the remaining capacity of the battery and the

  13. Anomalous oxygen isotopic charge state distribution in ECRIS : New evidence

    NARCIS (Netherlands)

    Drentje, AG; Girard, A; Hitz, D; Melin, G

    The highly performing Electron Cyclotron Resonance Ion Source CAPRICE in Grenoble was operated with a mixture of three oxygen isotopes. The summed currents per charge state show a distribution almost identical to that of natural oxygen. However, the distributions per isotope are distinctly and

  14. Protecting a Diamond Quantum Memory by Charge State Control.

    Science.gov (United States)

    Pfender, Matthias; Aslam, Nabeel; Simon, Patrick; Antonov, Denis; Thiering, Gergő; Burk, Sina; Fávaro de Oliveira, Felipe; Denisenko, Andrej; Fedder, Helmut; Meijer, Jan; Garrido, Jose A; Gali, Adam; Teraji, Tokuyuki; Isoya, Junichi; Doherty, Marcus William; Alkauskas, Audrius; Gallo, Alejandro; Grüneis, Andreas; Neumann, Philipp; Wrachtrup, Jörg

    2017-10-11

    In recent years, solid-state spin systems have emerged as promising candidates for quantum information processing. Prominent examples are the nitrogen-vacancy (NV) center in diamond, phosphorus dopants in silicon (Si:P), rare-earth ions in solids, and VSi-centers in silicon-carbide. The Si:P system has demonstrated that its nuclear spins can yield exceedingly long spin coherence times by eliminating the electron spin of the dopant. For NV centers, however, a proper charge state for storage of nuclear spin qubit coherence has not been identified yet. Here, we identify and characterize the positively charged NV center as an electron-spin-less and optically inactive state by utilizing the nuclear spin qubit as a probe. We control the electronic charge and spin utilizing nanometer scale gate electrodes. We achieve a lengthening of the nuclear spin coherence times by a factor of 4. Surprisingly, the new charge state allows switching of the optical response of single nodes facilitating full individual addressability.

  15. Multiple charge states of titanium ions in laser produced plasma

    Indian Academy of Sciences (India)

    W/cm-¾. ) focused on the solid target creates a hot ( 1 keV) and dense plasma having high ionization state. The multiple charged ions with high current densities produced during laser matter interaction have potential application in accelerators as an ion source. This paper presents generation and detection of highly ...

  16. Evaluation of intramolecular charge transfer state of 4-N, N ...

    Indian Academy of Sciences (India)

    Evaluation of intramolecular charge transfer state of. 4-N, N-dimethylamino cinnamaldehyde using time-dependent density functional theory. SURAJIT GHOSHa, K V S GIRISHb and SUBHADIP GHOSHb,∗. aDepartment of Physics and Technophysics, Vidyasagar University, Midnapore 721 102, India. bSchool of Chemical ...

  17. Protecting a Diamond Quantum Memory by Charge State Control

    Science.gov (United States)

    Pfender, Matthias; Aslam, Nabeel; Simon, Patrick; Antonov, Denis; Thiering, Gergő; Burk, Sina; Fávaro de Oliveira, Felipe; Denisenko, Andrej; Fedder, Helmut; Meijer, Jan; Garrido, Jose A.; Gali, Adam; Teraji, Tokuyuki; Isoya, Junichi; Doherty, Marcus William; Alkauskas, Audrius; Gallo, Alejandro; Grüneis, Andreas; Neumann, Philipp; Wrachtrup, Jörg

    2017-10-01

    In recent years, solid-state spin systems have emerged as promising candidates for quantum information processing (QIP). Prominent examples are the Nitrogen-Vacancy (NV) center in diamond, phosphorous dopants in silicon (Si:P), rare-earth ions in solids and V$_{\\text{Si}}$-centers in Silicon-carbide (SiC). The Si:P system has demonstrated, that by eliminating the electron spin of the dopant, its nuclear spins can yield exceedingly long spin coherence times. For NV centers, however, a proper charge state for storage of nuclear spin qubit coherence has not been identified yet. Here, we identify and characterize the positively charged NV center as an electron-spin-less and optically inactive state by utilizing the nuclear spin qubit as a probe. We control the electronic charge and spin utilizing nanometer scale gate electrodes. We achieve a lengthening of the nuclear spin coherence times by a factor of 20. Surprisingly, the new charge state allows switching the optical response of single nodes facilitating full individual addressability.

  18. Universal state-of-charge indication for portable applications

    NARCIS (Netherlands)

    Pop, V.

    2007-01-01

    Many leading semiconductors companies (e.g. Philips, Texas Instruments, Microchip, Maxim, etc.) are paying even more attention to accurate State-of-Charge (SoC) indication. Following the technological revolution and the appearance of more power consuming devices on the automotive electronics and

  19. Excited-state behavior of tryptamine and related indoles. Remarkably efficient intramolecular proton-induced quenching

    Energy Technology Data Exchange (ETDEWEB)

    Shizuka, H.; Serizawa, M.; Kobayashi, H.; Kameta, K.; Sugiyama, H.; Matsuura, T.; Saito, I.

    1988-03-16

    The excited state behavior of tryptamine and 1,2,3,4-tetrahydrocarbazoles possessing alkylamino side chains in the absence and presence of 18-crown-6 in MeOH-H/sub 2/O (9:1) mixtures has been studied by means of nanosecond single-photon counting, fluorimetry, and photochemical H-D isotope exchange. The fluorescence intensity of these indoles increases significantly with increasing concentration of 18-crown-6. The relatively short lifetime of the tryptamine ammonium ion 1 is not ascribed to external quenching but rather to internal quenching. The rate constant k/sub q/ for internal quenching can be estimated from the equation k/sub q/ = tau/sub 0//sup -1/ - tau/sub max//sup -1/, where tau/sub 0/ and tau/sub max/ represent the fluorescence lifetimes for free 1 and the 1:1 1-crown ether complex, respectively. Internal quenching originates from electrophilic proton attack by the -N/sup +/H/sub 3/ (or -N/sup +/D/sub 3/) group of 1 at the C-4 position of the excited indole ring. For 3 (the tetrahydrocarbazole derivative R(CH/sub 2/)/sub 3/N/sup +/H/sub 3/) the k/sub q/ value comprises the electrophilic proton attack at the C-8 position plus other quenching (probably charge-transfer quenching) between the excited indole moiety (R*) and the -N/sup +/H/sub 3/ (or -N/sup +/D/sub 3/) group. The stabilization constant K/sub g/ for the corresponding ammonium ion and 18-crown-6 can be determined by fluorimetry. The kinetic and thermodynamic parameters for the internal quenching and the complex formation, respectively, have been described.

  20. Fast electronic resistance switching involving hidden charge density wave states

    Science.gov (United States)

    Vaskivskyi, I.; Mihailovic, I. A.; Brazovskii, S.; Gospodaric, J.; Mertelj, T.; Svetin, D.; Sutar, P.; Mihailovic, D.

    2016-05-01

    The functionality of computer memory elements is currently based on multi-stability, driven either by locally manipulating the density of electrons in transistors or by switching magnetic or ferroelectric order. Another possibility is switching between metallic and insulating phases by the motion of ions, but their speed is limited by slow nucleation and inhomogeneous percolative growth. Here we demonstrate fast resistance switching in a charge density wave system caused by pulsed current injection. As a charge pulse travels through the material, it converts a commensurately ordered polaronic Mott insulating state in 1T-TaS2 to a metastable electronic state with textured domain walls, accompanied with a conversion of polarons to band states, and concurrent rapid switching from an insulator to a metal. The large resistance change, high switching speed (30 ps) and ultralow energy per bit opens the way to new concepts in non-volatile memory devices manipulating all-electronic states.

  1. Cluster decay of Ba isotopes from ground state and as an excited ...

    Indian Academy of Sciences (India)

    122 is studied by modifying the Coulomb and proximity potential model for both the ground and excited state decays ... 20 and they arise as multiple clusters and are accompanied by multiple light particles. (Z ≤ 2). ... all aspects of α and cluster decay from these isotopes from both ground and excited states beginning with ...

  2. New Rh2(II,II) Complexes for Solar Energy Applications: Panchromatic Absorption and Excited-State Reactivity.

    Science.gov (United States)

    Whittemore, Tyler J; Sayre, Hannah J; Xue, Congcong; White, Travis A; Gallucci, Judith C; Turro, Claudia

    2017-10-18

    The new heteroleptic paddlewheel complexes cis-[Rh 2 (μ-form) 2 (μ-np) 2 ][BF 4 ] 2 , where form = p-ditolylformamidinate (DTolF) or p-difluorobenzylformamidinate (F-form) and np = 1,8-napthyridyine, and cis-Rh 2 (μ-form) 2 (μ-npCOO) 2 (npCOO - = 1,8-naphthyridine-2-carboxylate), were synthesized and characterized. The complexes absorb strongly throughout the ultraviolet (λ max = 300 nm, ε = 20 300 M -1 cm -1 ) and visible regions (λ max = 640 nm ε = 3500 M -1 cm -1 ), making them potentially useful new dyes with panchromatic light absorption for solar energy conversion applications. Ultrafast and nanosecond transient absorption and time-resolved infrared spectroscopies were used to characterize the identity and dynamics of the excited states, where singlet and triplet Rh 2 /form-to-naphthyridine, metal/ligand-to-ligand charge-transfer (ML-LCT) excited states were observed in all four complexes. The npCOO - complexes exhibit red-shifted absorption profiles extending into the near-IR and undergo photoinitiated electron transfer to generate reduced methyl viologen, a species that persists in the presence of a sacrificial donor. The energy of the triplet excited state of each complex was estimated from energy-transfer quenching experiments using a series of organic triplet donors (E( 3 ππ*) from 1.83 to 0.78 eV). The singlet reduction (+0.6 V vs Ag/AgCl) potentials, and singlet and triplet oxidation potentials (-1.1 and -0.5 V vs Ag/AgCl, respectively) were determined. Based on the excited-state lifetimes and redox properties, these complexes represent a new class of light absorbers with potential application as dyes for charge injection into semiconductor solar cells and in sensitizer-catalyst assemblies for photocatalysis that operate with irradiation from the ultraviolet to ∼800 nm.

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

    CERN Document Server

    Coe, J P

    2014-01-01

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

  4. Ultrafast fluorescence study of the effect of carboxylic and carboxylate substituents on the excited state properties of anthracene

    Energy Technology Data Exchange (ETDEWEB)

    Rodríguez-Córdoba, William [Escuela de Física, Universidad Nacional de Colombia Sede Medellín, A.A. 3840, Medellín (Colombia); Noria-Moreno, Raquel; Navarro, Pedro [Universidad Nacional Autónoma de México, Instituto de Química, Ciudad Universitaria, 04510 México, DF (Mexico); Peon, Jorge, E-mail: jpeon@unam.mx [Universidad Nacional Autónoma de México, Instituto de Química, Ciudad Universitaria, 04510 México, DF (Mexico)

    2014-01-15

    With the objective of understanding the interaction between carboxylic substituents and aromatic systems in electronically excited states, we have studied the photophysics of anthracene-9-carboxylic acid and its conjugate base through spectroscopic and computational approaches. We measured the emission spectrum evolution with femtosecond resolution observing that the formation of the relaxed fluorescent state of the acid corresponds to a red shifting of the emission which takes place within the first picosecond after excitation, a time-scale defined by the solvent response (acetone). For the case of the anthracene-9-carboxylate system, the spectral evolution is practically absent, indicating a lack of relaxation of the substituent orientation in the S{sub 1} state. Computational work at the time-dependent density functional theory level, considering the novel state-specific formalism, indicates that for anthracene-9-carboxylic acid, the first electronically excited state evolves from a structure with a nearly 60° dihedral angle between the carboxylic and aromatic systems, to a relaxed structure with a nearly 30° angle. On the other hand, the calculations show that for the salt, the carboxylate group remains decoupled from the aromatic system both in the ground and fluorescent state, remaining in both states at nearly 90°. Our results elucidate that the emission spectra of the acid and conjugate base are defined by the degree of interaction between the carboxylic (or carboxylate) group and the aromatic system. Such interactions are drastically different from the formal charge present in the carboxylate ion. -- Highlights: • Understanding of the interaction between carboxylic substituents and aromatic systems in electronically excited states. • Elucidation of the excited state dynamics of 9-ACA and its conjugated base in acetone solutions. • The spectral evolution time-scale of the aromatic acid and its salt depends on the solvation dynamics. • The

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

    Energy Technology Data Exchange (ETDEWEB)

    Kamerdzhiev, S. P. [National Research Centre Kurchatov Institute (Russian Federation); Voitenkov, D. A., E-mail: dvoytenkov@ippe.ru [Institute for Physics and Power Engineering (Russian Federation)

    2016-11-15

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

  6. Transport properties of local thermodynamic equilibrium hydrogen plasmas including electronically excited states.

    Science.gov (United States)

    Capitelli, M; Celiberto, R; Gorse, C; Laricchiuta, A; Pagano, D; Traversa, P

    2004-02-01

    A study of the dependence of transport coefficients (thermal conductivity, viscosity, electrical conductivity) of local thermodynamic equilibrium H2 plasmas on the presence of electronically atomic excited states, H(n), is reported. The results show that excited states with their "abnormal" cross sections strongly affect the transport coefficients especially at high pressure. Large relative errors are found when comparing the different quantities with the corresponding values obtained by using ground-state transport cross sections. The accuracy of the present calculation is finally discussed in the light of the selection of transport cross sections and in dependence of the considered number of excited states.

  7. Properties of electronically excited states of four squaraine dyes and their complexes with fullerene C70: A theoretical investigation

    Science.gov (United States)

    Zhang, Jian; Li, Tingyu

    2017-09-01

    Solar cells sensitized by polypyridyl Ru(II) complexes exhibit relatively high efficiency, however those photo-sensitizers did not absorb the photons in the far-red and near-infrared region. At present, squaraine dyes have received considerable attention as their attractively intrinsic red light absorption and unusual high molar extinction coefficient. Here we applied density functional theory and time dependent density functional theory to investigate the properties of electronically excited states of four squaraine dyes and their complexes with fullerene C70. The influences of different functionals, basis sets and solvent effects are evaluated. To understand the photophysical properties, the investigations are basing on a classification method which splits the squaraine dyes and their complexes with fullerene C70 into two units to characterize the intramolecular density distribution. We present the signatures of their electronically excited states which are characterized as local excitation or charge-transfer excitation. The relationship between open-circuit voltage and the number of intramolecular hydrogen bonds in squaraine dyes are discussed.

  8. Charge exchange excitations in N not = Z nuclei: Vlasov and hydrodynamic equations

    Energy Technology Data Exchange (ETDEWEB)

    Lipparini, E.; Stringari, S.

    1987-06-01

    Macroscopic equations of motion for charge exchange reactions in N not = Z nuclei are derived starting from the time dependent Hartree-Fock theory. Application is made to the study of the dipole giant resonance in isospin channels and ..mu..- capture in N not = Z nuclei.

  9. Femtosecond photoelectron imaging of transient electronic states and Rydberg atom emission from electronically excited he droplets.

    Science.gov (United States)

    Kornilov, Oleg; Bünermann, Oliver; Haxton, Daniel J; Leone, Stephen R; Neumark, Daniel M; Gessner, Oliver

    2011-07-14

    Ultrafast relaxation of electronically excited pure He droplets is investigated by femtosecond time-resolved photoelectron imaging. Droplets are excited by extreme ultraviolet (EUV) pulses with photon energies below 24 eV. Excited states and relaxation products are probed by ionization with an infrared (IR) pulse with 1.6 eV photon energy. An initially excited droplet state decays on a time scale of 220 fs, leading predominantly to the emission of unaligned 1s3d Rydberg atoms. In a second relaxation channel, electronically aligned 1s4p Rydberg atoms are emitted from the droplet within less than 120 fs. The experimental results are described within a model that approximates electronically excited droplet states by localized, atomic Rydberg states perturbed by the local droplet environment in which the atom is embedded. The model suggests that, below 24 eV, EUV excitation preferentially leads to states that are localized in the surface region of the droplet. Electronically aligned 1s4p Rydberg atoms are expected to originate from excitations in the outermost surface regions, while nonaligned 1s3d Rydberg atoms emerge from a deeper surface region with higher local densities. The model is used to simulate the He droplet EUV absorption spectrum in good agreement with previously reported fluorescence excitation measurements.

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

    Science.gov (United States)

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

    2017-06-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Olguin, Marco [Computational Science Program, University of Texas at El Paso, El Paso, Texas 79968 (United States); Basurto, Luis; Zope, Rajendra R. [Department of Physics, The University of Texas at El Paso, El Paso, Texas 79968 (United States); Baruah, Tunna, E-mail: tbaruah@utep.edu [Computational Science Program, University of Texas at El Paso, El Paso, Texas 79968 (United States); Department of Physics, The University of Texas at El Paso, El Paso, Texas 79968 (United States)

    2014-05-28

    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 changes 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Blazhev, A; Braun, N; Jolie, J [Universitaet zu Koeln, Cologne (Germany); Grawe, H; Boutachkov, P; Gorska, M; Pietri, S; Domingo-Pardo, C; Kojouharov, I; Caceres, L; Engert, T; Farinon, F; Gerl, J; Goel, N [GSI, Darmstadt (Germany); Singh, B S Nara; Brock, T; Wadsworth, R [University of York, York (United Kingdom); Liu, Zh [University of Edinburgh, Edinburgh (United Kingdom); Nowacki, F [IPHC, Strasbourg (France); Grebosz, J, E-mail: a.blazhev@ikp.uni-koeln.d [IFJ PAN, Krakow (Poland)

    2010-01-01

    In {sup 98}Cd a new high-energy isomeric {gamma}-ray transition was identified, which confirms previous spin-parity assignments and enables for the first time the measurement of the E2 and E4 strength for the two decay branches of the isomer. Preliminary results on the {sup 98}Cd high-excitation level scheme are presented. A comparison to shell-model calculations as well as implications for the nuclear structure around {sup 100}Sn are discussed.

  13. Anisotropic charged physical models with generalized polytropic equation of state

    Science.gov (United States)

    Nasim, A.; Azam, M.

    2018-01-01

    In this paper, we found the exact solutions of Einstein-Maxwell equations with generalized polytropic equation of state (GPEoS). For this, we consider spherically symmetric object with charged anisotropic matter distribution. We rewrite the field equations into simple form through transformation introduced by Durgapal (Phys Rev D 27:328, 1983) and solve these equations analytically. For the physically acceptability of these solutions, we plot physical quantities like energy density, anisotropy, speed of sound, tangential and radial pressure. We found that all solutions fulfill the required physical conditions. It is concluded that all our results are reduced to the case of anisotropic charged matter distribution with linear, quadratic as well as polytropic equation of state.

  14. Ion-pair dissociation of highly excited carbon clusters: Size and charge effects

    OpenAIRE

    Launoy, Thibaut; Béroff, Karine; Chabot, Marin; Martinet, Guillaume; Le Padellec, A.; Pino, Thomas; Bouneau, S.; Vaeck, Nathalie; Liévin, Jacques; Féraud, Géraldine G.; Loreau, Jérôme; Mahajan, Thejus T. M

    2017-01-01

    We present measurements of ion-pair dissociation (IPD) of highly excited neutral and ionized carbon clusters Cn=2-5(q=0-3)+. The tool for producing these species was a high-velocity collision between Cn+ projectiles (v=2.25 a.u.) and helium atoms. The setup allowed us to detect in coincidence anionic and cationic fragments, event by event, leading to a direct and unambiguous identification of the IPD process. Compared with dissociation without anion emission, we found typical 10-4 IPD rates, ...

  15. Size effect of water cluster on the excited-state proton transfer in aqueous solvent

    Science.gov (United States)

    Liu, Yu-Hui; Chu, Tian-Shu

    2011-03-01

    Time-dependent density functional theory (TDDFT) was used to investigate the excited-state proton transfer (ESPT) dynamics of 6-hydroxyquinolinium (6HQc) in aqueous solvent, resulting in the excited zwitterionic form (6HQz). The optimized excited-state energy profiles of 6HQc:(H 2O) n complexes have been calculated along the phenolic O sbnd H bond to simulate the minimum energy pathway (MEP) in the excited state. The results suggested that the threshold of the size of the water cluster is 3 for the excited-state proton transfer of 6HQc in aqueous solvent, since the conformation of the stable hydrated proton requires proton transferring to the second or deeper shell of water solvent. Moreover, the stability of the hydrated proton can be improved significantly by adding one more H 2O molecule to form an Eigen cation in the excited-state 6HQz:H 9O 4+. The effect of the size of water cluster on the proton transfer is investigated theoretically in the excited state for the first time.

  16. Excited States of Dicyanovinyl-Substituted Oligothiophenes from Many-Body Green's Functions Theory.

    Science.gov (United States)

    Baumeier, Björn; Andrienko, Denis; Ma, Yuchen; Rohlfing, Michael

    2012-03-13

    Excited states of dicyanovinyl-substituted oligothiophenes are studied using many-body Green's functions theory within the GW approximation and the Bethe-Salpeter equation. By varying the number of oligomer repeat units, we investigate the effects of resonant-antiresonant transition coupling, dynamical screening, and molecular conformations on calculated excitations. We find that the full dynamically screened Bethe-Salpeter equation yields absorption and emission energies in good agreement with experimental data. The effect of resonant-antiresonant coupling on the first singlet π → π* excitation monotonically decreases with increasing size of the molecule, while dynamical screening effects uniformly lower the excitation energies.

  17. Excited-state entanglement and thermal mutual information in random spin chains

    Science.gov (United States)

    Huang, Yichen; Moore, Joel E.

    2014-12-01

    Entanglement properties of excited eigenstates (or of thermal mixed states) are difficult to study with conventional analytical methods. We approach this problem for random spin chains using a recently developed real-space renormalization group technique for excited states ("RSRG-X"). For the random XX and quantum Ising chains, which have logarithmic divergences in the entanglement entropy of their (infinite-randomness) critical ground states, we show that the entanglement entropy of excited eigenstates retains a logarithmic divergence while the mutual information of thermal mixed states does not. However, in the XX case the coefficient of the logarithmic divergence extends from the universal ground-state value to a universal interval due to the degeneracy of excited eigenstates. These models are noninteracting in the sense of having free-fermion representations, allowing strong numerical checks of our analytical predictions.

  18. Optical excitation of valley and spin currents of chiral edge states in graphene with Rashba spin-orbital coupling

    Science.gov (United States)

    Luo, Ma; Li, Zhibing

    2017-10-01

    Graphene on a substrate with a topological line defect possesses chiral edge states that exhibit linear dispersion and have opposite Fermi velocities for two valleys. The chiral edge states are localized at the line defect. With the presence of Rashba spin-orbital coupling, the dispersion of the chiral edge states splits into two. The optical excitation is modeled by the generalized semiconductor Bloch equation based on tight-binding theory. Charge, valley, and spin currents generated by normally incident plane waves through the photogalvanic effect as well as those generated by oblique light through the surface-plasmon drag effect are studied. Conditions for optical generation of purely localized valley or spin currents, which are solely originated from the chiral edge states, are discussed.

  19. Coherent manipulation of valley states at multiple charge configurations of a silicon quantum dot device.

    Science.gov (United States)

    Schoenfield, Joshua S; Freeman, Blake M; Jiang, HongWen

    2017-07-05

    Qubits based on silicon quantum dots are emerging as leading candidates for the solid-state implementation of quantum information processing. In silicon, valley states represent a degree of freedom in addition to spin and charge. Characterizing and controlling valley states is critical for the encoding and read-out of electrons-in-silicon-based qubits. Here, we report the coherent manipulation of a qubit, which is based on the two valley states of an electron confined in a silicon quantum dot. We carry out valley qubit operations at multiple charge configurations of the double quantum dot device. The dependence of coherent oscillations on pulse excitation level and duration allows us to map out the energy dispersion as a function of detuning as well as the phase coherence time of the valley qubit. The coherent manipulation also provides a method of measuring valley splittings that are too small to probe with conventional methods.Silicon quantum dots provide a promising platform for quantum computing based on manipulation of electron degrees of freedom in a well-characterized environment. Here, the authors demonstrate coherent control of electron valley states, yielding an accurate determination of the valley splitting.

  20. Effect of Molecular Packing and Charge Delocalization on the Nonradiative Recombination of Charge-Transfer States in Organic Solar Cells

    KAUST Repository

    Chen, Xian Kai

    2016-09-05

    In organic solar cells, a major source of energy loss is attributed to nonradiative recombination from the interfacial charge transfer states to the ground state. By taking pentacene–C60 complexes as model donor–acceptor systems, a comprehensive theoretical understanding of how molecular packing and charge delocalization impact these nonradiative recombination rates at donor–acceptor interfaces is provided.

  1. Normal-state diamagnetism of charged bosons in cuprate superconductors.

    Science.gov (United States)

    Alexandrov, A S

    2006-04-14

    Normal-state orbital diamagnetism of charged bosons quantitatively accounts for recent high-resolution magnetometery results near and above the resistive critical temperature T(c) of superconducting cuprates. The parameter-free descriptions of normal-state diamagnetism, T(c), upper critical fields, and specific heat anomalies support the 3D Bose-Einstein condensation of preformed real-space pairs with a zero off-diagonal order parameter above T(c) at variance with phase fluctuation scenarios of cuprates.

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

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Matthew P.; Zia, Ahmad [School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom); Horton, Peter [Department of Molecular Biology and Biotechnology, University of Sheffield, Firth Court, Western Bank, Sheffield S10 2TN (United Kingdom); Ruban, Alexander V., E-mail: a.ruban@qmul.ac.uk [School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London E1 4NS (United Kingdom)

    2010-07-19

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

  3. Photoinduced excitation and charge transfer processes of organic dyes with siloxane anchoring groups: a combined spectroscopic and computational study.

    Science.gov (United States)

    Castellucci, Elena; Monini, Marco; Bessi, Matteo; Iagatti, Alessandro; Bussotti, Laura; Sinicropi, Adalgisa; Calamante, Massimo; Zani, Lorenzo; Basosi, Riccardo; Reginato, Gianna; Mordini, Alessandro; Foggi, Paolo; Di Donato, Mariangela

    2017-06-14

    Dye-sensitized solar cells (DSSCs) have attracted significant interest in the last few years as effective low-cost devices for solar energy conversion. We have analyzed the excited state dynamics of several organic dyes bearing both cyanoacrylic acid and siloxane anchoring groups. The spectroscopic properties of the dyes have been studied both in solution and when adsorbed on a TiO2 film using stationary and time-resolved techniques, probing the sub-picosecond to nanosecond time interval. The comparison between the spectra registered in solution and on the solid substrate evidences different pathways for energy and electron relaxation. The transient spectra of the TiO2-adsorbed dyes show the appearance of a long wavelength excited state absorption band, attributed to the cationic dye species, which is absent in the spectra measured in solution. Furthermore, the kinetic traces of the samples adsorbed on the TiO2 film show a long decay component not present in solution which constitutes indirect evidence of electron transfer between the dye and the semiconductor. The interpretation of the experimental results has been supported by theoretical DFT calculations of the excited state energies and by the analysis of molecular orbitals of the analyzed dye molecules.

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

    Directory of Open Access Journals (Sweden)

    Lin Chien-Hung

    2011-01-01

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

  5. Probing defect states in polycrystalline GaN grown on Si(111) by sub-bandgap laser-excited scanning tunneling spectroscopy

    Science.gov (United States)

    Hsiao, F.-M.; Schnedler, M.; Portz, V.; Huang, Y.-C.; Huang, B.-C.; Shih, M.-C.; Chang, C.-W.; Tu, L.-W.; Eisele, H.; Dunin-Borkowski, R. E.; Ebert, Ph.; Chiu, Y.-P.

    2017-01-01

    We demonstrate the potential of sub-bandgap laser-excited cross-sectional scanning tunneling microscopy and spectroscopy to investigate the presence of defect states in semiconductors. The characterization method is illustrated on GaN layers grown on Si(111) substrates without intentional buffer layers. According to high-resolution transmission electron microscopy and cathodoluminescence spectroscopy, the GaN layers consist of nanoscale wurtzite and zincblende crystallites with varying crystal orientations and hence contain high defect state densities. In order to discriminate between band-to-band excitation and defect state excitations, we use sub-bandgap laser excitation. We probe a clear increase in the tunnel current at positive sample voltages during sub-bandgap laser illumination for the GaN layer with high defect density, but no effect is found for high quality GaN epitaxial layers. This demonstrates the excitation of free charge carriers at defect states. Thus, sub-bandgap laser-excited scanning tunneling spectroscopy is a powerful complimentary characterization tool for defect states.

  6. Photo-excited charge carrier suppress sub-terahertz phonon mode in silicon at room temperature

    Science.gov (United States)

    Liao, Bolin; Maznev, Alexei; Nelson, Keith; Chen, Gang

    There is a growing interest in the mode-by-mode understanding of electron and phonon transport for improving energy conversion technologies, such as thermoelectrics and photovoltaics. Whereas remarkable progress has been made in probing phonon-phonon interactions, it has been a challenge to directly measure electron-phonon interactions at the single-mode level, especially their effect on phonon transport above cryogenic temperatures. Here we use three-pulse photoacoustic spectroscopy to investigate the damping of a single sub-terahertz coherent phonon mode by free charge carriers in silicon at room temperature. Building upon conventional pump-probe photoacoustic spectroscopy, we introduce an additional laser pulse to optically generate charge carriers, and carefully design temporal sequence of the three pulses to unambiguously quantify the scattering rate of a single phonon mode due to the electron-phonon interaction. Our results confirm predictions from first-principles simulations and indicate the importance of the often-neglected effect of electron-phonon interaction on phonon transport in doped semiconductors. This work is supported by S3TEC, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Basic Energy Sciences, under Award No. DE-FG02-09ER46577.

  7. Spin-state transition in LaCoO3: direct neutron spectroscopic evidence of excited magnetic states.

    Science.gov (United States)

    Podlesnyak, A; Streule, S; Mesot, J; Medarde, M; Pomjakushina, E; Conder, K; Tanaka, A; Haverkort, M W; Khomskii, D I

    2006-12-15

    A gradual spin-state transition occurs in LaCoO3 around T approximately 80-120 K, whose detailed nature remains controversial. We studied this transition by means of inelastic neutron scattering and found that with increasing temperature an excitation at approximately 0.6 meV appears, whose intensity increases with temperature, following the bulk magnetization. Within a model including crystal-field interaction and spin-orbit coupling, we interpret this excitation as originating from a transition between thermally excited states located about 120 K above the ground state. We further discuss the nature of the magnetic excited state in terms of intermediate-spin (t(2g)(5)e(g)(1), S=1) versus high-spin (t(2g)(4)e(g)(2), S=2) states. Since the g factor obtained from the field dependence of the inelastic neutron scattering is g approximately 3, the second interpretation is definitely favored.

  8. Investigation of the charge-transfer in photo-excited nanoparticles for CO2 reduction in non-aqueous media

    Directory of Open Access Journals (Sweden)

    Dimitrijević Nada M.

    2013-01-01

    Full Text Available Photoinduced charge separation in TiO2 and Cu2O semiconductor nanoparticles was examined using Electron Paramagnetic Resonance spectroscopy in order to get insight into the photocatalytic reduction of CO2 in nonaqueous media. For dissolution/grafting of CO2 we have used carboxy-PEG4-amine, and as a solvent poly(ethylene glycol 200. We have found that, in this system, reduction of CO2 starts at potential of -0.5 V vs Ag/AgCl, which is significantly more positive than the potential for electrochemical reduction of CO2 in most organic solvents and water (-2.0 V vs. Ag/AgCl. The electron transfer from excited nanoparticles to CO2 is governed both by thermodynamic and kinetic parameters, namely by the redox potential of conduction band electrons and adsorption/binding of CO2 on the surface of nanoparticles.

  9. Charge state breeding experiences and plans at TRIUMF

    Energy Technology Data Exchange (ETDEWEB)

    Ames, F., E-mail: ames@triumf.ca; Marchetto, M.; Mjøs, A.; Morton, A. C. [TRIUMF, 4004 Wesbrook Mall, Vancouver, British Columbia V6T2A3 (Canada)

    2016-02-15

    At the Isotope Separation and ACceleration (ISAC) facility at TRIUMF, an electron cyclotron resonance ion source (ECRIS) has been set up for the charge state breeding of radioactive ions. In order to reduce background from stable ions generated in the ECRIS, several measures, including changing materials for the plasma chamber and the surrounding components, have been implemented. Further reduction has been achieved by using the post-accelerator chain as a mass filter. Since the implementation of those measures in 2013, physics experiments with accelerated radioactive isotopes of Rb, Sr, K, and Mg have been performed. In most cases, a charge breeding efficiency of several percent has been achieved. With the planned expansion of the isotope production capabilities at TRIUMF within the Advanced Rare IsotopE Laboratory project, two new target stations, one using photo-fission induced by a high-power electron beam at 50 MeV and the other one using 480 MeV protons as at ISAC, will be put into operation within the next 5 yr. Additionally, a new electron beam ion source (EBIS) based charge state breeding system will be installed. Background from such a source is expected to be much lower. The drawback is that for the efficient operation of such a system, pulsed beam operation is required, which makes the installation of an additional ion buncher in front of the EBIS necessary.

  10. Charge state breeding experiences and plans at TRIUMF

    Science.gov (United States)

    Ames, F.; Marchetto, M.; Mjøs, A.; Morton, A. C.

    2016-02-01

    At the Isotope Separation and ACceleration (ISAC) facility at TRIUMF, an electron cyclotron resonance ion source (ECRIS) has been set up for the charge state breeding of radioactive ions. In order to reduce background from stable ions generated in the ECRIS, several measures, including changing materials for the plasma chamber and the surrounding components, have been implemented. Further reduction has been achieved by using the post-accelerator chain as a mass filter. Since the implementation of those measures in 2013, physics experiments with accelerated radioactive isotopes of Rb, Sr, K, and Mg have been performed. In most cases, a charge breeding efficiency of several percent has been achieved. With the planned expansion of the isotope production capabilities at TRIUMF within the Advanced Rare IsotopE Laboratory project, two new target stations, one using photo-fission induced by a high-power electron beam at 50 MeV and the other one using 480 MeV protons as at ISAC, will be put into operation within the next 5 yr. Additionally, a new electron beam ion source (EBIS) based charge state breeding system will be installed. Background from such a source is expected to be much lower. The drawback is that for the efficient operation of such a system, pulsed beam operation is required, which makes the installation of an additional ion buncher in front of the EBIS necessary.

  11. Interception of excited vibrational quantum states by O2 in atmospheric association reactions.

    Science.gov (United States)

    Glowacki, David R; Lockhart, James; Blitz, Mark A; Klippenstein, Stephen J; Pilling, Michael J; Robertson, Struan H; Seakins, Paul W

    2012-08-31

    Bimolecular reactions in Earth's atmosphere are generally assumed to proceed between reactants whose internal quantum states are fully thermally relaxed. Here, we highlight a dramatic role for vibrationally excited bimolecular reactants in the oxidation of acetylene. The reaction proceeds by preliminary adduct formation between the alkyne and OH radical, with subsequent O(2) addition. Using a detailed theoretical model, we show that the product-branching ratio is determined by the excited vibrational quantum-state distribution of the adduct at the moment it reacts with O(2). Experimentally, we found that under the simulated atmospheric conditions O(2) intercepts ~25% of the excited adducts before their vibrational quantum states have fully relaxed. Analogous interception of excited-state radicals by O(2) is likely common to a range of atmospheric reactions that proceed through peroxy complexes.

  12. Tracking the Excited-State Time Evolution of the Visual Pigment with Multiconfigurational Quantum Chemistry

    National Research Council Canada - National Science Library

    Luis Manuel Frutos; Tadeusz Andruniów; Fabrizio Santoro; Nicolas Ferré; Massimo Olivucci

    2007-01-01

    ...). Here, we use a scaled quantum mechanics/molecular mechanics potential that reproduces the isomerization path determined with multiconfigurational perturbation theory to follow the excited-state evolution of bovine Rh...

  13. Final-state-resolved charge exchange in C5 + collisions with H

    Science.gov (United States)

    Nolte, J. L.; Stancil, P. C.; Liebermann, H. P.; Buenker, R. J.; Hui, Y.; Schultz, D. R.

    2012-12-01

    We report charge exchange cross sections for the collision system C5 + + H using the quantum mechanical molecular-orbital close-coupling method. The multi-reference single- and double-excitation configuration interaction method is used to produce potential and coupling data, and scattering calculations are performed for collision energies between 0.01 eV/u to 1 keV/u for all l,S-resolved states within the n = 3 and 4 manifolds. The n = 5 manifold is represented through the inclusion of the 5s state. To predict cross sections at higher energies, we include new results from atomic-orbital close-coupling and classical trajectory Monte Carlo calculations. We briefly discuss applications to x-ray emission within the solar system.

  14. State of charge classification for lithium-ion batteries using impedance based features

    Science.gov (United States)

    Patrik Felder, Marian; Götze, Jürgen

    2017-09-01

    Currently, the electrification of the drive train of passenger cars takes place, and the task of obtaining precise knowledge about the condition of the on board batteries gains importance. Due to a flat open circuit voltage (OCV) to state of charge (SoC) characteristic of lithium ion batteries, methods employed in applications with other cell chemistries cannot be adapted. Exploiting the higher significance of the impedance for state estimation for that chemistry, new impedance based features are proposed by this work. To evaluate the suitability of these features, simulations have been conducted using a simplified on-board power supply net as excitation source. The simulation outcome has been investigated regarding the cross correlation factor rxy and in a polynomial regression scenario. The results of the simulations show a best case error below 1 % SoC, which is 3 percentage points lower than using terminal voltage and impedance. When increasing the measurement uncertainty, the difference remains around 2 percent points.

  15. Long-lived charge-separated states in ligand-stabilized silver clusters

    KAUST Repository

    Pelton, Matthew

    2012-07-25

    Recently developed synthesis methods allow for the production of atomically monodisperse clusters of silver atoms stabilized in solution by aromatic thiol ligands, which exhibit intense absorption peaks throughout the visible and near-IR spectral regions. Here we investigated the time-dependent optical properties of these clusters. We observed two kinetic processes following ultrafast laser excitation of any of the absorption peaks: a rapid decay, with a time constant of 1 ps or less, and a slow decay, with a time constant that can be longer than 300 ns. Both time constants decrease as the polarity of the solvent increases, indicating that the two processes correspond to the formation and recombination, respectively, of a charge-separated state. The long lifetime of this state and the broad optical absorption spectrum mean that the ligand-stabilized silver clusters are promising materials for solar energy harvesting. © 2012 American Chemical Society.

  16. Metastable states in parametrically excited multimode Hamiltonian systems

    CERN Document Server

    Kirr, E

    2003-01-01

    Consider a linear autonomous Hamiltonian system with time periodic bound state solutions. In this paper we study their dynamics under time almost periodic perturbations which are small, localized and Hamiltonian. The analysis proceeds through a reduction of the original infinite dimensional dynamical system to the dynamics of two coupled subsystems: a dominant m-dimensional system of ordinary differential equations (normal form), governing the projections onto the bound states and an infinite dimensional dispersive wave equation. The present work generalizes previous work of the authors, where the case of a single bound state is considered. Here, the interaction picture is considerably more complicated and requires deeper analysis, due to a multiplicity of bound states and the very general nature of the perturbation's time dependence. Parametric forcing induces coupling of bound states to continuum radiation modes, bound states directly to bound states, as well as coupling among bound states, which is mediate...

  17. Description of ground and excited electronic states by ensemble density functional method with extended active space

    Science.gov (United States)

    Filatov, Michael; Martínez, Todd J.; Kim, Kwang S.

    2017-08-01

    An extended variant of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, the REKS(4,4) method, designed to describe the ground electronic states of strongly multireference systems is modified to enable calculation of excited states within the time-independent variational formalism. The new method, the state-interaction state-averaged REKS(4,4), i.e., SI-SA-REKS(4,4), is capable of describing several excited states of a molecule involving double bond cleavage, polyradical character, or multiple chromophoric units. We demonstrate that the new method correctly describes the ground and the lowest singlet excited states of a molecule (ethylene) undergoing double bond cleavage. The applicability of the new method for excitonic states is illustrated with π stacked ethylene and tetracene dimers. We conclude that the new method can describe a wide range of multireference phenomena.

  18. Nonaxial shapes of even–even lantanide and actinide nuclei in excited collective states

    Energy Technology Data Exchange (ETDEWEB)

    Nadirbekov, M. S., E-mail: nodirbekov@inp.uz; Bozarov, O. A. [Uzbek Academy of Sciences, Institute of Nuclear Physics (Uzbekistan)

    2016-07-15

    Quadrupole-type excited states of even–even nuclei are studied on the basis of arbitrary-triaxiality model. It is shown that the inclusion of high-order terms in the expansion of the rotational-energy operator in the variable γ improves substantially agreement between our theoretical results and respective experimental data. The proposed model makes it possible to explain the intricate character of the spectrum of excited states of even–even lanthanide and actinide nuclei.

  19. OPTIMIZATION OF A BOXCAR INTEGRATOR AVERAGER SYSTEM FOR EXCITED-STATE LIFETIME MEASUREMENTS

    OpenAIRE

    NOVO, JBM; PESSINE, FBT

    1992-01-01

    The instrumental distortions due to adjustable parameters of the SR250 boxcar integrator/averager system and a pulsed-laser luminescence spectrometer on the excited-state lifetime decay waveforms were investigated. A theoretical model which takes into account the exponential moving average for this instrument and also RC distortion on the time-dependent luminescence signal is presented. An analytical expression relating the sample's excited-state lifetime and the adjustable instrumental param...

  20. Influence of excited states on the energy loss of fast ions in a hydrogen plasma

    Energy Technology Data Exchange (ETDEWEB)

    Kaercher, B. (Max-Planck-Institut fuer Quantenoptik, D-8046 Garching, Germany (DE)); Peter, T. (Max-Planck-Institut fuer Chemie, D-6500 Mainz, Germany (DE))

    1991-04-01

    Stopping power calculations of fast ions penetrating a hydrogen plasma target in local thermodynamic equilibrium at arbitrary temperatures are performed. Excited state contributions to the energy loss are included in the framework of the Bethe formalism. Average ionization potentials for the excited ions are given in a quasiclassical approximation. It is shown that the net effect is an enhancement of the stopping power compared to the energy loss when assuming all atoms to be in their ground state.

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

    OpenAIRE

    Hohler, Paul M.; Rapp, Ralf

    2012-01-01

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

  2. Vibronic energy map and excited state vibrational characteristics of magnesium myoglobin determined by energy-selective fluorescence.

    OpenAIRE

    Kaposi, A D; Vanderkooi, J. M.

    1992-01-01

    The vibrational frequencies of the singlet excited state of Mg-substituted myoglobin and relative absorption probabilities were determined by fluorescence line-narrowing spectroscopy. These spectra contain information on the structure of the excited state species, and the availability of vibrationally resolved spectra from excited state biomolecules should aid in elucidating their structure and reactivity.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-03-21

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

  4. Strategic modulation of the photonic properties of conjugated organometallic Pt-Ir polymers exhibiting hybrid CT-excited states.

    Science.gov (United States)

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

    2015-04-01

    Polymer 6, ([trans-Pt(PBu3 )2 (C≡C)2 ]-[Ir(dFMeppy)2 (N^N)](PF6 ))n , (([Pt]-[Ir](PF6 ))n ; N^N = 5,5'-disubstituted-2,2'-bipyridyl; dFMeppy = 2-(2,4-difluoro-phenyl)-5-methylpyridine) is prepared along with model compounds. These complexes are investigated by absorption and emission spectroscopy and their photophysical and electrochemical properties are measured and compared with their corresponding non fluorinated complexes. Density functional theory (DFT) and time-dependent DFT computations corroborate the nature of the excited state as being a hybrid between the metal-to-ligand charge transfer ((1,3) MLCT) for the trans-Pt(PBu3 )2 (C≡CAr)2 unit, [Pt] and the metal-to-ligand/ligand-to-ligand' charge transfer ((1,3) ML'CT/LL'CT) for [Ir] with L = dFMeppy. Overall, the fluorination of the phenylpyridine group expectedly does not change the nature of the excited state but desirably induces a small blue shift of the absorption and emission bands along a slight decrease in emission quantum yields and lifetimes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Sakai S.

    2013-03-01

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

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

    Science.gov (United States)

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

    2013-09-15

    Laser flash photolysis (LFP) was used to characterize a triplet excited state species isolated from Black River and San Joaquin wetlands particulate organic matter (POM). The solubilized organic matter, isolated from POM by pH-independent diffusion in distilled water, was named PdOM. UV-visible absorption spectroscopy, excitation-emission matrix spectroscopy (EEMs), and (1)H NMR were used to characterize the PdOM. While LFP of dissolved organic matter (DOM) is known to generate the solvated electron, LFP of the PdOM transient in argon-, air-, and nitrous oxide-saturated solutions indicated that this was a triplet excited state species ((3)PdOM*). The lifetime and the reactivity of (3)PdOM* with sorbic acid, a triplet state quencher, were compared with that of the triplet excited state of benzophenone, a DOM proxy. A second excited state species (designated DOM*), with a longer lifetime, was reported in a number of previous studies but not characterized. The lifetime of DOM*, measured for seventeen organic matter isolates, lignin, tannic acid, and three wetlands plant extracts, was shown to differentiate allochthonous from autochthonous DOM. (3)POM* and DOM* were also observed in lake water and a constructed wetlands' water. Aqueous extracts of fresh and aged plant material from the same wetland were shown to be one source of these excited state species. This study provides evidence of a role for POM in the photochemistry of natural and constructed wetland waters. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-07-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Bhosale, J. S. [Intel Corporation, Hillsboro, Oregon 97124 (United States); Department of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); Moore, J. E.; Wang, X.; Bermel, P.; Lundstrom, M. S. [Department of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47907 (United States)

    2016-01-15

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

  10. Triphenylamine-benzimidazole derivatives: synthesis, excited-state characterization, and DFT studies.

    Science.gov (United States)

    Pina, João; Seixas de Melo, J Sérgio; Batista, Rosa M F; Costa, Susana P G; Raposo, M Manuela M

    2013-11-15

    The synthesis and comprehensive characterization of the excited states of four novel triphenylamine-benzimidazole derivatives has been undertaken in solution (ethanol and methylcyclohexane) at room temperature. This includes the determination of the absorption, fluorescence, and triplet-triplet absorption spectra, together with quantum yields of fluorescence, internal conversion, intersystem crossing, and singlet oxygen. From the overall data the radiative and radiationless rate constants could be obtained, and it is shown that the compounds are highly emissive with the radiative decay dominating, with more than 70% of the quanta loss through this deactivation channel. The basic structure of the triphenylamine-benzimidazole derivatives (1a) was modified at position 5 of the heterocyclic moiety with electron-donating (OH (1b), OCH3 (1c)) or electron-withdrawing groups (CN, (1d)). It was found that the photophysical properties remain basically unchanged with the different substitutions, although a marked Stokes shift was observed with 1d. The presence and nature of a charge-transfer transition is discussed with the help of theoretical (DFT and TDFT) data. All compounds displayed exceptionally high thermal stability (between 399 and 454 °C) as seen by thermogravimetric analysis.

  11. Radiation excited by a charged-particle bunch on a planar periodic wire structure

    Directory of Open Access Journals (Sweden)

    Andrey V. Tyukhtin

    2014-12-01

    Full Text Available The electromagnetic field of a bunch moving in the presence of a plane grid composed of thin parallel wires is considered by using the averaged boundary conditions method. Two different cases of motion are examined. In the first one, the bunch moves at a constant distance from the grid orthogonally to the wires. The excited surface wave is presented in the form of a spectral integral for a thin bunch with an arbitrary longitudinal profile. The wave propagates along the wires and does not decay with distance (if dissipation is negligible. Energy losses of the bunch over a unit path are obtained. In the second case, the bunch orthogonally crosses the wire grid. The volume and surface waves are separately analyzed. Properties of the spectral angular density of energy of volume radiation in the far-field zone are described. The energy losses due to the volume and surface radiation are determined. It is demonstrated that the structure of the surface waves in both cases allows determination of the length of the bunch.

  12. CrossRef Large numbers of cold positronium atoms created in laser-selected Rydberg states using resonant charge exchange

    CERN Document Server

    McConnell, R; Kolthammer, WS; Richerme, P; Müllers, A; Walz, J; Grzonka, D; Zielinski, M; Fitzakerley, D; George, MC; Hessels, EA; Storry, CH; Weel, M

    2016-01-01

    Lasers are used to control the production of highly excited positronium atoms (Ps*). The laser light excites Cs atoms to Rydberg states that have a large cross section for resonant charge-exchange collisions with cold trapped positrons. For each trial with 30 million trapped positrons, more than 700 000 of the created Ps* have trajectories near the axis of the apparatus, and are detected using Stark ionization. This number of Ps* is 500 times higher than realized in an earlier proof-of-principle demonstration (2004 Phys. Lett. B 597 257). A second charge exchange of these near-axis Ps* with trapped antiprotons could be used to produce cold antihydrogen, and this antihydrogen production is expected to be increased by a similar factor.

  13. Mapping of electron-hole excitations in the charge-density-wave system 1T-TiSe2 using resonant inelastic x-ray scattering.

    Science.gov (United States)

    Monney, C; Zhou, K J; Cercellier, H; Vydrova, Z; Garnier, M G; Monney, G; Strocov, V N; Berger, H; Beck, H; Schmitt, T; Aebi, P

    2012-07-27

    In high-resolution resonant inelastic x-ray scattering at the Ti L edge of the charge-density-wave system 1T-TiSe(2), we observe sharp low energy loss peaks from electron-hole pair excitations developing at low temperature. These excitations are strongly dispersing as a function of the transferred momentum of light. We show that the unoccupied bands close to the Fermi level can effectively be probed in this broadband material. Furthermore, we extract the order parameter of the charge-density-wave phase from temperature-dependent measurements.

  14. Delocalization and dielectric screening of charge transfer states in organic photovoltaic cells

    National Research Council Canada - National Science Library

    Bernardo, B; Cheyns, D; Verreet, B; Schaller, R D; Rand, B P; Giebink, N C

    2014-01-01

    Charge transfer (CT) states at a donor-acceptor heterojunction have a key role in the charge photogeneration process of organic solar cells, however, the mechanism by which these states dissociate efficiently into free...

  15. Droop-Control-Based State-of-Charge Balancing Method for Charging and Discharging Process in Autonomous DC Microgrids

    DEFF Research Database (Denmark)

    Lu, Xiaonan; Sun, Kai; Guerrero, Josep M.

    2014-01-01

    In this paper, a droop control based state-of-charge (SoC) balancing method in autonomous DC microgrids is proposed. Both charging and discharging process have been considered. In particular, in the charging process, the droop coefficient is set to be proportional to SoCn, and in the discharging ......C and injected/output power. It is demonstrated that with higher exponent n, the balancing speed is higher. Simulation model comprised of three ESUs is implemented by using MATLAB/Simulink. The proposed method is verified by the simulation results.......In this paper, a droop control based state-of-charge (SoC) balancing method in autonomous DC microgrids is proposed. Both charging and discharging process have been considered. In particular, in the charging process, the droop coefficient is set to be proportional to SoCn, and in the discharging...

  16. Electronic properties of excited states in single InAs quantum dots; Elektronische Struktur angeregter Zustaende einzelner InAs-Quantenpunkte

    Energy Technology Data Exchange (ETDEWEB)

    Warming, Till

    2009-02-20

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Botta-Cantcheff, Marcelo; Martínez, Pedro J.; Silva, Guillermo A. [Instituto de Física de La Plata - CONICET & Departamento de Física - UNLP,C.C. 67, 1900 La Plata (Argentina)

    2016-02-25

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-03-15

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

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

    Science.gov (United States)

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

    2015-02-14

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

  20. The charge state of hydrogen ions in metals and semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Bazhukov, S.I.; Kibardin, A.V.; Pyatkova, T.M.; Urmanov, A.R. (Urals Polytechnical Inst., Sverdlovsk (USSR))

    1991-06-01

    The charge state of hydrogen ions in metals and semiconductors has been studied based on a comparison of hydrogen ion stopping cross-sections in metal and semiconductor targets. It is shown that neutralization of the hydrogen ion in metals and semiconductors at ion speeds v{sub i} {proportional to} (1-2)v{sub 0}, where v{sub 0} = 2.2x10{sup 8} cm/s, is due to different mechanisms, i.e. to a bulk effect in metals and to a subsurface effect in semiconductors. (orig.).

  1. Dual fluorescence of ellipticine: excited state proton transfer from solvent versus solvent mediated intramolecular proton transfer.

    Science.gov (United States)

    Banerjee, Sanghamitra; Pabbathi, Ashok; Sekhar, M Chandra; Samanta, Anunay

    2011-08-25

    Photophysical properties of a natural plant alkaloid, ellipticine (5,11-dimethyl-6H-pyrido[4,3-b]carbazole), which comprises both proton donating and accepting sites, have been studied in different solvents using steady state and time-resolved fluorescence techniques primarily to understand the origin of dual fluorescence that this molecule exhibits in some specific alcoholic solvents. Ground and excited state calculations based on density functional theory have also been carried out to help interpretation of the experimental data. It is shown that the long-wavelength emission of the molecule is dependent on the hydrogen bond donating ability of the solvent, and in methanol, this emission band arises solely from an excited state reaction. However, in ethylene glycol, both ground and excited state reactions contribute to the long wavelength emission. The time-resolved fluorescence data of the system in methanol and ethylene glycol indicates the presence of two different hydrogen bonded species of ellipticine of which only one participates in the excited state reaction. The rate constant of the excited state reaction in these solvents is estimated to be around 4.2-8.0 × 10(8) s(-1). It appears that the present results are better understood in terms of solvent-mediated excited state intramolecular proton transfer reaction from the pyrrole nitrogen to the pyridine nitrogen leading to the formation of the tautomeric form of the molecule rather than excited state proton transfer from the solvents leading to the formation of the protonated form of ellipticine. © 2011 American Chemical Society

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-07

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

  3. Supersymmetric quantum mechanics, excited state energies and wave functions, and the Rayleigh-Ritz variational principle: a proof of principle study.

    Science.gov (United States)

    Kouri, Donald J; Markovich, Thomas; Maxwell, Nicholas; Bittner, Eric R

    2009-12-31

    In addition to ground state wave functions and energies, excited states and their energies are also obtained in a standard Rayleigh-Ritz variational calculation. However, their accuracy is generally much lower. Using the super-symmetric (SUSY) form of quantum mechanics, we show that better accuracy and more rapid convergence can be obtained by taking advantage of calculations of the ground states of higher sector SUSY Hamiltonians, followed by application of the SUSY "charge operators". Our proof of principle study uses a general family of one-dimensional anharmonic oscillator models. We first obtain the exact, analytic ground states for a general family of anharmonic systems. We give the general, factorized form of the Hamiltonian for the hierarchy that arises in SUSY theory. The "charge" operators can then be used to convert states among the sectors. We illustrate the approach with two specific anharmonic oscillator models. Using the ground state of the second sector Hamiltonian, we show that the corresponding excited state energies and wave functions of the first sector are accurately obtained by applying the charge operators, using significantly smaller basis sets than are required in a standard variational approach applied to the original Schrodinger equation. This is a consequence of the higher accuracy of the Rayleigh-Ritz variational method when applied for ground states.

  4. Hydrogen bonding and coordination bonding in the electronically excited states of Cu2(L)2 (L = 5-(4-pyridyl)tetrazole)MeOH: A TDDFT study

    Science.gov (United States)

    Meng, Yanfang; Zhang, Chunqing; Ji, Min; Hao, Ce; Qiu, Jieshan

    2013-05-01

    The luminescent metal organic framework (MOF), Cu2(L)2·MeOH (L = 5-(4-pyridyl)tetrazole), was studied using time-dependent density functional theory (TDDFT). A combination of frontier molecular orbitals and electronic configuration analysis revealed that the emission mechanism was a ligand to metal charge transition (LMCT) rather than a metal to ligand charge transfer (MLCT). Hydrogen bonding significantly changed the nature of the frontier orbital and the luminescence. Electronic transition energies predicted that the hydrogen bonding in excited state would become weaker with an electronic spectral blue-shift. The bond lengths, frequencies, and binding energies indicated weakening of the hydrogen bonding in the excited state, which can affect emissions in two ways, including: (i) a decrease in the electronic coupling between methanol and the motif and suppressing the occurrence of the photo-induced electron transfer (PET); and (ii) increasing the energy gap between S1 and S0, leading to radiative transition. Coordination bonding was also investigated in the excited state through bond lengths, frequencies, and bond orders. Coordination bonds were found to become stronger in the excited state leading to an enhancement of the luminescence.

  5. Relaxation dynamics in the excited states of a ketocyanine dye ...

    Indian Academy of Sciences (India)

    propdienylaniline)-cyclopentanone (MPAC), a ketocyanine dye, have been investigated using steady-state absorption and emission as well as femtosecond time-resolved absorption spectroscopic techniques. Following photoexcitation using 400 ...

  6. Existence of excited states for a nonlinear Dirac equation

    Energy Technology Data Exchange (ETDEWEB)

    Balabane, M.; Cazenave, T.; Douady, A.; Merle, F.

    1988-01-21

    We prove the existence of infinitely many stationary states for the nonlinear Dirac equation. Seeking eigenfunctions splitted in spherical coordinates leads to analyse a nonautonomous dynamical system in R/sup 2/. The number of eigenfunctions is given by the number of intersections of the stable manifold of the origin with the curve of admissible data. This proves the existence of infinitely many stationary states ordered by the number of nodes of the components

  7. Picosecond laser studies of the charge-transfer reaction of excited triplet diphenylcarbene with electron donors

    Science.gov (United States)

    Sitzmann, E. V.; Langan, J.; Eisenthal, K. B.

    1983-12-01

    Evidence of a one-electron transfer process in a carbene reaction has been observed for the first time. The example is the quenching of the photoexcited triplet state of diphenylcarbene ( 3*DPC) by electron donors. Measurement of the fluorescence lifetime as a function of donor concentration yielded the bimolecular rate constant, 3* k. An explanation is offered as to why 3* and 1DPC react efficiently with amines as well as alcohols, whereas the ground triplet, 3DPC, does not.

  8. Electronic excited states responsible for dimer formation upon UV absorption directly by thymine strands: joint experimental and theoretical study.

    Science.gov (United States)

    Banyasz, Akos; Douki, Thierry; Improta, Roberto; Gustavsson, Thomas; Onidas, Delphine; Vayá, Ignacio; Perron, Marion; Markovitsi, Dimitra

    2012-09-12

    The study addresses interconnected issues related to two major types of cycloadditions between adjacent thymines in DNA leading to cyclobutane dimers (TTs) and (6-4) adducts. Experimental results are obtained for the single strand (dT)(20) by steady-state and time-resolved optical spectroscopy, as well as by HPLC coupled to mass spectrometry. Calculations are carried out for the dinucleoside monophosphate in water using the TD-M052X method and including the polarizable continuum model; the reliability of TD-M052X is checked against CASPT2 calculations regarding the behavior of two stacked thymines in the gas phase. It is shown that irradiation at the main absorption band leads to cyclobutane dimers (TTs) and (6-4) adducts via different electronic excited states. TTs are formed via (1)ππ* excitons; [2 + 2] dimerization proceeds along a barrierless path, in line with the constant quantum yield (0.05) with the irradiation wavelength, the contribution of the (3)ππ* state to this reaction being less than 10%. The formation of oxetane, the reaction intermediate leading to (6-4) adducts, occurs via charge transfer excited states involving two stacked thymines, whose fingerprint is detected in the fluorescence spectra; it involves an energy barrier explaining the important decrease in the quantum yield of (6-4) adducts with the irradiation wavelength.

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

    CERN Document Server

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

    1999-01-01

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

  10. Charge States of Krypton and Xenon in the Solar Wind

    Science.gov (United States)

    Bochsler, Peter; Fludra, Andrzej; Giunta, Alessandra

    2017-09-01

    We calculate charge state distributions of Kr and Xe in a model for two different types of solar wind using the effective ionization and recombination rates provided from the OPEN_ADAS data base. The charge states of heavy elements in the solar wind are essential for estimating the efficiency of Coulomb drag in the inner corona. We find that xenon ions experience particularly low Coulomb drag from protons in the inner corona, comparable to the notoriously weak drag of protons on helium ions. It has been found long ago that helium in the solar wind can be strongly depleted near interplanetary current sheets, whereas coronal mass ejecta are sometimes strongly enriched in helium. We argue that if the extraordinary variability of the helium abundance in the solar wind is due to inefficient Coulomb drag, the xenon abundance must vary strongly. In fact, a secular decrease of the solar wind xenon abundance relative to the other heavier noble gases (Ne, Ar, Kr) has been postulated based on a comparison of noble gases in recently irradiated and ancient samples of ilmenite in the lunar regolith. We conclude that decreasing solar activity and decreasing frequency of coronal mass ejections over the solar lifetime might be responsible for a secularly decreasing abundance of xenon in the solar wind.

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

    Directory of Open Access Journals (Sweden)

    Yuyuan Zhang

    2016-11-01

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

  12. Doppler- and recoil-free laser excitation of Rydberg states via three-photon transitions

    OpenAIRE

    Ryabtsev, I. I.; Beterov, I. I.; Tretyakov, D. B.; Entin, V. M.; Yakshina, E. A.

    2011-01-01

    Three-photon laser excitation of Rydberg states by three different laser beams can be arranged in a star-like geometry that simultaneously eliminates the recoil effect and Doppler broadening. Our analytical and numerical calculations for a particular laser excitation scheme 5S_{1/2}->5P_{3/2}->6S_{1/2}->nP in Rb atoms have shown that compared to the one- and two-photon laser excitation this approach provides much narrower line width and longer coherence time for both cold atom samples and hot...

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

    Science.gov (United States)

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

    2014-01-21

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-21

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

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

    Science.gov (United States)

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

    2014-01-01

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

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

    Science.gov (United States)

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

    2014-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Mance, J. G.; Felver, J. J.; Dexheimer, S. L., E-mail: dexheimer@wsu.edu [Department of Physics and Astronomy, Washington State University, Pullman, Washington 99164-2814 (United States)

    2015-02-28

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

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

    Science.gov (United States)

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

    2008-03-27

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

  19. Locally Excited State-Charge Transfer State Coupled Dyes as Optically Responsive Neuron Firing Probes.

    Science.gov (United States)

    Sirbu, Dumitru; Butcher, John B; Waddell, Paul G; Andras, Peter; Benniston, Andrew C

    2017-10-17

    A selection of NIR-optically responsive neuron probes was produced comprising of a donor julolidyl group connected to a BODIPY core and several different styryl and vinylpyridinyl derived acceptor moieties. The strength of the donor-acceptor interaction was systematically modulated by altering the electron withdrawing nature of the aryl unit. The fluorescence quantum yield was observed to decrease as the electron withdrawing effect of the aryl subunit increased in line with changes of the Hammett parameter. The effectiveness of these fluorophores as optically responsive dyes for neuronal imaging was assessed by measuring the toxicity and signal-to-noise ratio (SNR) of each dye. A great improvement of SNR was obtained when compared to the first-generation BODIPY-based voltage sensitive dyes with concomitant toxicity decrease. The mechanism for the optical response is disparate from conventional cyanine-based dyes, opening up a new way to produce effective voltage sensitive dyes that respond well into the NIR region. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    Obaid, Rana [Institut für Theoretische Chemie, Universität Wien, Währinger Str. 17, 1090 Wien (Austria); Faculty of Pharmacy, Al-Quds University, Abu Dis, Palestine (Country Unknown); Kinzel, Daniel; Oppel, Markus, E-mail: markus.oppel@univie.ac.at; González, Leticia [Institut für Theoretische Chemie, Universität Wien, Währinger Str. 17, 1090 Wien (Austria)

    2014-10-28

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

  1. Excited-state annihilation reduces power dependence of single-molecule FRET experiments.

    Science.gov (United States)

    Nettels, Daniel; Haenni, Dominik; Maillot, Sacha; Gueye, Moussa; Barth, Anders; Hirschfeld, Verena; Hübner, Christian G; Léonard, Jérémie; Schuler, Benjamin

    2015-12-28

    Single-molecule Förster resonance energy transfer (FRET) experiments are an important method for probing biomolecular structure and dynamics. The results from such experiments appear to be surprisingly independent of the excitation power used, in contradiction to the simple photophysical mechanism usually invoked for FRET. Here we show that excited-state annihilation processes are an essential cause of this behavior. Singlet-singlet annihilation (SSA) is a mechanism of fluorescence quenching induced by Förster-type energy transfer between two fluorophores while they are both in their first excited singlet states (S1S1), which is usually neglected in the interpretation of FRET experiments. However, this approximation is only justified in the limit of low excitation rates. We demonstrate that SSA is evident in fluorescence correlation measurements for the commonly used FRET pair Alexa 488/Alexa 594, with a rate comparable to the rate of energy transfer between the donor excited state and the acceptor ground state (S1S0) that is exploited in FRET experiments. Transient absorption spectroscopy shows that SSA occurs exclusively via energy transfer from Alexa 488 to Alexa 594. Excitation-power dependent microsecond correlation experiments support the conclusion based on previously reported absorption spectra of triplet states that singlet-triplet annihilation (STA) analogously mediates energy transfer if the acceptor is in the triplet state. The results indicate that both SSA and STA have a pronounced effect on the overall FRET process and reduce the power dependence of the observed FRET efficiencies. The existence of annihilation processes thus seems to be essential for using FRET as a reliable spectroscopic ruler at the high excitation rates commonly employed in single-molecule spectroscopy.

  2. High-frequency conductivity of optically excited charge carriers in hydrogenated nanocrystalline silicon investigated by spectroscopic femtosecond pump–probe reflectivity measurements

    Energy Technology Data Exchange (ETDEWEB)

    He, Wei [University of Birmingham, School of Physics and Astronomy, Birmingham B15 2TT (United Kingdom); Yurkevich, Igor V. [Aston University, Nonlinearity and Complexity Research Group, Birmingham B4 7ET (United Kingdom); Zakar, Ammar [University of Birmingham, School of Physics and Astronomy, Birmingham B15 2TT (United Kingdom); Kaplan, Andrey, E-mail: a.kaplan.1@bham.ac.uk [University of Birmingham, School of Physics and Astronomy, Birmingham B15 2TT (United Kingdom)

    2015-10-01

    We report an investigation into the high-frequency conductivity of optically excited charge carriers far from equilibrium with the lattice. The investigated samples consist of hydrogenated nanocrystalline silicon films grown on a thin film of silicon oxide on top of a silicon substrate. For the investigation, we used an optical femtosecond pump–probe setup to measure the reflectance change of a probe beam. The pump beam ranged between 580 and 820 nm, whereas the probe wavelength spanned 770 to 810 nm. The pump fluence was fixed at 0.6 mJ/cm{sup 2}. We show that at a fixed delay time of 300 fs, the conductivity of the excited electron–hole plasma is described well by a classical conductivity model of a hot charge carrier gas found at Maxwell–Boltzmann distribution, while Fermi–Dirac statics is not suitable. This is corroborated by values retrieved from pump–probe reflectance measurements of the conductivity and its dependence on the excitation wavelength and carrier temperature. The conductivity decreases monotonically as a function of the excitation wavelength, as expected for a nondegenerate charge carrier gas. - Highlights: • We study high‐frequency conductivity of excited hydrogenated nanocrystalline silicon. • Reflectance change was measured as a function of pump and probe wavelength. • Maxwell–Boltzmann transport theory was used to retrieve the conductivity. • The conductivity decreases monotonically as a function of the pump wavelength.

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

    CERN Document Server

    Jiménez-Hoyos, Carlos A; Scuseria, Gustavo E

    2013-01-01

    Recent work from our research group has demonstrated that symmetry-projected Hartree--Fock (HF) methods provide a compact representation of molecular ground state wavefunctions based on a superposition of non-orthogonal Slater determinants. The symmetry-projected ansatz can account for static correlations in a computationally efficient way. Here we present a variational extension of this methodology applicable to excited states of the same symmetry as the ground state. Benchmark calculations on the C$_2$ dimer with a modest basis set, which allows comparison with full configuration interaction results, indicate that this extension provides a high quality description of the low-lying spectrum for the entire dissociation profile. We apply the same methodology to obtain the full low-lying vertical excitation spectrum of formaldehyde, in good agreement with available theoretical and experimental data, as well as to a challenging model $C_{2v}$ insertion pathway for BeH$_2$. The variational excited state methodolo...

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

    CERN Document Server

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

    2015-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Chien-Hao Lin

    2015-09-01

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

  6. Shannon information entropy in position space for doubly excited states of helium with finite confinements

    Science.gov (United States)

    Ou, Jen-Hao; Ho, Yew Kam

    2017-12-01

    Quantifying electron localization in quantum confined systems remains challenging, especially for excited states. A quantum dot (QD) is represented by a helium atom in a finite oscillator potential. The effect of dot width variation on the electron localization in QD is systematically examined via Shannon entropy for low-lying doubly excited states (2s21Se, 2p21Se, 2s3s 1Se) obtained using highly correlated Hylleraas functions. In particular, the most effective dot width where the electron density is the most localized is determined successfully and justified by the electron density plot for all three states.

  7. Structural Influence on Excited State Dynamics in Simple Amines

    DEFF Research Database (Denmark)

    Klein, Liv Bærenholdt

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

  8. Combined quantum-mechanical molecular mechanics calculations with NWChem and AMBER: Excited state properties of green fluorescent protein chromophore analogue in aqueous solution.

    Science.gov (United States)

    Pirojsirikul, Teerapong; Götz, Andreas W; Weare, John; Walker, Ross C; Kowalski, Karol; Valiev, Marat

    2017-07-05

    Combined quantum mechanical molecular mechanics (QM/MM) calculations have become a popular methodology for efficient and accurate description of large molecular systems. In this work we introduce our development of a QM/MM framework based on two well-known codes-NWChem and AMBER. As an initial application area we are focused on excited state properties of small molecules in an aqueous phase using an analogue of the green fluorescent protein (GFP) chromophore as a particular test case. Our approach incorporates high level coupled cluster theory for the analysis of excited states providing a reliable theoretical analysis of effects of an aqueous solvation environment on the photochemical properties of the GFP chromophore. Using a systematic approach, which involves comparison of gas phase and aqueous phase results for different protonation states and conformations, we resolve existing uncertainties regarding the theoretical interpretation of experimental data. We observe that the impact of aqueous environment on charged states generally results in blue shifts of the absorption spectra, but the magnitude of the effect is sensitive to both protonation state and conformation and can be rationalized based on charge movement into the area of higher/lower external electrostatic potentials. At neutral pH levels the experimentally observed absorption signal is most likely coming from the phenol protonated form. Our results also show that the high level electron correlated method is essential for a proper description of excited states of GFP. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  9. 'Memory' and sustention of microdischarges in a steady-state DBD: volume plasma or surface charge?

    Science.gov (United States)

    Akishev, Yuri; Aponin, Gregory; Balakirev, Anton; Grushin, Mikhail; Karalnik, Vladimir; Petryakov, Alexander; Trushkin, Nikolay

    2011-04-01

    The results of a numerical study on the spatio-temporal behavior of transient microdischarges (MDs) in a steady-state dielectric barrier discharge (DBD) excited by a sinusoidal voltage are presented. MDs have a spatial 'memory'—every subsequent MD appears at exactly the same location occupied by the MD at the preceding half-period (HP). In the majority of cases each MD appears at its location only once during every HP. For such a case, the memory effect is not attributed to the residual surface charge deposited by the preceding MD but determined by the residual MD plasma column shunting the gap right up to the beginning of the next HP. In contrast to good memory in space, each individual MD has a large scatter with time in its appearance within every HP, i.e. there is no 'memory' concerning the phase of an applied voltage. This MD jittering within the period is attributed to the stochastic nature of partial surface breakdowns around the bases of the MD plasma column. Numerical calculations show that surface breakdown provides an MD current splash at every HP. Hence, in the steady-state DBD, the volume plasma is responsible for the existence of MD spatial 'memory' (i.e. where the MD appears), and the deposited surface charge is responsible for MD jittering in time (i.e. when the MD appears). Hot topic report presented at the 20th ESCAMPIG, 13-17 July 2010, Novi Sad, Serbia.

  10. Switching of the triplet excited state of rhodamine-C60 dyads.

    Science.gov (United States)

    Wang, Fen; Cui, Xiaoneng; Lou, Zhangrong; Zhao, Jianzhang; Bao, Ming; Li, Xingwei

    2014-12-21

    Acid-switching of the triplet excited state in rhodamine-C60 dyads was achieved. The rhodamine moiety acts as an acid-activated visible light-harvesting antenna and C60 as the singlet energy acceptor and the spin converter, and production of the triplet state was enhanced in the presence of acid.

  11. Electron impact excitation of the D states of Mg, Ca and Sr atoms ...

    Indian Academy of Sciences (India)

    We have used non-relativistic and relativistic distorted wave approximation methods to study the excitation of the 1 states of magnesium ( = 3), calcium ( = 4) and strontium ( = 5) from the ground 1 state. Calculations have been performed for the complete set of parameters ( , L ~ ⊥ + , L ~ ⊥ − , ~ + , ~ − ) .

  12. Thermality and excited state Rényi entropy in two-dimensional CFT

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Feng-Li [Department of Physics, National Taiwan Normal University,Taipei 11677, Taiwan (China); Wang, Huajia [Department of Physics, University of Illinois,Urbana-Champaign, IL 61801 (United States); Zhang, Jia-ju [Dipartimento di Fisica, Università degli Studi di Milano-Bicocca,Piazza della Scienza 3, I-20126 Milano (Italy); Theoretical Physics Division, Institute of High Energy Physics, Chinese Academy of Sciences,19B Yuquan Rd, Beijing 100049 (China); Theoretical Physics Center for Science Facilities, Chinese Academy of Sciences,19B Yuquan Rd, Beijing 100049 (China)

    2016-11-21

    We evaluate one-interval Rényi entropy and entanglement entropy for the excited states of two-dimensional conformal field theory (CFT) on a cylinder, and examine their differences from the ones for the thermal state. We assume the interval to be short so that we can use operator product expansion (OPE) of twist operators to calculate Rényi entropy in terms of sum of one-point functions of OPE blocks. We find that the entanglement entropy for highly excited state and thermal state behave the same way after appropriate identification of the conformal weight of the state with the temperature. However, there exists no such universal identification for the Rényi entropy in the short-interval expansion. Therefore, the highly excited state does not look thermal when comparing its Rényi entropy to the thermal state one. As the Rényi entropy captures the higher moments of the reduced density matrix but the entanglement entropy only the average, our results imply that the emergence of thermality depends on how refined we look into the entanglement structure of the underlying pure excited state.

  13. ARTICLE Volume-conserved Twist Excited-state of π-Conjugated Molecules

    Science.gov (United States)

    Sun, Qin-chao; Liu, Jian-yong; Hao, Yan; Yang, Xi-chuan

    2010-12-01

    The excited state characters of HY103 have been studied by means of time-resolved photon emission (time-correlated single photon counting) and time dependent density functional theory calculations. The experimental and theoretical results demonstrate that HY103 dyes undergo an efficient one-bond-flip motion after photoexicitation at room temperature, which leads to a very short lifetime of the normal fluorescence state, and a weak fluorescence emission around 670 nm. However, when HY103 are excited in amorphous glasses at 77 K, the normal fluorescence emission is prolonged to nanoseconds time scale about 2 ns, and the fluorescence emission is enhanced. Furthermore, a new emission state is produced, which is characterized as a volume-conserved twisted (VCT) state. This is the first observation of a VCT state. The experiment indicates that the VCT motion of excited state of π-conjugated molecules in restricted environment can form a stable emission state, and the excited state character of π-conjugated molecules in restricted environment is complex.

  14. Relativistic and correlated calculations on the ground, excited, and ionized states of iodine

    NARCIS (Netherlands)

    de Jong, W.A.; Visscher, L; Nieuwpoort, W.C

    1997-01-01

    The electronic structure, spectroscopic, and bonding properties of the ground, excited, and ionized states of iodine are studied within a four-component relativistic framework using the MOLFDIR program package, The experimentally determined properties of the (1) Sigma(g)(+) ground state are well

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

    Science.gov (United States)

    Singh, Gaurav

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

  16. Ultrafast Excited-State Dynamics of Diketopyrrolopyrrole (DPP)-Based Materials: Static versus Diffusion-Controlled Electron Transfer Process

    KAUST Repository

    Alsulami, Qana

    2015-06-25

    Singlet-to-triplet intersystem crossing (ISC) and photoinduced electron transfer (PET) of platinum(II) containing diketopyrrolopyrrole (DPP) oligomer in the absence and presence of strong electron-acceptor tetracyanoethylene (TCNE) were investigated using femtosecond and nanosecond transient absorption spectroscopy with broadband capabilities. The role of platinum(II) incorporation in those photophysical properties was evaluated by comparing the excited-state dynamics of DPP with and without the metal centers. The steady-state measurements reveal that platinum(II) incorporation facilitates dramatically the interactions between DPP-Pt(acac) and TCNE, resulting in charge transfer (CT) complex formation. The transient absorption spectra in the absence of TCNE reveal ultrafast ISC of DPP-Pt(acac) followed by their long-lived triplet state. In the presence of TCNE, PET from the excited DPP-Pt(acac) and DPP to TCNE, forming the radical ion pairs. The ultrafast PET which occurs statically from DPP-Pt(acac) to TCNE in picosecond regime, is much faster than that from DPP to TCNE (nanosecond time scale) which is diffusion-controlled process, providing clear evidence that PET rate is eventually controlled by the platinum(II) incorporation.

  17. Three-body recombination and dynamics of electrons and excited states in the low-pressure argon afterglow

    Science.gov (United States)

    Tsankov, Tsanko Vaskov; Johnsen, Rainer; Czarnetzki, Uwe

    2016-09-01

    The afterglow phase occurs naturally during the power-off period in pulsed low-pressure plasmas and in atmospheric pressure ns discharges. During that period the electron energy rapidly declines and the charged particles are lost due to diffusion and recombination. In low-pressure discharges the dominant process is three-body recombination (TBR) of Ar+ ions with electrons. It leads to complex dynamics of the excited states, dominated by collisional-radiative cascades that eventually repopulate the metastable states. In this contribution the afterglow dynamics of an argon discharge is analyzed in detail to elucidate the roles played by the various processes. An analytical model for the fast drop of the electron energy by evaporative cooling and electron-ion collisions is combined with a time-dependent collisional radiative model for the atomic excited states that numerically solves the electron energy and density balance equations. By including further gas heating and cooling, the model leads to excellent agreement with experiments utilizing different diagnostic techniques, and hence gives insight into the interplay of the various processes in the afterglow. Work Supported by the DFG (Grant No. TS 307/1-1).

  18. Charge capture and impact excitation processes in H{sup +} on He{sup +} collisions: a case study by the time-dependent Schroedinger equation method

    Energy Technology Data Exchange (ETDEWEB)

    Tong Xiaomin [Cold Trapped Ions Project, ICORP, Japan Science and Technology Corporation (JST), Axis 3F, 1-40-2 Fuda Chofu, Tokyo 182-0024 (Japan)]. E-mail: tong@hci.jst.go.jp; Kato, Daiji; Watanabe, Tsutomu [Cold Trapped Ions Project, ICORP, Japan Science and Technology Corporation (JST), Axis 3F, 1-40-2 Fuda Chofu, Tokyo 182-0024 (Japan); Ohtani, Shunsuke [Cold Trapped Ions Project, ICORP, Japan Science and Technology Corporation (JST), Axis 3F, 1-40-2 Fuda Chofu, Tokyo 182-0024 (Japan); University of Electro-Communication, Chofu, Tokyo 182-0021 (Japan)

    2000-12-28

    We have studied the charge capture and impact excitation processes in H{sup +} on He{sup +} collisions over a wide range of collision energies by solving the time-dependent Schroedinger equation with the classical trajectory approximation for the projectile. The time-dependent Schroedinger equation is solved by the split-operator method with a generalized pseudospectral (non-uniform grid) method in the energy representation. The calculated charge capture cross sections are in good agreement with the available experimental measurements. Our calculated charge capture and impact excitation cross sections are also in reasonable agreement with various close-coupling calculations. Combined with time-dependent density functional theory, our Schroedinger equation method (time propagation) holds significant promise for studying many-electron processes in atom-ion collisions. (author)

  19. Role of the electronically excited-state hydrogen bonding and water clusters in the luminescent metal-organic framework.

    Science.gov (United States)

    Sui, Xiao; Ji, Min; Lan, Xin; Mi, Weihong; Hao, Ce; Qiu, Jieshan

    2013-05-20

    The electronically excited state and luminescence property of metal-organic framework Zn(3-tzba)(2,2'-bipy)(H2O)·nH2O have been investigated using the density functional theory (DFT) and time-dependent DFT (TDDFT). The calculated geometry and infrared spectra in the ground state are consistent with the experimental results. The frontier molecular orbitals and electronic configuration indicated that the origin of luminescence is attributed to a ligand-to-ligand charge transfer (LLCT). We theoretically demonstrated that the hydrogen bond H47···O5═C is weakened in the excited state S1; the weakening of the excited-state hydrogen bonding should be beneficial to the luminescence. To explore the effect of the water clusters on the luminescence, we studied four complexes Zn(3-tzba)(2,2'-bipy)(H2O)·3H2O, Zn(3-tzba)(2,2'-bipy)(H2O)·2H2O, Zn(3-tzba)(2,2'-bipy)(H2O)·H2O, and Zn(3-tzba)(2,2'-bipy)(H2O). The results reveal that the presence of water should play an important role in the emission characteristics of the MOF. Also, the UV-vis absorption and emission spectra of Zn(3-tzba)(2,2'-bipy)(H2O)·3H2O are in good agreement with the experimental results.

  20. Transient Development of Excited State Densities in Atomic Helium Plasmas

    Science.gov (United States)

    1976-03-01

    n s t i t u e n t s caus ing a t . ransfer to bound e l e c t r o n s b e t w e e n the l o w - l y i n g s t a t e s and u p p e r s t a t...r y and t h e s e a r e d i s c u s s e d in de ta i l . 4.1 ENERGY LEVELS The h e l i u m e n e r g y l e v e l s u s e d in th i s s...e t h e n d e t e r m i n e d f r o m t h e s e v a l u e s . 4] AEDC-TR-76-5 Table 1. Helium Energy Lwel$ State g E (i/cm) State g E (i

  1. Phase fluctuations and the absence of topological defects in a photo-excited charge-ordered nickelate

    Energy Technology Data Exchange (ETDEWEB)

    Lee, W. S.; Chuang, Y. D.; Moore, R. G.; Zhu, Y.; Patthey, L.; Trigo, M.; Lu, D. H.; Kirchmann, P. S.; Krupin, O.; Yi, M.; Langner, M.; Huse, N.; Robinson, J. S.; Chen, Y.; Zhou, S. Y.; Coslovich, G.; Huber, B.; Reis, D. A.; Kaindl, R. A.; Schoenlein, R. W.; Doering, D.; Denes, P.; Schlotter, W. F.; Turner, J. J.; Johnson, S. L.; Först, M.; Sasagawa, T.; Kung, Y. F.; Sorini, A. P.; Kemper, A. F.; Moritz, B.; Devereaux, T. P.; Lee, D. -H.; Shen, Z. X.; Hussain, Z.

    2012-05-15

    The dynamics of an order parameter's amplitude and phase determines the collective behaviour of novel states emerging in complex materials. Time- and momentum-resolved pump-probe spectroscopy, by virtue of measuring material properties at atomic and electronic time scales out of equilibrium, can decouple entangled degrees of freedom by visualizing their corresponding dynamics in the time domain. Here we combine time-resolved femotosecond optical and resonant X-ray diffraction measurements on charge ordered La1.75Sr0.25NiO4 to reveal unforeseen photoinduced phase fluctuations of the charge order parameter. Such fluctuations preserve long-range order without creating topological defects, distinct from thermal phase fluctuations near the critical temperature in equilibrium. Importantly, relaxation of the phase fluctuations is found to be an order of magnitude slower than that of the order parameter's amplitude fluctuations, and thus limits charge order recovery. This new aspect of phase fluctuations provides a more holistic view of the phase's importance in ordering phenomena of quantum matter.

  2. Excited-state properties from ground-state DFT descriptors: A QSPR approach for dyes.

    Science.gov (United States)

    Fayet, Guillaume; Jacquemin, Denis; Wathelet, Valérie; Perpète, Eric A; Rotureau, Patricia; Adamo, Carlo

    2010-02-26

    This work presents a quantitative structure-property relationship (QSPR)-based approach allowing an accurate prediction of the excited-state properties of organic dyes (anthraquinones and azobenzenes) from ground-state molecular descriptors, obtained within the (conceptual) density functional theory (DFT) framework. The ab initio computation of the descriptors was achieved at several levels of theory, so that the influence of the basis set size as well as of the modeling of environmental effects could be statistically quantified. It turns out that, for the entire data set, a statistically-robust four-variable multiple linear regression based on PCM-PBE0/6-31G calculations delivers a R(adj)(2) of 0.93 associated to predictive errors allowing for rapid and efficient dye design. All the selected descriptors are independent of the dye's family, an advantage over previously designed QSPR schemes. On top of that, the obtained accuracy is comparable to the one of the today's reference methods while exceeding the one of hardness-based fittings. QSPR relationships specific to both families of dyes have also been built up. This work paves the way towards reliable and computationally affordable color design for organic dyes. Copyright 2009 Elsevier Inc. All rights reserved.

  3. Energy-Looping Nanoparticles: Harnessing Excited-State Absorption for Deep-Tissue Imaging.

    Science.gov (United States)

    Levy, Elizabeth S; Tajon, Cheryl A; Bischof, Thomas S; Iafrati, Jillian; Fernandez-Bravo, Angel; Garfield, David J; Chamanzar, Maysamreza; Maharbiz, Michel M; Sohal, Vikaas S; Schuck, P James; Cohen, Bruce E; Chan, Emory M

    2016-09-27

    Near infrared (NIR) microscopy enables noninvasive imaging in tissue, particularly in the NIR-II spectral range (1000-1400 nm) where attenuation due to tissue scattering and absorption is minimized. Lanthanide-doped upconverting nanocrystals are promising deep-tissue imaging probes due to their photostable emission in the visible and NIR, but these materials are not efficiently excited at NIR-II wavelengths due to the dearth of lanthanide ground-state absorption transitions in this window. Here, we develop a class of lanthanide-doped imaging probes that harness an energy-looping mechanism that facilitates excitation at NIR-II wavelengths, such as 1064 nm, that are resonant with excited-state absorption transitions but not ground-state absorption. Using computational methods and combinatorial screening, we have identified Tm(3+)-doped NaYF4 nanoparticles as efficient looping systems that emit at 800 nm under continuous-wave excitation at 1064 nm. Using this benign excitation with standard confocal microscopy, energy-looping nanoparticles (ELNPs) are imaged in cultured mammalian cells and through brain tissue without autofluorescence. The 1 mm imaging depths and 2 μm feature sizes are comparable to those demonstrated by state-of-the-art multiphoton techniques, illustrating that ELNPs are a promising class of NIR probes for high-fidelity visualization in cells and tissue.

  4. Structural Monitoring of the Onset of Excited-State Aromaticity in a Liquid Crystal Phase.

    Science.gov (United States)

    Hada, Masaki; Saito, Shohei; Tanaka, Sei'ichi; Sato, Ryuma; Yoshimura, Masahiko; Mouri, Kazuhiro; Matsuo, Kyohei; Yamaguchi, Shigehiro; Hara, Mitsuo; Hayashi, Yasuhiko; Röhricht, Fynn; Herges, Rainer; Shigeta, Yasuteru; Onda, Ken; Miller, R J Dwayne

    2017-11-08

    Aromaticity of photoexcited molecules is an important concept in organic chemistry. Its theory, Baird's rule for triplet aromaticity since 1972 gives the rationale of photoinduced conformational changes and photochemical reactivities of cyclic π-conjugated systems. However, it is still challenging to monitor the dynamic structural change induced by the excited-state aromaticity, particularly in condensed materials. Here we report direct structural observation of a molecular motion and a subsequent packing deformation accompanied by the excited-state aromaticity. Photoactive liquid crystal (LC) molecules featuring a π-expanded cyclooctatetraene core unit are orientationally ordered but loosely packed in a columnar LC phase, and therefore a photoinduced conformational planarization by the excited-state aromaticity has been successfully observed by time-resolved electron diffractometry and vibrational spectroscopy. The structural change took place in the vicinity of excited molecules, producing a twisted stacking structure. A nanoscale torque driven by the excited-state aromaticity can be used as the working mechanism of new photoresponsive materials.

  5. Low charge state heavy ion production with sub-nanosecond laser.

    Science.gov (United States)

    Kanesue, T; Kumaki, M; Ikeda, S; Okamura, M

    2016-02-01

    We have investigated laser ablation plasma of various species using nanosecond and sub-nanosecond lasers for both high and low charge state ion productions. We found that with sub-nanosecond laser, the generated plasma has a long tail which has low charge state ions determined by an electrostatic ion analyzer even under the laser irradiation condition for highly charged ion production. This can be caused by insufficient laser absorption in plasma plume. This property might be suitable for low charge state ion production. We used a nanosecond laser and a sub-nanosecond laser for low charge state ion production to investigate the difference of generated plasma using the Zirconium target.

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

    Science.gov (United States)

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

    2009-12-03

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

  7. Determination and Comparison of Carbonyl Stretching Frequency of a Ketone in Its Ground State and the First Electronic Excited State

    Science.gov (United States)

    Bandyopadhyay, Subhajit; Roy, Saswata

    2014-01-01

    This paper describes an inexpensive experiment to determine the carbonyl stretching frequency of an organic keto compound in its ground state and first electronic excited state. The experiment is simple to execute, clarifies some of the fundamental concepts of spectroscopy, and is appropriate for a basic spectroscopy laboratory course. The…

  8. High Intensity High Charge State ECR Ion Sources

    CERN Document Server

    Leitner, Daniela

    2005-01-01

    The next-generation heavy ion beam accelerators such as the proposed Rare Isotope Accelerator (RIA), the Radioactive Ion Beam Factory at RIKEN, the GSI upgrade project, the LHC-upgrade, and IMP in Lanzhou require a great variety of high charge state ion beams with a magnitude higher beam intensity than currently achievable. High performance Electron Cyclotron Resonance (ECR) ion sources can provide the flexibility since they can routinely produce beams from hydrogen to uranium. Over the last three decades, ECR ion sources have continued improving the available ion beam intensities by increasing the magnetic fields and ECR heating frequencies to enhance the confinement and the plasma density. With advances in superconducting magnet technology, a new generation of high field superconducting sources is now emerging, designed to meet the requirements of these next generation accelerator projects. The talk will briefly review the field of high performance ECR ion sources and the latest developments for high intens...

  9. State of charge estimation in Ni-MH rechargeable batteries

    Energy Technology Data Exchange (ETDEWEB)

    Milocco, R.H. [Grupo Control Automatico y Sistemas (GCAyS), Depto. Electrotecnia, Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400, 8300 Neuquen (Argentina); Castro, B.E. [Instituto de Investigaciones Fisicoquimicas Teoricas y Aplicadas (INIFTA), Universidad Nacional de La Plata, Suc 4, CC16 (1900), La Plata (Argentina)

    2009-10-20

    In this work we estimate the state of charge (SOC) of Ni-MH rechargeable batteries using the Kalman filter based on a simplified electrochemical model. First, we derive the complete electrochemical model of the battery which includes diffusional processes and kinetic reactions in both Ni and MH electrodes. The full model is further reduced in a cascade of two parts, a linear time invariant dynamical sub-model followed by a static nonlinearity. Both parts are identified using the current and potential measured at the terminals of the battery with a simple 1-D minimization procedure. The inverse of the static nonlinearity together with a Kalman filter provide the SOC estimation as a linear estimation problem. Experimental results with commercial batteries are provided to illustrate the estimation procedure and to show the performance. (author)

  10. Instantaneous charge state of Uranium projectiles in fully ionized plasmas from energy loss experiments

    CERN Document Server

    Morales, Roberto; Casas, David

    2016-01-01

    The instantaneous charge state of uranium ions traveling through a fully ionized hydrogen plasma has been theoretically studied and compared with one of the first energy loss experiments in plasmas, carried out at GSI-Darmstadt by Hoffmann \\textit{et al.} in the 90's. For this purpose, two different methods to estimate the instantaneous charge state of the projectile have been employed: (1) rate equations using ionization and recombination cross sections, and (2) equilibrium charge state formulas for plasmas. Also, the equilibrium charge state has been obtained using these ionization and recombination cross sections, and compared with the former equilibrium formulas. The equilibrium charge state of projectiles in plasmas is not always reached, it depends mainly on the projectile velocity and the plasma density. Therefore, a non-equilibrium or an instantaneous description of the projectile charge is necessary. The charge state of projectile ions cannot be measured, except after exiting the target, and experime...

  11. Interfacial solvation and excited state photophysical properties of 7-aminocoumarins at silica/liquid interfaces

    Science.gov (United States)

    Roy, Debjani

    The properties of solutes adsorbed at interfaces can be very different compared to bulk solution limits. This thesis examines how polar, hydrophilic silica surfaces and different solvents systematically change a solute's equilibrium and dynamic solvation environment at solid/liquid interfaces. The primary tools used in these studies are steady state fluorescence spectroscopy and time correlated single photon counting (TCSPC) --a fluorescence method capable resolving fluorescence emission on the picosecond timescale. To sample adsorbed solutes, TCSPC experiments were carried out in total internal reflection (TIR) geometry. These studies used total of six different 7-aminocoumarin dyes to isolate the effects of molecular and electronic structure on solute photophysical behavior. Fluorescence lifetimes measured in the TIR geometry are compared to the lifetimes of coumarins in bulk solution using different solvents to infer interfacial polarity and excited state solute conformation and dynamics. Steady state emission experiments measuring the behavior of the coumarins adsorbed at silica surfaces from bulk methanol solutions show that all coumarins had a similar affinity DeltaG ads ˜ - 25-30 kJ/mole. Despite these similar adsorption energetics solute structure had a very pronounced effect on the tendency of solutes to aggregate and form multilayers. Our finding suggests that hydrogen bonding donating properties of the silica surface plays a dominant role in determining the interfacial behavior of these solutes. The silica surface also had pronounced effects on the time dependent emission of some solutes. In particular, the strong hydrogen bond donating properties of the silica surface inhibit formation of a planar, charge transfer state through hydrogen bond donation to the solute's amine group. A consequence of this interaction is that the time dependent emission from solutes adsorbed at the surface appears to be more similar to emission from solutes in nonpolar

  12. The effect of solvent additives on morphology and excited-state dynamics in PCPDTBT:PCBM photovoltaic blends.

    Science.gov (United States)

    Etzold, Fabian; Howard, Ian A; Forler, Nina; Cho, Don M; Meister, Michael; Mangold, Hannah; Shu, Jie; Hansen, Michael Ryan; Müllen, Klaus; Laquai, Frédéric

    2012-06-27

    The dependence of the thin film morphology and excited-state dynamics for the low-bandgap donor-acceptor copolymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) in pristine films and in blends (1:2) with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) on the use of the solvent additive 1,8-octanedithiol (ODT) is studied by solid-state nuclear magnetic resonance (NMR) spectroscopy and broadband visible and near-infrared pump-probe transient absorption spectroscopy (TAS) covering a spectral range from 500-2000 nm. The latter allows monitoring of the dynamics of excitons, bound interfacial charge-transfer (CT) states, and free charge carriers over a time range from femto- to microseconds. The broadband pump-probe experiments reveal that excitons are not only generated in the polymer but also in PCBM-rich domains. Depending on the morphology controlled by the use of solvent additives, polymer excitons undergo mainly ultrafast dissociation (photovoltaic devices.

  13. Excited states behavior of nucleobases in solution: insights from computational studies.

    Science.gov (United States)

    Improta, Roberto; Barone, Vincenzo

    2015-01-01

    We review the most significant results obtained in the study of isolated nucleobases in solution by quantum mechanical methods, trying to highlight also the most relevant open issues. We concisely discuss some methodological issues relevant to the study of molecular electronic excited molecular states in condensed phases, focussing on the methods most commonly applied to the study of nucleobases, i.e. continuum models as the Polarizable Continuum Model and explicit solvation models. We analyse how the solvent changes the relative energy of the lowest energy excited states in the Franck-Condon region, their minima and the Conical Intersections among the different states, interpreting the experimental optical spectra, both steady state and time-resolved. Several methods are available for accurately including solvent effects in the Franck-Condon region, and for most of the nucleobases the solvent shift on the different excited states can be considered assessed. The study of the excited state decay, both radiative and non-radiative, in solution still poses instead significant theoretical challenges.

  14. Surface-catalyzed recombination into excited electronic, vibrational, rotational, and kinetic energy states: A review

    Science.gov (United States)

    Kofsky, I. L.; Barrett, J. L.

    1985-01-01

    Laboratory experiments in which recombined CO, CO2, D2O, OH, N2, H2, and O2 molecules desorb from surfaces in excited internal and translational states are briefly reviewed. Unequilibrated distributions predominate from the principally catalytic metal substrates so far investigated. Mean kinetic energies have been observed up to approx. 3x, and in some cases less than, wall-thermal; the velocity distributions generally vary with emission angle, with non-Lambertian particle fluxes. The excitation state populations are found to depend on surface impurities, in an as yet unexplained way.

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

    DEFF Research Database (Denmark)

    Shelby, Megan L.; Lestrange, Patrick J.; Jackson, Nicholas E.

    2016-01-01

    Photoexcited Nickel(II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through multiple electronic states following an initial porphyrin-based excitation, some involving metal centered electronic configuration changes that could be harnessed catalytically......), structural dynamics before thermalization were not resolved due to the similar to 100 ps duration of the available X-ray probe pulse. Using the femtosecond (fs) X-ray pulses of the Linac Coherent Light Source (LCLS), the Ni center electronic configuration from the initial excited state to the relaxed (d...

  16. Pulsed radiation studies of carotenoid radicals and excited states

    Energy Technology Data Exchange (ETDEWEB)

    Burke, M

    2001-04-01

    The one-electron reduction potentials of the radical cations of five dietary carotenoids, in aqueous micellar environments, have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range 980 to 1060 mV. The decays of the carotenoid radical cations suggest a distribution of exponential lifetimes. The radicals persist for up to about one second, depending on the medium and may re-orientate within a biological environment to react with other biomolecules, such as tyrosine, cysteine or ascorbic acid, which was indeed confirmed. Spectral information of carotenoid pigmented liposomes has been collected, subsequently pulse radiolysis was used to generate the radical cations of {beta}-carotene, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoyl phosphatidyl choline. The rate constants for the 'repair' of these carotenoid radical cations by water-soluble vitamin C were found to be similar ({approx}1 x 10{sup 7} M{sup -1}s{sup -1}) for {beta}-carotene and zeaxanthin and somewhat lower ({approx}0.5 x 10{sup 7} M{sup -1}s{sup -1}) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for {beta}-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome. Studies investigating the ability of ingested lycopene to protect human lymphoid cells against singlet oxygen and nitrogen dioxide radical mediated cell damage have shown that a high lycopene diet is beneficial in protecting human cells against reactive oxygen species. Triplet states of carotenoids were produced in benzene solvent and their triplet lifetimes were found to depend on the concentration of the parent molecule. The rate constants obtained for ground state quenching correlate with the number

  17. Mean excitation energies for molecular ions

    DEFF Research Database (Denmark)

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

    2017-01-01

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

  18. Mean excitation energies for molecular ions

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-03-01

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

  19. Combined quantum-mechanical molecular mechanics calculations with NWChem and AMBER: Excited state properties of green fluorescent protein chromophore analogue in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Pirojsirikul, Teerapong [Department of Chemistry and Biochemistry, University of California San Diego, 9500 Gilman Drive La Jolla California 92093; Götz, Andreas W. [San Diego Supercomputer Center, University of California San Diego, 9500 Gilman Drive La Jolla California 92093; Weare, John [Department of Chemistry and Biochemistry, University of California San Diego, 9500 Gilman Drive La Jolla California 92093; Walker, Ross C. [Department of Chemistry and Biochemistry, University of California San Diego, 9500 Gilman Drive La Jolla California 92093; GlaxoSmithKline, 1250 S. Collegeville Road Collegeville Pennsylvania 19426; Kowalski, Karol [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P. O. Box 999 Richland Washington 99352; Valiev, Marat [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P. O. Box 999 Richland Washington 99352

    2017-05-03

    Green Fluorescent Protein (GFP) is a widely used fluorescent biomarker for the study of biological systems. Our investigation is focused on providing a reliable theoretical description of the GFP chromophore, the photochemical properties of which can be influenced through both the surrounding protein environment and pH levels. In this work we are specifically addressing the effect of an aqueous solvation environment , where a number of experimental measurements have been performed. Our approach is based on a combined quantum mechanics molecular mechanics (QM/MM) methodology, which incorporates high level coupled cluster theory for the analysis of excited states. It also presents the first application of the newly developed NWChem/AMBER QM/MM interface. Using a systematic approach, which involves comparison of gas phase and aqueous results for different protonation states and conformations, we have resolved existing uncertainties regarding theoretical interpretation of the experimental data. We observe that the impact of aqueous environment on charged states generally results in blue shifts, but the magnitude of the effect is sensitive to charge state and conformation and can be rationalized based on charge movement into the area of higher/lower external electrostatic potentials. At neutral pH levels the experimentally observed absorption signal is most likely coming from the phenol protonated form. Our results also show that the high level coupled description is essential for proper description of excited states of GFP.

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

    Science.gov (United States)

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

    2016-08-17

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

  1. Variation of excited-state dynamics in trifluoromethyl functionalized C 60 fullerenes

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-01

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

  2. Charge asymmetry and relativistic corrections in pure vibrational states of the HD+ ion

    Science.gov (United States)

    Stanke, Monika; Adamowicz, Ludwik

    2014-03-01

    In this work we present very accurate quantum-mechanical calculations of all bound pure vibrational states of the HD+ ion performed without the Born-Oppenheimer (BO) approximation. All three particles forming the system are treated on equal footing. The approach involves separating the center-of-mass motion from the laboratory-frame nonrelativistic Hamiltonian and expending the wave function of each considered state in terms of all-particle explicitly correlated Gaussian functions. The Gaussian exponential parameters are variationally optimized with the aid of the analytical energy gradient calculated with respect to these parameters. For each state the leading relativistic corrections are calculated as expectation values of the corresponding operators with the non-BO wave function of the state. The non-BO approach allows us to directly describe the charge asymmetry in HD+ which is due to the nuclear-mass asymmetry. The effect increases with the vibrational excitation and affects the values of the relativistic corrections. This phenomenon is the focus of the present study.

  3. Probing the excited state dynamics of a new family of Cu(I)-complexes with an enhanced light absorption capacity: excitation-wavelength dependent population of states through branching.

    Science.gov (United States)

    Papanikolaou, Panagiotis A; Tkachenko, Nikolai V

    2013-08-21

    The ultrafast dynamics of six homoleptic Cu(I)-complexes and their respective ligands was examined through time-resolved electronic absorption spectroscopy in the subpicosecond time domain, in a variety of solvents, and at different excitation wavelengths. Results indicate that after excitation of the complexes in the blue part of the spectrum, the initially formed intraligand (IL) singlet excited state decays via two pathways yielding simultaneously both the lower-lying MLCT excited state and the ligand locally excited triplet state. The latter is also observed in the case of the free ligands and relaxes back to the ground state in a timescale of 40 ps. Excitation in the red part results in the formation of the MLCT excited state of the complexes which decays to the ground state through the same intraligand triplet excited state. The solvent viscosity does not affect the overall relaxation kinetics. The short time constant observed for the intersystem crossing of the MLCT singlet excited state is discussed in terms of the contribution of the d-orbitals of copper to the wavefunction of these states.

  4. The MRSDCI/CIS study of excited electronic states of the SF 2 radical

    Science.gov (United States)

    Liu, Y.-J.; Huang, M.-B.; Zhou, X.; Yu, S.

    2001-09-01

    The vertical ( Tv) and adiabatic ( T0) excitation energies for singlet electronic excited states of the SF 2 radical have been calculated by using the multireference single and double excitation configuration interaction (MRSDCI) method and aug-cc-pVTZ basis sets augmented by Rydberg functions. The MRSDCI Tv calculations indicate that the X1A1, 1 1A2, 1 1B1, 2 1B1, 2 1A2, 2 1A1, 3 1B1, 4 1B1, 3 1A1, and 1 1B2 states are the 10 lowest-lying singlet states. Based on the MRSDCI//CIS T0 calculations (using CIS optimized geometries for excited states), the A, B, C, E, F, G, H, and I states of SF 2 are assigned to 1 1B1, 2 1B1, 3 1B1, 2 1A2, 2 1A1, 3 1A1, 4 1B1, and 1 1B2, respectively.

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

    CERN Document Server

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

    2016-05-02

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

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

    CERN Document Server

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

    2016-01-01

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

  7. DETERMINATION OF THE ABSOLUTE EXCITED-STATE DENSITY OF A SODIUM TARGET BY MEANS OF BEAM DEFLECTION MEASUREMENTS

    NARCIS (Netherlands)

    WIERSEMA, WP; SCHLATMANN, AR; MORGENSTERN, R

    1994-01-01

    The average deflection of a laser excited, divergent sodium beam with a broad velocity distribution is measured by means of a Langmuir-Taylor detector and exploited for determining the absolute density of the excited state in the interaction area. Simulations of the excitation and deflection process

  8. Photostability of a fluorescent marker under pulsed excited-state depletion through stimulated emission.

    Science.gov (United States)

    Dyba, Marcus; Hell, Stefan W

    2003-09-01

    Saturated stimulated-emission depletion (STED) of a fluorescent marker has been shown to break the diffraction barrier in far-field fluorescence microscopy and to facilitate spatial resolution down to a few tens of nanometers. Here we investigate the photostability of a fluorophore that, in this concept, is repeatedly excited and depleted by synchronized laser pulses. Our study of bacteria labeled with RH-414, a membrane marker, reveals that increasing the duration of the STED pulse from approximately 10 to 160 ps fundamentally improves the photostability of the dye. At the same time the STED efficiency is maintained. The observed photobleaching of RH-414 is due primarily to multiphoton absorption from its ground state. One can counteract photobleaching by employing STED pulses that range from 150 ps to approximately half of the lifetime of the excited state. The results also have implications for multiphoton excitation microscopy.

  9. Conformational analysis of acetamide in the ground and lowest excited electronic states

    Science.gov (United States)

    Tukachev, N. V.; Bataev, V. A.; Godunov, I. A.

    2017-05-01

    For acetamide molecule (CH3CONH2) in the ground (S0) and lowest excited singlet (S1) and triplet (T1) electronic states calculations of equilibrium geometry parameters, harmonic vibrational frequencies and barriers to conformational transitions (also conformer energy differences in excited states) using following ab initio methods: MP2, CCSD(T), CASSCF, CASPT2 and MRCI were performed. One-, two- and three-dimensional potential energy surface (PES) sections by different large amplitude motions (LAM) coordinates were calculated by means of MP2/aug-cc-pVTZ (S0) and CASPT2/cc-pVTZ (S1, T1). As a result of electronic excitation, both CCON and CNH2 fragments become pyramidal. On 2D PES sections by torsion (CN) and inversion coordinates there are six minima forming three pairs of enantiomers. Using PES sections different anharmonic vibrational problems were solved and the frequencies of large amplitude vibrations were estimated.

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

    CERN Document Server

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

    2010-01-01

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

  11. Selective two-photon excitation of a vibronic state by correlated photons.

    Science.gov (United States)

    Oka, Hisaki

    2011-03-28

    We theoretically investigate the two-photon excitation of a molecular vibronic state by correlated photons with energy anticorrelation. A Morse oscillator having three sets of vibronic states is used, as an example, to evaluate the selectivity and efficiency of two-photon excitation. We show that a vibrational mode can be selectively excited with high efficiency by the correlated photons, without phase manipulation or pulse-shaping techniques. This can be achieved by controlling the quantum correlation so that the photon pair concurrently has two pulse widths, namely, a temporally narrow width and a spectrally narrow width. Though this concurrence is seemingly contradictory, we can create such a photon pair by tailoring the quantum correlation between two photons.

  12. Zero-resistance states induced by electromagnetic-wave excitation in GaAs/AlGaAs heterostructures.

    Science.gov (United States)

    Mani, Ramesh G; Smet, Jürgen H; von Klitzing, Klaus; Narayanamurti, Venkatesh; Johnson, William B; Umansky, Vladimir

    2002-12-12

    The observation of vanishing electrical resistance in condensed matter has led to the discovery of new phenomena such as, for example, superconductivity, where a zero-resistance state can be detected in a metal below a transition temperature T(c) (ref. 1). More recently, quantum Hall effects were discovered from investigations of zero-resistance states at low temperatures and high magnetic fields in two-dimensional electron systems (2DESs). In quantum Hall systems and superconductors, zero-resistance states often coincide with the appearance of a gap in the energy spectrum. Here we report the observation of zero-resistance states and energy gaps in a surprising setting: ultrahigh-mobility GaAs/AlGaAs heterostructures that contain a 2DES exhibit vanishing diagonal resistance without Hall resistance quantization at low temperatures and low magnetic fields when the specimen is subjected to electromagnetic wave excitation. Zero-resistance-states occur about magnetic fields B = 4/5 Bf and B = 4/9 Bf, where Bf = 2pifm*/e,m* is the electron mass, e is the electron charge, and f is the electromagnetic-wave frequency. Activated transport measurements on the resistance minima also indicate an energy gap at the Fermi level. The results suggest an unexpected radiation-induced, electronic-state-transition in the GaAs/AlGaAs 2DES.

  13. Fluorescence excitation involving multiple electron transition states of N{sub 2} and CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Wu, C.Y.R.; Chen, F.Z.; Hung, T.; Judge, D.L. [Univ. of Southern California, Los Angeles, CA (United States)

    1997-04-01

    The electronic states and electronic structures of N{sub 2} and CO{sub 2} in the 8-50 eV energy region have been studied extensively both experimentally and theoretically. In the energy region higher than 25 eV there exists many electronic states including multiple electron transition (MET) states which are responsible for producing most of the dissociative photoionization products. The electronic states at energies higher than 50 eV have been mainly determined by Auger spectroscopy, double charge transfer, photofragment spectroscopy and ion-ion coincidence spectroscopy. The absorption and ionization spectra of these molecules at energies higher than 50 eV mainly show a monotonic decrease in cross section values and exhibit structureless features. The decay channels of MET and Rydberg (or superexcited) states include autoionization, ionization, dissociative ionization, predissociation, and dissociation while those of single ion and multiple ion states may involve predissociation. and dissociation processes. The study of fluorescence specifically probes electronically excited species resulting from the above-mentioned decay channels and provides information for understanding the competition among these channels.

  14. Role of charge-transfer states in bacterial photosynthesis

    NARCIS (Netherlands)

    Meech, S.R.; Hoff, A.J.

    1986-01-01

    Photon echo, photon-echo excitation, and "hole-burning" data recorded in the 800-990 nm region of Rhodobacter sphaeroides R26 and Rhodopseudomonas viridis reaction centers are reported. The primary process in these reaction centers, following excitation, was found to occur in ≈25 fsec; the

  15. Quantum Monte Carlo Characterization of Excited States and Energy-Level Alignment at Oligomer/Quantum-Dot Interfaces

    Science.gov (United States)

    Kanai, Yosuke; Dubois, Jonathan L.; Lee, Donghwa

    2012-02-01

    Charge separation of excitons in materials is one of the most important physical processes that need to take place in excitonic solar cells and in photocatalytic devices. Heterogeneous interfaces with the so-called type-II character are often employed for inducing the exciton dissociation through interfacial charge transfer. As the simplest criterion for designing such an interface, the energy alignment of the quasi-particle states is often discussed in literature, together with the exciton binding energy of electron-donating materials. Therefore, accurate characterization of the interfacial energy-level alignment and the exciton binding energy using first principles calculations is important for making systematic progresses in designing better materials for solar energy conversion. However, Density Functional Theory calculations need to be employed with caution in this context. First principles calculations such as Many-Body Perturbation Theory and Quantum Monte Carlo are promising alternatives for accurate characterization, but much more work is needed in this area to assess how well these methods perform in practice. In this talk, we will discuss our preliminary results using diffusion Quantum Monte Carlo on calculating the excited states and energy-level alignment of popular Oligomer/Quantum-Dot interfaces.

  16. Stark-induced adiabatic Raman ladder for preparing highly vibrationally excited quantum states of molecular hydrogen

    Science.gov (United States)

    Mukherjee, Nandini; Perreault, William E.; Zare, Richard N.

    2017-07-01

    We present a multi-color ladder excitation scheme that exploits Stark-induced adiabatic Raman passage to selectively populate a highly excited vibrational level of a molecule. We suggest that this multi-color coherent ladder excitation provides a practical way of accessing levels near the vibrational dissociation limit as well as the dissociative continuum, which would allow the generation of an entangled pair of fragments with near-zero relative kinetic energy. Specifically, we consider four- and six-photon coherent excitation of molecular hydrogen to high vibrational levels via intermediate vibrational levels, which are pairwise coupled by two-photon resonant interaction. Using a sequence of three partially overlapping, single-mode, nanosecond laser pulses we show that the sixth vibrational level of H2, which is too weakly coupled to be easily accessed by direct two-photon Raman excitation from the ground vibrational level, can be efficiently populated without leaving any population stranded in the intermediate level. Furthermore, we show that the fourteenth vibrational level of H2, which is the highest vibrational level in the ground electronic state with a binding energy of 22 meV, can be efficiently and selectively populated using a sequence of four pulses. The present technique offers the unique possibility of preparing entangled quantum states of H atoms without resorting to an ultracold system.

  17. Tetracarboxy-phthalocyanines: From excited state dynamics to photodynamic inactivation against Bovine herpesvirus type 1.

    Science.gov (United States)

    Cocca, Leandro H Z; Oliveira, Taise M A; Gotardo, Fernando; Teles, Amanda V; Menegatti, Ricardo; Siqueira, Jonathas P; Mendonça, Cleber R; Bataus, Luiz A M; Ribeiro, Anderson O; Souza, Thalita F M; Souza, Guilherme R L; Gonçalves, Pablo J; De Boni, Leonardo

    2017-10-01

    Herein we present the excited state dynamic of zinc and aluminum tetracarboxy-phthalocyanines (ZnPc and AlPc) and its application in the photodynamic inactivation (PDI) of Bovine herpesvirus type 1 (BoHV-1) in vitro. The excited state dynamic provides valuable data to describe the excited state properties of potential optical limiters and/or photosensitizers (PSs), such as: the excited state cross-sections, fluorescence lifetime and triplet state quantum yield. The excited state characterization was performed using three different Z-scan techniques: Single Pulse, White Light Continuum and Pulse Train. Considering the photodynamic inactivation of BoHV-1, an initial viral suspension containing 10 5.75 TCID 50 /mL was incubated with the PSs for 1h at 37°C under agitation and protected from light. The samples were placed in microtiter plates and irradiated (180mW/cm 2 ). During irradiation, a sample was taken every 15min and the viability of the virus was evaluated. The results show that both phthalocyanines were efficient against viruses. However, a higher photodynamic efficiency was observed by ZnPc, which can be attributed to its higher triplet and singlet quantum yields. The results presented here are important for animal health (treatment of BoHV-1) and also open up a field of studies to use AlPc and ZnPc as potential agents against a wide range of microorganisms of veterinary interest. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Before there was light : Excited state dynamics in luminescent (nano)materials

    NARCIS (Netherlands)

    Rabouw, F.T.|info:eu-repo/dai/nl/413318036

    2015-01-01

    In this thesis we examine two types of luminescent materials: colloidal semiconductor nanocrystals (also known as quantum dots), and crystals doped with lanthanide ions. These materials convert one color of light to another. By investigating the dynamics of the excited state, we gain new insights

  19. Excited states populated via nucleon transfer in the reaction [sup 32]S+[sup 208]Pb

    Energy Technology Data Exchange (ETDEWEB)

    Corradi, L.; Petrache, C.M.; Ackermann, D.; De Angelis, G.; Moreno, H.; Napoli, D.R.; Spolaore, P.; Stefanini, A.M. (INFN, Lab. Nazionali di Legnaro (Italy)); Beghini, S.; Montagnoli, G.; Scarlassara, F.; Segato, G.F.; Signorini, C. (Padua Univ. (Italy). Dipt. di Fisica INFN, Padua (Italy)); Pollarolo, G. (Turin Univ. (Italy). Dipt. di Fisica INFN, Turin (Italy))

    1993-01-01

    The population strengths of excited states in nuclei produced via transfer reactions in the 185 MeV[sup 32]S+[sup 208]Pb reaction have been investigated by heavy-ion-[gamma] coincidence techniques. The cross sections extracted from the [gamma] spectra, have been analyzed in the framework of the Complex WKB approximation theory. (orig.).

  20. Discrete excitation of mode pulses using a diode-pumped solid-state digital laser

    CSIR Research Space (South Africa)

    Ngcobo, Sandile

    2016-02-01

    Full Text Available In this paper, we experimentally demonstrate novel method of generating discrete excitation of on-demand Lagaurre-Gaussian (LG) mode pulses, in a diode pumped solid-state digital laser. The digital laser comprises of an intra-cavity spatial light...

  1. Temperature dependent excited state relaxation of a red emitting DNA-templated silver nanocluster

    DEFF Research Database (Denmark)

    Cerretani, Cecilia; Carro-Temboury, Miguel R.; Krause, Stefan

    2017-01-01

    The nanosecond excited state temporal and spectral relaxation of a purified, red-emitting DNA-templated silver nanocluster (DNA–AgNC) was characterized as a function of temperature. The findings are explained by introducing a phenomenological electronic structure diagram. The reproducibility...

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

    Directory of Open Access Journals (Sweden)

    Ding Thomas

    2013-03-01

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

  3. Fractionalized excitations in the spin-liquid state of a kagome-lattice antiferromagnet.

    Science.gov (United States)

    Han, Tian-Heng; Helton, Joel S; Chu, Shaoyan; Nocera, Daniel G; Rodriguez-Rivera, Jose A; Broholm, Collin; Lee, Young S

    2012-12-20

    The experimental realization of quantum spin liquids is a long-sought goal in physics, as they represent new states of matter. Quantum spin liquids cannot be described by the broken symmetries associated with conventional ground states. In fact, the interacting magnetic moments in these systems do not order, but are highly entangled with one another over long ranges. Spin liquids have a prominent role in theories describing high-transition-temperature superconductors, and the topological properties of these states may have applications in quantum information. A key feature of spin liquids is that they support exotic spin excitations carrying fractional quantum numbers. However, detailed measurements of these 'fractionalized excitations' have been lacking. Here we report neutron scattering measurements on single-crystal samples of the spin-1/2 kagome-lattice antiferromagnet ZnCu(3)(OD)(6)Cl(2) (also called herbertsmithite), which provide striking evidence for this characteristic feature of spin liquids. At low temperatures, we find that the spin excitations form a continuum, in contrast to the conventional spin waves expected in ordered antiferromagnets. The observation of such a continuum is noteworthy because, so far, this signature of fractional spin excitations has been observed only in one-dimensional systems. The results also serve as a hallmark of the quantum spin-liquid state in herbertsmithite.

  4. Ab initio excited states from the in-medium similarity renormalization group

    Science.gov (United States)

    Parzuchowski, N. M.; Morris, T. D.; Bogner, S. K.

    2017-04-01

    We present two new methods for performing ab initio calculations of excited states for closed-shell systems within the in-medium similarity renormalization group (IMSRG) framework. Both are based on combining the IMSRG with simple many-body methods commonly used to target excited states, such as the Tamm-Dancoff approximation (TDA) and equations-of-motion (EOM) techniques. In the first approach, a two-step sequential IMSRG transformation is used to drive the Hamiltonian to a form where a simple TDA calculation (i.e., diagonalization in the space of 1 p 1 h excitations) becomes exact for a subset of eigenvalues. In the second approach, EOM techniques are applied to the IMSRG ground-state-decoupled Hamiltonian to access excited states. We perform proof-of-principle calculations for parabolic quantum dots in two dimensions and the closed-shell nuclei 16O and 22O. We find that the TDA-IMSRG approach gives better accuracy than the EOM-IMSRG when calculations converge, but it is otherwise lacking the versatility and numerical stability of the latter. Our calculated spectra are in reasonable agreement with analogous EOM-coupled-cluster calculations. This work paves the way for more interesting applications of the EOM-IMSRG approach to calculations of consistently evolved observables such as electromagnetic strength functions and nuclear matrix elements, and extensions to nuclei within one or two nucleons of a closed shell by generalizing the EOM ladder operator to include particle-number nonconserving terms.

  5. Polarization of the excited states of twisted ethylene in a non-symmetrical environment

    NARCIS (Netherlands)

    Zijlstra, R.W J; van Duijnen, P.T.; de Vries, Alex

    1996-01-01

    The polarization behavior of the low lying excited states in the vicinity of the perpendicularly twisted (D-2d) ethylene has been investigated in a quantum mechanical CISD approach, in which the quantum system was embedded in a polarized dielectric continuum modeling a non-symmetrical distribution

  6. Probing lithium-ion batteries' state-of-charge using ultrasonic transmission - Concept and laboratory testing

    Science.gov (United States)

    Gold, Lukas; Bach, Tobias; Virsik, Wolfgang; Schmitt, Angelika; Müller, Jana; Staab, Torsten E. M.; Sextl, Gerhard

    2017-03-01

    For electrically powered applications such as consumer electronics and especially for electric vehicles a precise state-of-charge estimation for their lithium-ion batteries is desired to reduce aging, e.g. avoiding detrimental states-of-charge. Today, this estimation is performed by battery management systems that solely rely on charge bookkeeping and cell voltage measurements. In the present work we introduce a new, physical probe for the state-of-charge based on ultrasonic transmission. Within the simple experimental setup raised cosine pulses are applied to lithium-ion battery pouch cells, whose signals are sensitive to changes in porosity of the graphite anode during charging/dis-charging and, therefore, to the state-of-charge. The underlying physical principle can be related to Biot's theory about propagation of waves in fluid saturated porous media and by including scattering by boundary layers inside the cell.

  7. Universal bounds on charged states in 2d CFT and 3d gravity

    Energy Technology Data Exchange (ETDEWEB)

    Benjamin, Nathan; Dyer, Ethan [Stanford Institute for Theoretical Physics, Via Pueblo, Stanford, CA, 94305 (United States); Fitzpatrick, A. Liam [Boston University Physics Department, Commonwealth Avenue, Boston, MA, 02215 (United States); Kachru, Shamit [Stanford Institute for Theoretical Physics, Via Pueblo, Stanford, CA, 94305 (United States)

    2016-08-04

    We derive an explicit bound on the dimension of the lightest charged state in two dimensional conformal field theories with a global abelian symmetry. We find that the bound scales with c and provide examples that parametrically saturate this bound. We also prove that any such theory must contain a state with charge-to-mass ratio above a minimal lower bound. We comment on the implications for charged states in three dimensional theories of gravity.

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

    CERN Document Server

    Padmanath, M; Mathur, Nilmani; Peardon, Michael

    2013-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-07-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-12-15

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

  11. Terahertz spectra revealing the collective excitation mode in charge-density-wave single crystal LuFe{sub 2}O{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiumei; Jin, Zuanming; Lin, Xian; Ma, Guohong [Department of Physics, Shanghai University (China); Cheng, Zhenxiang [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW (Australia); Balakrishnan, Geetha [Department of Physics, University of Warwick, Coventry (United Kingdom)

    2017-09-15

    A low-energy collective excitation mode in charge-ordered multiferroic LuFe{sub 2}O{sub 4} is reported via terahertz time-domain spectroscopy. Upon cooling from 300 to 40 K, the central resonance frequency showed a pronounced hardening from 0.85 to 1.15 THz. In analogy to the well-known low-energy optical properties of LuFe{sub 2}O{sub 4}, this emerging resonance was attributed to the charge-density-wave (CDW) collective excitations. By using the Drude-Lorentz model fitting, the CDW collective mode becomes increasingly damped with the increasing temperature. Furthermore, the kinks of the CDW collective mode at the magnetic transition temperature are analyzed, which indicate the coupling of spin order with electric polarization. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Electron impact excitation of the D states of Mg, Ca and Sr atoms ...

    Indian Academy of Sciences (India)

    decay of the atom from D → P and then P → S) is required [3,7–9]. ... for the excitation of helium from its ground 1S state to the 3 1D state at 40 eV. We ..... Further, we use for the projectile electron distorted wave function. FDW i(f) the following relativistic form of partial wave expansion: F± ch,µch (kch, r) = 1. (2π)3/2 ∑ κm.

  13. Neutron correlations in the decay of the first excited state of {sup 11}Li

    Energy Technology Data Exchange (ETDEWEB)

    Smith, J.K., E-mail: jsmith@triumf.ca [National Superconducting Cyclotron Laboratory, East Lansing, MI 48824 (United States); Department of Physics, Michigan State University, East Lansing, MI 48824 (United States); Baumann, T.; Bazin, D. [National Superconducting Cyclotron Laboratory, East Lansing, MI 48824 (United States); Brown, J. [Department of Physics, Wabash College, Crawfordsville, IN 47933 (United States); DeYoung, P.A. [Department of Physics, Hope College, Holland, MI 49422 (United States); Frank, N. [Department of Physics and Astronomy, Augustana College, Rock Island, IL 61201 (United States); Jones, M.D. [National Superconducting Cyclotron Laboratory, East Lansing, MI 48824 (United States); Department of Physics, Michigan State University, East Lansing, MI 48824 (United States); Kohley, Z. [National Superconducting Cyclotron Laboratory, East Lansing, MI 48824 (United States); Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States); Luther, B. [Department of Physics, Concordia College, Moorhead, MN 56562 (United States); Marks, B. [Department of Physics, Hope College, Holland, MI 49422 (United States); Spyrou, A. [National Superconducting Cyclotron Laboratory, East Lansing, MI 48824 (United States); Department of Physics, Michigan State University, East Lansing, MI 48824 (United States); Stephenson, S.L. [Department of Physics, Gettysburg College, Gettysburg, PA 17325 (United States); Thoennessen, M. [National Superconducting Cyclotron Laboratory, East Lansing, MI 48824 (United States); Department of Physics, Michigan State University, East Lansing, MI 48824 (United States); Volya, A. [Department of Physics, Florida State University, Tallahassee, FL 32306 (United States)

    2016-11-15

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

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

    Science.gov (United States)

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

    2017-01-01

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

  15. Electronic, structural and optical properties of hydrogenated silicon nanocrystals: the role of the excited states

    Energy Technology Data Exchange (ETDEWEB)

    Cantele, G.; Ninno, D.; Iadonisi, G. [Coherentia-INFM and Universita di Napoli ' ' Federico II' ' - Dipartimento di Scienze Fisiche, Complesso Universitario Monte S. Angelo, Via Cintia, 80126 Napoli (Italy); Degoli, Elena; Bisi, O.; Ossicini, Stefano [INFM-S' ' 3 and Dipartimento di Scienze e Metodi dell' Ingegneria, Universita di Modena e Reggio Emilia, via Fogliani, 42100 Reggio Emilia (Italy); Luppi, Eleonora; Magri, Rita [INFM-S' ' 3 and Dipartimento di Fisica, Universita di Modena e Reggio Emilia, via Campi 213/A, 41100 Modena (Italy)

    2005-06-01

    In this paper we report on a first-principle calculation of the electronic and structural properties of hydrogenated silicon nanocrystals both in the ground- and in an excited-state configuration. The presence of an electron-hole pair created under excitation is taken into account and its effects on both the electronic spectrum and the cluster geometry are pointed out. The interpretation of the results is done within a four-level model, which also allows the explanation of the experimentally observed Stokes shift. Size-related aspects are also analysed and discussed. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    Directory of Open Access Journals (Sweden)

    Hermann Boos

    2011-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-11-07

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

  18. Excitation energy and spins of the Yrast superdeformed states in {sup 193}Tl; Energie d`excitation et spins des etats superdeformes Yrast de {sup 193}Tl

    Energy Technology Data Exchange (ETDEWEB)

    Bouneau, S.; Duprat, J.; Azaiez, F. [Experimental Research Division, Inst. de Physique Nucleaire, Paris-11 Univ., 91 - Orsay (France)] [and others

    1999-11-01

    Discrete {gamma}-rays of high energy connecting states of the two Yrast superdeformed bands in {sup 193}Tl to the normal deformed states have been identified. Thus, for the first time, in an odd SD nucleus, it has been possible to propose an excitation energy and spins of the two lowest bands. (authors) 3 refs., 2 figs.

  19. Depopulation of lowly excited ns-states of Rb colliding with the He atom

    Energy Technology Data Exchange (ETDEWEB)

    Verma, S.K. [Jagdam College, Chapra (India). Dept. of Physics; Khan, A.A. [ZAI College, Siwan (India). Dept. of Physics; Kumar, V. [Rajendra College, Chapra (India). Dept. of Physics; Kumar, A. [JP University, Chapra (India). Dept. of Physics

    1996-03-28

    A semiclassical impact-parameter method has been used to study the total depopulation of lowly excited ns-states of the Rb atom colliding with ground-state He in the thermal energy region. A fairly large basis set of STO has been used to generate MO states and then a 14-state calculation has been carried out to evaluate the total as well as individual cross sections for quenching. A comparative study with the previously investigated Li-He and Na-He pairs is also presented. (Author).

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

    Science.gov (United States)

    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.

  1. Doppler- and recoil-free laser excitation of Rydberg states via three-photon transitions

    Energy Technology Data Exchange (ETDEWEB)

    Ryabtsev, I. I.; Beterov, I. I.; Tretyakov, D. B.; Entin, V. M.; Yakshina, E. A. [A. V. Rzhanov Institute of Semiconductor Physics SB RAS, Prospekt Lavrentyeva 13, 630090 Novosibirsk (Russian Federation)

    2011-11-15

    Three-photon laser excitation of Rydberg states by three different laser beams can be arranged in a starlike geometry that simultaneously eliminates the recoil effect and Doppler broadening. Our analytical and numerical calculations for a particular laser excitation scheme 5S{sub 1/2}{yields}5P{sub 3/2}{yields}6S{sub 1/2}{yields}nP in Rb atoms have shown that, compared to the one- and two-photon laser excitation, this approach provides much narrower linewidth and longer coherence time for both cold atom samples and hot vapors, if the intermediate one-photon resonances of the three-photon transition are detuned by more than respective single-photon Doppler widths. This method can be used to improve fidelity of Rydberg quantum gates and precision of spectroscopic measurements in Rydberg atoms.

  2. Time-resolved study of excited states of N2 near its first ionization threshold

    Science.gov (United States)

    Moise, Angelica; Prince, Kevin C.; Richter, Robert

    2011-03-01

    Two-photon, two-color double-resonance ionization spectroscopy combining synchrotron vacuum ultraviolet radiation with a tunable near-infrared (NIR) laser has been used to investigate gerade symmetry states of the nitrogen molecule. The rotationally resolved spectrum of an autoionizing 1Σg- state has been excited via the intermediate c4 (v = 0) 1Πu Rydberg state. We present the analysis of the band located at Tv = 10 800.7 ± 2 cm-1 with respect to the intermediate state, 126 366 ± 11 cm-1 with respect to the ground state, approximately 700 cm-1 above the first ionization threshold. From the analysis a rotational constant of Bv = 1.700 ± 0.005 cm-1 has been determined for this band. Making use of the pulsed structure of the two radiation beams, lifetimes of several rotational levels of the intermediate state have been measured. We also report rotationally-averaged fluorescence lifetimes (300 K) of several excited electronic states accessible from the ground state by absorption of one photon in the range of 13.85-14.9 eV. The averaged lifetimes of the c4 (0) and c5 (0) states are 5.6 and 4.4 ns, respectively, while the b' (12), c'4 (4, 5, 6), and c'5 (0) states all have lifetimes in the range of hundreds of picoseconds.

  3. Charge-transfer excitations in low-gap systems under the influence of solvation and conformational disorder: Exploring range-separation tuning

    Science.gov (United States)

    de Queiroz, Thiago B.; Kümmel, Stephan

    2014-08-01

    Charge transfer excitations play a prominent role in the fields of molecular electronics and light harvesting. At the same time they have developed a reputation for being hard to predict with time-dependent density functional theory, which is the otherwise predominant method for calculating molecular structure and excitations. Recently, it has been demonstrated that range-separated hybrid functionals, in particular with an "optimally tuned" range separation parameter, describe charge-transfer excitations reliably for different molecules. Many of these studies focused on molecules in vacuum. Here we investigate the influence of solvation on the electronic excitations of thiophene oligomers, i.e., paradigm low gap systems. We take into account bulk solvation using a continuum solvation model and geometrical distortions from molecular dynamics. From our study, three main findings emerge. First, geometrical distortions increase absorption energies by about 0.5 eV for the longer thiophene oligomers. Second, combining optimal tuning of the range separation parameter with a continuum solvation method is not straightforward and has to be approached with great care. Third, optimally tuned range-separated hybrids without a short-range exchange component tend to inherit undesirable characteristics of semi-local functionals: with increasing system size the range separation parameter takes a smaller value, leading to a functional of effectively more semi-local nature and thus not accurately capturing, e.g., the saturation of the optical gap with increasing system size.

  4. Deterministic Electrical Charge-State Initialization of Single Nitrogen-Vacancy Center in Diamond

    Directory of Open Access Journals (Sweden)

    Y. Doi

    2014-03-01

    Full Text Available Apart from applications in classical information-processing devices, the electrical control of atomic defects in solids at room temperature will have a tremendous impact on quantum devices that are based on such defects. In this study, we demonstrate the electrical manipulation of individual prominent representatives of such atomic solid-state defects, namely, the negative charge state of single nitrogen-vacancy defect centers (NV^{−} in diamond. We experimentally demonstrate, deterministic, purely electrical charge-state initialization of individual NV centers. The NV centers are placed in the intrinsic region of a p-i-n diode structure that facilitates the delivery of charge carriers to the defect for charge-state switching. The charge-state dynamics of a single NV center were investigated by time-resolved measurements and a nondestructive single-shot readout of the charge state. Fast charge-state switching rates (from negative to neutrally charged defects, which are greater than 0.72 ± 0.10  μs^{−1}, were realized. Furthermore, in no-operation mode, the realized charge states were stable for presumably much more than 0.45 s. We believe that the results obtained are useful not only for ultrafast electrical control of qubits, long T_{2} quantum memory, and quantum sensors associated with single NV centers but also for classical memory devices based on single atomic storage bits working under ambient conditions.

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

    Science.gov (United States)

    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.

  6. Base sequence and higher-order structure induce the complex excited-state dynamics in DNA.

    Science.gov (United States)

    Schwalb, Nina K; Temps, Friedrich

    2008-10-10

    The high photostability of DNA is commonly attributed to efficient radiationless electronic relaxation processes. We used femtosecond time-resolved fluorescence spectroscopy to reveal that the ensuing dynamics are strongly dependent on base sequence and are also affected by higher-order structure. Excited electronic state lifetimes in dG-doped d(A)20 single-stranded DNA and dG.dC-doped d(A)20.d(T)20 double-stranded DNA decrease sharply with the substitution of only a few bases. In duplexes containing d(AGA).d(TCT) or d(AG).d(TC) repeats, deactivation of the fluorescing states occurs on the subpicosecond time scale, but the excited-state lifetimes increase again in extended d(G) runs. The results point at more complex and molecule-specific photodynamics in native DNA than may be evident in simpler model systems.

  7. Measurement of the excited-state transverse hyperfine coupling in NV centers via dynamic nuclear polarization

    Science.gov (United States)

    Poggiali, F.; Cappellaro, P.; Fabbri, N.

    2017-05-01

    Precise knowledge of a quantum system's Hamiltonian is a critical pre-requisite for its use in many quantum information technologies. Here, we report a method for the precise characterization of the nonsecular part of the excited-state Hamiltonian of an electronic-nuclear spin system in diamond. The method relies on the investigation of the dynamic nuclear polarization mediated by the electronic spin, which is currently exploited as a primary tool for initializing nuclear qubits and performing enhanced nuclear magnetic resonance. By measuring the temporal evolution of the population of the ground-state hyperfine levels of a nitrogen-vacancy center, we obtain the first direct estimation of the excited-state transverse hyperfine coupling between its electronic and nitrogen nuclear spin. Our method could also be applied to other electron-nuclear spin systems, such as those related to defects in silicon carbide.

  8. Contribution of the 4f-core-excited states in determination of atomic properties in the promethium isoelectronic sequence

    Science.gov (United States)

    Safronova, U. I.; Safronova, A. S.; Beiersdorfer, P.

    2013-09-01

    The atomic properties of Pm-like ions were comprehensively studied using relativistic atomic codes. Excitation energies of the 4f14nl (with nl=5s, 6s, 5p, 6p, 5d, 6d, and 5f) states in Pm-like ions with nuclear charge Z ranging from 74 to 100 are evaluated within the framework of relativistic many-body theory (RMBPT). First- and second-order Coulomb energies and first- and second-order Breit corrections to the energies are calculated. Two alternative treatments of the Breit interaction are investigated. In the first approach we omit Breit contributions to the Dirac-Fock potential and evaluate Coulomb and Breit-Coulomb corrections through second order perturbatively. In the second approach were included both Coulomb and Breit contributions on the same footing via the Breit-Dirac-Fock potential and then treat the residual Breit and Coulomb interactions perturbatively. The results obtained from the two approaches are compared and discussed. The important question of what is the ground state in Pm-like ions was answered. Properties of the 4f-core-excited states are evaluated using the multiconfiguration relativistic Hebrew University Lawrence Livermore atomic code (hullac code) and the Hartree-Fock-relativistic method (cowan code). We evaluate excitation energies and transition rates in Pm-like ions with nuclear charge Z ranging from 74 to 92. Our large scale calculations include the following set of configurations: 4f145s, 4f145p, 4f135s2, 4f135p2, 4f135s5p, 4f125s25p, 4f125s5p2, and 4f125p3. Trends of excitation energies as function of Z are shown graphically for selected states. Excitation energies, transition rates, and lifetimes in Pm-like tungsten are evaluated with additional inclusion of the 4f115s25p2, 4f115s5p3, 4f105s25p3, and 4f105s5p4 configurations. This represents an unusual example of an atomic system where the even-parity complex [4f145s+4f135s5p+4f125s5p2+4f115s5p3+4f105s5p4] and the odd-parity complex [4f145p+4f135s2+4f125s25p+4f115s25p2+4f105s25p3

  9. Resonant coherent excitation of channeled ions

    Energy Technology Data Exchange (ETDEWEB)

    Datz, S.; Moak, C.D.; Crawford, O.H.; Krause, H.F.; Dittner, P.F.; Gomez del Campo, J.; Biggerstaff, J.A.; Miller, P.D.; Hvelplund, P.; Knudsen, H.

    1978-03-27

    We have observed resonant excitation of swift channeled hydrogenlike ions (Z = 5 to Z = 9) and heliumlike F/sup 7 +/ which arises from a coherent periodic perturbation by the atoms in the bounding crystal rows. The resonance excitation was seen through the reduction in the transmission of fixed-charge-state ions through channels in thin crystals of Au and Ag.

  10. Switching of the triplet excited state of rhodamine/naphthaleneimide dyads: an experimental and theoretical study.

    Science.gov (United States)

    Cui, Xiaoneng; Zhao, Jianzhang; Lou, Zhangrong; Li, Shujing; Wu, Huijian; Han, Ke-Li

    2015-01-02

    Rhodamine-bromonaphthaleneimide (RB-NI) and rhodamine-bromonaphthalenediimide (RB-NDI) dyads were prepared for switching of the triplet excited states. Bromo-NI or bromo-NDI parts in the dyads are the spin converters, i.e., the triplet state producing modules, whereas the RB unit is the acid-activatable electron donor/energy acceptor. NI and NDI absorb at 359 and 541 nm, and the T1 state energy levels are 2.25 and 1.64 eV, respectively. RB undertakes the reversible spirolactam (RB-c) ↔ opened amide (RB-o) transformation. RB-c shows no visible light absorption, and the triplet-state energy level is ET1 = 3.36 eV. Conversely RB-o shows strong absorption at 557 nm, and ET1 is 1.73 eV. Thus, the acid-activated fluorescence-resonance-energy-transfer (FRET) competes with the ISC of NI or NDI. No triplet state was observed for the dyads with nanosecond time-resolved transient absorption spectroscopy. Upon addition of acid, strong fluorescence and long-living triplet excited states were observed. Thus, the producing of triplet state is acid-activatable. The triplet state of RB-NI is localized on RB-o part, whereas in RB-NDI the triplet state is delocalized on both the NDI and RB-o units. The ISC of spin converter was not outcompeted by RET. These studies are useful for switching of triplet excited state.

  11. Radius of {sup 12}C in the excited 2{sub 2} {sup +} Hoyle state

    Energy Technology Data Exchange (ETDEWEB)

    Ogloblin, A.A.; Danilov, A.N.; Demyanova, A.S. [RRC Kurchatov Institute, Moscow (Russian Federation); Belyaeva, T.L. [Universidad Autonoma del Estado de Mexico, C.P. 50000, Toluca (Mexico); Goncharov, S.A. [Lomonosov Moscow State University, Moscow (Russian Federation)

    2013-04-15

    The differential cross sections of the inelastic {alpha} + {sup 12}C scattering leading to the excitation of the short-lived 2{sub 2} {sup +} (E{sub x} = 9.84 or 9.6 MeV) state in {sup 12}C have been analysed within a modified diffraction model. We determined the diffraction radii of {sup 12}C in this excited state at E{sub {alpha}} = 386 and 240 MeV and compared them with the diffraction radius for the 0{sub 2} {sup +} (E{sub x} = 7.65 MeV) Hoyle state. We found that the rms radii for the 2{sub 2} {sup +} state is left angle R(2{sub 2} {sup +}) right angle = 3.07 {+-} 0.13fm, which agrees well with the rms radius of the 0{sub 2} {sup +}, 7.65 MeV Hoyle state and is a factor of 1.3 larger than the rms radius for the ground state of {sup 12}C. The similarity between the rms radii of the 0{sub 2} {sup +} and 2{sub 2} {sup +} states provides a strong argument in favor of a hypothesis that the 2{sub 2} {sup +} state is the first member of a rotational band based on the 0{sub 2} {sup +} Hoyle state. (orig.)

  12. Characterising excited states in and around the semi-magic nucleus $^{68}$ Ni using Coulomb excitation and one-neutron transfer

    CERN Multimedia

    It is proposed to investigate the structure of excited states in $^{68, 70}$Ni(Z =28, N=40, 42) via the measurement of electromagnetic matrix elements in a Coulomb excitation experiment in order to study the N = 40 harmonic-oscillator shell and the Z = 28 proton shell closures. The measured B(E2) values connecting low-lying 0$^{+}$ and 2$^{+}$ can be compared to shell-model predictions. It is also proposed to perform the one-neutron transfer reaction ${d}$($^{68}$Ni,$^{69}$Ni)${p}$, with the aim of populating excited states in $^{69}$Ni. Comparisons with the states populated in the recently performed ${d}$($^{66}$Ni,$^{67}$Ni)${p}$ reaction will be useful in determining the role of the neutron $d_{5/2}$ orbital in the semi-magic properties of $^{68}$Ni.

  13. State of charge monitoring methods for vanadium redox flow battery control

    Science.gov (United States)

    Skyllas-Kazacos, Maria; Kazacos, Michael

    2011-10-01

    During operation of redox flow batteries, differential transfer of ions and electrolyte across the membrane and gassing side reactions during charging, can lead to an imbalance between the two half-cells that results in loss of capacity. This capacity loss can be corrected by either simple remixing of the two solutions, or by chemical or electrochemical rebalancing. In order to develop automated electrolyte management systems therefore, the state-of-charge of each half-cell electrolyte needs to be known. In this study, two state-of-charge monitoring methods are investigated for use in the vanadium redox flow battery. The first method utilizes conductivity measurements to independently measure the state-of-charge of each half-cell electrolyte. The second method is based on spectrophotometric principles and uses the different colours of the charged and discharged anolyte and catholyte to monitor system balance and state-of charge of each half-cell of the VRB during operation.

  14. State of charge classification for lithium-ion batteries using impedance based features

    Directory of Open Access Journals (Sweden)

    M. P. Felder

    2017-09-01

    Full Text Available Currently, the electrification of the drive train of passenger cars takes place, and the task of obtaining precise knowledge about the condition of the on board batteries gains importance. Due to a flat open circuit voltage (OCV to state of charge (SoC characteristic of lithium ion batteries, methods employed in applications with other cell chemistries cannot be adapted. Exploiting the higher significance of the impedance for state estimation for that chemistry, new impedance based features are proposed by this work. To evaluate the suitability of these features, simulations have been conducted using a simplified on-board power supply net as excitation source. The simulation outcome has been investigated regarding the cross correlation factor rxy and in a polynomial regression scenario. The results of the simulations show a best case error below 1 % SoC, which is 3 percentage points lower than using terminal voltage and impedance. When increasing the measurement uncertainty, the difference remains around 2 percent points.

  15. Attaching naphthalene derivatives onto BODIPY for generating excited triplet state and singlet oxygen: Tuning PET-based photosensitizer by electron donors

    Science.gov (United States)

    Zhang, Xian-Fu; Feng, Nan

    2018-01-01

    meso-Naphthalene substituted BODIPY compounds were prepared in a facile one pot reaction. The naphthalene functionalization of BODIPY leads up to a 5-fold increase in the formation efficiency of excited triplet state and singlet oxygen in polar solvents. Steady state and time resolved fluorescence, laser flash photolysis, and quantum chemistry methods were used to reveal the mechanism. All measured data and quantum chemical results suggest that these systems can be viewed as electron donor-acceptor (D-A) pair (BODIPY acts as the acceptor), photoinduced charge transfer (PCT) or photoinduced electron transfer (PET) occurs upon photo excitation (D-A + hν → Dδ +-Aδ -, 0 PET-based photosensitizers (PSs) show different features from traditional PSs, such as the strong tunability by facile structural modification and good selectivity upon medium polarity. The new character for this type of PSs can lead to important applications in organic oxygenation reactions and photodynamic therapy of tumors.

  16. Phonon-like excitations in the two-state Bose-Hubbard model

    Directory of Open Access Journals (Sweden)

    I.V. Stasyuk

    2015-12-01

    Full Text Available The spectrum of phonon-like collective excitations in the system of Bose-atoms in optical lattice (more generally, in the system of quantum particles described by the Bose-Hubbard model is investigated. Such excitations appear due to displacements of particles with respect to their local equilibrium positions. The two-level model taking into account the transitions of bosons between the ground state and the first excited state in potential wells, as well as interaction between them, is used. Calculations are performed within the random phase approximation in the hard-core boson limit. It is shown that excitation spectrum in normal phase consists of the one exciton-like band, while in the phase with BE condensate an additional band appears. The positions, spectral weights and widths of bands strongly depend on chemical potential of bosons and temperature. The conditions of stability of a system with respect to the lowering of symmetry and displacement modulation are discussed.

  17. Determination of the excitation migration time in Photosystem II - Consequences for the membrane organization and charge separation parameters

    NARCIS (Netherlands)

    Broess, Koen; Trinkunas, Gediminas; van Hoek, Arie; Croce, Roberta; van Amerongen, Herbert

    The fluorescence decay kinetics of Photosystem II (PSII) membranes from spinach with open reaction centers (RCs), were compared after exciting at 420 and 484 nm. These wavelengths lead to preferential excitation of chlorophyll (Chl) a and Chl b, respectively, which causes different initial

  18. Beyond Time-Dependent Density Functional Theory Using Only Single Excitations: Methods for Computational Studies of Excited States in Complex Systems.

    Science.gov (United States)

    Herbert, John M; Zhang, Xing; Morrison, Adrian F; Liu, Jie

    2016-05-17

    Single-excitation methods, namely, configuration interaction singles and time-dependent density functional theory (TDDFT), along with semiempirical versions thereof, represent the most computationally affordable electronic structure methods for describing electronically excited states, scaling as [Formula: see text] absent further approximations. This relatively low cost, combined with a treatment of electron correlation, has made TDDFT the most widely used excited-state quantum chemistry method over the past 20+ years. Nevertheless, certain inherent problems (beyond just the accuracy of this or that exchange-correlation functional) limit the utility of traditional TDDFT. For one, it affords potential energy surfaces whose topology is incorrect in the vicinity of any conical intersection (CI) that involves the ground state. Since CIs are the conduits for transitions between electronic states, the TDDFT description of photochemistry (internal conversion and intersystem crossing) is therefore suspect. Second, the [Formula: see text] cost can become prohibitive in large systems, especially those that involve multiple electronically coupled chromophores, for example, the antennae structures of light-harvesting complexes or the conjugated polymers used in organic photovoltaics. In such cases, the smallest realistic mimics might already be quite large from the standpoint of ab initio quantum chemistry. This Account describes several new computational methods that address these problems. Topology around a CI can be rigorously corrected using a "spin-flip" version of TDDFT, which involves an α → β spin-flipping transition in addition to occupied → virtual excitation of one electron. Within this formalism, singlet states are generated via excitation from a high-spin triplet reference state, doublets from a quartet, etc. This provides a more balanced treatment of electron correlation between ground and excited states. Spin contamination is problematic away from the

  19. Role of the charge transfer state in organic donor-acceptor solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Deibel, Carsten; Strobel, Thomas [Experimental Physics VI, Julius-Maximilians-University of Wuerzburg (Germany); Dyakonov, Vladimir [Experimental Physics VI, Julius-Maximilians-University of Wuerzburg (Germany); Bavarian Centre for Applied, Energy Research (ZAE Bayern), Wuerzburg (Germany)

    2010-10-01

    Charge transfer complexes are interfacial charge pairs residing at the donor-acceptor heterointerface in organic solar cell. Experimental evidence shows that it is crucial for the photovoltaic performance, as both photocurrent and open circuit voltage directly depend on it. For charge photogeneration, charge transfer complexes represent the intermediate but essential step between exciton dissociation and charge extraction. Recombination of free charges to the ground state is via the bound charge transfer state before being lost to the ground state. In terms of the open circuit voltage, its maximum achievable value is determined by the energy of the charge transfer state. An important question is whether or not maximum photocurrent and maximum open circuit voltage can be achieved simultaneously. The impact of increasing the CT energy - in order to raise the open circuit voltage, but lowering the kinetic excess energy of the CT complexes at the same time - on the charge photogeneration will accordingly be discussed. Clearly, the fundamental understanding of the processes involving the charge transfer state is essential for an optimisation of the performance of organic solar cells. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  20. Lowest excited states and optical absorption spectra of donor–acceptor copolymers for organic photovoltaics: a new picture emerging from tuned long-range corrected density functionals

    KAUST Repository

    Pandey, Laxman

    2012-01-01

    Polymers with low optical gaps are of importance to the organic photovoltaics community due to their potential for harnessing a large portion of the solar energy spectrum. The combination along their backbones of electron-rich and electron-deficient fragments contributes to the presence of low-lying excited states that are expected to display significant charge-transfer character. While conventional hybrid functionals are known to provide unsatisfactory results for charge-transfer excitations at the time-dependent DFT level, long-range corrected (LRC) functionals have been reported to give improved descriptions in a number of systems. Here, we use such LRC functionals, considering both tuned and default range-separation parameters, to characterize the absorption spectra of low-optical-gap systems of interest. Our results indicate that tuned LRC functionals lead to simulated optical-absorption properties in good agreement with experimental data. Importantly, the lowest-lying excited states (excitons) are shown to present a much more localized nature than initially anticipated. © 2012 the Owner Societies.

  1. Up-Conversion Intersystem Crossing Rates in Organic Emitters for Thermally Activated Delayed Fluorescence: Impact of the Nature of Singlet vs Triplet Excited States

    KAUST Repository

    Samanta, Pralok Kumar

    2017-02-28

    The rates for up-conversion intersystem crossing (UISC) from the T1 state to the S1 state are calculated for a series of organic emitters with an emphasis on thermally activated delayed fluorescence (TADF) materials. Both the spin-orbit coupling and the energy difference between the S1 and T1 states (ΔEST) are evaluated, at the density functional theory (DFT) and time-dependent DFT levels. The calculated UISC rates and ΔEST values are found to be in good agreement with available experimental data. Our results underline that small ΔEST values and sizable spin-orbit coupling matrix elements have to be simultaneously realized in order to facilitate UISC and ultimately TADF. Importantly, the spatial separation of the highest occupied and lowest unoccupied molecular orbitals of the emitter, a widely accepted strategy for the design of TADF molecules, does not necessarily lead to a sufficient reduction in ΔEST; in fact, either a significant charge-transfer (CT) contribution to the T1 state or a minimal energy difference between the local-excitation and charge-transfer triplet states is required to achieve a small ΔEST. Also, having S1 and T1 states of a different nature is found to strongly enhance spin-orbit coupling, which is consistent with the El-Sayed rule for ISC rates. Overall, our results indicate that having either similar energies for the local-excitation and charge-transfer triplet states or the right balance between a substantial CT contribution to T1 and somewhat different natures of the S1 and T1 states, paves the way toward UISC enhancement and thus TADF efficiency improvement.

  2. Probing ground and low-lying excited states for HIO{sub 2} isomers

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Gabriel L. C. de [Departamento de Química, Universidade Federal de Mato Grosso, Cuiabá, Mato Grosso 78060-900 (Brazil); Instituto de Ciências Exatas e Tecnologia, Universidade Federal do Amazonas, Itacoatiara, Amazonas 69100-000 (Brazil); Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada); Brown, Alex, E-mail: alex.brown@ualberta.ca [Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada)

    2014-12-21

    We present a computational study on HIO{sub 2} molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10{sup −3})

  3. Pulsed excitation of Rydberg-atom-pair states in an ultracold Cs gas

    CERN Document Server

    Saßmannshausen, Heiner; Deiglmayr, Johannes

    2015-01-01

    Pulsed laser excitation of a dense ultracold Cs vapor has been used to study the pairwise interactions between Cs atoms excited to $n$p$_{3/2}$ Rydberg states of principal quantum numbers in the range $n=22-36$. Molecular resonances were observed that correspond to excitation of Rydberg-atom-pair states correlated not only to the $n$p$_{3/2}+n$p$_{3/2}$ dissociation asymptotes, but also to $n$s$_{1/2}+(n+1)$s$_{1/2}$, $n$s$_{1/2}+n'$f$_{j}$, and $(n-4)$f$_{j}+(n-3)$f$_{j}$ $(j=5/2,7/2)$ dissociation asymptotes. These pair resonances are interpreted as arising from dipole-dipole, and higher long-range-interaction terms between the Rydberg atoms on the basis of i) their spectral positions, ii) their response to static and pulsed electric fields, and iii) millimeter-wave spectra between pair states correlated to different pair-dissociation asymptotes. The Rydberg-atom--pair states were found to spontaneously decay by Penning ionization and the dynamics of the ionization process were investigated during the first...

  4. Reactions of excited states of phenoxazin-3-one dyes with amino acids.

    Science.gov (United States)

    Villegas, M L; Bertolotti, S G; Previtali, C M; Encinas, M V

    2005-01-01

    The interaction with amino acids of the excited states of the N-oxide resazurin and its deoxygenation product resorufin, has been studied in aqueous solution at pH 7.5. Steady-state and time-resolved studies show that the fluorescence is quenched by amino acids. Complexation of the dyes in the ground state with aromatic amino acids was also observed. The singlet quenching is attributed to electron transfer from the amino acids to the excited dye based on the dependence of the bimolecular rate constants with the ionization potential of quenchers. Flash photolysis experiments allowed determination of the quenching rate constants for the triplet deactivation of dyes by several amino acids, as well as the characterization of the transients formed in the process. These data show that the triplet is also deactivated by an electron transfer process. However, the deactivation of the N-oxide dye by tryptophan can be described by a hydrogen atom transfer. The protolytic dissociation constants of the dye radical ions are reported. The irradiation of rezasurin in the presence of amino acids leads to deoxygenation of the dye to give resorufin. This process involves the triplet excited state of resazurin and is efficient only in the presence of amino acids containing the -SH group.

  5. Unbound Excited States of the N = 16 Closed Shell Nucleus 24O

    Science.gov (United States)

    Rogers, W. F.; MoNA Collaboration

    2015-10-01

    The energies of two low-lying neutron-unbound excited states of 24O, which were populated by proton-knockout reactions on 26F, have been measured using the MoNA and LISA arrays in combination with the Sweeper Magnet at the Coupled Cyclotron Facility at the NSCL using invariant mass spectroscopy. The current measurement confirms for the first time the separate identity of 2+ and (1+) neutron-unbound excited states in 24O with decay energies 0.51(5) MeV state and 1.20(7) MeV, respectively, to the 23O ground state. These measured decay energies are consistent with two previous lower resolution measurements to within 2 σ. The level energies for the two states are computed using the decay energies and the 1-neutron separation energy for 24O, resulting in 4.70(15) MeV for the 2+ state and 5.39(16) MeV for the (1+) state. Errors in the level energies are dominated by uncertainty in the 24O neutron separation energy, underscoring the need for a higher resolution 24O ground state mass measurement. Results will be compared with 3 phenomenological and 2 ab initio model calculations. Work Supported by NSF Grants PHY-0922335, PHY-0922409, PHY-0922446, PHY-0922462, PHY-0922473, PHY-0922537, PHY-0922559, PHY-0922622, PHY-0922794, PHY-0969173, PHY-1101745, PHY-1205357, PHY- 1205537.

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

    CSIR Research Space (South Africa)

    de Clercq, L

    2010-09-01

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

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

    CSIR Research Space (South Africa)

    De Clercq, L

    2010-09-01

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

  8. Battery Management Systems: Accurate State-of-Charge Indication for Battery-Powered Applications

    NARCIS (Netherlands)

    Pop, V.; Bergveld, H.J.; Danilov, D.; Regtien, Paulus P.L.; Notten, P.H.L.

    2008-01-01

    Battery Management Systems – Universal State-of-Charge indication for portable applications describes the field of State-of-Charge (SoC) indication for rechargeable batteries. With the emergence of battery-powered devices with an increasing number of power-hungry features, accurately estimating the

  9. A Score Function for State of Charge Profiles for Rechargeable Batteries

    NARCIS (Netherlands)

    Ramsgaard Wognsen, Erik; Jongerden, M.R.; Haverkort, Boudewijn R.H.M.

    2015-01-01

    We propose a new score function to compare and evaluate the relative impact of state-of-charge profiles on overall battery lifetime. Our score function, based on on a discrete Fourier transform of the state-of-charge profile, formalizes and generalizes earlier ideas found in the literature, and can

  10. Argon charge states due to impact of H+ and He+ ions

    Science.gov (United States)

    Oona, H.

    1974-01-01

    Charge states of argon produced by bombardment with 100-keV to 1-MeV H+ and He+ projectiles were studied by examining high-resolution L-shell X-ray satellite spectra. Large differences appear in charge-state populations determined from X-ray data and Auger-electron data.-

  11. Relaxation of vibrationally excited states in solid "nitrate-nitrite" binary systems

    Science.gov (United States)

    Aliev, A. R.; Akhmedov, I. R.; Kakagasanov, M. G.; Aliev, Z. A.; Gafurov, M. M.; Rabadanov, K. Sh.; Amirov, A. M.

    2017-10-01

    The processes of molecular relaxation in the solid NaNO3-NaNO2 and KNO3-KNO2 "nitrate-nitrite" binary systems have been investigated by Raman spectroscopy. The relaxation time of the vibration ν1(A) of an NO- 3 anion in the binary system is found to be shorter than that in individual nitrate. The increase in the relaxation rate is explained by the existence of an additional mechanism of relaxation of vibrationally excited states of the nitrate ion in the system. This mechanism is related to the excitation of vibration of another anion (NO- 2) and generation of a lattice phonon. It has been established that this relaxation mechanism is implemented provided that the difference between the frequencies of the aforementioned vibrations correspond to the range of sufficiently high density of states in the phonon spectrum.

  12. Importance of local exact exchange potential in hybrid functionals for accurate excited states

    CERN Document Server

    Kim, Jaewook; Hwang, Sang-Yeon; Ryu, Seongok; Choi, Sunghwan; Kim, Woo Youn

    2016-01-01

    Density functional theory has been an essential analysis tool for both theoretical and experimental chemists since accurate hybrid functionals were developed. Here we propose a local hybrid method derived from the optimized effective potential (OEP) method and compare its distinct features with conventional nonlocal ones from the Hartree-Fock (HF) exchange operator. Both are formally exact for ground states and thus show similar accuracy for atomization energies and reaction barrier heights. For excited states, the local version yields virtual orbitals with N-electron character, while those of the nonlocal version have mixed characters between N- and (N+1)-electron orbitals. As a result, the orbital energy gaps from the former well approximate excitation energies with a small mean absolute error (MAE = 0.40 eV) for the Caricato benchmark set. The correction from time-dependent density functional theory with a simple local density approximation kernel further improves its accuracy by incorporating multi-config...

  13. On large amplitude motions of simplest amides in the ground and excited electronic states

    Science.gov (United States)

    Tukachev, N. V.; Bataev, V. A.; Godunov, I. A.

    2017-01-01

    For the formamide, acetamide, N-methylformamide and N-methylacetamide molecules in the ground (S0) and lowest excited singlet (S1) and triplet (T1) electronic states equilibrium geometry parameters, harmonic vibrational frequencies, barriers to conformational transitions and conformer energy differences were estimated by means of MP2, CCSD(T), CASSCF, CASPT2 and MRCI ab initio methods. One-, two- and three-dimensional potential energy surface (PES) sections corresponding to different large amplitude motions (LAM) were calculated by means of MP2/aug-cc-pVTZ (S0) and CASPT2/cc-pVTZ (S1,T1). For these molecules, in each excited electronic state six minima were found on 2D PES sections. Using PES sections, different anharmonic vibrational problems were solved and the frequencies of large amplitude vibrations were determined.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cejnar, Pavel; Stránský, Pavel, E-mail: stransky@ipnp.troja.mff.cuni.cz

    2017-03-18

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

  15. On large amplitude motions of simplest amides in the ground and excited electronic states

    Directory of Open Access Journals (Sweden)

    Tukachev N.V.

    2017-01-01

    Full Text Available For the formamide, acetamide, N-methylformamide and N-methylacetamide molecules in the ground (S0 and lowest excited singlet (S1 and triplet (T1 electronic states equilibrium geometry parameters, harmonic vibrational frequencies, barriers to conformational transitions and conformer energy differences were estimated by means of MP2, CCSD(T, CASSCF, CASPT2 and MRCI ab initio methods. One-, two- and three-dimensional potential energy surface (PES sections corresponding to different large amplitude motions (LAM were calculated by means of MP2/aug-cc-pVTZ (S0 and CASPT2/cc-pVTZ (S1,T1. For these molecules, in each excited electronic state six minima were found on 2D PES sections. Using PES sections, different anharmonic vibrational problems were solved and the frequencies of large amplitude vibrations were determined.

  16. Influence of argon and oxygen on charge-state-resolved ion energydistributions of filtered aluminum arcs

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, Johanna; Anders, Andre; Mraz, Stanislav; Atiser, Adil; Schneider, Jochen M.

    2006-03-23

    The charge-state-resolved ion energy distributions (IEDs) in filtered aluminum vacuum arc plasmas were measured and analyzed at different oxygen and argon pressures in the range 0.5 8.0 mTorr. A significant reduction of the ion energy was detected as the pressure was increased, most pronounced in an argon environment and for the higher charge states. The corresponding average charge state decreased from 1.87 to 1.0 with increasing pressure. The IEDs of all metal ions in oxygen were fitted with shifted Maxwellian distributions. The results show that it is possible to obtain a plasma composition with a narrow charge-state distribution as well as a narrow IED. These data may enable tailoring thin-film properties through selecting growth conditions that are characterized by predefined charge state and energy distributions.

  17. Two-neutrino double β decay of 96Zr to excited 2+ state of 96Mo

    Indian Academy of Sciences (India)

    pp. 517–522. Two-neutrino double β decay of 96Zr to excited. 2+ state of 96Mo. J SINGH1, R CHANDRA1, P K RAINA2 and P K RATH1. 1Department of Physics, University of Lucknow, Lucknow 226 007, India. 2Department of Physics, Indian Institute of Technology, Kharagpur 721 302, India. E-mail: pkrath lu@yahoo.co.in.

  18. Formation of H-atom in 2s excited state of proton-lithium and proton ...

    Indian Academy of Sciences (India)

    Abstract. The differential and total cross-sections have been investigated in the forma- tion of H-atom in the 2s excited state of proton-lithium and proton-sodium scattering by using the Coulomb projected Born (CPB) approximation in the energy range from 50 to. 10,000 keV. The results thus obtained are compared with the ...

  19. Determination of the Excited State Density Distribution within a Nonequilibrium, Freely Expanding Argon Arcjet Plume

    Science.gov (United States)

    1977-03-01

    transport problem for the radially dependent number densi- ties is required. The details of this inversion technique, based upon an " onion peel... chat of the arcJeC. The reference signal from the chopper and the preampllfled photomultlpller cube output signal were input to a PAR ® synchronous...condition for equilibrium with the free electron density and thus shows Chat the four lowest excited states are demonstrably nonequllibrium and lie

  20. The Microwave Spectroscopy of HCOO^{13}CH_3 in the Second Torsional Excited State

    Science.gov (United States)

    Kobayashi, Kaori; Kuwahara, Takuro; Urata, Yuki; Ohashi, Nobukimi; Fujitake, Masaharu

    2017-06-01

    Methyl formate (HCOOCH_3) is an abundant interstellar molecule, found almost everywhere in the star-forming region. The interstellar abundance of the ^{13}C is about 1/50 of ^{12}C. The ^{13}C substituted methyl formate in the ground and first excited states were already found toward massive star-forming regions including Orion KL. With the aid of the state-of-the-art telescope like ALMA, the pure rotational transitions in the second torsional excited may be identified in the near future and laboratory data are necessary. We recorded the spectra of HCOOCH_3 below 340 GHz by using conventional source-modulation microwave spectrometer. The assignment of the pure rotational spectra in the second torsional excited state and the analysis by using pseudo-PAM Hamiltonian, which was effective to analyze the normal species, will be reported. C. Favre, M. Carvajal, D. Field, J. K. Jørgensen, S. E. Bisschop, N. Brouillet, D. Despois, A. Baudry, I. Kleiner, E. A. Bergin, N. R. Crockett, J. L. Neill, L. Marguès, T. R. Huet, and J. Demaison, Astrophys. J. Suppl. Ser. 215, 25 (2014).

  1. Excited-State Interaction of Semiconducting Single-Walled Carbon Nanotubes with Their Wrapping Polymers.

    Science.gov (United States)

    Kahmann, Simon; Salazar Rios, Jorge M; Zink, Matthias; Allard, Sybille; Scherf, Ullrich; Dos Santos, Maria C; Brabec, Christoph J; Loi, Maria A

    2017-11-16

    We employ photoluminescence and pump-probe spectroscopy on films of semiconducting single-walled carbon nanotubes (CNTs) of different chirality wrapped with either a wide band gap polyfluorene derivative (PF12) or a polythiophene with narrower gap (P3DDT) to elucidate the excited states' interplay between the two materials. Excitation above the polymer band gap gives way to an ultrafast electron transfer from both polymers toward the CNTs. By monitoring the hole polaron on the polymer via its mid infrared signature, we show that also illumination below the polymer band gap leads to the formation of this fingerprint and infer that holes are also transferred toward the polymer. As this contradicts the standard way of discussing the involved energy levels, we propose that polymer-wrapped CNTs should be considered as a single hybrid system, exhibiting states shared between the two components. This proposition is validated through quantum chemical calculations that show hybridization of the first excited states, especially for the thiophene-CNT sample.

  2. Discrete charge states in nanowire flash memory with multiple Ta2O5 charge-trapping stacks

    Science.gov (United States)

    Zhu, Hao; Bonevich, John E.; Li, Haitao; Richter, Curt A.; Yuan, Hui; Kirillov, Oleg; Li, Qiliang

    2014-06-01

    In this work, multi-bit flash-like memory cell based on Si nanowire field-effect transistor and multiple Ta2O5 charge-trapping stacks have been fabricated and fully characterized. The memory cells exhibited staircase, discrete charged states at small gate voltages. Such discrete multi-bit on one memory cell is attractive for high memory density. These non-volatile memory devices exhibited fast programming/erasing speed, excellent retention, and endurance, indicating the advantages of integrating the multilayer of charge-storage stacks on the nanowire channel. Such high-performance flash-like non-volatile memory can be integrated into the microprocessor chip as the local memory which requires high density and good endurance.

  3. Storage battery operation technique of photovoltaic system to prevent the imbalance of state of charge

    Science.gov (United States)

    Kobayashi, Hirotake; Takigawa, Kiyoshi; Takeda, Yukihiro

    For the large scale storage battery system of a MW class photovoltaic system, simulation analyses were conducted to prevent the imbalance of state of charge. Effects of the charge and discharge I-V characteristics dispersion of individual storage battery on the dispersion of state of charge were elucidated through these analyses. Furthermore, a proper operation method to prevent the imbalance of state of charge was investigated. In the internal resistance and the electromotive voltage which determines the charge and discharge I-V characteristics, when the dispersion is found in the electromotive voltage in particular, the dispersion of state of charge gets larger. The electromotive voltage of storage battery depends on the specific gravity of electrolyte. Consequently, in order to prevent the imbalance of state of charge, it is important to control the specific gravity. For operating the system effectively preventing the imbalance of state of charge, the specific gravity should be controlled within (+ or -) 0.3 percent of approximate mean value.

  4. Equation of Motion Theory for Excited States in Variational Monte Carlo and the Jastrow Antisymmetric Geminal Power in Hilbert Space.

    Science.gov (United States)

    Zhao, Luning; Neuscamman, Eric

    2016-08-09

    An equation of motion formalism for excited states in variational Monte Carlo is derived, and a pilot implementation for the Jastrow-modified antisymmetric geminal power is tested. In single excitations across a range of small molecules, this combination is shown to be intermediate in accuracy between configuration interaction singles and equation of motion coupled cluster with singles and doubles. For double excitations, energy errors are found to be similar to those for coupled cluster.

  5. Excitation of the 3p states in electron-sodium scattering at intermediate energies

    Science.gov (United States)

    Kamali, M. Z. M.; Wong, B. R.; Chin, J. H.; Ratnavelu, K.

    2014-03-01

    A coupled-channel-optical method (CCOM), to investigate the excitation of the 3p states for e--Na scattering at intermediate energies, is reported. Nine atomic states( Na(3s), Na(3p), Na(4s), Na(3d), Na(4p), Na(5s), Na(4d), Na(5p), Na(5d) ) together with three optical potentials are used in this work. The inelastic differential cross sections (DCS) as well as the reduced Stokes parameters are compared with latest theoretical data and experimental measurements.

  6. Relative entropy of excited states in conformal field theories of arbitrary dimensions

    Energy Technology Data Exchange (ETDEWEB)

    Sárosi, Gábor [Theoretische Natuurkunde, Vrije Universiteit Brussels and International Solvay Institutes,Pleinlaan 2, Brussels, B-1050 (Belgium); David Rittenhouse Laboratory, University of Pennsylvania,Philadelphia, PA 19104 (United States); Ugajin, Tomonori [Kavli Institute for Theoretical Physics, University of California, Santa Barbara, CA 93106 (United States)

    2017-02-10

    Extending our previous work, we study the relative entropy between the reduced density matrices obtained from globally excited states in conformal field theories of arbitrary dimensions. We find a general formula in the small subsystem size limit. When one of the states is the vacuum of the CFT, our result matches with the holographic entanglement entropy computations in the corresponding bulk geometries, including AdS black branes. We also discuss the first asymmetric part of the relative entropy and comment on some implications of the results on the distinguishability of black hole microstates in AdS/CFT.

  7. The Total Gaussian Class of Quasiprobabilities and its Relation to Squeezed-State Excitations

    Science.gov (United States)

    Wuensche, Alfred

    1996-01-01

    The class of quasiprobabilities obtainable from the Wigner quasiprobability by convolutions with the general class of Gaussian functions is investigated. It can be described by a three-dimensional, in general, complex vector parameter with the property of additivity when composing convolutions. The diagonal representation of this class of quasiprobabilities is connected with a generalization of the displaced Fock states in direction of squeezing. The subclass with real vector parameter is considered more in detail. It is related to the most important kinds of boson operator ordering. The properties of a specific set of discrete excitations of squeezed coherent states are given.

  8. Cob(I)alamin: insight into the nature of electronically excited states elucidated via quantum chemical computations and analysis of absorption, CD and MCD data.

    Science.gov (United States)

    Kornobis, Karina; Ruud, Kenneth; Kozlowski, Pawel M

    2013-02-07

    The nature of electronically excited states of the super-reduced form of vitamin B(12) (i.e., cob(I)alamin or B(12s)), a ubiquitous B(12) intermediate, was investigated by performing quantum-chemical calculations within the time-dependent density functional theory (TD-DFT) framework and by establishing their correspondence to experimental data. Using response theory, the electronic absorption (Abs), circular dichroism (CD) and magnetic CD (MCD) spectra of cob(I)alamin were simulated and directly compared with experiment. Several issues have been taken into considerations while performing the TD-DFT calculations, such as strong dependence on the applied exchange-correlation (XC) functional or structural simplification imposed on the cob(I)alamin. In addition, the low-lying transitions were also validated by performing CASSCF/MC-XQDPT2 calculations. By comparing computational results with existing experimental data a new level of understanding of electronic excitations has been established at the molecular level. The present study extends and confirms conclusions reached for other cobalamins. In particular, the better performance of the BP86 functional, rather than hybrid-type, was observed in terms of the excitations associated with both Co d and corrin π localized transitions. In addition, the lowest energy band was associated with multiple metal-to-ligand charge transfer excitations as opposed to the commonly assumed view of a single π → π* transition followed by vibrational progression. Finally, the use of the full cob(I)alamin structure, instead of simplified molecular models, shed new light on the spectral analyses of cobalamin systems and revealed new challenges of this approach related to long-range charge transfer excitations involving side chains.

  9. Efficient enhancement of below-threshold harmonic generation by laser-driven excited states of Cs atom

    Science.gov (United States)

    Guo, Qiao-Ling; Li, Peng-Cheng; Zhou, Xiao-Xin; Chu, Shih-I.

    2018-03-01

    We propose an efficient method for the enhancement of below-threshold harmonic generation (BTHG) by mid-infrared laser-driven excited states of a Cs atom. The BTHG is calculated by solving three-dimensional time-dependent Schrödinger equation accurately and efficiently using the time-dependent generalized pseudospectral method. We adopt an excited state as the initial state of a Cs atom. As a result, the BTHG is significantly enhanced by two orders of magnitude compared with the case of the initial ground state. Furthermore, we find that a single vacuum-ultraviolet pulse can be generated by mid-infrared laser-driven excited states by superposing several below-threshold harmonics of a Cs atom. Our finding suggests that the generation of below-threshold harmonics by laser-driven excited states of an atom can provide a powerful methodology for the production of intense vacuum-ultraviolet pulses.

  10. Improved solid state electron-charge-storage device

    Science.gov (United States)

    Kuper, A. B.

    1970-01-01

    Storage device is applicable in memory systems and in high-resolution arrays for light-responsive image sensing. The device offers high yield in multiple arrays and allows charge release with light striking only the edge of a metal electrode.

  11. An EBIS for charge state breeding in the SPES project

    Indian Academy of Sciences (India)

    step towards the design and construction of a charge breeder for the SPES project. The new feature of BRIC, with respect to the classical EBIS, is given by the insertion, in the ion chamber, of a rf-quadrupole aiming at filtering the unwanted masses and then making a more efficient containment of the wanted ions.

  12. Non-typical fluorescence studies of excited and ground state proton and hydrogen transfer

    Science.gov (United States)

    Gil, Michał; Kijak, Michał; Piwoński, Hubert; Herbich, Jerzy; Waluk, Jacek

    2017-03-01

    Fluorescence studies of tautomerization have been carried out for various systems that exhibit single and double proton or hydrogen translocation in various environments, such as liquid and solid condensed phases, ultracold supersonic jets, and finally, polymer matrices with single emitters. We focus on less explored areas of application of fluorescence for tautomerization studies, using porphycene, a porphyrin isomer, as an example. Fluorescence anisotropy techniques allow investigations of self-exchange reactions, where the reactant and product are formally identical. Excitation with polarized light makes it possible to monitor tautomerization in single molecules and to detect their three-dimensional orientation. Analysis of fluorescence from single vibronic levels of jet-isolated porphycene not only demonstrates coherent tunneling of two internal protons, but also indicates that the process is vibrational mode-specific. Next, we present bifunctional proton donor-acceptor systems, molecules that are able, depending on the environment, to undergo excited state single intramolecular or double intermolecular proton transfer. For molecules that have donor and acceptor groups located in separate moieties linked by a single bond, excited state tautomerization can be coupled to mutual twisting of the two subunits.

  13. Non-typical fluorescence studies of excited and ground state proton and hydrogen transfer

    KAUST Repository

    Gil, Michał

    2017-02-03

    Fluorescence studies of tautomerization have been carried out for various systems that exhibit single and double proton or hydrogen translocation in various environments, such as liquid and solid condensed phases, ultracold supersonic jets, and finally, polymer matrices with single emitters.We focus on less explored areas of application of fluorescence for tautomerization studies, using porphycene, a porphyrin isomer, as an example. Fluorescence anisotropy techniques allow investigations of self-exchange reactions, where the reactant and product are formally identical. Excitation with polarized light makes it possible to monitor tautomerization in single molecules and to detect their three-dimensional orientation. Analysis of fluorescence from single vibronic levels of jet-isolated porphycene not only demonstrates coherent tunneling of two internal protons, but also indicates that the process is vibrational mode-specific. Next, we present bifunctional proton donoracceptor systems, molecules that are able, depending on the environment, to undergo excited state single intramolecular or double intermolecular proton transfer. For molecules that have donor and acceptor groups located in separate moieties linked by a single bond, excited state tautomerization can be coupled to mutual twisting of the two subunits.

  14. Preconditioning and excitability of the human orbicularis oculi reflex as a function of state.

    Science.gov (United States)

    Silverstein, L D; Graham, F K; Calloway, J M

    1980-04-01

    Reflex excitability and unstimulated activity of orbicularis oculi were found to vary as a function of state but the effects of weak conditioning stimuli, preceding reflex stimulation by 30--210 msec, were independent of state. Electromyographic activity was recorded from 23 young adults: 12 subjects with eyes closed during quiet wakefulness, 3 subjects during all-night sleep, 8 subjects during an afternoon nap. Stimulation with a 50 msec, 105 dB(A) white noise burst elicited a reflex response in 92% of waking trials and 87% of trials during REM sleep, but responses occurred in only 54% of trials during NREM sleep. Further, response latency was longer and magnitude less during the NREM state. Despite the differences in reflex excitability associated with state, state did not affect the modifications of reflex activity produced by a 20 msec, 70 dB(A) conditioning tone. At all lead intervals, reflex magnitude was reduced by the weak prestimulation even though, at the shortest interval, reflex activity was initiated more rapidly. The discordant changes in reflex size and latency have been seen in previous waking studies and appear to be mediated by different mechanisms. The persistence of both effects during sleep suggests that neither effect depends on high-level central processes.

  15. Excited-state dynamics in fac-[Re(CO)3(Me4phen)(L)]+.

    Science.gov (United States)

    Patrocinio, Antonio Otavio T; Brennaman, M Kyle; Meyer, Thomas J; Murakami Iha, Neyde Y

    2010-11-25

    Excited-state dynamics in fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+) (Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, L = 4-styrylpyridine (stpy) or 1,2-bis(4-pyridyl)ethylene (bpe)) were investigated by steady-state and time-resolved techniques. A complex equilibrium among three closely lying excited states, (3)IL(cis-L), (3)MLCT(Re→Me(4)phen), and (3)IL(Me(4)phen), has been established. Under UV irradiation, cis-to-trans isomerization of coordinated cis-L is observed with a quantum yield of 0.15 in acetonitrile solutions. This photoreaction competes with radiative decay from (3)MLCT(Re→Me(4)phen) and (3)IL(Me(4)phen) excited states, leading to a decrease in the emission quantum yield relative to the nonisomerizable complex fac-[Re(CO)(3)(Me(4)phen)(bpa)](+) (bpa = 1,2-bis(4-pyridyl)ethane). From temperature-dependent time-resolved emission measurements in solution and in poly(methyl methacrylate) (PMMA) films, energy barriers (ΔE(a)) for interconversion between (3)MLCT(Re→Me(4)phen) and (3)IL(Me(4)phen) emitting states were determined. For L = cis-stpy, ΔE(a) = 11 (920 cm(-1)) and 15 kJ mol(-1) (1254 cm(-1)) in 5:4 propionitrile/butyronitrile and PMMA, respectively. For L = cis-bpe, ΔE(a) = 13 kJ mol(-1) (1087 cm(-1)) in 5:4 propionitrile/butyronitrile. These energy barriers are sufficient to decrease the rate constant for internal conversion from higher-lying (3)IL(Me(4)phen) state to (3)MLCT(Re→Me(4)phen), k(i) ≅ 10(6) s(-1). The decrease in rate allows for the observation of intraligand phosphorescence, even in fluid medium at room temperature. Our results provide additional insight into the role of energy gap and excited-state dynamics on the photochemical and photophysical properties of Re(I) polypyridyl complexes.

  16. Ground state isomerism in betacarboline hydrogen bond complexes: The charge transfer nature of its large Stokes shifted emission

    Science.gov (United States)

    Sánchez-Coronilla, Antonio; Balón, Manuel; Muñoz, María A.; Hidalgo, José; Carmona, Carmen

    2008-07-01

    The hydrogen bonding and excited state proton transfer reactions between betacarboline, 9 H-pyrido[3,4- b]indole, BC, and 1,1,1,3,3,3-hexafluoropropan-2-ol, HFIP, have been studied in the aprotic solvents cyclohexane and toluene by absorption, steady state and time resolved fluorescence measurements. On the basis of these results and those of previous works (Refs. [A. Sánchez-Coronilla, C. Carmona, M.A. Muñoz, M. Balón, Chem. Phys., 327 (2006) 70] and [A. Sánchez-Coronilla, M. Balón, M.A. Muñoz, C. Carmona, Chem. Phys. 344 (2008) 72]) two main fundamental conclusions can be drawn on the photophysical behaviour of BC. Thus, it is shown, for the first time, that the non-cyclic double hydrogen bond complexes formed through both nitrogen atoms of BC, DHB, can suffer, in their ground state, an isomerisation process. These adducts acquire a quinoid structure in cyclohexane, but maintain a dipolar zwitterionic structure in toluene. Moreover, it is concluded that the observed large Stokes shifted emission, around 520 nm, is not due, as it has been so far generally accepted, to the emission of a BC zwitterionic phototautomer, but to the intramolecular charge transfer, ICT, excited state emissions of the DHB hydrogen bond adducts.

  17. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Tomin, Vladimir I., E-mail: tomin@apsl.edu.pl; Ushakou, Dzmitryi V.

    2015-10-15

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited-state

  18. Nonlinear excitations and charge transport in lithium niobate crystals investigated using femtosecond-light gratings; Nichtlineare Anregungen und Ladungstransport in Lithiumniobatkristallen untersucht mit Femtosekunden-Lichtgittern

    Energy Technology Data Exchange (ETDEWEB)

    Maxein, Karl Dominik

    2009-12-15

    Lithium niobate (LiNbO{sub 3}) is a widely employed material in nonlinear optics and photonics. Its usage is hampered by the photorefractive effect, which can destroy beam profiles and phase matching conditions. Existing methods to suppress photorefraction fail for the interesting regime of very high intensities and short pulses. Therefore, the photorefractive effect is investigated using femtosecond laser pulses: By utilizing so-called 2K holography, the occupation of energetically shallow traps is observed to occur in less than 100 fs after a two-photon excitation. Writing of photorefractive gratings into oxidized iron-doped LiNbO{sub 3} is much faster with pulses than with cw light. This is explained by the sensitization of the crystal due to charge trapping in photorefractive centers after nonlinear excitations. Finally, light-induced scattering of pulse light is suppressed compared to the scattering of cw light due to the small coherence length of pulses. (orig.)

  19. Theoretical study of the low-lying excited states of ABCO, DABCO and homologous cage amines

    Science.gov (United States)

    Galasso, V.

    1997-02-01

    The electronic spectra of 1-azabicyclo[2.2.2]octane (ABCO), 1,4-diazabicyclo[2.2.2]octane (DABCO), and their [1.1.1] and [3.3.3] congeners have been studied at the ab initio level using the symmetry adapted cluster configuration interaction method. A comprehensive theoretical prediction of the discrete excitation spectra, up to the HOMO → 5s transition, is presented. All the low-lying singlet and triplet electronic states of these symmetric cage amines are found to have essentially Rydberg nature and originate from excitations out of the n-type molecular orbitals. The theoretical results correlate with the available spectroscopic data satisfactorily and provide quantitative support to a number of experimental assignments based on REMPI and MCD measurements.

  20. Dynamics of Excited State Proton Transfer in Nitro Substituted 10-Hydroxybenzo[h]quinolines

    DEFF Research Database (Denmark)

    Marciak, H; Hristova, S.; Deneva, V

    2017-01-01

    of the ground state enol–keto tautomeric equilibrium (ΔG values of 1.03 and 0.62 kcal mol−1 respectively for 2 and 3). The fluorescence stems from the keto form even if the enol form is optically excited as proven by the shape of the excitation spectra indicating that ESIPT takes place. The Stokes shift...... of the substituted compounds is substantially lower compared to HBQ, which follows from the fact that the substitution occurs in the formal cyclohexa-2,4-dienone moiety and leads to a decrease of the HOMO level of the keto tautomer. The pump–probe experiments show that in the nitro substituted HBQs 2 and 3 ESIPT...