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Sample records for accurate excitation energies

  1. Accurate and efficient calculation of excitation energies with the active-space particle-particle random phase approximation

    NASA Astrophysics Data System (ADS)

    Zhang, Du; Yang, Weitao

    2016-10-01

    An efficient method for calculating excitation energies based on the particle-particle random phase approximation (ppRPA) is presented. Neglecting the contributions from the high-lying virtual states and the low-lying core states leads to the significantly smaller active-space ppRPA matrix while keeping the error to within 0.05 eV from the corresponding full ppRPA excitation energies. The resulting computational cost is significantly reduced and becomes less than the construction of the non-local Fock exchange potential matrix in the self-consistent-field (SCF) procedure. With only a modest number of active orbitals, the original ppRPA singlet-triplet (ST) gaps as well as the low-lying single and double excitation energies can be accurately reproduced at much reduced computational costs, up to 100 times faster than the iterative Davidson diagonalization of the original full ppRPA matrix. For high-lying Rydberg excitations where the Davidson algorithm fails, the computational savings of active-space ppRPA with respect to the direct diagonalization is even more dramatic. The virtues of the underlying full ppRPA combined with the significantly lower computational cost of the active-space approach will significantly expand the applicability of the ppRPA method to calculate excitation energies at a cost of O(K4), with a prefactor much smaller than a single SCF Hartree-Fock (HF)/hybrid functional calculation, thus opening up new possibilities for the quantum mechanical study of excited state electronic structure of large systems.

  2. Accurate and efficient calculation of excitation energies with the active-space particle-particle random phase approximation

    DOE PAGES

    Zhang, Du; Yang, Weitao

    2016-10-13

    An efficient method for calculating excitation energies based on the particle-particle random phase approximation (ppRPA) is presented. Neglecting the contributions from the high-lying virtual states and the low-lying core states leads to the significantly smaller active-space ppRPA matrix while keeping the error to within 0.05 eV from the corresponding full ppRPA excitation energies. The resulting computational cost is significantly reduced and becomes less than the construction of the non-local Fock exchange potential matrix in the self-consistent-field (SCF) procedure. With only a modest number of active orbitals, the original ppRPA singlet-triplet (ST) gaps as well as the low-lying single and doublemore » excitation energies can be accurately reproduced at much reduced computational costs, up to 100 times faster than the iterative Davidson diagonalization of the original full ppRPA matrix. For high-lying Rydberg excitations where the Davidson algorithm fails, the computational savings of active-space ppRPA with respect to the direct diagonalization is even more dramatic. The virtues of the underlying full ppRPA combined with the significantly lower computational cost of the active-space approach will significantly expand the applicability of the ppRPA method to calculate excitation energies at a cost of O(K^{4}), with a prefactor much smaller than a single SCF Hartree-Fock (HF)/hybrid functional calculation, thus opening up new possibilities for the quantum mechanical study of excited state electronic structure of large systems.« less

  3. The CHARMM-TURBOMOLE interface for efficient and accurate QM/MM molecular dynamics, free energies, and excited state properties.

    PubMed

    Riahi, Saleh; Rowley, Christopher N

    2014-10-30

    The quantum mechanical (QM)/molecular mechanical (MM) interface between Chemistry at HARvard Molecular Mechanics (CHARMM) and TURBOMOLE is described. CHARMM provides an extensive set of simulation algorithms, like molecular dynamics (MD) and free energy perturbation, and support for mature nonpolarizable and Drude polarizable force fields. TURBOMOLE provides fast QM calculations using density functional theory or wave function methods and excited state properties. CHARMM-TURBOMOLE is well-suited for extended QM/MM MD simulations using first principles methods with large (triple-ζ) basis sets. We demonstrate these capabilities with a QM/MM simulation of Mg(2+) (aq), where the MM outer sphere water molecules are represented using the SWM4-NDP Drude polarizable force field and the ion and inner coordination sphere are represented using QM PBE, PBE0, and MP2 methods. The relative solvation free energies of Mg(2+) and Zn(2+) were calculated using thermodynamic integration. We also demonstrate the features for excited state properties. We calculate the time-averaged solution absorption spectrum of indole, the emission spectrum of the indole 1La excited state, and the electronic circular dichroism spectrum of an oxacepham.

  4. An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings

    SciTech Connect

    Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas; Neugebauer, Johannes

    2013-02-07

    Quantum-mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those charge transfer excitations that take place between non-covalently bound molecules. In particular, we present a method that scales linearly with the number of non-covalently bound molecules in the system and is based on a two-pronged approach: The molecular electronic structure of broken-symmetry charge-localized states is obtained with the frozen density embedding formulation of subsystem density-functional theory; subsequently, in a post-SCF calculation, the full-electron Hamiltonian and overlap matrix elements among the charge-localized states are evaluated with an algorithm which takes full advantage of the subsystem DFT density partitioning technique. The method is benchmarked against coupled-cluster calculations and achieves chemical accuracy for the systems considered for intermolecular separations ranging from hydrogen-bond distances to tens of Angstroms. Numerical examples are provided for molecular clusters comprised of up to 56 non-covalently bound molecules.

  5. An accurate full-dimensional potential energy surface for H-Au(111): Importance of nonadiabatic electronic excitation in energy transfer and adsorption.

    PubMed

    Janke, Svenja M; Auerbach, Daniel J; Wodtke, Alec M; Kandratsenka, Alexander

    2015-09-28

    We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H-Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension, not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ≈3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab.

  6. An accurate full-dimensional potential energy surface for H–Au(111): Importance of nonadiabatic electronic excitation in energy transfer and adsorption

    SciTech Connect

    Janke, Svenja M.; Auerbach, Daniel J.; Kandratsenka, Alexander; Wodtke, Alec M.

    2015-09-28

    We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H–Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension, not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ≈3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab.

  7. Excitation energies from ensemble DFT

    NASA Astrophysics Data System (ADS)

    Borgoo, Alex; Teale, Andy M.; Helgaker, Trygve

    2015-12-01

    We study the evaluation of the Gross-Oliveira-Kohn expression for excitation energies E1-E0=ɛ1-ɛ0+∂E/xc,w[ρ] ∂w | ρ =ρ0. This expression gives the difference between an excitation energy E1 - E0 and the corresponding Kohn-Sham orbital energy difference ɛ1 - ɛ0 as a partial derivative of the exchange-correlation energy of an ensemble of states Exc,w[ρ]. Through Lieb maximisation, on input full-CI density functions, the exchange-correlation energy is evaluated accurately and the partial derivative is evaluated numerically using finite difference. The equality is studied numerically for different geometries of the H2 molecule and different ensemble weights. We explore the adiabatic connection for the ensemble exchange-correlation energy. The latter may prove useful when modelling the unknown weight dependence of the exchange-correlation energy.

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

    PubMed

    Robinson, David

    2014-12-01

    A method for the calculation of TDDFT/TDA excited state geometries within a reduced subspace of Kohn-Sham orbitals has been implemented and tested. Accurate geometries are found for all of the fluorophore-like molecules tested, with at most all valence occupied orbitals and half of the virtual orbitals included but for some molecules even fewer orbitals. Efficiency gains of between 15 and 30% are found for essentially the same level of accuracy as a standard TDDFT/TDA excited state geometry optimization calculation. PMID:26583218

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

    PubMed

    Zulfikri, Habiburrahman; Amovilli, Claudio; Filippi, Claudia

    2016-03-01

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

  10. Nonempirically Tuned Range-Separated DFT Accurately Predicts Both Fundamental and Excitation Gaps in DNA and RNA Nucleobases

    PubMed Central

    2012-01-01

    Using a nonempirically tuned range-separated DFT approach, we study both the quasiparticle properties (HOMO–LUMO fundamental gaps) and excitation energies of DNA and RNA nucleobases (adenine, thymine, cytosine, guanine, and uracil). Our calculations demonstrate that a physically motivated, first-principles tuned DFT approach accurately reproduces results from both experimental benchmarks and more computationally intensive techniques such as many-body GW theory. Furthermore, in the same set of nucleobases, we show that the nonempirical range-separated procedure also leads to significantly improved results for excitation energies compared to conventional DFT methods. The present results emphasize the importance of a nonempirically tuned range-separation approach for accurately predicting both fundamental and excitation gaps in DNA and RNA nucleobases. PMID:22904693

  11. Accurate free energy calculation along optimized paths.

    PubMed

    Chen, Changjun; Xiao, Yi

    2010-05-01

    The path-based methods of free energy calculation, such as thermodynamic integration and free energy perturbation, are simple in theory, but difficult in practice because in most cases smooth paths do not exist, especially for large molecules. In this article, we present a novel method to build the transition path of a peptide. We use harmonic potentials to restrain its nonhydrogen atom dihedrals in the initial state and set the equilibrium angles of the potentials as those in the final state. Through a series of steps of geometrical optimization, we can construct a smooth and short path from the initial state to the final state. This path can be used to calculate free energy difference. To validate this method, we apply it to a small 10-ALA peptide and find that the calculated free energy changes in helix-helix and helix-hairpin transitions are both self-convergent and cross-convergent. We also calculate the free energy differences between different stable states of beta-hairpin trpzip2, and the results show that this method is more efficient than the conventional molecular dynamics method in accurate free energy calculation.

  12. Multifrequency excitation method for rapid and accurate dynamic test of micromachined gyroscope chips.

    PubMed

    Deng, Yan; Zhou, Bin; Xing, Chao; Zhang, Rong

    2014-10-17

    A novel multifrequency excitation (MFE) method is proposed to realize rapid and accurate dynamic testing of micromachined gyroscope chips. Compared with the traditional sweep-frequency excitation (SFE) method, the computational time for testing one chip under four modes at a 1-Hz frequency resolution and 600-Hz bandwidth was dramatically reduced from 10 min to 6 s. A multifrequency signal with an equal amplitude and initial linear-phase-difference distribution was generated to ensure test repeatability and accuracy. The current test system based on LabVIEW using the SFE method was modified to use the MFE method without any hardware changes. The experimental results verified that the MFE method can be an ideal solution for large-scale dynamic testing of gyroscope chips and gyroscopes.

  13. Multifrequency Excitation Method for Rapid and Accurate Dynamic Test of Micromachined Gyroscope Chips

    PubMed Central

    Deng, Yan; Zhou, Bin; Xing, Chao; Zhang, Rong

    2014-01-01

    A novel multifrequency excitation (MFE) method is proposed to realize rapid and accurate dynamic testing of micromachined gyroscope chips. Compared with the traditional sweep-frequency excitation (SFE) method, the computational time for testing one chip under four modes at a 1-Hz frequency resolution and 600-Hz bandwidth was dramatically reduced from 10 min to 6 s. A multifrequency signal with an equal amplitude and initial linear-phase-difference distribution was generated to ensure test repeatability and accuracy. The current test system based on LabVIEW using the SFE method was modified to use the MFE method without any hardware changes. The experimental results verified that the MFE method can be an ideal solution for large-scale dynamic testing of gyroscope chips and gyroscopes. PMID:25330052

  14. Excitation energies along a range-separated adiabatic connection

    SciTech Connect

    Rebolini, Elisa Toulouse, Julien Savin, Andreas; Teale, Andrew M.; Helgaker, Trygve

    2014-07-28

    We present a study of the variation of total energies and excitation energies along a range-separated adiabatic connection. This connection links the non-interacting Kohn–Sham electronic system to the physical interacting system by progressively switching on the electron–electron interactions whilst simultaneously adjusting a one-electron effective potential so as to keep the ground-state density constant. The interactions are introduced in a range-dependent manner, first introducing predominantly long-range, and then all-range, interactions as the physical system is approached, as opposed to the conventional adiabatic connection where the interactions are introduced by globally scaling the standard Coulomb interaction. Reference data are reported for the He and Be atoms and the H{sub 2} molecule, obtained by calculating the short-range effective potential at the full configuration-interaction level using Lieb's Legendre-transform approach. As the strength of the electron–electron interactions increases, the excitation energies, calculated for the partially interacting systems along the adiabatic connection, offer increasingly accurate approximations to the exact excitation energies. Importantly, the excitation energies calculated at an intermediate point of the adiabatic connection are much better approximations to the exact excitation energies than are the corresponding Kohn–Sham excitation energies. This is particularly evident in situations involving strong static correlation effects and states with multiple excitation character, such as the dissociating H{sub 2} molecule. These results highlight the utility of long-range interacting reference systems as a starting point for the calculation of excitation energies and are of interest for developing and analyzing practical approximate range-separated density-functional methodologies.

  15. A highly accurate ab initio potential energy surface for methane

    NASA Astrophysics Data System (ADS)

    Owens, Alec; Yurchenko, Sergei N.; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2016-09-01

    A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of 12CH4 reproduced with a root-mean-square error of 0.70 cm-1. The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement.

  16. A highly accurate ab initio potential energy surface for methane.

    PubMed

    Owens, Alec; Yurchenko, Sergei N; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2016-09-14

    A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of (12)CH4 reproduced with a root-mean-square error of 0.70 cm(-1). The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement. PMID:27634258

  17. A highly accurate ab initio potential energy surface for methane.

    PubMed

    Owens, Alec; Yurchenko, Sergei N; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2016-09-14

    A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of (12)CH4 reproduced with a root-mean-square error of 0.70 cm(-1). The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement.

  18. New Accurate Oscillator Strengths and Electron Excitation Collision Strengths for N1

    NASA Technical Reports Server (NTRS)

    Tayal, S. S.

    2006-01-01

    The nonorthogonal orbitals technique in a multiconfiguration Hartree-Fock approach is used to calculate oscillator strengths and transition probabilities of N(I) lines. The relativistic effects are allowed by means of Breit-Pauli operators. The length and velocity forms of oscillator strengths show good agreement for most transitions. The B-spline R-matrix with pseudostates approach has been used to calculate electron excitation collision strengths and rates. The nonorthogonal orbitals are used for an accurate description of both target wave functions and the R-matrix basis functions. The 24 spectroscopic bound and autoionizing states together with 15 pseudostates are included in the close-coupling expansion. The collision strengths for transitions between fine-structure levels are calculated by transforming the LS-coupled K-matrices to K-matrices in an intermediate coupling scheme. Thermally averaged collision strengths have been determined by integrating collision strength over a Maxwellian distribution of electron energies over a temperature range suitable for the modeling of astrophysical plasmas. The oscillator strengths and thermally averaged collision strengths are presented for transitions between the fine-structure levels of the 2s(sup 2)p(sup 3) (sup 4)S(sup 0), (sup 2)D(sup 0), (sup 2)P(sup 0), 2s2p(sup 4) (sup 4)P, 2s(sup 2)2p(sup 2)3s (sup 4)P, and (sup 2)P terms and from these levels to the levels of the 2s(sup 2)2p(sup 2)3p (sup 2)S(sup 0), (sup 4)D(sup 0), (sup 4)P(sup 0), (sup 4)S(sup 0), (sup 2)D(sup 0), (sup 2)P(sup 0),2s(sup 2)2p(sup 2)3s(sup 2)D, 2s(sup 2)2p(sup 2)4s(sup 4)P, (sup 2)P, 2s(sup 2)2p(sup 2)3d(sup 2)P, (sup 4)F,(sup 2)F,(sup 4)P, (sup 4)D, and (sup 2)D terms. Thermally averaged collision strengths are tabulated over a temperature range from 500 to 50,000 K.

  19. Highly accurate analytical energy of a two-dimensional exciton in a constant magnetic field

    NASA Astrophysics Data System (ADS)

    Hoang, Ngoc-Tram D.; Nguyen, Duy-Anh P.; Hoang, Van-Hung; Le, Van-Hoang

    2016-08-01

    Explicit expressions are given for analytically describing the dependence of the energy of a two-dimensional exciton on magnetic field intensity. These expressions are highly accurate with the precision of up to three decimal places for the whole range of the magnetic field intensity. The results are shown for the ground state and some excited states; moreover, we have all formulae to obtain similar expressions of any excited state. Analysis of numerical results shows that the precision of three decimal places is maintained for the excited states with the principal quantum number of up to n=100.

  20. Accurate calculation and assignment of highly excited vibrational levels of floppy triatomic molecules in a basis of adiabatic vibrational eigenstates

    NASA Astrophysics Data System (ADS)

    Bačić, Z.

    1991-09-01

    We show that the triatomic adiabatic vibrational eigenstates (AVES) provide a convenient basis for accurate discrete variable representation (DVR) calculation and automatic assignment of highly excited, large amplitude motion vibrational states of floppy triatomic molecules. The DVR-AVES states are eigenvectors of the diagonal (in the stretch states) blocks of the adiabatically rearranged triatomic DVR-ray eigenvector (DVR-REV) Hamiltonian [J. C. Light and Z. Bačić, J. Chem. Phys. 87, 4008 (1987)]. The transformation of the full triatomic vibrational Hamiltonian from the DVR-REV basis to the new DVR-AVES basis is simple, and does not involve calculation of any new matrix elements. No dynamical approximation is made in the energy level calculation by the DVR-AVES approach; its accuracy and efficiency are identical to those of the DVR-REV method. The DVR-AVES states, as the adiabatic approximation to the vibrational states of a triatomic molecule, are labeled by three vibrational quantum numbers. Consequently, accurate large amplitude motion vibrational levels obtained by diagonalizing the full vibrational Hamiltonian transformed to the DVR-AVES basis, can be assigned automatically by the code, with the three quantum numbers of the dominant DVR-AVES state associated with the largest (by modulus) eigenvector element in the DVR-AVES basis. The DVR-AVES approach is used to calculate accurate highly excited localized and delocalized vibrational levels of HCN/HNC and LiCN/LiNC. A significant fraction of localized states of both systems, below and above the isomerization barrier, is assigned automatically, without inspection of wave function plots or separate approximate calculations.

  1. Accurate calculation of diffraction-limited encircled and ensquared energy.

    PubMed

    Andersen, Torben B

    2015-09-01

    Mathematical properties of the encircled and ensquared energy functions for the diffraction-limited point-spread function (PSF) are presented. These include power series and a set of linear differential equations that facilitate the accurate calculation of these functions. Asymptotic expressions are derived that provide very accurate estimates for the relative amount of energy in the diffraction PSF that fall outside a square or rectangular large detector. Tables with accurate values of the encircled and ensquared energy functions are also presented. PMID:26368873

  2. Peculiarities of collisional excitation transfer with excited screened energy levels of atoms

    SciTech Connect

    Gerasimov, V. A.; Gerasimov, V. V.; Pavlinskiy, A. V.

    2007-09-15

    We report an experimental discovery of deviations from the known regularities in collisional excitation transfer processes for metal atoms. The collisional excitation transfer with excited screened energy levels of thulium and dysprosium atoms is studied. The selecting role of the screening 6s shell in collisional excitation transfer is shown.

  3. Dynamics of excitation energy transfer in phycobiliproteins

    NASA Astrophysics Data System (ADS)

    Zheng, Xiguang; Wang, He Z.; Zhao, Fuli; Gao, Zhaolan; Yu, Zhenxin

    1994-08-01

    Theoretical descriptions of excitation energy transfer between chromophores in allophycocyanin are presented, including bilateral energy transfer paths between chromophores, and are expressed, based on Foster interaction mechanism, as Pauli master equations. Group analysis in C3 symmetry is performed to carry out analytic expressions for fluorescence decays which is generally of triexponential with effects of chromophore coupling and exciton splitting taken account. It is pointed out that the time constant of each decay component contains mixed information of different energy transfer paths, and therefore show its dependence on subtle configuration of chromophores, probably related to site heterogeneity and thus to inhomogeneous broadening previously observed.

  4. Excitation energy transfer in the photosystem I

    SciTech Connect

    Webber, Andrew N

    2012-09-25

    Photosystem I is a multimeric pigment protein complex in plants, green alage and cyanobacteria that functions in series with Photosystem II to use light energy to oxidize water and reduce carbon dioxide. The Photosystem I core complex contains 96 chlorophyll a molecules and 22 carotenoids that are involved in light harvesting and electron transfer. In eucaryotes, PSI also has a peripheral light harvesting complex I (LHCI). The role of specific chlorophylls in excitation and electron transfer are still unresolved. In particular, the role of so-called bridging chlorophylls, located between the bulk antenna and the core electron transfer chain, in the transfer of excitation energy to the reaction center are unknown. During the past funding period, site directed mutagenesis has been used to create mutants that effect the physical properties of these key chlorophylls, and to explore how this alters the function of the photosystem. Studying these mutants using ultrafast absorption spectroscopy has led to a better understanding of the process by which excitation energy is transferred from the antenna chlorophylls to the electron transfer chain chlorophylls, and what the role of connecting chlorophylls and A_0 chlorophylls is in this process. We have also used these mutants to investigate whch of the central group of six chlorophylls are involved in the primary steps of charge separation and electron transfer.

  5. Two-photon excitation energy transfer microscopy

    NASA Astrophysics Data System (ADS)

    Periasamy, Ammasi

    2000-04-01

    Fluorescence resonance energy transfer (FRET) imaging is a unique tool used to visualize the spaciotemporal dynamics of protein-protein interactions in living cells. We used FRET to study the dimerization of the pituitary-specific transcription factor of Pit-1 fused with blue flourescent protein and green fluorescent protein. Transcriptional activity of the GFP- and BFP-Pit-1 fusion proteins was demonstrated by their ability to activate the prolactin gene promoter. The energy transfer in the conventional fluorescence microscopy was less efficient due to photobleaching of the BFP-Pit-1 donor molecules. In our studies we developed two-photon excitation energy transfer microscopy, where the photobleaching of blue flourescent protein was considerably reduced. This 2p-FRET imaging system was used to acquire the donor and acceptor images for a living HeLa cell nucleus. We selected 732 nm from the tunable Verdi pumped ti:sapphire laser, in a way that only excites the BFP-Pit-1 and not the GFP-Pit-1 proteins. The efficiency of the 2p-FRET signal increased to 30 percent compared to the conventional FRET imaging, which clearly demonstrates that there is considerable reduction in photobleaching of donor molecules in the 2p-FRET microscopy.

  6. Fission dynamics at low excitation energy

    NASA Astrophysics Data System (ADS)

    Aritomo, Y.; Chiba, S.; Ivanyuk, F.

    2014-11-01

    The mass asymmetry in the fission of 236U at low excitation energy is clarified by the analysis of the trajectories obtained by solving the Langevin equations for the shape degrees of freedom. It is demonstrated that the position of the peaks in the mass distribution of fission fragments is determined mainly by the saddle point configuration originating from the shell correction energy. The width of the peaks, on the other hand, results from the shape fluctuations close to the scission point caused by the random force in the Langevin equation. We have found out that the fluctuations between elongated and compact shapes are essential for the fission process. According to our results the fission does not occur with continuous stretching in the prolate direction, similarly to that observed in starch syrup, but is accompanied by the fluctuations between elongated and compact shapes. This picture presents a new viewpoint of fission dynamics and the splitting mechanism.

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

    PubMed

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

    2016-02-01

    A correct description of electronically excited states is critical to the interpretation of visible-ultraviolet spectra, photochemical reactions, and excited-state charge-transfer processes in chemical systems. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory and a new kind of density functional called an on-top density functional. Here, we show that MC-PDFT with a first-generation on-top density functional performs as well as CASPT2 for an organic chemistry database including valence, Rydberg, and charge-transfer excitations. The results are very encouraging for practical applications. PMID:26794241

  8. Accurate nuclear radii and binding energies from a chiral interaction

    SciTech Connect

    Ekstrom, Jan A.; Jansen, G. R.; Wendt, Kyle A.; Hagen, Gaute; Papenbrock, Thomas F.; Carlsson, Boris; Forssen, Christian; Hjorth-Jensen, M.; Navratil, Petr; Nazarewicz, Witold

    2015-05-01

    With the goal of developing predictive ab initio capability for light and medium-mass nuclei, two-nucleon and three-nucleon forces from chiral effective field theory are optimized simultaneously to low-energy nucleon-nucleon scattering data, as well as binding energies and radii of few-nucleon systems and selected isotopes of carbon and oxygen. Coupled-cluster calculations based on this interaction, named NNLOsat, yield accurate binding energies and radii of nuclei up to 40Ca, and are consistent with the empirical saturation point of symmetric nuclear matter. In addition, the low-lying collective Jπ=3- states in 16O and 40Ca are described accurately, while spectra for selected p- and sd-shell nuclei are in reasonable agreement with experiment.

  9. Accurate nuclear radii and binding energies from a chiral interaction

    DOE PAGES

    Ekstrom, Jan A.; Jansen, G. R.; Wendt, Kyle A.; Hagen, Gaute; Papenbrock, Thomas F.; Carlsson, Boris; Forssen, Christian; Hjorth-Jensen, M.; Navratil, Petr; Nazarewicz, Witold

    2015-05-01

    With the goal of developing predictive ab initio capability for light and medium-mass nuclei, two-nucleon and three-nucleon forces from chiral effective field theory are optimized simultaneously to low-energy nucleon-nucleon scattering data, as well as binding energies and radii of few-nucleon systems and selected isotopes of carbon and oxygen. Coupled-cluster calculations based on this interaction, named NNLOsat, yield accurate binding energies and radii of nuclei up to 40Ca, and are consistent with the empirical saturation point of symmetric nuclear matter. In addition, the low-lying collective Jπ=3- states in 16O and 40Ca are described accurately, while spectra for selected p- and sd-shellmore » nuclei are in reasonable agreement with experiment.« less

  10. Mean excitation energies for stopping powers in various materials composed of elements hydrogen through argon

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Xu, Y. J.; Kamaratos, E.; Chang, C. K.

    1984-01-01

    The local plasma model is used to study the effects of the chemical and physical state of a medium on its stopping power. The relationship between that model and a more exact quantum treatment of bound systems is elucidated by examining related quantities in both theories for the case of one and two-electron systems. Atomic mean excitation energies and straggling parameters in the local plasma model are compared with the accurate calculations of Inokuti et al. (1975, 1978, 1981). The use of the Gordon-Kim electron gas model of molecular bonding is used to determine the effects of covalent chemical bond shifts on the mean excitation energies for elements of the first two rows. Calculations of mean excitation energies of ionic bonded substances are presented, and the mean excitation energies of metals are discussed.

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

    PubMed

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

    2014-07-21

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

  12. Modeling Electronic-Nuclear Interactions for Excitation Energy Transfer Processes in Light-Harvesting Complexes.

    PubMed

    Lee, Mi Kyung; Coker, David F

    2016-08-18

    An accurate approach for computing intermolecular and intrachromophore contributions to spectral densities to describe the electronic-nuclear interactions relevant for modeling excitation energy transfer processes in light harvesting systems is presented. The approach is based on molecular dynamics (MD) calculations of classical correlation functions of long-range contributions to excitation energy fluctuations and a separate harmonic analysis and single-point gradient quantum calculations for electron-intrachromophore vibrational couplings. A simple model is also presented that enables detailed analysis of the shortcomings of standard MD-based excitation energy fluctuation correlation function approaches. The method introduced here avoids these problems, and its reliability is demonstrated in accurate predictions for bacteriochlorophyll molecules in the Fenna-Matthews-Olson pigment-protein complex, where excellent agreement with experimental spectral densities is found. This efficient approach can provide instantaneous spectral densities for treating the influence of fluctuations in environmental dissipation on fast electronic relaxation.

  13. Modeling Electronic-Nuclear Interactions for Excitation Energy Transfer Processes in Light-Harvesting Complexes.

    PubMed

    Lee, Mi Kyung; Coker, David F

    2016-08-18

    An accurate approach for computing intermolecular and intrachromophore contributions to spectral densities to describe the electronic-nuclear interactions relevant for modeling excitation energy transfer processes in light harvesting systems is presented. The approach is based on molecular dynamics (MD) calculations of classical correlation functions of long-range contributions to excitation energy fluctuations and a separate harmonic analysis and single-point gradient quantum calculations for electron-intrachromophore vibrational couplings. A simple model is also presented that enables detailed analysis of the shortcomings of standard MD-based excitation energy fluctuation correlation function approaches. The method introduced here avoids these problems, and its reliability is demonstrated in accurate predictions for bacteriochlorophyll molecules in the Fenna-Matthews-Olson pigment-protein complex, where excellent agreement with experimental spectral densities is found. This efficient approach can provide instantaneous spectral densities for treating the influence of fluctuations in environmental dissipation on fast electronic relaxation. PMID:27472379

  14. Accurate determination of the binding energy of the formic acid dimer: the importance of geometry relaxation.

    PubMed

    Kalescky, Robert; Kraka, Elfi; Cremer, Dieter

    2014-02-28

    The formic acid dimer in its C2h-symmetrical cyclic form is stabilized by two equivalent H-bonds. The currently accepted interaction energy is 18.75 kcal/mol whereas the experimental binding energy D0 value is only 14.22 ±0.12 kcal/mol [F. Kollipost, R. W. Larsen, A. V. Domanskaya, M. Nörenberg, and M. A. Suhm, J. Chem. Phys. 136, 151101 (2012)]. Calculation of the binding energies De and D0 at the CCSD(T) (Coupled Cluster with Single and Double excitations and perturbative Triple excitations)/CBS (Complete Basis Set) level of theory, utilizing CCSD(T)/CBS geometries and the frequencies of the dimer and monomer, reveals that there is a 3.2 kcal/mol difference between interaction energy and binding energy De, which results from (i) not relaxing the geometry of the monomers upon dissociation of the dimer and (ii) approximating CCSD(T) correlation effects with MP2. The most accurate CCSD(T)/CBS values obtained in this work are De = 15.55 and D0 = 14.32 kcal/mol where the latter binding energy differs from the experimental value by 0.1 kcal/mol. The necessity of employing augmented VQZ and VPZ calculations and relaxing monomer geometries of H-bonded complexes upon dissociation to obtain reliable binding energies is emphasized.

  15. Accurate determination of the binding energy of the formic acid dimer: The importance of geometry relaxation

    NASA Astrophysics Data System (ADS)

    Kalescky, Robert; Kraka, Elfi; Cremer, Dieter

    2014-02-01

    The formic acid dimer in its C2h-symmetrical cyclic form is stabilized by two equivalent H-bonds. The currently accepted interaction energy is 18.75 kcal/mol whereas the experimental binding energy D0 value is only 14.22 ±0.12 kcal/mol [F. Kollipost, R. W. Larsen, A. V. Domanskaya, M. Nörenberg, and M. A. Suhm, J. Chem. Phys. 136, 151101 (2012)]. Calculation of the binding energies De and D0 at the CCSD(T) (Coupled Cluster with Single and Double excitations and perturbative Triple excitations)/CBS (Complete Basis Set) level of theory, utilizing CCSD(T)/CBS geometries and the frequencies of the dimer and monomer, reveals that there is a 3.2 kcal/mol difference between interaction energy and binding energy De, which results from (i) not relaxing the geometry of the monomers upon dissociation of the dimer and (ii) approximating CCSD(T) correlation effects with MP2. The most accurate CCSD(T)/CBS values obtained in this work are De = 15.55 and D0 = 14.32 kcal/mol where the latter binding energy differs from the experimental value by 0.1 kcal/mol. The necessity of employing augmented VQZ and VPZ calculations and relaxing monomer geometries of H-bonded complexes upon dissociation to obtain reliable binding energies is emphasized.

  16. Accurate energy levels for singly ionized platinum (Pt II)

    NASA Technical Reports Server (NTRS)

    Reader, Joseph; Acquista, Nicolo; Sansonetti, Craig J.; Engleman, Rolf, Jr.

    1988-01-01

    New observations of the spectrum of Pt II have been made with hollow-cathode lamps. The region from 1032 to 4101 A was observed photographically with a 10.7-m normal-incidence spectrograph. The region from 2245 to 5223 A was observed with a Fourier-transform spectrometer. Wavelength measurements were made for 558 lines. The uncertainties vary from 0.0005 to 0.004 A. From these measurements and three parity-forbidden transitions in the infrared, accurate values were determined for 28 even and 72 odd energy levels of Pt II.

  17. Accurate bond dissociation energies (D 0) for FHF- isotopologues

    NASA Astrophysics Data System (ADS)

    Stein, Christopher; Oswald, Rainer; Sebald, Peter; Botschwina, Peter; Stoll, Hermann; Peterson, Kirk A.

    2013-09-01

    Accurate bond dissociation energies (D 0) are determined for three isotopologues of the bifluoride ion (FHF-). While the zero-point vibrational contributions are taken from our previous work (P. Sebald, A. Bargholz, R. Oswald, C. Stein, P. Botschwina, J. Phys. Chem. A, DOI: 10.1021/jp3123677), the equilibrium dissociation energy (D e ) of the reaction ? was obtained by a composite method including frozen-core (fc) CCSD(T) calculations with basis sets up to cardinal number n = 7 followed by extrapolation to the complete basis set limit. Smaller terms beyond fc-CCSD(T) cancel each other almost completely. The D 0 values of FHF-, FDF-, and FTF- are predicted to be 15,176, 15,191, and 15,198 cm-1, respectively, with an uncertainty of ca. 15 cm-1.

  18. Accurate ab initio vibrational energies of methyl chloride

    SciTech Connect

    Owens, Alec; Yurchenko, Sergei N.; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2015-06-28

    Two new nine-dimensional potential energy surfaces (PESs) have been generated using high-level ab initio theory for the two main isotopologues of methyl chloride, CH{sub 3}{sup 35}Cl and CH{sub 3}{sup 37}Cl. The respective PESs, CBS-35{sup  HL}, and CBS-37{sup  HL}, are based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set (CBS) limit, and incorporate a range of higher-level (HL) additive energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms, scalar relativistic effects, and diagonal Born-Oppenheimer corrections. Variational calculations of the vibrational energy levels were performed using the computer program TROVE, whose functionality has been extended to handle molecules of the form XY {sub 3}Z. Fully converged energies were obtained by means of a complete vibrational basis set extrapolation. The CBS-35{sup  HL} and CBS-37{sup  HL} PESs reproduce the fundamental term values with root-mean-square errors of 0.75 and 1.00 cm{sup −1}, respectively. An analysis of the combined effect of the HL corrections and CBS extrapolation on the vibrational wavenumbers indicates that both are needed to compute accurate theoretical results for methyl chloride. We believe that it would be extremely challenging to go beyond the accuracy currently achieved for CH{sub 3}Cl without empirical refinement of the respective PESs.

  19. Dark matter scattering on electrons: Accurate calculations of atomic excitations and implications for the DAMA signal

    NASA Astrophysics Data System (ADS)

    Roberts, B. M.; Dzuba, V. A.; Flambaum, V. V.; Pospelov, M.; Stadnik, Y. V.

    2016-06-01

    We revisit the WIMP-type dark matter scattering on electrons that results in atomic ionization and can manifest itself in a variety of existing direct-detection experiments. Unlike the WIMP-nucleon scattering, where current experiments probe typical interaction strengths much smaller than the Fermi constant, the scattering on electrons requires a much stronger interaction to be detectable, which in turn requires new light force carriers. We account for such new forces explicitly, by introducing a mediator particle with scalar or vector couplings to dark matter and to electrons. We then perform state-of-the-art numerical calculations of atomic ionization relevant to the existing experiments. Our goals are to consistently take into account the atomic physics aspect of the problem (e.g., the relativistic effects, which can be quite significant) and to scan the parameter space—the dark matter mass, the mediator mass, and the effective coupling strength—to see if there is any part of the parameter space that could potentially explain the DAMA modulation signal. While we find that the modulation fraction of all events with energy deposition above 2 keV in NaI can be quite significant, reaching ˜50 %, the relevant parts of the parameter space are excluded by the XENON10 and XENON100 experiments.

  20. Roles of the Excitation in Harvesting Energy from Vibrations.

    PubMed

    Zhang, Hui; Ma, Tianwei

    2015-01-01

    The study investigated the role of excitation in energy harvesting applications. While the energy ultimately comes from the excitation, it was shown that the excitation may not always behave as a source. When the device characteristics do not perfectly match the excitation, the excitation alternately behaves as a source and a sink. The extent to which the excitation behaves as a sink determines the energy harvesting efficiency. Such contradictory roles were shown to be dictated by a generalized phase defined as the instantaneous phase angle between the velocity of the device and the excitation. An inductive prototype device with a diamagnetically levitated seismic mass was proposed to take advantage of the well established phase changing mechanism of vibro-impact to achieve a broader device bandwidth. Results suggest that the vibro-impact can generate an instantaneous, significant phase shift in response velocity that switches the role of the excitation. If introduced properly outside the resonance zone it could dramatically increase the energy harvesting efficiency.

  1. Roles of the Excitation in Harvesting Energy from Vibrations

    PubMed Central

    Zhang, Hui; Ma, Tianwei

    2015-01-01

    The study investigated the role of excitation in energy harvesting applications. While the energy ultimately comes from the excitation, it was shown that the excitation may not always behave as a source. When the device characteristics do not perfectly match the excitation, the excitation alternately behaves as a source and a sink. The extent to which the excitation behaves as a sink determines the energy harvesting efficiency. Such contradictory roles were shown to be dictated by a generalized phase defined as the instantaneous phase angle between the velocity of the device and the excitation. An inductive prototype device with a diamagnetically levitated seismic mass was proposed to take advantage of the well established phase changing mechanism of vibro-impact to achieve a broader device bandwidth. Results suggest that the vibro-impact can generate an instantaneous, significant phase shift in response velocity that switches the role of the excitation. If introduced properly outside the resonance zone it could dramatically increase the energy harvesting efficiency. PMID:26496183

  2. Linearity condition for orbital energies in density functional theory (V): Extension to excited state calculations

    NASA Astrophysics Data System (ADS)

    Imamura, Yutaka; Suzuki, Kensei; Iizuka, Takeshi; Nakai, Hiromi

    2015-01-01

    A new scheme is proposed for constructing an orbital-specific (OS) exchange-correlation functional that satisfies multiple linearity conditions for orbital energies (LCOEs). The Hartree-Fock exchange portions in the OS exchange-correlation functional, based on a multiply range-separated functional, are set so as to satisfy the multiple LCOEs. The current scheme has also been extended to calculations of core, valence, and Rydberg excitations. Numerical assessments on ionization potentials, electron affinities and excitation energies have confirmed accurate descriptions of core, valence, and Rydberg orbitals by the OS hybrid functional.

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

    SciTech Connect

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

    2015-02-07

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

  4. Accurate and highly efficient calculation of the highly excited pure OH stretching resonances of O(1D)HCl, using a combination of methods.

    PubMed

    Bian, Wensheng; Poirier, Bill

    2004-09-01

    Accurate calculation of the energies and widths of the resonances of HOCl--an important intermediate in the O(1D)HCl reactive system--poses a challenging benchmark for computational methods. The need for very large direct product basis sets, combined with an extremely high density of states, results in difficult convergence for iterative methods. A recent calculation of the highly excited OH stretch mode resonances using the filter diagonalization method, for example, required 462,000 basis functions, and 180,000 iterations. In contrast, using a combination of new methods, we are able to compute the same resonance states to higher accuracy with a basis less than half the size, using only a few hundred iterations-although the CPU cost per iteration is substantially greater. Similar performance enhancements are observed for calculations of the high-lying bound states, as reported in a previous paper [J. Theo. Comput. Chem. 2, 583 (2003)].

  5. Vibration energy harvesting from random force and motion excitations

    NASA Astrophysics Data System (ADS)

    Tang, Xiudong; Zuo, Lei

    2012-07-01

    A vibration energy harvester is typically composed of a spring-mass system with an electromagnetic or piezoelectric transducer connected in parallel with a spring. This configuration has been well studied and optimized for harmonic vibration sources. Recently, a dual-mass harvester, where two masses are connected in series by the energy transducer and a spring, has been proposed. The dual-mass vibration energy harvester is proved to be able to harvest more power and has a broader bandwidth than the single-mass configuration, when the parameters are optimized and the excitation is harmonic. In fact, some dual-mass vibration energy harvesters, such as regenerative vehicle suspensions and buildings with regenerative tuned mass dampers (TMDs), are subjected to random excitations. This paper is to investigate the dual-mass and single-mass vibration harvesters under random excitations using spectrum integration and the residue theorem. The output powers for these two types of vibration energy harvesters, when subjected to different random excitations, namely force, displacement, velocity and acceleration, are obtained analytically with closed-form expressions. It is also very interesting to find that the output power of the vibration energy harvesters under random excitations depends on only a few parameters in very simple and elegant forms. This paper also draws some important conclusions on regenerative vehicle suspensions and buildings with regenerative TMDs, which can be modeled as dual-mass vibration energy harvesters. It is found that, under white-noise random velocity excitation from road irregularity, the harvesting power from vehicle suspensions is proportional to the tire stiffness and road vertical excitation spectrum only. It is independent of the chassis mass, tire-wheel mass, suspension stiffness and damping coefficient. Under random wind force excitation, the power harvested from buildings with regenerative TMD will depends on the building mass only, not

  6. Spectroscopic probes of vibrationally excited molecules at chemically significant energies

    SciTech Connect

    Rizzo, T.R.

    1993-12-01

    This project involves the application of multiple-resonance spectroscopic techniques for investigating energy transfer and dissociation dynamics of highly vibrationally excited molecules. Two major goals of this work are: (1) to provide information on potential energy surfaces of combustion related molecules at chemically significant energies, and (2) to test theoretical modes of unimolecular dissociation rates critically via quantum-state resolved measurements.

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

    SciTech Connect

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

    2014-12-14

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  9. A scalable piezoelectric impulse-excited energy harvester for human body excitation

    NASA Astrophysics Data System (ADS)

    Pillatsch, P.; Yeatman, E. M.; Holmes, A. S.

    2012-11-01

    Harvesting energy from low-frequency and non-harmonic excitations typical of human motion presents specific challenges. While resonant devices do have an advantage in environments where the excitation frequency is constant, and while they can make use of the entire proof mass travel range in the case of excitation amplitudes that are smaller than the internal displacement limit, they are not suitable for body applications since the frequencies are random and the amplitudes tend to be larger than the device size. In this paper a piezoelectric, impulse-excited approach is presented. A cylindrical proof mass actuates an array of piezoelectric bi-morph beams through magnetic attraction. After the initial excitation these transducers are left to vibrate at their natural frequency. This increases the operational frequency range as well as the electromechanical coupling. The principle of impulse excitation is discussed and a centimetre-scale functional model is introduced as a proof of concept. The obtained data show the influence of varying the frequency, acceleration and proof mass. Finally, a commercially available integrated circuit for voltage regulation is tested. At a frequency of 2 Hz and an acceleration of 2.7 m s-2 a maximal power output of 2.1 mW was achieved.

  10. A simple formula for the energies of doubly excited states

    SciTech Connect

    Lin, C.D.; Watanabe, S.

    1986-11-01

    A simple formula for the energy levels of doubly excited states of atoms and multiply charged ions is derived and expressed in terms of a set of new correlation quantum numbers. The accuracy of the formula is checked by comparing with the results from other elaborate calculations. Modification of the formula for doubly excited states of multielectron atoms are also presented. 12 refs., 2 tabs.

  11. Excitation energy migration in uniaxially oriented polymer films

    NASA Astrophysics Data System (ADS)

    Bojarski, P.; Kamińska, A.; Kułak, L.; Sadownik, M.

    2003-07-01

    Multistep nonradiative excitation energy transport is for the first time studied in uniaxially stretched polymer films. Concentration depolarization studies performed for 3,3 '-diethylthiacarbocyanine iodide (DTCI) for stretched (system I) and unstretched (system II) polyvinyl alcohol films (PVA) yield extremely different results. As expected, disordered system II exhibits strong concentration depolarization due to energy migration between identical fluorophores. However, for stretched films, concentration depolarization effect is much weaker and it occurs at higher dye concentrations compared to system II. This fact is mostly due to strongly modified angular distribution of dipole moments of molecules taking part in the excitation energy migration.

  12. Predicting Accurate Electronic Excitation Transfer Rates via Marcus Theory with Boys or Edmiston-Ruedenberg Localized Diabatization

    SciTech Connect

    Subotnik, Joseph E.; Vura-Weis, Josh; Sodt, Alex J.; Ratner, Mark A.

    2010-05-06

    We model the triplet-triplet energy-transfer experiments from the Closs group [Closs, G. L.; et al. J. Am. Chem. Soc. 1988, 110, 2652.] using a combination of Marcus theory and either Boys or Edmiston-Ruedenberg localized diabatization, and we show that relative and absolute rates of electronic excitation transfer may be computed successfully. For the case where both the donor and acceptor occupy equatorial positions on a rigid cyclohexane bridge, we find βcalc = 2.8 per C-C bond, compared with the experimental value βexp = 2.6. This work highlights the power of using localized diabatization methods as a tool for modeling nonequilibrium processes.

  13. Energy harvesting under excitations of time-varying frequency

    NASA Astrophysics Data System (ADS)

    Seuaciuc-Osório, Thiago; Daqaq, Mohammed F.

    2010-06-01

    The design and optimization of energy harvesters capable of scavenging energy efficiently from realistic environments require a deep understanding of their transduction under non-stationary and random excitations. Otherwise, their small energy outputs can be further decreased lowering their efficiency and rendering many critical and possibly life saving technologies inefficient. As a first step towards this critical understanding, this effort investigates the response of energy harvesters to harmonic excitations of time-varying frequency. Such excitations can be used to represent the behavior of realistic vibratory environments whose frequency varies or drifts with time. Specifically, we consider a piezoelectric stack-type harvester subjected to a harmonic excitation of constant amplitude and a sinusoidally varying frequency. We analyze the response of the harvester in the fixed-frequency scenario then use the Jacobi-Anger's expansion to analyze the response in the time-varying case. We obtain analytical expressions for the harvester's response, output voltage, and power. In-depth analysis of the attained results reveals that the solution to the more complex time-varying frequency can be understood through a process which "samples" the fixed-frequency response curve at a discrete and fixed frequency interval then multiplies the response by proper weights. Extensive discussions addressing the effect of the excitation parameters on the output power is presented leading to some initial suggestions pertinent to the harvester's design and optimization in the sinusoidally varying frequency case.

  14. Excitation energy after a smooth quench in a Luttinger liquid

    SciTech Connect

    Dziarmaga, Jacek; Tylutki, Marek

    2011-12-01

    Low-energy physics of quasi-one-dimensional ultracold atomic gases is often described by a gapless Luttinger liquid (LL). It is nowadays routine to manipulate these systems by changing their parameters in time but, no matter how slow the manipulation is, it must excite a gapless system. We study a smooth change of parameters of the LL (a smooth ''quench'') with a variable quench time and find that the excitation energy decays with an inverse power of the quench time. This universal exponent is -2 at zero temperature and -1 for slow enough quenches at finite temperature. The smooth quench does not excite beyond the range of validity of the low-energy LL description.

  15. Intermediate-energy Coulomb excitation of {sup 52}Fe

    SciTech Connect

    Yurkewicz, K.L.; Brown, B.A.; Campbell, C.M.; Church, J.A.; Dinca, D.-C.; Glasmacher, T.; Olliver, H.; Terry, J.R.; Bazin, D.; Gade, A.; Mueller, W.F.; Honma, M.; Mizusaki, T.; Otsuka, T.; Riley, L.A.

    2004-09-01

    The nucleus {sup 52}Fe with (N=Z=26) has been investigated using intermediate-energy Coulomb excitation in inverse kinematics. A reduced transition probability of B(E2;0{sub 1}{sup +}{yields}2{sub 1}{sup +})=817(102) e{sup 2} fm{sup 4} to the first excited 2{sup +} state at 849.0(5) keV was deduced. The increase in excitation strength B(E2{up_arrow}) with respect to the even-mass neighbor {sup 54}Fe (B(E2{up_arrow})=620(50) e{sup 2} fm{sup 4}) agrees with shell-model expectations as the magic number N=28 is approached. This measurement completes the systematics of reduced transition strengths to the first excited 2{sup +} state for the even-even N=Z nuclei up to mass A=56.

  16. A survey of factors contributing to accurate theoretical predictions of atomization energies and molecular structures

    NASA Astrophysics Data System (ADS)

    Feller, David; Peterson, Kirk A.; Dixon, David A.

    2008-11-01

    High level electronic structure predictions of thermochemical properties and molecular structure are capable of accuracy rivaling the very best experimental measurements as a result of rapid advances in hardware, software, and methodology. Despite the progress, real world limitations require practical approaches designed for handling general chemical systems that rely on composite strategies in which a single, intractable calculation is replaced by a series of smaller calculations. As typically implemented, these approaches produce a final, or "best," estimate that is constructed from one major component, fine-tuned by multiple corrections that are assumed to be additive. Though individually much smaller than the original, unmanageable computational problem, these corrections are nonetheless extremely costly. This study presents a survey of the widely varying magnitude of the most important components contributing to the atomization energies and structures of 106 small molecules. It combines large Gaussian basis sets and coupled cluster theory up to quadruple excitations for all systems. In selected cases, the effects of quintuple excitations and/or full configuration interaction were also considered. The availability of reliable experimental data for most of the molecules permits an expanded statistical analysis of the accuracy of the approach. In cases where reliable experimental information is currently unavailable, the present results are expected to provide some of the most accurate benchmark values available.

  17. Physical Meaning of Virtual Kohn-Sham Orbitals and Orbital Energies: An Ideal Basis for the Description of Molecular Excitations.

    PubMed

    van Meer, R; Gritsenko, O V; Baerends, E J

    2014-10-14

    In recent years, several benchmark studies on the performance of large sets of functionals in time-dependent density functional theory (TDDFT) calculations of excitation energies have been performed. The tested functionals do not approximate exact Kohn-Sham orbitals and orbital energies closely. We highlight the advantages of (close to) exact Kohn-Sham orbitals and orbital energies for a simple description, very often as just a single orbital-to-orbital transition, of molecular excitations. Benchmark calculations are performed for the statistical average of orbital potentials (SAOP) functional for the potential [J. Chem. Phys. 2000, 112, 1344; 2001, 114, 652], which approximates the true Kohn-Sham potential much better than LDA, GGA, mGGA, and hybrid potentials do. An accurate Kohn-Sham potential does not only perform satisfactorily for calculated vertical excitation energies of both valence and Rydberg transitions but also exhibits appealing properties of the KS orbitals including occupied orbital energies close to ionization energies, virtual-occupied orbital energy gaps very close to excitation energies, realistic shapes of virtual orbitals, leading to straightforward interpretation of most excitations as single orbital transitions. We stress that such advantages are completely lost in time-dependent Hartree-Fock and partly in hybrid approaches. Many excitations and excitation energies calculated with local density, generalized gradient, and hybrid functionals are spurious. There is, with an accurate KS, or even the LDA or GGA potentials, nothing problematic about the "band gap" in molecules: the HOMO-LUMO gap is close to the first excitation energy (the optical gap).

  18. Vibration excitation and energy transfer during ultrasonically assisted drilling

    NASA Astrophysics Data System (ADS)

    Babitsky, V. I.; Astashev, V. K.; Meadows, A.

    2007-12-01

    Successful application of ultrasonically assisted drilling needs dynamic matching of the transducer with the drill bit considered as a continuous system loaded by the nonlinear processing load. When using standard tools this leads to the compatible choice of the transducer and accurate matching of the transducer and tool. The principal dynamical features of this matching are considered. Optimal position of excitation cross section of the drill bit, which depends on the relationship between elasto-dissipative characteristics of the transducer, the drill bit and the work load, is found in general analytical form. The optimal matching preserves the resonant tuning of the transducer and compensates the additional energy losses in the drill bit and processing. This produces also an amplification of vibration amplitude. The effect is achieved through the generation and maintenance of a nonlinear resonant mode of vibration and by active matching of the oscillating system with the dynamic loads imposed by the cutting process with the help of the intelligent electronic feedback circuitry. A prototype of an ultrasonic drilling system has been designed, manufactured. and tested. Improvements of machining characteristics due to superposition of ultrasonic vibration are demonstrated. Substantial improvements in the cutting performance of drill bits lead to benefits in drilling performance, which include faster penetration rates, reduction of tool wear, improvements in the surface finish, roundness and straightness of holes and, in ductile materials, the reduction or even complete elimination of burrs on both the entrance and exit faces of plates. The reduction in the reactive force experienced also causes greatly reduced deformation when drilling through thin, flexible plates and helps to alleviate delamination hazard.

  19. Low-energy Coulomb excitation of radioactive ^70Se

    NASA Astrophysics Data System (ADS)

    Hurst, Aaron

    2007-10-01

    An isobarically pure beam of ^70Se ions was post accelerated to an energy of 206 MeV using REX-ISOLDE. Coulomb-excitation yields for states in the beam and target nuclei were deduced by recording de-excitation γ rays in the highly segmented MINIBALL γ-ray spectrometer in coincidence with scattered particles in a silicon detector. At these energies, the Coulomb-excitation yield for the 2^+1 state in ^70Se is expected to be strongly sensitive to the sign of the spectroscopic quadrupole moment through the nuclear reorientation effect. Experimental evidence is presented here for a prolate shape for this state, using an earlier published lifetime measurement, reopening the question over whether there are deformed oblate shapes close to the ground state in the neutron-deficient selenium isotopes.

  20. Importance of excitation and trapping conditions in photosynthetic environment-assisted energy transport.

    PubMed

    León-Montiel, Roberto de J; Kassal, Ivan; Torres, Juan P

    2014-09-11

    It has been argued that excitonic energy transport in photosynthetic complexes is efficient because of a balance between coherent evolution and decoherence, a phenomenon called environment-assisted quantum transport (ENAQT). Studies of ENAQT have usually assumed that the excitation is initially localized on a particular chromophore, and that it is transferred to a reaction center through a similarly localized trap. However, these assumptions are not physically accurate. We show that more realistic models of excitation and trapping can lead to very different predictions about the importance of ENAQT. In particular, although ENAQT is a robust effect if one assumes a localized trap, its effect can be negligible if the trapping is more accurately modeled as Förster transfer to a reaction center. Our results call into question the suggested role of ENAQT in the photosynthetic process of green sulfur bacteria and highlight the subtleties associated with drawing lessons for designing biomimetic light-harvesting complexes.

  1. Communication: An accurate global potential energy surface for the ground electronic state of ozone

    SciTech Connect

    Dawes, Richard E-mail: hguo@unm.edu; Lolur, Phalgun; Li, Anyang; Jiang, Bin; Guo, Hua E-mail: hguo@unm.edu

    2013-11-28

    We report a new full-dimensional and global potential energy surface (PES) for the O + O{sub 2} → O{sub 3} ozone forming reaction based on explicitly correlated multireference configuration interaction (MRCI-F12) data. It extends our previous [R. Dawes, P. Lolur, J. Ma, and H. Guo, J. Chem. Phys. 135, 081102 (2011)] dynamically weighted multistate MRCI calculations of the asymptotic region which showed the widely found submerged reef along the minimum energy path to be the spurious result of an avoided crossing with an excited state. A spin-orbit correction was added and the PES tends asymptotically to the recently developed long-range electrostatic model of Lepers et al. [J. Chem. Phys. 137, 234305 (2012)]. This PES features: (1) excellent equilibrium structural parameters, (2) good agreement with experimental vibrational levels, (3) accurate dissociation energy, and (4) most-notably, a transition region without a spurious reef. The new PES is expected to allow insight into the still unresolved issues surrounding the kinetics, dynamics, and isotope signature of ozone.

  2. Mean excitation energy for molecules of hydrogen and carbon

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Kamaratos, E.

    1981-01-01

    The Gordon-Kim electron gas model of molecular bonding is used to calculate correction factors for the Bragg rule for molecules of hydrogen and carbon. General rules for molecular mean excitation energies are obtained that agree to about 4% with experimental values.

  3. Complex fragment emission at low and high excitation energy

    SciTech Connect

    Moretto, L.G.

    1986-08-01

    Complex fragment emission has been certified as a compound nucleus process at low energies. An extension of the measurements to heavy ion reactions up to 50 MeV/u shows that most complex fragments are emitted by highly excited compound nuclei formed in incomplete fusion reactions. 12 refs., 26 figs.

  4. Excitation energy dependent Raman spectrum of MoSe2

    PubMed Central

    Nam, Dahyun; Lee, Jae-Ung; Cheong, Hyeonsik

    2015-01-01

    Raman investigation of MoSe2 was carried out with eight different excitation energies. Seven peaks, including E1g, A1g, E2g1, and A2u2 peaks are observed in the range of 100–400 cm−1. The phonon modes are assigned by comparing the peak positions with theoretical calculations. The intensities of the peaks are enhanced at different excitation energies through resonance with different optical transitions. The A1g mode is enhanced at 1.58 and 3.82 eV, which are near the A exciton energy and the band-to-band transition between higher energy bands, respectively. The E2g1 mode is strongly enhanced with respect to the A1g mode for the 2.71- and 2.81-eV excitations, which are close to the C exciton energy. The different enhancements of the A1g and E2g1 modes are explained in terms of the symmetries of the exciton states and the exciton-phonon coupling. Other smaller peaks including E1g and A2u2 are forbidden but appear due to the resonance effect near optical transition energies. PMID:26601614

  5. The Calculation of Accurate Metal-Ligand Bond Energies

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W.; Partridge, Harry, III; Ricca, Alessandra; Arnold, James O. (Technical Monitor)

    1997-01-01

    The optimization of the geometry and calculation of zero-point energies are carried out at the B3LYP level of theory. The bond energies are determined at this level, as well as at the CCSD(T) level using very large basis sets. The successive OH bond energies to the first row transition metal cations are reported. For most systems there has been an experimental determination of the first OH. In general, the CCSD(T) values are in good agreement with experiment. The bonding changes from mostly covalent for the early metals to mostly electrostatic for the late transition metal systems.

  6. Structures and Low-Energy Excitations of Amorphous Gas Hydrates

    NASA Astrophysics Data System (ADS)

    Kikuchi, Tatsuya; Inamura, Yasuhiro; Onoda-Yamamuro, Noriko; Yamamuro, Osamu

    2012-09-01

    We have prepared amorphous clathrate hydrates of Ar, CD4, Xe, and SF6 by depositing mixed vapors of water and guest molecules on a substrate at ca. 10 K. The structure and vibrational density of states were investigated by neutron diffraction and inelastic scattering techniques, respectively. The radial distribution functions of the amorphous hydrates are larger than that of pure amorphous ice in the region around 4 Å (the center-edge distance of the 12-hedral cage), indicating that a local cagelike structure is maintained even in the amorphous solids. The incorporation of the guest molecules decreases the intensity of the phonon excitation below 7 meV, which is known as a low-energy excitation characteristic of amorphous ice. This may be due to the effect that the disorder, defects and distortion producing the low-energy excitation are reduced by a hydrophobic hydration between the guest and water molecules and the resultant hydrogen-bond formation. A similar effect was also observed in the libration mode of water molecules at about 60 meV. The present work has revealed the relation among the local cage formation, hydrogen bonds, and low energy excitations in amorphous hydrates that is the simplest hydrophobic hydration system (H2O--gas mixture).

  7. Heavy-ion fission probability calculations at high excitation energy

    SciTech Connect

    D'Arrigo, A.; Giardina, G.; Taccone, A. Istituto Nazionale di Fisica Nucleare, Gruppo Collegato di Messina, Messina Istituto di Tecniche Spettroscopiche del Consiglio Nazionale delle Ricerche, Messina )

    1991-12-01

    In the framework of the statistical theory of nuclear reactions we calculated the fission probability {ital P}{sub {ital f}} of the {sup 153}Tb, {sup 158}Er, {sup 159}Dy, {sup 175}Hf, {sup 179}Ta, {sup 186}Os, and {sup 188}Os nuclei with a mass number {ital A}=150--200 produced by heavy-ion reactions. Starting from the spectra of the single-particle levels as determined by Nix and Moeller, and utilizing a formalism we developed, we determined the excitation energy dependence of the effective level density parameters for the fission and the neutron emission channels. The agreement between the fission probability calculations and the experimental data was reached when a nonadiabatic estimate of the collective effects was used to calculate the nuclear level density. In the fission process at high excitation energies induced by ions heavier than the {alpha} particle, an energy dependence of the effective fission barrier has to be used.

  8. Elementary excitation and energy landscape in simple liquids

    NASA Astrophysics Data System (ADS)

    Egami, T.

    2014-06-01

    The nature of excitations in liquids has been a subject of debate for a long time. In liquids, phonons are extremely short-lived and marginalized. Instead, recent research results indicate that local topological or configurational excitations (anankeons) are the elementary excitations in high temperature metallic liquids. Local topological excitations are those which locally alter the atomic connectivity network by cutting or forming atomic bonds, and are directly tied to the atomistic origin of viscosity in the liquid. The local potential energy landscape (PEL) of anankeons represents the probability weighted projection of the global PEL to a single atom. The original PEL is an insightful concept, but is highly multi-dimensional and difficult to characterize or even to visualize. A description in terms of the local PEL for anankeons appears to offer a simpler and more effective approach toward this complex problem. At the base of these advances, is the recognition that atomic discreteness and the topology of atomic connectivity are the most crucial features of the structure in liquids, which current nonlinear continuum theories cannot fully capture. These discoveries could open the way to the explanation of various complex phenomena in liquids, such as atomic transport, fragility, and the glass transition, in terms of these excitations.

  9. Spectroscopically Accurate Calculations of the Rovibrational Energies of Diatomic Hydrogen

    NASA Astrophysics Data System (ADS)

    Perry, Jason

    2005-05-01

    The Born-Oppenheimer approximation has been used to calculate the rotational and vibrational states of diatomic hydrogen. Because it is an approximation, our group now wants to use a Born-Oppenheimer potential to calculate the electronic energy that has been corrected to match closely with spectroscopic results. We are using a code that has corrections for adiabatic, relativistic, radiative, and non-adiabatic effects. The rovibrational energies have now been calculated for both bound and quasi-bound states. We also want to compute quadrupole transition probabilities for diatomic hydrogen. These calculations aspire to investigate diatomic hydrogen in astrophysical environments.

  10. Intramolecular energy transfer and excitation coupling in metal-to-ligand charge transfer (MLCT) excited states

    NASA Astrophysics Data System (ADS)

    Riesen, Hans; Krausz, Elmars

    1995-02-01

    [Zn(bpy)3](ClO4)2 are indicated in our preliminary results. In inhomogeneously broadened systems such as frozen glasses or solutions, in which MLCT excitations involving different ligands on the same chromophore may differ in energy by 100 cm-1 or more, an effectively localized description of the low lying 3MLCT states is appropriate for [Os(bpy)3]2+.

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

    PubMed

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

    2016-05-01

    This article explores the excitation of different vibrational states in a spatially extended dynamical system through theory and experiment. As a prototypical example, we consider a one-dimensional packing of spherical particles (a so-called granular chain) that is subject to harmonic boundary excitation. The combination of the multimodal nature of the system and the strong coupling between the particles due to the nonlinear Hertzian contact force leads to broad regions in frequency where different vibrational states are possible. In certain parametric regions, we demonstrate that the nonlinear Schrödinger equation predicts the corresponding modes fairly well. The electromechanical model we apply predicts accurately the conversion from the obtained mechanical energy to the electrical energy observed in experiments. PMID:27300876

  12. The free energy cost of accurate biochemical oscillations

    PubMed Central

    Cao, Yuansheng; Wang, Hongli; Ouyang, Qi; Tu, Yuhai

    2015-01-01

    Oscillation is an important cellular process that regulates timing of different vital life cycles. However, in the noisy cellular environment, oscillations can be highly inaccurate due to phase fluctuations. It remains poorly understood how biochemical circuits suppress phase fluctuations and what is the incurred thermodynamic cost. Here, we study three different types of biochemical oscillations representing three basic oscillation motifs shared by all known oscillatory systems. In all the systems studied, we find that the phase diffusion constant depends on the free energy dissipation per period following the same inverse relation parameterized by system specific constants. This relationship and its range of validity are shown analytically in a model of noisy oscillation. Microscopically, we find that the oscillation is driven by multiple irreversible cycles that hydrolyze the fuel molecules such as ATP; the number of phase coherent periods is proportional to the free energy consumed per period. Experimental evidence in support of this general relationship and testable predictions are also presented. PMID:26566392

  13. The free-energy cost of accurate biochemical oscillations

    NASA Astrophysics Data System (ADS)

    Cao, Yuansheng; Wang, Hongli; Ouyang, Qi; Tu, Yuhai

    2015-09-01

    Oscillations within the cell regulate the timing of many important life cycles. However, in this noisy environment, oscillations can be highly inaccurate owing to phase fluctuations. It remains poorly understood how biochemical circuits suppress these phase fluctuations and what is the incurred thermodynamic cost. Here, we study three different types of biochemical oscillation, representing three basic oscillation motifs shared by all known oscillatory systems. In all the systems studied, we find that the phase diffusion constant depends on the free-energy dissipation per period, following the same inverse relation parameterized by system-specific constants. This relationship and its range of validity are shown analytically in a model of noisy oscillation. Microscopically, we find that the oscillation is driven by multiple irreversible cycles that hydrolyse fuel molecules such as ATP; the number of phase coherent periods is proportional to the free energy consumed per period. Experimental evidence in support of this general relationship and testable predictions are also presented.

  14. Accurate global potential energy surface for the H + OH+ collision

    NASA Astrophysics Data System (ADS)

    Gannouni, M. A.; Jaidane, N. E.; Halvick, P.; Stoecklin, T.; Hochlaf, M.

    2014-05-01

    We mapped the global three-dimensional potential energy surface (3D-PES) of the water cation at the MRCI/aug-cc-pV5Z including the basis set superposition (BSSE) correction. This PES covers the molecular region and the long ranges close to the H + OH+(X3Σ-), the O + H2+(X2Σg+), and the hydrogen exchange channels. The quality of the PES is checked after comparison to previous experimental and theoretical results of the spectroscopic constants of H2O+(tilde X2B1) and of the diatomic fragments, the vibronic spectrum, the dissociation energy, and the barrier to linearity for H2O+(tilde X2B1). Our data nicely approach those measured and computed previously. The long range parts reproduce quite well the diatomic potentials. In whole, a good agreement is found, which validates our 3D-PES.

  15. Additional correction for energy transfer efficiency calculation in filter-based Förster resonance energy transfer microscopy for more accurate results

    NASA Astrophysics Data System (ADS)

    Sun, Yuansheng; Periasamy, Ammasi

    2010-03-01

    Förster resonance energy transfer (FRET) microscopy is commonly used to monitor protein interactions with filter-based imaging systems, which require spectral bleedthrough (or cross talk) correction to accurately measure energy transfer efficiency (E). The double-label (donor+acceptor) specimen is excited with the donor wavelength, the acceptor emission provided the uncorrected FRET signal and the donor emission (the donor channel) represents the quenched donor (qD), the basis for the E calculation. Our results indicate this is not the most accurate determination of the quenched donor signal as it fails to consider the donor spectral bleedthrough (DSBT) signals in the qD for the E calculation, which our new model addresses, leading to a more accurate E result. This refinement improves E comparisons made with lifetime and spectral FRET imaging microscopy as shown here using several genetic (FRET standard) constructs, where cerulean and venus fluorescent proteins are tethered by different amino acid linkers.

  16. A generalized tool for accurate time-domain separation of excited modes in spin-torque oscillators

    SciTech Connect

    Siracusano, Giulio Puliafito, Vito; Finocchio, Giovanni

    2014-05-07

    We propose and develop an advanced signal processing technique that, combined with micromagnetic simulations, is able to deeply describe the non-stationary behavior of spin-torque oscillators, both in terms of time domain and spatial distribution of the magnetization dynamics. The Hilbert-Huang Transform is used for the identification of the time traces of each oscillation in a multimode excitation and enhanced with masking signals and the Ensemble Empirical Mode Decomposition. We emphasize that the technique developed here is general and can be used for any physical non-linear system in the presence of multimode dynamical excitation or intermittence.

  17. High-energy excited states in 98Cd

    NASA Astrophysics Data System (ADS)

    Blazhev, A.; Braun, N.; Grawe, H.; Boutachkov, P.; Nara Singh, B. S.; Brock, T.; Liu, Zh; Wadsworth, R.; Górska, M.; Jolie, J.; Nowacki, F.; Pietri, S.; Domingo-Pardo, C.; Kojouharov, I.; Caceres, L.; Engert, T.; Farinon, F.; Gerl, J.; Goel, N.; Grȩbosz, J.; Hoischen, R.; Kurz, N.; Nociforo, C.; Prochazka, A.; Schaffner, H.; Steer, S.; Weick, H.; Wollersheim, H.-J.; Ataç, A.; Bettermann, L.; Eppinger, K.; Faestermann, T.; Finke, F.; Geibel, K.; Hinke, C.; Gottardo, A.; Ilie, G.; Iwasaki, H.; Krücken, R.; Merchan, E.; Nyberg, J.; Pfützner, M.; Podolyák, Zs; Regan, P.; Reiter, P.; Rinta-Antila, S.; Rudolph, D.; Scholl, C.; Söderström, P.-A.; Warr, N.; Woods, P.

    2010-01-01

    In 98Cd a new high-energy isomeric γ-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 98Cd high-excitation level scheme are presented. A comparison to shell-model calculations as well as implications for the nuclear structure around 100Sn are discussed.

  18. An Accurate Potential Energy Surface for H2O

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

  19. Excitation-energy dependence of the giant dipole resonance width

    NASA Astrophysics Data System (ADS)

    Enders, G.; Berg, F. D.; Hagel, K.; Kühn, W.; Metag, V.; Novotny, R.; Pfeiffer, M.; Schwalb, O.; Charity, R. J.; Gobbi, A.; Freifelder, R.; Henning, W.; Hildenbrand, K. D.; Holzmann, R.; Mayer, R. S.; Simon, R. S.; Wessels, J. P.; Casini, G.; Olmi, A.; Stefanini, A. A.

    1992-07-01

    High-energy γ rays have been measured in coincidence with heavy fragents in deeply inelastic reactions of 136Xe+48Ti at 18.5 MeV/nucleon. The giant dipole resonance (GDR) strength function is deduced from an analysis of the photon spectra within the statistical model. The GDR width Γ is studied as a function of the fragment excitation energy E*. A saturation at about Γ=10 MeV is observed for E*/A>=1.0 MeV/nucleon.

  20. Excitation energy and nuclear dissipation probed with evaporation-residue cross sections

    SciTech Connect

    Ye, W.

    2011-04-15

    Using a Langevin equation coupled with a statistical decay model, we calculate the excess of evaporation-residue cross sections over its standard statistical-model value as a function of nuclear dissipation strength for {sup 200}Hg compound nuclei (CNs) under two distinct types of initial conditions for populated CNs: (i) high excitation energy but low angular momentum (produced via proton-induced spallation reactions at GeV energies and via peripheral heavy-ion collisions at relativistic energies) and (ii) high angular momentum but low excitation energy (produced through fusion mechanisms). We find that the conditions of case (ii) not only amplify the effect of dissipation on the evaporation residues, but also substantially increase the sensitivity of this excess to nuclear dissipation. These results suggest that, in experiments, to obtain accurate information of presaddle nuclear dissipation strength by measuring evaporation-residue cross sections, it is best to choose the heavy-ion-induced fusion reaction approach to yield excited compound nuclei.

  1. Boltzmann rovibrational collisional coarse-grained model for internal energy excitation and dissociation in hypersonic flows.

    PubMed

    Munafò, A; Panesi, M; Magin, T E

    2014-02-01

    A Boltzmann rovibrational collisional coarse-grained model is proposed to reduce a detailed kinetic mechanism database developed at NASA Ames Research Center for internal energy transfer and dissociation in N(2)-N interactions. The coarse-grained model is constructed by lumping the rovibrational energy levels of the N(2) molecule into energy bins. The population of the levels within each bin is assumed to follow a Boltzmann distribution at the local translational temperature. Excitation and dissociation rate coefficients for the energy bins are obtained by averaging the elementary rate coefficients. The energy bins are treated as separate species, thus allowing for non-Boltzmann distributions of their populations. The proposed coarse-grained model is applied to the study of nonequilibrium flows behind normal shock waves and within converging-diverging nozzles. In both cases, the flow is assumed inviscid and steady. Computational results are compared with those obtained by direct solution of the master equation for the rovibrational collisional model and a more conventional multitemperature model. It is found that the proposed coarse-grained model is able to accurately resolve the nonequilibrium dynamics of internal energy excitation and dissociation-recombination processes with only 20 energy bins. Furthermore, the proposed coarse-grained model provides a superior description of the nonequilibrium phenomena occurring in shock heated and nozzle flows when compared with the conventional multitemperature models.

  2. Intermediate-energy Coulomb excitation of {sup 30}Na

    SciTech Connect

    Ettenauer, S.; Adrich, P.; Bazin, D.; Campbell, C. M.; Lecouey, J.-L.; Mueller, W. F.; Yoneda, K.; Zwahlen, H.; Cook, J. M.; Davies, A. D.; Dinca, D.-C.; Gade, A.; Glasmacher, T.; Terry, J. R.; Otsuka, T.; Reynolds, R. R.; Riley, L. A.; Utsuno, Y.

    2008-07-15

    The neutron-rich nucleus {sup 30}Na in the vicinity of the 'Island of Inversion' was investigated using intermediate-energy Coulomb excitation. A single {gamma}-ray transition was observed and attributed to the 3{sub 1}{sup +}{yields}2{sub gs}{sup +} decay. A transition probability of B(E2;2{sub gs}{sup +}{yields}3{sub 1}{sup +})=147(21) e{sup 2} fm{sup 4} was determined and found in agreement with a previous experiment and with large-scale shell-model calculations. Evidence for the strong excitation of the 4{sub 1}{sup +} state predicted by the shell-model calculations was not observed.

  3. Entanglement of Low-Energy Excitations in Conformal Field Theory

    SciTech Connect

    Alcaraz, Francisco Castilho; Ibanez Berganza, Miguel; Sierra, German

    2011-05-20

    In a quantum critical chain, the scaling regime of the energy and momentum of the ground state and low-lying excitations are described by conformal field theory (CFT). The same holds true for the von Neumann and Renyi entropies of the ground state, which display a universal logarithmic behavior depending on the central charge. In this Letter we generalize this result to those excited states of the chain that correspond to primary fields in CFT. It is shown that the nth Renyi entropy is related to a 2n-point correlator of primary fields. We verify this statement for the critical XX and XXZ chains. This result uncovers a new link between quantum information theory and CFT.

  4. Amino Acid Mean Excitation Energies and Directional Dependencies from Core and Bond Calculations

    SciTech Connect

    Sabin, John R.; Oddershede, Jens; Sauer, Stephan P. A.

    2008-12-08

    We determine the mean excitation energies of several amino acids using a Bragg Rule developed for molecular fragments or functional groups. As the composition of the amino acids is very similar, we find that the amino acids have similar mean excitation energies (approximately 70 eV). Differences arise from variation of the side chains (-R); addition of-CH2-groups decreases the mean excitation energy. We also speculate concerning the directional dependence of the amino acid mean excitation energies.

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

    NASA Astrophysics Data System (ADS)

    Huo, Pengfei

    2011-12-01

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

  6. Distributed Multipolar Expansion Approach to Calculation of Excitation Energy Transfer Couplings.

    PubMed

    Błasiak, Bartosz; Maj, Michał; Cho, Minhaeng; Góra, Robert W

    2015-07-14

    We propose a new approach for estimating the electrostatic part of the excitation energy transfer (EET) coupling between electronically excited chromophores based on the transition density-derived cumulative atomic multipole moments (TrCAMM). In this approach, the transition potential of a chromophore is expressed in terms of truncated distributed multipolar expansion and analytical formulas for the TrCAMMs are derived. The accuracy and computational feasibility of the proposed approach is tested against the exact Coulombic couplings, and various multipole expansion truncation schemes are analyzed. The results of preliminary calculations show that the TrCAMM approach is capable of reproducing the exact Coulombic EET couplings accurately and efficiently and is superior to other widely used schemes: the transition charges from electrostatic potential (TrESP) and the transition density cube (TDC) method.

  7. Phonon-assisted excitation energy transfer in photosynthetic systems

    NASA Astrophysics Data System (ADS)

    Chen, Hao; Wang, Xin; Fang, Ai-Ping; Li, Hong-Rong

    2016-09-01

    The phonon-assisted process of energy transfer aiming at exploring the newly emerging frontier between biology and physics is an issue of central interest. This article shows the important role of the intramolecular vibrational modes for excitation energy transfer in the photosynthetic systems. Based on a dimer system consisting of a donor and an acceptor modeled by two two-level systems, in which one of them is coupled to a high-energy vibrational mode, we derive an effective Hamiltonian describing the vibration-assisted coherent energy transfer process in the polaron frame. The effective Hamiltonian reveals in the case that the vibrational mode dynamically matches the energy detuning between the donor and the acceptor, the original detuned energy transfer becomes resonant energy transfer. In addition, the population dynamics and coherence dynamics of the dimer system with and without vibration-assistance are investigated numerically. It is found that, the energy transfer efficiency and the transfer time depend heavily on the interaction strength of the donor and the high-energy vibrational mode, as well as the vibrational frequency. The numerical results also indicate that the initial state and dissipation rate of the vibrational mode have little influence on the dynamics of the dimer system. Results obtained in this article are not only helpful to understand the natural photosynthesis, but also offer an optimal design principle for artificial photosynthesis. Project supported by the National Natural Science Foundation of China (Grant No. 11174233).

  8. Enhanced luminescence excitation via efficient optical energy transfer (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Aad, Roy; Nomenyo, Komla D.; Bercu, Bogdan; Couteau, Christophe; Sallet, Vincent; Rogers, David J.; Molinari, Michael; Lérondel, Gilles

    2015-10-01

    Luminescent nanoscale materials (LNMs) have received widespread interest in sensing and lighting applications due to their enhanced emissive properties. For sensing applications, LNMs offer improved sensitivity and fast response time which allow for lower limits of detection. Meanwhile, for lighting applications, LNMs, such as quantum dots, offer an improved internal quantum efficiency and controlled color rendering which allow for better lighting performances. Nevertheless, due to their nanometric dimensions, nanoscale materials suffer from extremely weak luminescence excitation (i.e. optical absorption) limiting their luminescence intensity, which in turn results in a downgrade in the limits of detection and external quantum efficiencies. Therefore, enhancing the luminescence excitation is a major issue for sensing and lighting applications. In this work, we report on a novel photonic approach to increase the luminescence excitation of nanoscale materials. Efficient luminescence excitation increase is achieved via a gain-assisted waveguided energy transfer (G-WET). The G-WET concept consists on placing nanoscale materials atop of a waveguiding active (i.e. luminescent) layer with optical gain. Efficient energy transfer is thus achieved by exciting the nanoscale material via the tail of the waveguided mode of the active layer emission. The G-WET concept is demonstrated on both a nanothin layer of fluorescent sensitive polymer and on CdSe/ZnS quantum dots coated on ZnO thin film, experimentally proving up to an 8-fold increase in the fluorescence of the polymer and a 3-fold increase in the luminescence of the CdSe/ZnS depending of the active layer emission regime (stimulated vs spontaneous emission). Furthermore, we will discuss on the extended G-WET concept which consists on coating nanoscale materials on a nanostructured active layer. The nanostructured active layer offers the necessary photonic modulation and a high specific surface which can presumably lead to

  9. Piezoelectric compliant mechanism energy harvesters under large base excitations

    NASA Astrophysics Data System (ADS)

    Ma, Xiaokun; Trolier-McKinstry, Susan; Rahn, Christopher D.

    2016-09-01

    A piezoelectric compliant mechanism (PCM) energy harvester is designed, modeled, and analyzed that consists of a polyvinylidene diflouoride, PVDF unimorph clamped at its base and attached to a compliant mechanism at its tip. The compliant hinge stiffness is carefully tuned to approach a low frequency first mode with an efficient (nearly quadratic) shape that provides a uniform strain distribution. A nonlinear model of the PCM energy harvester under large base excitation is derived to determine the maximum power that can be generated by the device. Experiments with a fabricated PCM energy harvester prototype show that the compliant mechanism introduces a stiffening effect and a much wider bandwidth than a benchmark proof mass cantilever design. The PCM bridge structure self-limits the displacement and maximum strain at large excitations compared with the proof mass cantilever, improving the device robustness. The PCM outperforms the cantilever in both average power and power-strain sensitivity at high accelerations due to the PCM axial stretching effect and its more uniform strain distribution.

  10. Energy harvesting under excitation of clamped-clamped beam

    NASA Astrophysics Data System (ADS)

    Batra, Ashok; Alomari, Almuatasim; Aggarwal, Mohan; Bandyopadhyay, Alak

    2016-04-01

    In this article, a piezoelectric energy harvesting has been developed experimentally and theoretically based on Euler- Bernoulli Theory. A PVDF piezoelectric thick film has attached along of clamped-clamped beam under sinusoidal base excitation of shaker. The results showed a good agreement between the experimental and simulation of suggested model. The voltage output frequency response function (FRF), current FRF, and output power has been studied under short and open circuit conditions at first vibration mode. The mode shape of the clamped-clamped beam for first three resonance frequency has been modeled and investigated using COMSOL Multiphysics and MATLAB.

  11. Bosonization of the low energy excitations of Fermi liquids

    SciTech Connect

    Castro Neto, A.H.; Fradkin, E. )

    1994-03-07

    We bosonize the low energy excitations of Fermi liquids in any number of dimensions in the limit of long wavelengths. The bosons are a coherent superposition of electron-hole pairs and are related with the displacements of the Fermi surface in some arbitrary direction. A coherent-state path integral for the bosonized theory is derived and it is shown to represent histories of the shape of the Fermi surface. The Landau theory of Fermi liquids can be obtained from the formalism in the absence of nesting of the Fermi surface and singular interactions. We show that the Landau equation for sound waves is exact in the semiclassical approximation for the bosons.

  12. The Clinical Impact of Accurate Cystine Calculi Characterization Using Dual-Energy Computed Tomography.

    PubMed

    Haley, William E; Ibrahim, El-Sayed H; Qu, Mingliang; Cernigliaro, Joseph G; Goldfarb, David S; McCollough, Cynthia H

    2015-01-01

    Dual-energy computed tomography (DECT) has recently been suggested as the imaging modality of choice for kidney stones due to its ability to provide information on stone composition. Standard postprocessing of the dual-energy images accurately identifies uric acid stones, but not other types. Cystine stones can be identified from DECT images when analyzed with advanced postprocessing. This case report describes clinical implications of accurate diagnosis of cystine stones using DECT.

  13. Dependence of the energy transfer to graphene on the excitation energy

    SciTech Connect

    Mackowski, Sebastian Kamińska, Izabela

    2015-07-13

    Fluorescence studies of natural photosynthetic complexes on a graphene layer demonstrate pronounced influence of the excitation wavelength on the energy transfer efficiency to graphene. Ultraviolet light yields much faster decay of fluorescence, with average efficiencies of the energy transfer equal to 87% and 65% for excitation at 405 nm and 640 nm, respectively. This implies that focused light changes locally the properties of graphene affecting the energy transfer dynamics, in an analogous way as in the case of metallic nanostructures. Demonstrating optical control of the energy transfer is important for exploiting unique properties of graphene in photonic and sensing architectures.

  14. Collisional energy transfer from highly vibrationally excited triatomic molecules

    NASA Astrophysics Data System (ADS)

    Hynes, Robert G.; Sceats, Mark G.

    1989-12-01

    The atom-atom encounter model developed in the accompanying paper [M. G. Sceats, J. Chem. Phys. 91, 0000 (1989)] is applied to the collisional deactivation of highly vibrationally excited triatomic molecules CS2 and SO2 by the monatomic colliders He, Ne, Ar, Kr, and Xe at 300 K. The molecular inputs are a crude normal mode analysis, vibrational frequencies and effective anharmonicities, while the collisional inputs are parameters of the atom-atom potentials. The results for CS2 are compared with the simulations of Bruehl and Schatz and the experiments of Dove, Hippler, and Troe, while those for SO2 are compared with the simulations of Schranz and Troe and the experimental results of Heymann, Hippler, and Troe. Excellent agreement is found with experiment, and the superlinear energy dependence of the average energy transfer is attributed to anharmonicity of the triatomic molecule.

  15. Limit on rotational energy available to excite Jovian aurora

    NASA Technical Reports Server (NTRS)

    Eviatar, A.; Siscoe, G. L.

    1980-01-01

    There is a fundamental relationship between the power that is extracted from Jupiter's rotation to drive magnetospheric processes and the rate at which mass is injected into the Io plasma torus. Half of this power is consumed by bulk motion of the plasma and the other half represents an upper limit on the energy from rotation available for dissipation and in particular to excite the Jovian aurora. Since the rotation of the planet is the only plausible source of energy, the power inferred from the observed auroral intensities requires a plasma injection rate of 2.6 x 10 to the 29th AMU/sec or greater. This in turn leads to a residence time of a torus particle of 48 days or less. These results raise doubts about the applicability of equilibrium thermodynamics to the determination of plasma parameters in the Io torus.

  16. Low energy vibrational excitations characteristic of superionic glass

    NASA Astrophysics Data System (ADS)

    Nakamura, M.; Iwase, H.; Arai, M.; Kartini, E.; Russina, M.; Yokoo, T.; Taylor, J. W.

    2006-11-01

    The mechanism of high ionic conductivity in superionic glass constitutes an unsolved problem in the field of science. Here we performed inelastic neutron scattering measurements of superionic glass system (AgI)x(Ag2S)x(AgPO3) by using MARI spectrometer at ISIS, and found that the Q-dependence of inelastic intensity in the energy region from 1 to 3 meV of superionic phase glass shows an excess intensity above Q=1.8 Å-1 compared with insulator phase. Similar phenomena were also observed in another superionic glass (AgI)0.5(AgPO3)0.5 by using NEAT spectrometer at HMI with high resolution measurement. These results clearly suggest peculiar low energy vibrational excitations should be universal features of superionic glass.

  17. Coherence, Energy and Charge Transfers in De-Excitation Pathways of Electronic Excited State of Biomolecules in Photosynthesis

    NASA Astrophysics Data System (ADS)

    Bohr, Henrik G.; Malik, F. Bary

    2013-11-01

    The observed multiple de-excitation pathways of photo-absorbed electronic excited state in the peridinin-chlorophyll complex, involving both energy and charge transfers among its constituents, are analyzed using the bio-Auger (B-A) theory. It is also shown that the usually used Förster-Dexter theory, which does not allow for charge transfer, is a special case of B-A theory. The latter could, under appropriate circumstances, lead to excimers.

  18. Spectroscopic probes of vibrationally excited molecules at chemically significant energies

    SciTech Connect

    Rizzo, T.R.

    1992-03-01

    These experiments apply multiple-laser spectroscopic techniques to investigate the bond energies, potential surface topologies, and dissociation dynamics of highly vibrationally excited molecules. Infrared-optical double resonance pumping of light atom stretch vibrations in H{sub 2}O{sub 2} and HN{sub 3} prepares reactant molecules in single rovibrational states above the unimolecular dissociation threshold on the ground potential surface, and laser induced fluorescence detection of the OH or NH fragments monitors the partitioning of energy into individual product quantum states. Product energy partitioning data from H{sub 2}O{sub 2} dissociation provide a stringent test of statistical theories as well as potential energy surface calculations. Ongoing work on HN{sub 3} seeks to determine the height of the barrier to dissociation on the singlet potential energy surface. Our most recently developed spectroscopic scheme allows the measurement of high vibrational overtone spectra of jet-cooled molecules. This approach uses CO{sub 2} laser infrared multiphoton dissociation followed by laser induced fluorescence product detection to measure weak vibrational overtone transitions in low pressure environments. Application of this scheme to record the {Delta}V{sub OH}=4 and {Delta}V{sub OH}=5 transitions of CH{sub 3}OH cooled in a supersonic free-jet demonstrates both its feasibility and its utility for simplifying high vibrational overtone spectra.

  19. Criteria for the accuracy of small polaron quantum master equation in simulating excitation energy transfer dynamics

    SciTech Connect

    Chang, Hung-Tzu; Cheng, Yuan-Chung; Zhang, Pan-Pan

    2013-12-14

    The small polaron quantum master equation (SPQME) proposed by Jang et al. [J. Chem. Phys. 129, 101104 (2008)] is a promising approach to describe coherent excitation energy transfer dynamics in complex molecular systems. To determine the applicable regime of the SPQME approach, we perform a comprehensive investigation of its accuracy by comparing its simulated population dynamics with numerically exact quasi-adiabatic path integral calculations. We demonstrate that the SPQME method yields accurate dynamics in a wide parameter range. Furthermore, our results show that the accuracy of polaron theory depends strongly upon the degree of exciton delocalization and timescale of polaron formation. Finally, we propose a simple criterion to assess the applicability of the SPQME theory that ensures the reliability of practical simulations of energy transfer dynamics with SPQME in light-harvesting systems.

  20. Electron Attachment in Low-Energy Electron Elastic Collisions with Au and Pt Atoms: Identification of Excited Anions

    NASA Astrophysics Data System (ADS)

    Msezane, A. Z.; Eure, A.; Felfli, Z.; Sokolovski, D.

    2009-11-01

    The recent Regge-pole methodology has been benchmarked [1] on the accurately measured binding energies of the excited Ge= and Sn= anions [2] through the binding energies (BEs) extracted from the Regge-pole calculated elastic total cross sections (TCSs). Here the methodology is applied together with a Thomas-Fermi type potential that incorporates the vital core polarization interaction to investigate the possibility of forming excited Au= and Pt= anions in low-energy electron elastic collisions with Au and Pt atoms. From the positions of the characteristic extremely narrow resonances in the total cross sections, we extract the binding energies of the excited Au= and Pt= anions formed as Regge resonances during the collisions. The angular life of the complexes thus formed is used to differentiate the stable excited bound states of the anions from the shape resonances [3]. The BEs for the excited Au= and Pt= anions are found to be 0.475eVand 0.543eV, respectively, challenging both theory and experiment to verify. [1] A. Msezane et al, Phys. Rev. A, Submitted (2009) [2] M. Scheer et al, Phys. Rev. A 58, 2844 (1998) [3] Z. Felfli et al, Phys. Rev. A 79, 012714 (2009)

  1. Plunger lifetime measurements after Coulomb excitation at intermediate beam energies

    SciTech Connect

    Dewald, A.; Hackstein, M.; Rother, W.; Jolie, J.; Melon, B.; Pissulla, T.; Shimbara, Y.; Starosta, K.; Adrich, P.; Amthor, A. M.; Baumann, T.; Bazin, D.; Bowen, M.; Chester, A.; Dunomes, A.; Gade, A.; Galaviz, D.; Glasmacher, T.; Ginter, T.; Hausmann, M.

    2009-01-28

    Absolute transition probabilities of the first 2{sup +} state in {sup 110,114}Pd were remeasured using the recoil distance Doppler shift technique following projectile Coulomb excitation at intermediate beam energies for the first time. The {sup 110}Pd experiment served to check the novel technique as well as the method used for the data analysis which is based on the examination of {gamma}-ray lineshapes. Whereas the measured B(E2) value for {sup 110}Pd agrees very well with the literature, the value obtained for {sup 114}Pd differs considerably. The data is also used to test a novel concept, called the valence proton symmetry, which allows one to extrapolate nuclear properties to very neutron rich nuclei.

  2. Metallic bond effects on mean excitation energies for stopping powers

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Xu, Y. J.

    1982-01-01

    Mean excitation energies for first row metals are evaluated by means of the local plasma approximation. Particle corrections based on Pines' (1953) procedure and the Wigner Seitz (1934) model of the metallic state are included. The agreement with experimental values is remarkably good. In contrast to previous work, the calculations given here estimate shifts in the plasma frequency according to the theory for plane wave states in an extended plasma as calculated by Pines. It is demonstrated that the effects of the metallic bond in lithium and beryllium are quite large and that they appear mainly as a result of collective oscillations in the 'free' electron gas formed from the valence electrons. The usefulness of the plasma frequency shift derived for a degenerate electron gas in predicting the plasma frequency shift within the ion core is considered surprising.

  3. Accurate double many-body expansion potential energy surface of HS2A2A‧) by scaling the external correlation

    NASA Astrophysics Data System (ADS)

    Lu-Lu, Zhang; Yu-Zhi, Song; Shou-Bao, Gao; Yuan, Zhang; Qing-Tian, Meng

    2016-05-01

    A globally accurate single-sheeted double many-body expansion potential energy surface is reported for the first excited state of HS2 by fitting the accurate ab initio energies, which are calculated at the multireference configuration interaction level with the aug-cc-pVQZ basis set. By using the double many-body expansion-scaled external correlation method, such calculated ab initio energies are then slightly corrected by scaling their dynamical correlation. A grid of 2767 ab initio energies is used in the least-square fitting procedure with the total root-mean square deviation being 1.406 kcal·mol-1. The topographical features of the HS2(A2A‧) global potential energy surface are examined in detail. The attributes of the stationary points are presented and compared with the corresponding ab initio results as well as experimental and other theoretical data, showing good agreement. The resulting potential energy surface of HS2(A2A‧) can be used as a building block for constructing the global potential energy surfaces of larger S/H molecular systems and recommended for dynamic studies on the title molecular system. Project supported by the National Natural Science Foundation of China (Grant No. 11304185), the Taishan Scholar Project of Shandong Province, China, the Shandong Provincial Natural Science Foundation, China (Grant No. ZR2014AM022), the Shandong Province Higher Educational Science and Technology Program, China (Grant No. J15LJ03), the China Postdoctoral Science Foundation (Grant No. 2014M561957), and the Post-doctoral Innovation Project of Shandong Province, China (Grant No. 201402013).

  4. Calculated ground state potential surface and excitation energies for the copper trimer

    NASA Technical Reports Server (NTRS)

    Walch, S. P.; Laskowski, B. C.

    1986-01-01

    In the context of their relevance to catalysis and to materials science problems, transition metals and transition metal (TM) compounds are currently of considerable interest, and studies have been conducted of the copper trimer, Cu3. The present investigation is concerned with a study of the ground state surface and several groups of excited states in order to improve the understanding of the spectroscopy of Cu3. Differences of the current study from previous investigations are related to an employment of larger basis sets and a more extensive electron correlation. This was done with the objective to obtain a more accurate definition of the ground state surface. Features of the bonding in the copper dimer are considered to obtain a basis for an understanding of the copper trimer. Attention is given to calculational details, the ground state surface, and calculated vertical excitation energies. The results of SCF/SDCI calculations are reported for portions of the ground surface, for two groups of excited states, and for the ionization potential of Cu3.

  5. Chemically accurate energy barriers of small gas molecules moving through hexagonal water rings.

    PubMed

    Hjertenæs, Eirik; Trinh, Thuat T; Koch, Henrik

    2016-07-21

    We present chemically accurate potential energy curves of CH4, CO2 and H2 moving through hexagonal water rings, calculated by CCSD(T)/aug-cc-pVTZ with counterpoise correction. The barriers are extracted from a potential energy surface obtained by allowing the water ring to expand while the gas molecule diffuses through. State-of-the-art XC-functionals are evaluated against the CCSD(T) potential energy surface.

  6. Mean excitation energies for stopping powers in various materials using local plasma oscillator strengths

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Xu, Y. J.; Kamaratos, E.; Chang, C. K.

    1984-01-01

    The basic model of Lindhard and Scharff, known as the local plasma model, is used to study the effects on stopping power of the chemical and physical state of the medium. Unlike previous work with the local plasma model, in which individual electron shifts in the plasma frequency were estimated empirically, he Pines correction derived for a degenerate Fermi gas is shown herein to provide a reasonable estimate, even on the atomic scale. Thus, the model is moved to a complete theoretical base requiring no empirical adjustments, as characteristic of past applications. The principal remaining error is in the overestimation of the low-energy absorption properties that are characteristic of the plasma model in the region of the atomic discrete spectrum, although higher-energy phenomena are accurately represented, and even excitation-to-ionization ratios are given to fair accuracy. Mean excitation energies for covalent-bonded gases and solids, for ionic gases and crystals, and for metals are calculated using first-order models of the bonded states.

  7. Regulating energy transfer of excited carriers and the case for excitation-induced hydrogen dissociation on hydrogenated graphene

    PubMed Central

    Bang, Junhyeok; Meng, Sheng; Sun, Yi-Yang; West, Damien; Wang, Zhiguo; Gao, Fei; Zhang, S. B.

    2013-01-01

    Understanding and controlling of excited carrier dynamics is of fundamental and practical importance, particularly in photochemistry and solar energy applications. However, theory of energy relaxation of excited carriers is still in its early stage. Here, using ab initio molecular dynamics (MD) coupled with time-dependent density functional theory, we show a coverage-dependent energy transfer of photoexcited carriers in hydrogenated graphene, giving rise to distinctively different ion dynamics. Graphene with sparsely populated H is difficult to dissociate due to inefficient transfer of the excitation energy into kinetic energy of the H. In contrast, H can easily desorb from fully hydrogenated graphane. The key is to bring down the H antibonding state to the conduction band minimum as the band gap increases. These results can be contrasted to those of standard ground-state MD that predict H in the sparse case should be much less stable than that in fully hydrogenated graphane. Our findings thus signify the importance of carrying out explicit electronic dynamics in excited-state simulations. PMID:23277576

  8. Properties of Shell-Model Wavefunctions at High Excitation Energies

    NASA Astrophysics Data System (ADS)

    Frazier, Njema Jioni

    Within the framework of the nuclear shell model with a realistic residual hamiltonian one can obtain the exact solution of the many-body problem. This makes it possible to study the interrelation between regular and chaotic features of dynamics in a generic many-body system with strong interaction. As an important application, we analyse the fragmentation of simple configurations as a function of excitation energy and interaction strength and examine the transition strengths induced by simple operators as a function of excitation energy. The analysis is performed for two systems; that of 12 valence particles in the sd-shell, or 28Si, and that of 8 valence particles in the sd-shell, or 24Mg. For the system of 12 valence particles in the sd-shell, we examine the fragmentation of shell-model basis states. For the system of 8 valence nucleons in the sd-shell, we examine the fragmentation associated with single-nucleon transfer and Gamow-Teller transitions. For the fragmentation of basis states, we use our statistics to establish the generic shape of the strength function distribution in the region of strong mixing. For the realistic interaction, the strength function distribution is close to Gaussian in the central part of the energy spectra. The width of the distribution is larger than predicted by Fermi's golden rule (4). We then take this one step further and examine the strength distributions associated with the one-nucleon transfer operator, aλ†, and the Gamow-Teller (GT) operator, Σλλ'(σμ τ±) λλ'aλ†a λ'. The spectroscopic factor, which is proportional to the square of the matrix element for the aλ† operator, is the simplest quantity used in predicting experimental observables. In our discussion of Gamow-Teller transitions, we examine both the GT strength function distribution and the values of total strength B(GT). For all the cases we examine, we take advantage of the reliability of our model for low-lying levels and our statistics to explore

  9. Energy harvesting from human motion: exploiting swing and shock excitations

    NASA Astrophysics Data System (ADS)

    Ylli, K.; Hoffmann, D.; Willmann, A.; Becker, P.; Folkmer, B.; Manoli, Y.

    2015-02-01

    Modern compact and low power sensors and systems are leading towards increasingly integrated wearable systems. One key bottleneck of this technology is the power supply. The use of energy harvesting techniques offers a way of supplying sensor systems without the need for batteries and maintenance. In this work we present the development and characterization of two inductive energy harvesters which exploit different characteristics of the human gait. A multi-coil topology harvester is presented which uses the swing motion of the foot. The second device is a shock-type harvester which is excited into resonance upon heel strike. Both devices were modeled and designed with the key constraint of device height in mind, in order to facilitate the integration into the shoe sole. The devices were characterized under different motion speeds and with two test subjects on a treadmill. An average power output of up to 0.84 mW is achieved with the swing harvester. With a total device volume including the housing of 21 cm3 a power density of 40 μW cm-3 results. The shock harvester generates an average power output of up to 4.13 mW. The power density amounts to 86 μW cm-3 for the total device volume of 48 cm3. Difficulties and potential improvements are discussed briefly.

  10. Electron-Excited X-Ray Microanalysis at Low Beam Energy: Almost Always an Adventure!

    PubMed

    Newbury, Dale E; Ritchie, Nicholas W M

    2016-08-01

    Scanning electron microscopy with energy-dispersive spectrometry has been applied to the analysis of various materials at low-incident beam energies, E 0≤5 keV, using peak fitting and following the measured standards/matrix corrections protocol embedded in the National Institute of Standards and Technology Desktop Spectrum Analyzer-II analytical software engine. Low beam energy analysis provides improved spatial resolution laterally and in-depth. The lower beam energy restricts the atomic shells that can be ionized, reducing the number of X-ray peak families available to the analyst. At E 0=5 keV, all elements of the periodic table except H and He can be measured. As the beam energy is reduced below 5 keV, elements become inaccessible due to lack of excitation of useful characteristic X-ray peaks. The shallow sampling depth of low beam energy microanalysis makes the technique more sensitive to surface compositional modification due to formation of oxides and other reaction layers. Accurate and precise analysis is possible with the use of appropriate standards and by accumulating high count spectra of unknowns and standards (>1 million counts integrated from 0.1 keV to E 0). PMID:27515566

  11. Electron-Excited X-Ray Microanalysis at Low Beam Energy: Almost Always an Adventure!

    PubMed

    Newbury, Dale E; Ritchie, Nicholas W M

    2016-08-01

    Scanning electron microscopy with energy-dispersive spectrometry has been applied to the analysis of various materials at low-incident beam energies, E 0≤5 keV, using peak fitting and following the measured standards/matrix corrections protocol embedded in the National Institute of Standards and Technology Desktop Spectrum Analyzer-II analytical software engine. Low beam energy analysis provides improved spatial resolution laterally and in-depth. The lower beam energy restricts the atomic shells that can be ionized, reducing the number of X-ray peak families available to the analyst. At E 0=5 keV, all elements of the periodic table except H and He can be measured. As the beam energy is reduced below 5 keV, elements become inaccessible due to lack of excitation of useful characteristic X-ray peaks. The shallow sampling depth of low beam energy microanalysis makes the technique more sensitive to surface compositional modification due to formation of oxides and other reaction layers. Accurate and precise analysis is possible with the use of appropriate standards and by accumulating high count spectra of unknowns and standards (>1 million counts integrated from 0.1 keV to E 0).

  12. An accurate dynamical electron diffraction algorithm for reflection high-energy electron diffraction

    NASA Astrophysics Data System (ADS)

    Huang, J.; Cai, C. Y.; Lv, C. L.; Zhou, G. W.; Wang, Y. G.

    2015-12-01

    The conventional multislice method (CMS) method, one of the most popular dynamical electron diffraction calculation procedures in transmission electron microscopy, was introduced to calculate reflection high-energy electron diffraction (RHEED) as it is well adapted to deal with the deviations from the periodicity in the direction parallel to the surface. However, in the present work, we show that the CMS method is no longer sufficiently accurate for simulating RHEED with the accelerating voltage 3-100 kV because of the high-energy approximation. An accurate multislice (AMS) method can be an alternative for more accurate RHEED calculations with reasonable computing time. A detailed comparison of the numerical calculation of the AMS method and the CMS method is carried out with respect to different accelerating voltages, surface structure models, Debye-Waller factors and glancing angles.

  13. Excitation energies, polarizabilities, multipole transition rates, and lifetimes of ions along the francium isoelectronic sequence

    SciTech Connect

    Safronova, U. I.; Johnson, W. R.; Safronova, M. S.

    2007-10-15

    Relativistic many-body perturbation theory is applied to study properties of ions of the francium isoelectronic sequence. Specifically, energies of the 7s, 7p, 6d, and 5f states of Fr-like ions with nuclear charges Z=87-100 are calculated through third order; reduced matrix elements, oscillator strengths, transition rates, and lifetimes are determined for 7s-7p, 7p-6d, and 6d-5f electric-dipole transitions; and 7s-6d, 7s-5f, and 5f{sub 5/2}-5f{sub 7/2} multipole matrix elements are evaluated to obtain the lifetimes of low-lying excited states. Moreover, for the ions Z=87-92 calculations are also carried out using the relativistic all-order single-double method, in which single and double excitations of Dirac-Fock wave functions are included to all orders in perturbation theory. With the aid of the single-double wave functions, we obtain accurate values of energies, transition rates, oscillator strengths, and the lifetimes of these six ions. Ground state scalar polarizabilities in Fr I, Ra II, Ac III, and Th IV are calculated using relativistic third-order and all-order methods. Ground state scalar polarizabilities for other Fr-like ions are calculated using a relativistic second-order method. These calculations provide a theoretical benchmark for comparison with experiment and theory.

  14. An analytical approach for predicting the energy capture and conversion by impulsively-excited bistable vibration energy harvesters

    NASA Astrophysics Data System (ADS)

    Harne, R. L.; Zhang, Chunlin; Li, Bing; Wang, K. W.

    2016-07-01

    Impulsive energies are abundant throughout the natural and built environments, for instance as stimulated by wind gusts, foot-steps, or vehicle-road interactions. In the interest of maximizing the sustainability of society's technological developments, one idea is to capture these high-amplitude and abrupt energies and convert them into usable electrical power such as for sensors which otherwise rely on less sustainable power supplies. In this spirit, the considerable sensitivity to impulse-type events previously uncovered for bistable oscillators has motivated recent experimental and numerical studies on the power generation performance of bistable vibration energy harvesters. To lead to an effective and efficient predictive tool and design guide, this research develops a new analytical approach to estimate the electroelastic response and power generation of a bistable energy harvester when excited by an impulse. Comparison with values determined by direct simulation of the governing equations shows that the analytically predicted net converted energies are very accurate for a wide range of impulse strengths. Extensive experimental investigations are undertaken to validate the analytical approach and it is seen that the predicted estimates of the impulsive energy conversion are in excellent agreement with the measurements, and the detailed structural dynamics are correctly reproduced. As a result, the analytical approach represents a significant leap forward in the understanding of how to effectively leverage bistable structures as energy harvesting devices and introduces new means to elucidate the transient and far-from-equilibrium dynamics of nonlinear systems more generally.

  15. Methods for Efficiently and Accurately Computing Quantum Mechanical Free Energies for Enzyme Catalysis.

    PubMed

    Kearns, F L; Hudson, P S; Boresch, S; Woodcock, H L

    2016-01-01

    Enzyme activity is inherently linked to free energies of transition states, ligand binding, protonation/deprotonation, etc.; these free energies, and thus enzyme function, can be affected by residue mutations, allosterically induced conformational changes, and much more. Therefore, being able to predict free energies associated with enzymatic processes is critical to understanding and predicting their function. Free energy simulation (FES) has historically been a computational challenge as it requires both the accurate description of inter- and intramolecular interactions and adequate sampling of all relevant conformational degrees of freedom. The hybrid quantum mechanical molecular mechanical (QM/MM) framework is the current tool of choice when accurate computations of macromolecular systems are essential. Unfortunately, robust and efficient approaches that employ the high levels of computational theory needed to accurately describe many reactive processes (ie, ab initio, DFT), while also including explicit solvation effects and accounting for extensive conformational sampling are essentially nonexistent. In this chapter, we will give a brief overview of two recently developed methods that mitigate several major challenges associated with QM/MM FES: the QM non-Boltzmann Bennett's acceptance ratio method and the QM nonequilibrium work method. We will also describe usage of these methods to calculate free energies associated with (1) relative properties and (2) along reaction paths, using simple test cases with relevance to enzymes examples.

  16. Methods for Efficiently and Accurately Computing Quantum Mechanical Free Energies for Enzyme Catalysis.

    PubMed

    Kearns, F L; Hudson, P S; Boresch, S; Woodcock, H L

    2016-01-01

    Enzyme activity is inherently linked to free energies of transition states, ligand binding, protonation/deprotonation, etc.; these free energies, and thus enzyme function, can be affected by residue mutations, allosterically induced conformational changes, and much more. Therefore, being able to predict free energies associated with enzymatic processes is critical to understanding and predicting their function. Free energy simulation (FES) has historically been a computational challenge as it requires both the accurate description of inter- and intramolecular interactions and adequate sampling of all relevant conformational degrees of freedom. The hybrid quantum mechanical molecular mechanical (QM/MM) framework is the current tool of choice when accurate computations of macromolecular systems are essential. Unfortunately, robust and efficient approaches that employ the high levels of computational theory needed to accurately describe many reactive processes (ie, ab initio, DFT), while also including explicit solvation effects and accounting for extensive conformational sampling are essentially nonexistent. In this chapter, we will give a brief overview of two recently developed methods that mitigate several major challenges associated with QM/MM FES: the QM non-Boltzmann Bennett's acceptance ratio method and the QM nonequilibrium work method. We will also describe usage of these methods to calculate free energies associated with (1) relative properties and (2) along reaction paths, using simple test cases with relevance to enzymes examples. PMID:27498635

  17. Exploring the vibrational fingerprint of the electronic excitation energy via molecular dynamics

    SciTech Connect

    Deyne, Andy Van Yperen-De; Pauwels, Ewald; Ghysels, An; Waroquier, Michel; Van Speybroeck, Veronique; Hemelsoet, Karen; De Meyer, Thierry; De Clerck, Karen

    2014-04-07

    A Fourier-based method is presented to relate changes of the molecular structure during a molecular dynamics simulation with fluctuations in the electronic excitation energy. The method implies sampling of the ground state potential energy surface. Subsequently, the power spectrum of the velocities is compared with the power spectrum of the excitation energy computed using time-dependent density functional theory. Peaks in both spectra are compared, and motions exhibiting a linear or quadratic behavior can be distinguished. The quadratically active motions are mainly responsible for the changes in the excitation energy and hence cause shifts between the dynamic and static values of the spectral property. Moreover, information about the potential energy surface of various excited states can be obtained. The procedure is illustrated with three case studies. The first electronic excitation is explored in detail and dominant vibrational motions responsible for changes in the excitation energy are identified for ethylene, biphenyl, and hexamethylbenzene. The proposed method is also extended to other low-energy excitations. Finally, the vibrational fingerprint of the excitation energy of a more complex molecule, in particular the azo dye ethyl orange in a water environment, is analyzed.

  18. Reliable Spectroscopic Constants for CCH-, NH2- and Their Isotopomers from an Accurate Potential Energy Function

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Dateo, Christopher E.; Schwenke, David W.; Chaban, Galina M.

    2005-01-01

    Accurate quartic force fields have been determined for the CCH- and NH2- molecular anions using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, CCSD(T). Very large one-particle basis sets have been used including diffuse functions and up through g-type functions. Correlation of the nitrogen and carbon core electrons has been included, as well as other "small" effects, such as the diagonal Born-Oppenheimer correction, and basis set extrapolation, and corrections for higher-order correlation effects and scalar relativistic effects. Fundamental vibrational frequencies have been computed using standard second-order perturbation theory as well as variational methods. Comparison with the available experimental data is presented and discussed. The implications of our research for the astronomical observation of molecular anions will be discussed.

  19. Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

    SciTech Connect

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-12-28

    A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S{sub 0}) electronic state has been constructed by fitting ∼37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm{sup −1}. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm{sup −1} above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.

  20. An accurate, convective energy equation based automated meshing technique for analysis of blood vessels and tissues.

    PubMed

    White, J A; Dutton, A W; Schmidt, J A; Roemer, R B

    2000-01-01

    An automated three-element meshing method for generating finite element based models for the accurate thermal analysis of blood vessels imbedded in tissue has been developed and evaluated. The meshing method places eight noded hexahedral elements inside the vessels where advective flows exist, and four noded tetrahedral elements in the surrounding tissue. The higher order hexahedrals are used where advective flow fields occur, since high accuracy is required and effective upwinding algorithms exist. Tetrahedral elements are placed in the remaining tissue region, since they are computationally more efficient and existing automatic tetrahedral mesh generators can be used. Five noded pyramid elements connect the hexahedrals and tetrahedrals. A convective energy equation (CEE) based finite element algorithm solves for the temperature distributions in the flowing blood, while a finite element formulation of a generalized conduction equation is used in the surrounding tissue. Use of the CEE allows accurate solutions to be obtained without the necessity of assuming ad hoc values for heat transfer coefficients. Comparisons of the predictions of the three-element model to analytical solutions show that the three-element model accurately simulates temperature fields. Energy balance checks show that the three-element model has small, acceptable errors. In summary, this method provides an accurate, automatic finite element gridding procedure for thermal analysis of irregularly shaped tissue regions that contain important blood vessels. At present, the models so generated are relatively large (in order to obtain accurate results) and are, thus, best used for providing accurate reference values for checking other approximate formulations to complicated, conjugated blood heat transfer problems.

  1. Excitation energy sharing in binary peripheral heavy ion reactions at Fermi energies

    NASA Astrophysics Data System (ADS)

    Piantelli, S.; Mangiarotti, A.; Maurenzig, P. R.; Olmi, A.; Bardelli, L.; Bini, M.; Casini, G.; Pasquali, G.; Poggi, G.; Stefanini, A. A.

    2008-12-01

    Evidence for the dependence of excitation energy sharing between two heavy remnants on the difference in the lost mass in two-body peripheral heavy ion reactions at Fermi energy is presented, based on experimental results for the reactions Nb93+Sn116, Sn116+Nb93, and Nb93+Nb93 at 38A MeV. An observable based on the experimental velocities of the heavy residues is used to select reactions with equal preevaporative masses of projectile-like fragments and target-like fragments. The excitation energy, evaluated by means of a complete average calorimetry, is found to be larger for the nucleus that finally retains a larger part of the hot interaction region.

  2. Fractionally Charged Zero-Energy Single-Particle Excitations in a Driven Fermi Sea

    NASA Astrophysics Data System (ADS)

    Moskalets, Michael

    2016-07-01

    A voltage pulse of a Lorentzian shape carrying half of the flux quantum excites out of a zero-temperature Fermi sea an electron in a mixed state, which looks like a quasiparticle with an effectively fractional charge e /2 . A prominent feature of such an excitation is a narrow peak in the energy distribution function lying exactly at the Fermi energy μ . Another spectacular feature is that the distribution function has symmetric tails around μ , which results in a zero-energy excitation. This sounds improbable since at zero temperature all available states below μ are fully occupied. The resolution lies in the fact that such a voltage pulse also excites electron-hole pairs, which free some space below μ and thus allow a zero-energy quasiparticle to exist. I discuss also how to address separately electron-hole pairs and a fractionally charged zero-energy excitation in an experiment.

  3. Field-dependent molecular ionization and excitation energies: Implications for electrically insulating liquids

    NASA Astrophysics Data System (ADS)

    Davari, N.; Åstrand, P.-O.; Unge, M.; Lundgaard, L. E.; Linhjell, D.

    2014-03-01

    The molecular ionization potential has a relatively strong electric-field dependence as compared to the excitation energies which has implications for electrical insulation since the excited states work as an energy sink emitting light in the UV/VIS region. At some threshold field, all the excited states of the molecule have vanished and the molecule is a two-state system with the ground state and the ionized state, which has been hypothesized as a possible origin of different streamer propagation modes. Constrained density-functional theory is used to calculate the field-dependent ionization potential of different types of molecules relevant for electrically insulating liquids. The low singlet-singlet excitation energies of each molecule have also been calculated using time-dependent density functional theory. It is shown that low-energy singlet-singlet excitation of the type n → π* (lone pair to unoccupied π* orbital) has the ability to survive at higher fields. This type of excitation can for example be found in esters, diketones and many color dyes. For alkanes (as for example n-tridecane and cyclohexane) on the other hand, all the excited states, in particular the σ → σ* excitations vanish in electric fields higher than 10 MV/cm. Further implications for the design of electrically insulating dielectric liquids based on the molecular ionization potential and excitation energies are discussed.

  4. Excitation energy transfer in vitro between phycobiliproteins and thylakoid photosystem II of higher plants

    NASA Astrophysics Data System (ADS)

    Wu, Xiaonan; Tseng, C. K.

    1992-12-01

    The excitation energy transfer from phycobiliproteins to thylakoid PSII of higher plants was investigated. When incubated with spinach thylakoids, phycobiliproteins isolated from red and blue-green algae transferred light energy absorbed to spinach PSII. The efficiency of energy transfer was dependent on the kind of phycobiliproteins used. If spinach thylakoids were replaced by the thylakoids of Brassica chinensis, R-phycoerythin or C-phycocyanin did not transfer their excitation energy to PSII of Brassica chinensis unless allophycocyanin was present.

  5. A Quasiclassical Study of the F((2)P) + CHD3 (ν1 = 0,1) Reactive System on an Accurate Potential Energy Surface.

    PubMed

    Palma, Juliana; Manthe, Uwe

    2015-12-17

    Quasiclassical trajectories (QCT) have been employed to elucidate the effect of exciting the C-H bond in F + CHD3 collisions. The calculations were performed on a new potential energy surface that accurately describes the van der Waals complexes in the entrance channel of the reaction. It was found that exciting the C-H bond significantly enhances the yield of HF + CD3, whereas it has a minor effect on the production of DF + CHD2. Therefore, the net effect is that the total reactivity increases upon excitation. This result strongly contradicts recent experimental findings. Significant differences in regard to the yield of each product channel were also found between QCT results calculated with the new surface and those obtained with the surface previously developed by Czakó et al. This shows that relatively small variations in the topography of the entrance channel can result in huge discrepancies in the predicted DF/HF branching ratio. However, in regard to other attributes of the reaction, the agreement between QCT results computed with different surfaces, and between them and experimental results, is good. For the F + CHD3 → HF + CD3 reaction, at a collisional energy of 9.0 kcal/mol, experiments and QCT calculations agree, indicating that the extra energy deposited in the C-H bond is channelled into the HF product. In addition, the angular distribution of CD3 is backward oriented and is not sensitive to the excitation of the C-H bond. PMID:26270126

  6. On enhancement of vibration-based energy harvesting by a random parametric excitation

    NASA Astrophysics Data System (ADS)

    Bobryk, Roman V.; Yurchenko, Daniil

    2016-03-01

    An electromechanical linear oscillator with a random ambient excitation and telegraphic noise parametric excitation is considered as an energy harvester model. It is shown that a parametric colored excitation can have a dramatic effect on the enhancement of the energy harvesting. A close relation with mean-square stability of the oscillator is established. Four sources of the ambient excitation are considered: the white noise, the Ornstein-Uhlenbeck noise, the harmonic noise and the periodic function. Analytical expressions for stationary electrical net mean power are presented for all the considered cases, confirming the proposed approach.

  7. Validation of local hybrid functionals for TDDFT calculations of electronic excitation energies

    NASA Astrophysics Data System (ADS)

    Maier, Toni M.; Bahmann, Hilke; Arbuznikov, Alexei V.; Kaupp, Martin

    2016-02-01

    The first systematic evaluation of local hybrid functionals for the calculation of electronic excitation energies within linear-response time-dependent density functional theory (TDDFT) is reported. Using our recent efficient semi-numerical TDDFT implementation [T. M. Maier et al., J. Chem. Theory Comput. 11, 4226 (2015)], four simple, thermochemically optimized one-parameter local hybrid functionals based on local spin-density exchange are evaluated against a database of singlet and triplet valence excitations of organic molecules, and against a mixed database including also Rydberg, intramolecular charge-transfer (CT) and core excitations. The four local hybrids exhibit comparable performance to standard global or range-separated hybrid functionals for common singlet valence excitations, but several local hybrids outperform all other functionals tested for the triplet excitations of the first test set, as well as for relative energies of excited states. Evaluation for the combined second test set shows that local hybrids can also provide excellent Rydberg and core excitations, in the latter case rivaling specialized functionals optimized specifically for such excitations. This good performance of local hybrids for different excitation types could be traced to relatively large exact-exchange (EXX) admixtures in a spatial region intermediate between valence and asymptotics, as well as close to the nucleus, and lower EXX admixtures in the valence region. In contrast, the tested local hybrids cannot compete with the best range-separated hybrids for intra- and intermolecular CT excitation energies. Possible directions for improvement in the latter category are discussed. As the used efficient TDDFT implementation requires essentially the same computational effort for global and local hybrids, applications of local hybrid functionals to excited-state problems appear promising in a wide range of fields. Influences of current-density dependence of local kinetic-energy

  8. Two-photon excited quantum dots as energy donors for photosensitizer chlorin e6.

    PubMed

    Skripka, Artiom; Valanciunaite, Jurga; Dauderis, Gediminas; Poderys, Vilius; Kubiliute, Reda; Rotomskis, Ricardas

    2013-07-01

    The excitation-related problems in photodynamic therapy of cancer might be solved by combining two-photon (TP) irradiation and quantum dots (QDs) as effective energy donors for conventional photosensitizers (PS). Here, it is demonstrated for the first time that QD-chlorin e6 (Ce6) complex formed due to the hydrophobic interaction between Ce6 molecules and lipid coating of QDs can be effectively excited via TP irradiation at 1030 nm, which spectrally coincides with the biological tissue optical window. TP absorption cross-section for free QDs and Ce6 at 1030 nm was 3325 and 13 Goeppert-Mayer, respectively. Upon TP excitation of QD-Ce6 solution, the fluorescence band of bound Ce6 molecules was observed via energy transfer from excited QDs. Increasing concentration of Ce6 resulted in quenching of the photoluminescence of QDs and an increase in the fluorescence intensity of bound Ce6 molecules. These intensity changes coincided well with those observed upon single-photon excitation of QD-Ce6 solution when QDs alone are excited. The efficiency of energy transfer in QD-Ce6 complex upon TP excitation was about 80% (QD∶Ce61∶5). These results indicate that the effective excitation of PS with a low TP absorption cross-section is possible in such type noncovalent complexes via energy transfer from TP excited QDs.

  9. Two-photon excited quantum dots as energy donors for photosensitizer chlorin e6.

    PubMed

    Skripka, Artiom; Valanciunaite, Jurga; Dauderis, Gediminas; Poderys, Vilius; Kubiliute, Reda; Rotomskis, Ricardas

    2013-07-01

    The excitation-related problems in photodynamic therapy of cancer might be solved by combining two-photon (TP) irradiation and quantum dots (QDs) as effective energy donors for conventional photosensitizers (PS). Here, it is demonstrated for the first time that QD-chlorin e6 (Ce6) complex formed due to the hydrophobic interaction between Ce6 molecules and lipid coating of QDs can be effectively excited via TP irradiation at 1030 nm, which spectrally coincides with the biological tissue optical window. TP absorption cross-section for free QDs and Ce6 at 1030 nm was 3325 and 13 Goeppert-Mayer, respectively. Upon TP excitation of QD-Ce6 solution, the fluorescence band of bound Ce6 molecules was observed via energy transfer from excited QDs. Increasing concentration of Ce6 resulted in quenching of the photoluminescence of QDs and an increase in the fluorescence intensity of bound Ce6 molecules. These intensity changes coincided well with those observed upon single-photon excitation of QD-Ce6 solution when QDs alone are excited. The efficiency of energy transfer in QD-Ce6 complex upon TP excitation was about 80% (QD∶Ce61∶5). These results indicate that the effective excitation of PS with a low TP absorption cross-section is possible in such type noncovalent complexes via energy transfer from TP excited QDs. PMID:23864017

  10. Electron-impact excitation and ionization of atomic boron at low and intermediate energies

    NASA Astrophysics Data System (ADS)

    Wang, Kedong; Zatsarinny, Oleg; Bartschat, Klaus

    2016-05-01

    We present a comprehensive study of electron collisions with neutral boron atoms. The calculations were performed with the B-Spline R-matrix (close-coupling) method, by employing a parallelized version of the associated computer code. Elastic, excitation, and ionization cross sections were obtained for all transitions involving the lowest 11 states of boron, for incident electron energies ranging from threshold to 100 eV. A multiconfiguration Hartree-Fock method with nonorthogonal term-dependent orbitals was used to generate accurate wave functions for the target states. Close-coupling expansions including 13, 51, and 999 physical and pseudo states were set up to check the sensitivity of the predictions to variations in the theoretical model. The cross-section dataset generated in this work is expected to be the most accurate one available today and should be sufficiently comprehensive for most modeling applications involving neutral boron. Work supported by the China Scholarship Council and the United States National Science Foundation under Grants PHY-1403245 and PHY-1520970, and by the XSEDE allocation PHY-090031.

  11. Ground- and excited-state diatomic bond lengths, vibrational levels, and potential-energy curves from conventional and localized Hartree-Fock-based density-functional theory

    NASA Astrophysics Data System (ADS)

    Teale, Andrew M.; Tozer, David J.

    2005-01-01

    Ground- and excited-state diatomic bond lengths, vibrational levels, and potential-energy curves are determined using conventional and localized Hartree-Fock (LHF)-based density-functional theory. Exchange only and hybrid functionals (with various fractions of exchange) are considered, together with a standard generalized gradient approximation (GGA). Ground-state bond lengths and vibrational wave numbers are relatively insensitive to whether orbital exchange is treated using the conventional or LHF approach. Excited-state calculations are much more sensitive. For a standard fraction of orbital exchange, N2 and CO vertical excitation energies at experimental bond lengths are accurately described by both conventional and LHF-based approaches, providing an asymptotic correction is present. Excited-state bond lengths and vibrational levels are more accurate with the conventional approach. The best quality, however, is obtained with an asymptotically corrected GGA functional. For the ground and lowest four singlet excited states, the GGA mean absolute errors in bond lengths are 0.006 Å (0.5%) and 0.011 Å (0.8%) for N2 and CO, respectively. Mean absolute errors in fundamental vibrational wavenumbers are 49 cm-1 (2.7%) and 68 cm-1 (5.0%), respectively. The GGA potential-energy curves are compared with near-exact Rydberg-Klein-Rees curves. Agreement is very good for the ground and first excited state, but deteriorates for the higher states.

  12. Ab Initio Potential Energy Surfaces and the Calculation of Accurate Vibrational Frequencies

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Dateo, Christopher E.; Martin, Jan M. L.; Taylor, Peter R.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Due to advances in quantum mechanical methods over the last few years, it is now possible to determine ab initio potential energy surfaces in which fundamental vibrational frequencies are accurate to within plus or minus 8 cm(exp -1) on average, and molecular bond distances are accurate to within plus or minus 0.001-0.003 Angstroms, depending on the nature of the bond. That is, the potential energy surfaces have not been scaled or empirically adjusted in any way, showing that theoretical methods have progressed to the point of being useful in analyzing spectra that are not from a tightly controlled laboratory environment, such as vibrational spectra from the interstellar medium. Some recent examples demonstrating this accuracy will be presented and discussed. These include the HNO, CH4, C2H4, and ClCN molecules. The HNO molecule is interesting due to the very large H-N anharmonicity, while ClCN has a very large Fermi resonance. The ab initio studies for the CH4 and C2H4 molecules present the first accurate full quartic force fields of any kind (i.e., whether theoretical or empirical) for a five-atom and six-atom system, respectively.

  13. Energy harvesting from coherent resonance of horizontal vibration of beam excited by vertical base motion

    SciTech Connect

    Lan, C. B.; Qin, W. Y.

    2014-09-15

    This letter investigates the energy harvesting from the horizontal coherent resonance of a vertical cantilever beam subjected to the vertical base excitation. The potential energy of the system has two symmetric potential wells. So, under vertical excitation, the system can jump between two potential wells, which will lead to the large vibration in horizontal direction. Two piezoelectric patches are pasted to harvest the energy. From experiment, it is found that the vertical excitation can make the beam turn to be bistable. The system can transform vertical vibration into horizontal vibration of low frequency when excited by harmonic motion. The horizontal coherence resonance can be observed when excited by a vertical white noise. The corresponding output voltages of piezoelectric films reach high values.

  14. Excitation energies and Stokes shifts from a restricted open-shell Kohn-Sham approach

    NASA Astrophysics Data System (ADS)

    Kowalczyk, Tim; Tsuchimochi, Takashi; Chen, Po-Ta; Top, Laken; Van Voorhis, Troy

    2013-04-01

    Restricted open-shell Kohn-Sham (ROKS) theory provides a powerful computational tool for calculating singlet excited state energies and dynamics. However, the possibility of multiple solutions to the ROKS equations — with the associated difficulty of automatically selecting the physically meaningful solution — limits its usefulness for intensive applications such as long-time Born-Oppenheimer molecular dynamics. We present an implementation of ROKS for excited states which prescribes the physically correct solution from an overlap criterion and guarantees that this solution is stationary, allowing for straightforward evaluation of nuclear gradients. The method is used to benchmark ROKS for vertical excitation energies of small and large organic dyes and for the calculation of Stokes shifts. With common density functional approximations, ROKS vertical excitation energies, and Stokes shifts show similar accuracy to those from time-dependent density functional theory and Δ-self-consistent-field approaches. Advantages of the ROKS approach for excited state structure and molecular dynamics are discussed.

  15. Toward an Accurate Estimate of the Exfoliation Energy of Black Phosphorus: A Periodic Quantum Chemical Approach.

    PubMed

    Sansone, Giuseppe; Maschio, Lorenzo; Usvyat, Denis; Schütz, Martin; Karttunen, Antti

    2016-01-01

    The black phosphorus (black-P) crystal is formed of covalently bound layers of phosphorene stacked together by weak van der Waals interactions. An experimental measurement of the exfoliation energy of black-P is not available presently, making theoretical studies the most important source of information for the optimization of phosphorene production. Here, we provide an accurate estimate of the exfoliation energy of black-P on the basis of multilevel quantum chemical calculations, which include the periodic local Møller-Plesset perturbation theory of second order, augmented by higher-order corrections, which are evaluated with finite clusters mimicking the crystal. Very similar results are also obtained by density functional theory with the D3-version of Grimme's empirical dispersion correction. Our estimate of the exfoliation energy for black-P of -151 meV/atom is substantially larger than that of graphite, suggesting the need for different strategies to generate isolated layers for these two systems. PMID:26651397

  16. Toward an Accurate Estimate of the Exfoliation Energy of Black Phosphorus: A Periodic Quantum Chemical Approach.

    PubMed

    Sansone, Giuseppe; Maschio, Lorenzo; Usvyat, Denis; Schütz, Martin; Karttunen, Antti

    2016-01-01

    The black phosphorus (black-P) crystal is formed of covalently bound layers of phosphorene stacked together by weak van der Waals interactions. An experimental measurement of the exfoliation energy of black-P is not available presently, making theoretical studies the most important source of information for the optimization of phosphorene production. Here, we provide an accurate estimate of the exfoliation energy of black-P on the basis of multilevel quantum chemical calculations, which include the periodic local Møller-Plesset perturbation theory of second order, augmented by higher-order corrections, which are evaluated with finite clusters mimicking the crystal. Very similar results are also obtained by density functional theory with the D3-version of Grimme's empirical dispersion correction. Our estimate of the exfoliation energy for black-P of -151 meV/atom is substantially larger than that of graphite, suggesting the need for different strategies to generate isolated layers for these two systems.

  17. Accurate nonrelativistic ground-state energies of 3d transition metal atoms

    SciTech Connect

    Scemama, A.; Applencourt, T.; Giner, E.; Caffarel, M.

    2014-12-28

    We present accurate nonrelativistic ground-state energies of the transition metal atoms of the 3d series calculated with Fixed-Node Diffusion Monte Carlo (FN-DMC). Selected multi-determinantal expansions obtained with the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) method and including the most prominent determinants of the full configuration interaction expansion are used as trial wavefunctions. Using a maximum of a few tens of thousands determinants, fixed-node errors on total DMC energies are found to be greatly reduced for some atoms with respect to those obtained with Hartree-Fock nodes. To the best of our knowledge, the FN-DMC/(CIPSI nodes) ground-state energies presented here are the lowest variational total energies reported so far. They differ from the recently recommended non-variational values of McCarthy and Thakkar [J. Chem. Phys. 136, 054107 (2012)] only by a few percents of the correlation energy. Thanks to the variational property of FN-DMC total energies, our results provide exact lower bounds for the absolute value of all-electron correlation energies, |E{sub c}|.

  18. Hyperfine structure in 229gTh3+ as a probe of the 229gTh→ 229mTh nuclear excitation energy.

    PubMed

    Beloy, K

    2014-02-14

    We identify a potential means to extract the 229gTh→ 229mTh nuclear excitation energy from precision microwave spectroscopy of the 5F(5/2,7/2) hyperfine manifolds in the ion 229gTh3+. The hyperfine interaction mixes this ground fine structure doublet with states of the nuclear isomer, introducing small but observable shifts to the hyperfine sublevels. We demonstrate how accurate atomic structure calculations may be combined with the measurement of the hyperfine intervals to quantify the effects of this mixing. Further knowledge of the magnetic dipole decay rate of the isomer, as recently reported, allows an indirect determination of the nuclear excitation energy.

  19. Do Bond Functions Help for the Calculation of Accurate Bond Energies?

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Arnold, James (Technical Monitor)

    1998-01-01

    The bond energies of 8 chemically bound diatomics are computed using several basis sets with and without bond functions (BF). The bond energies obtained using the aug-pVnZ+BF basis sets (with a correction for basis set superposition error, BSSE) tend to be slightly smaller that the results obtained using the aug-pV(n+I)Z basis sets, but slightly larger than the BSSE corrected aug-pV(n+I)Z results. The aug-cc-pVDZ+BF and aug-cc-pVTZ+BF basis sets yield reasonable estimates of bond energies, but, in most cases, these results cannot be considered highly accurate. Extrapolation of the results obtained with basis sets including bond functions appears to be inferior to the results obtained by extrapolation using atom-centered basis sets. Therefore bond functions do not appear to offer a path for obtaining highly accurate results for chemically bound systems at a lower computational cost than atom centered basis sets.

  20. Effect of Solvation on Electron Detachment and Excitation Energies of a Green Fluorescent Protein Chromophore Variant.

    PubMed

    Bose, Samik; Chakrabarty, Suman; Ghosh, Debashree

    2016-05-19

    Hybrid quantum mechanics/molecular mechanics (QM/MM) is applied to the fluorinated green fluorescent protein (GFP) chromophore (DFHBDI) in its deprotonated form to understand the solvatochromic shifts in its vertical detachment energy (VDE) and vertical excitation energy (VEE). This variant of the GFP chromophore becomes fluorescent in an RNA environment and has a wide range of applications in biomedical and biochemical fields. From microsolvation studies, we benchmark (with respect to full QM) the accuracy of our QM/MM calculations with effective fragment potential (EFP) as the MM method of choice. We show that while the solvatochromic shift in the VEE is minimal (0.1 eV blue shift) and its polarization component is only 0.03 eV, the effect of the solvent on the VDE is quite large (3.85 eV). We also show by accurate calculations on the solvatochromic shift of the VDE that polarization accounts for ∼0.23 eV and therefore cannot be neglected. The effect of the counterions on the VDE of the deprotonated chromophore in solvation is studied in detail, and a charge-smearing scheme is suggested for charged chromophores. PMID:27116477

  1. Accurate Energy Spectrum for the Quantum Yang-Mills Mechanics with Nonlinear Color Oscillations

    NASA Astrophysics Data System (ADS)

    Pedram, Pouria

    2015-01-01

    Yang-Mills theory as the foundation for quantum chromodynamics is a non-Abelian gauge theory with self-interactions between vector particles. Here, we study the Yang-Mills Hamiltonian with nonlinear color oscillations in the absence of external sources corresponding to the group SU(2). In the quantum domain, we diagonalize the Hamiltonian using the optimized trigonometric basis expansion method and find accurate energy eigenvalues and eigenfunctions for one and two degrees of freedom. We also compare our results with the semiclassical solutions.

  2. Accurate thermochemistry for larger molecules : gaussian-2 theory with bond separation energies.

    SciTech Connect

    Raghavachari, K.; Stefanov, B. B.; Curtiss, L. A.; Lucent Tech.

    1997-04-22

    Gaussian-2 (G2) theory is combined with isodesmic bond separation reaction energies to yield accurate thermochemistry for larger molecules. For a test set of 40 molecules composed of H, C, O, and N, our method yields enthalpies of formation, {Delta}H{sub f}{sup 0}(298 K), with a mean absolute deviation from experiment of only 0.5 kcal/mol. This is an improvement of a factor of three over the deviation of 1.5 kcal/mol seen in standard G2 theory.

  3. Construction of an accurate potential energy surface by interpolation with Cartesian weighting coordinates

    NASA Astrophysics Data System (ADS)

    Rhee, Young Min

    2000-10-01

    A modified method to construct an accurate potential energy surface by interpolation is presented. The modification is based on the use of Cartesian coordinates in the weighting function. The translational and rotational invariance of the potential is incorporated by a proper definition of the distance between two Cartesian configurations. A numerical algorithm to find the distance is developed. It is shown that the present method is more exact in describing a planar system compared to the previous methods with weightings in internal coordinates. The applicability of the method to reactive systems is also demonstrated by performing classical trajectory simulations on the surface.

  4. Spectroscopic probes of vibrationally excited molecules at chemically significant energies

    SciTech Connect

    Rizzo, T.R.

    1993-04-01

    Infrared-optical double resonance is being used to study the unimolecular dissociation dynamics of hydrazoic acid (HN[sub 3]). 6[nu][sub NH] vibrational overtone excitation spectra are given for HN[sub 3]. Work was begun to determine the feasibility of extending the infrared-optical double resonance photofragment spectroscopy to small free radicals, and to be able to monitor atomic dissociation fragments via laser induced fluorescence in the VUV spectrum. 1 fig.

  5. Proceedings of the 1984 workshop on high-energy excitations in condensed matter. Volume II

    SciTech Connect

    Silver, R.N.

    1984-12-01

    This volume covers electronic excitations, momentum distributions, high energy photons, and a wrap-up session. Abstracts of individual items from the conference were prepared separately for the data base. (GHT)

  6. Low energy nuclear spin excitations in Ho metal investigated by high resolution neutron spectroscopy.

    PubMed

    Chatterji, Tapan; Jalarvo, Niina

    2013-04-17

    We have investigated the low energy excitations in metallic Ho by high resolution neutron spectroscopy. We found at T = 3 K clear inelastic peaks in the energy loss and energy gain sides, along with the central elastic peak. The energy of this low energy excitation, which is 26.59 ± 0.02 μeV at T = 3 K, decreased continuously and became zero at TN ≈ 130 K. By fitting the data in the temperature range 100-127.5 K with a power law we obtained the power-law exponent β = 0.37 ± 0.02, which agrees with the expected value β = 0.367 for a three-dimensional Heisenberg model. Thus the energy of the low energy excitations can be associated with the order parameter.

  7. Excitation of positive ions by low-energy electrons - Relevance to the Io Torus

    NASA Astrophysics Data System (ADS)

    Smith, S. J.; Chutjian, A.; Mawhorter, R. J.; Williams, I. D.; Shemansky, D. E.

    1993-03-01

    The importance of measuring electron-ion excitation cross sections in singly and multiply charged positive ions is outlined, and recent results for Mg II and O II ions are given using the JPL's electron energy-loss merged-beams apparatus. Theoretical comparisons are given with two five-state close-coupling calculations. The energy variation of the collision strength is fitted with a semiempirical analytic function which includes approximations to polarization, resonance, and exchange contributions. In O II, first spectra anywhere of electron excitation of the optically allowed transitions are presented. In addition, excitations of two low lying, optically forbidden transitions are detected for the first time.

  8. Measurement of the excitation spectrum of a Bose condensate, and direct observation of the phonon energy

    NASA Astrophysics Data System (ADS)

    Ozeri, Roee; Steinhauer, Jeff; Katz, Nadav; Davidson, Nir

    2002-05-01

    The excitation spectrum gives the energy, hw(k), of each excitation in the Bose condensate (BEC) as a function of its wave vector k. We report the first measurement of the excitation spectrum [1]. The excitation spectrum is measured by Bragg spectroscopy [2]. The response of the condensate to the two-photon Bragg pulse is extracted from time of flight (TOF) images. The resonance frequency of the excitation for momentum hk is taken as w(k). The measured w(k) agrees with the Bogoliubov spectrum predictions. A linear phonon regime is seen for low k. The superfluid critical velocity is bounded by w(k)/k of this regime. In addition, the energy and momentum of the atoms are measured directly from the TOF image, computerized tomography is used to reconstruct the cylindrical density distribution, from a single absorption picture [3]. The excitation energies measured this way are in agreement with the value measured using Bragg spectroscopy. Our measurements also indicate that all of the excitation energy is carried by the atoms in the released-phonon cloud. [1] J. Steinhauer et. al. Phys. Rev. Lett. in press (Cond. Mat. 0111438). [2] J. Stenger, et. al. Phys. Rev. Lett. 82, 4569-4573 (1999). [3] R. Ozeri, et. al. Cond. Mat. 0112496.

  9. Enhanced energy transfer in respiratory-deficient endothelial cells probed by microscopic fluorescence excitation spectroscopy

    NASA Astrophysics Data System (ADS)

    Schneckenburger, Herbert; Gschwend, Michael H.; Bauer, Manfred; Strauss, Wolfgang S. L.; Steiner, Rudolf W.

    1996-12-01

    Mitochondrial malfunction may be concomitant with changes of the redox states of the coenzymes nicotinamide adenine dinucleotide (NAD+/NADH), as well as flavin.mononucleotide or dinucleotide. The intrinsic fluorescence of these coenzymes was therefore proposed to be a measure of malfunction. Since mitochondrial fluorescence is strongly superposed by autofluorescence from various cytoplasmatic fluorophores, cultivated endothelial cells were incubated with the mitochondrial marker rhodamine 123 (R123), and after excitation of flavin molecules, energy transfer to R123 was investigated. Due to spectral overlap of flavin and R123 fluorescence, energy transfer flavin yields R123 could not be detected from their emission spectra. Therefore, the method of microscopic fluorescence excitation spectroscopy was established. When detecting R123 fluorescence, excitation maxima at 370 - 390 nm and 420-460 nm were assigned to flavins, whereas a pronounced excitation band at 465 - 490 nm was attributed to R123. Therefore, excitation at 475 nm reflected the intracellular concentration of R123, whereas excitation at 385 nm reflected flavin excitation with a subsequent energy transfer to R123 molecules. An enhanced energy transfer after inhibition of specific enzyme complexes of the respiratory chain is discussed in the present article.

  10. An accurate global potential energy surface, dipole moment surface, and rovibrational frequencies for NH3

    NASA Astrophysics Data System (ADS)

    Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

    2008-12-01

    A global potential energy surface (PES) that includes short and long range terms has been determined for the NH3 molecule. The singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations and the internally contracted averaged coupled-pair functional electronic structure methods have been used in conjunction with very large correlation-consistent basis sets, including diffuse functions. Extrapolation to the one-particle basis set limit was performed and core correlation and scalar relativistic contributions were included directly, while the diagonal Born-Oppenheimer correction was added. Our best purely ab initio PES, denoted "mixed," is constructed from two PESs which differ in whether the ic-ACPF higher-order correlation correction was added or not. Rovibrational transition energies computed from the mixed PES agree well with experiment and the best previous theoretical studies, but most importantly the quality does not deteriorate even up to 10300cm-1 above the zero-point energy (ZPE). The mixed PES was improved further by empirical refinement using the most reliable J =0-2 rovibrational transitions in the HITRAN 2004 database. Agreement between high-resolution experiment and rovibrational transition energies computed from our refined PES for J =0-6 is excellent. Indeed, the root mean square (rms) error for 13 HITRAN 2004 bands for J =0-2 is 0.023cm-1 and that for each band is always ⩽0.06cm-1. For J =3-5 the rms error is always ⩽0.15cm-1. This agreement means that transition energies computed with our refined PES should be useful in the assignment of new high-resolution NH3 spectra and in correcting mistakes in previous assignments. Ideas for further improvements to our refined PES and for extension to other isotopolog are discussed.

  11. Low-energy structures of benzene clusters with a novel accurate potential surface.

    PubMed

    Bartolomei, M; Pirani, F; Marques, J M C

    2015-12-01

    The benzene-benzene (Bz-Bz) interaction is present in several chemical systems and it is known to be crucial in understanding the specificity of important biological phenomena. In this work, we propose a novel Bz-Bz analytical potential energy surface which is fine-tuned on accurate ab initio calculations in order to improve its reliability. Once the Bz-Bz interaction is modeled, an analytical function for the energy of the Bzn clusters may be obtained by summing up over all pair potentials. We apply an evolutionary algorithm (EA) to discover the lowest-energy structures of Bzn clusters (for n=2-25), and the results are compared with previous global optimization studies where different potential functions were employed. Besides the global minimum, the EA also gives the structures of other low-lying isomers ranked by the corresponding energy. Additional ab initio calculations are carried out for the low-lying isomers of Bz3 and Bz4 clusters, and the global minimum is confirmed as the most stable structure for both sizes. Finally, a detailed analysis of the low-energy isomers of the n = 13 and 19 magic-number clusters is performed. The two lowest-energy Bz13 isomers show S6 and C3 symmetry, respectively, which is compatible with the experimental results available in the literature. The Bz19 structures reported here are all non-symmetric, showing two central Bz molecules surrounded by 12 nearest-neighbor monomers in the case of the five lowest-energy structures.

  12. Dynamics of Energy Transfer in a Conjugated Dendrimer Driven by Ultrafast Localization of Excitations.

    PubMed

    Galindo, Johan F; Atas, Evrim; Altan, Aysun; Kuroda, Daniel G; Fernandez-Alberti, Sebastian; Tretiak, Sergei; Roitberg, Adrian E; Kleiman, Valeria D

    2015-09-16

    Solar energy conversion starts with the harvest of light, and its efficacy depends on the spatial transfer of the light energy to where it can be transduced into other forms of energy. Harnessing solar power as a clean energy source requires the continuous development of new synthetic materials that can harvest photon energy and transport it without significant losses. With chemically-controlled branched architectures, dendrimers are ideally suited for these initial steps, since they consist of arrays of chromophores with relative positioning and orientations to create energy gradients and to spatially focus excitation energies. The spatial localization of the energy delimits its efficacy and has been a point of intense research for synthetic light harvesters. We present the results of a combined theoretical experimental study elucidating ultrafast, unidirectional, electronic energy transfer on a complex molecule designed to spatially focus the initial excitation onto an energy sink. The study explores the complex interplay between atomic motions, excited-state populations, and localization/delocalization of excitations. Our findings show that the electronic energy-transfer mechanism involves the ultrafast collapse of the photoexcited wave function due to nonadiabatic electronic transitions. The localization of the wave function is driven by the efficient coupling to high-frequency vibrational modes leading to ultrafast excited-state dynamics and unidirectional efficient energy funneling. This work provides a long-awaited consistent experiment-theoretical description of excited-state dynamics in organic conjugated dendrimers with atomistic resolution, a phenomenon expected to universally appear in a variety of synthetic conjugated materials.

  13. Dynamics of Energy Transfer in a Conjugated Dendrimer Driven by Ultrafast Localization of Excitations.

    PubMed

    Galindo, Johan F; Atas, Evrim; Altan, Aysun; Kuroda, Daniel G; Fernandez-Alberti, Sebastian; Tretiak, Sergei; Roitberg, Adrian E; Kleiman, Valeria D

    2015-09-16

    Solar energy conversion starts with the harvest of light, and its efficacy depends on the spatial transfer of the light energy to where it can be transduced into other forms of energy. Harnessing solar power as a clean energy source requires the continuous development of new synthetic materials that can harvest photon energy and transport it without significant losses. With chemically-controlled branched architectures, dendrimers are ideally suited for these initial steps, since they consist of arrays of chromophores with relative positioning and orientations to create energy gradients and to spatially focus excitation energies. The spatial localization of the energy delimits its efficacy and has been a point of intense research for synthetic light harvesters. We present the results of a combined theoretical experimental study elucidating ultrafast, unidirectional, electronic energy transfer on a complex molecule designed to spatially focus the initial excitation onto an energy sink. The study explores the complex interplay between atomic motions, excited-state populations, and localization/delocalization of excitations. Our findings show that the electronic energy-transfer mechanism involves the ultrafast collapse of the photoexcited wave function due to nonadiabatic electronic transitions. The localization of the wave function is driven by the efficient coupling to high-frequency vibrational modes leading to ultrafast excited-state dynamics and unidirectional efficient energy funneling. This work provides a long-awaited consistent experiment-theoretical description of excited-state dynamics in organic conjugated dendrimers with atomistic resolution, a phenomenon expected to universally appear in a variety of synthetic conjugated materials. PMID:26122872

  14. Potential energy surface of excited semiconductors: Graphene quantum dot and BODIPY

    NASA Astrophysics Data System (ADS)

    Colherinhas, Guilherme; Fileti, Eudes Eterno; Chaban, Vitaly V.

    2016-08-01

    Binding energy (BE) is an important descriptor in chemistry, which determines thermodynamics and phase behavior of a given substance. BE between two molecules is not directly accessible from the experiment. It has to be reconstructed from cohesive energies, vaporization heats, etc. We report BE for the excited states of two semiconductor molecules - boron-dipyrromethene (BODIPY) and graphene quantum dot (GQD) - with water. We show, for the first time, that excitation increases BE twofold at an optimal separation (energy minimum position), whereas higher separations lead to higher differences. Interestingly, the effects of excitation are similar irrespective of the dominant binding interactions (van der Waals or electrostatic) in the complex. This new knowledge is important for simulations of the excited semiconductors by simplified interaction functions.

  15. Accurate Zero Parameter Correlation Energy Functional Obtained from the Homogeneous Electron Gas with an Energy Gap

    NASA Astrophysics Data System (ADS)

    Krieger, J. B.; Chen, Jiqiang; Iafrate, G. J.; Savin, A.

    1998-03-01

    We have obtained an analytic approximation to E_c(r_g, ζ,G) where G is an energy gap separating the occupied and unoccupied states of a homogeneous electron gas for ζ=3D0 and ξ=3D1. When G=3D0, E_c(r_g, ζ) reduces to the usual LSD result. This functional is employed in calculating correlation energies for unpolarized atoms and ions for Z <= 18 by taking G[n]=3D1/8|nabla ln n|^2, which reduces to the ionization energy in the large r limit in an exact Kohn-Sham (KS) theory. The resulting functional is self-interaction-corrected employing a method which is invariant under a unitary transformation. We find that the application of this approach to the calculation of the Ec functional reduces the error in the LSD result by more than 95%. When the value of G is approximately corrected to include the effect of higher lying unoccupied localized states, the resulting values of Ec are within a few percent of the exact results.

  16. Accurate calculation of binding energies for molecular clusters - Assessment of different models

    NASA Astrophysics Data System (ADS)

    Friedrich, Joachim; Fiedler, Benjamin

    2016-06-01

    In this work we test different strategies to compute high-level benchmark energies for medium-sized molecular clusters. We use the incremental scheme to obtain CCSD(T)/CBS energies for our test set and carefully validate the accuracy for binding energies by statistical measures. The local errors of the incremental scheme are <1 kJ/mol. Since they are smaller than the basis set errors, we obtain higher total accuracy due to the applicability of larger basis sets. The final CCSD(T)/CBS benchmark values are ΔE = - 278.01 kJ/mol for (H2O)10, ΔE = - 221.64 kJ/mol for (HF)10, ΔE = - 45.63 kJ/mol for (CH4)10, ΔE = - 19.52 kJ/mol for (H2)20 and ΔE = - 7.38 kJ/mol for (H2)10 . Furthermore we test state-of-the-art wave-function-based and DFT methods. Our benchmark data will be very useful for critical validations of new methods. We find focal-point-methods for estimating CCSD(T)/CBS energies to be highly accurate and efficient. For foQ-i3CCSD(T)-MP2/TZ we get a mean error of 0.34 kJ/mol and a standard deviation of 0.39 kJ/mol.

  17. Hydration free energies of cyanide and hydroxide ions from molecular dynamics simulations with accurate force fields

    USGS Publications Warehouse

    Lee, M.W.; Meuwly, M.

    2013-01-01

    The evaluation of hydration free energies is a sensitive test to assess force fields used in atomistic simulations. We showed recently that the vibrational relaxation times, 1D- and 2D-infrared spectroscopies for CN(-) in water can be quantitatively described from molecular dynamics (MD) simulations with multipolar force fields and slightly enlarged van der Waals radii for the C- and N-atoms. To validate such an approach, the present work investigates the solvation free energy of cyanide in water using MD simulations with accurate multipolar electrostatics. It is found that larger van der Waals radii are indeed necessary to obtain results close to the experimental values when a multipolar force field is used. For CN(-), the van der Waals ranges refined in our previous work yield hydration free energy between -72.0 and -77.2 kcal mol(-1), which is in excellent agreement with the experimental data. In addition to the cyanide ion, we also study the hydroxide ion to show that the method used here is readily applicable to similar systems. Hydration free energies are found to sensitively depend on the intermolecular interactions, while bonded interactions are less important, as expected. We also investigate in the present work the possibility of applying the multipolar force field in scoring trajectories generated using computationally inexpensive methods, which should be useful in broader parametrization studies with reduced computational resources, as scoring is much faster than the generation of the trajectories.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

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

    SciTech Connect

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

    2015-06-07

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

  20. Analytical Energy Gradients for Excited-State Coupled-Cluster Methods

    NASA Astrophysics Data System (ADS)

    Wladyslawski, Mark; Nooijen, Marcel

    The equation-of-motion coupled-cluster (EOM-CC) and similarity transformed equation-of-motion coupled-cluster (STEOM-CC) methods have been firmly established as accurate and routinely applicable extensions of single-reference coupled-cluster theory to describe electronically excited states. An overview of these methods is provided, with emphasis on the many-body similarity transform concept that is the key to a rationalization of their accuracy. The main topic of the paper is the derivation of analytical energy gradients for such non-variational electronic structure approaches, with an ultimate focus on obtaining their detailed algebraic working equations. A general theoretical framework using Lagrange's method of undetermined multipliers is presented, and the method is applied to formulate the EOM-CC and STEOM-CC gradients in abstract operator terms, following the previous work in [P.G. Szalay, Int. J. Quantum Chem. 55 (1995) 151] and [S.R. Gwaltney, R.J. Bartlett, M. Nooijen, J. Chem. Phys. 111 (1999) 58]. Moreover, the systematics of the Lagrange multiplier approach is suitable for automation by computer, enabling the derivation of the detailed derivative equations through a standardized and direct procedure. To this end, we have developed the SMART (Symbolic Manipulation and Regrouping of Tensors) package of automated symbolic algebra routines, written in the Mathematica programming language. The SMART toolkit provides the means to expand, differentiate, and simplify equations by manipulation of the detailed algebraic tensor expressions directly. The Lagrangian multiplier formulation establishes a uniform strategy to perform the automated derivation in a standardized manner: A Lagrange multiplier functional is constructed from the explicit algebraic equations that define the energy in the electronic method; the energy functional is then made fully variational with respect to all of its parameters, and the symbolic differentiations directly yield the explicit

  1. Multi-excitation Raman difference spectroscopy based on modified multi-energy constrained iterative deconvolution algorithm

    NASA Astrophysics Data System (ADS)

    Zou, Wenlong; Cai, Zhijian; Zhou, Hongwu; Wu, Jianhong

    2013-12-01

    Raman spectroscopy is fast and nondestructive, and it is widely used in chemistry, biomedicine, food safety and other areas. However, Raman spectroscopy is often hampered by strong fluorescence background, especially in food additives detection and biomedicine researching. In this paper, one efficient technique was the multi-excitation Raman difference spectroscopy (MERDS) which incorporated a series of small wavelength-shift wavelengths as excitation sources. A modified multi-energy constrained iterative deconvolution (MMECID) algorithm was proposed to reconstruct the Raman Spectroscopy. Computer simulation and experiments both demonstrated that the Raman spectrum can be well reconstructed from large fluorescence background. The more excitation sources used, the better signal to noise ratio got. However, many excitation sources were equipped on the Raman spectrometer, which increased the complexity of the experimental system. Thus, a trade-off should be made between the number of excitation frequencies and experimental complexity.

  2. Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional

    NASA Astrophysics Data System (ADS)

    Sun, Jianwei; Remsing, Richard C.; Zhang, Yubo; Sun, Zhaoru; Ruzsinszky, Adrienn; Peng, Haowei; Yang, Zenghui; Paul, Arpita; Waghmare, Umesh; Wu, Xifan; Klein, Michael L.; Perdew, John P.

    2016-09-01

    One atom or molecule binds to another through various types of bond, the strengths of which range from several meV to several eV. Although some computational methods can provide accurate descriptions of all bond types, those methods are not efficient enough for many studies (for example, large systems, ab initio molecular dynamics and high-throughput searches for functional materials). Here, we show that the recently developed non-empirical strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation (meta-GGA) within the density functional theory framework predicts accurate geometries and energies of diversely bonded molecules and materials (including covalent, metallic, ionic, hydrogen and van der Waals bonds). This represents a significant improvement at comparable efficiency over its predecessors, the GGAs that currently dominate materials computation. Often, SCAN matches or improves on the accuracy of a computationally expensive hybrid functional, at almost-GGA cost. SCAN is therefore expected to have a broad impact on chemistry and materials science.

  3. Extensions and applications of the A24 data set of accurate interaction energies.

    PubMed

    Řezáč, Jan; Dubecký, Matúš; Jurečka, Petr; Hobza, Pavel

    2015-07-15

    The A24 data set (Řezáč and Hobza, J. Chem. Theory Comput. 2013, 9, 2151-2155) is a set of noncovalent complexes large enough to showcase various types of interactions yet small enough to make highly accurate calculations possible. It is intended for the testing of accurate computational methods which are then used as a benchmark in larger model systems. In this work, we improve the best estimate of the interaction energies in the set by updating their CCSD(T)/CBS and CCSDT(Q) components with calculations in larger basis sets. The data set is then used to test a large number of composite CCSD(T) approaches. Special attention is paid to the use of the explicitly correlated MP2-F12 method in these composite calculations. It is shown that an accuracy of 1-2% can be achieved with setups applicable to larger molecules. The effect of frozen natural orbital approximation on the accuracy of composite CCSD(T)/CBS calculations is also quantified. In four trivially saturated complexes where CCSDT(Q)/CBS data are now available, the convergence of the many-body correlation effects is assessed by fixed-node diffusion Monte Carlo (FN-DMC) calculations. A good agreement is achieved between FN-DMC and high-level coupled-cluster which represents an important cross-check of both approaches.

  4. Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional.

    PubMed

    Sun, Jianwei; Remsing, Richard C; Zhang, Yubo; Sun, Zhaoru; Ruzsinszky, Adrienn; Peng, Haowei; Yang, Zenghui; Paul, Arpita; Waghmare, Umesh; Wu, Xifan; Klein, Michael L; Perdew, John P

    2016-09-01

    One atom or molecule binds to another through various types of bond, the strengths of which range from several meV to several eV. Although some computational methods can provide accurate descriptions of all bond types, those methods are not efficient enough for many studies (for example, large systems, ab initio molecular dynamics and high-throughput searches for functional materials). Here, we show that the recently developed non-empirical strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation (meta-GGA) within the density functional theory framework predicts accurate geometries and energies of diversely bonded molecules and materials (including covalent, metallic, ionic, hydrogen and van der Waals bonds). This represents a significant improvement at comparable efficiency over its predecessors, the GGAs that currently dominate materials computation. Often, SCAN matches or improves on the accuracy of a computationally expensive hybrid functional, at almost-GGA cost. SCAN is therefore expected to have a broad impact on chemistry and materials science. PMID:27554409

  5. Temperature dependent effective potential method for accurate free energy calculations of solids

    NASA Astrophysics Data System (ADS)

    Hellman, Olle; Steneteg, Peter; Abrikosov, I. A.; Simak, S. I.

    2013-03-01

    We have developed a thorough and accurate method of determining anharmonic free energies, the temperature dependent effective potential technique (TDEP). It is based on ab initio molecular dynamics followed by a mapping onto a model Hamiltonian that describes the lattice dynamics. The formalism and the numerical aspects of the technique are described in detail. A number of practical examples are given, and results are presented, which confirm the usefulness of TDEP within ab initio and classical molecular dynamics frameworks. In particular, we examine from first principles the behavior of force constants upon the dynamical stabilization of the body centered phase of Zr, and show that they become more localized. We also calculate the phase diagram for 4He modeled with the Aziz potential and obtain results which are in favorable agreement both with respect to experiment and established techniques.

  6. Screened exchange hybrid density functional for accurate and efficient structures and interaction energies.

    PubMed

    Brandenburg, Jan Gerit; Caldeweyher, Eike; Grimme, Stefan

    2016-06-21

    We extend the recently introduced PBEh-3c global hybrid density functional [S. Grimme et al., J. Chem. Phys., 2015, 143, 054107] by a screened Fock exchange variant based on the Henderson-Janesko-Scuseria exchange hole model. While the excellent performance of the global hybrid is maintained for small covalently bound molecules, its performance for computed condensed phase mass densities is further improved. Most importantly, a speed up of 30 to 50% can be achieved and especially for small orbital energy gap cases, the method is numerically much more robust. The latter point is important for many applications, e.g., for metal-organic frameworks, organic semiconductors, or protein structures. This enables an accurate density functional based electronic structure calculation of a full DNA helix structure on a single core desktop computer which is presented as an example in addition to comprehensive benchmark results. PMID:27240749

  7. Generation IV nuclear energy systems and the need of accurate nuclear data

    NASA Astrophysics Data System (ADS)

    Colonna, N.

    2009-05-01

    To satisfy the world's demand of energy, constantly increasing over the years, a suitable mix of different energy sources has to be envisaged. In this scenario, an important role may be played by nuclear energy, provided that major safety, waste and proliferation issues affecting current nuclear reactors are satisfactorily addressed. In this respect, a large effort is under way since a few years towards the development of advanced nuclear systems that would use more efficiently the uranium resources, and produce a minimal amount of long-lived nuclear waste. The main activity concerns Generation IV reactors, with full or partial waste recycling capability. Their design requires R&D in numerous fields. Among the different needs, it is of fundamental importance to improve the knowledge of basic nuclear data, such as cross-sections for neutron-induced reactions on actinides. The main characteristics and principle of operation of the new generation nuclear systems are here described, together with the related needs of new and accurate nuclear data. Finally, an example of activity currently undergoing in the field is shown, with the recent experimental results obtained at the neutron facility n_TOF at CERN.

  8. SCAN: An Efficient Density Functional Yielding Accurate Structures and Energies of Diversely-Bonded Materials

    NASA Astrophysics Data System (ADS)

    Sun, Jianwei

    The accuracy and computational efficiency of the widely used Kohn-Sham density functional theory (DFT) are limited by the approximation to its exchange-correlation energy Exc. The earliest local density approximation (LDA) overestimates the strengths of all bonds near equilibrium (even the vdW bonds). By adding the electron density gradient to model Exc, generalized gradient approximations (GGAs) generally soften the bonds to give robust and overall more accurate descriptions, except for the vdW interaction which is largely lost. Further improvement for covalent, ionic, and hydrogen bonds can be obtained by the computationally more expensive hybrid GGAs, which mix GGAs with the nonlocal exact exchange. Meta-GGAs are still semilocal in computation and thus efficient. Compared to GGAs, they add the kinetic energy density that enables them to recognize and accordingly treat different bonds, which no LDA or GGA can. We show here that the recently developed non-empirical strongly constrained and appropriately normed (SCAN) meta-GGA improves significantly over LDA and the standard Perdew-Burke-Ernzerhof GGA for geometries and energies of diversely-bonded materials (including covalent, metallic, ionic, hydrogen, and vdW bonds) at comparable efficiency. Often SCAN matches or improves upon the accuracy of a hybrid functional, at almost-GGA cost. This work has been supported by NSF under DMR-1305135 and CNS-09-58854, and by DOE BES EFRC CCDM under DE-SC0012575.

  9. Accurate halo-model matter power spectra with dark energy, massive neutrinos and modified gravitational forces

    NASA Astrophysics Data System (ADS)

    Mead, A. J.; Heymans, C.; Lombriser, L.; Peacock, J. A.; Steele, O. I.; Winther, H. A.

    2016-06-01

    We present an accurate non-linear matter power spectrum prediction scheme for a variety of extensions to the standard cosmological paradigm, which uses the tuned halo model previously developed in Mead et al. We consider dark energy models that are both minimally and non-minimally coupled, massive neutrinos and modified gravitational forces with chameleon and Vainshtein screening mechanisms. In all cases, we compare halo-model power spectra to measurements from high-resolution simulations. We show that the tuned halo-model method can predict the non-linear matter power spectrum measured from simulations of parametrized w(a) dark energy models at the few per cent level for k < 10 h Mpc-1, and we present theoretically motivated extensions to cover non-minimally coupled scalar fields, massive neutrinos and Vainshtein screened modified gravity models that result in few per cent accurate power spectra for k < 10 h Mpc-1. For chameleon screened models, we achieve only 10 per cent accuracy for the same range of scales. Finally, we use our halo model to investigate degeneracies between different extensions to the standard cosmological model, finding that the impact of baryonic feedback on the non-linear matter power spectrum can be considered independently of modified gravity or massive neutrino extensions. In contrast, considering the impact of modified gravity and massive neutrinos independently results in biased estimates of power at the level of 5 per cent at scales k > 0.5 h Mpc-1. An updated version of our publicly available HMCODE can be found at https://github.com/alexander-mead/hmcode.

  10. Accurate calculation of conformational free energy differences in explicit water: the confinement-solvation free energy approach.

    PubMed

    Esque, Jeremy; Cecchini, Marco

    2015-04-23

    The calculation of the free energy of conformation is key to understanding the function of biomolecules and has attracted significant interest in recent years. Here, we present an improvement of the confinement method that was designed for use in the context of explicit solvent MD simulations. The development involves an additional step in which the solvation free energy of the harmonically restrained conformers is accurately determined by multistage free energy perturbation simulations. As a test-case application, the newly introduced confinement/solvation free energy (CSF) approach was used to compute differences in free energy between conformers of the alanine dipeptide in explicit water. The results are in excellent agreement with reference calculations based on both converged molecular dynamics and umbrella sampling. To illustrate the general applicability of the method, conformational equilibria of met-enkephalin (5 aa) and deca-alanine (10 aa) in solution were also analyzed. In both cases, smoothly converged free-energy results were obtained in agreement with equilibrium sampling or literature calculations. These results demonstrate that the CSF method may provide conformational free-energy differences of biomolecules with small statistical errors (below 0.5 kcal/mol) and at a moderate computational cost even with a full representation of the solvent.

  11. Trapping on demand: External regulation of excitation energy transfer in a photoswitchable smart matrix

    NASA Astrophysics Data System (ADS)

    Schmidt, R.; Pärs, M.; Weller, T.; Thelakkat, M.; Köhler, J.

    2014-01-01

    A thin film of polystyrene has been doped with small amounts of dithienylcyclopentene (DCP) based molecular switches and perylene bisimide (PBI) chromophores to obtain a photoswitchable smart matrix. The photochromic DCP can be converted by light between two bistable conformations and thereby changes the energetic position of its lowest excited singlet state. We exploit this feature to regulate the transfer of excitation energy between PBI and DCP as a function of the externally controllable illumination conditions in such a blend.

  12. Excitation energies of particle-hole states in {sup 208}Pb and the surface delta interaction

    SciTech Connect

    Heusler, A.; Jolos, R. V.; Brentano, P. von

    2013-07-15

    The schematic shell model without residual interaction (SSM) assumes the same excitation energy for all spins in each particle-hole configuration multiplet. In {sup 208}Pb, more than forty states are known to contain almost the full strength of a single particle-hole configuration. The experimental excitation energy for a state with a certain spin differs from the energy predicted by the SSM by -0.2 to +0.6 MeV. The multiplet splitting is calculated with the surface delta interaction; it corresponds to the diagonal matrix element of the residual interaction in the SSM. For states containing more than 90% strength of a certain configuration and for the centroid of several completely observed configurations, the calculated multiplet splitting often approximates the experimental excitation energy within 30 keV. The strong mixing within some pairs of states containing the full strengths of two configurations is explained.

  13. Low-energy electron elastic scattering cross sections for excited Au and Pt atoms

    NASA Astrophysics Data System (ADS)

    Felfli, Zineb; Eure, Amanda R.; Msezane, Alfred Z.; Sokolovski, Dmitri

    2010-05-01

    Electron elastic total cross sections (TCSs) and differential cross sections (DCSs) in both impact energy and scattering angle for the excited Au and Pt atoms are calculated in the electron impact energy range 0 ⩽ E ⩽ 4.0 eV. The cross sections are found to be characterized by very sharp long-lived resonances whose positions are identified with the binding energies of the excited anions formed during the collisions. The recent novel Regge-pole methodology wherein is embedded through the Mulholland formula the electron-electron correlations is used together with a Thomas-Fermi type potential incorporating the crucial core-polarization interaction for the calculations of the TCSs. The DCSs are evaluated using a partial wave expansion. The Ramsauer-Townsend minima, the shape resonances and the binding energies of the excited Au - and Pt - anions are extracted from the cross sections, while the critical minima are determined from the DCSs.

  14. Electron energy-loss spectroscopy of excited states of the pyridine molecules

    NASA Astrophysics Data System (ADS)

    Linert, Ireneusz; Zubek, Mariusz

    2016-04-01

    Electron energy-loss spectra of the pyridine, C5H5N, molecules in the gas phase have been measured to investigate electronic excitation in the energy range 3.5-10 eV. The applied wide range of residual electron energy and the scattering angle range from 10° to 180° enabled to differentiate between optically-allowed and -forbidden transitions. These measurements have allowed vertical excitation energies of the triplet excited states of pyridine to be determined and tentative assignments of these states to be proposed. Some of these states have not been identified in the previous works. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  15. Level-energy-dependent mean velocities of excited tungsten atoms sputtered by krypton-ion bombardment

    SciTech Connect

    Nogami, Keisuke; Sakai, Yasuhiro; Mineta, Shota; Kato, Daiji; Murakami, Izumi; Sakaue, Hiroyuki A.; Kenmotsu, Takahiro; Furuya, Kenji; Motohashi, Kenji

    2015-11-15

    Visible emission spectra were acquired from neutral atoms sputtered by 35–60 keV Kr{sup +} ions from a polycrystalline tungsten surface. Mean velocities of excited tungsten atoms in seven different 6p states were also obtained via the dependence of photon intensities on the distance from the surface. The average velocities parallel to the surface normal varied by factors of 2–4 for atoms in the different 6p energy levels. However, they were almost independent of the incident ion kinetic energy. The 6p-level energy dependence indicated that the velocities of the excited atoms were determined by inelastic processes that involve resonant charge exchange.

  16. Differential cross sections for electron-impact vibrational-excitation of tetrahydrofuran at intermediate impact energies

    SciTech Connect

    Do, T. P. T.; Lopes, M. C. A.; Konovalov, D. A.; White, R. D.; Brunger, M. J. E-mail: darryl.jones@flinders.edu.au; Jones, D. B. E-mail: darryl.jones@flinders.edu.au

    2015-03-28

    We report differential cross sections (DCSs) for electron-impact vibrational-excitation of tetrahydrofuran, at intermediate incident electron energies (15-50 eV) and over the 10°-90° scattered electron angular range. These measurements extend the available DCS data for vibrational excitation for this species, which have previously been obtained at lower incident electron energies (≤20 eV). Where possible, our data are compared to the earlier measurements in the overlapping energy ranges. Here, quite good agreement was generally observed where the measurements overlapped.

  17. Generating Excitement: Build Your Own Generator to Study the Transfer of Energy

    ERIC Educational Resources Information Center

    Fletcher, Kurt; Rommel-Esham, Katie; Farthing, Dori; Sheldon, Amy

    2011-01-01

    The transfer of energy from one form to another can be difficult to understand. The electrical energy that turns on a lamp may come from the burning of coal, water falling at a hydroelectric plant, nuclear reactions, or gusts of wind caused by the uneven heating of the Earth. The authors have developed and tested an exciting hands-on activity to…

  18. Double-well potential energy curve of cadmium-krypton molecule in the B1(5(3)P1) excited state.

    PubMed

    Lukomski, M; Koperski, J; Czajkowski, M

    2002-06-01

    The real shape of a double-well B1(5(3)P1)-state potential in CdKr van der Waals molecule was reconstructed applying both the experimental data, using a Birge-Sponer method-based analysis of the B1 <-- X0+(5(1)S0) transition in excitation spectrum, and theoretical result of recent ab initio calculation. An inverse perturbation approach method was used for defining an accurate B1-state potential energy curve.

  19. Probing ultrafast excitation energy transfer of the chlorosome with exciton-phonon variational dynamics.

    PubMed

    Somoza Márquez, Alejandro; Chen, Lipeng; Sun, Kewei; Zhao, Yang

    2016-07-27

    The chlorosome antenna complex is a fascinating structure which due to its immense scale, accurate simulation of excitation energy transfer (EET) dynamics supposes a genuine computational challenge. Resonant vibronic modes have been recently identified in 2D spectra of the chlorosome which motivates our present endeavour of modelling electronic and vibrational degrees of freedom on an equal footing. Following the Dirac-Frenkel time-dependent variational principle, we exploit a general theory of polaron dynamics in two-dimensional lattices based on the Holstein molecular crystal model and investigate a single rod model of pigment aggregates. Unlike reduced formalisms, explicit integration of the degrees of freedom of both the system and the bath requires extensive computational resources. We exploit the architecture of graphic processor units (GPUs) by implementing our simulations on this platform. The simulation of dynamic properties of hundreds or even thousands of pigments is thus achievable in just a few hours. The potential investigation and design of natural or engineered two-dimensional pigment networks can thus be accommodated. Due to the lack of consensus regarding the precise arrangement of chromophores in the chlorosome, helicity and dimerization are investigated independently, extracting their contributions to both optical and EET properties. The presence of dimerization is found to slow down the delocalization process. Exciton delocalization is completed in 100 fs in a single rod aggregate whose dimensions (20 nm) fairly exceed the estimated extent of a coherent domain. Ultrafast energy relaxation in the exciton manifold occurs in 50 fs and the duration of super-diffusive transport is found to last for about 80 fs. PMID:26792106

  20. Tensor numerical methods in quantum chemistry: from Hartree-Fock to excitation energies.

    PubMed

    Khoromskaia, Venera; Khoromskij, Boris N

    2015-12-21

    We resume the recent successes of the grid-based tensor numerical methods and discuss their prospects in real-space electronic structure calculations. These methods, based on the low-rank representation of the multidimensional functions and integral operators, first appeared as an accurate tensor calculus for the 3D Hartree potential using 1D complexity operations, and have evolved to entirely grid-based tensor-structured 3D Hartree-Fock eigenvalue solver. It benefits from tensor calculation of the core Hamiltonian and two-electron integrals (TEI) in O(n log n) complexity using the rank-structured approximation of basis functions, electron densities and convolution integral operators all represented on 3D n × n × n Cartesian grids. The algorithm for calculating TEI tensor in a form of the Cholesky decomposition is based on multiple factorizations using algebraic 1D "density fitting" scheme, which yield an almost irreducible number of product basis functions involved in the 3D convolution integrals, depending on a threshold ε > 0. The basis functions are not restricted to separable Gaussians, since the analytical integration is substituted by high-precision tensor-structured numerical quadratures. The tensor approaches to post-Hartree-Fock calculations for the MP2 energy correction and for the Bethe-Salpeter excitation energies, based on using low-rank factorizations and the reduced basis method, were recently introduced. Another direction is towards the tensor-based Hartree-Fock numerical scheme for finite lattices, where one of the numerical challenges is the summation of electrostatic potentials of a large number of nuclei. The 3D grid-based tensor method for calculation of a potential sum on a L × L × L lattice manifests the linear in L computational work, O(L), instead of the usual O(L(3) log L) scaling by the Ewald-type approaches. PMID:26016539

  1. An efficient computational scheme for electronic excitation spectra of molecules in solution using the symmetry-adapted cluster–configuration interaction method: The accuracy of excitation energies and intuitive charge-transfer indices

    SciTech Connect

    Fukuda, Ryoichi Ehara, Masahiro

    2014-10-21

    Solvent effects on electronic excitation spectra are considerable in many situations; therefore, we propose an efficient and reliable computational scheme that is based on the symmetry-adapted cluster-configuration interaction (SAC-CI) method and the polarizable continuum model (PCM) for describing electronic excitations in solution. The new scheme combines the recently proposed first-order PCM SAC-CI method with the PTE (perturbation theory at the energy level) PCM SAC scheme. This is essentially equivalent to the usual SAC and SAC-CI computations with using the PCM Hartree-Fock orbital and integrals, except for the additional correction terms that represent solute-solvent interactions. The test calculations demonstrate that the present method is a very good approximation of the more costly iterative PCM SAC-CI method for excitation energies of closed-shell molecules in their equilibrium geometry. This method provides very accurate values of electric dipole moments but is insufficient for describing the charge-transfer (CT) indices in polar solvent. The present method accurately reproduces the absorption spectra and their solvatochromism of push-pull type 2,2{sup ′}-bithiophene molecules. Significant solvent and substituent effects on these molecules are intuitively visualized using the CT indices. The present method is the simplest and theoretically consistent extension of SAC-CI method for including PCM environment, and therefore, it is useful for theoretical and computational spectroscopy.

  2. Excitation energy transfer in a classical analogue of photosynthetic antennae.

    PubMed

    Mančal, Tomáš

    2013-09-26

    We formulate a classical pure dephasing system-bath interaction model in a full correspondence to the well-studied quantum model of natural light-harvesting antennae. The equations of motion of our classical model not only represent the correct classical analogy to the quantum description of excitonic systems, but they also have exactly the same functional form. We demonstrate derivation of classical dissipation and relaxation tensor in second order perturbation theory. We find that the only difference between the classical and quantum descriptions is in the interpretation of the state and in certain limitations imposed on the parameters of the model by classical physics. The effects of delocalization, transfer pathway interference, and the transition from coherent to diffusive transfer can be found already in the classical realm. The only qualitatively new effect occurring in quantum systems is the preference for a downhill energy transfer and the resulting possibility of trapping the energy in the lowest energy state.

  3. No galaxy left behind: accurate measurements with the faintest objects in the Dark Energy Survey

    NASA Astrophysics Data System (ADS)

    Suchyta, E.; Huff, E. M.; Aleksić, J.; Melchior, P.; Jouvel, S.; MacCrann, N.; Ross, A. J.; Crocce, M.; Gaztanaga, E.; Honscheid, K.; Leistedt, B.; Peiris, H. V.; Rykoff, E. S.; Sheldon, E.; Abbott, T.; Abdalla, F. B.; Allam, S.; Banerji, M.; Benoit-Lévy, A.; Bertin, E.; Brooks, D.; Burke, D. L.; Rosell, A. Carnero; Kind, M. Carrasco; Carretero, J.; Cunha, C. E.; D'Andrea, C. B.; da Costa, L. N.; DePoy, D. L.; Desai, S.; Diehl, H. T.; Dietrich, J. P.; Doel, P.; Eifler, T. F.; Estrada, J.; Evrard, A. E.; Flaugher, B.; Fosalba, P.; Frieman, J.; Gerdes, D. W.; Gruen, D.; Gruendl, R. A.; James, D. J.; Jarvis, M.; Kuehn, K.; Kuropatkin, N.; Lahav, O.; Lima, M.; Maia, M. A. G.; March, M.; Marshall, J. L.; Miller, C. J.; Miquel, R.; Neilsen, E.; Nichol, R. C.; Nord, B.; Ogando, R.; Percival, W. J.; Reil, K.; Roodman, A.; Sako, M.; Sanchez, E.; Scarpine, V.; Sevilla-Noarbe, I.; Smith, R. C.; Soares-Santos, M.; Sobreira, F.; Swanson, M. E. C.; Tarle, G.; Thaler, J.; Thomas, D.; Vikram, V.; Walker, A. R.; Wechsler, R. H.; Zhang, Y.; DES Collaboration

    2016-03-01

    Accurate statistical measurement with large imaging surveys has traditionally required throwing away a sizable fraction of the data. This is because most measurements have relied on selecting nearly complete samples, where variations in the composition of the galaxy population with seeing, depth, or other survey characteristics are small. We introduce a new measurement method that aims to minimize this wastage, allowing precision measurement for any class of detectable stars or galaxies. We have implemented our proposal in BALROG, software which embeds fake objects in real imaging to accurately characterize measurement biases. We demonstrate this technique with an angular clustering measurement using Dark Energy Survey (DES) data. We first show that recovery of our injected galaxies depends on a variety of survey characteristics in the same way as the real data. We then construct a flux-limited sample of the faintest galaxies in DES, chosen specifically for their sensitivity to depth and seeing variations. Using the synthetic galaxies as randoms in the Landy-Szalay estimator suppresses the effects of variable survey selection by at least two orders of magnitude. With this correction, our measured angular clustering is found to be in excellent agreement with that of a matched sample from much deeper, higher resolution space-based Cosmological Evolution Survey (COSMOS) imaging; over angular scales of 0.004° < θ < 0.2°, we find a best-fitting scaling amplitude between the DES and COSMOS measurements of 1.00 ± 0.09. We expect this methodology to be broadly useful for extending measurements' statistical reach in a variety of upcoming imaging surveys.

  4. No Galaxy Left Behind: Accurate Measurements with the Faintest Objects in the Dark Energy Survey

    DOE PAGES

    Suchyta, E.

    2016-01-27

    Accurate statistical measurement with large imaging surveys has traditionally required throwing away a sizable fraction of the data. This is because most measurements have have relied on selecting nearly complete samples, where variations in the composition of the galaxy population with seeing, depth, or other survey characteristics are small. We introduce a new measurement method that aims to minimize this wastage, allowing precision measurement for any class of stars or galaxies detectable in an imaging survey. We have implemented our proposal in Balrog, a software package which embeds fake objects in real imaging in order to accurately characterize measurement biases.more » We also demonstrate this technique with an angular clustering measurement using Dark Energy Survey (DES) data. We first show that recovery of our injected galaxies depends on a wide variety of survey characteristics in the same way as the real data. We then construct a flux-limited sample of the faintest galaxies in DES, chosen specifically for their sensitivity to depth and seeing variations. Using the synthetic galaxies as randoms in the standard LandySzalay correlation function estimator suppresses the effects of variable survey selection by at least two orders of magnitude. Now our measured angular clustering is found to be in excellent agreement with that of a matched sample drawn from much deeper, higherresolution space-based COSMOS imaging; over angular scales of 0.004° < θ < 0.2 ° , we find a best-fit scaling amplitude between the DES and COSMOS measurements of 1.00 ± 0.09. We expect this methodology to be broadly useful for extending the statistical reach of measurements in a wide variety of coming imaging surveys.« less

  5. A new accurate ground-state potential energy surface of ethylene and predictions for rotational and vibrational energy levels

    NASA Astrophysics Data System (ADS)

    Delahaye, Thibault; Nikitin, Andrei; Rey, Michaël; Szalay, Péter G.; Tyuterev, Vladimir G.

    2014-09-01

    In this paper we report a new ground state potential energy surface for ethylene (ethene) C2H4 obtained from extended ab initio calculations. The coupled-cluster approach with the perturbative inclusion of the connected triple excitations CCSD(T) and correlation consistent polarized valence basis set cc-pVQZ was employed for computations of electronic ground state energies. The fit of the surface included 82 542 nuclear configurations using sixth order expansion in curvilinear symmetry-adapted coordinates involving 2236 parameters. A good convergence for variationally computed vibrational levels of the C2H4 molecule was obtained with a RMS(Obs.-Calc.) deviation of 2.7 cm-1 for fundamental bands centers and 5.9 cm-1 for vibrational bands up to 7800 cm-1. Large scale vibrational and rotational calculations for 12C2H4, 13C2H4, and 12C2D4 isotopologues were performed using this new surface. Energy levels for J = 20 up to 6000 cm-1 are in a good agreement with observations. This represents a considerable improvement with respect to available global predictions of vibrational levels of 13C2H4 and 12C2D4 and rovibrational levels of 12C2H4.

  6. Modeling energy-loss spectra due to phonon excitation

    NASA Astrophysics Data System (ADS)

    Forbes, B. D.; Allen, L. J.

    2016-07-01

    We discuss a fundamental theory of how to calculate the phonon-loss sector of the energy-loss spectrum for electrons scattering from crystalline solids. A correlated model for the atomic motion is used for calculating the vibrational modes. Spectra are calculated for crystalline silicon illuminated by a plane wave and by an atomic-scale focused coherent probe, in which case the spectra depend on probe position. These spectra are also affected by the size of the spectrometer aperture. The correlated model is contrasted with the Einstein model in which atoms in the specimen are assumed to vibrate independently. We also discuss how both the correlated and Einstein models relate to a classical view of the energy-loss process.

  7. Study of low energy excitations of carbon nanotubes with DMRG

    NASA Astrophysics Data System (ADS)

    Struck, Alexander; Reyes, Sebastian A.; Eggert, Sebastian

    2010-03-01

    We examine the low-energy properties of impure carbon nanotubes including short-ranged electron-electron interactions. In particular, we calculate the local density of states (LDOS) close to selected impurities such as Stone-Wales defect and half-fullerene caps at the tube ends using the density matrix renormalization group (DMRG). We discuss the possibility to identify interaction strength and range from LDOS patterns, which reveal the interplay of electron interactions and impurities.

  8. Excitation of torsional modes of proteins via collisional energy transfer: A quantum dynamical approach

    NASA Astrophysics Data System (ADS)

    Clary, David C.; Meijer, Anthony J. H. M.

    2002-06-01

    Quantum dynamical calculations have been carried out on the excitation of the torsional vibrations of a protein by collision with a solvent molecule. This energy transfer process represents the first step in the unfolding of the protein. The method developed for this purpose is the torsional close coupling, infinite order sudden approximation. Both time-independent and time dependent methods are used to solve the scattering problem and individual excitation of all the torsional modes of the protein is treated. The method is applied to the excitation of the HIV protein gp41 colliding with a water molecule. This protein has 1101 atoms, 56 amino acids, and 452 torsional modes. A major mode-selective effect is found in the computations: it is much easier to excite backbone torsions than sidechain torsions in the protein. In addition, resonances arise in the collisional process and these complexes involve temporary trapping of the water molecule inside the pockets of the protein.

  9. Sensitivity of de-excitation energies of superdeformed secondary minima to the density dependence of symmetry energy with the relativistic mean-field theory

    NASA Astrophysics Data System (ADS)

    Jiang, W. Z.; Ren, Z. Z.; Sheng, Z. Q.; Zhu, Z. Y.

    2010-06-01

    The relationship between de-excitation energies of superdeformed secondary minima relative to ground states and the density dependence of the symmetry energy is investigated for heavy nuclei using the relativistic mean-field (RMF) model. It is shown that the de-excitation energies of superdeformed secondary minima are sensitive to differences in the symmetry energy that are mimicked by the isoscalar-isovector coupling included in the model. With deliberate investigations on a few Hg isotopes that have data of de-excitation energies, we find that the description for the de-excitation energies can be improved due to the softening of the symmetry energy. Further, we have investigated de-excitation energies of odd-odd heavy nuclei that are nearly independent of pairing correlations, and have discussed the possible extraction of the constraint on the density dependence of the symmetry energy with the measurement of de-excitation energies of these nuclei.

  10. Relativistic Energy Density Functionals: Exotic modes of excitation

    SciTech Connect

    Vretenar, D.; Paar, N.; Marketin, T.

    2008-11-11

    The framework of relativistic energy density functionals has been applied to the description of a variety of nuclear structure phenomena, not only in spherical and deformed nuclei along the valley of {beta}-stability, but also in exotic systems with extreme isospin values and close to the particle drip-lines. Dynamical aspects of exotic nuclear structure have been investigated with the relativistic quasiparticle random-phase approximation. We present results for the evolution of low-lying dipole (pygmy) strength in neutron-rich nuclei, and charged-current neutrino-nucleus cross sections.

  11. Theoretical characterization of excitation energy transfer in chlorosome light-harvesting antennae from green sulfur bacteria.

    PubMed

    Fujita, Takatoshi; Huh, Joonsuk; Saikin, Semion K; Brookes, Jennifer C; Aspuru-Guzik, Alán

    2014-06-01

    We present a theoretical study of excitation dynamics in the chlorosome antenna complex of green photosynthetic bacteria based on a recently proposed model for the molecular assembly. Our model for the excitation energy transfer (EET) throughout the antenna combines a stochastic time propagation of the excitonic wave function with molecular dynamics simulations of the supramolecular structure and electronic structure calculations of the excited states. We characterized the optical properties of the chlorosome with absorption, circular dichroism and fluorescence polarization anisotropy decay spectra. The simulation results for the excitation dynamics reveal a detailed picture of the EET in the chlorosome. Coherent energy transfer is significant only for the first 50 fs after the initial excitation, and the wavelike motion of the exciton is completely damped at 100 fs. Characteristic time constants of incoherent energy transfer, subsequently, vary from 1 ps to several tens of ps. We assign the time scales of the EET to specific physical processes by comparing our results with the data obtained from time-resolved spectroscopy experiments.

  12. The energy flux of MHD wave modes excited by realistic photospheric drivers

    NASA Astrophysics Data System (ADS)

    Fedun, Viktor; Von Fay-Siebenburgen, Erdélyi Robert; Mumford, Stuart

    The mechanism(s) responsible for solar coronal heating are still an unresolved and challenging task. In the framework of 3D numerical modelling of MHD wave excitation and propagation in the strongly stratified solar atmosphere we analyse the mode coupling and estimate the wave energy partition which can be supplied to the upper layers of the solar atmosphere by locally decomposed slow, fast and Alfven modes. These waves are excited by a number of realistic photospheric drivers which are mimicking the random granular buffeting, the coherent global solar oscillations and swirly motion observed in e.g. magnetic bright points. Based on a self-similar approach, a realistic magnetic flux tubes configuration is constructed and implemented in the VALIIIC model of the solar atmosphere. A novel method for decomposing the velocity perturbations into parallel, perpendicular and azimuthal components in 3D geometry is developed using field lines to trace a volume of constant energy flux. This method is used to identify the excited wave modes propagating upwards from the photosphere and to compute the percentage energy contribution of each mode. We have found, that for all cases where torsional motion is present, the main contribution to the flux (60%) is by Alfven wave. In the case of the vertical driver it is found to mainly excite the fast- and slow-sausage modes and a horizontal driver primarily excites the slow kink mode.

  13. Stationary response of nonlinear magneto-piezoelectric energy harvester systems under stochastic excitation

    NASA Astrophysics Data System (ADS)

    Martens, W.; von Wagner, U.; Litak, G.

    2013-09-01

    Recent years have shown increasing interest of researchers in energy harvesting systems designed to generate electrical energy from ambient energy sources, such as mechanical excitations. In a lot of cases excitation patterns of such systems exhibit random rather than deterministic behaviour with broad-band frequency spectra. In this paper, we study the efficiency of vibration energy harvesting systems with stochastic ambient excitations by solving corresponding Fokker-Planck equations. In the system under consideration, mechanical energy is transformed by a piezoelectric transducer in the presence of mechanical potential functions which are governed by magnetic fields applied to the device. Depending on the magnet positions and orientations the vibrating piezo beam system is subject to characteristic potential functions, including single and double well shapes. Considering random excitation, the probability density function (pdf) of the state variables can be calculated by solving the corresponding Fokker-Planck equation. For this purpose, the pdf is expanded into orthogonal polynomials specially adapted to the problem and the residual is minimized by a Galerkin procedure. The power output has been estimated as a function of basic potential function parameters determining the characteristic pdf shape.

  14. Kinetic Energy Distribution of H(2p) Atoms from Dissociative Excitation of H2

    NASA Technical Reports Server (NTRS)

    Ajello, Joseph M.; Ahmed, Syed M.; Kanik, Isik; Multari, Rosalie

    1995-01-01

    The kinetic energy distribution of H(2p) atoms resulting from electron impact dissociation of H2 has been measured for the first time with uv spectroscopy. A high resolution uv spectrometer was used for the measurement of the H Lyman-alpha emission line profiles at 20 and 100 eV electron impact energies. Analysis of the deconvolved 100 eV line profile reveals the existence of a narrow line peak and a broad pedestal base. Slow H(2p) atoms with peak energy near 80 meV produce the peak profile, which is nearly independent of impact energy. The wings of H Lyman-alpha arise from dissociative excitation of a series of doubly excited Q(sub 1) and Q(sub 2) states, which define the core orbitals. The fast atom energy distribution peaks at 4 eV.

  15. High spin spectroscopy near the N=Z line: Channel selection and excitation energy systematics

    SciTech Connect

    Svensson, C.E.; Cameron, J.A.; Flibotte, S.

    1996-12-31

    The total {gamma}-ray and charged-particle energies emitted in fusion-evaporation reactions leading to N=Z compound systems in the A = 50-70 mass region have been measured with the 8{pi} {gamma}-ray spectrometer and the miniball charged-particle detector array. A new method of channel selection has been developed which combines particle identification with these total energy measurements and greatly improves upon the selectivity possible with particle detection alone. In addition, the event by event measurement of total {gamma}-ray energies using the BGO ball of the 8{pi} spectrometer has allowed a determination of excitation energies following particle evaporation for a large number of channels in several different reactions. The new channel selection procedure and excitation energy systematics are illustrated with data from the reaction of {sup 24}Mg on {sup 40}Ca at E{sub lab} = 80MeV.

  16. Alpha-helices direct excitation energy flow in the Fenna Matthews Olson protein.

    PubMed

    Müh, Frank; Madjet, Mohamed El-Amine; Adolphs, Julia; Abdurahman, Ayjamal; Rabenstein, Björn; Ishikita, Hiroshi; Knapp, Ernst-Walter; Renger, Thomas

    2007-10-23

    In photosynthesis, light is captured by antenna proteins. These proteins transfer the excitation energy with almost 100% quantum efficiency to the reaction centers, where charge separation takes place. The time scale and pathways of this transfer are controlled by the protein scaffold, which holds the pigments at optimal geometry and tunes their excitation energies (site energies). The detailed understanding of the tuning of site energies by the protein has been an unsolved problem since the first high-resolution crystal structure of a light-harvesting antenna appeared >30 years ago [Fenna RE, Matthews BW (1975) Nature 258:573-577]. Here, we present a combined quantum chemical/electrostatic approach to compute site energies that considers the whole protein in atomic detail and provides the missing link between crystallography and spectroscopy. The calculation of site energies of the Fenna-Matthews-Olson protein results in optical spectra that are in quantitative agreement with experiment and reveals an unexpectedly strong influence of the backbone of two alpha-helices. The electric field from the latter defines the direction of excitation energy flow in the Fenna-Matthews-Olson protein, whereas the effects of amino acid side chains, hitherto thought to be crucial, largely compensate each other. This result challenges the current view of how energy flow is regulated in pigment-protein complexes and demonstrates that attention has to be paid to the backbone architecture. PMID:17940020

  17. Excitation of the lowest electronic transitions in ethanol by low-energy electrons

    NASA Astrophysics Data System (ADS)

    Hargreaves, L. R.; Khakoo, M. A.; Winstead, C.; McKoy, V.

    2016-09-01

    We report absolute differential and integral cross sections for electronic excitation of ethanol, by low-energy electron impact. Cross sections for low-lying excited states were measured at incident electron energies from 9 to 20 eV and at scattering angles from {5}\\circ through {130}\\circ . Our results include cross sections for excitation of the 1{}3A\\prime \\prime and 1{}1A\\prime \\prime states as well as for the 2{}3A\\prime \\prime + 1{}3A\\prime and 2{}1A\\prime \\prime + 2{}1A\\prime cross section sums. Corresponding calculations were also performed using the Schwinger multichannel method, within an 11-channel close-coupling scheme.

  18. Linear-response theory for Mukherjee's multireference coupled-cluster method: Excitation energies

    NASA Astrophysics Data System (ADS)

    Jagau, Thomas-C.; Gauss, Jürgen

    2012-07-01

    The recently presented linear-response function for Mukherjee's multireference coupled-cluster method (Mk-MRCC) [T.-C. Jagau and J. Gauss, J. Chem. Phys. 137, 044115 (2012)], 10.1063/1.4734308 is employed to determine vertical excitation energies within the singles and doubles approximation (Mk-MRCCSD-LR) for ozone as well as for o-benzyne, m-benzyne, and p-benzyne, which display increasing multireference character in their ground states. In order to assess the impact of a multireference ground-state wavefunction on excitation energies, we compare all our results to those obtained at the single-reference coupled-cluster level of theory within the singles and doubles as well as within the singles, doubles, and triples approximation. Special attention is paid to the artificial splitting of certain excited states which arises from the redundancy intrinsic to Mk-MRCC theory and hinders the straightforward application of the Mk-MRCC-LR method.

  19. Dynamics of Excitation Energy Transfer Between the Subunits of Photosystem II Dimer.

    PubMed

    Yoneda, Yusuke; Katayama, Tetsuro; Nagasawa, Yutaka; Miyasaka, Hiroshi; Umena, Yasufumi

    2016-09-14

    Energy transfer dynamics in monomer and dimer of the photosystem II core complex (PSII-CC) was investigated by means of femtosecond transient absorption (TA) spectroscopy. There is no profound difference between the TA dynamics of the monomer and the dimer in the weak excitation intensity condition (≤21 nJ). However, the fast recovery of the ground state bleach was pronounced at higher excitation intensities, and the excitation intensity dependence of the dimer was more significant than that of the monomer. This result indicates efficient exciton-exciton annihilation taking place in the dimer due to energy transfer between the two monomer units. The annihilation dynamics was reproduced by a simple model based on binomial theorem, which indicated that although PSII-CC dimer has two reaction centers, only one charge-separated state remained after annihilation. PMID:27541744

  20. Collision-induced energy transfer in intermediate excited states of cesium

    NASA Astrophysics Data System (ADS)

    Lukaszewski, M.; Jackowska, I.

    1993-09-01

    We report an application of laser spectroscopy techniques to a study of collision-induced interactions in atomic excited states. Due to pulsed dye laser excitation a considerable selective population of highly excited states of ccsium is obtained. Collision-induced transfer of excitation energy between the excited states results in modifications in time and spectral characteristics of observed atomic fluorescence. Quantitative information on the efficiency of collisional processes can be obtained from the measurements of time constants of the time-resolved fluorescence signals and/or from those of the integrated intensities of the fluorescence lines. Both possibilities are used in the present work. Perturbation of nD (n=8-14) and nS (n=1O-15) states of cesium in collisions with noble-gas atoms is investigated. The cross sections for the transfer of excitation between fine-structure substates of the nD states (J mixing) and for the nS-(n-4)F intermultiplet transfer are obtained.

  1. Computing dispersive, polarizable, and electrostatic shifts of excitation energy in supramolecular systems: PTCDI crystal.

    PubMed

    Megow, Jörg

    2016-09-01

    The gas-to-crystal-shift denotes the shift of electronic excitation energies, i.e., the difference between ground and excited state energies, for a molecule transferred from the gas to the bulk phase. The contributions to the gas-to-crystal-shift comprise electrostatic as well as inductive polarization and dispersive energy shifts of the molecular excitation energies due to interaction with environmental molecules. For the example of 3,4,9,10-perylene-tetracarboxylic-diimide (PTCDI) bulk, the contributions to the gas-to-crystal shift are investigated. In the present work, electrostatic interaction is calculated via Coulomb interaction of partial charges while inductive and dispersive interactions are obtained using respective sum over states expressions. The coupling of higher transition densities for the first 4500 excited states of PTCDI was computed using transition partial charges based on an atomistic model of PTCDI bulk obtained from molecular dynamics simulations. As a result it is concluded that for the investigated model system of a PTCDI crystal, the gas to crystal shift is dominated by dispersive interaction. PMID:27608991

  2. Computing dispersive, polarizable, and electrostatic shifts of excitation energy in supramolecular systems: PTCDI crystal

    NASA Astrophysics Data System (ADS)

    Megow, Jörg

    2016-09-01

    The gas-to-crystal-shift denotes the shift of electronic excitation energies, i.e., the difference between ground and excited state energies, for a molecule transferred from the gas to the bulk phase. The contributions to the gas-to-crystal-shift comprise electrostatic as well as inductive polarization and dispersive energy shifts of the molecular excitation energies due to interaction with environmental molecules. For the example of 3,4,9,10-perylene-tetracarboxylic-diimide (PTCDI) bulk, the contributions to the gas-to-crystal shift are investigated. In the present work, electrostatic interaction is calculated via Coulomb interaction of partial charges while inductive and dispersive interactions are obtained using respective sum over states expressions. The coupling of higher transition densities for the first 4500 excited states of PTCDI was computed using transition partial charges based on an atomistic model of PTCDI bulk obtained from molecular dynamics simulations. As a result it is concluded that for the investigated model system of a PTCDI crystal, the gas to crystal shift is dominated by dispersive interaction.

  3. Ionic bond effects on the mean excitation energy for stopping power

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Chang, C. K.; Kamaratos, E.; Xu, Y. J.

    1982-01-01

    Molecular mean excitation energies for ionic bonded molecules calculated according to the local plasma approximation are compared to the Bragg rule. Adjustments of 15% are calculated for LiF in agreement with experiments while 6% adjustments are predicted for HF and 3% for LiH.

  4. Highly correlated systems. Excitation energies of first row transition metals Sc-Cu

    NASA Astrophysics Data System (ADS)

    Raghavachari, Krishnan; Trucks, Gary W.

    1989-07-01

    The low-lying dns2→dn+1s1 excitation energies of the first row transition metal atoms Sc-Cu are calculated using fourth-order M≂ller-Plesset perturbation theory (MP4) as well as quadratic configuration interaction (QCI) techniques with large spd and spdf basis sets. The MP4 method performs well for Sc-Mn but fails dramatically for Fe-Cu. In contrast, the QCI technique performs uniformly for all excitation energies with a mean deviation from experiment of only 0.14 eV after including relativistic corrections. f functions contribute 0.1-0.4 eV to the excitation energies for these systems. The highly correlated d10 state of the Ni atom is also considered in detail. The QCI technique obtains the d9s1→d10 splitting of the Ni atom with an error of only 0.13 eV. The results show that single-configuration Hartree-Fock based methods can be successful in calculating excitation energies of transition metal atoms.

  5. Influence of the excitation parameters of the mechanical subsystem on effectiveness of energy harvesting system

    NASA Astrophysics Data System (ADS)

    Buchacz, A.; Banaś, W.; Płaczek, M.

    2015-11-01

    Piezoelectric transducers are used more and more often in modern technical devices. The wide range of their possible applications is a result of the possibility to use both direct and reverse piezoelectric effect. Nowadays, application of piezoelectric transducers in energy harvesting systems is getting more and more popular. It is caused by the easy way to convert energy of mechanical vibration to the electric voltage using piezoelectric transducers. This paper presents results of influence analysis of the vibrating mechanical subsystem's excitation parameters on the effectiveness of the system designed for energy harvesting. The considered vibrating system is a composite plate with piezoelectric transducer bonded to its surface. Vibrations of the system are excited by means of an actuator with possibility to change the excitation amplitude and frequency. Recovering of electrical energy from mechanical vibrations is possible by using the direct piezoelectric effect - generation of the electric voltage while the transducer is mechanically deformed. In carried out test Macro Fiber Composite (MFC) piezoelectric transducers were used. It was proved that the time that is necessary for switch on the output voltage in analyzed system depends on the frequency of the excitation.

  6. Restricted second random phase approximations and Tamm-Dancoff approximations for electronic excitation energy calculations

    NASA Astrophysics Data System (ADS)

    Peng, Degao; Yang, Yang; Zhang, Peng; Yang, Weitao

    2014-12-01

    In this article, we develop systematically second random phase approximations (RPA) and Tamm-Dancoff approximations (TDA) of particle-hole and particle-particle channels for calculating molecular excitation energies. The second particle-hole RPA/TDA can capture double excitations missed by the particle-hole RPA/TDA and time-dependent density-functional theory (TDDFT), while the second particle-particle RPA/TDA recovers non-highest-occupied-molecular-orbital excitations missed by the particle-particle RPA/TDA. With proper orbital restrictions, these restricted second RPAs and TDAs have a formal scaling of only O(N4). The restricted versions of second RPAs and TDAs are tested with various small molecules to show some positive results. Data suggest that the restricted second particle-hole TDA (r2ph-TDA) has the best overall performance with a correlation coefficient similar to TDDFT, but with a larger negative bias. The negative bias of the r2ph-TDA may be induced by the unaccounted ground state correlation energy to be investigated further. Overall, the r2ph-TDA is recommended to study systems with both single and some low-lying double excitations with a moderate accuracy. Some expressions on excited state property evaluations, such as < hat{S}2rangle are also developed and tested.

  7. Nonequilibrium phenomena in charge recombination of excited donor-acceptor complexes and free energy gap law.

    PubMed

    Yudanov, Vladislav V; Mikhailova, Valentina A; Ivanov, Anatoly I

    2010-12-23

    The charge recombination dynamics of excited donor-acceptor complexes in polar solvents has been investigated within the framework of the stochastic approach. The model involves the excited state formation by the pump pulse and accounts for the reorganization of a number of intramolecular high-frequency vibrational modes, for their relaxation as well as for the solvent reorganization following nonexponential relaxation. The hot transitions accelerate the charge recombination in the low exergonic region and suppress it in the region of moderate exothermicity. This straightens the dependence of the logarithm of the charge recombination rate constant on the free energy gap to the form that can be fitted to the experimental data. The free energy dependence of the charge recombination rate constant can be well fitted to the multichannel stochastic model if the donor-acceptor complexes are separated into a few groups with different values of the electronic coupling. The model provides correct description of the nonexponential charge recombination dynamics in excited donor-acceptor complexes, in particular, nearly exponential recombination in perylene-tetracyanoethylene complex in acetonitrile. It appears that majority of the initially excited donor-acceptor complexes recombines in a nonthermal (hot) stage when the nonequilibrium wave packet passes through a number of term crossings corresponding to transitions toward vibrational excited states of the electronic ground state in the area of the low and moderate exothermicity.

  8. Restricted second random phase approximations and Tamm-Dancoff approximations for electronic excitation energy calculations

    SciTech Connect

    Peng, Degao; Yang, Yang; Zhang, Peng; Yang, Weitao

    2014-12-07

    In this article, we develop systematically second random phase approximations (RPA) and Tamm-Dancoff approximations (TDA) of particle-hole and particle-particle channels for calculating molecular excitation energies. The second particle-hole RPA/TDA can capture double excitations missed by the particle-hole RPA/TDA and time-dependent density-functional theory (TDDFT), while the second particle-particle RPA/TDA recovers non-highest-occupied-molecular-orbital excitations missed by the particle-particle RPA/TDA. With proper orbital restrictions, these restricted second RPAs and TDAs have a formal scaling of only O(N{sup 4}). The restricted versions of second RPAs and TDAs are tested with various small molecules to show some positive results. Data suggest that the restricted second particle-hole TDA (r2ph-TDA) has the best overall performance with a correlation coefficient similar to TDDFT, but with a larger negative bias. The negative bias of the r2ph-TDA may be induced by the unaccounted ground state correlation energy to be investigated further. Overall, the r2ph-TDA is recommended to study systems with both single and some low-lying double excitations with a moderate accuracy. Some expressions on excited state property evaluations, such as 〈S{sup ^2}〉 are also developed and tested.

  9. Energy-Looping Nanoparticles: Harnessing Excited-State Absorption for Deep-Tissue Imaging.

    PubMed

    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. PMID:27603228

  10. A new accurate ground-state potential energy surface of ethylene and predictions for rotational and vibrational energy levels

    SciTech Connect

    Delahaye, Thibault Rey, Michaël Tyuterev, Vladimir G.; Nikitin, Andrei; Szalay, Péter G.

    2014-09-14

    In this paper we report a new ground state potential energy surface for ethylene (ethene) C{sub 2}H{sub 4} obtained from extended ab initio calculations. The coupled-cluster approach with the perturbative inclusion of the connected triple excitations CCSD(T) and correlation consistent polarized valence basis set cc-pVQZ was employed for computations of electronic ground state energies. The fit of the surface included 82 542 nuclear configurations using sixth order expansion in curvilinear symmetry-adapted coordinates involving 2236 parameters. A good convergence for variationally computed vibrational levels of the C{sub 2}H{sub 4} molecule was obtained with a RMS(Obs.–Calc.) deviation of 2.7 cm{sup −1} for fundamental bands centers and 5.9 cm{sup −1} for vibrational bands up to 7800 cm{sup −1}. Large scale vibrational and rotational calculations for {sup 12}C{sub 2}H{sub 4}, {sup 13}C{sub 2}H{sub 4}, and {sup 12}C{sub 2}D{sub 4} isotopologues were performed using this new surface. Energy levels for J = 20 up to 6000 cm{sup −1} are in a good agreement with observations. This represents a considerable improvement with respect to available global predictions of vibrational levels of {sup 13}C{sub 2}H{sub 4} and {sup 12}C{sub 2}D{sub 4} and rovibrational levels of {sup 12}C{sub 2}H{sub 4}.

  11. Accurate bond energies of biodiesel methyl esters from multireference averaged coupled-pair functional calculations.

    PubMed

    Oyeyemi, Victor B; Keith, John A; Carter, Emily A

    2014-09-01

    Accurate bond dissociation energies (BDEs) are important for characterizing combustion chemistry, particularly the initial stages of pyrolysis. Here we contribute to evaluating the thermochemistry of biodiesel methyl ester molecules using ab initio BDEs derived from a multireference averaged coupled-pair functional (MRACPF2)-based scheme. Having previously validated this approach for hydrocarbons and a variety of oxygenates, herein we provide further validation for bonds within carboxylic acids and methyl esters, finding our scheme predicts BDEs within chemical accuracy (i.e., within 1 kcal/mol) for these molecules. Insights into BDE trends with ester size are then analyzed for methyl formate through methyl crotonate. We find that the carbonyl group in the ester moiety has only a local effect on BDEs. C═C double bonds in ester alkyl chains are found to increase the strengths of bonds adjacent to the double bond. An important exception are bonds beta to C═C or C═O bonds, which produce allylic-like radicals upon dissociation. The observed trends arise from different degrees of geometric relaxation and resonance stabilization in the radicals produced. We also compute BDEs in various small alkanes and alkenes as models for the long hydrocarbon chain of actual biodiesel methyl esters. We again show that allylic bonds in the alkenes are much weaker than those in the small methyl esters, indicating that hydrogen abstractions are more likely at the allylic site and even more likely at bis-allylic sites of alkyl chains due to more electrons involved in π-resonance in the latter. Lastly, we use the BDEs in small surrogates to estimate heretofore unknown BDEs in large methyl esters of biodiesel fuels.

  12. Accurate bond energies of biodiesel methyl esters from multireference averaged coupled-pair functional calculations.

    PubMed

    Oyeyemi, Victor B; Keith, John A; Carter, Emily A

    2014-09-01

    Accurate bond dissociation energies (BDEs) are important for characterizing combustion chemistry, particularly the initial stages of pyrolysis. Here we contribute to evaluating the thermochemistry of biodiesel methyl ester molecules using ab initio BDEs derived from a multireference averaged coupled-pair functional (MRACPF2)-based scheme. Having previously validated this approach for hydrocarbons and a variety of oxygenates, herein we provide further validation for bonds within carboxylic acids and methyl esters, finding our scheme predicts BDEs within chemical accuracy (i.e., within 1 kcal/mol) for these molecules. Insights into BDE trends with ester size are then analyzed for methyl formate through methyl crotonate. We find that the carbonyl group in the ester moiety has only a local effect on BDEs. C═C double bonds in ester alkyl chains are found to increase the strengths of bonds adjacent to the double bond. An important exception are bonds beta to C═C or C═O bonds, which produce allylic-like radicals upon dissociation. The observed trends arise from different degrees of geometric relaxation and resonance stabilization in the radicals produced. We also compute BDEs in various small alkanes and alkenes as models for the long hydrocarbon chain of actual biodiesel methyl esters. We again show that allylic bonds in the alkenes are much weaker than those in the small methyl esters, indicating that hydrogen abstractions are more likely at the allylic site and even more likely at bis-allylic sites of alkyl chains due to more electrons involved in π-resonance in the latter. Lastly, we use the BDEs in small surrogates to estimate heretofore unknown BDEs in large methyl esters of biodiesel fuels. PMID:24621192

  13. Hot-electron-mediated desorption rates calculated from excited-state potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Olsen, Thomas; Gavnholt, Jeppe; Schiøtz, Jakob

    2009-01-01

    We present a model for desorption induced by (multiple) electronic transitions [DIET (DIMET)] based on potential energy surfaces calculated with the delta self-consistent field extension of density-functional theory. We calculate potential energy surfaces of CO and NO molecules adsorbed on various transition-metal surfaces and show that classical nuclear dynamics does not suffice for propagation in the excited state. We present a simple Hamiltonian describing the system with parameters obtained from the excited-state potential energy surface and show that this model can describe desorption dynamics in both the DIET and DIMET regimes and reproduce the power-law behavior observed experimentally. We observe that the internal stretch degree of freedom in the molecules is crucial for the energy transfer between the hot electrons and the molecule when the coupling to the surface is strong.

  14. An accurate potential energy curve for helium based on ab initio calculations

    NASA Astrophysics Data System (ADS)

    Janzen, A. R.; Aziz, R. A.

    1997-07-01

    Korona, Williams, Bukowski, Jeziorski, and Szalewicz [J. Chem. Phys. 106, 1 (1997)] constructed a completely ab initio potential for He2 by fitting their calculations using infinite order symmetry adapted perturbation theory at intermediate range, existing Green's function Monte Carlo calculations at short range and accurate dispersion coefficients at long range to a modified Tang-Toennies potential form. The potential with retardation added to the dipole-dipole dispersion is found to predict accurately a large set of microscopic and macroscopic experimental data. The potential with a significantly larger well depth than other recent potentials is judged to be the most accurate characterization of the helium interaction yet proposed.

  15. Quantum dynamics study of fulvene double bond photoisomerization: The role of intramolecular vibrational energy redistribution and excitation energy

    SciTech Connect

    Blancafort, Lluis; Gatti, Fabien; Meyer, Hans-Dieter

    2011-10-07

    The double bond photoisomerization of fulvene has been studied with quantum dynamics calculations using the multi-configuration time-dependent Hartree method. Fulvene is a test case to develop optical control strategies based on the knowledge of the excited state decay mechanism. The decay takes place on a time scale of several hundred femtoseconds, and the potential energy surface is centered around a conical intersection seam between the ground and excited state. The competition between unreactive decay and photoisomerization depends on the region of the seam accessed during the decay. The dynamics are carried out on a four-dimensional model surface, parametrized from complete active space self-consistent field calculations, that captures the main features of the seam (energy and locus of the seam and associated branching space vectors). Wave packet propagations initiated by single laser pulses of 5-25 fs duration and 1.85-4 eV excitation energy show the principal characteristics of the first 150 fs of the photodynamics. Initially, the excitation energy is transferred to a bond stretching mode that leads the wave packet to the seam, inducing the regeneration of the reactant. The photoisomerization starts after the vibrational energy has flowed from the bond stretching to the torsional mode. In our propagations, intramolecular energy redistribution (IVR) is accelerated for higher excess energies along the bond stretch mode. Thus, the competition between unreactive decay and isomerization depends on the rate of IVR between the bond stretch and torsion coordinates, which in turn depends on the excitation energy. These results set the ground for the development of future optical control strategies.

  16. Optical excitation energies, Stokes shift, and spin-splitting of C24H72Si14.

    PubMed

    Zope, Rajendra R; Baruah, Tunna; Richardson, Steven L; Pederson, Mark R; Dunlap, Brett I

    2010-07-21

    As an initial step toward the synthesis and characterization of sila-diamondoids, such as sila-adamantane (Si(10)H(16),T(d)), the synthesis of a fourfold silylated sila-adamantane molecule (C(24)H(72)Si(14),T(d)) has been reported in literature [Fischer et al., Science 310, 825 (2005)]. We present the electronic structure, ionization energies, quasiparticle gap, and the excitation energies for the Si(14)(CH(3))(24) and the exact silicon analog of adamantane Si(10)H(16) obtained at the all-electron level using the delta-self-consistent-field and transitional state methods within two different density functional models: (i) Perdew-Burke-Ernzerhof generalized gradient approximation and (ii) fully analytic density functional (ADFT) implementation with atom dependent potential. The ADFT is designed so that molecules separate into atoms having exact atomic energies. The calculations within the two models agree well, to within 0.25 eV for optical excitations. The effect of structural relaxation in the presence of electron-hole-pair excitations is examined to obtain its contribution to the luminescence Stokes shift. The spin-influence on exciton energies is also determined. Our calculations indicate overall decrease in the absorption, emission, quasiparticle, and highest occupied molecular orbital-lowest unoccupied molecular orbital gaps, ionization energies, Stokes shift, and exciton binding energy when passivating hydrogens in the Si(10)H(16) are replaced with electron donating groups such as methyl (Me) and trimehylsilyl (-Si(Me)(3)).

  17. Dissociative recombination and vibrational excitation of BF+ in low energy electron collisions

    NASA Astrophysics Data System (ADS)

    Mezei, J. Zs; Colboc, F.; Pop, N.; Ilie, S.; Chakrabarti, K.; Niyonzima, S.; Lepers, M.; Bultel, A.; Dulieu, O.; Motapon, O.; Tennyson, J.; Hassouni, K.; Schneider, I. F.

    2016-10-01

    The latest molecular data—potential energy curves and Rydberg-valence interactions—characterising the super-excited electronic states of BF are reviewed in order to provide the input for the study of their fragmentation dynamics. Starting from this input, the main paths and mechanisms of BF+ dissociative recombination and vibrational excitation are analysed. Their cross sections are computed for the first time using a method based on the multichannel quantum defect theory (MQDT), and Maxwellian rate-coefficients are calculated and displayed in ready-to-be-used format for low temperature plasma kinetics simulations.

  18. Surface-catalyzed recombination into excited electronic, vibrational, rotational, and kinetic energy states: A review

    NASA Technical Reports Server (NTRS)

    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.

  19. Nonequilibrium generalization of Förster Dexter theory for excitation energy transfer

    NASA Astrophysics Data System (ADS)

    Jang, Seogjoo; Jung, YounJoon; Silbey, Robert J.

    2002-01-01

    Förster-Dexter theory for excitation energy transfer (EET) is generalized for the account of short time nonequilibrium kinetics due to the nonstationary bath relaxation. The final rate expression is presented as a spectral overlap between the time dependent stimulated emission and the stationary absorption profiles, which allows experimental determination of the time dependent rate. For a harmonic oscillator bath model, an explicit rate expression is derived and model calculations are performed in order to examine the dependence of the nonequilibrium kinetics on the excitation-bath coupling strength and the temperature. Relevance of the present theory with recent experimental findings and possible future theoretical directions are discussed.

  20. UV absorption study of collisional energy transfer in vibrationally highly excited SO/sub 2/ molecules

    SciTech Connect

    Heymann, M.; Hippler, H.; Nahr, D.; Plach, H.J.; Troe, J.

    1988-09-22

    Transient UV absorption spectra after UV laser excitation of SO/sub 2/ were recorded and analyzed with respect to collisional energy transfer. Byuse of previously determined calibration curves, the absorption-time signals were converted into average energy-number of collision profiles. Energy-dependent average energies transferred per collision (..delta..E) were derived for 22 different collision partners. The temperature dependence of (..delta..E) was determined over the range 300-1500 K by experiments in a CO/sub 2/ CW laser-heated reactor and in shock waves.

  1. Accurate ab initio potential energy surface, thermochemistry, and dynamics of the Br(2P, 2P(3∕2)) + CH4 → HBr + CH3 reaction.

    PubMed

    Czakó, Gábor

    2013-04-01

    Chemically accurate full-dimensional non-spin-orbit and spin-orbit (SO) ground-state potential energy surfaces (PESs) are obtained for the Br + CH4 → HBr + CH3 reaction by fitting 21 574 composite ab initio energy points. The composite method considers electron correlation methods up to CCSD(T), basis sets up to aug-cc-pwCVTZ-PP, correlation of the core electrons, scalar relativistic effects via an effective core potential (ECP), and SO corrections, thereby achieving an accuracy better than 0.5 kcal∕mol. Benchmark structures and relative energies are computed for the stationary points using the ab initio focal-point analysis (FPA) scheme based on both ECP and Douglas-Kroll approaches providing all-electron relativistic CCSDT(Q)∕complete-basis-set quality energies. The PESs accurately describe the saddle point of the abstraction reaction and the van der Waals complexes in the entrance and product channels. The SO-corrected PES provides a classical barrier height of 7285(7232 ± 50) cm(-1), De values of 867(799 ± 10) and 399(344 ± 10) cm(-1) for the complexes CH3-HBr and CH3-BrH, respectively, and reaction endothermicity of 7867(7857 ± 50) cm(-1), in excellent agreement with the new, FPA-based benchmark data shown in parentheses. The difference between the Br + CH4 asymptotes of the non-SO and SO PESs is 1240 cm(-1), in good agreement with the experiment (1228 cm(-1)). Quasiclassical trajectory calculations based on more than 13 million trajectories for the late-barrier Br + CH4(vk = 0, 1) [k = 1, 2, 3, 4] reactions show that the vibrational energy, especially the excitation of the stretching modes, activates the reaction much more efficiently than translational energy, in agreement with the extended Polanyi rules. Angular distributions show dominant backward scattering for the ground-state reaction and forward scattering for the stretching-excited reactions. The reactivity on the non-SO PES is about 3-5 times larger than that on the SO PES in a wide

  2. Excitation-energy dependence of solvation dynamics in room-temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Kim, Daekeon; Park, Sang-Won; Shim, Youngseon; Kim, Hyung J.; Jung, YounJoon

    2016-07-01

    Influence of the excitation energy of a probe solute molecule on its solvation dynamics and emission spectrum in 1-ethyl-3-methylimidazolium hexafluorophosphate (EMI+PF6-) is studied via molecular dynamics simulations using a coarse-grained model description. By exciting the probe at different energies, each with an extremely narrow distribution, ensuing solvent relaxation and its dynamic variance are monitored using the isoconfigurational ensemble method. Resulting Stokes shift function, S(t), indicates that long-time solvent relaxation becomes slower with the decreasing excitation energy and approaches the equilibrium correlation function, C(t), of solvent fluctuations. This suggests that the system excited at the red-edge of the spectrum observes linear response better than that at the blue-edge. A detailed analysis of nonequilibrium trajectories shows that the effect of initial configurations on variance of relaxation dynamics is mainly confined to short times; it reaches a maximum around 0.1 ≲ t ≲ 1 ps and diminishes as time further increases. The influence of the initial velocity distribution, on the other hand, tends to grow with time and dominates the long-time variations of dynamics. The emission spectrum shows the red-edge effect in accord with previous studies.

  3. Excitation-energy dependence of solvation dynamics in room-temperature ionic liquids.

    PubMed

    Kim, Daekeon; Park, Sang-Won; Shim, Youngseon; Kim, Hyung J; Jung, YounJoon

    2016-07-28

    Influence of the excitation energy of a probe solute molecule on its solvation dynamics and emission spectrum in 1-ethyl-3-methylimidazolium hexafluorophosphate (EMI(+)PF6 (-)) is studied via molecular dynamics simulations using a coarse-grained model description. By exciting the probe at different energies, each with an extremely narrow distribution, ensuing solvent relaxation and its dynamic variance are monitored using the isoconfigurational ensemble method. Resulting Stokes shift function, S(t), indicates that long-time solvent relaxation becomes slower with the decreasing excitation energy and approaches the equilibrium correlation function, C(t), of solvent fluctuations. This suggests that the system excited at the red-edge of the spectrum observes linear response better than that at the blue-edge. A detailed analysis of nonequilibrium trajectories shows that the effect of initial configurations on variance of relaxation dynamics is mainly confined to short times; it reaches a maximum around 0.1 ≲ t ≲ 1 ps and diminishes as time further increases. The influence of the initial velocity distribution, on the other hand, tends to grow with time and dominates the long-time variations of dynamics. The emission spectrum shows the red-edge effect in accord with previous studies.

  4. Low-Energy Electron Impact Excitation of the (010) Bending Mode of CO2

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.; Langhoff, Stephen R. (Technical Monitor)

    1996-01-01

    Low-energy electron impact excitation of the fundamental modes of CO2 has been extensively studied, both experimentally and theoretically. Much attention has been paid to the virtual state feature in the the (100) mode excitation and the (sup 2)II(sub upsilon) resonance feature around 3.8 eV, which is observable in all three fundamental modes. For the excitation of the (010) mode away from the resonance region, the Born dipole approximation was generally considered adequate. The present study employs the Born dipole approximation to treat the long range interaction and the Schwinger multichannel method for the short range interaction. The roles of the two interaction potentials will be compared.

  5. Effective collision strengths for excitation and de-excitation of nebular [O III] optical and infrared lines with κ distributed electron energies

    NASA Astrophysics Data System (ADS)

    Storey, P. J.; Sochi, Taha

    2015-05-01

    We present effective collision strengths for electron excitation and de-excitation of the 10 forbidden transitions between the five lowest energy levels of the astronomically abundant doubly ionized oxygen ion, O2+. The raw collision strength data were obtained from an R-matrix intermediate coupling calculation using the Breit-Pauli relativistic approximation published previously by the authors. The effective collision strengths were calculated with κ-distributed electron energies and are tabulated as a function of the electron temperature and κ.

  6. Intermediate energy electron impact excitation of composite vibrational modes in phenol

    SciTech Connect

    Neves, R. F. C.; Jones, D. B.; Lopes, M. C. A.; Nixon, K. L.; Oliveira, E. M. de; Lima, M. A. P.; Costa, R. F. da; Varella, M. T. do N.; Bettega, M. H. F.; Silva, G. B. da; Brunger, M. J.

    2015-05-21

    We report differential cross section results from an experimental investigation into the electron impact excitation of a number of the low-lying composite (unresolved) vibrational modes in phenol (C{sub 6}H{sub 5}OH). The measurements were carried out at incident electron energies in the range 15–40 eV and for scattered-electron angles in the range 10–90°. The energy resolution of those measurements was typically ∼80 meV. Calculations, using the GAMESS code, were also undertaken with a B3LYP/aug-cc-pVDZ level model chemistry, in order to enable us to assign vibrational modes to the features observed in our energy loss spectra. To the best of our knowledge, the present cross sections are the first to be reported for vibrational excitation of the C{sub 6}H{sub 5}OH molecule by electron impact.

  7. Intermediate-energy differential and integral cross sections for vibrational excitation in α-tetrahydrofurfuryl alcohol.

    PubMed

    Duque, H V; Chiari, L; Jones, D B; Pettifer, Z; da Silva, G B; Limão-Vieira, P; Blanco, F; García, G; White, R D; Lopes, M C A; Brunger, M J

    2014-06-01

    Differential and integral cross section measurements, for incident electron energies in the 20-50 eV range, are reported for excitation of several composite vibrational modes in α-tetrahydrofurfuryl alcohol (THFA). Optimisation and frequency calculations, using GAUSSIAN 09 at the B3LYP/aug-cc-pVDZ level, were also undertaken for the two most abundant conformers of THFA, with results being reported for their respective mode classifications and excitation energies. Those calculations assisted us in the experimental assignments of the composite features observed in our measured energy loss spectra. There are, to the best of our knowledge, no other experimental or theoretical data currently available in the literature against which we can compare the present results.

  8. Energy transfer from PO excited states to alkali metal atoms in the phosphorus chemiluminescence flame

    PubMed Central

    Khan, Ahsan U.

    1980-01-01

    Phosphorus chemiluminescence under ambient conditions of a phosphorus oxidation flame is found to offer an efficient electronic energy transferring system to alkali metal atoms. The lowest resonance lines, 2P3 / 2,½→2S½, of potassium and sodium are excited by energy transfer when an argon stream at 80°C carrying potassium or sodium atoms intersects a phosphorus vapor stream, either at the flame or in the postflame region. The lowest electronically excited metastable 4IIi state of PO or the (PO[unk]PO)* excimer is considered to be the probable energy donor. The (PO[unk]PO)* excimer results from the interaction of the 4IIi state of one PO molecule with the ground 2IIr state of another. Metastability of the donor state is strongly indicated by the observation of intense sensitized alkali atom fluorescence in the postflame region. PMID:16592925

  9. Pressure variation of 4f excitation energies in Eu and Tm metals

    NASA Astrophysics Data System (ADS)

    Herbst, J. F.; Wilkins, J. W.

    1987-08-01

    Calculations of 4f-electron excitation energies as functions of the Wigner-Seitz radius rWS in europium and thulium metals are reported. Crystal potentials are constructed by the renormalized-atom method for integrally-occupied 4f configurations, and each excitation energy is derived from a difference of band total energies. As rWS decreases for each metal the 6s and 5d levels are progressively depopulated, leading to enhancement of the 4f occupancy at elevated pressures. In particular our results predict a 4f7-->4f8 transition in Eu at a pressure P~44 Mbar and a 4f12-->4f13 transition in Tm at P~3 Mbar.

  10. Response of energy envelop in complex oscillator networks to external stochastic excitations

    NASA Astrophysics Data System (ADS)

    Jin, Xiao-Ling; Huang, Zhi-Long; Chen, Guanrong; Leung, Andrew Y. T.

    2010-07-01

    The response of energy envelop in complex nonlinear oscillator networks to stochastic excitations is studied. First, by using the stochastic averaging method for quasi-nonintegrable-Hamiltonian systems, the averaged Fokker-Planck-Kolmogorov equation governing the probability density of the Hamiltonian is established. Then, the stationary probability density of the Hamiltonian is derived, and the stationary probability density of the averaged energy as well as the statistical moments of the Hamiltonian is obtained. To that end, an illustrative example is provided with the analytical relationship between the response and the network parameters as well as the network structure. Specific solutions are presented for five representative topological structures. Throughout extensive simulations, the effects of system parameters, such as the network size, coupling strength and intensities of stochastic excitations on the response of the energy envelop of the networks, are carefully observed and analyzed.

  11. Intermediate-energy differential and integral cross sections for vibrational excitation in α-tetrahydrofurfuryl alcohol

    SciTech Connect

    Duque, H. V.; Chiari, L.; Jones, D. B.; Pettifer, Z.; Silva, G. B. da; Limão-Vieira, P.; Blanco, F.; García, G.; White, R. D.; Lopes, M. C. A.; Brunger, M. J.

    2014-06-07

    Differential and integral cross section measurements, for incident electron energies in the 20–50 eV range, are reported for excitation of several composite vibrational modes in α-tetrahydrofurfuryl alcohol (THFA). Optimisation and frequency calculations, using GAUSSIAN 09 at the B3LYP/aug-cc-pVDZ level, were also undertaken for the two most abundant conformers of THFA, with results being reported for their respective mode classifications and excitation energies. Those calculations assisted us in the experimental assignments of the composite features observed in our measured energy loss spectra. There are, to the best of our knowledge, no other experimental or theoretical data currently available in the literature against which we can compare the present results.

  12. Benchmarking the completely renormalised equation-of-motion coupled-cluster approaches for vertical excitation energies

    SciTech Connect

    Piecuch, Piotr; Hansen, Jared A.; Ajala, Adeayo O.

    2015-09-15

    When vertical energies are excited for a comprehensive test set of about 150 singlet excited states of 28 medium-sized organic molecules computed using two variants of the completely renormalised (CR) equation-of-motion (EOM) coupled-cluster (CC) method with singles, doubles, and non-iterative triples, abbreviated as δ-CR-EOMCCSD(T), and the analogous two variants of the newer, left-eigenstate δ-CR-EOMCC(2,3) approach are benchmarked against the previously published CASPT2, CC3, and EOMCCSDT-3 results, as well as the suggested theoretical best estimate (TBE) values. The δ-CR-EOMCC approaches are also used to identify and characterise about 50 additional excited states, including several states having substantial two-electron excitation components, which have not been found in the previous work and which can be used in future benchmark studies. We demonstrated that the non-iterative triples corrections to the EOMCCSD excitation energies defining the relatively inexpensive, single-reference, black-box δ-CR-EOMCC approaches provide significant improvements in the EOMCCSD data, while closely matching the results of the iterative and considerably more expensive CC3 and EOMCCSDT-3 calculations and their CASPT2 and TBE counterparts. It is also shown that the δ-CR-EOMCC methods, especially δ-CR-EOMCC(2,3), are capable of bringing the results of the CC3 and EOMCCSDT-3 calculations to a closer agreement with the CASPT2 and TBE data, demonstrating the utility of the cost-effective δ-CR-EOMCC methods in applications involving molecular electronic spectra. Finally, we show that there may exist a relationship between the magnitude of the triples corrections defining δ-CR-EOMCC approaches and the reduced excitation level diagnostic resulting from EOMCCSD.

  13. Benchmarking the completely renormalised equation-of-motion coupled-cluster approaches for vertical excitation energies

    DOE PAGES

    Piecuch, Piotr; Hansen, Jared A.; Ajala, Adeayo O.

    2015-09-15

    When vertical energies are excited for a comprehensive test set of about 150 singlet excited states of 28 medium-sized organic molecules computed using two variants of the completely renormalised (CR) equation-of-motion (EOM) coupled-cluster (CC) method with singles, doubles, and non-iterative triples, abbreviated as δ-CR-EOMCCSD(T), and the analogous two variants of the newer, left-eigenstate δ-CR-EOMCC(2,3) approach are benchmarked against the previously published CASPT2, CC3, and EOMCCSDT-3 results, as well as the suggested theoretical best estimate (TBE) values. The δ-CR-EOMCC approaches are also used to identify and characterise about 50 additional excited states, including several states having substantial two-electron excitation components, whichmore » have not been found in the previous work and which can be used in future benchmark studies. We demonstrated that the non-iterative triples corrections to the EOMCCSD excitation energies defining the relatively inexpensive, single-reference, black-box δ-CR-EOMCC approaches provide significant improvements in the EOMCCSD data, while closely matching the results of the iterative and considerably more expensive CC3 and EOMCCSDT-3 calculations and their CASPT2 and TBE counterparts. It is also shown that the δ-CR-EOMCC methods, especially δ-CR-EOMCC(2,3), are capable of bringing the results of the CC3 and EOMCCSDT-3 calculations to a closer agreement with the CASPT2 and TBE data, demonstrating the utility of the cost-effective δ-CR-EOMCC methods in applications involving molecular electronic spectra. Finally, we show that there may exist a relationship between the magnitude of the triples corrections defining δ-CR-EOMCC approaches and the reduced excitation level diagnostic resulting from EOMCCSD.« less

  14. Energy Dispersive XAFS: Characterization of Electronically Excited States of Copper(I) Complexes

    PubMed Central

    2013-01-01

    Energy dispersive X-ray absorption spectroscopy (ED-XAS), in which the whole XAS spectrum is acquired simultaneously, has been applied to reduce the real-time for acquisition of spectra of photoinduced excited states by using a germanium microstrip detector gated around one X-ray bunch of the ESRF (100 ps). Cu K-edge XAS was used to investigate the MLCT states of [Cu(dmp)2]+ (dmp =2,9-dimethyl-1,10-phenanthroline) and [Cu(dbtmp)2]+ (dbtmp =2,9-di-n-butyl-3,4,7,8-tetramethyl-1,10-phenanthroline) with the excited states created by excitation at 450 nm (10 Hz). The decay of the longer lived complex with bulky ligands, was monitored for up to 100 ns. DFT calculations of the longer lived MLCT excited state of [Cu(dbp)2]+ (dbp =2,9-di-n-butyl-1,10-phenanthroline) with the bulkier diimine ligands, indicated that the excited state behaves as a Jahn–Teller distorted Cu(II) site, with the interligand dihedral angle changing from 83 to 60° as the tetrahedral coordination geometry flattens and a reduction in the Cu–N distance of 0.03 Å. PMID:23718738

  15. Energy level decay and excited state absorption processes in erbium-doped tellurite glass

    NASA Astrophysics Data System (ADS)

    Gomes, Laércio; Oermann, Michael; Ebendorff-Heidepriem, Heike; Ottaway, David; Monro, Tanya; Felipe Henriques Librantz, André; Jackson, Stuart D.

    2011-10-01

    The fundamental excited state decay processes relating to the 4I11/2 → 4I13/2 transition in singly Er3+-doped tellurite (TZNL) glass have been investigated in detail using time-resolved fluorescence spectroscopy. Selective laser excitation of the 4I11/2 energy level at 970 nm and selective laser excitation of the 4I13/2 energy level at 1485 nm has established that energy transfer upconversion by way of a dipole-dipole interaction between two excited erbium ions in the 4I13/2 level populates the 4I11/2 upper laser level of the 3 μm transition. This upconversion has been analyzed for Er2O3 concentrations between 0.5 mol. % and 2.2 mol. %. The 4I13/2 and 4I11/2 energy levels emit luminescence with peaks located at 1532 nm and 2734 nm, respectively, with radiative decay efficiencies of 65% and 6.8% for the higher (2.2 mol. %) concentration sample. The low 2.7 μm emission efficiency is due to the non-radiative decay bridging the 4I11/2 → 4I13/2 transition and energy transfer to the OH- groups in the glass. Excited state absorption was observed to occur from the 4I13/2 and 4I11/2 levels with peak absorptions occurring at 1550 nm and 971 nm, respectively. The decay time of the 4I11/2 excited state decreased with an increase in the Er3+ concentration, which related to energy transfer to OH- ions that had a measured concentration of 6.6 × 1018 cm-3. Results from numerical simulations showed that a population inversion is reached at a threshold pumping intensity of ˜80 kW cm-2 for a cw laser pump at 976 nm if [Er3+] ≥ 1.2 × 1021 cm-3 (or [Er2O3] ≥ 2.65 mol. %) without OH- impurities being present.

  16. Influence of the excited states on the electron-energy distribution function in low-pressure microwave argon plasmas

    SciTech Connect

    Yanguas-Gil, A.; Cotrino, J.; Gonzalez-Elipe, A.R.

    2005-07-01

    In this work the influence of the excited states on the electron-energy distribution function has been determined for an argon microwave discharge at low pressure. A collisional-radiative model of argon has been developed taking into account the most recent experimental and theoretical values of argon-electron-impact excitation cross sections. The model has been solved along with the electron Boltzmann equation in order to study the influence of the inelastic collisions from the argon excited states on the electron-energy distribution function. Results show that under certain conditions the excited states can play an important role in determining the shape of the distribution function and the mean kinetic energy of the electrons, deplecting the high-energy tail due to inelastic processes from the excited states, especially from the 4s excited configuration. It has been found that from the populations of the excited states an excitation temperature can be defined. This excitation temperature, which can be experimentally determined by optical emission spectroscopy, is lower than the electron kinetic temperature obtained from the electron-energy distribution function.

  17. A proposal for fs-electron microscopy experiments on high-energy excitations in solids.

    PubMed

    Piazza, L; Musumeci, P; Luiten, O J; Carbone, Fabrizio

    2014-08-01

    Recent advances in ultrafast technology enable both the study and the control of materials properties thanks to the ability to record high temporal resolution movies of their transformations, or the ability to generate new states of matter by selecting ad hoc an excitation to drive the system out of equilibrium. The holy grail of this type of experiments is to combine a high tuneability of the excitation with a wide observation window. For example, this is achieved in multidimensional optical spectroscopy where the response to several excitation energies is monitored in a broad energy range by a large bandwidth optical pulse. In this article, the possibility to combine the chemical sensitivity of intense tuneable X-rays pulses from a free electron laser, with the wide range of observables available in an ultrafast transmission electron microscope is discussed. The requirements for such experiments are quantified via estimates based on state of the art experiments and simulations, and it is proposed that ultrafast electron imaging, diffraction and spectroscopy experiments can be performed in combination with a chemically selective X-ray excitation of materials. PMID:24631423

  18. Excitation energy transfer between Light-harvesting complex II and Photosystem I in reconstituted membranes.

    PubMed

    Akhtar, Parveen; Lingvay, Mónika; Kiss, Teréz; Deák, Róbert; Bóta, Attila; Ughy, Bettina; Garab, Győző; Lambrev, Petar H

    2016-04-01

    Light-harvesting complex II (LHCII), the major peripheral antenna of Photosystem II in plants, participates in several concerted mechanisms for regulation of the excitation energy and electron fluxes in thylakoid membranes. In part, these include interaction of LHCII with Photosystem I (PSI) enhancing the latter's absorption cross-section - for example in the well-known state 1 - state 2 transitions or as a long-term acclimation to high light. In this work we examined the capability of LHCII to deliver excitations to PSI in reconstituted membranes in vitro. Proteoliposomes with native plant thylakoid membrane lipids and different stoichiometric ratios of LHCII:PSI were reconstituted and studied by steady-state and time-resolved fluorescence spectroscopy. Fluorescence emission from LHCII was strongly decreased in PSI-LHCII membranes due to trapping of excitations by PSI. Kinetic modelling of the time-resolved fluorescence data revealed the existence of separate pools of LHCII distinguished by the time scale of energy transfer. A strongly coupled pool, equivalent to one LHCII trimer per PSI, transferred excitations to PSI with near-unity efficiency on a time scale of less than 10ps but extra LHCIIs also contributed significantly to the effective antenna size of PSI, which could be increased by up to 47% in membranes containing 3 LHCII trimers per PSI. The results demonstrate a remarkable competence of LHCII to increase the absorption cross-section of PSI, given the opportunity that the two types of complexes interact in the membrane.

  19. Energy conversion based on molecular excited states: Redox splitting in soluble polymers. Final report

    SciTech Connect

    Meyer, T.J.

    1995-12-31

    A general method was developed for preparing complexes of Ru(II) with three different bidentate ligands; it is being extended to monodentate ligands for more synthetic versatility. This method was used to prepare a series of complexes with pre-designed absorption properties, with the goal of ``black absorbers`` for use as antenna chromophores in a light-to-chemical energy conversion array. The energy gap law for nonradiative decay was studied for preparing near-IR luminophores with long excited state lifetimes. The problem of destructive dd excited states in Ru(II) polypyridyl complexes was focused on, with success in preparing an extremely photo-inert complex with monodentate pyridine ligands. Time-resolved resonance Raman and infrared spectroscopy were used to study subtle excited state properties of complexes of Ru(II), Os(II), and Re(I). Success was achieved in controlled immobilization of d{sup 6} chromophores and quenchers on styrenic polymers. Having perfected our synthetic technique, we have begun to optimize the ground and excited state properties such as chromophore density, dipole orientation, and lifetime.

  20. Coherent transport and energy flow patterns in photosynthesis under incoherent excitation.

    PubMed

    Pelzer, Kenley M; Can, Tankut; Gray, Stephen K; Morr, Dirk K; Engel, Gregory S

    2014-03-13

    Long-lived coherences have been observed in photosynthetic complexes after laser excitation, inspiring new theories regarding the extreme quantum efficiency of photosynthetic energy transfer. Whether coherent (ballistic) transport occurs in nature and whether it improves photosynthetic efficiency remain topics of debate. Here, we use a nonequilibrium Green's function analysis to model exciton transport after excitation from an incoherent source (as opposed to coherent laser excitation). We find that even with an incoherent source, the rate of environmental dephasing strongly affects exciton transport efficiency, suggesting that the relationship between dephasing and efficiency is not an artifact of coherent excitation. The Green's function analysis provides a clear view of both the pattern of excitonic fluxes among chromophores and the multidirectionality of energy transfer that is a feature of coherent transport. We see that even in the presence of an incoherent source, transport occurs by qualitatively different mechanisms as dephasing increases. Our approach can be generalized to complex synthetic systems and may provide a new tool for optimizing synthetic light harvesting materials.

  1. Impulse excitation of piezoelectric bimorphs for energy harvesting: a dimensionless model

    NASA Astrophysics Data System (ADS)

    Pozzi, Michele

    2014-04-01

    Energy harvesting (EH) is a multidisciplinary research area, involving physics, materials science and engineering, with the objective of providing renewable sources of power sufficient to operate targeted low-power applications. Piezoelectric transducers are often used for inertial vibrational as well as direct excitation EH. However, due to the stiffness of the most common material (PZT), compact and light-weight harvesters have high resonant frequencies, making them inefficient at extracting low-frequency power from the environment. The technique of frequency up-conversion, in the form of either plucking or impulse excitation, aims to bridge this frequency gap. In this paper, the technique is modelled analytically with focus on impulse excitation via impact or shock. An analytical model is developed in a standard way starting from the Euler-Bernoulli beam equations adapted to a piezoelectric bimorph. A set of dimensionless variables and parameters is defined and a system of differential equations derived. Here the system is solved numerically for a wide range of the two group parameters present, covering piezoelectric coupling strength between PVDF and PMN-PT. One major result is that the strength of the coupling strongly affects the timescale of the process, but has only a minor effect on the total energy converted. The model can be readily adapted to different excitation profiles.

  2. Excitation Mechanisms in Moderate-Energy Na+-He and K+-He Collisions

    NASA Astrophysics Data System (ADS)

    Kita, Shigetomo; Hattori, Takehito; Shimakura, Noriyuki

    2015-01-01

    Excitation mechanisms in Na+-He and K+-He collisions were studied at laboratory collision energies of 1000 ≤ Elab ≤ 1500 eV by differential scattering spectroscopy. Extensive measurements were performed at Elab = 1500 eV. Double differential cross sections σ(Θ)k were measured over a wide range of center-of-mass scattering angles, 7.3 ≤ Θ ≤ 173°, by detecting all the scattered particles (Na+, Na, K+, K, He+, and He), where the subscript k denotes the number of exit channels in the reactions. At the collision energy of Elab = 1500 eV, one- and two-electron excitations were observed appreciably for the Na+-He collisions, while only one-electron excitations were observed in the K+-He collisions. The analyses of the experimental results for these collision systems indicate that the electronic transitions in the Na+-He and K+-He collisions take place at the internuclear distances of R < RC = 0.63 × 10-10 m [potential height V(R) > 49 eV] and R < RC = 0.80 × 10-10 m [V(R) > 36 eV], respectively. For these asymmetric systems, at Elab= 1500 eV, the electronic transition probabilities around the threshold angles are so small that the integral excitation cross sections have small values of Sex < 1.2 × 10-21 m2.

  3. Excitation energy transfer between erythrosin B and malachite green adsorbed on a microheterogeneous polymer latex

    NASA Astrophysics Data System (ADS)

    Dutta, A. K.

    1995-07-01

    In this article electronic excitation energy transfer between the aggregates of the donor erythrosin B (EB) and the acceptor malachite green (MG) has been studied in polystyrenebutylmethacrylate latex. Steady state flourescence quenching studies reveal that with the increasing latex concentration the rate of quenching decreases initially, attains a minimum and then increases again. Such a behaviour has been attributed to aggregation of the dye molecules at low latex concentration and redistribution at larger latex concentrations. These results illustrate the role of the microenvironment in modifying the energy transfer reaction rates and provides a model system for understanding energy transfer mechanisms in context to photosynthesis in real living systems.

  4. Quantum electrodynamical theory of high-efficiency excitation energy transfer in laser-driven nanostructure systems

    NASA Astrophysics Data System (ADS)

    Weeraddana, Dilusha; Premaratne, Malin; Gunapala, Sarath D.; Andrews, David L.

    2016-08-01

    A fundamental theory is developed for describing laser-driven resonance energy transfer (RET) in dimensionally constrained nanostructures within the framework of quantum electrodynamics. The process of RET communicates electronic excitation between suitably disposed emitter and detector particles in close proximity, activated by the initial excitation of the emitter. Here, we demonstrate that the transfer rate can be significantly increased by propagation of an auxiliary laser beam through a pair of nanostructure particles. This is due to the higher order perturbative contribution to the Förster-type RET, in which laser field is applied to stimulate the energy transfer process. We construct a detailed picture of how excitation energy transfer is affected by an off-resonant radiation field, which includes the derivation of second and fourth order quantum amplitudes. The analysis delivers detailed results for the dependence of the transfer rates on orientational, distance, and laser intensity factor, providing a comprehensive fundamental understanding of laser-driven RET in nanostructures. The results of the derivations demonstrate that the geometry of the system exercises considerable control over the laser-assisted RET mechanism. Thus, under favorable conformational conditions and relative spacing of donor-acceptor nanostructures, the effect of the auxiliary laser beam is shown to produce up to 70% enhancement in the energy migration rate. This degree of control allows optical switching applications to be identified.

  5. Spectra, Emission Yields, Cross Sections, and Kinetic Energy Distributions of Hydrogen Atoms from H2 X 1Eg+-d 3IIu Excitation by Electron Impact

    NASA Astrophysics Data System (ADS)

    Liu, Xianming; Shemansky, Donald E.; Yoshii, Jean; Johnson, Paul V.; Malone, Charles P.; Ajello, Joseph M.

    2016-02-01

    Electron-impact excitation of H2 triplet states plays an important role in the heating of outer planet upper thermospheres. The {d}3{{{\\Pi }}}u state is the third ungerade triplet state, and the {d}3{{{\\Pi }}}u-a{}3{{{Σ }}}g+ emission is the largest cascade channel for the a{}3{{{Σ }}}g+ state. Accurate energies of the d{}3{{{\\Pi }}}u-(v, J) levels are calculated from an ab initio potential energy curve. Radiative lifetimes of the {d}3{{{\\Pi }}}u(v, J) levels are obtained by an accurate evaluation of the {d}3{{{\\Pi }}}u-a{}3{{{Σ }}}g+ transition probabilities. The emission yields are determined from experimental lifetimes and calculated radiative lifetimes and are further verified by comparing experimental and synthetic {d}3{{{\\Pi }}}u-a{}3{{{Σ }}}g+ spectra at 20 eV impact energy. Spectral analysis revealed that multipolar components beyond the dipolar term are required to model the {X}1{{{Σ }}}g+-{d}3{{{\\Pi }}}u excitation, and significant cascade excitation occurs at the {d}3{{{\\Pi }}}u(v = 0,1) levels. Kinetic energy (Ek) distributions of H atoms produced via predissociation of the {d}3{{{\\Pi }}}u state and the {d}3{{{\\Pi }}}u-a{}3{{{Σ }}}g+-b{}3{{{Σ }}}u+ cascade dissociative emission are obtained. Predissociation of the {d}3{{{\\Pi }}}u state produces H atoms with an average Ek of 2.3 ± 0.4 eV/atom, while the Ek distribution of the {d}3{{{\\Pi }}}u-a{}3{{{Σ }}}g+-b{}3{{{Σ }}}u+ channel is similar to that of the {X}1{{{Σ }}}g+-a{}3{{{Σ }}}g+-b{}3{{{Σ }}}u+ channel and produces H(1s) atoms with an average Ek of 1.15 ± 0.05 eV/atom. On average, each H2 excited to the {d}3{{{\\Pi }}}u state in an H2-dominated atmosphere deposits 3.3 ± 0.4 eV into the atmosphere, while each H2 directly excited to the a{}3{{{Σ }}}g+ state gives 2.2-2.3 eV to the atmosphere. The spectral distribution of the calculated a{}3{{{Σ }}}g+ -b{}3{{{Σ }}}u+ continuum emission due to the {X}1{{{Σ }}}g+-{d}3{{{\\Pi }}}u excitation is significantly different from

  6. Properties of triplet-excited [N]cycloparaphenylenes (N = 8-12): excitation energies lower than those of linear oligomers and polymers.

    PubMed

    Fujitsuka, Mamoru; Lu, Chao; Iwamoto, Takahiro; Kayahara, Eiichi; Yamago, Shigeru; Majima, Tetsuro

    2014-06-26

    Cycloparaphenylenes (CPPs), a class of hoop-shaped conjugated macrocycles, have attracted the attention of researchers in various fields because of their interesting properties. Although their properties in the singlet-excited state have been reported, there is no systematic information on the triplet-excited state. In the present study, the properties of triplet-excited [n]CPP (n = 8-12, where n denotes the number of phenyl rings) were comprehensively investigated. The phosphorescence peak shifted to the shorter-wavelength side with increasing ring size of the CPPs, indicating smaller triplet energy for smaller CPPs. It was found that the triplet energy of a smaller CPP is even smaller than those of poly(p-phenylene)s, indicating that small hoop-shaped conjugated macrocycles are effective in realizing low-band gap materials. By applying laser flash photolysis, the Tn-T1 absorption spectra of CPPs were obtained, from which the size-dependence of energy levels of higher triplet states were also determined. Generation of singlet oxygen by the energy transfer from a triplet-excited CPP was confirmed. The generation yield became smaller with increasing size of the CPP in accordance with the triplet yield. From these observations, the size-dependence of the deactivation pathways is explained. PMID:24914824

  7. A model for energy transfer in collisions of atoms with highly excited molecules.

    PubMed

    Houston, Paul L; Conte, Riccardo; Bowman, Joel M

    2015-05-21

    A model for energy transfer in the collision between an atom and a highly excited target molecule has been developed on the basis of classical mechanics and turning point analysis. The predictions of the model have been tested against the results of trajectory calculations for collisions of five different target molecules with argon or helium under a variety of temperatures, collision energies, and initial rotational levels. The model predicts selected moments of the joint probability distribution, P(Jf,ΔE) with an R(2) ≈ 0.90. The calculation is efficient, in most cases taking less than one CPU-hour. The model provides several insights into the energy transfer process. The joint probability distribution is strongly dependent on rotational energy transfer and conservation laws and less dependent on vibrational energy transfer. There are two mechanisms for rotational excitation, one due to motion normal to the intermolecular potential and one due to motion tangential to it and perpendicular to the line of centers. Energy transfer is found to depend strongly on the intermolecular potential and only weakly on the intramolecular potential. Highly efficient collisions are a natural consequence of the energy transfer and arise due to collisions at "sweet spots" in the space of impact parameter and molecular orientation. PMID:25907301

  8. Energy shift of collective electron excitations in highly corrugated graphitic nanostructures: Experimental and theoretical investigation

    SciTech Connect

    Sedelnikova, O. V. Bulusheva, L. G.; Okotrub, A. V.; Asanov, I. P.; Yushina, I. V.

    2014-04-21

    Effect of corrugation of hexagonal carbon network on the collective electron excitations has been studied using optical absorption and X-ray photoelectron spectroscopy in conjunction with density functional theory calculations. Onion-like carbon (OLC) was taken as a material, where graphitic mantle enveloping agglomerates of multi-shell fullerenes is strongly curved. Experiments showed that positions of π and π + σ plasmon modes as well as π → π* absorption peak are substantially redshifted for OLC as compared with those of highly ordered pyrolytic graphite and thermally exfoliated graphite consisted of planar sheets. This effect was reproduced in behavior of dielectric functions of rippled graphite models calculated within the random phase approximation. We conclude that the energy of electron excitations in graphitic materials could be precisely tuned by a simple bending of hexagonal network without change of topology. Moreover, our investigation suggests that in such materials optical exciton can transfer energy to plasmon non-radiatively.

  9. Low-energy singlet excitations in spin-1/2 Heisenberg antiferromagnet on square lattice

    NASA Astrophysics Data System (ADS)

    Aktersky, A. Yu.; Syromyatnikov, A. V.

    2016-05-01

    We present an approach based on a dimer expansion which describes low-energy singlet excitations (singlons) in spin-1/2 Heisenberg antiferromagnet on simple square lattice. An operator ("effective Hamiltonian") is constructed whose eigenvalues give the singlon spectrum. The "effective Hamiltonian" looks like a Hamiltonian of a spin-1/2 magnet in strong external magnetic field and it has a gapped spectrum. It is found that singlet states lie above triplet ones (magnons) in the whole Brillouin zone except in the vicinity of the point (π , 0), where their energies are slightly smaller. Based on this finding, we suggest that a magnon decay is possible near (π , 0) into another magnon and a singlon which may contribute to the dip of the magnon spectrum near (π , 0) and reduce the magnon lifetime. It is pointed out that the singlon-magnon continuum may contribute to the continuum of excitations observed recently near (π , 0).

  10. Unusual characteristics of electromagnetic waves excited by cometary newborn ions with large perpendicular energies

    NASA Technical Reports Server (NTRS)

    Brinca, A. L.; Tsurutani, B. T.

    1987-01-01

    The characteristics of electromagnetic waves excited by cometary newborn ions with large perpendicular energies are examined using a model of solar wind permeated by dilute drifting ring distributions of electrons and oxygen ions with finite thermal spreads. The model has parameters compatible with the ICE observations at the Giacobini-Zinner comet. It is shown that cometary newborn ions with large perpendicular energies can excite a wave mode with rest frame frequencies in the order of the heavy ion cyclotron frequency, Omega(i), and unusual propagation characteristics at small obliquity angles. For parallel propagation, the mode is left-hand circularly polarized, might be unstable in a frequency range containing Omega(i), and moves in the direction of the newborn ion drift along the static magnetic field.

  11. Current status of free radicals and electronically excited metastable species as high energy propellants

    NASA Technical Reports Server (NTRS)

    Rosen, G.

    1973-01-01

    A survey is presented of free radicals and electronically excited metastable species as high energy propellants for rocket engines. Nascent or atomic forms of diatomic gases are considered free radicals as well as the highly reactive diatomic triatomic molecules that posess unpaired electrons. Manufacturing and storage problems are described, and a review of current experimental work related to the manufacture of atomic hydrogen propellants is presented.

  12. Frontiers in propulsion research: Laser, matter-antimatter, excited helium, energy exchange thermonuclear fusion

    NASA Technical Reports Server (NTRS)

    Papailiou, D. D. (Editor)

    1975-01-01

    Concepts are described that presently appear to have the potential for propulsion applications in the post-1990 era of space technology. The studies are still in progress, and only the current status of investigation is presented. The topics for possible propulsion application are lasers, nuclear fusion, matter-antimatter annihilation, electronically excited helium, energy exchange through the interaction of various fields, laser propagation, and thermonuclear fusion technology.

  13. Population of bound excited states in intermediate-energy fragmentation reactions

    SciTech Connect

    Obertelli, A.; Gade, A.; Bazin, D.; Hansen, P.G.; Hoagland, T.; Lecouey, J.-L.; Mueller, W.F.; Yoneda, K.; Campbell, C.M.; Cook, J.M.; Davies, A.D.; Dinca, D.-C.; Glasmacher, T.; Terry, J.R.; Zwahlen, H.; Cottle, P.D.; Kemper, K.W.; Reynolds, R.R.; Roeder, B.T.; Tostevin, J.A.

    2006-04-15

    Fragmentation reactions with intermediate-energy heavy-ion beams exhibit a wide range of reaction mechanisms, ranging from direct reactions to statistical processes. We examine this transition by measuring the relative population of excited states in several sd-shell nuclei produced by fragmentation with the number of removed nucleons ranging from two to sixteen. The two-nucleon removal is consistent with a non-dissipative process, whereas the removal of more than five nucleons appears to be mainly statistical.

  14. Energy spectrum of the low-lying gluon excitations in the Coulomb gauge

    SciTech Connect

    Szczepaniak, Adam P.; Krupinski, Pawel

    2006-06-01

    We compute the energy spectrum of low-lying gluonic excitations in the presence of static quark-antiquark sources using Coulomb gauge and the quasiparticle representation. Within the valence sector of the Fock space we reproduce both, the overall normalization and the ordering of the spin-parity multiplets. We discus how the interactions induced by the nonabelian Coulomb kernel are central in to fine structure of the spectrum.

  15. Transient energy excitation in shortcuts to adiabaticity for the time-dependent harmonic oscillator

    SciTech Connect

    Chen Xi; Muga, J. G.

    2010-11-15

    We study for the time-dependent harmonic oscillator the transient energy excitation in speed-up processes ('shortcuts to adiabaticity') designed to reproduce the initial populations at some predetermined final frequency and time. We provide lower bounds and examples. Implications for the limits imposed to the process times and for the principle of unattainability of the absolute zero, in a single expansion or in quantum refrigerator cycles, are drawn.

  16. Low-energy Coulomb excitation of neutron-rich zinc isotopes

    NASA Astrophysics Data System (ADS)

    van de Walle, J.; Aksouh, F.; Behrens, T.; Bildstein, V.; Blazhev, A.; Cederkäll, J.; Clément, E.; Cocolios, T. E.; Davinson, T.; Delahaye, P.; Eberth, J.; Ekström, A.; Fedorov, D. V.; Fedosseev, V. N.; Fraile, L. M.; Franchoo, S.; Gernhauser, R.; Georgiev, G.; Habs, D.; Heyde, K.; Huber, G.; Huyse, M.; Ibrahim, F.; Ivanov, O.; Iwanicki, J.; Jolie, J.; Kester, O.; Köster, U.; Kröll, T.; Krücken, R.; Lauer, M.; Lisetskiy, A. F.; Lutter, R.; Marsh, B. A.; Mayet, P.; Niedermaier, O.; Pantea, M.; Raabe, R.; Reiter, P.; Sawicka, M.; Scheit, H.; Schrieder, G.; Schwalm, D.; Seliverstov, M. D.; Sieber, T.; Sletten, G.; Smirnova, N.; Stanoiu, M.; Stefanescu, I.; Thomas, J.-C.; Valiente-Dobón, J. J.; Duppen, P. Van; Verney, D.; Voulot, D.; Warr, N.; Weisshaar, D.; Wenander, F.; Wolf, B. H.; Zielińska, M.

    2009-01-01

    At the radioactive ion beam facility REX-ISOLDE, neutron-rich zinc isotopes were investigated using low-energy Coulomb excitation. These experiments have resulted in B(E2,21+→01+) values in Zn74-80, B(E2,41+→21+) values in Zn74,76 and the determination of the energy of the first excited 21+ states in Zn78,80. The zinc isotopes were produced by high-energy proton- (A=74,76,80) and neutron- (A=78) induced fission of U238, combined with selective laser ionization and mass separation. The isobaric beam was postaccelerated by the REX linear accelerator and Coulomb excitation was induced on a thin secondary target, which was surrounded by the MINIBALL germanium detector array. In this work, it is shown how the selective laser ionization can be used to deal with the considerable isobaric beam contamination and how a reliable normalization of the experiment can be achieved. The results for zinc isotopes and the N=50 isotones are compared to collective model predictions and state-of-the-art large-scale shell-model calculations, including a recent empirical residual interaction constructed to describe the present experimental data up to 2004 in this region of the nuclear chart.

  17. Supporting middle school students' development of an accurate and applicable energy concept

    NASA Astrophysics Data System (ADS)

    Nordine, Jeffrey Carl

    Energy is a fundamental unifying concept of science, yet common approaches to energy instruction in middle school have shown little success with helping students develop their naive ideas about energy into more sophisticated understandings that are useful for making sense of their experiences. While traditional approaches to energy focus on performing calculations in idealized systems, our development team produced a new middle school energy unit that focuses qualitatively on the energy transformations that occur in everyday, non-idealized, systems. This approach uses project-based pedagogy to contextualize instruction with the driving question, "How can I use trash to power my stereo?" In this study, I investigate the effectiveness of our approach by tracking 8th grade students' conceptual development during the unit, following up with students who participated in the unit a year previously, and comparing the energy conceptions and content knowledge between energy unit participants and older students in the same school who learned about energy in an approach that did not emphasize energy transformations in non-idealized systems. Results indicate that during instruction, students' energy conceptions progress from a set of disconnected ideas toward a coherent understanding that is organized around the principle of transformation. After instruction, students who participated in the energy unit were generally more capable of using their understanding of energy to make sense of everyday scenarios than were older non-participants. Furthermore, 9th grade students who participated in the energy unit in their 8th grade year continued to develop more sophisticated understandings of energy during their 9th grade biology course. These 9th grade students seemed better prepared to learn about energy content in their biology course than 10th graders, who did not participate in the energy unit, but took the same biology course during their 9th grade year. Overall, my results

  18. Targeted energy transfers and passive acoustic wave redirection in a two-dimensional granular network under periodic excitation

    SciTech Connect

    Zhang, Yijing Moore, Keegan J.; Vakakis, Alexander F.; McFarland, D. Michael

    2015-12-21

    We study passive pulse redirection and nonlinear targeted energy transfer in a granular network composed of two semi-infinite, ordered homogeneous granular chains mounted on linear elastic foundations and coupled by weak linear stiffnesses. Periodic excitation in the form of repetitive half-sine pulses is applied to one of the chains, designated as the “excited chain,” whereas the other chain is initially at rest and is regarded as the “absorbing chain.” We show that passive pulse redirection and targeted energy transfer from the excited to the absorbing chain can be achieved by macro-scale realization of the spatial analog of the Landau-Zener quantum tunneling effect. This is realized by finite stratification of the elastic foundation of the excited chain and depends on the system parameters (e.g., the percentage of stratification) and on the parameters of the periodic excitation. Utilizing empirical mode decomposition and numerical Hilbert transforms, we detect the existence of two distinct nonlinear phenomena in the periodically forced network; namely, (i) energy localization in the absorbing chain due to sustained 1:1 resonance capture leading to irreversible pulse redirection from the excited chain, and (ii) continuous energy exchanges in the form of nonlinear beats between the two chains in the absence of resonance capture. Our results extend previous findings of transient passive energy redirection in impulsively excited granular networks and demonstrate that steady state passive pulse redirection in these networks can be robustly achieved under periodic excitation.

  19. Potential Energy Curves for Excited States of the Hydrogen-Antihydrogen System

    SciTech Connect

    Sharipov, V.; Labzowsky, L.; Plunien, G.

    2006-09-08

    The potential energy curves for the hydrogen-antihydrogen (HH) system in states with a leptonic orbital angular momentum projection {lambda}=0, 1, 2, 6, and 30 are presented. Within the framework of the adiabatic picture, explicitly correlated Gaussians are used as basis functions which describe accurately the hydrogen-antihydrogen interaction. The critical internuclear distances where the system transforms into positronium and protonium atoms are found. Adiabatic corrections to the potential energy curves are also estimated.

  20. Potential energy curves for excited states of the hydrogen-antihydrogen system.

    PubMed

    Sharipov, V; Labzowsky, L; Plunien, G

    2006-09-01

    The potential energy curves for the hydrogen-antihydrogen (HH) system in states with a leptonic orbital angular momentum projection Lambda=0, 1, 2, 6, and 30 are presented. Within the framework of the adiabatic picture, explicitly correlated Gaussians are used as basis functions which describe accurately the hydrogen-antihydrogen interaction. The critical internuclear distances where the system transforms into positronium and protonium atoms are found. Adiabatic corrections to the potential energy curves are also estimated.

  1. Combining energy and Laplacian regularization to accurately retrieve the depth of brain activity of diffuse optical tomographic data

    NASA Astrophysics Data System (ADS)

    Chiarelli, Antonio M.; Maclin, Edward L.; Low, Kathy A.; Mathewson, Kyle E.; Fabiani, Monica; Gratton, Gabriele

    2016-03-01

    Diffuse optical tomography (DOT) provides data about brain function using surface recordings. Despite recent advancements, an unbiased method for estimating the depth of absorption changes and for providing an accurate three-dimensional (3-D) reconstruction remains elusive. DOT involves solving an ill-posed inverse problem, requiring additional criteria for finding unique solutions. The most commonly used criterion is energy minimization (energy constraint). However, as measurements are taken from only one side of the medium (the scalp) and sensitivity is greater at shallow depths, the energy constraint leads to solutions that tend to be small and superficial. To correct for this bias, we combine the energy constraint with another criterion, minimization of spatial derivatives (Laplacian constraint, also used in low resolution electromagnetic tomography, LORETA). Used in isolation, the Laplacian constraint leads to solutions that tend to be large and deep. Using simulated, phantom, and actual brain activation data, we show that combining these two criteria results in accurate (error <2 mm) absorption depth estimates, while maintaining a two-point spatial resolution of <24 mm up to a depth of 30 mm. This indicates that accurate 3-D reconstruction of brain activity up to 30 mm from the scalp can be obtained with DOT.

  2. Exact kinetic energy enables accurate evaluation of weak interactions by the FDE-vdW method

    SciTech Connect

    Sinha, Debalina; Pavanello, Michele

    2015-08-28

    The correlation energy of interaction is an elusive and sought-after interaction between molecular systems. By partitioning the response function of the system into subsystem contributions, the Frozen Density Embedding (FDE)-vdW method provides a computationally amenable nonlocal correlation functional based on the adiabatic connection fluctuation dissipation theorem applied to subsystem density functional theory. In reproducing potential energy surfaces of weakly interacting dimers, we show that FDE-vdW, either employing semilocal or exact nonadditive kinetic energy functionals, is in quantitative agreement with high-accuracy coupled cluster calculations (overall mean unsigned error of 0.5 kcal/mol). When employing the exact kinetic energy (which we term the Kohn-Sham (KS)-vdW method), the binding energies are generally closer to the benchmark, and the energy surfaces are also smoother.

  3. Fluorescence depolarization in the presence of excitation energy migration in partly ordered polymer films

    NASA Astrophysics Data System (ADS)

    Synak, A.; Gondek, G.; Bojarski, P.; Kułak, L.; Kubicki, A.; Szabelski, M.; Kwiek, P.

    2004-11-01

    Excitation energy migration is studied for 3,3'-diethylthiacyanine iodide in uniaxially stretched and unstretched poly(vinyl alcohol) films. Time-resolved and steady-state measurements of fluorescence depolarization yield quite different results for disordered and partly ordered systems. Contrary to disordered systems, for which strong concentration depolarization was observed, partly ordered systems exhibit much weaker depolarization as a result of preferential angular distribution of transition dipole moments of identical fluorophores participating in energy migration. Difference of the same origin was found for time-resolved emission anisotropy measurements. These results are in agreement with those obtained from the Monte-Carlo simulation.

  4. The role of the partner atom and resonant excitation energy in ICD in rare gas dimers

    NASA Astrophysics Data System (ADS)

    O'Keeffe, Patrick; Ripani, Enrico; Bolognesi, Paola; Coreno, Marcello; Avaldi, Lorenzo; Devetta, Michele; Callegari, Carlo; Di Praia, Michele; Prince, Kevin; Richter, Robert; Alagial, Michele; Kivimäkil, Antti

    2014-04-01

    We show experimental evidence for Interatomic Coulombic Decay (ICD) in mixed rare gas dimers following resonant Auger decay. A velocity map imaging apparatus together with a cooled supersonic beam containing Ar2, ArNe and ArKr dimers was used to record electron VMI images in coincidence with two mass selected ions following excitation on five resonances converging to the Ar+ 2p-11/2 and 2p-13/2 thresholds using the synchrotron radiation. The results show that the kinetic energy distribution of the ICD electrons observed in coincidence with the ions from Coulomb explosion of the dimers depends on the partner ion and resonant photon energy.

  5. Low-energy excitations in α- and γ-Ce observed by photoemission

    NASA Astrophysics Data System (ADS)

    Patthey, F.; Delley, B.; Schneider, W.-D.; Baer, Y.

    1985-09-01

    uv-photoemission spectra of the α- and γ-phases of Ce have been measured with an unprecedented resolution (20 meV). A detailed many-body calculation based on the Anderson impurity model and including the 4f1 spin-orbit splitting has been performed. It accounts perfectly for the fine structures observed in the spectra. Within the energy range corresponding to the ground-state lowering by the f-d hybridization, the f contribution to the spectra reveals the density of low-energy excitations culminating at EF.

  6. Excitation energies of double isobar-analog states in heavy nuclei

    SciTech Connect

    Poplavskii, I. V.

    1988-12-01

    Several new relationships are established for isomultiplets on the basis of a theory in which the Coulomb coupling constant (CCC) is allowed to be complex. In particular, the following rule is formulated: the energies for fission or decay of members of an isomultiplet into a charged cluster and members of the corresponding daughter isomultiplet are equidistant. This relationship is well satisfied for isomultiplets with /ital A/less than or equal to60. By extrapolating the rule for fission and decay energies to the region of heavy nuclei, the excitation energies /ital E//sub /ital x// of double isobar-analog states (DIASs) are found for the nuclei /sup 197,199/Hg, /sup 205/Pb, /sup 205 - -209/Po, /sup 209/At, and /sup 238/Pu. A comparison of the computed energies /ital E//sub /ital x// with the experimentally measured values for /sup 208/Po attest to the reliability and good accuracy of the method proposed here when used to determine the excitation energies of DIASs in heavy nuclei.

  7. Construction of a molecular beacon based on two-photon excited fluorescence resonance energy transfer with quantum dot as donor.

    PubMed

    Liu, Lingzhi; Li, Hui; Qiu, Ting; Zhou, Guohua; Wong, Kwok-Yin; He, Zhike; Liu, Zhihong

    2011-03-01

    A new molecular beacon (MB) driven by two-photon excitation (TPE) using quantum dots as energy donor is constructed, which provides reduced direct excitation of acceptor and is free of interferences from autofluorescence or scattering light in a complicated biological matrix.

  8. Linear energy relationships in ground state proton transfer and excited state proton-coupled electron transfer.

    PubMed

    Gamiz-Hernandez, Ana P; Magomedov, Artiom; Hummer, Gerhard; Kaila, Ville R I

    2015-02-12

    Proton-coupled electron transfer (PCET) processes are elementary chemical reactions involved in a broad range of radical and redox reactions. Elucidating fundamental PCET reaction mechanisms are thus of central importance for chemical and biochemical research. Here we use quantum chemical density functional theory (DFT), time-dependent density functional theory (TDDFT), and the algebraic diagrammatic-construction through second-order (ADC(2)) to study the mechanism, thermodynamic driving force effects, and reaction barriers of both ground state proton transfer (pT) and photoinduced proton-coupled electron transfer (PCET) between nitrosylated phenyl-phenol compounds and hydrogen-bonded t-butylamine as an external base. We show that the obtained reaction barriers for the ground state pT reactions depend linearly on the thermodynamic driving force, with a Brønsted slope of 1 or 0. Photoexcitation leads to a PCET reaction, for which we find that the excited state reaction barrier depends on the thermodynamic driving force with a Brønsted slope of 1/2. To support the mechanistic picture arising from the static potential energy surfaces, we perform additional molecular dynamics simulations on the excited state energy surface, in which we observe a spontaneous PCET between the donor and the acceptor groups. Our findings suggest that a Brønsted analysis may distinguish the ground state pT and excited state PCET processes.

  9. [Influence of the Experiment Energy Dispersive X-Ray Fluorescence Measurement of Uranium by Different Excitation Source].

    PubMed

    Xiong, Chao; Ge, Liang-quan; Liu, Duan; Zhang, Qing-xian; Gu, Yi; Luo, Yao-yao; Zhao, Jian-kun

    2016-03-01

    Aiming at the self-excitation effect on the interference of measurements which exist in the process of Energy dispersive X-ray fluorescence method for uranium measurement. To solve the problem of radioactive isotopes only used as excitation source in determination of uranium. Utilizing the micro X-ray tube to test Self-excitation effect to get a comparison of the results obtained by three different uranium ore samples--109 Cd, 241 Am and Mirco X-ray tube. The results showed that self-excitation effect produced the area measure of characteristic X-ray peak is less than 1% of active condition, also the interference of measurements can be negligible. Photoelectric effect cross-section excited by 109 Cd is higher, corresponding fluorescence yield is higher than excited by 241 Am as well due to characteristics X-ray energy of 109 Cd, 22.11 & 24.95 KeV adjacent to absorption edge energy of L(α), 21.75 KeV, based on the above, excitation efficiency by 109 Cd is higher than 241 Am; The fact that measurement error excited by 241 Am is significantly greater than by 109 Cd is mainly due to peak region overlap between L energy peaks of uranium and Scattering peak of 241 Am, 26.35 keV, These factors above caused the background of measured Spectrum higher; The error between the uranium content in ore samples which the X-ray tube as the excitation source and the chemical analysis results is within 10%. Conclusion: This paper come to the conclusion that the technical quality of uranium measurement used X-ray tube as excitation source is superior to that in radioactive source excitation mode. PMID:27400534

  10. [Influence of the Experiment Energy Dispersive X-Ray Fluorescence Measurement of Uranium by Different Excitation Source].

    PubMed

    Xiong, Chao; Ge, Liang-quan; Liu, Duan; Zhang, Qing-xian; Gu, Yi; Luo, Yao-yao; Zhao, Jian-kun

    2016-03-01

    Aiming at the self-excitation effect on the interference of measurements which exist in the process of Energy dispersive X-ray fluorescence method for uranium measurement. To solve the problem of radioactive isotopes only used as excitation source in determination of uranium. Utilizing the micro X-ray tube to test Self-excitation effect to get a comparison of the results obtained by three different uranium ore samples--109 Cd, 241 Am and Mirco X-ray tube. The results showed that self-excitation effect produced the area measure of characteristic X-ray peak is less than 1% of active condition, also the interference of measurements can be negligible. Photoelectric effect cross-section excited by 109 Cd is higher, corresponding fluorescence yield is higher than excited by 241 Am as well due to characteristics X-ray energy of 109 Cd, 22.11 & 24.95 KeV adjacent to absorption edge energy of L(α), 21.75 KeV, based on the above, excitation efficiency by 109 Cd is higher than 241 Am; The fact that measurement error excited by 241 Am is significantly greater than by 109 Cd is mainly due to peak region overlap between L energy peaks of uranium and Scattering peak of 241 Am, 26.35 keV, These factors above caused the background of measured Spectrum higher; The error between the uranium content in ore samples which the X-ray tube as the excitation source and the chemical analysis results is within 10%. Conclusion: This paper come to the conclusion that the technical quality of uranium measurement used X-ray tube as excitation source is superior to that in radioactive source excitation mode.

  11. Size-extensivity-corrected multireference configuration interaction schemes to accurately predict bond dissociation energies of oxygenated hydrocarbons

    SciTech Connect

    Oyeyemi, Victor B.; Krisiloff, David B.; Keith, John A.; Libisch, Florian; Pavone, Michele; Carter, Emily A.

    2014-01-28

    Oxygenated hydrocarbons play important roles in combustion science as renewable fuels and additives, but many details about their combustion chemistry remain poorly understood. Although many methods exist for computing accurate electronic energies of molecules at equilibrium geometries, a consistent description of entire combustion reaction potential energy surfaces (PESs) requires multireference correlated wavefunction theories. Here we use bond dissociation energies (BDEs) as a foundational metric to benchmark methods based on multireference configuration interaction (MRCI) for several classes of oxygenated compounds (alcohols, aldehydes, carboxylic acids, and methyl esters). We compare results from multireference singles and doubles configuration interaction to those utilizing a posteriori and a priori size-extensivity corrections, benchmarked against experiment and coupled cluster theory. We demonstrate that size-extensivity corrections are necessary for chemically accurate BDE predictions even in relatively small molecules and furnish examples of unphysical BDE predictions resulting from using too-small orbital active spaces. We also outline the specific challenges in using MRCI methods for carbonyl-containing compounds. The resulting complete basis set extrapolated, size-extensivity-corrected MRCI scheme produces BDEs generally accurate to within 1 kcal/mol, laying the foundation for this scheme's use on larger molecules and for more complex regions of combustion PESs.

  12. Size-extensivity-corrected multireference configuration interaction schemes to accurately predict bond dissociation energies of oxygenated hydrocarbons

    NASA Astrophysics Data System (ADS)

    Oyeyemi, Victor B.; Krisiloff, David B.; Keith, John A.; Libisch, Florian; Pavone, Michele; Carter, Emily A.

    2014-01-01

    Oxygenated hydrocarbons play important roles in combustion science as renewable fuels and additives, but many details about their combustion chemistry remain poorly understood. Although many methods exist for computing accurate electronic energies of molecules at equilibrium geometries, a consistent description of entire combustion reaction potential energy surfaces (PESs) requires multireference correlated wavefunction theories. Here we use bond dissociation energies (BDEs) as a foundational metric to benchmark methods based on multireference configuration interaction (MRCI) for several classes of oxygenated compounds (alcohols, aldehydes, carboxylic acids, and methyl esters). We compare results from multireference singles and doubles configuration interaction to those utilizing a posteriori and a priori size-extensivity corrections, benchmarked against experiment and coupled cluster theory. We demonstrate that size-extensivity corrections are necessary for chemically accurate BDE predictions even in relatively small molecules and furnish examples of unphysical BDE predictions resulting from using too-small orbital active spaces. We also outline the specific challenges in using MRCI methods for carbonyl-containing compounds. The resulting complete basis set extrapolated, size-extensivity-corrected MRCI scheme produces BDEs generally accurate to within 1 kcal/mol, laying the foundation for this scheme's use on larger molecules and for more complex regions of combustion PESs.

  13. Excited-state nuclear forces on adiabatic potential-energy surfaces by time-dependent density-functional theory

    NASA Astrophysics Data System (ADS)

    Haruyama, Jun; Suzuki, Takahiro; Hu, Chunping; Watanabe, Kazuyuki

    2012-01-01

    We present a simple and computationally efficient method to calculate excited-state nuclear forces on adiabatic potential-energy surfaces (APES) from linear-response time-dependent density-functional theory within a real-space framework. The Casida ansatz, which has been validated for computing first-order nonadiabatic couplings in previous studies, was applied to the calculation of the excited-state forces. Our method is validated by the consistency of results in the lower excited states, which reproduce well those obtained by the numerical derivative of each APES. We emphasize the usefulness of this technique by demonstrating the excited-state molecular-dynamics simulation.

  14. Excitation of vibrational quanta in furfural by intermediate-energy electrons

    SciTech Connect

    Jones, D. B.; Neves, R. F. C.; Lopes, M. C. A.; Costa, R. F. da; Varella, M. T. do N.; Bettega, M. H. F.; Lima, M. A. P.; García, G.; and others

    2015-12-14

    We report cross sections for electron-impact excitation of vibrational quanta in furfural, at intermediate incident electron energies (20, 30, and 40 eV). The present differential cross sections are measured over the scattered electron angular range 10°–90°, with corresponding integral cross sections subsequently being determined. Furfural is a viable plant-derived alternative to petrochemicals, being produced via low-temperature plasma treatment of biomass. Current yields, however, need to be significantly improved, possibly through modelling, with the present cross sections being an important component of such simulations. To the best of our knowledge, there are no other cross sections for vibrational excitation of furfural available in the literature, so the present data are valuable for this important molecule.

  15. Excitation of vibrational quanta in furfural by intermediate-energy electrons

    NASA Astrophysics Data System (ADS)

    Jones, D. B.; Neves, R. F. C.; Lopes, M. C. A.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Lima, M. A. P.; García, G.; Blanco, F.; Brunger, M. J.

    2015-12-01

    We report cross sections for electron-impact excitation of vibrational quanta in furfural, at intermediate incident electron energies (20, 30, and 40 eV). The present differential cross sections are measured over the scattered electron angular range 10°-90°, with corresponding integral cross sections subsequently being determined. Furfural is a viable plant-derived alternative to petrochemicals, being produced via low-temperature plasma treatment of biomass. Current yields, however, need to be significantly improved, possibly through modelling, with the present cross sections being an important component of such simulations. To the best of our knowledge, there are no other cross sections for vibrational excitation of furfural available in the literature, so the present data are valuable for this important molecule.

  16. Accurate Intermolecular Interactions at Dramatically Reduced Cost and a Many-Body Energy Decomposition Scheme for XPol+SAPT

    NASA Astrophysics Data System (ADS)

    Lao, Ka Un; Herbert, John M.

    2013-06-01

    An efficient, monomer-based electronic structure method is introduced for computing non-covalent interactions in molecular and ionic clusters. It builds upon our ``explicit polarization" (XPol) with pairwise-additive symmetry-adapted perturbation theory (SAPT) using the Kohn-Sham (KS) version of SAPT, but replaces the problematic and expensive sum-over-states dispersion terms with empirical potentials. This modification reduces the scaling from {O}(N^5) to {O}(N^3) and also facilitates the use of Kohn-Sham density functional theory (KS-DFT) as a low-cost means to capture intramolecular electron correlation. Accurate binding energies are obtained for benchmark databases of dimer binding energies, and potential energy curves are also captured accurately, for a variety of challenging systems. As compared to traditional DFT-SAPT or SAPT(DFT) methods, it removes the limitation to dimers and extends SAPT-based methodology to many-body systems. For many-body systems such as water clusters and halide-water cluster anions, the new method is superior to established density-functional methods for non-covalent interactions. We suggest that using different asymptotic corrections for different monomers is necessary to get good binding energies in general, as DFT-SAPT or SAPT(DFT), especially for hydrogen-bonded complexes. We also introduce a decomposition scheme for the interaction energy that extends traditional SAPT energy decomposition analysis to systems containing more than two monomers, and we find that the various energy components (electrostatic, exchange, induction, and dispersion) are in very good agreement with high-level SAPT benchmarks for dimers. For (H_2O)_6, the many-body contribution to the interaction energy agrees well with that obtained from traditional Kitaura-Morokuma energy decomposition analysis.

  17. Quantum Dynamics of Vinylidene Photodetachment on an Accurate Global Acetylene-Vinylidene Potential Energy Surface.

    PubMed

    Guo, Lifen; Han, Huixian; Ma, Jianyi; Guo, Hua

    2015-08-01

    Vinylidene is a high-energy isomer of acetylene, and the rearrangement of bonds in the two species serves as a prototype for isomerization reactions. Here, a full-dimensional quantum mechanical study of the vinylidene vibration is carried out on a recently developed global acetylene-vinylidene potential energy surface by simulating the photodetachment dynamics of the vinylidene anion. Several low-lying vibrational levels of the anion were first determined on a new ab initio based potential energy surface, and their photoelectron spectra were obtained within the Condon approximation. The vibrational features of the vinylidene isomer are found to agree well with the experiment in both positions and intensities, validating the global acetylene-vinylidene potential energy surface.

  18. An Energy-Efficient Strategy for Accurate Distance Estimation in Wireless Sensor Networks

    PubMed Central

    Tarrío, Paula; Bernardos, Ana M.; Casar, José R.

    2012-01-01

    In line with recent research efforts made to conceive energy saving protocols and algorithms and power sensitive network architectures, in this paper we propose a transmission strategy to minimize the energy consumption in a sensor network when using a localization technique based on the measurement of the strength (RSS) or the time of arrival (TOA) of the received signal. In particular, we find the transmission power and the packet transmission rate that jointly minimize the total consumed energy, while ensuring at the same time a desired accuracy in the RSS or TOA measurements. We also propose some corrections to these theoretical results to take into account the effects of shadowing and packet loss in the propagation channel. The proposed strategy is shown to be effective in realistic scenarios providing energy savings with respect to other transmission strategies, and also guaranteeing a given accuracy in the distance estimations, which will serve to guarantee a desired accuracy in the localization result. PMID:23202218

  19. Revisiting the blind tests in crystal structure prediction: accurate energy ranking of molecular crystals.

    PubMed

    Asmadi, Aldi; Neumann, Marcus A; Kendrick, John; Girard, Pascale; Perrin, Marc-Antoine; Leusen, Frank J J

    2009-12-24

    In the 2007 blind test of crystal structure prediction hosted by the Cambridge Crystallographic Data Centre (CCDC), a hybrid DFT/MM method correctly ranked each of the four experimental structures as having the lowest lattice energy of all the crystal structures predicted for each molecule. The work presented here further validates this hybrid method by optimizing the crystal structures (experimental and submitted) of the first three CCDC blind tests held in 1999, 2001, and 2004. Except for the crystal structures of compound IX, all structures were reminimized and ranked according to their lattice energies. The hybrid method computes the lattice energy of a crystal structure as the sum of the DFT total energy and a van der Waals (dispersion) energy correction. Considering all four blind tests, the crystal structure with the lowest lattice energy corresponds to the experimentally observed structure for 12 out of 14 molecules. Moreover, good geometrical agreement is observed between the structures determined by the hybrid method and those measured experimentally. In comparison with the correct submissions made by the blind test participants, all hybrid optimized crystal structures (apart from compound II) have the smallest calculated root mean squared deviations from the experimentally observed structures. It is predicted that a new polymorph of compound V exists under pressure.

  20. Revisiting the blind tests in crystal structure prediction: accurate energy ranking of molecular crystals.

    PubMed

    Asmadi, Aldi; Neumann, Marcus A; Kendrick, John; Girard, Pascale; Perrin, Marc-Antoine; Leusen, Frank J J

    2009-12-24

    In the 2007 blind test of crystal structure prediction hosted by the Cambridge Crystallographic Data Centre (CCDC), a hybrid DFT/MM method correctly ranked each of the four experimental structures as having the lowest lattice energy of all the crystal structures predicted for each molecule. The work presented here further validates this hybrid method by optimizing the crystal structures (experimental and submitted) of the first three CCDC blind tests held in 1999, 2001, and 2004. Except for the crystal structures of compound IX, all structures were reminimized and ranked according to their lattice energies. The hybrid method computes the lattice energy of a crystal structure as the sum of the DFT total energy and a van der Waals (dispersion) energy correction. Considering all four blind tests, the crystal structure with the lowest lattice energy corresponds to the experimentally observed structure for 12 out of 14 molecules. Moreover, good geometrical agreement is observed between the structures determined by the hybrid method and those measured experimentally. In comparison with the correct submissions made by the blind test participants, all hybrid optimized crystal structures (apart from compound II) have the smallest calculated root mean squared deviations from the experimentally observed structures. It is predicted that a new polymorph of compound V exists under pressure. PMID:19950907

  1. Intermediate energy cross sections for electron-impact vibrational-excitation of pyrimidine

    SciTech Connect

    Jones, D. B.; Ellis-Gibbings, L.; García, G.; Nixon, K. L.; Lopes, M. C. A.; Brunger, M. J.

    2015-09-07

    We report differential cross sections (DCSs) and integral cross sections (ICSs) for electron-impact vibrational-excitation of pyrimidine, at incident electron energies in the range 15–50 eV. The scattered electron angular range for the DCS measurements was 15°–90°. The measurements at the DCS-level are the first to be reported for vibrational-excitation in pyrimidine via electron impact, while for the ICS we extend the results from the only previous condensed-phase study [P. L. Levesque, M. Michaud, and L. Sanche, J. Chem. Phys. 122, 094701 (2005)], for electron energies ⩽12 eV, to higher energies. Interestingly, the trend in the magnitude of the lower energy condensed-phase ICSs is much smaller when compared to the corresponding gas phase results. As there is no evidence for the existence of any shape-resonances, in the available pyrimidine total cross sections [Baek et al., Phys. Rev. A 88, 032702 (2013); Fuss et al., ibid. 88, 042702 (2013)], between 10 and 20 eV, this mismatch in absolute magnitude between the condensed-phase and gas-phase ICSs might be indicative for collective-behaviour effects in the condensed-phase results.

  2. Correlation between excitation temperature and electron temperature with two groups of electron energy distributions

    SciTech Connect

    Park, Hoyong; Choe, Wonho; You, S. J.

    2010-10-15

    The relationship between the electron excitation temperature (T{sub exc}) determined by optical emission spectroscopy and the electron temperature (T{sub e}) using a rf-compensated Langmuir probe was investigated in argon capacitively coupled plasmas. In the experiment performed at the gas pressure range of 30 mTorr to 1 Torr and the rf power range of 5-37 W, the electron energy probability function (EEPF) obtained from the probe current versus voltage characteristic curve showed two energy groups of electrons. The measured EEPF demonstrated that the electron energy distribution changed from Druyvesteyn to single Maxwellian as the discharge current was increased and from bi-Maxwellian to Druyvesteyn as the pressure was increased. As a result, T{sub exc} showed a tendency identical to that of T{sub e} of the high energy part of electrons as pressure and rf power were varied. This suggests that electron temperature can be determined from the measured T{sub exc} through a calibration experiment by which the ratio between electron and excitation temperatures is measured.

  3. Accurate Diels-Alder reaction energies from efficient density functional calculations.

    PubMed

    Mezei, Pál D; Csonka, Gábor I; Kállay, Mihály

    2015-06-01

    We assess the performance of the semilocal PBE functional; its global hybrid variants; the highly parametrized empirical M06-2X and M08-SO; the range separated rCAM-B3LYP and MCY3; the atom-pairwise or nonlocal dispersion corrected semilocal PBE and TPSS; the dispersion corrected range-separated ωB97X-D; the dispersion corrected double hybrids such as PWPB95-D3; the direct random phase approximation, dRPA, with Hartree-Fock, Perdew-Burke-Ernzerhof, and Perdew-Burke-Ernzerhof hybrid reference orbitals and the RPAX2 method based on a Perdew-Burke-Ernzerhof exchange reference orbitals for the Diels-Alder, DARC; and self-interaction error sensitive, SIE11, reaction energy test sets with large, augmented correlation consistent valence basis sets. The dRPA energies for the DARC test set are extrapolated to the complete basis set limit. CCSD(T)/CBS energies were used as a reference. The standard global hybrid functionals show general improvements over the typical endothermic energy error of semilocal functionals, but despite the increased accuracy the precision of the methods increases only slightly, and thus all reaction energies are simply shifted into the exothermic direction. Dispersion corrections give mixed results for the DARC test set. Vydrov-Van Voorhis 10 correction to the reaction energies gives superior quality results compared to the too-small D3 correction. Functionals parametrized for energies of noncovalent interactions like M08-SO give reasonable results without any dispersion correction. The dRPA method that seamlessly and theoretically correctly includes noncovalent interaction energies gives excellent results with properly chosen reference orbitals. As the results for the SIE11 test set and H2(+) dissociation show that the dRPA methods suffer from delocalization error, good reaction energies for the DARC test set from a given method do not prove that the method is free from delocalization error. The RPAX2 method shows good performance for the DARC

  4. Accurate and Rigorous Prediction of the Changes in Protein Free Energies in a Large-Scale Mutation Scan.

    PubMed

    Gapsys, Vytautas; Michielssens, Servaas; Seeliger, Daniel; de Groot, Bert L

    2016-06-20

    The prediction of mutation-induced free-energy changes in protein thermostability or protein-protein binding is of particular interest in the fields of protein design, biotechnology, and bioengineering. Herein, we achieve remarkable accuracy in a scan of 762 mutations estimating changes in protein thermostability based on the first principles of statistical mechanics. The remaining error in the free-energy estimates appears to be due to three sources in approximately equal parts, namely sampling, force-field inaccuracies, and experimental uncertainty. We propose a consensus force-field approach, which, together with an increased sampling time, leads to a free-energy prediction accuracy that matches those reached in experiments. This versatile approach enables accurate free-energy estimates for diverse proteins, including the prediction of changes in the melting temperature of the membrane protein neurotensin receptor 1. PMID:27122231

  5. Accurate potential energy curve of the LiH{sup +} molecule calculated with explicitly correlated Gaussian functions

    SciTech Connect

    Tung, Wei-Cheng; Adamowicz, Ludwik

    2014-03-28

    Very accurate calculations of the ground-state potential energy curve (PEC) of the LiH{sup +} ion performed with all-electron explicitly correlated Gaussian functions with shifted centers are presented. The variational method is employed. The calculations involve optimization of nonlinear exponential parameters of the Gaussians performed with the aid of the analytical first derivatives of the energy determined with respect to the parameters. The diagonal adiabatic correction is also calculated for each PEC point. The PEC is then used to calculate the vibrational energies of the system. In that calculation, the non-adiabatic effects are accounted for by using an effective vibrational mass obtained by the minimization of the difference between the vibrational energies obtained from the calculations where the Born-Oppenheimer approximation was not assumed and the results of the present calculations.

  6. Accurate intermolecular ground-state potential-energy surfaces of the HCCH-He, Ne, and Ar van der Waals complexes.

    PubMed

    Munteanu, Cristian Robert; Fernández, Berta

    2005-07-01

    Accurate ground-state intermolecular potential-energy surfaces are obtained for the HCCH-He, Ne, and Ar van der Waals complexes. The interaction energies are calculated at the coupled cluster singles and doubles including connected triple excitations level and fitted to analytic functions. For the three complexes we start with systematic basis set studies carried out at several intermolecular geometries, and using augmented correlation consistent polarized valence basis sets x-aug-cc-pVXZ (x=-,d; X=D,T,Q,5), also extended with a set of 3s3p2d1f1g midbond functions. The aug-cc-pVQZ-33211 surfaces of HCCH-He, Ne, and Ar complexes are characterized by absolute minima of -24.22, -50.20, and -122.17 cm(-1) at distances R between the rare-gas atom and the HCCH centers of mass of 4.35, 3.95, and 3.99 A, respectively; and at angles between the vector R and the HCCH main symmetry axis of 0 degrees , 43.3 degrees , and 60.6 degrees . The results are compared and considerably improve those previously available.

  7. Neural network approach to quantum-chemistry data: Accurate prediction of density functional theory energies

    NASA Astrophysics Data System (ADS)

    Balabin, Roman M.; Lomakina, Ekaterina I.

    2009-08-01

    Artificial neural network (ANN) approach has been applied to estimate the density functional theory (DFT) energy with large basis set using lower-level energy values and molecular descriptors. A total of 208 different molecules were used for the ANN training, cross validation, and testing by applying BLYP, B3LYP, and BMK density functionals. Hartree-Fock results were reported for comparison. Furthermore, constitutional molecular descriptor (CD) and quantum-chemical molecular descriptor (QD) were used for building the calibration model. The neural network structure optimization, leading to four to five hidden neurons, was also carried out. The usage of several low-level energy values was found to greatly reduce the prediction error. An expected error, mean absolute deviation, for ANN approximation to DFT energies was 0.6±0.2 kcal mol-1. In addition, the comparison of the different density functionals with the basis sets and the comparison of multiple linear regression results were also provided. The CDs were found to overcome limitation of the QD. Furthermore, the effective ANN model for DFT/6-311G(3df,3pd) and DFT/6-311G(2df,2pd) energy estimation was developed, and the benchmark results were provided.

  8. Communication: Simple and accurate uniform electron gas correlation energy for the full range of densities

    NASA Astrophysics Data System (ADS)

    Chachiyo, Teepanis

    2016-07-01

    A simple correlation energy functional for the uniform electron gas is derived based on the second-order Moller-Plesset perturbation theory. It can reproduce the known correlation functional in the high-density limit, while in the mid-density range maintaining a good agreement with the near-exact correlation energy of the uniform electron gas to within 2 × 10-3 hartree. The correlation energy is a function of a density parameter rs and is of the form a * ln ( 1 + /b r s + /b rs 2 ) . The constants "a" and "b" are derived from the known correlation functional in the high-density limit. Comparisons to the Ceperley-Alder's near-exact Quantum Monte Carlo results and the Vosko-Wilk-Nusair correlation functional are also reported.

  9. Blackbody radiation shift, multipole polarizabilities, oscillator strengths, lifetimes, hyperfine constants, and excitation energies in Ca{sup +}

    SciTech Connect

    Safronova, M. S.; Safronova, U. I.

    2011-01-15

    A systematic study of Ca{sup +} atomic properties is carried out using a high-precision relativistic all-order method where all single, double, and partial triple excitations of the Dirac-Fock wave functions are included to all orders of perturbation theory. Reduced matrix elements, oscillator strengths, transition rates, and lifetimes are determined for the levels up to n=7. Recommended values and estimates of their uncertainties are provided for a large number of electric-dipole transitions. Electric-dipole scalar polarizabilities for the 5s, 6s, 7s, 8s, 4p{sub j}, 5p{sub j}, 3d{sub j}, and 4d{sub j} states and tensor polarizabilities for the 4p{sub 3/2}, 5p{sub 3/2}, 3d{sub j}, and 4d{sub j} states in Ca{sup +} are calculated. Methods are developed to accurately treat the contributions from highly excited states, resulting in significant (factor of 3) improvement in the accuracy of the 3d{sub 5/2} static polarizability value, 31.8(3)a{sub 0}{sup 3}, in comparison with the previous calculation [Arora et al., Phys. Rev. A 76, 064501 (2007).]. The blackbody radiation shift of the 4s-3d{sub 5/2} clock transition in Ca{sup +} is calculated to be 0.381(4) Hz at room temperature, T=300 K. Electric-quadrupole 4s-nd and electric-octupole 4s-nf matrix elements are calculated to obtain the ground-state multipole E2 and E3 static polarizabilities. Excitation energies of the ns, np, nd, nf, and ng states with n{<=} 7 in are evaluated and compared with experiment. Recommended values are provided for the 7p{sub 1/2}, 7p{sub 3/2}, 8p{sub 1/2}, and 8p{sub 3/2} removal energies for which experimental measurements are not available. The hyperfine constants A are determined for the low-lying levels up to n=7. The quadratic Stark effect on hyperfine structure levels of {sup 43}Ca{sup +} ground state is investigated. These calculations provide recommended values critically evaluated for their accuracy for a number of Ca{sup +} atomic properties for use in planning and analysis of

  10. An application of a statistical model for the calculation of the logarithmic mean excitation energy of molecules Molecular hydrogen

    NASA Technical Reports Server (NTRS)

    Kamaratos, E.

    1985-01-01

    A statistical model, the local plasma approximation, is considered for the calculation of the logarithmic mean excitation energy for stopping power of chemically bound particles by taking into consideration chemical bonding. This statistical model is applied to molecular hydrogen and leads to results that suggest a value for the logarithmic mean excitation energy of molecular hydrogen that is larger than the accepted experimental and theoretical values.

  11. High-Accurate Intermolecular Potential Energy Surface of HCN-H_2 Complex with Intramolecular Vibrational Mode of HCN Included

    NASA Astrophysics Data System (ADS)

    Zhai, Yu; Li, Hui

    2016-06-01

    ydrogen is one of the most abundant interstellar species. Observation of rotational and vibrational spectra of H_2 containing complexes is of great importance because they are possible candidates for radio-astronomical detection. CO, HCN, HCCH are as isoelectronic molecules of N_2, each with a strong triple bond. It had been a big challenge to predict reliable theoretical rovibrational spectra of complexes including such species because the higher order electron correlation energy plays a non-negligible role in improving the accuracy. However, recent works on CO-H_2 have shown that it is possible to reproduce the experimental spectra quantitatively. In this work, we calculate a five-dimension potential energy surface (PES) of HCN-H_2 complex which explicitly include the intramolecular asymmetric stretching vibrational mode(C-H,Q_3) coordinate at CCSD(T)/aug-cc-pVQZ+3s3p2d1f1g level, corrected with electron correlation energy from the triple and quadruple excitation. Vibrational average over intramolecular vibration mode is made with HCN monomer at ground and the first excited vibrational states respectively, and the averaged data are fitted to two four-dimension Morse/Long-Range (MLR) potential energy functions. Based on the MLR PESs, for the first time, we calculated the spectra of HCN-{para}H_2} and {HCN-{ortho}H_2}. The results for HCN-{ortho}H_2} are in good agreement with the published experimental data with root-mean-square-difference (RMSD) only 0.01wn, which validates the accuracy of the PESs. J. Chem. Phys., 139, 164315 (2013); Science, 336, 1147 (2012). J. Chem. Phys., 115, 5137 (2001).

  12. Measurement of the fusion excitation function for 19O + 12C at near barrier energies

    NASA Astrophysics Data System (ADS)

    Singh, Varinderjit; Steinbach, T. K.; Vadas, J.; Wiggins, B. B.; Hudan, S.; Desouza, R. T.; Baby, L. T.; Tripathi, V.; Kuvin, S. A.; Wiedenhover, I.

    2015-10-01

    Fusion of neutron-rich light nuclei in the outer crust of an accreting neutron star has been proposed as responsible for triggering X-ray super-bursts. The underlying hypothesis in this proposition is that the fusion of neutron-rich nuclei is enhanced as compared to stable nuclei. To investigate this hypothesis, an experiment has been performed to measure the fusion excitation function for 18O and 19O nuclei incident on a 12C target. A beam of 19O was produced by the 18O(d,p) reaction at Florida State University and separated using the RESOLUT mass spectrometer. The resulting 19O beam bombarded a 100 μg/cm2 12C target at an intensity of 2-4 × 103 p/s. Evaporation residues resulting from the de-excitation of the fusion product were distinguished by measuring their energy and time-of-flight. Using silicon detectors, micro-channel plate detectors, and an ionization chamber, evaporation residues were detected in the angular range θlab <= 23° with high efficiency. Initial experimental results including measurement of the fusion cross-section to approximately the 100 mb level will be presented. The measured excitation function will be compared to theoretical predictions. Supported by the US DOE under Grand No. DEFG02-88ER-40404.

  13. Reduction in ignition energy for single-shot microthrusters using pulsedlaser excitation

    NASA Astrophysics Data System (ADS)

    Hansen, William W.; Janson, Siegfried W.; Helvajian, Henry

    2002-09-01

    An experiment has been conducted to compare the ignition energy of an existing digital thruster design between a pulsed electrical and laser excitations. A 355nm Nd-YAG pulsed laser is used to ignite the stored lead styphnate propellant charge. Given the device design, roughly 800 μJ is necessary to ignite a 180 μg charge volume with a 90% probability of ignition. This energy value is considered an upper limit. Under equivalent conditions, roughly 2.4mJ of electrical energy is required to ignite the same volume. The digital thruster concept is one approach to provide a valveless, slap-on propulsion capability for small (1kg mass class) and large satellites (1000kg mass class) to help maintain attitude or control the damping of low frequency oscillations in extended surfaces.

  14. Excited-state charging energies in quantum dots investigated by terahertz photocurrent spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Shibata, K.; Nagai, N.; Ndebeka-Bandou, C.; Bastard, G.; Hirakawa, K.

    2016-06-01

    We have investigated the excited-state (ES) charging energies in quantum dots (QDs) by measuring a terahertz (THz)-induced photocurrent in a single-electron transistor (SET) geometry that contains a single InAs QD between metal nanogap electrodes. A photocurrent is produced in the QD SETs through THz intersublevel transitions and the subsequent resonant tunneling. We have found that the photocurrent exhibits stepwise change even within one Coulomb blockaded region as the electrochemical potential in the QD is swept by the gate voltage. From the threshold for the photocurrent generation, we have determined the charging energies for adding an electron in the photoexcited state in the QD. Furthermore, the charging energies for the ESs with different electron configurations are clearly resolved. The present THz photocurrent measurements are essentially dynamical experiments and allow us to analyze electronic properties in off-equilibrium states in the QD.

  15. Transfer of the Excitation Energy in Anacystis nidulans Grown to Obtain Different Pigment Ratios

    PubMed Central

    Ghosh, A. K.; Govindjee

    1966-01-01

    The blue-green alga, Anacystis nidulans, was grown in lights of different colors and intensities, and its absorption and fluorescence properties were studied. Strong orange light, absorbed mainly by phycocyanin, causes reduction in the ratio of phycocyanin to chlorophyll a; strong red light, absorbed mainly by chlorophyll, causes an increase in this ratio. This confirms the earlier findings of Brody and Emerson (12) on Porphyridum, and of Jones and Myers (8) on Anacystis. Anacystis cultures grown in light of low intensity show, upon excitation of phycocyanin, emission peaks at 600 mμ and 680 mμ, due to the fluorescence of phycocyanin and chlorophyll a, respectively. Changes in the efficiency of energy transfer from phycocyanin to chlorophyll a are revealed by changes in the ratios of these two bands. A decrease in efficiency of energy transfer from phycocyanin to chlorophyll a seems to occur whenever the ratio of chlorophyll a to phycocyanin deviates from the normal. Algae grown in light of high intensity show, upon excitation of phycocyanin, only a fluorescence band at 660 mμ and no band at 680 mμ. This suggests reduced efficiency of energy transfer from phycocyanin to the strongly fluorescent form of chlorophyll a (chlorophyll a2) and perhaps increased transfer to the weakly fluorescent form of chlorophyll a (chlorophyll a1). PMID:5970565

  16. Excitation of the 3p states in electron-sodium scattering at intermediate energies

    SciTech Connect

    Kamali, M. Z. M.; Wong, B. R.; Chin, J. H.; Ratnavelu, K.

    2014-03-05

    A coupled-channel-optical method (CCOM), to investigate the excitation of the 3p states for e{sup −}-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.

  17. Spatial distribution of fluorescent light emitted from neon and nitrogen excited by low energy electron beams

    SciTech Connect

    Morozov, A.; Kruecken, R.; Ulrich, A.; Wieser, J.

    2006-11-01

    Side-view intensity profiles of fluorescent light were measured for neon and nitrogen excited with 12 keV electron beams at gas pressures from 250 to 1400 hPa. The intensity profiles were compared with theoretical profiles calculated using the CASINO program which performs Monte Carlo simulations of electron scattering. It was assumed that the spatial distribution of fluorescent intensity is directly proportional to the spatial distribution of energy loss by primary electrons. The comparison shows good correlation of experimental data and the results of numeric simulations.

  18. Improving DOE-2's RESYS routine: User defined functions to provide more accurate part load energy use and humidity predictions

    SciTech Connect

    Henderson, Hugh I.; Parker, Danny; Huang, Yu J.

    2000-08-04

    In hourly energy simulations, it is important to properly predict the performance of air conditioning systems over a range of full and part load operating conditions. An important component of these calculations is to properly consider the performance of the cycling air conditioner and how it interacts with the building. This paper presents improved approaches to properly account for the part load performance of residential and light commercial air conditioning systems in DOE-2. First, more accurate correlations are given to predict the degradation of system efficiency at part load conditions. In addition, a user-defined function for RESYS is developed that provides improved predictions of air conditioner sensible and latent capacity at part load conditions. The user function also provides more accurate predictions of space humidity by adding ''lumped'' moisture capacitance into the calculations. The improved cooling coil model and the addition of moisture capacitance predicts humidity swings that are more representative of the performance observed in real buildings.

  19. Accurate one-dimensional potential energy curve of the linear (H2)2 cluster

    NASA Astrophysics Data System (ADS)

    Tung, Wei-Cheng; Pavanello, Michele; Adamowicz, Ludwik

    2010-09-01

    We present a sub-0.3 K accuracy, ground-state one-dimensional potential energy curve of the metastable linear configuration of the (H2)2 cluster calculated exclusively with explicitly correlated Gaussian functions with shifted centers. The H2 internuclear distance is kept at the isolated H2 vibrational ground-state average value of 1.448 736 bohr and the intermonomer separation is varied between 2 and 100 bohrs. The analytical gradient of the energy with respect to the nonlinear parameters of the Gaussians (i.e., the exponents and the coordinates of the shifts) has been employed in the variational optimization of the wave function. Procedures for enlarging the basis set and for adjusting the centers of the Gaussians to the varying intermonomer separation have been developed and used in the calculations.

  20. Communication: Accurate hydration free energies at a wide range of temperatures from 3D-RISM.

    PubMed

    Misin, Maksim; Fedorov, Maxim V; Palmer, David S

    2015-03-01

    We present a new model for computing hydration free energies by 3D reference interaction site model (3D-RISM) that uses an appropriate initial state of the system (as suggested by Sergiievskyi et al.). The new adjustment to 3D-RISM theory significantly improves hydration free energy predictions for various classes of organic molecules at both ambient and non-ambient temperatures. An extensive benchmarking against experimental data shows that the accuracy of the model is comparable to (much more computationally expensive) molecular dynamics simulations. The calculations can be readily performed with a standard 3D-RISM algorithm. In our work, we used an open source package AmberTools; a script to automate the whole procedure is available on the web (https://github.com/MTS-Strathclyde/ISc). PMID:25747054

  1. Accurate calculations of the hydration free energies of druglike molecules using the reference interaction site model.

    PubMed

    Palmer, David S; Sergiievskyi, Volodymyr P; Jensen, Frank; Fedorov, Maxim V

    2010-07-28

    We report on the results of testing the reference interaction site model (RISM) for the estimation of the hydration free energy of druglike molecules. The optimum model was selected after testing of different RISM free energy expressions combined with different quantum mechanics and empirical force-field methods of structure optimization and atomic partial charge calculation. The final model gave a systematic error with a standard deviation of 2.6 kcal/mol for a test set of 31 molecules selected from the SAMPL1 blind challenge set [J. P. Guthrie, J. Phys. Chem. B 113, 4501 (2009)]. After parametrization of this model to include terms for the excluded volume and the number of atoms of different types in the molecule, the root mean squared error for a test set of 19 molecules was less than 1.2 kcal/mol.

  2. Accurate Exchange-Correlation Energies for the Warm Dense Electron Gas.

    PubMed

    Malone, Fionn D; Blunt, N S; Brown, Ethan W; Lee, D K K; Spencer, J S; Foulkes, W M C; Shepherd, James J

    2016-09-01

    The density matrix quantum Monte Carlo (DMQMC) method is used to sample exact-on-average N-body density matrices for uniform electron gas systems of up to 10^{124} matrix elements via a stochastic solution of the Bloch equation. The results of these calculations resolve a current debate over the accuracy of the data used to parametrize finite-temperature density functionals. Exchange-correlation energies calculated using the real-space restricted path-integral formalism and the k-space configuration path-integral formalism disagree by up to ∼10% at certain reduced temperatures T/T_{F}≤0.5 and densities r_{s}≤1. Our calculations confirm the accuracy of the configuration path-integral Monte Carlo results available at high density and bridge the gap to lower densities, providing trustworthy data in the regime typical of planetary interiors and solids subject to laser irradiation. We demonstrate that the DMQMC method can calculate free energies directly and present exact free energies for T/T_{F}≥1 and r_{s}≤2.

  3. Accurate Exchange-Correlation Energies for the Warm Dense Electron Gas

    NASA Astrophysics Data System (ADS)

    Malone, Fionn D.; Blunt, N. S.; Brown, Ethan W.; Lee, D. K. K.; Spencer, J. S.; Foulkes, W. M. C.; Shepherd, James J.

    2016-09-01

    The density matrix quantum Monte Carlo (DMQMC) method is used to sample exact-on-average N -body density matrices for uniform electron gas systems of up to 10124 matrix elements via a stochastic solution of the Bloch equation. The results of these calculations resolve a current debate over the accuracy of the data used to parametrize finite-temperature density functionals. Exchange-correlation energies calculated using the real-space restricted path-integral formalism and the k -space configuration path-integral formalism disagree by up to ˜10 % at certain reduced temperatures T /TF≤0.5 and densities rs≤1 . Our calculations confirm the accuracy of the configuration path-integral Monte Carlo results available at high density and bridge the gap to lower densities, providing trustworthy data in the regime typical of planetary interiors and solids subject to laser irradiation. We demonstrate that the DMQMC method can calculate free energies directly and present exact free energies for T /TF≥1 and rs≤2 .

  4. An accurate and efficient computation method of the hydration free energy of a large, complex molecule.

    PubMed

    Yoshidome, Takashi; Ekimoto, Toru; Matubayasi, Nobuyuki; Harano, Yuichi; Kinoshita, Masahiro; Ikeguchi, Mitsunori

    2015-05-01

    The hydration free energy (HFE) is a crucially important physical quantity to discuss various chemical processes in aqueous solutions. Although an explicit-solvent computation with molecular dynamics (MD) simulations is a preferable treatment of the HFE, huge computational load has been inevitable for large, complex solutes like proteins. In the present paper, we propose an efficient computation method for the HFE. In our method, the HFE is computed as a sum of 〈UUV〉/2 (〈UUV〉 is the ensemble average of the sum of pair interaction energy between solute and water molecule) and the water reorganization term mainly reflecting the excluded volume effect. Since 〈UUV〉 can readily be computed through a MD of the system composed of solute and water, an efficient computation of the latter term leads to a reduction of computational load. We demonstrate that the water reorganization term can quantitatively be calculated using the morphometric approach (MA) which expresses the term as the linear combinations of the four geometric measures of a solute and the corresponding coefficients determined with the energy representation (ER) method. Since the MA enables us to finish the computation of the solvent reorganization term in less than 0.1 s once the coefficients are determined, the use of the MA enables us to provide an efficient computation of the HFE even for large, complex solutes. Through the applications, we find that our method has almost the same quantitative performance as the ER method with substantial reduction of the computational load. PMID:25956125

  5. Accurate Exchange-Correlation Energies for the Warm Dense Electron Gas.

    PubMed

    Malone, Fionn D; Blunt, N S; Brown, Ethan W; Lee, D K K; Spencer, J S; Foulkes, W M C; Shepherd, James J

    2016-09-01

    The density matrix quantum Monte Carlo (DMQMC) method is used to sample exact-on-average N-body density matrices for uniform electron gas systems of up to 10^{124} matrix elements via a stochastic solution of the Bloch equation. The results of these calculations resolve a current debate over the accuracy of the data used to parametrize finite-temperature density functionals. Exchange-correlation energies calculated using the real-space restricted path-integral formalism and the k-space configuration path-integral formalism disagree by up to ∼10% at certain reduced temperatures T/T_{F}≤0.5 and densities r_{s}≤1. Our calculations confirm the accuracy of the configuration path-integral Monte Carlo results available at high density and bridge the gap to lower densities, providing trustworthy data in the regime typical of planetary interiors and solids subject to laser irradiation. We demonstrate that the DMQMC method can calculate free energies directly and present exact free energies for T/T_{F}≥1 and r_{s}≤2. PMID:27661699

  6. A new set of atomic radii for accurate estimation of solvation free energy by Poisson-Boltzmann solvent model.

    PubMed

    Yamagishi, Junya; Okimoto, Noriaki; Morimoto, Gentaro; Taiji, Makoto

    2014-11-01

    The Poisson-Boltzmann implicit solvent (PB) is widely used to estimate the solvation free energies of biomolecules in molecular simulations. An optimized set of atomic radii (PB radii) is an important parameter for PB calculations, which determines the distribution of dielectric constants around the solute. We here present new PB radii for the AMBER protein force field to accurately reproduce the solvation free energies obtained from explicit solvent simulations. The presented PB radii were optimized using results from explicit solvent simulations of the large systems. In addition, we discriminated PB radii for N- and C-terminal residues from those for nonterminal residues. The performances using our PB radii showed high accuracy for the estimation of solvation free energies at the level of the molecular fragment. The obtained PB radii are effective for the detailed analysis of the solvation effects of biomolecules.

  7. Accurate Potential Energy Curves for the Ground Electronic States of NeH^{+} and ArH^{+}

    NASA Astrophysics Data System (ADS)

    Coxon, John A.; Hajigeorgiou, Photos G.

    2013-06-01

    All available microwave and infrared spectroscopic line positions for the ground electronic states of the molecular cations NeH^{+} and ArH^{+} were employed in a direct potential fitting procedure to determine compact analytical potential curves and radial functions describing breakdown of the Born-Oppenheimer approximation. For NeH^{+}, 17 adjustable parameters were required to represent a total of 183 line positions for 4 isotopologues, whereas for ArH^{+}, 23 adjustable parameters were required to represent 440 line positions for 6 isotopologues. The MLR3 potential energy functional form was employed, taking full account of the proper 1/r{^4} limiting long-range dependence of the ion-atom dispersion energy interactions. Accurate vibrational energies, rotational constants and centrifugal distortion constants have been calculated for both diatomic cations.

  8. Accurate energies of hydrogen bonded nucleic acid base pairs and triplets in tRNA tertiary interactions

    PubMed Central

    2006-01-01

    Tertiary interactions are crucial in maintaining the tRNA structure and functionality. We used a combined sequence analysis and quantum mechanics approach to calculate accurate energies of the most frequent tRNA tertiary base pairing interactions. Our analysis indicates that six out of the nine classical tertiary interactions are held in place mainly by H-bonds between the bases. In the remaining three cases other effects have to be considered. Tertiary base pairing interaction energies range from −8 to −38 kcal/mol in yeast tRNAPhe and are estimated to contribute roughly 25% of the overall tRNA base pairing interaction energy. Six analyzed posttranslational chemical modifications were shown to have minor effect on the geometry of the tertiary interactions. Modifications that introduce a positive charge strongly stabilize the corresponding tertiary interactions. Non-additive effects contribute to the stability of base triplets. PMID:16461956

  9. Efficient Calculation of Accurate Reaction Energies-Assessment of Different Models in Electronic Structure Theory.

    PubMed

    Friedrich, Joachim

    2015-08-11

    In this work we analyze the accuracy and the efficiency of different schemes to obtain the complete basis set limit for CCSD(T). It is found that composite schemes using an MP2 increment to reach the basis set limit provide high accuracy combined with high efficiency. In these composite schemes the MP2-F12/cc-pVTZ-F12 method is suitable to compute the MP2 contribution at the basis set limit. We propose to use the def2-TZVP or the TZVPP basis sets at the coupled cluster level in combination with the cc-pVTZ-F12 basis set at the MP2 level to compute reaction energies close to the basis set limit, if high accuracy methods like CCSD(T)(F12*) or 56-extrapolations are no longer feasible due to the computational effort. The standard deviation of CCSD(T)+ΔMP2/cc-pVTZ-F12/def2-TZVP and CCSD(T)+ΔMP2/cc-pVTZ-F12/TZVPP is found to be only 0.93 and 0.65 kJ/mol for a test set of 51 closed shell reactions. Furthermore, we provide a comprehensive list of different computational strategies to obtain CCSD(T) reaction energies with an efficiency and accuracy measure. Finally we analyze how different choices of the exponent in the correlation factor (γ) change the results when using explicitly correlated methods. The statistical results in this study are based on a set of 51 reaction energies in the range of 0.7 to 631.5 kJ/mol.

  10. Iterative linearized density matrix propagation for modeling coherent excitation energy transfer in photosynthetic light harvesting.

    PubMed

    Huo, P; Coker, D F

    2010-11-14

    Rather than incoherent hopping between chromophores, experimental evidence suggests that the excitation energy transfer in some biological light harvesting systems initially occurs coherently, and involves coherent superposition states in which excitation spreads over multiple chromophores separated by several nanometers. Treating such delocalized coherent superposition states in the presence of decoherence and dissipation arising from coupling to an environment is a significant challenge for conventional theoretical tools that either use a perturbative approach or make the Markovian approximation. In this paper, we extend the recently developed iterative linearized density matrix (ILDM) propagation scheme [E. R. Dunkel et al., J. Chem. Phys. 129, 114106 (2008)] to study coherent excitation energy transfer in a model of the Fenna-Matthews-Olsen light harvesting complex from green sulfur bacteria. This approach is nonperturbative and uses a discrete path integral description employing a short time approximation to the density matrix propagator that accounts for interference between forward and backward paths of the quantum excitonic system while linearizing the phase in the difference between the forward and backward paths of the environmental degrees of freedom resulting in a classical-like treatment of these variables. The approach avoids making the Markovian approximation and we demonstrate that it successfully describes the coherent beating of the site populations on different chromophores and gives good agreement with other methods that have been developed recently for going beyond the usual approximations, thus providing a new reliable theoretical tool to study coherent exciton transfer in light harvesting systems. We conclude with a discussion of decoherence in independent bilinearly coupled harmonic chromophore baths. The ILDM propagation approach in principle can be applied to more general descriptions of the environment.

  11. Accurate electron affinity of Pb and isotope shifts of binding energies of Pb(.).

    PubMed

    Chen, Xiaolin; Ning, Chuangang

    2016-08-28

    Lead (Pb) was the last element of the group IVA whose electron affinity had a low accuracy around 10 meV before the present work. This was due to the generic threshold photodetachment measurement that cannot extent well below 0.5 eV due to the light source limitation. In the present work, the electron affinity of Pb was determined to be 2877.33(13) cm(-1) or 0.356 743(16) eV for the isotope m = 208. The accuracy was improved by a factor of 500 with respect to the previous laser photodetachment electron spectroscopy. Moreover, remarkable isotope shifts of the binding energy of Pb(-) 6p(3) (4)S3/2 - Pb 6p(2) (3)P2 were observed for m = 206, 207, and 208. PMID:27586918

  12. Accurate electron affinity of Pb and isotope shifts of binding energies of Pb-

    NASA Astrophysics Data System (ADS)

    Chen, Xiaolin; Ning, Chuangang

    2016-08-01

    Lead (Pb) was the last element of the group IVA whose electron affinity had a low accuracy around 10 meV before the present work. This was due to the generic threshold photodetachment measurement that cannot extent well below 0.5 eV due to the light source limitation. In the present work, the electron affinity of Pb was determined to be 2877.33(13) cm-1 or 0.356 743(16) eV for the isotope m = 208. The accuracy was improved by a factor of 500 with respect to the previous laser photodetachment electron spectroscopy. Moreover, remarkable isotope shifts of the binding energy of Pb- 6p3 4S3/2 - Pb 6p2 3P2 were observed for m = 206, 207, and 208.

  13. Accurate human tissue characterization for energy-efficient wireless on-body communications.

    PubMed

    Vallejo, Mónica; Recas, Joaquín; del Valle, Pablo García; Ayala, José L

    2013-06-10

    The demand for Wireless Body Sensor Networks (WBSNs) is rapidly increasing due to the revolution in wearable systems demonstrated by the penetration of on-the-body sensors in hospitals, sports medicine and general health-care practices. In WBSN, the body acts as a communication channel for the propagation of electromagnetic (EM) waves, where losses are mainly due to absorption of power in the tissue. This paper shows the effects of the dielectric properties of biological tissues in the signal strength and, for the first time, relates these effects with the human body composition. After a careful analysis of results, this work proposes a reactive algorithm for power transmission to alleviate the effect of body movement and body type. This policy achieves up to 40.8% energy savings in a realistic scenario with no performance overhead.

  14. Accurate Human Tissue Characterization for Energy-Efficient Wireless On-Body Communications

    PubMed Central

    Vallejo, Mónica; Recas, Joaquín; del Valle, Pablo García; Ayala, José L.

    2013-01-01

    The demand for Wireless Body Sensor Networks (WBSNs) is rapidly increasing due to the revolution in wearable systems demonstrated by the penetration of on-the-body sensors in hospitals, sports medicine and general health-care practices. In WBSN, the body acts as a communication channel for the propagation of electromagnetic (EM) waves, where losses are mainly due to absorption of power in the tissue. This paper shows the effects of the dielectric properties of biological tissues in the signal strength and, for the first time, relates these effects with the human body composition. After a careful analysis of results, this work proposes a reactive algorithm for power transmission to alleviate the effect of body movement and body type. This policy achieves up to 40.8% energy savings in a realistic scenario with no performance overhead. PMID:23752565

  15. Full Dimensional Vibrational Calculations for Methane Using AN Accurate New AB Initio Based Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Majumder, Moumita; Dawes, Richard; Wang, Xiao-Gang; Carrington, Tucker; Li, Jun; Guo, Hua; Manzhos, Sergei

    2014-06-01

    New potential energy surfaces for methane were constructed, represented as analytic fits to about 100,000 individual high-level ab initio data. Explicitly-correlated multireference data (MRCI-F12(AE)/CVQZ-F12) were computed using Molpro [1] and fit using multiple strategies. Fits with small to negligible errors were obtained using adaptations of the permutation-invariant-polynomials (PIP) approach [2,3] based on neural-networks (PIP-NN) [4,5] and the interpolative moving least squares (IMLS) fitting method [6] (PIP-IMLS). The PESs were used in full-dimensional vibrational calculations with an exact kinetic energy operator by representing the Hamiltonian in a basis of products of contracted bend and stretch functions and using a symmetry adapted Lanczos method to obtain eigenvalues and eigenvectors. Very close agreement with experiment was produced from the purely ab initio PESs. References 1- H.-J. Werner, P. J. Knowles, G. Knizia, 2012.1 ed. 2012, MOLPRO, a package of ab initio programs. see http://www.molpro.net. 2- Z. Xie and J. M. Bowman, J. Chem. Theory Comput 6, 26, 2010. 3- B. J. Braams and J. M. Bowman, Int. Rev. Phys. Chem. 28, 577, 2009. 4- J. Li, B. Jiang and Hua Guo, J. Chem. Phys. 139, 204103 (2013). 5- S Manzhos, X Wang, R Dawes and T Carrington, JPC A 110, 5295 (2006). 6- R. Dawes, X-G Wang, A.W. Jasper and T. Carrington Jr., J. Chem. Phys. 133, 134304 (2010).

  16. Dependence of Fission-Fragment Properties On Excitation Energy For Neutron-Rich Actinides

    NASA Astrophysics Data System (ADS)

    Ramos, D.; Rodríguez-Tajes, C.; Caamaño, M.; Farget, F.; Audouin, L.; Benlliure, J.; Casarejos, E.; Clement, E.; Cortina, D.; Delaune, O.; Derkx, X.; Dijon, A.; Doré, D.; Fernández-Domínguez, B.; de France, G.; Heinz, A.; Jacquot, B.; Navin, A.; Paradela, C.; Rejmund, M.; Roger, T.; Salsac, M. D.; Schmitt, C.

    2016-03-01

    Experimental access to full isotopic fragment distributions is very important to determine the features of the fission process. However, the isotopic identification of fission fragments has been, in the past, partial and scarce. A solution based on the use of inverse kinematics to study transfer-induced fission of exotic actinides was carried out at GANIL, resulting in the first experiment accessing the full identification of a collection of fissioning systems and their corresponding fission fragment distribution. In these experiments, a 238U beam at 6.14 AMeV impinged on a carbon target to produce fissioning systems from U to Am by transfer reactions, and Cf by fusion reactions. Isotopic fission yields of 250Cf, 244Cm, 240Pu, 239Np and 238U are presented in this work. With this information, the average number of neutrons as a function of the atomic number of the fragments is calculated, which reflects the impact of nuclear structure around Z=50, N=80 on the production of fission fragments. The characteristics of the Super Long, Standard I, Standard II, and Standard III fission channels were extracted from fits of the fragment yields for different ranges of excitation energy. The position and contribution of the fission channels as function of excitation energy are presented.

  17. Live-cell visualization of excitation energy dynamics in chloroplast thylakoid structures.

    PubMed

    Iwai, Masakazu; Yokono, Makio; Kurokawa, Kazuo; Ichihara, Akira; Nakano, Akihiko

    2016-01-01

    The intricate molecular processes underlying photosynthesis have long been studied using various analytic approaches. However, the three-dimensional (3D) dynamics of such photosynthetic processes remain unexplored due to technological limitations related to investigating intraorganellar mechanisms in vivo. By developing a system for high-speed 3D laser scanning confocal microscopy combined with high-sensitivity multiple-channel detection, we visualized excitation energy dynamics in thylakoid structures within chloroplasts of live Physcomitrella patens cells. Two distinct thylakoid structures in the chloroplast, namely the grana and stroma lamellae, were visualized three-dimensionally in live cells. The simultaneous detection of the shorter (than ~670 nm) and longer (than ~680 nm) wavelength regions of chlorophyll (Chl) fluorescence reveals different spatial characteristics-irregular and vertical structures, respectively. Spectroscopic analyses showed that the shorter and longer wavelength regions of Chl fluorescence are affected more by free light-harvesting antenna proteins and photosystem II supercomplexes, respectively. The high-speed 3D time-lapse imaging of the shorter and longer wavelength regions also reveals different structural dynamics-rapid and slow movements within 1.5 seconds, respectively. Such structural dynamics of the two wavelength regions of Chl fluorescence would indicate excitation energy dynamics between light-harvesting antenna proteins and photosystems, reflecting the energetically active nature of photosynthetic proteins in thylakoid membranes. PMID:27416900

  18. Calculation of excitation energies from the CC2 linear response theory using Cholesky decomposition

    SciTech Connect

    Baudin, Pablo; Marín, José Sánchez; Cuesta, Inmaculada García; Sánchez de Merás, Alfredo M. J.

    2014-03-14

    A new implementation of the approximate coupled cluster singles and doubles CC2 linear response model is reported. It employs a Cholesky decomposition of the two-electron integrals that significantly reduces the computational cost and the storage requirements of the method compared to standard implementations. Our algorithm also exploits a partitioning form of the CC2 equations which reduces the dimension of the problem and avoids the storage of doubles amplitudes. We present calculation of excitation energies of benzene using a hierarchy of basis sets and compare the results with conventional CC2 calculations. The reduction of the scaling is evaluated as well as the effect of the Cholesky decomposition parameter on the quality of the results. The new algorithm is used to perform an extrapolation to complete basis set investigation on the spectroscopically interesting benzylallene conformers. A set of calculations on medium-sized molecules is carried out to check the dependence of the accuracy of the results on the decomposition thresholds. Moreover, CC2 singlet excitation energies of the free base porphin are also presented.

  19. Distributed parameter model and experimental validation of a compressive-mode energy harvester under harmonic excitations

    NASA Astrophysics Data System (ADS)

    Li, H. T.; Yang, Z.; Zu, J.; Qin, W. Y.

    2016-08-01

    This paper presents the modeling and parametric analysis of the recently proposed nonlinear compressive-mode energy harvester (HC-PEH) under harmonic excitation. Both theoretical and experimental investigations are performed in this study over a range of excitation frequencies. Specially, a distributed parameter electro-elastic model is analytically developed by means of the energy-based method and the extended Hamilton's principle. An analytical formulation of bending and stretching forces are derived to gain insight on the source of nonlinearity. Furthermore, the analytical model is validated against with experimental data and a good agreement is achieved. Both numerical simulations and experiment illustrate that the harvester exhibits a hardening nonlinearity and hence a broad frequency bandwidth, multiple coexisting solutions and a large-amplitude voltage response. Using the derived model, a parametric study is carried out to examine the effect of various parameters on the harvester voltage response. It is also shown from parametric analysis that the harvester's performance can be further improved by selecting the proper length of elastic beams, proof mass and reducing the mechanical damping.

  20. Live-cell visualization of excitation energy dynamics in chloroplast thylakoid structures

    PubMed Central

    Iwai, Masakazu; Yokono, Makio; Kurokawa, Kazuo; Ichihara, Akira; Nakano, Akihiko

    2016-01-01

    The intricate molecular processes underlying photosynthesis have long been studied using various analytic approaches. However, the three-dimensional (3D) dynamics of such photosynthetic processes remain unexplored due to technological limitations related to investigating intraorganellar mechanisms in vivo. By developing a system for high-speed 3D laser scanning confocal microscopy combined with high-sensitivity multiple-channel detection, we visualized excitation energy dynamics in thylakoid structures within chloroplasts of live Physcomitrella patens cells. Two distinct thylakoid structures in the chloroplast, namely the grana and stroma lamellae, were visualized three-dimensionally in live cells. The simultaneous detection of the shorter (than ~670 nm) and longer (than ~680 nm) wavelength regions of chlorophyll (Chl) fluorescence reveals different spatial characteristics—irregular and vertical structures, respectively. Spectroscopic analyses showed that the shorter and longer wavelength regions of Chl fluorescence are affected more by free light-harvesting antenna proteins and photosystem II supercomplexes, respectively. The high-speed 3D time-lapse imaging of the shorter and longer wavelength regions also reveals different structural dynamics—rapid and slow movements within 1.5 seconds, respectively. Such structural dynamics of the two wavelength regions of Chl fluorescence would indicate excitation energy dynamics between light-harvesting antenna proteins and photosystems, reflecting the energetically active nature of photosynthetic proteins in thylakoid membranes. PMID:27416900

  1. Live-cell visualization of excitation energy dynamics in chloroplast thylakoid structures.

    PubMed

    Iwai, Masakazu; Yokono, Makio; Kurokawa, Kazuo; Ichihara, Akira; Nakano, Akihiko

    2016-07-15

    The intricate molecular processes underlying photosynthesis have long been studied using various analytic approaches. However, the three-dimensional (3D) dynamics of such photosynthetic processes remain unexplored due to technological limitations related to investigating intraorganellar mechanisms in vivo. By developing a system for high-speed 3D laser scanning confocal microscopy combined with high-sensitivity multiple-channel detection, we visualized excitation energy dynamics in thylakoid structures within chloroplasts of live Physcomitrella patens cells. Two distinct thylakoid structures in the chloroplast, namely the grana and stroma lamellae, were visualized three-dimensionally in live cells. The simultaneous detection of the shorter (than ~670 nm) and longer (than ~680 nm) wavelength regions of chlorophyll (Chl) fluorescence reveals different spatial characteristics-irregular and vertical structures, respectively. Spectroscopic analyses showed that the shorter and longer wavelength regions of Chl fluorescence are affected more by free light-harvesting antenna proteins and photosystem II supercomplexes, respectively. The high-speed 3D time-lapse imaging of the shorter and longer wavelength regions also reveals different structural dynamics-rapid and slow movements within 1.5 seconds, respectively. Such structural dynamics of the two wavelength regions of Chl fluorescence would indicate excitation energy dynamics between light-harvesting antenna proteins and photosystems, reflecting the energetically active nature of photosynthetic proteins in thylakoid membranes.

  2. Development and optimization of an energy-regenerative suspension system under stochastic road excitation

    NASA Astrophysics Data System (ADS)

    Huang, Bo; Hsieh, Chen-Yu; Golnaraghi, Farid; Moallem, Mehrdad

    2015-11-01

    In this paper a vehicle suspension system with energy harvesting capability is developed, and an analytical methodology for the optimal design of the system is proposed. The optimization technique provides design guidelines for determining the stiffness and damping coefficients aimed at the optimal performance in terms of ride comfort and energy regeneration. The corresponding performance metrics are selected as root-mean-square (RMS) of sprung mass acceleration and expectation of generated power. The actual road roughness is considered as the stochastic excitation defined by ISO 8608:1995 standard road profiles and used in deriving the optimization method. An electronic circuit is proposed to provide variable damping in the real-time based on the optimization rule. A test-bed is utilized and the experiments under different driving conditions are conducted to verify the effectiveness of the proposed method. The test results suggest that the analytical approach is credible in determining the optimality of system performance.

  3. Mass-number and excitation-energy dependence of the spin cutoff parameter

    NASA Astrophysics Data System (ADS)

    Grimes, S. M.; Voinov, A. V.; Massey, T. N.

    2016-07-01

    The spin cutoff parameter determining the nuclear level density spin distribution ρ (J ) is defined through the spin projection as 1 /2 or equivalently for spherical nuclei, ( 3 ) 1 /2. It is needed to divide the total level density into levels as a function of J . To obtain the total level density at the neutron binding energy from the s -wave resonance count, the spin cutoff parameter is also needed. The spin cutoff parameter has been calculated as a function of excitation energy and mass with a super-conducting Hamiltonian. Calculations have been compared with two commonly used semiempirical formulas. A need for further measurements is also observed. Some complications for deformed nuclei are discussed. The quality of spin cut off parameter data derived from isomeric ratio measurement is examined.

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

    NASA Astrophysics Data System (ADS)

    Manser, Joseph S.

    travel 220 nm over the course of 2 ns after photoexcitation, with an extrapolated diffusion length greater than one micrometer over the full excited state lifetime. The solution-processability of metal halide perovskites necessarily raises questions as to the properties of the solvated precursors and their connection to the final solid-state perovskite phase. Through structural and steady-state and time-resolved absorption studies, the important link between the excited state properties of the precursor components, composed of solvated and solid-state halometallate complexes, and CH3NH3PbI3 is evinced. This connection provides insight into optical nonlinearities and electronic properties of the perovskite phase. Fundamental studies of CH 3NH3PbI3 ultimately serve as a foundation for application of this and other related materials in high-performance devices. In the final chapter, the operation of CH3NH3PbI 3 solar cells in a tandem architecture is presented. The quest for economic, large scale hydrogen production has motivated the search for new materials and device designs capable of splitting water using only energy from the sun. In light of this, we introduce an all solution-processed tandem water splitting assembly composed of a BiVO4 photoanode and a single-junction CH3NH3PbI3 hybrid perovskite solar cell. This unique configuration allows efficient solar photon management, with the metal oxide photoanode selectively harvesting high energy visible photons and the underlying perovskite solar cell capturing lower energy visible-near IR wavelengths in a single-pass excitation. Operating without external bias under standard terrestrial one sun illumination, the photoanode-photovoltaic architecture, in conjunction with an earthabundant cobalt phosphate catalyst, exhibits a solar-to-hydrogen conversion efficiency of 2.5% at neutral pH. The design of low-cost tandem water splitting assemblies employing single-junction hybrid perovskite materials establishes a potentially

  5. Effective approach for accurately calculating individual energy of polar heterojunction interfaces

    NASA Astrophysics Data System (ADS)

    Akiyama, Toru; Nakane, Harunobu; Nakamura, Kohji; Ito, Tomonori

    2016-09-01

    We propose a direct approach for calculating individual energy of polar semiconductor interfaces using density functional theory calculations. This approach is applied to polar interfaces between group-III nitrides (AlN and GaN) and SiC and clarifies the interplay of chemical bonding and charge neutrality at the interface, which is crucial for the stability and polarity of group-III nitrides on SiC substrates. The ideal interface is stabilized among various atomic arrangements over the wide range of the chemical potential on Si-face SiC, whereas those with intermixing are favorable on C-face SiC. The stabilization of the ideal interfaces resulting in Ga-polar GaN and Al-polar AlN films on Si-face SiC is consistent with experiments, suggesting that our approach is versatile to evaluate various polar heterojunction interfaces as well as group-III nitrides on semiconductor substrates.

  6. Spatial Pattern Classification for More Accurate Forecasting of Variable Energy Resources

    NASA Astrophysics Data System (ADS)

    Novakovskaia, E.; Hayes, C.; Collier, C.

    2014-12-01

    The accuracy of solar and wind forecasts is becoming increasingly essential as grid operators continue to integrate additional renewable generation onto the electric grid. Forecast errors affect rate payers, grid operators, wind and solar plant maintenance crews and energy traders through increases in prices, project down time or lost revenue. While extensive and beneficial efforts were undertaken in recent years to improve physical weather models for a broad spectrum of applications these improvements have generally not been sufficient to meet the accuracy demands of system planners. For renewables, these models are often used in conjunction with additional statistical models utilizing both meteorological observations and the power generation data. Forecast accuracy can be dependent on specific weather regimes for a given location. To account for these dependencies it is important that parameterizations used in statistical models change as the regime changes. An automated tool, based on an artificial neural network model, has been developed to identify different weather regimes as they impact power output forecast accuracy at wind or solar farms. In this study, improvements in forecast accuracy were analyzed for varying time horizons for wind farms and utility-scale PV plants located in different geographical regions.

  7. Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies

    PubMed Central

    Bardhan, Jaydeep P.; Jungwirth, Pavel; Makowski, Lee

    2012-01-01

    Two mechanisms have been proposed to drive asymmetric solvent response to a solute charge: a static potential contribution similar to the liquid-vapor potential, and a steric contribution associated with a water molecule's structure and charge distribution. In this work, we use free-energy perturbation molecular-dynamics calculations in explicit water to show that these mechanisms act in complementary regimes; the large static potential (∼44 kJ/mol/e) dominates asymmetric response for deeply buried charges, and the steric contribution dominates for charges near the solute-solvent interface. Therefore, both mechanisms must be included in order to fully account for asymmetric solvation in general. Our calculations suggest that the steric contribution leads to a remarkable deviation from the popular “linear response” model in which the reaction potential changes linearly as a function of charge. In fact, the potential varies in a piecewise-linear fashion, i.e., with different proportionality constants depending on the sign of the charge. This discrepancy is significant even when the charge is completely buried, and holds for solutes larger than single atoms. Together, these mechanisms suggest that implicit-solvent models can be improved using a combination of affine response (an offset due to the static potential) and piecewise-linear response (due to the steric contribution). PMID:23020318

  8. An atlas of RNA base pairs involving modified nucleobases with optimal geometries and accurate energies

    PubMed Central

    Chawla, Mohit; Oliva, Romina; Bujnicki, Janusz M.; Cavallo, Luigi

    2015-01-01

    Posttranscriptional modifications greatly enhance the chemical information of RNA molecules, contributing to explain the diversity of their structures and functions. A significant fraction of RNA experimental structures available to date present modified nucleobases, with half of them being involved in H-bonding interactions with other bases, i.e. ‘modified base pairs’. Herein we present a systematic investigation of modified base pairs, in the context of experimental RNA structures. To this end, we first compiled an atlas of experimentally observed modified base pairs, for which we recorded occurrences and structural context. Then, for each base pair, we selected a representative for subsequent quantum mechanics calculations, to find out its optimal geometry and interaction energy. Our structural analyses show that most of the modified base pairs are non Watson–Crick like and are involved in RNA tertiary structure motifs. In addition, quantum mechanics calculations quantify and provide a rationale for the impact of the different modifications on the geometry and stability of the base pairs they participate in. PMID:26117545

  9. An atlas of RNA base pairs involving modified nucleobases with optimal geometries and accurate energies.

    PubMed

    Chawla, Mohit; Oliva, Romina; Bujnicki, Janusz M; Cavallo, Luigi

    2015-08-18

    Posttranscriptional modifications greatly enhance the chemical information of RNA molecules, contributing to explain the diversity of their structures and functions. A significant fraction of RNA experimental structures available to date present modified nucleobases, with half of them being involved in H-bonding interactions with other bases, i.e. 'modified base pairs'. Herein we present a systematic investigation of modified base pairs, in the context of experimental RNA structures. To this end, we first compiled an atlas of experimentally observed modified base pairs, for which we recorded occurrences and structural context. Then, for each base pair, we selected a representative for subsequent quantum mechanics calculations, to find out its optimal geometry and interaction energy. Our structural analyses show that most of the modified base pairs are non Watson-Crick like and are involved in RNA tertiary structure motifs. In addition, quantum mechanics calculations quantify and provide a rationale for the impact of the different modifications on the geometry and stability of the base pairs they participate in. PMID:26117545

  10. Analytic energy gradient of excited electronic state within TDDFT/MMpol framework: Benchmark tests and parallel implementation

    SciTech Connect

    Zeng, Qiao; Liang, WanZhen

    2015-10-07

    The time-dependent density functional theory (TDDFT) has become the most popular method to calculate the electronic excitation energies, describe the excited-state properties, and perform the excited-state geometric optimization of medium and large-size molecules due to the implementation of analytic excited-state energy gradient and Hessian in many electronic structure software packages. To describe the molecules in condensed phase, one usually adopts the computationally efficient hybrid Quantum Mechanics/Molecular Mechanics (QM/MM) models. Here, we extend our previous work on the energy gradient of TDDFT/MM excited state to account for the mutual polarization effects between QM and MM regions, which is believed to hold a crucial position in the potential energy surface of molecular systems when the photoexcitation-induced charge rearrangement in the QM region is drastic. The implementation of a simple polarizable TDDFT/MM (TDDFT/MMpol) model in Q-Chem/CHARMM interface with both the linear response and the state-specific features has been realized. Several benchmark tests and preliminary applications are exhibited to confirm our implementation and assess the effects of different treatment of environmental polarization on the excited-state properties, and the efficiency of parallel implementation is demonstrated as well.

  11. Analytic energy gradient of excited electronic state within TDDFT/MMpol framework: Benchmark tests and parallel implementation.

    PubMed

    Zeng, Qiao; Liang, WanZhen

    2015-10-01

    The time-dependent density functional theory (TDDFT) has become the most popular method to calculate the electronic excitation energies, describe the excited-state properties, and perform the excited-state geometric optimization of medium and large-size molecules due to the implementation of analytic excited-state energy gradient and Hessian in many electronic structure software packages. To describe the molecules in condensed phase, one usually adopts the computationally efficient hybrid Quantum Mechanics/Molecular Mechanics (QM/MM) models. Here, we extend our previous work on the energy gradient of TDDFT/MM excited state to account for the mutual polarization effects between QM and MM regions, which is believed to hold a crucial position in the potential energy surface of molecular systems when the photoexcitation-induced charge rearrangement in the QM region is drastic. The implementation of a simple polarizable TDDFT/MM (TDDFT/MMpol) model in Q-Chem/CHARMM interface with both the linear response and the state-specific features has been realized. Several benchmark tests and preliminary applications are exhibited to confirm our implementation and assess the effects of different treatment of environmental polarization on the excited-state properties, and the efficiency of parallel implementation is demonstrated as well. PMID:26450289

  12. Analytic energy gradient of excited electronic state within TDDFT/MMpol framework: Benchmark tests and parallel implementation.

    PubMed

    Zeng, Qiao; Liang, WanZhen

    2015-10-01

    The time-dependent density functional theory (TDDFT) has become the most popular method to calculate the electronic excitation energies, describe the excited-state properties, and perform the excited-state geometric optimization of medium and large-size molecules due to the implementation of analytic excited-state energy gradient and Hessian in many electronic structure software packages. To describe the molecules in condensed phase, one usually adopts the computationally efficient hybrid Quantum Mechanics/Molecular Mechanics (QM/MM) models. Here, we extend our previous work on the energy gradient of TDDFT/MM excited state to account for the mutual polarization effects between QM and MM regions, which is believed to hold a crucial position in the potential energy surface of molecular systems when the photoexcitation-induced charge rearrangement in the QM region is drastic. The implementation of a simple polarizable TDDFT/MM (TDDFT/MMpol) model in Q-Chem/CHARMM interface with both the linear response and the state-specific features has been realized. Several benchmark tests and preliminary applications are exhibited to confirm our implementation and assess the effects of different treatment of environmental polarization on the excited-state properties, and the efficiency of parallel implementation is demonstrated as well.

  13. Energy transfer kinetics of the np5(n + 1)p excited states of Ne and Kr.

    PubMed

    Kabir, Md Humayun; Heaven, Michael C

    2011-09-01

    Energy transfer rate constants for Ne(2p(5)3p) and Kr(4p(5)5p) atoms colliding with ground state rare gas atoms (Rg) have been measured. In part, this study is motivated by the possibility of using excited rare gas atoms as the active species in optically pumped laser systems. Rg(np(5)(n + 1)s) metastable states may be produced using low-power electrical discharges. The potential then exits for optical pumping and laser action on the np(5)(n + 1)p ↔ np(5)(n + 1)s transitions. Knowledge of the rate constants for collisional energy transfer and deactivation of the np(5)(n + 1)p states is required to evaluate the laser potential for various Rg + buffer gas combinations. In the present study we have characterized energy transfer processes for Ne (2p(5)3p) + He for the six lowest energy states of the multiplet. Rate constants for state-to-state transfer have been determined. Deactivation of the lowest energy level of Kr (4p(5)5p) by He, Ne, and Kr has also been characterized. Initial results suggest that Kr (4p(5)5p) + Ne mixtures may be the best suited for optically pumped laser applications.

  14. Excitation energies, oscillator strengths and lifetimes in Mg-like vanadium

    NASA Astrophysics Data System (ADS)

    Gupta, G. P.; Msezane, A. Z.

    2013-08-01

    Excitation energies from the ground state for 86 fine-structure levels as well as oscillator strengths and radiative decay rates for all fine-structure transitions among the levels of the terms (1s22s22p6)3s2(1S), 3s3p(1,3Po), 3s3d(1,3D), 3s4s(1,3S), 3s4p(1,3Po), 3s4d(1,3D), 3s4f(1,3Fo), 3p2(1S, 3P, 1D), 3p3d(1,3Po, 1,3Do, 1,3Fo), 3p4s(1,3Po), 3p4p(1,3S, 1,3P, 1,3D), 3p4d(1,3Po, 1,3Do, 1,3Fo), 3p4f(1,3D, 1,3F, 1,3G) and 3d2(1S, 3P, 1D,3F,1G) of V XII are calculated using extensive configuration-interaction wave functions obtained with the configuration-interaction version 3 computer code of Hibbert. The important relativistic effects in intermediate coupling are included through the Breit-Pauli approximation. In order to keep our calculated energy splittings as close as possible to the corresponding experimental values, we have made small adjustments to the diagonal elements of the Hamiltonian matrices. The mixing among several fine-structure levels is found to be very strong. Our fine-tuned excitation energies, including their ordering, are in excellent agreement (better than 0.25%) with the available experimental results. From our calculated radiative decay rates, we have also calculated the radiative lifetimes of fine-structure levels. Generally, our calculated data for the excitation energies and radiative decay rates are found to agree reasonably well with other available calculations. However, significant differences between our calculated lifetimes and those from the calculation of Froese Fischer et al (2006 At. Data Nucl. Data Tables 92 607) for a few fine-structure levels, mainly those belonging to the 3p4d configuration, are noted and discussed. Also, our calculated lifetime for the longer-lived level 3s3p(3P1) is found to be in excellent agreement with the corresponding value of Curtis (1991 Phys. Scr. 43 137). ) for all 1108 transitions in V XII are available with the first author ().

  15. Ergodicity, configurational entropy and free energy in pigment solutions and plant photosystems: influence of excited state lifetime.

    PubMed

    Jennings, Robert C; Zucchelli, Giuseppe

    2014-01-01

    We examine ergodicity and configurational entropy for a dilute pigment solution and for a suspension of plant photosystem particles in which both ground and excited state pigments are present. It is concluded that the pigment solution, due to the extreme brevity of the excited state lifetime, is non-ergodic and the configurational entropy approaches zero. Conversely, due to the rapid energy transfer among pigments, each photosystem is ergodic and the configurational entropy is positive. This decreases the free energy of the single photosystem pigment array by a small amount. On the other hand, the suspension of photosystems is non-ergodic and the configurational entropy approaches zero. The overall configurational entropy which, in principle, includes contributions from both the single excited photosystems and the suspension which contains excited photosystems, also approaches zero. Thus the configurational entropy upon photon absorption by either a pigment solution or a suspension of photosystem particles is approximately zero.

  16. Electron hole pair mediated vibrational excitation in CO scattering from Au(111): Incidence energy and surface temperature dependence

    SciTech Connect

    Shirhatti, Pranav R.; Werdecker, Jörn; Golibrzuch, Kai; Wodtke, Alec M.; Bartels, Christof

    2014-09-28

    We investigated the translational incidence energy (E{sub i}) and surface temperature (T{sub s}) dependence of CO vibrational excitation upon scattering from a clean Au(111) surface. We report absolute v = 0 → 1 excitation probabilities for E{sub i} between 0.16 and 0.84 eV and T{sub s} between 473 and 973 K. This is now only the second collision system where such comprehensive measurements are available – the first is NO on Au(111). For CO on Au(111), vibrational excitation occurs via direct inelastic scattering through electron hole pair mediated energy transfer – it is enhanced by incidence translation and the electronically non-adiabatic coupling is about 5 times weaker than in NO scattering from Au(111). Vibrational excitation via the trapping desorption channel dominates at E{sub i} = 0.16 eV and quickly disappears at higher E{sub i}.

  17. Scaled Second Order Perturbation Corrections to Configuration Interaction Singles: Efficient and Reliable Excitation Energy Methods

    SciTech Connect

    Rhee, Young Min; Head-Gordon, Martin

    2007-02-01

    Two modifications of the perturbative doubles correction to configuration interaction with single substitutions (CIS(D)) are suggested, which are excited state analogs of ground state scaled second order Moeller-Plesset (MP2) methods. The first approach employs two parameters to scale the two spin components of the direct term of CIS(D), starting from the two-parameter spin-component scaled (SCS) MP2 ground state, and is termed SCS-CIS(D). An efficient resolution-of-the-identity (RI) implementation of this approach is described. The second approach employs a single parameter to scale only the opposite-spin direct term of CIS(D), starting from the one-parameter scaled opposite spin (SOS) MP2 ground state, and is called SOS-CIS(D). By utilizing auxiliary basis expansions and a Laplace transform, a fourth order algorithm for SOS-CIS(D) is described and implemented. The parameters describing SCS-CIS(D) and SOS-CIS(D) are optimized based on a training set including valence excitations of various organic molecules and Rydberg transitions of water and ammonia, and they significantly improve upon CIS(D) itself. The accuracy of the two methods is found to be comparable. This arises from a strong correlation between the same-spin and opposite-spin portions of the excitation energy terms. The methods are successfully applied to the zincbacteriochlorin-bacteriochlorin charge transfer transition, for which time-dependent density functional theory, with presently available exchange-correlation functionals, is known to fail. The methods are also successfully applied to describe various electronic transitions outside of the training set. The efficiency of SOS-CIS(D) and the auxiliary basis implementation of CIS(D) and SCS-CIS(D) are confirmed with a series of timing tests.

  18. Energy Migration Engineering of Bright Rare-Earth Upconversion Nanoparticles for Excitation by Light-Emitting Diodes.

    PubMed

    Zhong, Yeteng; Rostami, Iman; Wang, Zihua; Dai, Hongjie; Hu, Zhiyuan

    2015-11-01

    A novel Nd(3+) -sensitized upconversion nanoparticle (UCNP) that can be excited by near-infrared 740 nm light-emitting diode (LED) lamps with bright upconversion luminescence is designed. Yb(3+) ion distribution is engineered to increase the energy migration efficiency. The benefit of the novel LED-excited UCNPs is demonstrated by imaging of breast cancer cells and enabling an economic handheld semiquantitative visual measurement device. PMID:26393770

  19. Azole energetic materials: Initial mechanisms for the energy release from electronical excited nitropyrazoles

    SciTech Connect

    Yuan, Bing; Yu, Zijun; Bernstein, Elliot R.

    2014-01-21

    Decomposition of energetic material 3,4-dinitropyrazole (DNP) and two model molecules 4-nitropyrazole and 1-nitropyrazole is investigated both theoretically and experimentally. The initial decomposition mechanisms for these three nitropyrazoles are explored with complete active space self-consistent field (CASSCF) level. The NO molecule is observed as an initial decomposition product from all three materials subsequent to UV excitation. Observed NO products are rotationally cold (<50 K) for all three systems. The vibrational temperature of the NO product from DNP is (3850 ± 50) K, 1350 K hotter than that of the two model species. Potential energy surface calculations at the CASSCF(12,8)/6-31+G(d) level illustrate that conical intersections plays an essential role in the decomposition mechanism. Electronically excited S{sub 2} nitropyraozles can nonradiatively relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{sub 1}/S{sub 0}){sub CI} conical intersection and undergo a nitro-nitrite isomerization to generate NO product either in the S{sub 1} state or S{sub 0} state. In model systems, NO is generated in the S{sub 1} state, while in the energetic material DNP, NO is produced on the ground state surface, as the S{sub 1} decomposition pathway is energetically unavailable. The theoretically predicted mechanism is consistent with the experimental results, as DNP decomposes in a lower electronic state than do the model systems and thus the vibrational energy in the NO product from DNP should be hotter than from the model systems. The observed rotational energy distributions for NO are consistent with the final structures of the respective transition states for each molecule.

  20. New ab initio adiabatic potential energy surfaces and bound state calculations for the singlet ground X˜ 1A1 and excited C˜ 1B2(21A') states of SO2

    NASA Astrophysics Data System (ADS)

    Kłos, Jacek; Alexander, Millard H.; Kumar, Praveen; Poirier, Bill; Jiang, Bin; Guo, Hua

    2016-05-01

    We report new and more accurate adiabatic potential energy surfaces (PESs) for the ground X˜ 1A1 and electronically excited C˜ 1B2(21A') states of the SO2 molecule. Ab initio points are calculated using the explicitly correlated internally contracted multi-reference configuration interaction (icMRCI-F12) method. A second less accurate PES for the ground X ˜ state is also calculated using an explicitly correlated single-reference coupled-cluster method with single, double, and non-iterative triple excitations [CCSD(T)-F12]. With these new three-dimensional PESs, we determine energies of the vibrational bound states and compare these values to existing literature data and experiment.

  1. Nuclear structure effects of the nuclei {sup 152,154,156}Dy at high excitation energy and large angular momentum

    SciTech Connect

    Martin, V.; Egido, J.L.

    1995-06-01

    Using the finite-temperature Hartree-Fock-Bogoliubov formalism we analyze the properties of the nuclei {sup 152,154,156}Dy at the quasicontinuum region from {ital I}=0{h_bar} to 70{h_bar} and excitation energy up to approximately 16 MeV. We discuss energy gaps, shapes, moments of inertia, and entropy among others. The role of shape fluctuations is studied in the frame of classical statistics and we find large effects on several observables. A very rich structure is found in terms of excitation energy and angular momentum.

  2. Investigation of the energy-averaged double transition density of isoscalar monopole excitations in medium-heavy mass spherical nuclei

    NASA Astrophysics Data System (ADS)

    Gorelik, M. L.; Shlomo, S.; Tulupov, B. A.; Urin, M. H.

    2016-11-01

    The particle-hole dispersive optical model, developed recently, is applied to study properties of high-energy isoscalar monopole excitations in medium-heavy mass spherical nuclei. The energy-averaged strength functions of the isoscalar giant monopole resonance and its overtone in 208Pb are analyzed. In particular, we analyze the energy-averaged isoscalar monopole double transition density, the key quantity in the description of the hadron-nucleus inelastic scattering, and studied the validity of the factorization approximation using semi classical and microscopic one body transition densities, respectively, in calculating the cross sections for the excitation of isoscalar giant resonances by inelastic alpha scattering.

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

    SciTech Connect

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

    1997-04-01

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

  4. Performance of SOPPA-based methods in the calculation of vertical excitation energies and oscillator strengths

    NASA Astrophysics Data System (ADS)

    Sauer, Stephan P. A.; Pitzner-Frydendahl, Henrik F.; Buse, Mogens; Jensen, Hans Jørgen Aa.; Thiel, Walter

    2015-07-01

    We present two new modifications of the second-order polarization propagator approximation (SOPPA), SOPPA(SCS-MP2) and SOPPA(SOS-MP2), which employ either spin-component-scaled or scaled opposite-spin MP2 correlation coefficients instead of the regular MP2 coefficients. The performance of these two methods, the original SOPPA method as well as SOPPA(CCSD) and RPA(D) in the calculation of vertical electronic excitation energies and oscillator strengths is investigated for a large benchmark set of 28 medium-sized molecules with 139 singlet and 71 triplet excited states. The results are compared with the corresponding CC3 and CASPT2 results from the literature for both the TZVP set and the larger and more diffuse aug-cc-pVTZ basis set. In addition, the results with the aug-cc-pVTZ basis set are compared with the theoretical best estimates for this benchmark set. We find that the original SOPPA method gives overall the smallest mean deviations from the reference values and the most consistent results.

  5. Evidence for a cysteine-mediated mechanism of excitation energy regulation in a photosynthetic antenna complex.

    PubMed

    Orf, Gregory S; Saer, Rafael G; Niedzwiedzki, Dariusz M; Zhang, Hao; McIntosh, Chelsea L; Schultz, Jason W; Mirica, Liviu M; Blankenship, Robert E

    2016-08-01

    Light-harvesting antenna complexes not only aid in the capture of solar energy for photosynthesis, but regulate the quantity of transferred energy as well. Light-harvesting regulation is important for protecting reaction center complexes from overexcitation, generation of reactive oxygen species, and metabolic overload. Usually, this regulation is controlled by the association of light-harvesting antennas with accessory quenchers such as carotenoids. One antenna complex, the Fenna-Matthews-Olson (FMO) antenna protein from green sulfur bacteria, completely lacks carotenoids and other known accessory quenchers. Nonetheless, the FMO protein is able to quench energy transfer in aerobic conditions effectively, indicating a previously unidentified type of regulatory mechanism. Through de novo sequencing MS, chemical modification, and mutagenesis, we have pinpointed the source of the quenching action to cysteine residues (Cys49 and Cys353) situated near two low-energy bacteriochlorophylls in the FMO protein from Chlorobaculum tepidum Removal of these cysteines (particularly removal of the completely conserved Cys353) through N-ethylmaleimide modification or mutagenesis to alanine abolishes the aerobic quenching effect. Electrochemical analysis and electron paramagnetic resonance spectra suggest that in aerobic conditions the cysteine thiols are converted to thiyl radicals which then are capable of quenching bacteriochlorophyll excited states through electron transfer photochemistry. This simple mechanism has implications for the design of bio-inspired light-harvesting antennas and the redesign of natural photosynthetic systems. PMID:27335466

  6. [Spatial distribution of electrons with high energy in atmospheric pressure glow discharge excited by DC voltage].

    PubMed

    Liu, Zhi-qiang; Jia, Peng-ying; Liu, Tie

    2013-09-01

    Atmospheric pressure glow discharge excited by a DC voltage was realized in a 6 mm air gap by using a needle-water electrode discharge device. The atompheric pressure glow discharge has characteristic regions such as a cathode fall, a negative glow, a Faraday dark space, a positive column and an anode glow. The discharge is a normal glow through analyzing its voltage-current curve. The emission intensity of 337.1 nm spectral line from the second positive system of N2 was investigated because it can indicate the electron density with high energy. Results show that the maxima of high energy electrons appears in the vicinity of the needle tip, and it almost remains constant at other locations. The density of high energy electrons decreases with increasing the voltage. Similarly, it decreases with increasing the value of the ballast resistor. Oxygen atom is important for the sterilization and disinfection. The distribution of oxygen atom was also investigated by optical emission spectroscopy. It was found that the oxygen distribution is similar with the distribution of high energy electrons. These results are important for the application of atmospheric pressure glow discharge in environmental protection and biological treatment. PMID:24369623

  7. Response analysis of a nonlinear magnetoelectric energy harvester under harmonic excitation

    NASA Astrophysics Data System (ADS)

    Naifar, S.; Bradai, S.; Viehweger, C.; Kanoun, O.

    2015-11-01

    Magnetostrictive (MS) piezoelectric composites provide interesting possibilities to harvest energy from low amplitude and low frequency vibrations with a relative high energy outcome. In this paper a magnetoelectric (ME) vibration energy harvester has been designed, which consists of two ME transducers a magnetic circuit and a magnetic spring. The ME transducers consist of three layered Terfenol-D and Lead Zirconate Titanate (PZT) laminated composites. The outcoming energy is collected directly from the piezo layer to avoid electrical losses. In the system under consideration, the magnetic forces between the ME transducers and the magnetic circuit introduce additional stiffness on the magnetic spring. The one degree of freedom system is analysed analytically and the corresponding governing equation is solved with the Lindstedt-Poincaré method. The effects of the structure parameters, such as the nonlinear magnetic forces and the magnetic field distribution, are analysed based on finite element analysis for optimization of electric output performances. Investigations demonstrate that 1.56 mW output power across 8 MΩ load resistance can be harvested for an excitation amplitude of 1 mm at 21.84 Hz.

  8. Relativistic many-body calculations of excitation energies and transition rates from core-excited states in copperlike ions

    NASA Astrophysics Data System (ADS)

    Safronova, U. I.; Johnson, W. R.; Shlyaptseva, A.; Hamasha, S.

    2003-05-01

    Energies of (3s23p63d94l4l'), (3s23p53d104l4l'), and (3s3p63d104l4l') states for Cu-like ions with Z=30 100 are evaluated to second order in relativistic many-body perturbation theory (RMBPT) starting from a Ni-like Dirac-Fock potential. Second-order Coulomb and Breit-Coulomb interactions are included. Correction for the frequency dependence of the Breit interaction is taken into account in lowest order. The Lamb shift correction to energies is also included in lowest order. Intrinsic particle-particle-hole contributions to energies are found to be 20 30 % of the sum of one- and two-body contributions. Transition rates and line strengths are calculated for the 3l-4l' electric-dipole (E1) transitions in Cu-like ions with nuclear charge Z=30 100. RMBPT including the Breit interaction is used to evaluate retarded E1 matrix elements in length and velocity forms. First-order RMBPT is used to obtain intermediate coupling coefficients, and second-order RMBPT is used to calculate transition matrix elements. A detailed discussion of the various contributions to the dipole- matrix elements and energy levels is given for copperlike tungsten (Z=74). The transition energies used in the calculation of oscillator strengths and transition rates are from second-order RMBPT. Trends of the transition rates as functions of Z are illustrated graphically for selected transitions. Comparisons are made with available experimental data. These atomic data are important in the modeling of M-shell radiation spectra of heavy ions generated in electron-beam ion trap experiments and in M-shell diagnostics of plasmas.

  9. Progress Towards the Accurate Calculation of Anharmonic Vibrational States of Fluxional Molecules and Clusters Without a Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Petit, Andrew S.; McCoy, Anne B.

    2011-06-01

    The accurate calculation of anharmonic vibrational states of highly fluxional systems is complicated by the need to first obtain the full-dimensional potential energy surface(PES). Although commonly exploited as a way around this problem, grid-based methodologies scale exponentially with system size while reduced dimensional approaches are highly system dependent, both in terms of the details of their application and in terms of their suitability. Moreover, the achievement of converged variational calculations of highly anharmonic systems is complicated by the necessity of using a very large basis and hence the construction and diagonalization of enormous Hamiltonian matrices. We report here our recent efforts to develop an algorithm capable of accurately calculating anharmonic vibrational energies, even for very floppy systems, without first obtaining a PES and using only a handful of basis functions per degree of freedom. More specifically, the potential energy and G-matrix elements are calculated on a set of points obtained from a Monte Carlo sampling of the most important regions of configuration space, allowing for a significant reduction in the number of required sampling points. The Hamiltonian matrix is then constructed using an evolving basis which, with each iteration, captures the effect of building H from an ever-expanding basis despite the fact that the actual dimensionality of H is fixed throughout the calculation. This latter property of the algorithm also greatly reduces the size of basis needed for the calculation relative to more traditional variational approaches. The results obtained from the application of our method to several test systems, including ion water complexes, will be reported along with its observed convergence properties.

  10. Fully Coriolis-coupled quantum studies of the H + O2 (upsilon i = 0-2, j i = 0,1) --> OH + O reaction on an accurate potential energy surface: integral cross sections and rate constants.

    PubMed

    Lin, Shi Ying; Sun, Zhigang; Guo, Hua; Zhang, Dong Hui; Honvault, Pascal; Xie, Daiqian; Lee, Soo-Y

    2008-01-31

    We present accurate quantum calculations of the integral cross section and rate constant for the H + O2 --> OH + O combustion reaction on a recently developed ab initio potential energy surface using parallelized time-dependent and Chebyshev wavepacket methods. Partial wave contributions up to J = 70 were computed with full Coriolis coupling, which enabled us to obtain the initial state-specified integral cross sections up to 2.0 eV of the collision energy and thermal rate constants up to 3000 K. The integral cross sections show a large reaction threshold due to the quantum endothermicity of the reaction, and they monotonically increase with the collision energy. As a result, the temperature dependence of the rate constant is of the Arrhenius type. In addition, it was found that reactivity is enhanced by reactant vibrational excitation. The calculated thermal rate constant shows a significant improvement over that obtained on the DMBE IV potential, but it still underestimates the experimental consensus.

  11. Accurate ab initio potential energy surface, thermochemistry, and dynamics of the F- + CH3F SN2 and proton-abstraction reactions

    NASA Astrophysics Data System (ADS)

    Szabó, István; Telekes, Hajnalka; Czakó, Gábor

    2015-06-01

    We develop a full-dimensional global analytical potential energy surface (PES) for the F- + CH3F reaction by fitting about 50 000 energy points obtained by an explicitly correlated composite method based on the second-order Møller-Plesset perturbation-F12 and coupled-cluster singles, doubles, and perturbative triples-F12a methods and the cc-pVnZ-F12 [n = D, T] basis sets. The PES accurately describes the (a) back-side attack Walden inversion mechanism involving the pre- and post-reaction (b) ion-dipole and (c) hydrogen-bonded complexes, the configuration-retaining (d) front-side attack and (e) double-inversion substitution pathways, as well as (f) the proton-abstraction channel. The benchmark quality relative energies of all the important stationary points are computed using the focal-point analysis (FPA) approach considering electron correlation up to coupled-cluster singles, doubles, triples, and perturbative quadruples method, extrapolation to the complete basis set limit, core-valence correlation, and scalar relativistic effects. The FPA classical(adiabatic) barrier heights of (a), (d), and (e) are -0.45(-0.61), 46.07(45.16), and 29.18(26.07) kcal mol-1, respectively, the dissociation energies of (b) and (c) are 13.81(13.56) and 13.73(13.52) kcal mol-1, respectively, and the endothermicity of (f) is 42.54(38.11) kcal mol-1. Quasiclassical trajectory computations of cross sections, scattering (θ) and initial attack (α) angle distributions, as well as translational and internal energy distributions are performed for the F- + CH3F(v = 0) reaction using the new PES. Apart from low collision energies (Ecoll), the SN2 excitation function is nearly constant, the abstraction cross sections rapidly increase with Ecoll from a threshold of ˜40 kcal mol-1, and retention trajectories via double inversion are found above Ecoll = ˜ 30 kcal mol-1, and at Ecoll = ˜ 50 kcal mol-1, the front-side attack cross sections start to increase very rapidly. At low Ecoll, the

  12. Accurate ab initio potential energy surface, thermochemistry, and dynamics of the F(-) + CH3F SN2 and proton-abstraction reactions.

    PubMed

    Szabó, István; Telekes, Hajnalka; Czakó, Gábor

    2015-06-28

    We develop a full-dimensional global analytical potential energy surface (PES) for the F(-) + CH3F reaction by fitting about 50 000 energy points obtained by an explicitly correlated composite method based on the second-order Møller-Plesset perturbation-F12 and coupled-cluster singles, doubles, and perturbative triples-F12a methods and the cc-pVnZ-F12 [n = D, T] basis sets. The PES accurately describes the (a) back-side attack Walden inversion mechanism involving the pre- and post-reaction (b) ion-dipole and (c) hydrogen-bonded complexes, the configuration-retaining (d) front-side attack and (e) double-inversion substitution pathways, as well as (f) the proton-abstraction channel. The benchmark quality relative energies of all the important stationary points are computed using the focal-point analysis (FPA) approach considering electron correlation up to coupled-cluster singles, doubles, triples, and perturbative quadruples method, extrapolation to the complete basis set limit, core-valence correlation, and scalar relativistic effects. The FPA classical(adiabatic) barrier heights of (a), (d), and (e) are -0.45(-0.61), 46.07(45.16), and 29.18(26.07) kcal mol(-1), respectively, the dissociation energies of (b) and (c) are 13.81(13.56) and 13.73(13.52) kcal mol(-1), respectively, and the endothermicity of (f) is 42.54(38.11) kcal mol(-1). Quasiclassical trajectory computations of cross sections, scattering (θ) and initial attack (α) angle distributions, as well as translational and internal energy distributions are performed for the F(-) + CH3F(v = 0) reaction using the new PES. Apart from low collision energies (Ecoll), the SN2 excitation function is nearly constant, the abstraction cross sections rapidly increase with Ecoll from a threshold of ∼40 kcal mol(-1), and retention trajectories via double inversion are found above Ecoll = ∼ 30 kcal mol(-1), and at Ecoll = ∼ 50 kcal mol(-1), the front-side attack cross sections start to increase very rapidly. At

  13. Accurate ab initio potential energy surface, thermochemistry, and dynamics of the F(-) + CH3F SN2 and proton-abstraction reactions.

    PubMed

    Szabó, István; Telekes, Hajnalka; Czakó, Gábor

    2015-06-28

    We develop a full-dimensional global analytical potential energy surface (PES) for the F(-) + CH3F reaction by fitting about 50 000 energy points obtained by an explicitly correlated composite method based on the second-order Møller-Plesset perturbation-F12 and coupled-cluster singles, doubles, and perturbative triples-F12a methods and the cc-pVnZ-F12 [n = D, T] basis sets. The PES accurately describes the (a) back-side attack Walden inversion mechanism involving the pre- and post-reaction (b) ion-dipole and (c) hydrogen-bonded complexes, the configuration-retaining (d) front-side attack and (e) double-inversion substitution pathways, as well as (f) the proton-abstraction channel. The benchmark quality relative energies of all the important stationary points are computed using the focal-point analysis (FPA) approach considering electron correlation up to coupled-cluster singles, doubles, triples, and perturbative quadruples method, extrapolation to the complete basis set limit, core-valence correlation, and scalar relativistic effects. The FPA classical(adiabatic) barrier heights of (a), (d), and (e) are -0.45(-0.61), 46.07(45.16), and 29.18(26.07) kcal mol(-1), respectively, the dissociation energies of (b) and (c) are 13.81(13.56) and 13.73(13.52) kcal mol(-1), respectively, and the endothermicity of (f) is 42.54(38.11) kcal mol(-1). Quasiclassical trajectory computations of cross sections, scattering (θ) and initial attack (α) angle distributions, as well as translational and internal energy distributions are performed for the F(-) + CH3F(v = 0) reaction using the new PES. Apart from low collision energies (Ecoll), the SN2 excitation function is nearly constant, the abstraction cross sections rapidly increase with Ecoll from a threshold of ∼40 kcal mol(-1), and retention trajectories via double inversion are found above Ecoll = ∼ 30 kcal mol(-1), and at Ecoll = ∼ 50 kcal mol(-1), the front-side attack cross sections start to increase very rapidly. At

  14. The Cr(+)-D(2) cation complex: Accurate experimental dissociation energy, intermolecular bond length, and vibrational parameters.

    PubMed

    Dryza, V; Bieske, E J

    2009-10-28

    The infrared spectrum of the T-shaped (52)Cr(+)-D(2) complex is measured over the 2742-2820 cm(-1) range by detecting Cr(+) photofragments. The main band, due to the D-D stretch excitation, is shifted at 215 cm(-1) to lower energy from the Q(0) (1) transition of the free D(2) molecule and displays clearly resolved rovibrational transitions. Observation of a photodissociation onset for the N(')=8 rotational level is used to infer that the dissociation energy of Cr(+)-D(2), with respect to ground-state Cr(+) and D(2) fragments, lies between 2839.7 and 2856.9 cm(-1). Perturbations to the upper state levels are presumed to arise from interactions with quasibound combination levels involving the intermolecular stretch and bend vibrational modes. A vibrationally averaged Cr(+)...D(2) separation of 2.023 A and an estimate of 394 cm(-1) for the intermolecular harmonic stretching frequency are derived from the measured rotational constants.

  15. The Cr+-D2 cation complex: Accurate experimental dissociation energy, intermolecular bond length, and vibrational parameters

    NASA Astrophysics Data System (ADS)

    Dryza, V.; Bieske, E. J.

    2009-10-01

    The infrared spectrum of the T-shaped C52r+-D2 complex is measured over the 2742-2820 cm-1 range by detecting Cr+ photofragments. The main band, due to the D-D stretch excitation, is shifted at 215 cm-1 to lower energy from the Q01 transition of the free D2 molecule and displays clearly resolved rovibrational transitions. Observation of a photodissociation onset for the N'=8 rotational level is used to infer that the dissociation energy of Cr+-D2, with respect to ground-state Cr+ and D2 fragments, lies between 2839.7 and 2856.9 cm-1. Perturbations to the upper state levels are presumed to arise from interactions with quasibound combination levels involving the intermolecular stretch and bend vibrational modes. A vibrationally averaged Cr+⋯D2 separation of 2.023 Å and an estimate of 394 cm-1 for the intermolecular harmonic stretching frequency are derived from the measured rotational constants.

  16. Formation of H{sub 2} from internally heated polycyclic aromatic hydrocarbons: Excitation energy dependence

    SciTech Connect

    Chen, T. E-mail: henning@fysik.su.se; Gatchell, M.; Stockett, M. H.; Schmidt, H. T.; Cederquist, H.; Zettergren, H. E-mail: henning@fysik.su.se; Delaunay, R.; Rousseau, P.; Adoui, L.; Domaracka, A.; Huber, B. A.; Tielens, A. G. G. M.

    2015-04-14

    We have investigated the effectiveness of molecular hydrogen (H{sub 2}) formation from Polycyclic Aromatic Hydrocarbons (PAHs) which are internally heated by collisions with keV ions. The present and earlier experimental results are analyzed in view of molecular structure calculations and a simple collision model. We estimate that H{sub 2} formation becomes important for internal PAH temperatures exceeding about 2200 K, regardless of the PAH size and the excitation agent. This suggests that keV ions may effectively induce such reactions, while they are unlikely due to, e.g., absorption of single photons with energies below the Lyman limit. The present analysis also suggests that H{sub 2} emission is correlated with multi-fragmentation processes, which means that the [PAH-2H]{sup +} peak intensities in the mass spectra may not be used for estimating H{sub 2}-formation rates.

  17. Excitation of the copper resonance lines by low-energy electrons

    NASA Astrophysics Data System (ADS)

    Flynn, Connor; Wei, Zuyi; Stumpf, Bernhard

    1993-08-01

    The optical-excitation-function method has been used in a crossed-atom and electron-beam arrangement to measure the electron-impact cross section of the copper 4 2P-->4 2S resonance lines (324.8, 327.4 nm) from threshold (3.8 eV) to 8 eV. Relative experimental cross-section data are normalized at an energy of 1000 eV with respect to first Born theory that includes the 4 2S-->4 2P resonance transition with an oscillator strength of 0.652 and cascading from the (3d10nd)2D states with n=4,...,10. The measured Cu 4 2S-->4 2P cross section is compared with recent theoretical calculations in close-coupling approximation. Very good agreement is found with the ten-state close-coupling theory of Scheibner and Hazi (private communication).

  18. Formation of H2 from internally heated polycyclic aromatic hydrocarbons: excitation energy dependence.

    PubMed

    Chen, T; Gatchell, M; Stockett, M H; Delaunay, R; Domaracka, A; Micelotta, E R; Tielens, A G G M; Rousseau, P; Adoui, L; Huber, B A; Schmidt, H T; Cederquist, H; Zettergren, H

    2015-04-14

    We have investigated the effectiveness of molecular hydrogen (H2) formation from Polycyclic Aromatic Hydrocarbons (PAHs) which are internally heated by collisions with keV ions. The present and earlier experimental results are analyzed in view of molecular structure calculations and a simple collision model. We estimate that H2 formation becomes important for internal PAH temperatures exceeding about 2200 K, regardless of the PAH size and the excitation agent. This suggests that keV ions may effectively induce such reactions, while they are unlikely due to, e.g., absorption of single photons with energies below the Lyman limit. The present analysis also suggests that H2 emission is correlated with multi-fragmentation processes, which means that the [PAH-2H](+) peak intensities in the mass spectra may not be used for estimating H2-formation rates.

  19. Excited baryon form-factors at high momentum transfer at CEBAF at higher energies

    SciTech Connect

    Stoler, P.

    1994-04-01

    The possibilities of measuring the properties of excited nucleons at high Q{sup 2} by means of exclusive single meson production at CEBAF with an electron energy of 8 GeV is considered. The motivation is to access short range phenomena in baryon structure, and to investigate the transition from the low Q{sup 2} non-perturbative QCD regime, where constituent quark models are valid, to higher Q{sup 2} where it is believed perturbative QCD plays an increasingly important role. It is found that high quality baryon decay angular distributions can be obtained for the most prominent states up to Q{sup 2} {approximately} 12 GeV{sup 2}/c{sup 2} using a set of moderate resolution, large solid angle magnetic spectrometers.

  20. Direct Delta-MBPT(2) method for ionization potentials, electron affinities, and excitation energies using fractional occupation numbers

    SciTech Connect

    Beste, Ariana; Vazquez-Mayagoitia, Alvaro; Ortiz, J. Vincent

    2013-01-01

    A direct method (D-Delta-MBPT(2)) to calculate second-order ionization potentials (IPs), electron affinities (EAs), and excitation energies is developed. The Delta-MBPT(2) method is defined as the correlated extension of the Delta-HF method. Energy differences are obtained by integrating the energy derivative with respect to occupation numbers over the appropriate parameter range. This is made possible by writing the second-order energy as a function of the occupation numbers. Relaxation effects are fully included at the SCF level. This is in contrast to linear response theory, which makes the D-Delta-MBPT(2) applicable not only to single excited but also higher excited states. We show the relationship of the D-Delta-MBPT(2) method for IPs and EAs to a second-order approximation of the effective Fock-space coupled-cluster Hamiltonian and a second-order electron propagator method. We also discuss the connection between the D-Delta-MBPT(2) method for excitation energies and the CIS-MP2 method. Finally, as a proof of principle, we apply our method to calculate ionization potentials and excitation energies of some small molecules. For IPs, the Delta-MBPT(2) results compare well to the second-order solution of the Dyson equation. For excitation energies, the deviation from EOM-CCSD increases when correlation becomes more important. When using the numerical integration technique, we encounter difficulties that prevented us from reaching the Delta-MBPT(2) values. Most importantly, relaxation beyond the Hartree Fock level is significant and needs to be included in future research.

  1. Low energy excitations in iridates studied with Resonant Inelastic X-ray Scattering

    NASA Astrophysics Data System (ADS)

    Liu, Xuerong

    2013-03-01

    In the iridium oxides, the strong spin-orbit coupling (SOC) of the 5d iridium electrons entangles the orbital and spin degrees of freedom, providing opportunities for exotic magnetic states with highly anisotropic exchange interactions. At the same time, the spatially extended 5d electrons are expected to have much stronger hybridization with the oxygen 2p orbitals, comparing with that in 3d transition element compounds. Both factors make crystal symmetry and local environment crucial in determining the electronic and magnetic properties of the iridates. We present here our resonant inelastic X-ray scattering (RIXS) studies of a number of octahedrally coordinated iridates with special structures, exploring these effects. In particular, for the 1-D spin 1/2 chain compound, Sr3CuIrO6, the wavefunction of the hole in the t2g manifold was reconstructed based on the RIXS spectra. Our results show that it is significantly modified from the isotropic shape expected for Jeff = 1 / 2 states in the strong SOC limit, due to the distortion of the oxygen octahedral cage. This distortion is comparable to, or smaller than, that present in most iridates and thus this work emphasizes the importance of local symmetry for the iridate families. Further, the magnetic excitations of this material were also measured. A large gap of ~30 meV, was found, comparable to the magnetic dispersion bandwidth. This is in contrast to the gapless dispersion expected for linear chain with isotropic Heisenberg exchange interaction. We also studied Na4Ir3O8 which has a hyperkagome lattice, and is a candidate quantum spin liquid. Here, a low energy continuum is observed below the d-d excitations. Optical conductivity measurements performed on the same sample and polarization dependence of the RIXS signal suggest that these excitations are magnetic in origin, agreeing with the spin-liquid state prediction. The work at Brookhaven was supported by the U.S. Department of Energy, Division of Materials Science

  2. Noise assisted excitation energy transfer in a linear model of a selectivity filter backbone strand.

    PubMed

    Bassereh, Hassan; Salari, Vahid; Shahbazi, Farhad

    2015-07-15

    In this paper, we investigate the effect of noise and disorder on the efficiency of excitation energy transfer (EET) in a N = 5 sites linear chain with 'static' dipole-dipole couplings. In fact, here, the disordered chain is a toy model for one strand of the selectivity filter backbone in ion channels. It has recently been discussed that the presence of quantum coherence in the selectivity filter is possible and can play a role in mediating ion-conduction and ion-selectivity in the selectivity filter. The question is 'how a quantum coherence can be effective in such structures while the environment of the channel is dephasing (i.e. noisy)?' Basically, we expect that the presence of the noise should have a destructive effect in the quantum transport. In fact, we show that such expectation is valid for ordered chains. However, our results indicate that introducing the dephasing in the disordered chains leads to the weakening of the localization effects, arising from the multiple back-scatterings due to the randomness, and then increases the efficiency of quantum energy transfer. Thus, the presence of noise is crucial for the enhancement of EET efficiency in disordered chains. We also show that the contribution of both classical and quantum mechanical effects are required to improve the speed of energy transfer along the chain. Our analysis may help for better understanding of fast and efficient functioning of the selectivity filters in ion channels.

  3. Sub-barrier fusion excitation function data and energy dependent Woods-Saxon potential

    NASA Astrophysics Data System (ADS)

    Gautam, Manjeet Singh

    2016-07-01

    This paper analyzed the role of intrinsic degrees of freedom of colliding nuclei in the enhancement of sub-barrier fusion cross-section data of various heavy ion fusion reactions. The influences of inelastic surface vibrations of colliding pairs are found to be dominant and their couplings result in the significantly larger fusion enhancement over the predictions of the one dimensional barrier penetration model at sub-barrier energies. The theoretical calculations are performed by using energy dependent Woods-Saxon potential model (EDWSP model) in conjunction with the one dimensional Wong formula. The effects of dominant intrinsic channels are entertained within framework of the coupled channel calculations obtained by using the code CCFULL. It is quite interesting to note that the energy dependence in Woods-Saxon potential simulates the effects of inelastic surface vibrational states of reactants wherein significantly larger value of diffuseness parameter ranging from a = 0.85 fm to a = 0.95 fm is required to address the observed fusion excitation function data of the various heavy ion fusion reactions.

  4. Characterization of one- and two-photon excitation fluorescence resonance energy transfer microscopy.

    PubMed

    Elangovan, Masilamani; Wallrabe, Horst; Chen, Ye; Day, Richard N; Barroso, Margarida; Periasamy, Ammasi

    2003-01-01

    Advances in molecular biology provide various methods to define the structure and function of the individual proteins that form the component parts of subcellular structures. The ability to see the dynamic behavior of a specific protein inside the living cell became possible through the application of advanced fluorescence resonance energy transfer (FRET) microscope techniques. The fluorophore molecule used for FRET imaging has a characteristic absorption and emission spectrum that should be considered for characterizing the FRET signal. In this article we describe the system development for the image acquisition for one- and two-photon excitation FRET microscopy. We also describe the precision FRET (PFRET) data analysis algorithm that we developed to remove spectral bleed-through and variation in the fluorophore expression level (or concentration) for the donor and acceptor molecules. The acquired images have been processed using a PFRET algorithm to calculate the energy transfer efficiency and the distance between donor and acceptor molecules. We implemented the software correction to study the organization of the apical endosome in epithelial polarized MDCK cells and dimerization of the CAATT/enhancer binding protein alpha (C/EBPalpha). For these proteins, the results revealed that the extent of correction affects the conventionally calculated energy transfer efficiency (E) and the distance (r) between donor and acceptor molecules by 38 and 9%, respectively. PMID:12543072

  5. Geometric constraints in semiclassical initial value representation calculations in Cartesian coordinates: accurate reduction in zero-point energy.

    PubMed

    Issack, Bilkiss B; Roy, Pierre-Nicholas

    2005-08-22

    An approach for the inclusion of geometric constraints in semiclassical initial value representation calculations is introduced. An important aspect of the approach is that Cartesian coordinates are used throughout. We devised an algorithm for the constrained sampling of initial conditions through the use of multivariate Gaussian distribution based on a projected Hessian. We also propose an approach for the constrained evaluation of the so-called Herman-Kluk prefactor in its exact log-derivative form. Sample calculations are performed for free and constrained rare-gas trimers. The results show that the proposed approach provides an accurate evaluation of the reduction in zero-point energy. Exact basis set calculations are used to assess the accuracy of the semiclassical results. Since Cartesian coordinates are used, the approach is general and applicable to a variety of molecular and atomic systems.

  6. The need for accurate reporting and archival of data for innovative energy conversion devices: the INE database

    SciTech Connect

    Bailey, P.G.; Grotz, T.; Hurtak, J.J.

    1998-07-01

    A methodology is presented to collect, document, and summarize the findings of the various experiments, motors, generators, devices, and demonstrations in the innovative energy conversion areas that have been reported in the past several years to produce very high-efficiency or so-called over-unity operation. The concepts of free-energy and over-unity devices are not new, and many examples of such devices have been built utilizing various forms of potential energy within the last 100 years, such as hydro-electric dams and nuclear reactors. As many such devices and experiments are currently being reported, it has become very important and necessary to collect the data available on each, cross-check the data with other researchers, and maintain an accurate and truthful accounting of the status of each device and experiment. The INE Database has become an internationally recognized summary of such data. This paper presents a complete description of this database, its location on the publicly available internet, provides detailed instruction on how to add new devices and experiments to this database, and also explains how to modify and update any of the existing data. Selection criteria based upon technical interest, and also on commercialization interest, allow these data to be easily ranked for comparison and reference.

  7. Excitation Energies with Cost-Reduced Variant of the Active-Space EOMCCSDT Method: The EOMCCSDt-3̅ Approach.

    PubMed

    Hu, Han-Shi; Kowalski, Karol

    2013-11-12

    In this paper, we discuss the performance of several simplified variants of equation-of-motion coupled cluster method (EOMCC) with iterative inclusion of singles, doubles, and active-space triples (EOMCCSDt). In particular, we explore simplified EOMCCSDt approaches that enable one to generate the triply excited amplitudes in an on-the-fly manner. The original EOMCCSDt formulation has already demonstrated great success in encapsulating the most important excited-state correlation effects due to triples. In analogy to the original EOMCCSDT-3 formulation, the proposed approach can bypass the typical bottlenecks associated with the need for storing triply excited amplitudes. In this paper, we illustrate the performance of several approximate EOMCCSDt methods, named EOMCCSDt-3̅ and EOMCCSDt-3̅, on typical benchmark systems including C2, N2, ozone, ethene, and E-butadiene molecules. These new methods yield excitation energies close to the EOMCCSDt ones. The extrapolation of excitation energies for basis sets ranging from cc-pVDZ to cc-pV6Z for N2 and C2 shows very good convergence to the experimental results for states dominated by single excitations. The performance of the EOMCCSDt-3̅x approach is also compared with the results obtained with popular CCSDR(3) and CC3 approaches. PMID:26583394

  8. Excitation and photon decay of giant multipole resonances - the role and future of medium-energy heavy ions

    SciTech Connect

    Bertrand, F.E.; Beene, J.R.; Horen, D.J.

    1988-01-01

    Inelastic scattering of medium energy heavy ions provides very large cross sections and peak-to-continuum ratios for excitation of giant resonances. For energies above about 50 MeV/nucleon, giant resonances are excited primarily through Coulomb excitation, which is indifferent to isospin, thus providing a good probe for the study of isovector giant resonances. The extremely large cross sections available from heavy ion excitation permit the study of rare decay modes of the photon decay of giant resonances following excitation by 22 and 84 MeV/nucleon /sup 17/O projectiles. The singles results at 84 MeV/nucleon yield peak cross sections for the isoscalar giant quadrupole resonance and the isovector giant dipole resonance of approximately 0.8 and 3 barns/sr, respectively. Data on the ground state decay of the isoscalar giant quadrupole and isovector giant dipole resonances are presented and compared with calculations. Decays to low-lying excited states are also discussed. Preliminary results from an experiment to isolate the /sup 208/Pb isovector quadrupole resonance using its gamma decay are presented.

  9. LiF TLD-100 as a Dosimeter in High Energy Proton Beam Therapy-Can It Yield Accurate Results?

    SciTech Connect

    Zullo, John R. Kudchadker, Rajat J.; Zhu, X. Ronald; Sahoo, Narayan; Gillin, Michael T.

    2010-04-01

    In the region of high-dose gradients at the end of the proton range, the stopping power ratio of the protons undergoes significant changes, allowing for a broad spectrum of proton energies to be deposited within a relatively small volume. Because of the potential linear energy transfer dependence of LiF TLD-100 (thermolumescent dosimeter), dose measurements made in the distal fall-off region of a proton beam may be less accurate than those made in regions of low-dose gradients. The purpose of this study is to determine the accuracy and precision of dose measured using TLD-100 for a pristine Bragg peak, particularly in the distal fall-off region. All measurements were made along the central axis of an unmodulated 200-MeV proton beam from a Probeat passive beam-scattering proton accelerator (Hitachi, Ltd., Tokyo, Japan) at varying depths along the Bragg peak. Measurements were made using TLD-100 powder flat packs, placed in a virtual water slab phantom. The measurements were repeated using a parallel plate ionization chamber. The dose measurements using TLD-100 in a proton beam were accurate to within {+-}5.0% of the expected dose, previously seen in our past photon and electron measurements. The ionization chamber and the TLD relative dose measurements agreed well with each other. Absolute dose measurements using TLD agreed with ionization chamber measurements to within {+-} 3.0 cGy, for an exposure of 100 cGy. In our study, the differences in the dose measured by the ionization chamber and those measured by TLD-100 were minimal, indicating that the accuracy and precision of measurements made in the distal fall-off region of a pristine Bragg peak is within the expected range. Thus, the rapid change in stopping power ratios at the end of the range should not affect such measurements, and TLD-100 may be used with confidence as an in vivo dosimeter for proton beam therapy.

  10. Evidence of additional excitation energy transfer pathways in the phycobiliprotein antenna system of Acaryochloris marina.

    PubMed

    Nganou, A C; David, L; Adir, N; Pouhe, D; Deen, M J; Mkandawire, M

    2015-02-01

    To improve the energy conversion efficiency of solar organic cells, the clue may lie in the development of devices inspired by an efficient light harvesting mechanism of some aquatic photosynthetic microorganisms that are adapted to low light intensity. Consequently, we investigated the pathways of excitation energy transfer (EET) from successive light harvesting pigments to the low energy level inside the phycobiliprotein antenna system of Acaryochloris marina, a cyanobacterium, using a time resolved absorption difference spectroscopy with a resolution time of 200 fs. The objective was to understand the actual biochemical process and pathways that determine the EET mechanism. Anisotropy of the EET pathway was calculated from the absorption change trace in order to determine the contribution of excitonic coupling. The results reveal a new electron energy relaxation pathway of 14 ps inside the phycocyanin component, which runs from phycocyanin to the terminal emitter. The bleaching of the 660 nm band suggests a broader absorption of the terminal emitter between 660 nm and 675 nm. Further, there are trimer depolarization kinetics of 450 fs and 500 fs in high and low ionic strength, respectively, which arise from the relaxation of the β84 and α84 in adjacent monomers of phycocyanin. Under conditions of low ionic strength buffer solution, the evolution of the kinetic amplitude during the depolarization of the trimer is suggestive of trimer conservation within the phycocyanin hexamer. The anisotropy values were 0.38 and 0.40 in high and in low ionic strength, respectively, indicating that there is no excitonic delocalization in the high energy level of phycocyanin hexamers.

  11. Energy levels, Auger branching ratios, and radiative rates of the core-excited states of B-like carbon

    SciTech Connect

    Sun Yan; Gou Bingcong; Chen Feng

    2011-09-28

    Energy levels, Auger branching ratios, and radiative rates of the core-excited states of B-like carbon are calculated by the saddle-point variation and saddle-point complex-rotation methods. Relativistic and mass polarization corrections are included using first-order perturbation theory. Calculated Auger channel energies and branching ratios are used to identify high-resolution Auger spectrum in the 300-keV C{sup +}{yields} CH{sub 4} collision experiment. It is found that Auger decay of these five-electron core-excited states gives significant contributions to Auger spectrum in the range of 238-280 eV.

  12. Vibrational excitation in CO by electron impact in the energy range 10-90 eV.

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Truhlar, D. G.; Williams, W.; Trajmar, S.

    1972-01-01

    The ratio of the scattering intensity for the v double prime = 1 excitation to the elastic scattering intensity at 40- and 80-deg scattering angles has been determined for 10- to 90-eV impact energies for electron scattering by CO. These ratio curves exhibit broad peaks near 20-eV impact energy which cannot be accounted for by plane-wave calculations based on potential scattering models. The peaks are indicative of a resonant excitation process (or processes) in the v double prime = 1 channel in the range from 15 to 25 eV.

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

    PubMed

    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. Influence of environment induced correlated fluctuations in electronic coupling on coherent excitation energy transfer dynamics in model photosynthetic systems

    NASA Astrophysics Data System (ADS)

    Huo, Pengfei; Coker, David F.

    2012-03-01

    Two-dimensional photon-echo experiments indicate that excitation energy transfer between chromophores near the reaction center of the photosynthetic purple bacterium Rhodobacter sphaeroides occurs coherently with decoherence times of hundreds of femtoseconds, comparable to the energy transfer time scale in these systems. The original explanation of this observation suggested that correlated fluctuations in chromophore excitation energies, driven by large scale protein motions could result in long lived coherent energy transfer dynamics. However, no significant site energy correlation has been found in recent molecular dynamics simulations of several model light harvesting systems. Instead, there is evidence of correlated fluctuations in site energy-electronic coupling and electronic coupling-electronic coupling. The roles of these different types of correlations in excitation energy transfer dynamics are not yet thoroughly understood, though the effects of site energy correlations have been well studied. In this paper, we introduce several general models that can realistically describe the effects of various types of correlated fluctuations in chromophore properties and systematically study the behavior of these models using general methods for treating dissipative quantum dynamics in complex multi-chromophore systems. The effects of correlation between site energy and inter-site electronic couplings are explored in a two state model of excitation energy transfer between the accessory bacteriochlorophyll and bacteriopheophytin in a reaction center system and we find that these types of correlated fluctuations can enhance or suppress coherence and transfer rate simultaneously. In contrast, models for correlated fluctuations in chromophore excitation energies show enhanced coherent dynamics but necessarily show decrease in excitation energy transfer rate accompanying such coherence enhancement. Finally, for a three state model of the Fenna-Matthews-Olsen light

  15. Energy transfer in aminonaphthalimide-boron-dipyrromethene (BODIPY) dyads upon one- and two-photon excitation: applications for cellular imaging.

    PubMed

    Collado, Daniel; Remón, Patricia; Vida, Yolanda; Najera, Francisco; Sen, Pratik; Pischel, Uwe; Perez-Inestrosa, Ezequiel

    2014-03-01

    Aminonaphthalimide-BODIPY energy transfer cassettes were found to show very fast (kEET ≈ 10(10)-10(11) s(-1) and efficient BODIPY fluorescence sensitization. This was observed upon one- and two-photon excitation, which extends the application range of the investigated bichromophoric dyads in terms of accessible excitation wavelengths. In comparison with the direct excitation of the BODIPY chromophore, the two-photon absorption cross-section δ of the dyads is significantly incremented by the presence of the aminonaphthalimide donor [δ ≈ 10 GM for the BODIPY versus 19-26 GM in the dyad at λ(exc)=840 nm; 1 GM (Goeppert-Mayer unit)=10(-50) cm(4) smolecule(-1) photon-(1)]. The electronic decoupling of the donor and acceptor, which is a precondition for the energy transfercassette concept, was demonstrated by time-dependent density functional theory calculations. The applicability of the new probes in the one- and twophoton excitation mode was demonstrated in a proof-of-principle approach in the fluorescence imaging of HeLa cells. To the best of our knowledge, this is the first demonstration of the merging of multiphoton excitation with the energy transfer cassette concept for a BODIPY-containing dyad. PMID:24730057

  16. Energy transfer in aminonaphthalimide-boron-dipyrromethene (BODIPY) dyads upon one- and two-photon excitation: applications for cellular imaging.

    PubMed

    Collado, Daniel; Remón, Patricia; Vida, Yolanda; Najera, Francisco; Sen, Pratik; Pischel, Uwe; Perez-Inestrosa, Ezequiel

    2014-03-01

    Aminonaphthalimide-BODIPY energy transfer cassettes were found to show very fast (kEET ≈ 10(10)-10(11) s(-1) and efficient BODIPY fluorescence sensitization. This was observed upon one- and two-photon excitation, which extends the application range of the investigated bichromophoric dyads in terms of accessible excitation wavelengths. In comparison with the direct excitation of the BODIPY chromophore, the two-photon absorption cross-section δ of the dyads is significantly incremented by the presence of the aminonaphthalimide donor [δ ≈ 10 GM for the BODIPY versus 19-26 GM in the dyad at λ(exc)=840 nm; 1 GM (Goeppert-Mayer unit)=10(-50) cm(4) smolecule(-1) photon-(1)]. The electronic decoupling of the donor and acceptor, which is a precondition for the energy transfercassette concept, was demonstrated by time-dependent density functional theory calculations. The applicability of the new probes in the one- and twophoton excitation mode was demonstrated in a proof-of-principle approach in the fluorescence imaging of HeLa cells. To the best of our knowledge, this is the first demonstration of the merging of multiphoton excitation with the energy transfer cassette concept for a BODIPY-containing dyad.

  17. Theoretical Studies of Possible Synthetic Routes for the High Energy Density Material Td N4: Excited Electronic States

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Dateo, Christopher E.

    2001-01-01

    Vertical electronic excitation energies for single states have been computed for the high energy density material (HEDM) Td N4 in order to assess possible synthetic routes that originate from excited electronic states of N2 molecules. Several ab initio theoretical approaches have been used, including complete active space self-consistent field (CASSCF), state averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D)) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD), which is the highest level of theory employed. Standard double zeta polarized (DZP) and triple zeta double polarized (TZ2P) one-particle basis sets were used. The CASSCF calculations are found to overestimate the excitation energies, while the SA-CASSCF approach rectifies this error to some extent, but not completely. The accuracy of the CIS calculations varied depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results are in generally good agreement. Based on the LRCCSD calculations, the lowest six excited singlet states are 9.35(l(sup)T1), 10.01(l(sup)T2), 10.04(1(sup)A2), 10.07(1(sup)E), 10.12(2(sup)T1), and 10.42(2(sup)T2) eV above the ground state, respectively. Comparison of these excited state energies with the energies of possible excited states of N2+N2 fragments, leads us to propose that the most likely synthetic route for Td N4 involving this mechanism arises from combination of two bound quintet states of N2.

  18. Accurate all-electron G0W0 quasiparticle energies employing the full-potential augmented plane-wave method

    NASA Astrophysics Data System (ADS)

    Nabok, Dmitrii; Gulans, Andris; Draxl, Claudia

    2016-07-01

    The G W approach of many-body perturbation theory has become a common tool for calculating the electronic structure of materials. However, with increasing number of published results, discrepancies between the values obtained by different methods and codes become more and more apparent. For a test set of small- and wide-gap semiconductors, we demonstrate how to reach the numerically best electronic structure within the framework of the full-potential linearized augmented plane-wave (FLAPW) method. We first evaluate the impact of local orbitals in the Kohn-Sham eigenvalue spectrum of the underlying starting point. The role of the basis-set quality is then further analyzed when calculating the G0W0 quasiparticle energies. Our results, computed with the exciting code, are compared to those obtained using the projector-augmented plane-wave formalism, finding overall good agreement between both methods. We also provide data produced with a typical FLAPW basis set as a benchmark for other G0W0 implementations.

  19. YIELDS OF IONS AND EXCITED STATES IN NONPOLAR LIQUIDS EXPOSED TO X-RAYS OF 1 TO 30 KEV ENERGY

    SciTech Connect

    HOLROYD,R.A.

    1999-08-18

    When x-rays from a synchrotron source are absorbed in a liquid, the x-ray energy (E{sub x}) is converted by the photoelectric effect into the kinetic energy of the electrons released. For hydrocarbons, absorption by the K-electrons of carbon dominates. Thus the energy of the photoelectron (E{sub pe}) is E{sub x}-E{sub b}, where E{sub b} is the K-shell binding energy of carbon. Additional electrons with energy equal to E{sub b} is released in the Auger process that fills the hole in the K-shell. These energetic electrons will produce many ionizations, excitations and products. The consequences of the high density of ionizations and excitations along the track of the photoelectron and special effects near the K-edge are examined here.

  20. The effect of electron beams on cyclotron maser emission excited by lower-energy cutoffs

    NASA Astrophysics Data System (ADS)

    Zhao, G. Q.; Feng, H. Q.; Wu, D. J.

    2016-05-01

    Electron-cyclotron maser (ECM) is one of the most important emission mechanisms in astrophysics and can be excited efficiently by lower-energy cutoffs of power-law electrons. These non-thermal electrons probably propagate as a directed collimated beam along ambient magnetic fields. This paper investigates the ECM, in which the effect of electron beams is emphasized. Results show the dependence of emission properties of the ECM on the beam feature. The maximum growth rate of the extraordinary mode (X2) rapidly decreases as the beam momentum increases, while the growth rate of the ordinary mode (O1) changes slightly. In particular, the ordinary mode can overcome the extraordinary mode and becomes the fastest growth mode once the beam momentum is large enough. This research presents an extension of the conventional studies on ECM driven by lower-energy cutoffs and may be helpful to understand better the emission process of solar type I radio bursts, which are dominated by the ordinary mode emission.

  1. Ground state spin and excitation energies in half-filled Lieb lattices

    NASA Astrophysics Data System (ADS)

    Ţolea, M.; Niţǎ, M.

    2016-10-01

    We present detailed spectral calculations for small Lieb lattices having up to N =4 number of cells, in the regime of half-filling, an instance of particular relevance for the nanomagnetism of discrete systems such as quantum dot arrays, due to the degenerate levels at midspectrum. While for the Hubbard interaction model—and even number of sites—the ground state spin is given by the Lieb theorem, the inclusion of long-range interaction—or odd number of sites—makes the spin state not known a priori, which justifies our approach. We calculate also the excitation energies, which are of experimental importance, and find significant variation induced by the interaction potential. One obtains insights on the mechanisms involved that impose as ground state the Lieb state with lower spin rather than the Hund one with maximum spin for the degenerate levels, showing this in the first and second orders of the interaction potential for the smaller lattices. The analytical results agree with the numerical ones, which are performed by exact diagonalization calculations or by a combined mean-field and configuration interaction method. While the Lieb state is always lower in energy than the Hund state, for strong long-range interaction, when possible, another minimal spin state is imposed as ground state.

  2. A versatile phenomenological model for the S-shaped temperature dependence of photoluminescence energy for an accurate determination of the exciton localization energy in bulk and quantum well structures

    NASA Astrophysics Data System (ADS)

    Dixit, V. K.; Porwal, S.; Singh, S. D.; Sharma, T. K.; Ghosh, Sandip; Oak, S. M.

    2014-02-01

    Temperature dependence of the photoluminescence (PL) peak energy of bulk and quantum well (QW) structures is studied by using a new phenomenological model for including the effect of localized states. In general an anomalous S-shaped temperature dependence of the PL peak energy is observed for many materials which is usually associated with the localization of excitons in band-tail states that are formed due to potential fluctuations. Under such conditions, the conventional models of Varshni, Viña and Passler fail to replicate the S-shaped temperature dependence of the PL peak energy and provide inconsistent and unrealistic values of the fitting parameters. The proposed formalism persuasively reproduces the S-shaped temperature dependence of the PL peak energy and provides an accurate determination of the exciton localization energy in bulk and QW structures along with the appropriate values of material parameters. An example of a strained InAs0.38P0.62/InP QW is presented by performing detailed temperature and excitation intensity dependent PL measurements and subsequent in-depth analysis using the proposed model. Versatility of the new formalism is tested on a few other semiconductor materials, e.g. GaN, nanotextured GaN, AlGaN and InGaN, which are known to have a significant contribution from the localized states. A quantitative evaluation of the fractional contribution of the localized states is essential for understanding the temperature dependence of the PL peak energy of bulk and QW well structures having a large contribution of the band-tail states.

  3. Accurate relativistic energy-consistent pseudopotentials for the superheavy elements 111 to 118 including quantum electrodynamic effects

    NASA Astrophysics Data System (ADS)

    Hangele, Tim; Dolg, Michael; Hanrath, Michael; Cao, Xiaoyan; Schwerdtfeger, Peter

    2012-06-01

    Energy-consistent two-component semi-local pseudopotentials for the superheavy elements with atomic numbers 111-118 have been adjusted to fully relativistic multi-configuration Dirac-Hartree-Fock calculations based on the Dirac-Coulomb Hamiltonian, including perturbative corrections for the frequency-dependent Breit interaction in the Coulomb gauge and lowest-order quantum electrodynamic effects. The pseudopotential core includes 92 electrons corresponding to the configuration [Xe]4f 145d105f 14. The parameters for the elements 111-118 were fitted by two-component multi-configuration Hartree-Fock calculations in the intermediate coupling scheme to the total energies of 267 up to 797 J levels arising from 31 up to 62 nonrelativistic configurations, including also anionic and highly ionized states, with mean absolute errors clearly below 0.02 eV for averages corresponding to nonrelativistic configurations. Primitive basis sets for one- and two-component pseudopotential calculations have been optimized for the ground and excited states and exhibit finite basis set errors with respect to the finite-difference Hartree-Fock limit below 0.01 and 0.02 eV, respectively. General contraction schemes have been applied to obtain valence basis sets of polarized valence double- to quadruple-zeta quality. Results of atomic test calculations in the intermediate coupling scheme at the Fock-space coupled-cluster level are in good agreement with those of corresponding fully relativistic all-electron calculations based on the Dirac-Coulomb-Breit Hamiltonian. The results demonstrate besides the well-known need of a relativistic treatment at the Dirac-Coulomb level also the necessity to include higher-order corrections for the superheavy elements.

  4. Accurate relativistic energy-consistent pseudopotentials for the superheavy elements 111 to 118 including quantum electrodynamic effects.

    PubMed

    Hangele, Tim; Dolg, Michael; Hanrath, Michael; Cao, Xiaoyan; Schwerdtfeger, Peter

    2012-06-01

    Energy-consistent two-component semi-local pseudopotentials for the superheavy elements with atomic numbers 111-118 have been adjusted to fully relativistic multi-configuration Dirac-Hartree-Fock calculations based on the Dirac-Coulomb Hamiltonian, including perturbative corrections for the frequency-dependent Breit interaction in the Coulomb gauge and lowest-order quantum electrodynamic effects. The pseudopotential core includes 92 electrons corresponding to the configuration [Xe]4f(14)5d(10)5f(14). The parameters for the elements 111-118 were fitted by two-component multi-configuration Hartree-Fock calculations in the intermediate coupling scheme to the total energies of 267 up to 797 J levels arising from 31 up to 62 nonrelativistic configurations, including also anionic and highly ionized states, with mean absolute errors clearly below 0.02 eV for averages corresponding to nonrelativistic configurations. Primitive basis sets for one- and two-component pseudopotential calculations have been optimized for the ground and excited states and exhibit finite basis set errors with respect to the finite-difference Hartree-Fock limit below 0.01 and 0.02 eV, respectively. General contraction schemes have been applied to obtain valence basis sets of polarized valence double- to quadruple-zeta quality. Results of atomic test calculations in the intermediate coupling scheme at the Fock-space coupled-cluster level are in good agreement with those of corresponding fully relativistic all-electron calculations based on the Dirac-Coulomb-Breit Hamiltonian. The results demonstrate besides the well-known need of a relativistic treatment at the Dirac-Coulomb level also the necessity to include higher-order corrections for the superheavy elements. PMID:22697528

  5. Accurate energy bands calculated by the hybrid quasiparticle self-consistent GW method implemented in the ecalj package

    NASA Astrophysics Data System (ADS)

    Deguchi, Daiki; Sato, Kazunori; Kino, Hiori; Kotani, Takao

    2016-05-01

    We have recently implemented a new version of the quasiparticle self-consistent GW (QSGW) method in the ecalj package released at http://github.com/tkotani/ecalj. Since the new version of the ecalj package is numerically stable and more accurate than the previous versions, we can perform calculations easily without being bothered with tuning input parameters. Here we examine its ability to describe energy band properties, e.g., band-gap energy, eigenvalues at special points, and effective mass, for a variety of semiconductors and insulators. We treat C, Si, Ge, Sn, SiC (in 2H, 3C, and 4H structures), (Al, Ga, In) × (N, P, As, Sb), (Zn, Cd, Mg) × (O, S, Se, Te), SiO2, HfO2, ZrO2, SrTiO3, PbS, PbTe, MnO, NiO, and HgO. We propose that a hybrid QSGW method, where we mix 80% of QSGW and 20% of LDA, gives universally good agreement with experiments for these materials.

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

    PubMed

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

    2015-06-18

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

  7. Excitation laser energy dependence of surface-enhanced fluorescence showing plasmon-induced ultrafast electronic dynamics in dye molecules

    NASA Astrophysics Data System (ADS)

    Itoh, Tamitake; Yamamoto, Yuko S.; Tamaru, Hiroharu; Biju, Vasudevanpillai; Murase, Norio; Ozaki, Yukihiro

    2013-06-01

    We find unique properties accompanying surface-enhanced fluorescence (SEF) from dye molecules adsorbed on Ag nanoparticle aggregates, which generate surface-enhanced Raman scattering. The properties are observed in excitation laser energy dependence of SEF after excluding plasmonic spectral modulation in SEF. The unique properties are large blue shifts of fluorescence spectra, deviation of ratios between anti-Stokes SEF intensity and Stokes from those of normal fluorescence, super-broadening of Stokes spectra, and returning to original fluorescence by lower energy excitation. We elucidate that these properties are induced by electromagnetic enhancement of radiative decay rates exceeding the vibrational relaxation rates within an electronic excited state, which suggests that molecular electronic dynamics in strong plasmonic fields can be largely deviated from that in free space.

  8. Accurate calculation of the absolute free energy of binding for drug molecules† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc02678d Click here for additional data file.

    PubMed Central

    Aldeghi, Matteo; Heifetz, Alexander; Bodkin, Michael J.; Knapp, Stefan

    2016-01-01

    Accurate prediction of binding affinities has been a central goal of computational chemistry for decades, yet remains elusive. Despite good progress, the required accuracy for use in a drug-discovery context has not been consistently achieved for drug-like molecules. Here, we perform absolute free energy calculations based on a thermodynamic cycle for a set of diverse inhibitors binding to bromodomain-containing protein 4 (BRD4) and demonstrate that a mean absolute error of 0.6 kcal mol–1 can be achieved. We also show a similar level of accuracy (1.0 kcal mol–1) can be achieved in pseudo prospective approach. Bromodomains are epigenetic mark readers that recognize acetylation motifs and regulate gene transcription, and are currently being investigated as therapeutic targets for cancer and inflammation. The unprecedented accuracy offers the exciting prospect that the binding free energy of drug-like compounds can be predicted for pharmacologically relevant targets. PMID:26798447

  9. Modeling of energy transfer from vibrationally excited CO2 molecules: cross sections and probabilities for kinetic modeling of atmospheres, flows, and plasmas.

    PubMed

    Lombardi, Andrea; Faginas-Lago, Noelia; Pacifici, Leonardo; Costantini, Alessandro

    2013-11-14

    We present extended applications of an established theoretical and computational machinery suitable for the study of the dynamics of CO2+CO2 collisions, focusing on vibrational energy exchange, considered over a wide range of energies and rotational temperatures. Calculations are based on quasi-classical trajectories on a potential energy function (a critical component of dynamics simulations), tailored to accurately describe the intermolecular interactions, modeled by the recently proposed bond-bond semiempirical formulation that allows the colliding molecules to be stretchable, rather than frozen at their equilibrium geometry. In a previous work, the same potential energy surface has been used to show that modifications in the geometry (and in physical properties such as polarizability and charge distribution) of the colliding partners affect the intermolecular interaction and determine the features of the energy exchange, to a large extent driven by long-range forces. As initial partitioning of the energy among the molecular degrees of freedom, we consider the excitation of the vibrational bending mode, assuming an initial rotational distribution and a rotational temperature. The role of the vibrational angular momentum is also carefully assessed. Results are obtained by portable implementations of this approach in a Grid-computing framework and on high performance platforms. Cross sections are basic ingredients to obtain rate constants of use in advanced state-to-state kinetic models, under equilibrium or nonequilibrium conditions, and this approach is suitable for gas dynamics applications to plasmas and modeling of hypersonic flows.

  10. A five-dimensional potential-energy surface for the rotational excitation of SO2 by H2 at low temperatures.

    PubMed

    Spielfiedel, A; Senent, M-L; Dayou, F; Balança, C; Cressiot-Vincent, L; Faure, A; Wiesenfeld, L; Feautrier, N

    2009-07-01

    The SO(2) molecule is detected in a large variety of astronomical objects, notably molecular clouds and star-forming regions. An accurate modeling of the observations needs a very good knowledge of the collisional excitation rates with H(2) because of competition between collisional and radiative processes that excite and quench the different rotational levels of SO(2). We report here a five-dimensional, rigid-body, interaction potential for SO(2)-H(2). As a first application, we present rate constants for excitation/de-excitation of the 31 first levels of SO(2) by para-H(2) at low temperatures. Propensity rules are discussed.

  11. Intramolecular triplet energy transfer via higher triplet excited state during stepwise two-color two-laser irradiation.

    PubMed

    Oseki, Yosuke; Fujitsuka, Mamoru; Sakamoto, Masanori; Majima, Tetsuro

    2007-10-01

    We studied the energy transfer processes in the molecular array consisting of pyrene (Py), biphenyl (Ph2), and bisphthalimidethiophene (ImT), (Py-Ph2)2-ImT, during two-color two-laser flash photolysis (2-LFP). The first laser irradiation predominantly generates ImT in the lowest triplet excited state (ImT(T1)) because of the efficient singlet energy transfer from Py in the lowest singlet excited state to ImT and, then, intersystem crossing of ImT. ImT(T1) was excited to the higher triplet excited state (Tn) with the second laser irradiation. Then, the triplet energy was rapidly transferred to Py via a two-step triplet energy transfer (TET) process through Ph2. The efficient generation of Py(T1) was suggested from the nanosecond-picosecond 2-LFP. The back-TET from Py(T1) to ImT was observed for several tens of microseconds after the second laser irradiation. The estimated intramolecular TET rate from Py(T1) to ImT was as slow as 3.1 x 104 s-1. Hence, long-lived Py(T1) was selectively and efficiently produced during the 2-LFP.

  12. The structure of the high-energy spin excitations in YBa2Cu3O6+x

    NASA Astrophysics Data System (ADS)

    Hayden, Stephen

    2005-03-01

    The most obvious feature in the magnetic excitations of high-Tc superconductors is the so-called `resonance-mode'. This mode is strongly coupled to the superconductivity, however, it has not been found in the La2-x(Ba,Sr)xCuO4 family and is not universally present in Bi2Sr2CaCu2O8+δ. Here we use inelastic neutron scattering to characterize other excitations at higher energies which may be relevant to the superconductive pairing in YBa2Cu3O6.6. We observe a square-shaped continuum of excitations in reciprocal space [1]. These excitations have energies greater than the superconducting pairing energy, are present at Tc, and have spectral weight far exceeding that of the `resonance'. The discovery of similar excitations in La2-xBaxCuO4 [2] suggests that they are a general property of the copper oxides, and a candidate for mediating the electron pairing. Our data show that the high-energy magnetic excitations in the high-temperature superconductor YBa2Cu3O6.6 consists of a continuum of scattering bounded by a square and peaked at wavevector positions Qɛ =(1/2±ɛ,1/2±ɛ) and (1/2±ɛ,1/2ɛ). A similar structure is observed in the high-energy magnetic excitations of the magnetically ordered but weakly superconducting compound La1.85Ba0.125CuO4 [2]. This suggests there is universality, both in the low-energy and the high-energy spin dynamics between two very different classes of high-Tc superconductor. [1] S.M. Hayden, H.A. Mook, P.C. Dai, T.G. Perring, and F. Dogan, Nature 429, 531-534 (2004) [2] J.M. Tranquada, H. Woo, T.G. Perring, H. Goka, G.D. Gu , G. Xu, M. Fujita, K.Yamada K, Nature 429, 534-538 (2004).

  13. Low-energy electromagnetic excitation strengths in 121Sb and 123Sb

    NASA Astrophysics Data System (ADS)

    Bryssinck, J.; Govor, L.; Bauwens, F.; Belic, D.; von Brentano, P.; de Frenne, D.; Fransen, C.; Gade, A.; Jacobs, E.; Kneissl, U.; Kohstall, C.; Linnemann, A.; Nord, A.; Pietralla, N.; Pitz, H. H.; Scheck, M.; Stedile, F.; Werner, V.

    2002-02-01

    Results are presented from nuclear resonance fluorescence experiments on the odd-mass nuclei 121Sb and 123Sb with Z=51. The improved sensitivity reached with the present NRF facility, installed at the 4.3 MV Dynamitron accelerator of the Stuttgart University, allowed the detection of huge numbers of weak photoexcitations in the stable Sb nuclei 121Sb (164 transitions) and 123Sb (83 transitions) in the energy range up to 4 MeV and 3.5 MeV, respectively. The data are compared to former results for odd-mass nuclei near the Z=50 and N=82 shell closures (117Sn, 139La, 141Pr, and 143Nd). In the odd-mass nuclei within the Z=50 region, a similar total amount of electromagnetic excitation strength below 4 MeV is found; however, in 121Sb and 123Sb (Z=51) this strength is much more fragmented than in 117Sn with a closed proton shell (Z=50).

  14. Self-Excited Fluidic Energy Harvesters with Finite-Length Cylinders

    NASA Astrophysics Data System (ADS)

    Akaydin, Huseyin; Duquesnois, Chloe; Elvin, Niell; Andreopoulos, Yiannis

    2011-11-01

    In this experimental work, we explore the possibility of using piezoelectric materials for harvesting electrical energy from fluid flow. Such harvesters may be used for powering small sensors and obviate the need for batteries and/or power lines. Piezoelectric harvesters behave as AC-coupled devices and need oscillatory motion to generate an electrical output. The harvester should be designed to be ``self-excited,'' i.e. capable of initiating and sustaining the necessary oscillations in steady and uniform flows. The present configuration consists of a piezoelectric cantilever beam with a cylindrical tip body which promotes aeroelastic vibrations induced by vortex shedding. The harvester was tested in a wind tunnel and it produced 0.1 mW of electrical power at a flow speed of about 1.19 m/s. Using strain measurements and a distributed parameter model, the harvested electrical power was predicted, and a reasonable agreement is obtained with the measurements. The magnitude and frequency of the driving aerodynamic forces were also estimated. Results were comparable with literature data on flow past oscillating cylinders. Finally, the effect of using various shapes of tip body is presented. Sponsored by NSF Grant: CBET #1033117.

  15. Potential energy curves for the ground and low-lying excited states of CuAg

    SciTech Connect

    Alizadeh, Davood; Shayesteh, Alireza E-mail: ashayesteh@ut.ac.ir; Jamshidi, Zahra E-mail: ashayesteh@ut.ac.ir

    2014-10-21

    The ground and low-lying excited states of heteronuclear diatomic CuAg are examined by multi-reference configuration interaction (MRCI) method. Relativistic effects were treated and probed in two steps. Scalar terms were considered using the spin-free DKH Hamiltonian as a priori and spin-orbit coupling was calculated perturbatively via the spin-orbit terms of the Breit-Pauli Hamiltonian based on MRCI wavefunctions. Potential energy curves of the spin-free states and their corresponding Ω components correlating with the separated atom limits {sup 2}S(Cu) + {sup 2}S(Ag) and {sup 2}D(Cu) + {sup 2}S(Ag) are obtained. The results are in fine agreement with the experimental measurements and tentative conclusions for the ion-pair B0{sup +} state are confirmed by our theoretical calculations. Illustrative results are presented to reveal the relative importance and magnitude of the scalar and spin-orbit effects on the spectroscopic properties of this molecule. Time dependent density functional theory calculations, using the LDA, BLYP, B3LYP, and SAOP functionals have been carried out for CuAg and the accuracy of TD-DFT has been compared with ab initio results.

  16. Improvement of energy efficiency via spectrum optimization of excitation sequence for multichannel simultaneously triggered airborne sonar system

    NASA Astrophysics Data System (ADS)

    Meng, Qing-Hao; Yao, Zhen-Jing; Peng, Han-Yang

    2009-12-01

    Both the energy efficiency and correlation characteristics are important in airborne sonar systems to realize multichannel ultrasonic transducers working together. High energy efficiency can increase echo energy and measurement range, and sharp autocorrelation and flat cross correlation can help eliminate cross-talk among multichannel transducers. This paper addresses energy efficiency optimization under the premise that cross-talk between different sonar transducers can be avoided. The nondominated sorting genetic algorithm-II is applied to optimize both the spectrum and correlation characteristics of the excitation sequence. The central idea of the spectrum optimization is to distribute most of the energy of the excitation sequence within the frequency band of the sonar transducer; thus, less energy is filtered out by the transducers. Real experiments show that a sonar system consisting of eight-channel Polaroid 600 series electrostatic transducers excited with 2 ms optimized pulse-position-modulation sequences can work together without cross-talk and can measure distances up to 650 cm with maximal 1% relative error.

  17. Improvement of energy efficiency via spectrum optimization of excitation sequence for multichannel simultaneously triggered airborne sonar system.

    PubMed

    Meng, Qing-Hao; Yao, Zhen-Jing; Peng, Han-Yang

    2009-12-01

    Both the energy efficiency and correlation characteristics are important in airborne sonar systems to realize multichannel ultrasonic transducers working together. High energy efficiency can increase echo energy and measurement range, and sharp autocorrelation and flat cross correlation can help eliminate cross-talk among multichannel transducers. This paper addresses energy efficiency optimization under the premise that cross-talk between different sonar transducers can be avoided. The nondominated sorting genetic algorithm-II is applied to optimize both the spectrum and correlation characteristics of the excitation sequence. The central idea of the spectrum optimization is to distribute most of the energy of the excitation sequence within the frequency band of the sonar transducer; thus, less energy is filtered out by the transducers. Real experiments show that a sonar system consisting of eight-channel Polaroid 600 series electrostatic transducers excited with 2 ms optimized pulse-position-modulation sequences can work together without cross-talk and can measure distances up to 650 cm with maximal 1% relative error.

  18. Band-Filling Correction Method for Accurate Adsorption Energy Calculations: A Cu/ZnO Case Study.

    PubMed

    Hellström, Matti; Spångberg, Daniel; Hermansson, Kersti; Broqvist, Peter

    2013-11-12

    We present a simple method, the "band-filling correction", to calculate accurate adsorption energies (Eads) in the low coverage limit from finite-size supercell slab calculations using DFT. We show that it is necessary to use such a correction if charge transfer takes place between the adsorbate and the substrate, resulting in the substrate bands either filling up or becoming depleted. With this correction scheme, we calculate Eads of an isolated Cu atom adsorbed on the ZnO(101̅0) surface. Without the correction, the calculated Eads is highly coverage-dependent, even for surface supercells that would typically be considered very large (in the range from 1 nm × 1 nm to 2.5 nm × 2.5 nm). The correction scheme works very well for semilocal functionals, where the corrected Eads is converged within 0.01 eV for all coverages. The correction scheme also works well for hybrid functionals if a large supercell is used and the exact exchange interaction is screened. PMID:26583386

  19. One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: determination of accurate ionization energy and cationic structure.

    PubMed

    Lee, Yu Ran; Kang, Do Won; Kim, Hong Lae; Kwon, Chan Ho

    2014-11-01

    Ionization energies and cationic structures of pyridine were intensively investigated utilizing one-photon mass-analyzed threshold ionization (MATI) spectroscopy with vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. The present one-photon high-resolution MATI spectrum of pyridine demonstrated a much finer and richer vibrational structure than that of the previously reported two-photon MATI spectrum. From the MATI spectrum and photoionization efficiency curve, the accurate ionization energy of the ionic ground state of pyridine was confidently determined to be 73,570 ± 6 cm(-1) (9.1215 ± 0.0007 eV). The observed spectrum was almost completely assigned by utilizing Franck-Condon factors and vibrational frequencies calculated through adjustments of the geometrical parameters of cationic pyridine at the B3LYP/cc-pVTZ level. A unique feature unveiled through rigorous analysis was the prominent progression of the 10 vibrational mode, which corresponds to in-plane ring bending, and the combination of other totally symmetric fundamentals with the ring bending overtones, which contribute to the geometrical change upon ionization. Notably, the remaining peaks originate from the upper electronic state ((2)A2), as predicted by high-resolution photoelectron spectroscopy studies and symmetry-adapted cluster configuration interaction calculations. Based on the quantitatively good agreement between the experimental and calculated results, it was concluded that upon ionization the pyridine cation in the ground electronic state should have a planar structure of C(2v) symmetry through the C-N axis.

  20. One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure

    SciTech Connect

    Lee, Yu Ran; Kang, Do Won; Kim, Hong Lae E-mail: hlkim@kangwon.ac.kr; Kwon, Chan Ho E-mail: hlkim@kangwon.ac.kr

    2014-11-07

    Ionization energies and cationic structures of pyridine were intensively investigated utilizing one-photon mass-analyzed threshold ionization (MATI) spectroscopy with vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. The present one-photon high-resolution MATI spectrum of pyridine demonstrated a much finer and richer vibrational structure than that of the previously reported two-photon MATI spectrum. From the MATI spectrum and photoionization efficiency curve, the accurate ionization energy of the ionic ground state of pyridine was confidently determined to be 73 570 ± 6 cm{sup −1} (9.1215 ± 0.0007 eV). The observed spectrum was almost completely assigned by utilizing Franck-Condon factors and vibrational frequencies calculated through adjustments of the geometrical parameters of cationic pyridine at the B3LYP/cc-pVTZ level. A unique feature unveiled through rigorous analysis was the prominent progression of the 10 vibrational mode, which corresponds to in-plane ring bending, and the combination of other totally symmetric fundamentals with the ring bending overtones, which contribute to the geometrical change upon ionization. Notably, the remaining peaks originate from the upper electronic state ({sup 2}A{sub 2}), as predicted by high-resolution photoelectron spectroscopy studies and symmetry-adapted cluster configuration interaction calculations. Based on the quantitatively good agreement between the experimental and calculated results, it was concluded that upon ionization the pyridine cation in the ground electronic state should have a planar structure of C{sub 2v} symmetry through the C-N axis.

  1. Photon-energy dependence of single-photon simultaneous core ionization and core excitation in CO2

    NASA Astrophysics Data System (ADS)

    Carniato, S.; Selles, P.; Lablanquie, P.; Palaudoux, J.; Andric, L.; Nakano, M.; Hikosaka, Y.; Ito, K.; Marchenko, T.; Travnikova, O.; Goldsztejn, G.; Journel, L.; Guillemin, R.; Céolin, D.; Simon, M.; Piancastelli, M. N.; Penent, F.

    2016-07-01

    We have studied the K-2V process corresponding to simultaneous K -shell ionization and K -shell excitation in the C O2 molecule. We define these K-2V states as super shake-up, at variance with the "conventional" K-1v-1V shake-up states. While the nature and evolution with photon energy of the conventional shake-up satellites has been the object of many studies, no such data on a large photon-energy range were previously reported on super shake-up. The C O2 molecule is a textbook example because it exhibits two well-isolated K-2V resonances (with V being 2 πu* and 5 σg* ) with different symmetries resulting from shake-up processes of different origin populated in comparable proportions. The variation of the excitation cross section of these two resonances with photon energy is reported, using two different experimental approaches, which sheds light on the excitation mechanisms. Furthermore, double-core-hole spectroscopy is shown to be able to integrate and even expand information provided by conventional single-core-hole X-ray Photoelectron Spectroscopy (XPS) and Near-Edge X-ray Absorption Fine Structure (NEXAFS) techniques, revealing, for instance, g -g dipole forbidden transitions which are only excited in NEXAFS spectra through vibronic coupling.

  2. Absolute cross sections for vibrational excitations of cytosine by low energy electron impact

    NASA Astrophysics Data System (ADS)

    Michaud, M.; Bazin, M.; Sanche, L.

    2012-09-01

    The absolute cross sections (CSs) for vibrational excitations of cytosine by electron impact between 0.5 and 18 eV were measured by electron-energy loss (EEL) spectroscopy of the molecule deposited at monolayer coverage on an inert Ar substrate. The vibrational energies compare to those that have been reported from IR spectroscopy of cytosine isolated in Ar matrix, IR and Raman spectra of polycrystalline cytosine, and ab initio calculation. The CSs for the various H bending modes at 142 and 160 meV are both rising from their energy threshold up to 1.7 and 2.1 × 10-17 cm2 at about 4 eV, respectively, and then decrease moderately while maintaining some intensity at 18 eV. The latter trend is displayed as well for the CS assigned to the NH2 scissor along with bending of all H at 179 meV. This overall behavior in electron-molecule collision is attributed to direct processes such as the dipole, quadrupole, and polarization contributions, etc. of the interaction of the incident electron with a molecule. The CSs for the ring deformation at 61 meV, the ring deformation with N-H symmetric wag at 77 meV, and the ring deformations with symmetric bending of all H at 119 meV exhibit common enhancement maxima at 1.5, 3.5, and 5.5 eV followed by a broad hump at about 12 eV, which are superimposed on the contribution due to the direct processes. At 3.5 eV, the CS values for the 61-, 77-, and 119-meV modes reach 4.0, 3.0, and 4.5 × 10-17 cm2, respectively. The CS for the C-C and C-O stretches at 202 meV, which dominates in the intermediate EEL region, rises sharply until 1.5 eV, reaches its maximum of 5.7 × 10-17 cm2 at 3.5 eV and then decreases toward 18 eV. The present vibrational enhancements, correspond to the features found around 1.5 and 4.5 eV in electron transmission spectroscopy (ETS) and those lying within 1.5-2.1 eV, 5.2-6.8 eV, and 9.5-10.9 eV range in dissociative electron attachment (DEA) experiments with cytosine in gas phase. While the ETS features are ascribed

  3. Absolute cross sections for vibrational excitations of cytosine by low energy electron impact.

    PubMed

    Michaud, M; Bazin, M; Sanche, L

    2012-09-21

    The absolute cross sections (CSs) for vibrational excitations of cytosine by electron impact between 0.5 and 18 eV were measured by electron-energy loss (EEL) spectroscopy of the molecule deposited at monolayer coverage on an inert Ar substrate. The vibrational energies compare to those that have been reported from IR spectroscopy of cytosine isolated in Ar matrix, IR and Raman spectra of polycrystalline cytosine, and ab initio calculation. The CSs for the various H bending modes at 142 and 160 meV are both rising from their energy threshold up to 1.7 and 2.1 × 10(-17) cm(2) at about 4 eV, respectively, and then decrease moderately while maintaining some intensity at 18 eV. The latter trend is displayed as well for the CS assigned to the NH(2) scissor along with bending of all H at 179 meV. This overall behavior in electron-molecule collision is attributed to direct processes such as the dipole, quadrupole, and polarization contributions, etc. of the interaction of the incident electron with a molecule. The CSs for the ring deformation at 61 meV, the ring deformation with N-H symmetric wag at 77 meV, and the ring deformations with symmetric bending of all H at 119 meV exhibit common enhancement maxima at 1.5, 3.5, and 5.5 eV followed by a broad hump at about 12 eV, which are superimposed on the contribution due to the direct processes. At 3.5 eV, the CS values for the 61-, 77-, and 119-meV modes reach 4.0, 3.0, and 4.5 × 10(-17) cm(2), respectively. The CS for the C-C and C-O stretches at 202 meV, which dominates in the intermediate EEL region, rises sharply until 1.5 eV, reaches its maximum of 5.7 × 10(-17) cm(2) at 3.5 eV and then decreases toward 18 eV. The present vibrational enhancements, correspond to the features found around 1.5 and 4.5 eV in electron transmission spectroscopy (ETS) and those lying within 1.5-2.1 eV, 5.2-6.8 eV, and 9.5-10.9 eV range in dissociative electron attachment (DEA) experiments with cytosine in gas phase. While the ETS features

  4. The low-energy, charge-transfer excited states of 4-amino-4-prime-nitrodiphenyl sulfide

    NASA Technical Reports Server (NTRS)

    O'Connor, Donald B.; Scott, Gary W.; Tran, Kim; Coulter, Daniel R.; Miskowski, Vincent M.; Stiegman, Albert E.; Wnek, Gary E.

    1992-01-01

    Absorption and emission spectra of 4-amino-4-prime-nitrodiphenyl sulfide in polar and nonpolar solvents were used to characterize and assign the low-energy excited states of the molecule. Fluorescence-excitation anisotropy spectra and fluorescence quantum yields were also used to characterize the photophysics of these states. The lowest-energy fluorescent singlet state was determined to be an intramolecular charge transfer (ICT) state involving transfer of a full electron charge from the amino to the nitro group yielding a dipole moment of about 50 D. A low-energy, intense absorption band is assigned as a transition to a different ICT state involving a partial electron charge transfer from sulfur to the nitro group.

  5. Effect of multipole excitations in electron energy-loss spectroscopy of surface plasmon modes in silver nanowires

    SciTech Connect

    Zhou, Xiuli; Norris, Theodore B.; Hörl, Anton; Trügler, Andreas; Hohenester, Ulrich; Herzing, Andrew A.

    2014-12-14

    We have characterized the surface plasmon resonance (SPR) in silver nanowires using spatially resolved electron energy loss spectroscopy (EELS) in the scanning transmission electron microscope. Non-symmetric EELS spectra due to high-k SPR propagation along the nanowire and spectral shifts due to higher-order mode excitation are observed when the beam is positioned near the tip of the nanowire. When the beam is far from the tip region and on the side of nanowire, no spectral shifts are observed as the beam is scanned in the radial direction of the nanowire. The experimental spectra are compared with three different theoretical approaches: direct numerical calculation of the energy loss, analytical models for energy loss, and numerical simulations using an optical model. All three models reproduce the spectral shifts as the electron beam approaches the cap of the nanowire. The analytical model reveals the origin of the shifts in high-order plasmon mode excitation.

  6. Sensitization of ultra-long-range excited-state electron transfer by energy transfer in a polymerized film

    PubMed Central

    Ito, Akitaka; Stewart, David J.; Fang, Zhen; Brennaman, M. Kyle; Meyer, Thomas J.

    2012-01-01

    Distance-dependent energy transfer occurs from the Metal-to-Ligand Charge Transfer (MLCT) excited state to an anthracene-acrylate derivative (Acr-An) incorporated into the polymer network of a semirigid poly(ethyleneglycol)dimethacrylate monolith. Following excitation, to Acr-An triplet energy transfer occurs followed by long-range, Acr-3An—Acr-An → Acr-An—Acr-3An, energy migration. With methyl viologen dication (MV2+) added as a trap, Acr-3An + MV2+ → Acr-An+ + MV+ electron transfer results in sensitized electron transfer quenching over a distance of approximately 90 Å. PMID:22949698

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

    PubMed

    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. Exciton description of chlorosome to baseplate excitation energy transfer in filamentous anoxygenic phototrophs and green sulfur bacteria.

    PubMed

    Linnanto, Juha M; Korppi-Tommola, Jouko E I

    2013-09-26

    A description of intra-chlorosome and from chlorosome to baseplate excitation energy transfer in green sulfur bacteria and in filamentous anoxygenic phototrophs is presented. Various shapes and sizes, single and multiwalled tubes, cylindrical spirals and lamellae of the antenna elements mimicking pigment organization in chlorosomes were generated by using molecular mechanics calculations, and the absorption, LD, and CD spectra of these were predicted by using exciton theory. Calculated absorption and LD spectra were similar for all modeled antenna structures; on the contrary, CD spectra turned out to be sensitive to the size and pigment orientations in the antenna. It was observed that, bringing two tubular antennae at close enough interaction distance, the exciton density of the lowest energy state became localized on pigments facing each other in the antenna dimer. Calculations predicted for stacked tubular antenna elements extremely fast, faster than 500 fs, intra-chlorosome energy transfer toward the baseplates in the direction perpendicular to the chlorosome long axis. Downhill excitation energy transfer according to our model is driven by interactions of the antennae with their immediate surroundings. Energy transfer from the chlorosome to the baseplate, consisting of 2D lattices of monomeric and dimeric bacteriochlorophyll a molecules, was predicted to occur in 5-15 ps, in agreement with experimental findings. Advancement of excitation through a double tube antenna stack, a model for antenna element organization in chlorosomes of green sulfur bacteria, to a monomeric baseplate was visualized in space and in time.

  9. Ultrafast redistribution of vibrational energy after excitation of NH stretching modes in DNA oligomers

    NASA Astrophysics Data System (ADS)

    Kozich, V.; Szyc, Ł.; Nibbering, E. T. J.; Werncke, W.; Elsaesser, T.

    2009-04-01

    Vibrational relaxation after spectrally selective excitation within the NH stretching band of adenine-thymine base pairs in DNA oligomers was studied by subpicosecond infrared-pump/anti-Stokes Raman-probe spectroscopy. The decay of the different NH stretching vibrations populates distinct accepting modes in the NH bending range with a rise time of 0.6 ps that is close to the NH stretching decay times. The population of thymine fingerprint modes after excitation of the adenine antisymmetric NH 2 stretching mode points to an ultrafast excitation transfer to the thymine NH stretching vibration before relaxation. The nonequilibrium fingerprint populations decay on a time scale of several picoseconds.

  10. Application of recent double-hybrid density functionals to low-lying singlet-singlet excitation energies of large organic compounds

    NASA Astrophysics Data System (ADS)

    Meo, F. Di; Trouillas, P.; Adamo, C.; Sancho-García, J. C.

    2013-10-01

    The present work assesses some recently developed double-hybrid density functionals (B2π-PLYP, PBE0-DH, and PBE0-2) using linear-response Tamm-Dancoff Time-Dependent Density Functional Theory. This assessment is achieved against experimentally derived low-lying excitation energies of large organic dyes of recent interest, including some excitations dominated by charge-transfer transitions. Comparisons are made with some of the best-performing methods established from the literature, such as PBE0 or B3LYP hybrid or the recently proposed B2-PLYP and B2GP-PLYP double-hybrid models, to ascertain their quality and robustness on equal footing. The accuracy of parameter-free or empirical forms of double-hybrid functionals is also briefly discussed. Generally speaking, it turns out that double-hybrid expressions always provide more accurate estimates than corresponding hybrid methods. Double-hybrid functionals actually reach averaged accuracies of 0.2 eV, that can be admittedly considered close to any intended accuracy limit within the present theoretical framework.

  11. Excited baryons

    SciTech Connect

    Mukhopadhyay, N.C.

    1986-01-01

    The status of the theory of the low-energy approach to hadron structure is reviewed briefly by surveying a few relevant models. A few examples of tests needed to sort out the predictions of different models pertaining to the quark-gluon structure of hadrons are discussed, and given the resulting physics objectives, a few experimental options for excited baryon research at CFBAF are suggested. (LEW)

  12. Collisional excitation of interstellar methyl cyanide

    NASA Technical Reports Server (NTRS)

    Green, Sheldon

    1986-01-01

    Theoretical calculations are used to determine the collisional excitation rates of methyl cyanide under interstellar molecular cloud conditions. The required Q(L,M) as a function of kinetic temperature were determined by averaging fixed energy IOS (infinite order sudden) results over appropriate Boltzmann distributions of collision energies. At a kinetic temperature of 40 K, rates within a K ladder were found to be accurate to generally better than about 30 percent.

  13. Quantum size effects in the volume plasmon excitation of bismuth nanoparticles investigated by electron energy loss spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Y. W.; Kim, J. S.; Kim, G. H.; Kim, Kwang S.

    2006-04-01

    Quantum size effects in volume plasmon excitation of bismuth nanoparticles with diameters ranging from 5to500nm have been studied by electron energy loss spectroscopy. The Bi nanoparticles were prepared by reducing Bi3+ with sodium borohydride in the presence of poly(vinylpyrroldone). The volume plasmon energy and its peak width increase with decreasing nanoparticle diameter, due to the quantum size effect. For the particles with diameter less than 40nm, the increase of the volume plasmon energy is proportional to the inverse square of the nanoparticle diameter, confirming the semimetal to semiconductor transition in Bi nanoparticles.

  14. Tensor numerical methods in quantum chemistry: from Hartree-Fock to excitation energies

    NASA Astrophysics Data System (ADS)

    Khoromskaia, Venera; Khoromskij, Boris N.

    We resume the recent successes of the grid-based tensor numerical methods and discuss their prospects in real-space electronic structure calculations. These methods, based on the low-rank representation of the multidimensional functions and integral operators, led to entirely grid-based tensor-structured 3D Hartree-Fock eigenvalue solver. It benefits from tensor calculation of the core Hamiltonian and two-electron integrals (TEI) in $O(n\\log n)$ complexity using the rank-structured approximation of basis functions, electron densities and convolution integral operators all represented on 3D $n\\times n\\times n $ Cartesian grids. The algorithm for calculating TEI tensor in a form of the Cholesky decomposition is based on multiple factorizations using algebraic 1D ``density fitting`` scheme. The basis functions are not restricted to separable Gaussians, since the analytical integration is substituted by high-precision tensor-structured numerical quadratures. The tensor approaches to post-Hartree-Fock calculations for the MP2 energy correction and for the Bethe-Salpeter excited states, based on using low-rank factorizations and the reduced basis method, were recently introduced. Another direction is related to the recent attempts to develop a tensor-based Hartree-Fock numerical scheme for finite lattice-structured systems, where one of the numerical challenges is the summation of electrostatic potentials of a large number of nuclei. The 3D grid-based tensor method for calculation of a potential sum on a $L\\times L\\times L$ lattice manifests the linear in $L$ computational work, $O(L)$, instead of the usual $O(L^3 \\log L)$ scaling by the Ewald-type approaches.

  15. Benchmark atomization energy of ethane : importance of accurate zero-point vibrational energies and diagonal Born-Oppenheimer corrections for a 'simple' organic molecule.

    SciTech Connect

    Karton, A.; Martin, J. M. L.; Ruscic, B.; Chemistry; Weizmann Institute of Science

    2007-06-01

    A benchmark calculation of the atomization energy of the 'simple' organic molecule C2H6 (ethane) has been carried out by means of W4 theory. While the molecule is straightforward in terms of one-particle and n-particle basis set convergence, its large zero-point vibrational energy (and anharmonic correction thereto) and nontrivial diagonal Born-Oppenheimer correction (DBOC) represent interesting challenges. For the W4 set of molecules and C2H6, we show that DBOCs to the total atomization energy are systematically overestimated at the SCF level, and that the correlation correction converges very rapidly with the basis set. Thus, even at the CISD/cc-pVDZ level, useful correlation corrections to the DBOC are obtained. When applying such a correction, overall agreement with experiment was only marginally improved, but a more significant improvement is seen when hydrogen-containing systems are considered in isolation. We conclude that for closed-shell organic molecules, the greatest obstacles to highly accurate computational thermochemistry may not lie in the solution of the clamped-nuclei Schroedinger equation, but rather in the zero-point vibrational energy and the diagonal Born-Oppenheimer correction.

  16. Characterization of a rotary piezoelectric energy harvester based on plucking excitation for knee-joint wearable applications

    NASA Astrophysics Data System (ADS)

    Pozzi, Michele; Zhu, Meiling

    2012-05-01

    Wearable medical and electronic devices demand a similarly wearable electrical power supply. Human-based piezoelectric energy harvesters may be the solution, but the mismatch between the typical frequencies of human activities and the optimal operating frequencies of piezoelectric generators calls for the implementation of a frequency up-conversion technique. A rotary piezoelectric energy harvester designed to be attached to the knee-joint is here implemented and characterized. The wearable harvester is based on the plucking method of frequency up-conversion, where a piezoelectric bimorph is deflected by a plectrum and permitted to vibrate unhindered upon release. Experiments were conducted to characterize the energy produced by the rotary piezoelectric energy harvester with different electric loads and different excitation speeds, covering the range between 0.1 and 1 rev s-1 to simulate human gait speeds. The electrical loads were connected to the generator either directly or through a rectifying bridge, as would be found in most power management circuits. The focus of the paper is to study the capability of energy generation of the harvester for knee-joint wearable applications, and study the effects of the different loads and different excitation speeds. It is found that the energy harvested is around 160-490 µJ and strongly depends on the angular speed, the connected electric loads and also the manufacturing quality of the harvester. Statistical analysis is used to predict the potential energy production of a harvester manufactured to tighter tolerances than the one presented here.

  17. Passive broadband targeted energy transfers and control of self-excited vibrations

    NASA Astrophysics Data System (ADS)

    Lee, Young S.

    This work consists of the three main parts---Nonlinear energy pumping (that is, passive broadband targeted energy transfers---TETs), and its applications to theoretical and experimental suppression of aeroelastic instabilities. In the first part, nonlinear energy pumping (or TETs) in coupled oscillators is studied. The system is composed of a primary linear subsystem coupled through an essentially nonlinear stiffness and a linear viscous damper to an additional mass (which is called, as a whole, a nonlinear energy sink---NES). By considering the linear damping as a perturbation to the system, periodic solutions of the underlying Hamiltonian system are formulated by means of the non-smooth temporal transformation and solved numerically by a shooting method. The special periodic orbits, which are corresponding to the impulsive initial conditions for the primary subsystem, bear their importance as baits for initiating localized transfers of a significant portion of energy to the NES. The second part theoretically deals with suppression of limit cycle oscillations (LCOs) in self-excited systems by means of passive energy localizations. As a pilot scheme, suppression or even complete elimination of the LCO in a van der Pol (VDP) oscillator coupled with two types of NESS---grounded and ungrounded---is studied. Computational parametric study proves the efficacy of LCO elimination by means of passive nonlinear energy pumping from the VDP oscillator to appropriately designed NESs. The numerical study of the transient dynamics of the system showed that the dynamical mechanism for LCO suppression is a series of 1:1 and 1:3 transient resonance captures, with the damped transient dynamics following closely corresponding resonant manifolds of the underlying Hamiltonian system. It is through the TRCs that energy gets transferred from the VDP oscillator to the NES, thus causing LCO suppression. By performing an additional bifurcation analysis of the steady state responses through

  18. An Accurate Quartic Force Field, Fundamental Frequencies, and Binding Energy for the High Energy Density Material T(d)N4

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Martin, Jan M. L.; Kwak, Dochan (Technical Monitor)

    2002-01-01

    The CCSD(T) method has been used to compute a highly accurate quartic force field and fundamental frequencies for all N-14 and N-15 isotopomers of the high energy density material T(sub d)N(sub 4). The computed fundamental frequencies show beyond doubt that the bands observed in a matrix isolation experiment by Radziszewski and coworkers are not due to different isotopomers of T(sub d)N(sub 4). The most sophisticated thermochemical calculations to date yield a N(sub 4) -> 2N(sub 2) heat of reaction of 182.22 +/- 0.5 kcal/mol at 0 K (180.64 +/- 0.5 at 298 K). It is hoped that the data reported herein will aid in the ultimate detection of T(sub d)N(sub 4).

  19. Highly Accurate Potential Energy Surface, Dipole Moment Surface, Rovibrational Energy Levels, and Infrared Line List for (32)S(16)O2 up to 8000 cm(exp -1)

    NASA Technical Reports Server (NTRS)

    Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

    2014-01-01

    A purely ab initio potential energy surface (PES) was refined with selected (32)S(16)O2 HITRAN data. Compared to HITRAN, the root-mean-squares error (RMS) error for all J=0-80 rovibrational energy levels computed on the refined PES (denoted Ames-1) is 0.013 cm(exp -1). Combined with a CCSD(T)/aug-cc-pV(Q+d)Z dipole moment surface (DMS), an infrared (IR) line list (denoted Ames-296K) has been computed at 296K and covers up to 8,000 cm(exp -1). Compared to the HITRAN and CDMS databases, the intensity agreement for most vibrational bands is better than 85-90%. Our predictions for (34)S(16)O2 band origins, higher energy (32)S(16)O2 band origins and missing (32)S(16)O2 IR bands have been verified by most recent experiments and available HITRAN data. We conclude that the Ames-1 PES is able to predict (32/34)S(16)O2 band origins below 5500 cm(exp -1) with 0.01-0.03 cm(exp -1) uncertainties, and the Ames-296K line list provides continuous, reliable and accurate IR simulations. The Ka-dependence of both line position and line intensity errors is discussed. The line list will greatly facilitate SO2 IR spectral experimental analysis, as well as elimination of SO2 lines in high-resolution astronomical observations.

  20. Highly accurate potential energy surface, dipole moment surface, rovibrational energy levels, and infrared line list for ³²S¹⁶O₂ up to 8000 cm⁻¹.

    PubMed

    Huang, Xinchuan; Schwenke, David W; Lee, Timothy J

    2014-03-21

    A purely ab initio potential energy surface (PES) was refined with selected (32)S(16)O2 HITRAN data. Compared to HITRAN, the root-mean-squares error (σ(RMS)) for all J = 0-80 rovibrational energy levels computed on the refined PES (denoted Ames-1) is 0.013 cm(-1). Combined with a CCSD(T)/aug-cc-pV(Q+d)Z dipole moment surface (DMS), an infrared (IR) line list (denoted Ames-296K) has been computed at 296 K and covers up to 8000 cm(-1). Compared to the HITRAN and CDMS databases, the intensity agreement for most vibrational bands is better than 85%-90%. Our predictions for (34)S(16)O2 band origins, higher energy (32)S(16)O2 band origins and missing (32)S(16)O2 IR bands have been verified by most recent experiments and available HITRAN data. We conclude that the Ames-1 PES is able to predict (32/34)S(16)O2 band origins below 5500 cm(-1) with 0.01-0.03 cm(-1) uncertainties, and the Ames-296K line list provides continuous, reliable and accurate IR simulations. The K(a)-dependence of both line position and line intensity errors is discussed. The line list will greatly facilitate SO2 IR spectral experimental analysis, as well as elimination of SO2 lines in high-resolution astronomical observations. PMID:24655184

  1. Development of infrared sensors using energy transfer/energy upconversion processes: Study of laser excited fluorescence in rare Earth ion doped crystals

    NASA Technical Reports Server (NTRS)

    Nash-Stevenson, S. K.; Reddy, B. R.; Venkateswarlu, P.

    1994-01-01

    A summary is presented of the spectroscopic study of three systems: LaF3:Ho(3+), LaF3:Er(3+) and CaF2:Nd(3+). When the D levels of Ho(3+) in LaF3 were resonantly excited with a laser beam of 640 nm, upconverted emissions were detected from J (416 nm), F (485 nm), and E (546 nm) levels. Energy upconverted emissions were also observed from F and E levels of Ho(3+) when the material was excited with an 800 nm near infrared laser. When the D levels of Er(3+) in LaF3 were resonantly excited with a laser beam of 637 nm, upconverted emissions were detected from the E (540 nm) and P (320, 400, and 468 nm) levels. Energy upconverted emissions were also observed from F, E, and D levels of Er(3+) when the material was resonantly excited with an 804 nm near infrared laser. When the D levels of Nd(3+) in CaF2 were resonantly excited with a laser beam of 577 nm, upconverted emissions were detected from the L (360 and 382 nm), K (418 nm), and I (432 nm) levels. Very weak upconverted emissions were detected when this system was irradiated with a near infrared laser. The numbers in parentheses are the wavelengths of the emissions.

  2. Diode laser probing of CO2 and CO vibrational excitation produced by collisions with high energy electrons from 193 nm excimer laser photolysis of iodine

    NASA Astrophysics Data System (ADS)

    Hewitt, Scott A.; Zhu, Lei; Flynn, George W.

    1992-11-01

    The vibrational, rotational, and translational excitation of CO2 and CO following excimer laser photolysis of iodine is evaluated by means of time-domain absorption spectroscopy. In spite of the lack of change in the rotational and translational molecular energy, pronounced vibrational excitation is noted. The excimer laser photolysis of the iodine is thought to generate hot electrons that collide with the CO2 leading to vibrationally excited molecules.

  3. The clinical impact of uncertainties in the mean excitation energy of human tissues during proton therapy

    NASA Astrophysics Data System (ADS)

    Besemer, Abigail; Paganetti, Harald; Bednarz, Bryan

    2013-02-01

    Uncertainties in the estimated mean excitation energies (I-values) needed for calculating proton stopping powers can be in the order of 10-15%, which introduces a fundamental limitation in the accuracy of proton range determination. Previous efforts have quantified shifts in proton depth dose distributions due to I-value uncertainties in water and homogenous tissue phantoms. This study is the first to quantify the clinical impact of I-value uncertainties on proton dose distributions within patient geometries. A previously developed Geant4 based Monte Carlo code was used to simulate a proton treatment plan for three patients (prostate, pancreases, and liver) with varying tissue I-values. A uniform variation study was conducted in which the tissue I-values were varied by ±5% and ±10% of the nominal values as well as a probabilistic variation study in which the I-values were randomly sampled according to a normal distribution with the mean equal to the nominal I-value and a standard deviation of 5 and 10% of the nominal values. Modification of tissue I-values impacted both the proton range and SOBP width. R90 range shifts up to 7.7 mm (4.4.%) and R80 range shifts up to 4.8 mm (1.9%) from the nominal range were recorded. Modulating the tissue I-values by 10% the nominal value resulted in up to a 3.5% difference mean dose in the target volumes and organs at risk compared to the nominal case. The range and dose differences were the largest for the deeper-seated prostate and pancreas cases. The treatments that were simulated with randomly sampled I-values resulted in range and dose differences that were generally within the upper and lower bounds set by the 10% uniform variations. This study demonstrated the impact of I-value uncertainties on patient dose distributions. Clearly, sub-millimeter precision in proton therapy would necessitate a reduction in I-value uncertainties to ensure an efficacious clinical outcome.

  4. Exciting forces for a wave energy device consisting of a pair of coaxial cylinders in water of finite depth

    NASA Astrophysics Data System (ADS)

    Hassan, Mohammad; Bora, Swaroop Nandan

    2013-09-01

    Two coaxial vertical cylinders-one is a riding hollow cylinder and the other a solid cylinder of greater radius at some distance above an impermeable horizontal bottom, were considered. This problem of diffraction by these two cylinders, which were considered as idealization of a buoy and a circular plate, can be considered as a wave energy device. The wave energy that is created and transferred by this device can be appropriately used in many applications in lieu of conventional energy. Method of separation of variables was used to obtain the analytical expressions for the diffracted potentials in four clearly identified regions. By applying the appropriate matching conditions along the three virtual boundaries between the regions, a system of linear equations was obtained, which was solved for the unknown coefficients. The potentials allowed us to obtain the exciting forces acting on both cylinders. Sets of exciting forces were obtained for different radii of the cylinders and for different gaps between the cylinders. It was observed that changes in radius and the gap had significant effect on the forces. It was found that mostly the exciting forces were significant only at lower frequencies. The exciting forces almost vanished at higher frequencies. The problem was also investigated for the base case of no plate arrangement, i.e., the case having only the floating cylinder tethered to the sea-bed. Comparison of forces for both arrangements was carried out. In order to take care of the radiation of the cylinders due to surge motion, the corresponding added mass and the damping coefficients for both cylinders were also computed. All the results were depicted graphically and compared with available results.

  5. The fluorescence action spectra of some saturated hydrocarbon liquids for excitation energies above and below their ionization thresholds

    SciTech Connect

    Ostafin, A.E.; Lipsky, S. )

    1993-04-01

    Fluorescence action spectra have been obtained for the neat liquids, [ital cis]-decalin, [ital trans]-decalin, bicyclohexyl, cyclohexane, methylcyclohexane, isobutylcyclohexane, 2,3,4-trimethylpentane, 2,3-dimethylbutane, 3-methylhexane, 3-methylpentane, [ital n]-decane, [ital n]-dodecane, and [ital n]-pentadecane at excitation energies, [epsilon], ranging from their absorption onsets (at ca. 7 eV) to 10.3 eV. For all compounds, with the exception of [ital cis]-decalin, the fluorescence quantum yield is observed to monotonically decline with increasing [epsilon], reaching a minimum value at an energy, [epsilon][sub [ital m

  6. High-frequency vibration energy harvesting from impulsive excitation utilizing intentional dynamic instability caused by strong nonlinearity

    NASA Astrophysics Data System (ADS)

    Remick, Kevin; Dane Quinn, D.; Michael McFarland, D.; Bergman, Lawrence; Vakakis, Alexander

    2016-05-01

    The authors investigate a vibration-based energy harvesting system utilizing essential (nonlinearizable) nonlinearities and electromagnetic coupling elements. The system consists of a grounded, weakly damped linear oscillator (primary system) subjected to a single impulsive load. This primary system is coupled to a lightweight, damped oscillating attachment (denoted as nonlinear energy sink, NES) via a neodymium magnet and an inductance coil, and a piano wire, which generates an essential geometric cubic stiffness nonlinearity. Under impulsive input, the transient damped dynamics of this system exhibit transient resonance captures (TRCs) causing intentional large-amplitude and high-frequency instabilities in the response of the NES. These TRCs result in strong energy transfer from the directly excited primary system to the light-weight attachment. The energy is harvested by the electromagnetic elements in the coupling and, in the present case, dissipated in a resistive element in the electrical circuit. The primary goal of this work is to numerically, analytically, and experimentally demonstrate the efficacy of employing this type of intentional high-frequency dynamic instability to achieve enhanced vibration energy harvesting under impulsive excitation.

  7. Revealing the high-energy electronic excitations underlying the onset of high-temperature superconductivity in cuprates

    PubMed Central

    Giannetti, Claudio; Cilento, Federico; Conte, Stefano Dal; Coslovich, Giacomo; Ferrini, Gabriele; Molegraaf, Hajo; Raichle, Markus; Liang, Ruixing; Eisaki, Hiroshi; Greven, Martin; Damascelli, Andrea; van der Marel, Dirk; Parmigiani, Fulvio

    2011-01-01

    In strongly correlated systems the electronic properties at the Fermi energy (EF) are intertwined with those at high-energy scales. One of the pivotal challenges in the field of high-temperature superconductivity (HTSC) is to understand whether and how the high-energy scale physics associated with Mott-like excitations (|E−EF|>1 eV) is involved in the condensate formation. Here, we report the interplay between the many-body high-energy CuO2 excitations at 1.5 and 2 eV, and the onset of HTSC. This is revealed by a novel optical pump-supercontinuum-probe technique that provides access to the dynamics of the dielectric function in Bi2Sr2Ca0.92Y0.08Cu2O8+δ over an extended energy range, after the photoinduced suppression of the superconducting pairing. These results unveil an unconventional mechanism at the base of HTSC both below and above the optimal hole concentration required to attain the maximum critical temperature (Tc). PMID:21673674

  8. Positron-electron decay of 28Si at an excitation energy of 50 MeV

    NASA Astrophysics Data System (ADS)

    Buda, A.; Bacelar, J. C.; Balanda, A.; van der Ploeg, H.; Sujkowski, Z.; van der Woude, A.

    1993-03-01

    The electron-position pair decay of 28Si at 50 MeV excitation produced by the isospin T=0 (α + 24Mg) and the mixed isospin T=0,1 (3He + 25Mg) reactions has been studied using a special designed Positron-Electron pair spectrometer PEPSI.

  9. Efficient pathways of excitation energy transfer from delocalized S2 excitons in the peridinin-chlorophyll a-protein complex.

    PubMed

    Bricker, William P; Lo, Cynthia S

    2015-05-01

    Excitation energy transfer (EET) in peridinin-chlorophyll-protein (PCP) complexes is dominated by the S1 → Qy pathway, but the high efficiencies cannot be solely explained by this one pathway. We postulate that EET from peridinin S2 excitons may also be important. We use complete active space configuration interaction calculations and the transition density cube method to calculate Coulombic couplings between peridinin and chlorophyll a in the PCP complex of the dinoflagellate Amphidinium carterae and compare monomeric and dimeric delocalized peridinin S2 excited states. Our calculations show that the S2 → Qy EET pathway from peridinin to chlorophyll a is the dominant energy transfer pathway from the S2 excited state in PCP, with several values in the sub-picosecond range. This result suggests that the S2 → Qy EET pathway may be responsible for the reported chlorophyll a bleaching signature seen in experiment at around 200 fs, and not the S2 → Qx pathway as previously suggested.

  10. High electronic excitations and ion beam mixing effects in high energy ion irradiated Fe/Si multilayers

    SciTech Connect

    Bauer, P.; Dufour, C.; Jaouen, C.; Marchal, G.; Pacaud, J.; Grilhe, J.; Jousset, J.C.

    1997-01-01

    M{umlt o}ssbauer spectroscopy ({sup 57}Fe) shows evidence for mixing effects induced by electronic energy deposition in nanoscale Fe/Si multilayers irradiated with swift heavy ions. A decrease in the mixing efficiency with electronic stopping power is reported; a threshold is found, under which iron environment modifications no longer occur. The kinetics of Fe{endash}Si phase formation after irradiation suggests the existence of three regimes: (i) for high excitation levels, a magnetic amorphous phase is formed directly in the wake of the incoming ion and an almost complete mixing is reached at low fluence (10{sup 13} U/cm{sup 2}); (ii) for low excitation levels, a paramagnetic Si-rich amorphous phase is favored at the interface while crystalline iron subsists at high fluences; (iii) for intermediate excitation levels, saturation effects are observed and the formation rate of both magnetic and paramagnetic phases points to direct mixing in the ion wake but with a reduced track length in comparison to U irradiation. The measured interfacial mixing cross section induced by electronic energy deposition suggests that a thermal diffusion process is mainly involved in addition to damage creation. {copyright} {ital 1997 American Institute of Physics.}

  11. Nonlocal thermodynamic equilibrium effects in stratospheric HF by collisional energy transfer from electronically excited O2 and implications for infrared remote sensing

    NASA Technical Reports Server (NTRS)

    Kaye, Jack A.

    1989-01-01

    A possible nonlocal thermodynamic equilibrium (non-LTE) effect involving stratospheric HF arising from the direct photochemical excitation of vibrationally excited HF by collisional energy transfer from electronically excited O2 is presented. Although this non-LTE effect is smaller that one associated with the direct solar excitation of both HF(nv = 1) and HF(nv = 2), calculations show that inclusion of the mechanism into retrieval algorithms is necessary if correct daytime upper stratosphere HF profiles are to be inferred in future IR thermal emission measurements.

  12. CONDENSED MATTER: STRUCTURE, MECHANICAL AND THERMAL PROPERTIES: Low-Energy Collective Excitation of Bose-Einstein Condensates in an Anisotropic Magnetic Trap

    NASA Astrophysics Data System (ADS)

    Yang, Lu; Wang, Xiao-Rui; Li, Ke; Tan, Xin-Zhou; Xiong, Hong-Wei; Lu, Bao-Long

    2009-07-01

    We experimentally investigate the collective excitation of 87Rb Bose-Einstein condensates confined in a cigar-shaped magnetic trap (QUIC trap). Using a method of magnetic perturbation, the center-of-mass oscillation of the condensate is excited, so that the radial trapping frequency of the QUIC trap can be precisely determined. A high-order excitation, characterized by a fast shape oscillation, also occurs simultaneously, with a noticeable damping in the oscillation amplitude compared with the oscillation of the center of mass. The measured oscillation frequencies, associated with these two low-energy excitation modes, agree well with theoretical predictions based on the Gross-Pitaevskii equation.

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

    PubMed

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

    2016-08-01

    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.

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

    PubMed

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

    2016-08-01

    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. PMID:27340904

  15. Spectroscopy of nitrophenolates in vacuo: effect of spacer, configuration, and microsolvation on the charge-transfer excitation energy.

    PubMed

    Brøndsted Nielsen, Steen; Brøndsted Nielsen, Mogens; Rubio, Angel

    2014-04-15

    In a charge-transfer (CT) transition, electron density moves from one end of the molecule (donor) to the other end (acceptor). This type of transition is of paramount importance in nature, for example, in photosynthesis, and it governs the excitation of several protein biochromophores and luminophores such as the oxyluciferin anion that accounts for light emission from fireflies. Both transition energy and oscillator strength are linked to the coupling between the donor and acceptor groups: The weaker the coupling, the smaller the excitation energy. But a weak coupling necessarily also causes a low oscillator strength possibly preventing direct excitation (basically zero probability in the noncoupling case). The coupling is determined by the actual spacer between the two groups, and whether the spacer acts as an insulator or a conductor. However, it can be difficult or even impossible to distinguish the effect of the spacer from that of local solvent molecules that often cause large solvent shifts due to different ground-state and excited-state stabilization. This calls for gas-phase spectroscopy experiments where absorption by the isolated molecule is identified to unequivocally establish the intrinsic molecular properties with no perturbations from a microenvironment. From such insight, the effect of a protein microenvironment on the CT excited state can be deduced. In this Account, we review our results over the last 5 years from mass spectroscopy experiments using specially designed apparatus on several charged donor-acceptor ions that are based on the nitrophenolate moiety and π-extended derivatives, which are textbook examples of donor-acceptor chromophores. The phenolate oxygen is the donor, and the nitro group is the acceptor. The choice of this system is also based on the fact that phenolate is a common structural motif of biochromophores and luminophores, for example, it is a constituent of the oxyluciferin anion. A presentation of the setups used for

  16. Spectroscopy of nitrophenolates in vacuo: effect of spacer, configuration, and microsolvation on the charge-transfer excitation energy.

    PubMed

    Brøndsted Nielsen, Steen; Brøndsted Nielsen, Mogens; Rubio, Angel

    2014-04-15

    In a charge-transfer (CT) transition, electron density moves from one end of the molecule (donor) to the other end (acceptor). This type of transition is of paramount importance in nature, for example, in photosynthesis, and it governs the excitation of several protein biochromophores and luminophores such as the oxyluciferin anion that accounts for light emission from fireflies. Both transition energy and oscillator strength are linked to the coupling between the donor and acceptor groups: The weaker the coupling, the smaller the excitation energy. But a weak coupling necessarily also causes a low oscillator strength possibly preventing direct excitation (basically zero probability in the noncoupling case). The coupling is determined by the actual spacer between the two groups, and whether the spacer acts as an insulator or a conductor. However, it can be difficult or even impossible to distinguish the effect of the spacer from that of local solvent molecules that often cause large solvent shifts due to different ground-state and excited-state stabilization. This calls for gas-phase spectroscopy experiments where absorption by the isolated molecule is identified to unequivocally establish the intrinsic molecular properties with no perturbations from a microenvironment. From such insight, the effect of a protein microenvironment on the CT excited state can be deduced. In this Account, we review our results over the last 5 years from mass spectroscopy experiments using specially designed apparatus on several charged donor-acceptor ions that are based on the nitrophenolate moiety and π-extended derivatives, which are textbook examples of donor-acceptor chromophores. The phenolate oxygen is the donor, and the nitro group is the acceptor. The choice of this system is also based on the fact that phenolate is a common structural motif of biochromophores and luminophores, for example, it is a constituent of the oxyluciferin anion. A presentation of the setups used for

  17. Estimation of the activation energy in the Belousov-Zhabotinsky reaction by temperature effect on excitable waves.

    PubMed

    Zhang, Jinzhong; Zhou, Luqun; Ouyang, Qi

    2007-02-15

    We report the temperature effect on the propagation of excitable traveling waves in a quasi-two-dimensional Belousov-Zhabotinsky reaction-diffusion system. The onset of excitable waves as a function of the sulfuric acid concentration and temperature is identified, on which the sulfuric acid concentration exhibits an Arrhenius dependence on temperature. On the basis of this experimental data, the activation energy of the self-catalyzed reaction in the Oregonator model is estimated to be 83-113 kJ/mol, which is further supported by our numerical simulations. The estimation proceeds without analyzing detailed reaction steps but rather through observing the global dynamic behaviors in the BZ reaction. For a supplement, the wave propagation velocities are calculated based on our results and compared with the experimental observations. PMID:17249646

  18. Excitation energy transfer between photosystem II and photosystem I in red algae: larger amounts of phycobilisome enhance spillover.

    PubMed

    Yokono, Makio; Murakami, Akio; Akimoto, Seiji

    2011-07-01

    We examined energy transfer dynamics from the photosystem II reaction center (PSII-RC) in intact red algae cells of Porphyridium cruentum, Bangia fuscopurpurea, Porphyra yezoensis, Chondrus giganteus, and Prionitis crispata. Time resolved fluorescence measurements were conducted in the range of 0-80ns at -196°C. The delayed fluorescence spectra were then determined, where the delayed fluorescence was derived from the charge recombination between P680(+) and pheophytin a in PSII-RC. Therefore, the delayed fluorescence spectrum reflected the energy migration processes including PSII-RC. All samples examined showed prominent distribution of delayed fluorescence in PSII and PSI, which suggests that a certain amount of PSII attaches to PSI to share excitation energy in red algae. The energy transfer from PSII to PSI was found to be dominant when the amount of phycoerythrobilin was increased.

  19. Comparison of calculated and experimentally resolved rate constants for excitation energy transfer in C-phycocyanin. 1. Monomers

    SciTech Connect

    Debreczeny, M.P.; Sauer, K.; Zhou, J.; Bryant, D.A.

    1995-05-18

    Rate constants for excitation energy transfer in light-harvesting protein, C-phycocyanin (PC), in the monomeric aggregation state, isolated from the cyanobacterium cynechococcus sp. PCC 7002, are calculated, using Foerster theory and compared with the results of time-resolved fluorescence measurements. The assignments of the energy-transfer rate constants in PC monomers are confirmed here by time-resolved fluorescence anisotropy measurements of the PC monomers isolated from both the wild-type and a mutant strain (cpcB/C155S) whose PC is missing the {beta}{sub 155} chromophore. It is concluded that the Foerster model of resonant energy transfer in the weak coupling limit successfully describes the dominant energy-transfer processes in this protein in the monomeric state. 31 refs., 3 figs., 4 tabs.

  20. Ab initio ground and excited state potential energy surfaces for NO-Kr complex and dynamics of Kr solids with NO impurity.

    PubMed

    Castro-Palacios, Juan Carlos; Rubayo-Soneira, Jesús; Ishii, Keisaku; Yamashita, Koichi

    2007-04-01

    The intermolecular potentials for the NO(X 2Pi)-Kr and NO(A 2Sigma+)-Kr systems have been calculated using highly accurate ab initio calculations. The spin-restricted coupled cluster method for the ground 1 2A' state [NO(X 2Pi)-Kr] and the multireference singles and doubles configuration interaction method for the excited 2 2A' state [NO(A 2Sigma+)-Kr], respectively, were used. The potential energy surfaces (PESs) show two linear wells and one that is almost in the perpendicular position. An analytical representation of the PESs has been constructed for the triatomic systems and used to carry out molecular dynamics (MD) simulations of the NO-doped krypton matrix response after excitation of NO. MD results are shown comparatively for three sets of potentials: (1) anisotropic ab initio potentials [NO molecule direction fixed during the dynamics and considered as a point (its center of mass)], (2) isotropic ab initio potentials (isotropic part in a Legendre polynomial expansion of the PESs), and (3) fitted Kr-NO potentials to the spectroscopic data. An important finding of this work is that the anisotropic and isotropic ab initio potentials calculated for the Kr-NO triatomic system are not suitable for describing the dynamics of structural relaxation upon Rydberg excitation of a NO impurity in the crystal. However, the isotropic ab initio potential in the ground state almost overlaps the published experimental potential, being almost independent of the angle asymmetry. This fact is also manifested in the radial distribution function around NO. However, in the case of the excited state the isotropic ab initio potential differs from the fitted potentials, which indicates that the Kr-NO interaction in the matrix is quite different because of the presence of the surrounding Kr atoms acting on the NO molecule. MD simulations for isotropic potentials reasonably reproduce the experimental observables for the femtosecond response and the bubble size but do not match

  1. A semiempirical study of the optimized ground and excited state potential energy surfaces of retinal and its protonated Schiff base

    NASA Technical Reports Server (NTRS)

    Parusel, A. B.; Pohorille, A.

    2001-01-01

    The electronic ground and first excited states of retinal and its Schiff base are optimized for the first time using the semiempirical AM1 Hamiltonian. The barrier for rotation about the C(11)-C(12) double bond is characterized by variation of both the twist angle delta(C(10)-C(11)-C(12)-C(13)) and the bond length d(C(11)-C(12)). The potential energy surface is obtained by varying these two parameters. The calculated ground state rotational barrier is equal to 15.6 kcal/mol for retinal and 20.5 kcal/mol for its Schiff base. The all-trans conformation is more stable by 3.7 kcal/mol than the 11-cis geometry. For the first excited state, S(1,) the 90 degrees twisted geometry represents a saddle point for retinal with the rotational barrier of 14.6 kcal/mol. In contrast, this conformation is an energy minimum for the Schiff base. It can be easily reached at room temperature from the planar minima since it is separated from them by a barrier of only 0.6 kcal/mol. The 90 degrees minimum conformation is more stable than the all-trans by 8.6 kcal/mol. We are thus able to present a reaction path on the S(1) surface of the retinal Schiff base with an almost barrier-less geometrical relaxation into a twisted minimum geometry, as observed experimentally. The character of the ground and first excited singlet states underscores the need for the inclusion of double excitations in the calculations.

  2. Effect of NaCl Salts on the Activation Energy of Excited-State Proton Transfer Reaction of Coumarin 183.

    PubMed

    Joung, Joonyoung F; Kim, Sangin; Park, Sungnam

    2015-12-17

    Coumarin 183 (C183) was used as a photoacid to study excited-state proton transfer (ESPT) reactions. Here, we studied the effect of ions on the ESPT of C183 in aqueous NaCl solutions using a steady-state fluorescence spectroscopy and time-correlated single photon counting (TCSPC) method. The acid dissociation equilibrium of excited-state C183 and the activation energy for the ESPT of C183 were determined as a function of NaCl concentration. The change in the equilibrium constant was found to be correlated with the solvation energy of deprotonated C183. Frequency-resolved TCSPC signals measured at several temperatures were analyzed by using a global fitting analysis method which enabled us to extract all the rate constants involving the ESPT reaction and the spectra of individual species. The activation energy for the ESPT reaction of C183 was highly dependent on NaCl concentration. Quantum chemical calculations were used to calculate the local hydrogen-bond (H-bond) configurations around C183 in aqueous NaCl solutions. It was found that the activation energy for the ESPT was determined by the local H-bond configurations around C183 which were significantly influenced by the dissolved ions.

  3. Direct observation of low energy nuclear spin excitations in HoCrO3 by high resolution neutron spectroscopy.

    PubMed

    Chatterji, T; Jalarvo, N; Kumar, C M N; Xiao, Y; Brückel, Th

    2013-07-17

    We have investigated low energy nuclear spin excitations in the strongly correlated electron compound HoCrO3. We observe clear inelastic peaks at E = 22.18 ± 0.04 μeV in both energy loss and gain sides. The energy of the inelastic peaks remains constant in the temperature range 1.5-40 K at which they are observed. The intensity of the inelastic peak increases at first with increasing temperature and then decreases at higher temperatures. The temperature dependence of the energy and intensity of the inelastic peaks is very unusual compared to that observed in other Nd, Co, V and also simple Ho compounds. Huge quasielastic scattering appears at higher temperatures presumably due to the fluctuating electronic moments of the Ho ions that get increasingly disordered at higher temperatures. The strong quasielastic scattering may also originate in the first Ho crystal-field excitations at about 1.5 meV.

  4. Comparison of the activation time effects and the internal energy distributions for the CID, PQD and HCD excitation modes.

    PubMed

    Ichou, Farid; Schwarzenberg, Adrian; Lesage, Denis; Alves, Sandra; Junot, Christophe; Machuron-Mandard, Xavier; Tabet, Jean-Claude

    2014-06-01

    Reproducibility among different types of excitation modes is a major bottleneck in the field of tandem mass spectrometry library development in metabolomics. In this study, we specifically evaluated the influence of collision voltage and activation time parameters on tandem mass spectrometry spectra for various excitation modes [collision-induced dissociation (CID), pulsed Q dissociation (PQD) and higher-energy collision dissociation (HCD)] of Orbitrap-based instruments. For this purpose, internal energy deposition was probed using an approach based on Rice-Rampserger-Kassel-Marcus modeling with three thermometer compounds of different degree of freedom (69, 228 and 420) and a thermal model. This model treats consecutively the activation and decomposition steps, and the survival precursor ion populations are characterized by truncated Maxwell-Boltzmann internal energy distributions. This study demonstrates that the activation time has a significant impact on MS/MS spectra using the CID and PQD modes. The proposed model seems suitable to describe the multiple collision regime in the PQD and HCD modes. Linear relationships between mean internal energy and collision voltage are shown for the latter modes and the three thermometer molecules. These results suggest that a calibration based on the collision voltage should provide reproducible for PQD, HCD to be compared with CID in tandem in space instruments. However, an important signal loss is observed in PQD excitation mode whatever the mass of the studied compounds, which may affect not only parent ions but also fragment ions depending on the fragmentation parameters. A calibration approach for the CID mode based on the variation of activation time parameter is more appropriate than one based on collision voltage. In fact, the activation time parameter in CID induces a modification of the collisional regime and thus helps control the orientation of the fragmentation pathways (competitive or consecutive dissociations).

  5. Molecular Simulation of the Free Energy for the Accurate Determination of Phase Transition Properties of Molecular Solids

    NASA Astrophysics Data System (ADS)

    Sellers, Michael; Lisal, Martin; Brennan, John

    2015-06-01

    Investigating the ability of a molecular model to accurately represent a real material is crucial to model development and use. When the model simulates materials in extreme conditions, one such property worth evaluating is the phase transition point. However, phase transitions are often overlooked or approximated because of difficulty or inaccuracy when simulating them. Techniques such as super-heating or super-squeezing a material to induce a phase change suffer from inherent timescale limitations leading to ``over-driving,'' and dual-phase simulations require many long-time runs to seek out what frequently results in an inexact location of phase-coexistence. We present a compilation of methods for the determination of solid-solid and solid-liquid phase transition points through the accurate calculation of the chemical potential. The methods are applied to the Smith-Bharadwaj atomistic potential's representation of cyclotrimethylene trinitramine (RDX) to accurately determine its melting point (Tm) and the alpha to gamma solid phase transition pressure. We also determine Tm for a coarse-grain model of RDX, and compare its value to experiment and atomistic counterpart. All methods are employed via the LAMMPS simulator, resulting in 60-70 simulations that total 30-50 ns. Approved for public release. Distribution is unlimited.

  6. High resolution IR diode laser study of collisional energy transfer between highly vibrationally excited monofluorobenzene and CO2: the effect of donor fluorination on strong collision energy transfer.

    PubMed

    Kim, Kilyoung; Johnson, Alan M; Powell, Amber L; Mitchell, Deborah G; Sevy, Eric T

    2014-12-21

    Collisional energy transfer between vibrational ground state CO2 and highly vibrationally excited monofluorobenzene (MFB) was studied using narrow bandwidth (0.0003 cm(-1)) IR diode laser absorption spectroscopy. Highly vibrationally excited MFB with E' = ∼41,000 cm(-1) was prepared by 248 nm UV excitation followed by rapid radiationless internal conversion to the electronic ground state (S1→S0*). The amount of vibrational energy transferred from hot MFB into rotations and translations of CO2 via collisions was measured by probing the scattered CO2 using the IR diode laser. The absolute state specific energy transfer rate constants and scattering probabilities for single collisions between hot MFB and CO2 were measured and used to determine the energy transfer probability distribution function, P(E,E'), in the large ΔE region. P(E,E') was then fit to a bi-exponential function and extrapolated to the low ΔE region. P(E,E') and the biexponential fit data were used to determine the partitioning between weak and strong collisions as well as investigate molecular properties responsible for large collisional energy transfer events. Fermi's Golden rule was used to model the shape of P(E,E') and identify which donor vibrational motions are primarily responsible for energy transfer. In general, the results suggest that low-frequency MFB vibrational modes are primarily responsible for strong collisions, and govern the shape and magnitude of P(E,E'). Where deviations from this general trend occur, vibrational modes with large negative anharmonicity constants are more efficient energy gateways than modes with similar frequency, while vibrational modes with large positive anharmonicity constants are less efficient at energy transfer than modes of similar frequency.

  7. Excitation photon energy dependence of the relaxation processes of the photoexcited states in a quasi-one-dimensional halogen bridged Pt complex

    NASA Astrophysics Data System (ADS)

    Wada, Y.; Matsushita, N.; Ohashi, N.

    Excitation photon energy dependence of the relaxation processes of the photoexcited states in a quasi-one-dimensional halogenbridged platinum complex has been investigated by femto second transient absorption measurements. In a Pt complex, [Pt(en)2][Pt(en)2I2](SO4)2.6H2O (Pt-I-SO4), a photo-induced absorption (PA) band caused by self trapped excitons (STE's) has been observed when the excitation photon energy is close to the peak energy, 1.44 eV, of the absorption band of the one photon allowed charge transfer (CT) exciton with odd parity. In addition, a long lived PA bands caused by charged solitons (CS's) has been observed. The intensity of these long lived CS absorption band shows quadratic excitation power dependence. This shows that CS's pairs are not generated from odd-CT-excitons but from the higher energy two photon excited states. When the excitation photon energy is close to a half of the of the even CT- exciton energy, 1.84 eV, PA bands caused by STE's and CS's have been observed. These states are generated from the two photon excited even CT-excitons. When the excitation photon energy is much higher than the energy of the odd CT-exciton, PA bands caused by CS's and polarons have been observed. The intensities of these PA bands show linear excitation power dependences. Photo-generated free electron hole pairs are considered to relax into CS's and polarons.

  8. Bifurcations of self-excitation regimes in a Van der Pol oscillator with a nonlinear energy sink

    NASA Astrophysics Data System (ADS)

    Gendelman, O. V.; Bar, T.

    2010-02-01

    The paper investigates regimes of self-excitation in a Van der Pol oscillator with an attached nonlinear energy sink (NES). Initial equations are reduced by averaging to a 3D system. The small relative mass of the NES justifies analysis of this averaged system as singularly perturbed with two “slow” and one “super-slow” variable. Such an approach, in turn, provides a complete analytic description of possible response regimes. In addition to almost unperturbed limit cycle oscillations (LCOs), the system can exhibit complete elimination of self-excitation, small-amplitude LCOs as well as excitation of a quasiperiodic strongly modulated response (SMR). In the space of parameters, the latter can be approached by three distinct bifurcation mechanisms: canard explosion, Shil’nikov bifurcation and heteroclinic bifurcation. Some of the above oscillatory regimes can co-exist for the same values of the system parameters. In this case, it is possible to establish the basins of attraction for the co-existing regimes. Direct numeric simulations demonstrate good coincidence with the analytic predictions.

  9. Collisional excitation of CH(X²Π) by He: new ab initio potential energy surfaces and scattering calculations.

    PubMed

    Marinakis, Sarantos; Dean, Indigo Lily; Kłos, Jacek; Lique, François

    2015-09-01

    We present a new set of potential energy surfaces (PESs) for the CH(X(2)Π)-He van der Waals system. Ab initio calculations of the CH-He PES were carried out using the open-shell single- and double-excitation coupled cluster approach with non-iterative perturbational treatment of triple excitations [RCCSD(T)]. The augmented correlation-consistent polarized valence quadruple-zeta (aug-cc-pVQZ) basis set was employed augmented by mid-bond functions. Integral cross sections for the rotational excitation in CH-He collisions were calculated using the new PES and compared with available experimental results. The newly constructed PES reproduces the available experimental results for CH(X(2)Π, v = 0)-He collisions better than any previously available PES. Differential cross sections (DCS) are presented for the first time for this system and discussed within the context of rotational rainbows. Finally, our work provides the first rate thermal coefficients for this system that are crucially needed for astrochemical modelling and future anticipated experiments in CH(X(2)Π)-He collisions. PMID:26220835

  10. Phase-matched emission from an optically thin medium following one-photon pulse excitation: Energy considerations

    SciTech Connect

    Berman, P. R.; Le Goueet, J.-L.

    2011-03-15

    Scully and coworkers [M. O. Scully, E. S. Fry, C. H. R. Oii, and K. Wodkiewicz, Phys. Rev. Lett. 96, 010501 (2006)] demonstrated that there is directional, phase-matched emission following the excitation of an ensemble of atoms by a single-photon pulse. While the phase-matched emission intensity is proportional to the the number of atoms, for optically thin samples the total energy emitted in the phase-matched direction is much less than that radiated in other directions. Moreover, even for optically thin samples, it is necessary to take into account effects related to cooperative decay if energy is to be conserved in the overall emission process. An analytic calculation is presented to show explicitly how cooperative decay reduces the incoherent emission and restores energy conservation in this low-density limit.

  11. Single Molecule Spectroscopy and Scanning Probe Microscopy to Investigate Excited State Energy Transport in Quantum Dot Higher Order Structures

    NASA Astrophysics Data System (ADS)

    van Orden, Alan; Gelfand, Martin; Ryan, Duncan; Whitcomb, Kevin

    2014-03-01

    Single molecule fluorescence spectroscopy and scanning probe microscopy have been used to investigate small isolated clusters of CdSe/ZnS nanocrystalline quantum dots dispersed on insulating, conducting, and semiconducting surfaces. The aggregated quantum dots exhibit excited state energy transfer and charge transport which affects the time dependent autocorrelation of the photoluminescence (PL) emission intensity, photon counting statistics, blinking statistics, and PL lifetime, as observed by single molecule fluorescence spectroscopy. The structural arrangement of the nanocrystals and the electron transfer between the quantum dots and substrate can be investigated using atomic force microscopy, transmission electron microscopy, and scanning tunneling microscopy. These combined experiments provide novel perspectives on energy and electron transport in quantum dot higher order structures and the effects of structural arrangements, substrates, and attached ligands. These insights will enhance the development of technological applications of quantum dots, including bioimaging, display technology, and alternative energy technology. Research supported by NSF Grant 1059089.

  12. Excitation energy transfer in Chlamydomonas reinhardtii deficient in the PSI core or the PSII core under conditions mimicking state transitions.

    PubMed

    Wlodarczyk, Lucyna M; Dinc, Emine; Croce, Roberta; Dekker, Jan P

    2016-06-01

    The efficient use of excitation energy in photosynthetic membranes is achieved by a dense network of pigment-protein complexes. These complexes fulfill specific functions and interact dynamically with each other in response to rapidly changing environmental conditions. Here, we studied how in the intact cells of Chlamydomonas reinhardtii (C.r.) the lack of the photosystem I (PSI) core or the photosystem II (PSII) core affects these interactions. To that end the mutants F15 and M18 (both PSI-deficient) and FUD7 (PSII-deficient) were incubated under conditions known to promote state transitions in wild-type. The intact cells were then instantly frozen to 77K and the full-spectrum time-resolved fluorescence emission of the cells was measured by means of streak camera. In the PSI-deficient mutants excitation energy transfer (EET) towards light-harvesting complexes of PSI (Lhca) occurs in less than 0.5 ns, and fluorescence from Lhca decays in 3.1 ns. Decreased trapping by PSII and increased fluorescence of Lhca upon state 1 (S1)→state 2 (S2) transition appears in the F15 and less in the M18 mutant. In the PSII-deficient mutant FUD7, quenched (0.5 ns) and unquenched (2 ns) light-harvesting complexes of PSII (LHCII) are present in both states, with the quenched form more abundant in S2 than in S1. Moreover, EET of 0.4 ns from the remaining LHCII to PSI increases upon S1→S2 transition. We relate the excitation energy kinetics observed in F15, M18 and FUD7 to the remodeling of the photosynthetic apparatus in these mutants under S1 and S2 conditions.

  13. Excitation energy transfer in Chlamydomonas reinhardtii deficient in the PSI core or the PSII core under conditions mimicking state transitions.

    PubMed

    Wlodarczyk, Lucyna M; Dinc, Emine; Croce, Roberta; Dekker, Jan P

    2016-06-01

    The efficient use of excitation energy in photosynthetic membranes is achieved by a dense network of pigment-protein complexes. These complexes fulfill specific functions and interact dynamically with each other in response to rapidly changing environmental conditions. Here, we studied how in the intact cells of Chlamydomonas reinhardtii (C.r.) the lack of the photosystem I (PSI) core or the photosystem II (PSII) core affects these interactions. To that end the mutants F15 and M18 (both PSI-deficient) and FUD7 (PSII-deficient) were incubated under conditions known to promote state transitions in wild-type. The intact cells were then instantly frozen to 77K and the full-spectrum time-resolved fluorescence emission of the cells was measured by means of streak camera. In the PSI-deficient mutants excitation energy transfer (EET) towards light-harvesting complexes of PSI (Lhca) occurs in less than 0.5 ns, and fluorescence from Lhca decays in 3.1 ns. Decreased trapping by PSII and increased fluorescence of Lhca upon state 1 (S1)→state 2 (S2) transition appears in the F15 and less in the M18 mutant. In the PSII-deficient mutant FUD7, quenched (0.5 ns) and unquenched (2 ns) light-harvesting complexes of PSII (LHCII) are present in both states, with the quenched form more abundant in S2 than in S1. Moreover, EET of 0.4 ns from the remaining LHCII to PSI increases upon S1→S2 transition. We relate the excitation energy kinetics observed in F15, M18 and FUD7 to the remodeling of the photosynthetic apparatus in these mutants under S1 and S2 conditions. PMID:26946087

  14. Some rotations like it hot: selective energy partitioning in the state resolved dynamics of collisions between CO 2 and highly vibrationally excited pyrazine

    NASA Astrophysics Data System (ADS)

    Mullin, Amy S.; Park, Jeunghee; Chou, James Z.; Flynn, George W.; Weston, Ralph E.

    1993-09-01

    The collisional quenching of highly vibrationally excited pyrazine by CO2 molecules has been studied with high resolution diode laser spectroscopy. The vibrationally hot pyrazine molecules are formed by 248 nm excimer laser pumping, followed by rapid radiationless transitions to the ground electronic state. The nascent rotational population distributions in the 0000 and 0001 vibrational levels of CO2 produced by collisions with hot pyrazine were probed at short times following excitation of pyrazine by the excimer laser pulse. In addition, the CO2 translational recoil velocity was measured for a number of rotational levels in each vibrational state. The results of these experiments reveal that very little rotational and translational excitation accompanies the energy transfer from hot pyrazine to excited vibrational levels of CO2. In contrast, rotational excitation of the CO2 ground state due to collisions with highly excited pyrazine is significant and is accompanied by a substantial enhancement in the CO2 translational energy. These results are consistent with a picture in which vibration-vibration (V → V) energy transfer processes, leading to vibrational excitation of the bath, are dominated by long range attractive forces, and vibration-translation/rotation (V → T/R) energy transfer, which leaves the bath vibrations unexcited, is dominated by short range repulsive forces.

  15. Complex frequency-dependent polarizability through the π → π* excitation energy of azobenzene molecules by a combined charge-transfer and point-dipole interaction model.

    PubMed

    Haghdani, Shokouh; Davari, Nazanin; Sandnes, Runar; Åstrand, Per-Olof

    2014-11-26

    The complex frequency-dependent polarizability and π → π* excitation energy of azobenzene compounds are investigated by a combined charge-transfer and point-dipole interaction (CT/PDI) model. To parametrize the model, we adopted time-dependent density functional theory (TDDFT) calculations of the frequency-dependent polarizability extended with excited-state lifetimes to include also its imaginary part. The results of the CT/PDI model are compared with the TDDFT calculations and experimental data demonstrating that the CT/PDI model is fully capable to reproduce the static polarizability as well as the π → π* excitation energy for these compounds. In particular, azobenzene molecules with different functional groups in the para-position have been included serving as a severe test of the model. The π → π* excitation is to a large extent localized to the azo bond, and substituting with electron-donating or electron-attracting groups on the phenyl rings results in charge-transfer effects and a shift in the excitation energy giving rise to azobenzene compounds with a range of different colors. In the CT/PDI model, the π → π* excitation in azobenzenes is manifested as drastically increasing atomic induced dipole moments in the azo group as well as in the adjacent carbon atoms, whereas the shifts in the excitation energies are due to charge-transfer effects.

  16. ATOMIC AND MOLECULAR PHYSICS: High Accuracy Calculation for Excited-State Energies of H Atoms in a Magnetic Field

    NASA Astrophysics Data System (ADS)

    Zhao, Li-Bo; Du, Meng-Li

    2009-08-01

    Using the recently developed finite-basis-set method with B splines, excited states of H atoms in a magnetic field have been calculated. Energy levels are presented for the ten excited states, 2s0, 3d'0, 3p0, 3p-1, 3d-1, 4d-1, 3d-2, 4d-2, 4f-2, and 5f-2 as a function of magnetic field strengths with a range from zero up to 2.35 × 106 T. The obtained results are compared with available high accuracy theoretical data reported in the literature and found to be in excellent agreement. The comparison also shows that the current method can produce energy levels with an accuracy higher than the existing high accuracy method [Phys. Rev. A 54 (1996) 287]. Here high accuracy energy levels are for the first time reported for the 3d'0, 4d-1, 4d-2, 4f-2, and 5f-2 states.

  17. Ionization potentials, electron affinities, resonance excitation energies, oscillator strengths, and ionic radii of element Uus (Z = 117) and astatine.

    PubMed

    Chang, Zhiwei; Li, Jiguang; Dong, Chenzhong

    2010-12-30

    Multiconfiguration Dirac-Fock (MCDF) method was employed to calculate the first five ionization potentials, electron affinities, resonance excitation energies, oscillator strengths, and radii for the element Uus and its homologue At. Main valence correlation effects were taken into account. The Breit interaction and QED effects were also estimated. The uncertainties of calculated IPs, EAs, and IR for Uus and At were reduced through an extrapolation procedure. The good consistency with available experimental and other theoretical values demonstrates the validity of the present results. These theoretical data therefore can be used to predict some unknown physicochemical properties of element Uus, Astatine, and their compounds. PMID:21141866

  18. Ab initio ground and the first excited adiabatic and quasidiabatic potential energy surfaces of H + + CO system

    NASA Astrophysics Data System (ADS)

    George, D. X. F.; Kumar, Sanjay

    2010-08-01

    Ab initio global adiabatic as well as quasidiabatic potential energy surfaces for the ground and the first excited electronic states of the H + + CO system have been computed as a function of the Jacobi coordinates ( R, r, γ) using Dunning's cc-pVTZ basis set at the internally contracted multi-reference (single and double) configuration interaction level of accuracy. In addition, nonadiabatic coupling matrix elements arising from radial motion, mixing angle and coupling potential have been computed using the ab initio procedure [Simah et al. (1999) [66

  19. Ionization potentials, electron affinities, resonance excitation energies, oscillator strengths, and ionic radii of element Uus (Z = 117) and astatine.

    PubMed

    Chang, Zhiwei; Li, Jiguang; Dong, Chenzhong

    2010-12-30

    Multiconfiguration Dirac-Fock (MCDF) method was employed to calculate the first five ionization potentials, electron affinities, resonance excitation energies, oscillator strengths, and radii for the element Uus and its homologue At. Main valence correlation effects were taken into account. The Breit interaction and QED effects were also estimated. The uncertainties of calculated IPs, EAs, and IR for Uus and At were reduced through an extrapolation procedure. The good consistency with available experimental and other theoretical values demonstrates the validity of the present results. These theoretical data therefore can be used to predict some unknown physicochemical properties of element Uus, Astatine, and their compounds.

  20. Energy Loss of Solar p Modes due to the Excitation of Magnetic Sausage Tube Waves: Importance of Coupling the Upper Atmosphere

    NASA Astrophysics Data System (ADS)

    Gascoyne, A.; Jain, R.; Hindman, B. W.

    2014-07-01

    We consider damping and absorption of solar p modes due to their energy loss to magnetic tube waves that can freely carry energy out of the acoustic cavity. The coupling of p modes and sausage tube waves is studied in a model atmosphere composed of a polytropic interior above which lies an isothermal upper atmosphere. The sausage tube waves, excited by p modes, propagate along a magnetic fibril which is assumed to be a vertically aligned, stratified, thin magnetic flux tube. The deficit of p-mode energy is quantified through the damping rate, Γ, and absorption coefficient, α. The variation of Γ and α as a function of frequency and the tube's plasma properties is studied in detail. Previous similar studies have considered only a subphotospheric layer, modeled as a polytrope that has been truncated at the photosphere. Such studies have found that the resulting energy loss by the p modes is very sensitive to the upper boundary condition, which, due to the lack of an upper atmosphere, have been imposed in a somewhat ad hoc manner. The model presented here avoids such problems by using an isothermal layer to model the overlying atmosphere (chromosphere, and, consequently, allows us to analyze the propagation of p-mode-driven sausage waves above the photosphere. In this paper, we restrict our attention to frequencies below the acoustic cut off frequency. We demonstrate the importance of coupling all waves (acoustic, magnetic) in the subsurface solar atmosphere with the overlying atmosphere in order to accurately model the interaction of solar f and p modes with sausage tube waves. In calculating the absorption and damping of p modes, we find that for low frequencies, below ≈3.5 mHz, the isothermal atmosphere, for the two-region model, behaves like a stress-free boundary condition applied at the interface (z = -z 0).

  1. Energy loss of solar p modes due to the excitation of magnetic sausage tube waves: Importance of coupling the upper atmosphere

    SciTech Connect

    Gascoyne, A.; Jain, R.; Hindman, B. W. E-mail: r.jain@sheffield.ac.uk

    2014-07-10

    We consider damping and absorption of solar p modes due to their energy loss to magnetic tube waves that can freely carry energy out of the acoustic cavity. The coupling of p modes and sausage tube waves is studied in a model atmosphere composed of a polytropic interior above which lies an isothermal upper atmosphere. The sausage tube waves, excited by p modes, propagate along a magnetic fibril which is assumed to be a vertically aligned, stratified, thin magnetic flux tube. The deficit of p-mode energy is quantified through the damping rate, Γ, and absorption coefficient, α. The variation of Γ and α as a function of frequency and the tube's plasma properties is studied in detail. Previous similar studies have considered only a subphotospheric layer, modeled as a polytrope that has been truncated at the photosphere. Such studies have found that the resulting energy loss by the p modes is very sensitive to the upper boundary condition, which, due to the lack of an upper atmosphere, have been imposed in a somewhat ad hoc manner. The model presented here avoids such problems by using an isothermal layer to model the overlying atmosphere (chromosphere, and, consequently, allows us to analyze the propagation of p-mode-driven sausage waves above the photosphere. In this paper, we restrict our attention to frequencies below the acoustic cut off frequency. We demonstrate the importance of coupling all waves (acoustic, magnetic) in the subsurface solar atmosphere with the overlying atmosphere in order to accurately model the interaction of solar f and p modes with sausage tube waves. In calculating the absorption and damping of p modes, we find that for low frequencies, below ≈3.5 mHz, the isothermal atmosphere, for the two-region model, behaves like a stress-free boundary condition applied at the interface (z = –z{sub 0}).

  2. Accurate high level ab initio-based global potential energy surface and dynamics calculations for ground state of CH2(+).

    PubMed

    Li, Y Q; Zhang, P Y; Han, K L

    2015-03-28

    A global many-body expansion potential energy surface is reported for the electronic ground state of CH2 (+) by fitting high level ab initio energies calculated at the multireference configuration interaction level with the aug-cc-pV6Z basis set. The topographical features of the new global potential energy surface are examined in detail and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. In turn, in order to validate the potential energy surface, a test theoretical study of the reaction CH(+)(X(1)Σ(+))+H((2)S)→C(+)((2)P)+H2(X(1)Σg (+)) has been carried out with the method of time dependent wavepacket on the title potential energy surface. The total integral cross sections and the rate coefficients have been calculated; the results determined that the new potential energy surface can both be recommended for dynamics studies of any type and as building blocks for constructing the potential energy surfaces of larger C(+)/H containing systems.

  3. The luminescence of BaF{sub 2} nanoparticles upon high-energy excitation

    SciTech Connect

    Vistovskyy, V. V. Zhyshkovych, A. V.; Halyatkin, O. O.; Voloshinovskii, A. S.; Mitina, N. E.; Zaichenko, A. S.; Rodnyi, P. A.; Vasil'ev, A. N.; Gektin, A. V.

    2014-08-07

    The dependence of X-ray excited luminescence intensity on BaF{sub 2} nanoparticle size was studied. A sharp decrease of self-trapped exciton luminescence intensity was observed when the nanoparticle size is less than 80 nm. The main mechanism of the luminescence quenching is caused by the escape of electrons from the nanoparticles. Escape of electrons from nanoparticles is confirmed by the considerable increase of luminescence intensity of the polystyrene scintillator with embedded BaF{sub 2} nanoparticles comparing with pure polystyrene scintillator.

  4. The transmission of acoustic energy by a finite cylindrical shell excited by external plane waves

    NASA Astrophysics Data System (ADS)

    Cacciolati, C.; Gotteland, M.; Barbe, M.

    A qualitative method is presented for sensitivity analyses of acoustic coupling between cylindrical shells such as found in aerospace structures. The shells are excited by an exterior plane wave. The analysis is carried out in terms of coupling among the exterior and structural natural modes and the structural and cavity natural modes. Strong coupling is shown to be limited to cases of coincidence of resonance frequencies and when numerous identical incident waves arrive from multiple directions. Coupling will in any case be confined to low frequencies. Limits are defined for the necessary number of frequencies which must be considered when predicting whether or not coupling will occur.

  5. Chaotic versus nonchaotic stochastic dynamics in Monte Carlo simulations: a route for accurate energy differences in N-body systems.

    PubMed

    Assaraf, Roland; Caffarel, Michel; Kollias, A C

    2011-04-15

    We present a method to efficiently evaluate small energy differences of two close N-body systems by employing stochastic processes having a stability versus chaos property. By using the same random noise, energy differences are computed from close trajectories without reweighting procedures. The approach is presented for quantum systems but can be applied to classical N-body systems as well. It is exemplified with diffusion Monte Carlo simulations for long chains of hydrogen atoms and molecules for which it is shown that the long-standing problem of computing energy derivatives is solved. PMID:21568537

  6. Calculations of Excitation Functions of Some Structural Fusion Materials for ( n, t) Reactions up to 50 MeV Energy

    NASA Astrophysics Data System (ADS)

    Tel, E.; Durgu, C.; Aktı, N. N.; Okuducu, Ş.

    2010-06-01

    Fusion serves an inexhaustible energy for humankind. Although there have been significant research and development studies on the inertial and magnetic fusion reactor technology, there is still a long way to go to penetrate commercial fusion reactors to the energy market. Tritium self-sufficiency must be maintained for a commercial power plant. For self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. So, the working out the systematics of ( n, t) reaction cross sections is of great importance for the definition of the excitation function character for the given reaction taking place on various nuclei at different energies. In this study, ( n, t) reactions for some structural fusion materials such as 27Al, 51V, 52Cr, 55Mn, and 56Fe have been investigated. The new calculations on the excitation functions of 27Al( n, t)25Mg, 51V( n, t)49Ti, 52Cr( n, t)50V, 55Mn( n, t)53Cr and 56Fe( n, t)54Mn reactions have been carried out up to 50 MeV incident neutron energy. In these calculations, the pre-equilibrium and equilibrium effects have been investigated. The pre-equilibrium calculations involve the new evaluated the geometry dependent hybrid model, hybrid model and the cascade exciton model. Equilibrium effects are calculated according to the Weisskopf-Ewing model. Also in the present work, we have calculated ( n, t) reaction cross-sections by using new evaluated semi-empirical formulas developed by Tel et al. at 14-15 MeV energy. The calculated results are discussed and compared with the experimental data taken from the literature.

  7. An accurate potential energy surface for the F + H2 → HF + H reaction by the coupled-cluster method

    NASA Astrophysics Data System (ADS)

    Chen, Jun; Sun, Zhigang; Zhang, Dong H.

    2015-01-01

    A three dimensional potential energy surface for the F + H2 → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2)Q] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H2 reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface.

  8. An accurate potential energy surface for the F + H2 → HF + H reaction by the coupled-cluster method.

    PubMed

    Chen, Jun; Sun, Zhigang; Zhang, Dong H

    2015-01-14

    A three dimensional potential energy surface for the F + H2 → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2)Q] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H2 reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface.

  9. The geometrical change and intramolecular energy transfer upon S{sub 1}←S{sub 0} excitation in cyclopentanone

    SciTech Connect

    Wang, Yanmei Liu, Zhiming; Xu, Yanqi; Zhang, Bing

    2015-08-14

    The ultrafast dynamics in vibrationally hot S{sub 1} electronic excited state in cyclopentanone molecule was discovered with time resolved spectroscopy. Investigation of the geometry change upon the S{sub 1}←S{sub 0} excitation and D{sub 0}←S{sub 1} ionization has shown that the dihedral angle between the C=O bond and the plane given by the carbonyl and the α-carbons is 180° either in S{sub 0} or D{sub 0} state and is reduced to 145.8° by out-out-plane deformation of the oxygen in S{sub 1} state according to the theoretical calculation. The time domain experiments with femtosecond resolution have given rich insights into the energy transfer of the cyclopentanone molecule. The molecules are excited to the vibrationally hot S{sub 1} (n,  π{sup ∗}) state following absorption of one 267-nm photon. It is found that the population of the S{sub 1} (n, π{sup ∗}) state undergoes ultrafast internal conversion to the highly vibrationally hot S{sub 0} state within 80 fs and nonradiative deactivation by intersystem crossing to triplet T{sub 1} (n, π{sup *}) state occurring in 3.14 ps. Several Rydberg states have worked as stepping stones during the ionization. The available energy was distributed in the symmetric methylene group wagging and the symmetric skeletal ring breathing modes in D{sub 0} state.

  10. A strategy to minimize the energy offset in carrier injection from excited dyes to inorganic semiconductors for efficient dye-sensitized solar energy conversion.

    PubMed

    Fujisawa, Jun-Ichi; Osawa, Ayumi; Hanaya, Minoru

    2016-08-10

    Photoinduced carrier injection from dyes to inorganic semiconductors is a crucial process in various dye-sensitized solar energy conversions such as photovoltaics and photocatalysis. It has been reported that an energy offset larger than 0.2-0.3 eV (threshold value) is required for efficient electron injection from excited dyes to metal-oxide semiconductors such as titanium dioxide (TiO2). Because the energy offset directly causes loss in the potential of injected electrons, it is a crucial issue to minimize the energy offset for efficient solar energy conversions. However, a fundamental understanding of the energy offset, especially the threshold value, has not been obtained yet. In this paper, we report the origin of the threshold value of the energy offset, solving the long-standing questions of why such a large energy offset is necessary for the electron injection and which factors govern the threshold value, and suggest a strategy to minimize the threshold value. The threshold value is determined by the sum of two reorganization energies in one-electron reduction of semiconductors and typically-used donor-acceptor (D-A) dyes. In fact, the estimated values (0.21-0.31 eV) for several D-A dyes are in good agreement with the threshold value, supporting our conclusion. In addition, our results reveal that the threshold value is possible to be reduced by enlarging the π-conjugated system of the acceptor moiety in dyes and enhancing its structural rigidity. Furthermore, we extend the analysis to hole injection from excited dyes to semiconductors. In this case, the threshold value is given by the sum of two reorganization energies in one-electron oxidation of semiconductors and D-A dyes.

  11. A strategy to minimize the energy offset in carrier injection from excited dyes to inorganic semiconductors for efficient dye-sensitized solar energy conversion.

    PubMed

    Fujisawa, Jun-Ichi; Osawa, Ayumi; Hanaya, Minoru

    2016-08-10

    Photoinduced carrier injection from dyes to inorganic semiconductors is a crucial process in various dye-sensitized solar energy conversions such as photovoltaics and photocatalysis. It has been reported that an energy offset larger than 0.2-0.3 eV (threshold value) is required for efficient electron injection from excited dyes to metal-oxide semiconductors such as titanium dioxide (TiO2). Because the energy offset directly causes loss in the potential of injected electrons, it is a crucial issue to minimize the energy offset for efficient solar energy conversions. However, a fundamental understanding of the energy offset, especially the threshold value, has not been obtained yet. In this paper, we report the origin of the threshold value of the energy offset, solving the long-standing questions of why such a large energy offset is necessary for the electron injection and which factors govern the threshold value, and suggest a strategy to minimize the threshold value. The threshold value is determined by the sum of two reorganization energies in one-electron reduction of semiconductors and typically-used donor-acceptor (D-A) dyes. In fact, the estimated values (0.21-0.31 eV) for several D-A dyes are in good agreement with the threshold value, supporting our conclusion. In addition, our results reveal that the threshold value is possible to be reduced by enlarging the π-conjugated system of the acceptor moiety in dyes and enhancing its structural rigidity. Furthermore, we extend the analysis to hole injection from excited dyes to semiconductors. In this case, the threshold value is given by the sum of two reorganization energies in one-electron oxidation of semiconductors and D-A dyes. PMID:27452717

  12. Ab initio nonadiabatic molecular dynamics of the ultrafast excitation energy transfer in small semiconducting carbon nanotube aggregates

    NASA Astrophysics Data System (ADS)

    Postupna, Olena; Long, Run; Prezhdo, Oleg

    2012-02-01

    Outstanding physical properties of carbon nanotubes (CNTs), such as well-defined optical resonance and ultrafast nonlinear response, result in CNTs gaining popularity in academic and industrial endeavors as potential effective energy generating devices. Following recent experiments on ultrafast excitation energy transfer in small semiconducting carbon nanotube aggregates [1], we report results of ab initio nonadiabatic molecular dynamics simulation of the energy transfer taking place in two carbon nanotube systems. We investigate the energy transfer between (8,4) and (10,0) CNTs, as well as (8,4) and (13,0) CNTs. In both cases, the CNTs are orthogonal to each other. Luer et al. in [1] elucidate the second excitonic transitions followed by fast intratube relaxation and energy transfer from the (8,4) CNT toward other acceptor tubes. Our project aims to provide a better understanding of the energy transfer mechanism in the given systems, which should foster development of a theory for the electronic structure and dynamics of CNT networks, hence enhancing their tailoring and application in the future. References 1.Larry Luer, Jared Crochet, Tobias Hertel, Giulio Cerullo, Gugliermo Lanzani. ACSNano. Vol.4, No. 7, 4265-4273

  13. Harvesting energy from the sloshing motion of ferrofluids in an externally excited container: Analytical modeling and experimental validation

    NASA Astrophysics Data System (ADS)

    Alazmi, S.; Xu, Y.; Daqaq, M. F.

    2016-07-01

    When a container carrying a magnetized ferrofluid is subjected to external mechanical stimuli, the sloshing motion of the magnetized ferrofluid generates a time-varying magnetic flux, which can be used to induce an electromotive force in a coil placed adjacent to the container. This process generates an electric current in the coil, and therewith, can be used to transduce external vibrations into electric energy. In this article, we develop a nonlinear analytical model, which governs the electro-magneto-hydrodynamics of an electromagnetic ferrofluid-based vibratory energy harvester. Using perturbation methods, we obtain an approximate analytical solution of the model for a case involving primary resonance excitation of the first mode and a two-to-one internal resonance between the first two modes. This occurs when the external excitation is harmonic with a frequency close to the fundamental sloshing frequency and when the second modal frequency is nearly twice the first modal frequency. Theoretical results are compared to experimental findings illustrating very good qualitative agreement.

  14. Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory

    SciTech Connect

    Silverstein, Daniel W.; Govind, Niranjan; van Dam, Hubertus J. J.; Jensen, Lasse

    2013-12-10

    A parallel implementation of analytical time-dependent density functional theory gradients is presented for the quantum chemistry program NWChem. The implementation is based on the Lagrangian approach developed by Furche and Ahlrichs. To validate our implementation, we first calculate the Stokes shifts for a range of organic dye molecules using a diverse set of exchange-correlation functionals (traditional density functionals, global hybrids, and range-separated hybrids) followed by simulations of the one-photon absorption and resonance Raman scattering spectrum of the phenoxyl radical, the well-studied dye molecule rhodamine 6G, and a molecular host–guest complex (TTFcCBPQT4+). The study of organic dye molecules illustrates that B3LYP and CAM-B3LYP generally give the best agreement with experimentally determined Stokes shifts unless the excited state is a charge transfer state. Absorption, resonance Raman, and fluorescence simulations for the phenoxyl radical indicate that explicit solvation may be required for accurate characterization. For the host–guest complex and rhodamine 6G, it is demonstrated that absorption spectra can be simulated in good agreement with experimental data for most exchange-correlation functionals. Finally, however, because one-photon absorption spectra generally lack well-resolved vibrational features, resonance Raman simulations are necessary to evaluate the accuracy of the exchange-correlation functional for describing a potential energy surface.

  15. Local CC2 response method based on the Laplace transform: analytic energy gradients for ground and excited states.

    PubMed

    Ledermüller, Katrin; Schütz, Martin

    2014-04-28

    A multistate local CC2 response method for the calculation of analytic energy gradients with respect to nuclear displacements is presented for ground and electronically excited states. The gradient enables the search for equilibrium geometries of extended molecular systems. Laplace transform is used to partition the eigenvalue problem in order to obtain an effective singles eigenvalue problem and adaptive, state-specific local approximations. This leads to an approximation in the energy Lagrangian, which however is shown (by comparison with the corresponding gradient method without Laplace transform) to be of no concern for geometry optimizations. The accuracy of the local approximation is tested and the efficiency of the new code is demonstrated by application calculations devoted to a photocatalytic decarboxylation process of present interest.

  16. Global Analysis of Response in the Piezomagnetoelastic Energy Harvester System under Harmonic and Poisson White Noise Excitations

    NASA Astrophysics Data System (ADS)

    Yue, Xiao-Le; Xu, Wei; Zhang, Ying; Wang, Liang

    2015-10-01

    The piezomagnetoelastic energy harvester system subjected to harmonic and Poisson white noise excitations is studied by using the generalized cell mapping method. The transient and stationary probability density functions (PDFs) of response based on the global viewpoint are obtained by the matrix analysis method. Monte Carlo simulation results verify the accuracy of this method. It can be observed that evolutionary direction of transient and stationary PDFs is in accordance with the unstable manifold for this system, and a stochastic P-bifurcation occurs as the intensity of Poisson white noise increases. This study presents an efficient numerical tool to solve the stochastic response of a three-dimensional dynamical system and provides a new idea to analyze the energy harvester system. Supported by the National Natural Science Foundation of China under Grant Nos. 11302170, 11202160, 11302171, and the Fundamental Research Funds for the Central Universities under Grant No. 3102014JCQ01079

  17. Energy loss in gas-surface dynamics: Electron-hole pair and phonon excitation upon adsorbate relaxation

    NASA Astrophysics Data System (ADS)

    Novko, D.; Blanco-Rey, M.; Juaristi, J. I.; Alducin, M.

    2016-09-01

    We study the effect of electron and phonon degrees of freedom on the relaxation dynamics of adsorption processes in gas-surface systems by using ab initio molecular dynamics that incorporates an electronic friction force (AIMDEF). As representative cases we have chosen three systems with different adsorption energies and adsorbate-to-surface atom mass ratios: H on Pd(1 0 0), N on Ag(1 1 1), and N2 on Fe(1 1 0). We show, through inspection of the total energies and trajectories of the hot adsorbates on the surface, that electron-hole (e-h) pair excitations dominate relaxation of the light gas species, while the phonon channel is dominant for the heavy species. In the latter case e-h pairs become more important at the final thermalization stages.

  18. Measurements of Excitation Functions and Line Polarizations for Electron Impact Excitation of the n = 2, 3 States of Atomic Hydrogen in the Energy Range 11 - 2000 eV

    NASA Technical Reports Server (NTRS)

    James, G. K.; Ajello, J. M.; Kanik, I.; Slevin, J.; Franklin, B.; Shemansky, D.

    1993-01-01

    The electron-atomic hydrogen scattering system is an important testing ground for theoretical models and has received a great deal of attention from experimentalists and theoreticians alike over the years. A complete description of the excitation process requires a knowledge of many different parameters, and experimental measurements of these parameters have been performed in various laboratories around the world. As far as total cross section data are concerned it has been noted that the discrepancy between the data of Long et al. and Williams for n = 2 excitations needs to be resolved in the interests of any further refinement of theory. We report new measurements of total cross sections and atomic line polarizations for both n=2 and n=3 excitations at energies from threshold to 2000 eV...

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

    NASA Astrophysics Data System (ADS)

    Koh, Yang Wei

    2016-04-01

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

  20. Cryogenic exciter

    SciTech Connect

    Bray, James William; Garces, Luis Jose

    2012-03-13

    The disclosed technology is a cryogenic static exciter. The cryogenic static exciter is connected to a synchronous electric machine that has a field winding. The synchronous electric machine is cooled via a refrigerator or cryogen like liquid nitrogen. The static exciter is in communication with the field winding and is operating at ambient temperature. The static exciter receives cooling from a refrigerator or cryogen source, which may also service the synchronous machine, to selected areas of the static exciter and the cooling selectively reduces the operating temperature of the selected areas of the static exciter.

  1. Challenges facing an understanding of the nature of low-energy excited states in photosynthesis.

    PubMed

    Reimers, Jeffrey R; Biczysko, Malgorzata; Bruce, Douglas; Coker, David F; Frankcombe, Terry J; Hashimoto, Hideki; Hauer, Jürgen; Jankowiak, Ryszard; Kramer, Tobias; Linnanto, Juha; Mamedov, Fikret; Müh, Frank; Rätsep, Margus; Renger, Thomas; Styring, Stenbjörn; Wan, Jian; Wang, Zhuan; Wang-Otomo, Zheng-Yu; Weng, Yu-Xiang; Yang, Chunhong; Zhang, Jian-Ping; Freiberg, Arvi; Krausz, Elmars

    2016-09-01

    While the majority of the photochemical states and pathways related to the biological capture of solar energy are now well understood and provide paradigms for artificial device design, additional low-energy states have been discovered in many systems with obscure origins and significance. However, as low-energy states are naively expected to be critical to function, these observations pose important challenges. A review of known properties of low energy states covering eight photochemical systems, and options for their interpretation, are presented. A concerted experimental and theoretical research strategy is suggested and outlined, this being aimed at providing a fully comprehensive understanding.

  2. Challenges facing an understanding of the nature of low-energy excited states in photosynthesis.

    PubMed

    Reimers, Jeffrey R; Biczysko, Malgorzata; Bruce, Douglas; Coker, David F; Frankcombe, Terry J; Hashimoto, Hideki; Hauer, Jürgen; Jankowiak, Ryszard; Kramer, Tobias; Linnanto, Juha; Mamedov, Fikret; Müh, Frank; Rätsep, Margus; Renger, Thomas; Styring, Stenbjörn; Wan, Jian; Wang, Zhuan; Wang-Otomo, Zheng-Yu; Weng, Yu-Xiang; Yang, Chunhong; Zhang, Jian-Ping; Freiberg, Arvi; Krausz, Elmars

    2016-09-01

    While the majority of the photochemical states and pathways related to the biological capture of solar energy are now well understood and provide paradigms for artificial device design, additional low-energy states have been discovered in many systems with obscure origins and significance. However, as low-energy states are naively expected to be critical to function, these observations pose important challenges. A review of known properties of low energy states covering eight photochemical systems, and options for their interpretation, are presented. A concerted experimental and theoretical research strategy is suggested and outlined, this being aimed at providing a fully comprehensive understanding. PMID:27372198

  3. Universal properties of materials with the Dirac dispersion relation of low-energy excitations

    SciTech Connect

    Protogenov, A. P.; Chulkov, E. V.

    2015-12-15

    The N-terminal scheme is considered for studying the contribution of edge states to the response of a two-dimensional topological insulator. A universal distribution of the nonlocal resistance between terminals is determined in the ballistic transport approach. The calculated responses are identical to experimentally observed values. The spectral properties of surface electronic states in Weyl semimetals are also studied. The density of surface states is accurately determined. The universal behavior of these characteristics is a distinctive feature of the considered Dirac materials which can be used in practical applications.

  4. Spectroscopic probes of vibrationally excited molecules at chemically significant energies. Progress report, August 15, 1991--August 14, 1992

    SciTech Connect

    Rizzo, T.R.

    1992-03-01

    These experiments apply multiple-laser spectroscopic techniques to investigate the bond energies, potential surface topologies, and dissociation dynamics of highly vibrationally excited molecules. Infrared-optical double resonance pumping of light atom stretch vibrations in H{sub 2}O{sub 2} and HN{sub 3} prepares reactant molecules in single rovibrational states above the unimolecular dissociation threshold on the ground potential surface, and laser induced fluorescence detection of the OH or NH fragments monitors the partitioning of energy into individual product quantum states. Product energy partitioning data from H{sub 2}O{sub 2} dissociation provide a stringent test of statistical theories as well as potential energy surface calculations. Ongoing work on HN{sub 3} seeks to determine the height of the barrier to dissociation on the singlet potential energy surface. Our most recently developed spectroscopic scheme allows the measurement of high vibrational overtone spectra of jet-cooled molecules. This approach uses CO{sub 2} laser infrared multiphoton dissociation followed by laser induced fluorescence product detection to measure weak vibrational overtone transitions in low pressure environments. Application of this scheme to record the {Delta}V{sub OH}=4 and {Delta}V{sub OH}=5 transitions of CH{sub 3}OH cooled in a supersonic free-jet demonstrates both its feasibility and its utility for simplifying high vibrational overtone spectra.

  5. Simple model of bulk and surface excitation effects to inelastic scattering in low-energy electron beam irradiation of multi-walled carbon nanotubes

    SciTech Connect

    Kyriakou, Ioanna; Emfietzoglou, Dimitris; Garcia-Molina, Rafael; Abril, Isabel; Kostarelos, Kostas

    2011-09-01

    The effect of bulk and surface excitations to inelastic scattering in low-energy electron beam irradiation of multi-walled carbon nanotubes (MWNTs) is studied using the dielectric formalism. Calculations are based on a semiempirical dielectric response function for MWCNTs determined by means of a many-pole plasmon model with parameters adjusted to available experimental spectroscopic data under theoretical sum-rule constrains. Finite-size effects are considered in the context of electron gas theory via a boundary correction term in the plasmon dispersion relations, thus, allowing a more realistic extrapolation of the electronic excitation spectrum over the whole energy-momentum plane. Energy-loss differential and total inelastic scattering cross sections as a function of electron energy and distance from the surface, valid over the energy range {approx}50-30,000 eV, are calculated with the individual contribution of bulk and surface excitations separated and analyzed for the case of normally incident and escaping electrons. The sensitivity of the results to the various approximations for the spatial dispersion of the electronic excitations is quantified. Surface excitations are shown to have a strong influence upon the shape and intensity of the energy-loss differential cross section in the near surface region whereas the general notion of a spatially invariant inelastic mean free path inside the material is found to be of good approximation.

  6. A Simple and Accurate Method To Calculate Free Energy Profiles and Reaction Rates from Restrained Molecular Simulations of Diffusive Processes.

    PubMed

    Ovchinnikov, Victor; Nam, Kwangho; Karplus, Martin

    2016-08-25

    A method is developed to obtain simultaneously free energy profiles and diffusion constants from restrained molecular simulations in diffusive systems. The method is based on low-order expansions of the free energy and diffusivity as functions of the reaction coordinate. These expansions lead to simple analytical relationships between simulation statistics and model parameters. The method is tested on 1D and 2D model systems; its accuracy is found to be comparable to or better than that of the existing alternatives, which are briefly discussed. An important aspect of the method is that the free energy is constructed by integrating its derivatives, which can be computed without need for overlapping sampling windows. The implementation of the method in any molecular simulation program that supports external umbrella potentials (e.g., CHARMM) requires modification of only a few lines of code. As a demonstration of its applicability to realistic biomolecular systems, the method is applied to model the α-helix ↔ β-sheet transition in a 16-residue peptide in implicit solvent, with the reaction coordinate provided by the string method. Possible modifications of the method are briefly discussed; they include generalization to multidimensional reaction coordinates [in the spirit of the model of Ermak and McCammon (Ermak, D. L.; McCammon, J. A. J. Chem. Phys. 1978, 69, 1352-1360)], a higher-order expansion of the free energy surface, applicability in nonequilibrium systems, and a simple test for Markovianity. In view of the small overhead of the method relative to standard umbrella sampling, we suggest its routine application in the cases where umbrella potential simulations are appropriate.

  7. ATOMIC AND MOLECULAR PHYSICS: High order correlation-polarization potential for vibrational excitation scattering of diatomic molecules by low-energy electrons

    NASA Astrophysics Data System (ADS)

    Feng, Hao; Sun, Wei-Guo; Zeng, Yang-Yang

    2009-11-01

    This paper introduces a correlation-polarization potential with high order terms for vibrational excitation in electron-molecule scattering. The new polarization potential generalizes the two-term approximation so that it can better reflect the dependence of correlation and polarization effects on the position coordinate of the scattering electron. It applies the new potential on the vibrational excitation scattering from N2 in an energy range which includes the 2Πg shape resonance. The good agreement of theoretical resonant peaks with experiments shows that polarization potentials with high order terms are important and should be included in vibrational excitation scattering.

  8. A compact and accurate semi-global potential energy surface for malonaldehyde from constrained least squares regression

    SciTech Connect

    Mizukami, Wataru Tew, David P.; Habershon, Scott

    2014-10-14

    We present a new approach to semi-global potential energy surface fitting that uses the least absolute shrinkage and selection operator (LASSO) constrained least squares procedure to exploit an extremely flexible form for the potential function, while at the same time controlling the risk of overfitting and avoiding the introduction of unphysical features such as divergences or high-frequency oscillations. Drawing from a massively redundant set of overlapping distributed multi-dimensional Gaussian functions of inter-atomic separations we build a compact full-dimensional surface for malonaldehyde, fit to explicitly correlated coupled cluster CCSD(T)(F12*) energies with a root mean square deviations accuracy of 0.3%–0.5% up to 25 000 cm{sup −1} above equilibrium. Importance-sampled diffusion Monte Carlo calculations predict zero point energies for malonaldehyde and its deuterated isotopologue of 14 715.4(2) and 13 997.9(2) cm{sup −1} and hydrogen transfer tunnelling splittings of 21.0(4) and 3.2(4) cm{sup −1}, respectively, which are in excellent agreement with the experimental values of 21.583 and 2.915(4) cm{sup −1}.

  9. A compact and accurate semi-global potential energy surface for malonaldehyde from constrained least squares regression

    NASA Astrophysics Data System (ADS)

    Mizukami, Wataru; Habershon, Scott; Tew, David P.

    2014-10-01

    We present a new approach to semi-global potential energy surface fitting that uses the least absolute shrinkage and selection operator (LASSO) constrained least squares procedure to exploit an extremely flexible form for the potential function, while at the same time controlling the risk of overfitting and avoiding the introduction of unphysical features such as divergences or high-frequency oscillations. Drawing from a massively redundant set of overlapping distributed multi-dimensional Gaussian functions of inter-atomic separations we build a compact full-dimensional surface for malonaldehyde, fit to explicitly correlated coupled cluster CCSD(T)(F12*) energies with a root mean square deviations accuracy of 0.3%-0.5% up to 25 000 cm-1 above equilibrium. Importance-sampled diffusion Monte Carlo calculations predict zero point energies for malonaldehyde and its deuterated isotopologue of 14 715.4(2) and 13 997.9(2) cm-1 and hydrogen transfer tunnelling splittings of 21.0(4) and 3.2(4) cm-1, respectively, which are in excellent agreement with the experimental values of 21.583 and 2.915(4) cm-1.

  10. Extended Adaptive Biasing Force Algorithm. An On-the-Fly Implementation for Accurate Free-Energy Calculations.

    PubMed

    Fu, Haohao; Shao, Xueguang; Chipot, Christophe; Cai, Wensheng

    2016-08-01

    Proper use of the adaptive biasing force (ABF) algorithm in free-energy calculations needs certain prerequisites to be met, namely, that the Jacobian for the metric transformation and its first derivative be available and the coarse variables be independent and fully decoupled from any holonomic constraint or geometric restraint, thereby limiting singularly the field of application of the approach. The extended ABF (eABF) algorithm circumvents these intrinsic limitations by applying the time-dependent bias onto a fictitious particle coupled to the coarse variable of interest by means of a stiff spring. However, with the current implementation of eABF in the popular molecular dynamics engine NAMD, a trajectory-based post-treatment is necessary to derive the underlying free-energy change. Usually, such a posthoc analysis leads to a decrease in the reliability of the free-energy estimates due to the inevitable loss of information, as well as to a drop in efficiency, which stems from substantial read-write accesses to file systems. We have developed a user-friendly, on-the-fly code for performing eABF simulations within NAMD. In the present contribution, this code is probed in eight illustrative examples. The performance of the algorithm is compared with traditional ABF, on the one hand, and the original eABF implementation combined with a posthoc analysis, on the other hand. Our results indicate that the on-the-fly eABF algorithm (i) supplies the correct free-energy landscape in those critical cases where the coarse variables at play are coupled to either each other or to geometric restraints or holonomic constraints, (ii) greatly improves the reliability of the free-energy change, compared to the outcome of a posthoc analysis, and (iii) represents a negligible additional computational effort compared to regular ABF. Moreover, in the proposed implementation, guidelines for choosing two parameters of the eABF algorithm, namely the stiffness of the spring and the mass

  11. Extended Adaptive Biasing Force Algorithm. An On-the-Fly Implementation for Accurate Free-Energy Calculations.

    PubMed

    Fu, Haohao; Shao, Xueguang; Chipot, Christophe; Cai, Wensheng

    2016-08-01

    Proper use of the adaptive biasing force (ABF) algorithm in free-energy calculations needs certain prerequisites to be met, namely, that the Jacobian for the metric transformation and its first derivative be available and the coarse variables be independent and fully decoupled from any holonomic constraint or geometric restraint, thereby limiting singularly the field of application of the approach. The extended ABF (eABF) algorithm circumvents these intrinsic limitations by applying the time-dependent bias onto a fictitious particle coupled to the coarse variable of interest by means of a stiff spring. However, with the current implementation of eABF in the popular molecular dynamics engine NAMD, a trajectory-based post-treatment is necessary to derive the underlying free-energy change. Usually, such a posthoc analysis leads to a decrease in the reliability of the free-energy estimates due to the inevitable loss of information, as well as to a drop in efficiency, which stems from substantial read-write accesses to file systems. We have developed a user-friendly, on-the-fly code for performing eABF simulations within NAMD. In the present contribution, this code is probed in eight illustrative examples. The performance of the algorithm is compared with traditional ABF, on the one hand, and the original eABF implementation combined with a posthoc analysis, on the other hand. Our results indicate that the on-the-fly eABF algorithm (i) supplies the correct free-energy landscape in those critical cases where the coarse variables at play are coupled to either each other or to geometric restraints or holonomic constraints, (ii) greatly improves the reliability of the free-energy change, compared to the outcome of a posthoc analysis, and (iii) represents a negligible additional computational effort compared to regular ABF. Moreover, in the proposed implementation, guidelines for choosing two parameters of the eABF algorithm, namely the stiffness of the spring and the mass

  12. Excited About Excitons (A "Life at the Frontiers of Energy Research" contest entry from the 2011 Energy Frontier Research Centers (EFRCs) Summit and Forum)

    SciTech Connect

    Baldo, Marc; Center for Excitonics Staff

    2011-05-01

    'Excited about Excitons' was submitted by the Center for Excitonics to the 'Life at the Frontiers of Energy Research' video contest at the 2011 Science for Our Nation's Energy Future: Energy Frontier Research Centers (EFRCs) Summit and Forum. Twenty-six EFRCs created short videos to highlight their mission and their work. This video was selected as one of five winners by a distinguished panel of judges for its 'outstanding portrayal of young scientists'. The Center for Excitonics, an EFRC directed by Marc Baldo at the Massachusetts Institute of Technology (MIT) is a partnership of scientists from three institutions: MIT (lead), Brookhaven National Laboratory, and Harvard University. The Office of Basic Energy Sciences in the U.S. Department of Energy's Office of Science established the 46 Energy Frontier Research Centers (EFRCs) in 2009. These collaboratively-organized centers conduct fundamental research focused on 'grand challenges' and use-inspired 'basic research needs' recently identified in major strategic planning efforts by the scientific community. The overall purpose is to accelerate scientific progress toward meeting the nation's critical energy challenges. The mission of the Center for Excitonics is 'to understand the transport of charge carriers in synthetic disordered systems, which hold promise as new materials for conversion of solar energy to electricity and electrical energy storage.' Research topics are: solar photovoltaic, photonic, solid state lighting, photosynthesis, novel materials synthesis, charge transport, defect tolerant materials, scalable processing, and self-assembly.

  13. Excitation energy migration between elongated fluorophores in uniaxially oriented polyvinyl alcohol films

    NASA Astrophysics Data System (ADS)

    Bojarski, P.; Gryczyński, I.; Kułak, L.; Synak, A.; Barnett, A.

    2006-11-01

    Nonradiative multistep energy migration is studied for 3,3'-diethylthiacarbocyanine iodide (DTCI) in uniaxially stretched and unstretched poly(vinyl alcohol) films. The results of fluorescence anisotropy decay measurements were found to be extremely different for unstretched and (stretched) systems. For disordered systems, fast depolarization was observed due to effective energy migration between randomly distributed fluorophores. However, for partly ordered systems, much slower depolarization was found as a result of preferential angular distribution of transition dipole moments of identical fluorophores. These results and properties of energy transport in uniaxially stretched polymer films are analyzed using the technique of Monte-Carlo simulation.

  14. On the use of explicitly correlated treatment methods for the generation of accurate polyatomic -He/H2 interaction potential energy surfaces: The case of C3-He complex and generalization

    NASA Astrophysics Data System (ADS)

    Al Mogren, M. M.; Denis-Alpizar, O.; Abdallah, D. Ben; Stoecklin, T.; Halvick, P.; Senent, M.-L.; Hochlaf, M.

    2014-07-01

    Through the study of the C3({tilde X}1Σg+) + He(1S) astrophysical relevant system using standard (CCSD(T)) and explicitly correlated (CCSD(T)-F12) coupled cluster approaches, we show that the CCSD(T)-F12/aug-cc-pVTZ level represents a good compromise between accuracy and low computational cost for the generation of multi-dimensional potential energy surfaces (PESs) over both intra- and inter-monomer degrees of freedom. Indeed, the CCSD(T)-F12/aug-cc-pVTZ 2D-PES for linear C3 and the CCSD(T)-F12/aug-cc-pVTZ 4D-PES for bent C3 configurations gently approach those mapped at the CCSD(T)/aug-cc-pVXZ (X = T,Q) + bond functions level, whereas a strong reduction of computational effort is observed. After exact dynamical computations, the pattern of the rovibrational levels of the intermediate C3-He complex and the rotational and rovibrational (de-) excitation of C3 by He derived using both sets of PESs agree quite well. Since C3 shows a floppy character, the interaction PES is defined in four dimensions to obtain realistic collisional parameters. The C-C-C bending mode, which fundamental lies at 63 cm-1 and can be excited at very low temperatures is explicitly considered as independent coordinate. Our work suggests hence that CCSD(T)-F12/aug-cc-pVTZ methodology is the key method for the generation of accurate polyatomic - He/H2 multi-dimensional PESs.

  15. Communication: Rate coefficients of the H + CH4 → H2 + CH3 reaction from ring polymer molecular dynamics on a highly accurate potential energy surface.

    PubMed

    Meng, Qingyong; Chen, Jun; Zhang, Dong H

    2015-09-14

    The ring polymer molecular dynamics (RPMD) calculations are performed to calculate rate constants for the title reaction on the recently constructed potential energy surface based on permutation invariant polynomial (PIP) neural-network (NN) fitting [J. Li et al., J. Chem. Phys. 142, 204302 (2015)]. By inspecting convergence, 16 beads are used in computing free-energy barriers at 300 K ≤ T ≤ 1000 K, while different numbers of beads are used for transmission coefficients. The present RPMD rates are in excellent agreement with quantum rates computed on the same potential energy surface, as well as with the experimental measurements, demonstrating further that the RPMD is capable of producing accurate rates for polyatomic chemical reactions even at rather low temperatures.

  16. Communication: Rate coefficients of the H + CH4 → H2 + CH3 reaction from ring polymer molecular dynamics on a highly accurate potential energy surface

    NASA Astrophysics Data System (ADS)

    Meng, Qingyong; Chen, Jun; Zhang, Dong H.

    2015-09-01

    The ring polymer molecular dynamics (RPMD) calculations are performed to calculate rate constants for the title reaction on the recently constructed potential energy surface based on permutation invariant polynomial (PIP) neural-network (NN) fitting [J. Li et al., J. Chem. Phys. 142, 204302 (2015)]. By inspecting convergence, 16 beads are used in computing free-energy barriers at 300 K ≤ T ≤ 1000 K, while different numbers of beads are used for transmission coefficients. The present RPMD rates are in excellent agreement with quantum rates computed on the same potential energy surface, as well as with the experimental measurements, demonstrating further that the RPMD is capable of producing accurate rates for polyatomic chemical reactions even at rather low temperatures.

  17. Theoretical characterization of the potential energy surface for H + N2 yields HN2. III - Calculations for the excited state surfaces

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1991-01-01

    Additional calculations which characterize potential energy sources (PESs) for the excited 3A-double-prime state, for a bound 2(2A-prime) state, for HN2(+), and for the Rydberg states associated with HN2(+). It is anticipated that these excited state PESs will be important in interpreting and designing experiments to characterize the ground state HN2 species via neutralized ion beam techniques.

  18. Investigation of effect of excitation frequency on electron energy distribution functions in low pressure radio frequency bounded plasmas

    SciTech Connect

    Bhattacharjee, Sudeep; Lafleur, Trevor; Charles, Christine; Boswell, Rod

    2011-07-15

    Particle in cell (PIC) simulations are employed to investigate the effect of excitation frequency {omega} on electron energy distribution functions (EEDFs) in a low pressure radio frequency (rf) discharge. The discharge is maintained over a length of 0.10 m, bounded by two infinite parallel plates, with the coherent heating field localized at the center of the discharge over a distance of 0.05 m and applied perpendicularly along the y and z directions. On varying the excitation frequency f (={omega}/2{pi}) in the range 0.01-50 MHz, it is observed that for f {<=} 5 MHz the EEDF shows a trend toward a convex (Druyvesteyn-like) distribution. For f > 5 MHz, the distribution resembles more like a Maxwellian with the familiar break energy visible in most of the distributions. A prominent ''hot tail'' is observed at f{>=} 20 MHz and the temperature of the tail is seen to decrease with further increase in frequency (e.g., at 30 MHz and 50 MHz). The mechanism for the generation of the ''hot tail'' is considered to be due to preferential transit time heating of energetic electrons as a function of {omega}, in the antenna heating field. There exists an optimum frequency for which high energy electrons are maximally heated. The occurrence of the Druyvesteyn-like distributions at lower {omega} may be explained by a balance between the heating of the electrons in the effective electric field and elastic cooling due to electron neutral collision frequency {nu}{sub en}; the transition being dictated by {omega} {approx} 2{pi}{nu}{sub en}.

  19. Investigation of effect of excitation frequency on electron energy distribution functions in low pressure radio frequency bounded plasmas

    NASA Astrophysics Data System (ADS)

    Bhattacharjee, Sudeep; Lafleur, Trevor; Charles, Christine; Boswell, Rod

    2011-07-01

    Particle in cell (PIC) simulations are employed to investigate the effect of excitation frequency ω on electron energy distribution functions (EEDFs) in a low pressure radio frequency (rf) discharge. The discharge is maintained over a length of 0.10 m, bounded by two infinite parallel plates, with the coherent heating field localized at the center of the discharge over a distance of 0.05 m and applied perpendicularly along the y and z directions. On varying the excitation frequency f (=ω/2π) in the range 0.01-50 MHz, it is observed that for f ≤ 5 MHz the EEDF shows a trend toward a convex (Druyvesteyn-like) distribution. For f > 5 MHz, the distribution resembles more like a Maxwellian with the familiar break energy visible in most of the distributions. A prominent "hot tail" is observed at f ≥ 20 MHz and the temperature of the tail is seen to decrease with further increase in frequency (e.g., at 30 MHz and 50 MHz). The mechanism for the generation of the "hot tail" is considered to be due to preferential transit time heating of energetic electrons as a function of ω, in the antenna heating field. There exists an optimum frequency for which high energy electrons are maximally heated. The occurrence of the Druyvesteyn-like distributions at lower ω may be explained by a balance between the heating of the electrons in the effective electric field and elastic cooling due to electron neutral collision frequency νen; the transition being dictated by ω ˜ 2πνen.

  20. Temperature dependence of vibrational energy transfer between vibrationally excited polyatomic molecules and bath gases

    NASA Astrophysics Data System (ADS)

    Zalesskaya, G. A.; Yakovlev, D. L.; Sambor, E. G.

    2000-08-01

    Efficiency of vibrational energy transfer (VET) in vibrational quasicontinuum of triplet states was estimated from the dependence of time-resolved delayed fluorescence of benzophenone and anthraquinone on bath gas pressure. The negative temperature dependence for vibration-vibration (V-V) and positive for vibration-translation (V-T) energy transfers from benzophenone and anthraquinone to bath gases (C 2H 4, SF 6, CCl 4, C 5H 12) were obtained between 373 and 553 K. Polarizability and dipole moment of colliding molecules seem to affect the efficiency of V-V relaxation. These data reflect the dominance of long-range attractive interactions in V-V energy transfer and short-range repulsive interactions in V-T energy transfer.