757 research outputs found

    Nonadiabatic quantum transition-state theory in the golden-rule limit. I. Theory and application to model systems

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    We propose a new quantum transition-state theory for calculating Fermi's golden-rule rates in complex multidimensional systems. This method is able to account for the nuclear quantum effects of delocalization, zero-point energy and tunnelling in an electron-transfer reaction. It is related to instanton theory but can be computed by path-integral sampling and is thus applicable to treat molecular reactions in solution. A constraint functional based on energy conservation is introduced which ensures that the dominant paths contributing to the reaction rate are sampled. We prove that the theory gives exact results for a system of crossed linear potentials and also the correct classical limit for any system. In numerical tests, the new method is also seen to be accurate for anharmonic systems, and even gives good predictions for rates in the Marcus inverted regime.Comment: 18 pages and 6 figure

    The nature and role of the gold-krypton interactions in small neutral gold clusters

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    © 2015 American Chemical Society. We investigate the nature and role of krypton embedding in small neutral gold clusters. For some of these clusters, we observe a particular site-dependent character of the Kr binding that does not completely follow the criterion of binding at low-coordinated sites, widely accepted for interaction of a noble gas with closed-shell metal systems such as metal surfaces. We aim at understanding the effect of low dimensionality and open-shell electronic structure of the odd-numbered clusters on the noble gas-metal cluster interaction. First, we investigate the role of attractive and repulsive forces, and the frontier molecular orbitals. Second, we investigate the Au-Kr interaction in terms of reactivity and bonding character. We use a reactivity index derived from Fukui formalism, and criteria provided by the electron localization function (ELF), in order to classify the type of bonding. We carry out this study on the minimum energy structures of neutral gold clusters, as obtained using pseudo potential plane-wave density functional theory (DFT). A model is proposed that includes the effect of attractive electrostatic, van der Waals and repulsive forces, together with effects originating from orbital overlap. This satisfactorily explains minimum configurations of the noble gas-gold cluster systems, the site preference of the noble gas atoms, and changes in electronic properties

    Physics

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    Ion cyclotron resonance study of energy dependence of ion-molecule reaction in gaseous hydrogen, and fluorine 19 isotopic NMR chemical shifts due to chlorine 35 and chlorine 37 isotope

    Far-from-equilibrium noise heating and laser cooling dynamics in radio-frequency Paul traps

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    We study the stochastic dynamics of a particle in a periodically driven potential. For atomic ions trapped in radio-frequency Paul traps, noise heating and laser cooling typically act slowly in comparison with the unperturbed motion. These stochastic processes can be accounted for in terms of a probability distribution defined over the action variables, which would otherwise be conserved within the regular regions of the Hamiltonian phase space. We present a semiclassical theory of low-saturation laser cooling applicable from the limit of low-amplitude motion to large-amplitude motion, accounting fully for the time-dependent and anharmonic trap. We employ our approach to a detailed study of the stochastic dynamics of a single ion, drawing general conclusions regarding the nonequilibrium dynamics of laser-cooled trapped ions. We predict a regime of anharmonic motion in which laser cooling becomes diffusive (i.e., it is equally likely to cool the ion as it is to heat it), and can also turn into effective heating. This implies that a high-energy ion could be easily lost from the trap despite being laser cooled; however, we find that this loss can be counteracted using a laser detuning much larger than Doppler detuning.Comment: 23 pages, 7 figure

    Multi-Instantons and Exact Results I: Conjectures, WKB Expansions, and Instanton Interactions

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    We consider specific quantum mechanical model problems for which perturbation theory fails to explain physical properties like the eigenvalue spectrum even qualitatively, even if the asymptotic perturbation series is augmented by resummation prescriptions to "cure" the divergence in large orders of perturbation theory. Generalizations of perturbation theory are necessary which include instanton configurations, characterized by nonanalytic factors exp(-a/g) where a is a constant and g is the coupling. In the case of one-dimensional quantum mechanical potentials with two or more degenerate minima, the energy levels may be represented as an infinite sum of terms each of which involves a certain power of a nonanalytic factor and represents itself an infinite divergent series. We attempt to provide a unified representation of related derivations previously found scattered in the literature. For the considered quantum mechanical problems, we discuss the derivation of the instanton contributions from a semi-classical calculation of the corresponding partition function in the path integral formalism. We also explain the relation with the corresponding WKB expansion of the solutions of the Schroedinger equation, or alternatively of the Fredholm determinant det(H-E) (and some explicit calculations that verify this correspondence). We finally recall how these conjectures naturally emerge from a leading-order summation of multi-instanton contributions to the path integral representation of the partition function. The same strategy could result in new conjectures for problems where our present understanding is more limited.Comment: 66 pages, LaTeX; refs. to part II preprint update

    Josephson dynamics for coupled polariton modes under the atom-field interaction in the cavity

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    We consider a new approach to the problem of Bose-Einstein condensation (BEC) of polaritons for atom-field interaction under the strong coupling regime in the cavity. We investigate the dynamics of two macroscopically populated polariton modes corresponding to the upper and lower branch energy states coupled via Kerr-like nonlinearity of atomic medium. We found out the dispersion relations for new type of collective excitations in the system under consideration. Various temporal regimes like linear (nonlinear) Josephson transition and/or Rabi oscillations, macroscopic quantum self-trapping (MQST) dynamics for population imbalance of polariton modes are predicted. We also examine the switching properties for time-averaged population imbalance depending on initial conditions, effective nonlinear parameter of atomic medium and kinetic energy of low-branch polaritons.Comment: 10 pages, 6 postscript figures, uses svjour.cl

    Surface-enhanced pair transfer in quadrupole states of neutron-rich Sn isotopes

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    We investigate the neutron pair transfer modes associated with the low-lying quadrupole states in neutron-rich Sn isotopes by means of the quasiparticle random phase approximation based on the Skyrme-Hartree-Fock-Bogoliubov mean field model. The transition strength of the quadrupole pair-addition mode feeding the 21+2_1^+ state is enhanced in the Sn isotopes with A≥132A \geq 132. The transition density of the pair-addition mode has a large spatial extension in the exterior of nucleus, reaching far to r∼12−13r\sim 12-13 fm. The quadrupole pair-addition mode reflects sensitively a possible increase of the effective pairing interaction strength in the surface and exterior regions of neutron-rich nuclei.Comment: 14 page
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