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Semiclassical Surface Hopping Methods for Nonadiabatic Transitions in Condensed Phases

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Theoretical Methods in Condensed Phase Chemistry

Part of the book series: Progress in Theoretical Chemistry and Physics ((PTCP,volume 5))

Abstract

A semiclassical surface hopping method for the evaluation of rates and time dependent probabilities for transitions between quantum states of a molecule in a condensed phase system is discussed. The surface hopping procedure, which includes all semiclassical phases and prefactors, has been previously shown to provide accurate results for time dependent quantum wavefunctions in model problems. It is shown how this semiclassical nonadiabatic propagator can be cast in the HK propagator from. The semiclassical propagator is employed in the propagation of the density for condensed phase systems, and expressions are derived for the transition probability between different quantum states in these systems. It is argued that the semiclassical propagation of the density need only be considered for short times in most condensed phase system undergoing quantum transitions, even if the transition rate is slow. This need for only short time propagation of the density arises due to phase decoherence effects and loss of correlation in the interstate coupling. It is shown how the transition probability expression can often be numerically simplified by employing short time approximations for this short time density propagation. Results are presented from calculations of vibrational relaxation rates in condensed system. These calculations investigate when the short time approximations are valid.

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Authors and Affiliations

  1. Department of Chemistry, Tulane University, New Orleans, LA, 70118, USA

    Michael F. Herman

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  1. Michael F. Herman
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Editors and Affiliations

  1. Albert Einstein College of Medicine, New York City, USA

    Steven D. Schwartz

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© 2002 Kluwer Academic Publishers

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Herman, M.F. (2002). Semiclassical Surface Hopping Methods for Nonadiabatic Transitions in Condensed Phases. In: Schwartz, S.D. (eds) Theoretical Methods in Condensed Phase Chemistry. Progress in Theoretical Chemistry and Physics, vol 5. Springer, Dordrecht. https://doi.org/10.1007/0-306-46949-9_6

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  • DOI: https://doi.org/10.1007/0-306-46949-9_6

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-0-7923-6687-4

  • Online ISBN: 978-0-306-46949-7

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