Finite temperature application of the corrected propagator method to reactive dynamics in a condensed-phase environment

David Gelman, Steven D Schwartz

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1 Citation (Scopus)

Abstract

The recently proposed mixed quantum-classical method is extended to applications at finite temperatures. The method is designed to treat complex systems consisting of a low-dimensional quantum part (the primary system) coupled to a dissipative bath described classically. The method is based on a formalism showing how to systematically correct the approximate zeroth-order evolution rule. The corrections are defined in terms of the total quantum Hamiltonian and are taken to the classical limit by introducing the frozen Gaussian approximation for the bath degrees of freedom. The evolution of the primary system is governed by the corrected propagator yielding the exact quantum dynamics. The method has been tested on a standard model system describing proton transfer in a condensed-phase environment: a symmetric double-well potential bilinearly coupled to a bath of harmonic oscillators. Flux correlation functions and thermal rate constants have been calculated at two different temperatures for a range of coupling strengths. The results have been compared to the fully quantum simulations of Topaler and Makri [J. Chem. Phys. 101, 7500 (1994)] with the real path integral method.

Original languageEnglish (US)
Article number034109
JournalThe Journal of Chemical Physics
Volume134
Issue number3
DOIs
StatePublished - Jan 21 2011
Externally publishedYes

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baths
Hamiltonians
Temperature
Proton transfer
Baths
propagation
Large scale systems
Rate constants
Fluxes
complex systems
harmonic oscillators
temperature
degrees of freedom
formalism
protons
Protons
approximation
Hot Temperature
simulation

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

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