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Keywords:

  • reaction rates;
  • H transfer;
  • path integrals

Abstract

We present a new method for the numerical calculation of canonical reaction rate constants in complex molecular systems, which is based on a path integral formulation of the flux–flux correlation function. Central is the partitioning of the total system into a relevant part coupled to a dual bath. The latter consists of two parts: First, there is a set of strongly coupled harmonic modes, describing, for example, intramolecular degrees of freedom. They are treated on the basis of a reaction surface Hamiltonian approach. Second, there is a set of bath modes mimicking an unspecific environment modeled by means of a continuous spectral density. After deriving general equations expressing the canonical rate constant in terms of appropriate influence functionals, several approximations are introduced to provide an efficient numerical implementation. Results for an initial application to the H-transfer in 6-aminofulvene-1-aldimine are discussed. © 2011 Wiley Periodicals, Inc.