Gaussian approximation for the structure function in semiclassical forward-backward initial value representations of time correlation functions

Abstract

Initial value representations (IVRs) of semiclassical (SC) theory provide a general approach for adding quantum mechanical effects to classical molecular dynamics simulations of large molecular systems. Of the various versions of SC-IVR methodology for evaluating time correlation functions, the Fourier transform forward-backward (FB) approach is the simplest one that is able to describe true quantum coherence effects, so it is of considerable importance to find efficient and systematic ways for implementing it. It is shown in this paper that a Gaussian approximation for the "structure function"-the dependence of the correlation function on the (typically) momentum jump parameter-provides an efficient and accurate way for doing so. The approach is illustrated by an application to the time-dependent radial distribution function of I(2) (after photoexcitation) in a cluster of (up to 16) argon atoms.