TWO APPROACHES TO STOCHASTIC RATE THEORY

摘要

A comparison is made between two approaches to a Kramers-type reaction rate theory. The usual one is based on a Linear coupling model between a particle and the medium oscillators. Use is made of two different separable reaction coordinates in the absence and presence of coupling, respectively. A more general model consists of assuming an arbitrary (nonlinear) coupling between the reactant and medium, making use of a single (curvilinear) reaction coordinate of the entire many-dimensional system (reactant + medium). A comparison with the exact dynamic rate theory is made, showing its equivalence with the generalized stochastic theory. (C) 1997 John Wiley & Sons, Inc. [References: 28]