RATE-PROCESSES IN DISSIPATIVE SYSTEMS - SCALING IN THE CANONICAL VARIATIONAL TRANSITION-STATE THEORY

We study the activated barrier crossing (ABC) problem using the canonical variational transition state theory (CVTST) of Pollak et al. with general potentials and memory friction kernels. Our proposed scaling hypothesis is obeyed in the limit of large bath correlation times. In the scaling region, the ABC rates obtained in the CVTST reduce to those of Grote and Hynes (GH) with corrections coming from the finiteness of the barrier height. In the core of the critical region, where a transition takes place from the strong coupling to the weak coupling region, these corrections give an improved bound on the critical amplitude. The results are illustrated in the particular case of a parabolic barrier with a perfectly reflecting wall (PRW).