Collison Model for Activated Rate Processes: Turnover Behavior of the Rate Constant

A. M. Berezhkovskii

Laboratory of Physical and Structural Biology, National Institute of Child Health and Human Development, National Institutes of Health, Bethesda, Maryland 20892
and Karpov Institute of Physical Chemistry, Ul. Voronstovo Pole 10, 103064 Moscow, K-64, Russia

D. J. Bicout

Laboratory of Chemical Physics, National Institutes of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, Maryland 20892

G. H. Weiss

Center for Information Technology, National Institutes of Health, Bethesda, Maryland 20892

Abstract

A theory of reaction rates is developed on the basis of the Bhatnagar-Gross-Krook model which assumes instantaneous Maxwellization of the particle velocity at each collision. This model may be regarded as an alternative to the Kramers model for reaction dynamics in the condensed phase. The main results are two expressions for the rate constant for singel- and double- well potentials which cover the rate constant as a function of the collision frequency, analogous to the Kramers-Mel'nikov-Meshkov solution for the rate constant in the Kramers model. In contrast to the prediction for the Kramers model, the maximal value of the rate constant is noticeably below the transition state theory estimate even for so high a barrier as 30kBT. This is a consequence of two facts: 1. The rate constant grows slowly from zero at small collision frequencies. 2. In addition, the rate of growth increases weakly with the barrier height, delta U, as ln(delta U/kBT). Simulated results indicate good agreement with theory.