Kinetics of diffusion-influenced bimolecular reactions in solution. II. Effects of the gating mode and orientation-dependent reactivity

Abstract

The formalism presented in the preceding paper is applied to investigate the combined effects of gating modes and orientation-dependent reactivity on the rate of diffusion-influenced bimolecular reactions. A general expression for the rate coefficient is derived for reactions involving a sink function that is highly localized along the orientational and gating coordinates. For reactions involving spherical molecules, of which one species has a diffusive gating coordinate, the expression for the rate coefficient is evaluated analytically. For the general case involving arbitrarily complicated molecules, a methodology for evaluating the expression for the rate coefficient by Brownian dynamics simulations is described, and test results on two simple model reactions are presented. For these cases the present method converges more rapidly than other Brownian dynamics approaches.