Friction dependence of reaction rates in simple barrierless reactions

Abstract

We have investigated the dynamics of simple chemical reactions which proceed without an activation barrier along the reaction coordinate. In the absence of the barrier the solvent friction is the only impediment to the reactive motion. By numerical simulation we show that in the low-friction limit the reaction rate increases as a fractional power of the friction coefficient. The power law dependence is sensitive to the initial conditions of the reactive coordinate. After exhibiting a maximum, the behaviour crosses over to that of inverse friction dependence in the high-friction limit. We have compared our results with earlier approximate analytical treatments and differences are pointed out.