Reaction rates and the noisy saddle-node bifurcation: Renormalization group for barrier crossing

Abstract

Barrier crossing calculations in chemical reaction-rate theory typically assume that the barrier is large compared to the temperature. When the barrier vanishes, however, there is a qualitative change in behavior. Instead of crossing a barrier, particles slide down a sloping potential. We formulate a renormalization group description of this noisy saddle-node transition. We derive the universal scaling behavior and corrections to scaling for the mean escape time in overdamped systems with arbitrary barrier height. We also develop an accurate approximation to the full distribution of barrier escape times by approximating the eigenvalues of the Fokker-Plank operator as equally spaced. This lets us derive a family of distributions that captures the barrier crossing times for arbitrary barrier height. Our critical theory draws links between barrier crossing in chemistry, the renormalization group, and bifurcation theory.