Fractional power dependence of rate on activation energy for reactions with very low internal barriers

Abstract

The dynamics of reactions with low internal barriers are studied both analytically and numerically for two different models. Exact expressions for the average rate, k_I, are obtained by solving the associated first passage time problems. Both the average rate constant, k_I, and the numerically calculated long-time rate constant, k_L, show a fractional power law dependence on the barrier height for very low barriers. The crossover of the reaction dynamics from low to high barrier is investigated.