Non-Markovian rate theory on a multidimensional reaction surface: Complex interplay between enhanced configuration space and memory

Abstract

A theory of barrier crossing rate on a multidimensional reaction energy surface is presented. The theory is a generalization of the earlier theoretical schemes to higher dimensions, with the inclusion of non-Markovian friction along both the reactive and the nonreactive coordinates. The theory additionally includes the bilinear coupling between the reactive and the nonreactive modes at the Hamiltonian level. Under suitable conditions, we recover the rate expressions of Langer and Hynes and establish a connection with the rate treatment of Pollak. Within the phenomenology of generalized Langevin equation description, our formulation provides an improvement over the existing ones because we explicitly include both the non-Markovian effects along the reaction coordinate and the bilinear coupling at the Hamiltonian level. At intermediate-to-large friction, an increase in dimensionality by itself tends to reduce the rate, while the inclusion of the memory effects increases the rate. The theory predicts an increase in rate when off-diagonal friction terms are included. We present a model calculation to study isomerization of a stilbene-like molecule using the prescription of Hochstrasser and co-workers on a two-dimensional reaction energy surface, employing Zwanzig–Bixon hydrodynamic theory of frequency-dependent friction. The calculated rate shows a departure from the predictions of Langer’s theory and also from the two-dimensional transition state theory.