Nonadiabatic instanton rate theory beyond the golden-rule limit

Abstract

Fermi's golden rule (GR) describes the leading-order behavior of the reaction rate as a function of the diabatic coupling. Its asymptotic (h → 0) limit is the semiclassical golden-rule instanton rate theory, which rigorously approximates nuclear quantum effects, lends itself to efficient numerical computation, and gives physical insight into reaction mechanisms. However, the golden rule by itself becomes insufficient as the strength of the diabatic coupling increases, so higher-order terms must be additionally considered. In this work, we give a first-principles derivation of the next-order term beyond the golden rule, represented as a sum of three components. Two of them lead to new instanton pathways that extend the GR case and, among other factors, account for effects of recrossing on the full rate. The remaining component derives from the equilibrium partition function and accounts for changes in potential energy around the reactant and product wells due to diabatic coupling. The new semiclassical theory demands little computational effort beyond a GR instanton calculation. It makes it possible to rigorously assess the accuracy of the GR approximation and sets the stage for future work on general semiclassical nonadiabatic rate theories.