Semiclassical Instanton Theory of Nonadiabatic Reaction Rate Constant. I. Formulation

Abstract

The reaction rate constant of electronically nonadiabatic chemical reactions is formulated by extending the semiclassical instanton theory of adiabatic chemical reaction with use of the Zhu-Nakamura theory of nonadiabatic transition. The instanton trajectory at a given temperature can be searched efficiently by the method used for multi-dimensional tunneling splitting. A compact expression of the rate constant applicable to multi-dimensional systems is derived.