Nonlocal ionization in encounter theory

Abstract

A nonadiabatic theory of electron transfer in solutions is proposed in which the spatial dispersion of both intercenter interaction and activation energy is taken into account as well as the mutual diffusion of particles and diffusion along the reaction coordinate to the intersection point of potential energy terms. When spatial diffusion is considered to be the slowest step, the transition to the conventional theory is demonstrated and the generalized local probability of the transition is introduced to describe correctly the activationless electron transfer. It has been found that in the opposite case when diffusion along the reaction coordinate is hampered, the theory is actually nonlocal but allows the calculation of the rate constant which may be kinetic, pseudodiffusive or superdiffusive depending on the reaction heat.