Theory of non-Markovian rate processes

Starting from a multidimensional reaction kinetic equation with a general time evolution operator and a reaction sink function K, we derive formally exact expressions for the survival probability, reaction time distribution, and mean reaction time by using the projection operator technique. These rate expressions are given in the rational function form, with the irreducible memory function Omegairr as the key ingredient. This approach has an advantage over the direct perturbation approaches that use the reaction term as the small parameter, in that Omegairr has a structure that can be perturbatively treated with (K - K) as the small parameter. The well-known Wilemski-Fixman-type rate expressions are reproduced as the zeroth-order approximation from the present theory. Practical methods for evaluating the formal rate expressions are presented, and the results calculated for a model of electron transfer in non-Debye solvents are compared with computer simulations. It is found that the present approach is very promising for the study of non-Markovian dispersive kinetics.