THEORY OF DIFFUSION-INFLUENCED RADICAL RECOMBINATION - INTERPLAY BETWEEN GEMINATE AND BULK RECOMBINATION

We have formulated a theory for describing the time-dependent rate of the photolytic radical recombination reaction occuring in a viscous me dium. The recombination after flash photolysis consists of an initial geminate-pair recombination phase followed by a slower balk recombinat ion phase in which radicals from different parent molecules encounter via diffusion and combine. In most theories of photolytic radical reco mbination reactions, however, only the dynamics of a single geminate p air was considered and the intervention of surrounding radicals in the geminate pair dynamics was neglected. The present theory treats the i nterplay of the geminate-pair and the bulk recombinations within a uni fied framework. Numerical calculations show that prediction of the pre sent theory differs significantly from that of conventional theories.