Correlation effects in the kinetics of bimolecular diffusion-mediated reactions

Abstract

Analytical and numerical methods are used to study the kinetics of a bimolecular reaction such as A + B = 0 when interparticle correlations are taken into account in the Kirkwood superposition approximation for a three-particle reagent distribution function. A detailed analys is made of the dependence of the reagent concentration decay rate on the value of the initial concentration c(0) and of the parameter k that characterises the reaction efficiency in reagent collision. It is shown that in the reaction depth range 0.5≲η≲5 (η = log[ c(0)/ c])the concentration decay is described by a dependence of the form c( t)∼ −α and the values of α are obtained as a function of the parameters c(0) and k. At long time (η>5) the dependence of the concentration decay goes to the “three-fourth” law, c( t∼ t − 3 4 .