Dynamic effects of pair correlation functions and hydrodynamic interactions on reaction kinetics in liquids

Abstract

The time-dependent reaction rate and cumulative reaction probability are solved numerically with the incorporation of an effective force and hydrodynamic interaction in the relative diffusion expression. The use of finite difference methods permits the solution no matter how complex the form of the pair correlation function (pcf) and the hydrodynamic interaction utilized. In particular, a Percus–Yevick pcf as well as pcf’s derived from Debye–Hückel theory are utilized to account for the initial distribution and interacting forces for the reactant (pair) molecules. Two measures of time-dependent reactivity, namely the cumulative reaction probability and the observed reaction rate, are found to exhibit significant effects of molecular interaction.