KCS

A rigorous theoretical framework for diffusion-influenced reaction kinetics is presented. Starting from the classical Liouville equation governing the evolution of the phase-space probability density function of all particles in the reaction system, a system of hierarchical kinetic equations for the nonequilibrium reduced distribution functions of reactant molecules is derived. In the low reactant concentration limit, a time-correlation function expression is obtained which provides an efficient computer simulation method for calculating the time-dependent rate coefficient. As an application, the rates of dismutation of the superoxide anion radical catalyzed by Cu/Zn superoxide dismutases are evaluated. For the cases with higher reactant concentrations, many-particle kernel theories are derived which provide very accurate estimates of the many-particle effects on the reaction kinetics.