Kinetic Equations of Physicochemical Processes with Allowance for Multi-Particle Effects in the Lattice Gas Model

Abstract

Abstract A way of deriving kinetic equations of physicochemical processes in dense phases is developed on the basis of the discrete–continuous description of the spatial distribution of components in the lattice gas model (LGM), with allowance for multi-particle effects. The emergence of multi-particle effects is associated with the simultaneous influence of all neighbors on the rate of the elementary stage with the participation of a given particle. They include multi-particle potentials of interaction, including quantum–chemical energy calculations, the effect the configurations of neighboring molecules have on the internal motion of the central particle, and the effects of the indirect correlation of interacting particles that occurs for any potential of pair interaction, assuming the internal motions of particles do not depend on the local configurations of neighbors. Multi-particle effects take models beyond the quasi-chemical approximation, which reflects direct correlations of interacting particles through pair distribution functions, and require the use of correlation functions for a larger number of particles in describing their kinetics. The rates of elementary one- and two-node stages are calculated within the theory of absolute rates of reactions in non-ideal reaction systems. Ways of calculating approximate rates of the elementary stages of mono- and bimolecular processes are discussed, along with the possibilities of generalizing the derived equations.