Dynamics of liquid state chemical reactions: R-dependent correlation functions for I.+I. in CCl4

Abstract

Reagent configuration dependent solvent correlation functions, which are required for implementation of the MTGLE approach [S. A. Adelman, J. Chem. Phys. 73, 3145 (1980)] to problems in liquid state chemical reaction dynamics, are calculated via the molecular dynamics (MD) method for a Lennard‐Jones system designed to simulate two interacting iodine atoms dissolved in liquid carbon tetrachloride. For this case, the correlation functions depend only on the iodine–iodine internuclear separation R. The R‐dependence of the correlation functions, and related computed quantities of the MTGLE parameters, is found to be governed mainly by excluded volume effects arising from ’’squeeze‐out’’ of solvent molecules from the region between the iodine atoms. Additional calculations designed to test approximations in the theory and simplifications, like use of small box‐sizes and the superposition approximation, are also presented.