A theory of diffusion controlled reactions in polyatomic molecule system

摘要

The conventional Smoluchowski equation has been extensively utilized to investigate diffusion controlled reactions. However, application of the equation is limited to spherical-particle system. In the present study, a new Smoluchowski equation for polyatomic molecular system is derived based on Zwanzig-Mori projection operator method and reference interaction site model (RISM) theory. The theory is applied to monoatomic molecular liquid, and the obtained time-dependent rate constant is virtually identical with that from conventional Smoluchowski equation. For diatomic molecular liquid, time-dependent distribution function and rate constant are obtained, showing a good agreement with those from molecular dynamics simulation. Published by AIP Publishing.