Mode-coupling theory for reaction dynamics in liquids

TL;DR

This paper develops a microscopic mode-coupling theory for chemical reaction dynamics in liquids, combining kinetic and mode-coupling theories to accurately predict reaction rates in condensed phases.

Contribution

It introduces a novel analytical framework for calculating dynamic friction in liquids, improving understanding of reaction mechanisms in realistic environments.

Findings

Good agreement with numerical simulations for a Lennard-Jones fluid

Accurate prediction of transmission coefficients at various solvent densities

Provides a powerful tool for studying reactions in condensed phases

Abstract

A theory for chemical reaction dynamics in condensed phase systems based on the generalized Langevin formalism of Grote and Hynes is presented. A microscopic approach to calculate the dynamic friction is developed within the framework of a combination of kinetic and mode-coupling theories. The approach provides a powerful analytic tool to study chemical reactions in realistic condensed phase environments. The accuracy of the approach is tested for a model isomerization reaction in a Lennard-Jones fluid. Good agreement is obtained for the transmission coefficient at different solvent densities, in comparison with numerical simulations based on the reactive-flux approach.