Molecular dynamics of the A+BC reaction in rare gas solution

Abstract

Molecular dynamics are computed for model atom transfers A+BC→AB+C in rare gas solvents at liquid densities. We find that the reaction dynamics can be understood in terms of a simple picture which consists of three stages: (1) activation of reactants, (2) barrier crossing, and (3) deactivation of products. The effects seen in stages (1) and (3) can be largely interpreted in terms of existing models of energy and phase decay in solution, while the effects seen in stage (2) can be largely interpreted in terms of gas phase A+BC barrier crossing dynamics. We find that transition state theory is in perfect agreement with the simulations for the 20 and 10 kcal/mol barrier reactions and is a very good description for a 5 kcal/mol reaction barrier. At low barrier curvature, dynamical effects due to the solvent are shown to induce some recrossings of the transition state barrier, thus causing rate constants calculated by simple transition state theory to be slightly too high. The Grote–Hynes modification of transition state theory, which considers the effect of the time dependent friction of the solvent on the dynamics at the transition state, predicts corrections to the rate constants in good agreement with the results from the simulations.