Solvent softness effects on unimolecular chemical reaction rate constants

Abstract

The stochastic hard collision (SHC) model for a coarse-grained solvent has been used to solvate a class of model chemical reactions. Although there is precedent from our prior work that the use of nondeterministic interaction potentials can lead to accurate dynamics at long-enough time scales, this work provides evidence that this model has dynamical consistency specifically in the response to the reactant motion. That is, the agreement between the theoretical rate constants and those obtained from the stochastic simulations provides support for the SHC solvent without sacrificing the correlations in the dynamics of the reacting solutes.