Two simulation studies of chemical dynamics in liquids

Abstract

We discuss the analysis of two different examples of activated processes in liquids. In one, the isomerization of cyclohexane, we consider reactive flux correlation functions computed from stochastic trajectories. Our analysis shows that the experimentally observed rates for isomerization coincide with the breakdown of both transition-state theory and also the RRKM picture of unimolecular kinetics. In the second example, we present the results of computer-simulation calculations of the activation free energy for aqueous Fe^II-Fe^III electron transfer. The computed free-energy function agrees well with the functional form proposed by Marcus, and the value of the activation free energy agrees well with experiment.