Variational theory of reaction rates: Application to F+H2⇄HF+H

Abstract

The classical variational theory of reaction rates is coupled with a Monte Carlo trajectory analysis to yield reaction rates and energy distributions of reactants and products for the forward and reverse reactions: F+H2⇄HF+H at 300°K. The results are compared with those of a standard quasiclassical trajectory analysis of the forward reaction using the same potential energy surface. Differences are attributed to the quantized distributions of reactants in the quasiclassical calculations. The combination of the two methods allows a substantial reduction in computation requirements for determining the characteristics of reactions in systems with reactants in thermal equilibrium.