MONTE CARLO METHODS FOR RATE PROCESSES

Recently developed microcanonical Monte Carlo sampling methods are described and applications to the evaluation of classical transition-state theory rate constant expressions are presented. These include unimolecular and bimolecular gas-phase reaction rates and a method for computing nonadiabatic unimolecular reaction rates. Monte Carlo methods for estimating thermal desorption, diffusion and tunnelling rates in solids and on surfaces are also discussed. The methods described provide a bridge between simple models and full molecular dynamics simulations, and are of particular use for the study of reaction rates in large molecular systems where quantum mechanical techniques cannot be easily applied.