A test of two approximate two-state treatments for the dynamics of H-atom transfers between two heavy particles

Abstract

Reactive transition probabilities and Boltzmann-averaged reactive transition probabilities for a slightly off-resonant model H-atom transfer system with an appreciable energy barrier are calculated using the approximate methods of Babamov et al. and of Crothers–Stückelberg. Both are compared with the corresponding quantities obtained from a numerical two-state treatment of the same model system. The method of Babamov et al. is seen to give more accurate results for the transition probabilities at energies below and around the reaction threshold, and much more accurate results for the Boltzmann-averaged probabilities in a wide range of temperatures than the second method. The relative merits of the two formulas are discussed.