Collisional Energy Transfer in Thermal Unimolecular Reactions

Abstract

AbstractThe master equation of a thermal unimolecular reaction in the low pressure limit is solved analytically for a three‐parameter, versatile model of the collisional transition probabilities. This model is compared with the statistical theory of energy exchange. The overall rate constant of the reaction is found to depend predominantly on the mean energy Δ E transferred per collision and only slightly on shape factors of the collisional transition probability. The theory allows for a direct, simple derivation of Δ E from thermal unimolecular reaction data.