Vibrational energy consumption in endoergic atom diatom reactions

Abstract

Recently it has been shown that reagent vibrational energy has an opposite effect (as compared to the statistical limit) in the endothermic and exothermic regimes of a given endoergic reaction. A generalization of the exponential gap law to reactive bimolecular collisions is shown to account for this behaviour. The surprisal analysis for several systems is shown to be in accordance with the generalized gap law. A collinear model for the gap law, based on the transfer of momentum constraint and the Born approximation is presented. The model accounts for the quantitative behaviour of the systems analyzed.