The reactive collision mechanism evinced: stereodynamical control of the elementary Br + H2 → H + HBr reaction

Abstract

From a kinetics standpoint, reactive molecular collisions are the building blocks of the mechanisms of chemical reactions. In contrast, a dynamics standpoint reveals molecular collisions to have their own internal mechanisms, which are not mere theoretical abstractions: through suitable preparation of the reactants internal and stereochemical states, features of the mechanisms of a reactive molecular collision can be made evident and used as “handles” to control the reaction outcome. Using time-independent quantum dynamical calculations, we demonstrate this for the Br + H₂(v = 0–1, j = 2) → H + HBr reaction in the 1.0–1.6 eV range of total energies. Despite its pronounced effect on reactivity, which is in agreement with the predictions from Polanyi rules, reactant vibration is found to have little effect on the mechanism of this endoergic, late-barrier reaction. Analysis of the correlations between directional reaction properties shows that the collision stereochemistry strongly depends on the total energy, but not on how this energy is partitioned between reactant translation and vibration. The stereodynamical preferences implied by the collision mechanisms determine how and to what extent one can control the reaction. Regarding the overall reaction, the extent of control is found to be large near the reaction threshold but not when the total energy is high. Regarding state-to-state reactions, the effect of reactant stereochemistry on the product rotational state distribution is found to be nontrivial and energy dependent.