A quasiclassical trajectory study of the four-center reactions: HBr+Cl2 and HBr+BrCl

Abstract

A quasiclassical trajectory study has been made of the dynamics of two four-center reactions: HBr+Cl2→HCl+BrCl, HBr+BrCl→HCl+Br2. Semiempirical, valence-bond potential-energy surfaces were employed, with potential parameters obtained from related atom–diatomic molecule systems. Reaction probabilities and cross sections were computed as functions of reactant vibration, rotation, and translation. Extrapolated cross section curves were used to make estimates of thermal rate coefficients. The dependence of the reaction probability on other dynamics variables such as impact parameter and orientation angles was also investigated. These results indicate that under attainable laboratory conditions (including IR excitation) the reaction proceeds at a rate too slow to be observed by usual methods.