Theoretical dynamics studies of the CH3 + HBr → CH4 + Br reaction: integral cross sections, rate constants and microscopic mechanism

Abstract

Quantum and quasi-classical dynamics calculations have been performed for the reaction of HBr with CH₃. The accurate ab initio-based potential energy surface function developed earlier for this reaction displays a potential well corresponding to a reactant complex and a submerged potential barrier. The integral cross sections were calculated on this potential energy surface using both a six-degree-of-freedom reduced dimensional quantum dynamics and the quasi-classical trajectory method and very good agreement was found between the two approaches. The cross sections were found to diverge when the collision energy decreases, indicating that the reactant attraction is responsible for the dynamics at low collision energy. The quantum mechanical and the quasi-classical rate constants also agree very well and almost exactly reproduce the experimental results at low temperatures up to 540 K. The negative activation energy observed experimentally is confirmed by the calculations and is a consequence of the long-range attraction between the reactants. From the classical trajectories mechanistic details have been extracted. It is found that at very low collision energy, the reacting system crosses the potential barrier because the forces within the complex guide them, although some 30% is reflected from the product side of the barrier. When the collision energy increases, the system does not follow the most favorable path and the reactants are, with increasing probability, reflected from the repulsive walls of the nonreactive parts of the reactants, providing a picture beyond the decreasing excitation function.