Non-adiabatic transitions in the reaction of fluorine with methane.

Abstract

Reactions of methane with different atoms are benchmark examples of elementary reaction processes intensively studied by theory and experiment. Due to the presence of conical intersections and spin-orbit coupling, non-adiabatic transitions can occur in reactions with F, Cl, or O atoms. Extending detailed quantum theory beyond the Born-Oppenheimer approximation for polyatomic reaction processes, non-adiabatic wave packet dynamics calculations studying the F(2P3/2)/F*(2P1/2) + CHD3 → HF + CD3 reaction on accurate vibronically and spin-orbit coupled diabatic potential energy surfaces are presented. Non-adiabatic transitions are found to increase the reactivity compared to Born-Oppenheimer theory and are more prominent than in triatomic reactions previously studied. Furthermore, the lifetimes of reactive resonances are reduced. The reactivity of F(2P3/2) is found to exceed the one of F*(2P1/2) even at low collision energies.