Theoretical Study of the Validity of the Born-Oppenheimer Approximation in the Cl + H ₂ → HCl + H Reaction

Abstract

Reactivity of the excited spin-orbit state of Cl with H2 to yield ground-state HCl products is forbidden by the Born-Oppenheimer (BO) approximation. We used new ab initio potential energy surfaces and exact quantum scattering calculations to explore the extent of electronic nonadiabaticity in this reaction. In direct contrast to recent experiments, we predict that the BO-allowed reaction of the ground spin-orbit state will be much more efficient than the BO-forbidden reaction of the excited spin-orbit state. Also, Coriolis coupling opens up an electronically nonadiabatic inelastic channel, which competes substantially with reaction.