Modulations of Transition-State Control of State-to-State Dynamics in the F + H2O → HF + OH Reaction.

Abstract

The full-dimensional quantum dynamics of the F + H2O → HF + OH reaction is investigated at the state-to-state level for the first time using a transition-state wave packet method on an accurate global potential energy surface. It is found that the H2O rotation enhances the reactivity and the product-state distribution is dominated by HF vibrational excitation while the OH moiety serves effectively as a spectator. These observations underscore the transition-state control of the reaction dynamics, as both the H2O rotational and HF vibrational modes are strongly coupled to the reaction coordinate at the transition state. It is also shown that the transition-state dominance of the reaction dynamics is modulated by other features on the potential energy surface, such as the prereaction well.