Theoretical calculations of the prereaction process of the H−···HD van der Waals molecule

Abstract

Photoinduced prereaction processes for the H⁻···HD van der Waals molecule to produce H₂ + D⁻ have been theoretically studied using time-independent reactive scattering theory. The accurate ab initio potential energy surface developed by Stärck and Meyer has been employed. We have found that the prereaction process occurs for the H⁻···HD(v=1) van der Waals resonance with a probability of 5–10%. For other van der Waals resonances, in which the HD molecule is rotationally excited, the prereaction probability is very small and the resonance states decay only via predissociation. This result indicates that the rotationally nonadiabatic transition probability is large for the H⁻···HD van der Waals system.