Role of van der Waals resonances in the vibrational relaxation of HF by collisions with H atoms

Abstract

Vibrational relaxation of HF(v) in collisions with H atoms can occur by three pathways: inelastic scattering with and without H atom exchange, and, for v>or=3, the HF+H-->F+H2 reaction. Fully quantum, reactive scattering calculations on the Stark-Werner FH2 potential energy surface reveal narrow peaks in the energy dependence of the integral cross sections for each of these processes. By means of an adiabatic-bender analysis, we show that each of these peaks corresponds to the position of quasibound HF-H vibrational states trapped in the weak van der Waals well. The width of these resonances indicates that the lifetime of the quasibound states is up to 30 periods of the HF-H van der Waals vibration.