UC Davis

The cross section and final state distribution for mutual neutralization in collisions of H⁺ with Cl^- have been calculated using an ab initio quantum mechanical approach. It is based on potential energy curves and nonadiabatic coupling elements for the six lowest ¹Σ⁺ states of HCl computed with the multireference configuration interaction method. The reaction is found to be driven by nonadiabatic interactions occurring at relatively small internuclear distances (R < 6 a₀). Effects on the mutual neutralization cross section with respect to the asymptotic form of the potential energy curves, inclusion of closed channels, as well as isotopic substitution are investigated. The effect of spin-orbit interaction is investigated using a semiempirical model and found to be small. A simple two-state Landau-Zener calculation fails to predict the cross section.