Curve Crossing in Collisional Dissociation of Alkali Halide Molecules

Abstract

The primary dissociation step for alkali halide diatomics in argon has been studied in order to determine whether collisional dissociation produces ions, atoms, or a mixture of both types of products. The method is based on time‐resolved absorption spectroscopy of shock‐heated vapors. Results show that the cesium halides, and the rubidium and potassium halides, with the exception of the two iodides, dissociate essentially completely to ions; that the lithium salts and NaI and NaBr dissociate essentially completely to atoms; and that the other alkali halides (KI, RbI, NaCl, and probably NaF) dissociate to mixtures of atoms and ions, at least under some conditions. The branching ratio of atom pairs/ion pairs is interpreted in terms of the effective width of the adiabatic dissociation channel, compared with the spacing of the vibrational levels of the diabatic bound state.