Curve Crossing in Collisional Dissociation of Alkali Halide Molecules

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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.

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