Ab initio theoretical study of the electronic structure, stability and bonding of dialkali halide cations

Abstract

The ground state electronic structures and dissociation energies of the dialkali halide cations M1M2M+ (M1, M2 = Li, Na; X = F, Cl) have been calculated at the HF and post-HF (MPn) levels using a variety of basis sets. The calculated values are in good agreement with the corresponding experimental data. All the species are predicted to be linear with only one minimum in the corresponding potential energy surface. In the formation of mixed halides, the reaction between M+1 and M2X, where M1 is lighter than M2, is more exothermic than the alternative reaction. A bonding analysis has been made on the basis of Mulliken and natural atomic charges and bond orders.