A theoretical study on the structure and stability of the PCl n and PCl −n series, n=1–6

Abstract

The electronic and geometrical structure of the ground and low-lying excited states for the phosphorus chlorides PCl n , n=1–6, and their singly charged anions have been studied by an approximate density functional theory. The vertical and adiabatic electron affinities of the neutrals, first ionization potentials of the anions and fragmentation energies of various decay channels of both series are evaluated. The neutral PCl 6 is found to be highly unstable towards dissociation to PCl 4+PCl 2 and the species PCl 5, PCl − 5, and PCl − 6 are near the stability threshold. According to the results of the calculations, all the neutrals considered possess the positive adiabatic electron affinities. The PCl − n anions ( n=1–4) possess at least one excited state which is stable towards the loss of an extra electron and dissociation.