A THEORETICAL-STUDY ON THE STRUCTURE AND STABILITY OF THE PC1(N) AND PC1(N)(-) SERIES, N=1-6

The electronic and geometrical structure of the ground and low-lying excited states for the phosphorus chlorides PCln, 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 PCl6 is found to be highly unstable towards dissociation to PCl4+PCl2 and the species PCl5, PCl5-, and PCl6- are near the stability threshold. According to the results of the calculations, all the neutrals considered possess the positive adiabatic electron affinities. The PCln- anions (n=1-4) possess at least one excited state which is stable towards the loss of an extra electron and dissociation.