Diatomics-in-molecules study of the geometric and electronic structure of Xe-n(+) clusters

Abstract

Dissociation energies as well as electronic and geometric structure of singly charged xenon cluster cations, Xen+ (n=3–35), are calculated using the extended diatomics-in-molecules method (including the spin–orbit coupling and the most important ionic and neutral three-body interactions) and the state-of-the-art ab initio diatomic curves for Xe2+ due to Paidarová and Gadéa [Chem. Phys. 274 (2001) 1]. Cluster growth of Xen+ and size dependence of the positive charge delocalization are discussed. The calculated dissociation energies are used to estimate the evaporation energies for Xen+→Xen−1++Xe and to study the stability of the Xen+ clusters. The results obtained are compared with available experimental and theoretical data.