Electronic structure of the noble gas dimer ions. I. Potential energy curves and spectroscopic constants

Abstract

A systematic study of the electronic structure and chemical binding in the dimer ion sequence, Ne2+, Ar2+, Kr+2, and Xe2+, has been carried out using density functional methods. For comparison, ab initio configuration-interaction calculations were also performed for the Ar2+ ion. These studies include detailed calculations of the pertinent potential energy curves and an analysis of the calculated spectroscopic properties of the bound states of these ions. A regular progression is found in the spectroscopic properties for the ground A 2Σ+1/2u state which leads to some remarkably simple conclusions concerning the nature of the binding and the size of these dimer ions. For the heavier systems, Kr2+ and Xe+2, spin–orbit coupling becomes important, resulting in a strong mixture of the Λ–S coupled Σ and Π states. This mixing affects the strength of the binding in the ground state. A comparison with other ab initio studies and an analysis of the asymptotic behavior at large internuclear separations is given. These dimer ion species illustrate the classic Hartree–Fock symmetry dilemma arising from improper dissociation character. The nature of this problem for ionized homopolar species is discussed.