On the bonding in doubly charged diatomics

Summary The potential energy of interacting atomic ions A⁺+B⁺ often shows a shallow local minimum separated by a broad potential barrier from the dissociation products at much lower energy. Early interpretations of dication potential shapes were based on the similarity of the electronic structure between isoelectronic neutral and ionic species and led to a picture of a chemical bond superimposed on a repulsive Coulomb potential. More recently, barriers in dication potentials have commonly been interpreted as avoided curve crossings involving covalent and ionic structures. In this paper, we demonstrate that the former model is the appropriate one except in cases with very small asymptotic ionic/covalent energy splittings. By deriving dication wavefunctions from their neutral isoelectronic counterparts, we obtain upper bound dication potential curves which show all the characteristic features. By further modeling induction effects, we arrive at an almost quantitative fit of accurateab initio dication potentials. The chemical bond plus electrostatic repulsion interpretation of dication interactions also explains why the accurate calculation of potential curves appears to be much more demanding for dications than for isoelectronic neutrals.Dedicated in the honor of Prof. Klaus Ruedenberg