Theoretical study of metal noble-gas positive ions

Abstract

Theoretical calculations have been performed to determine the spectroscopic constants for the ground and selected low-lying electronic states of the transition-metal noble-gas ions VAr+, FeAr+, CoAr+, CuHe+, CuAr+, and CuKr+. Analogous calculations have been performed for the ground states of the alkali noble-gas ions LiAr+, LiKr+, NaAr+, and KAr+ and the alkaline-earth noble-gas ion MgAr+ to contrast the difference in binding energies between the simple and transition-metal noble-gas ions. The binding energies increase with increasing polarizability of the noble-gas ions, as expected for a charge-induced dipole bonding mechanism. We find that the spectroscopic constants of the X 1Σ+ states of the alkali noble-gas ions are well described at the self-consistent field level. In contrast, the binding energies of the transition-metal noble-gas ions are substantially increased by electron correlation. The difference arises from the contribution of metal-neutral noble-gas-ion character in the wave functions. This correlation effect increases as the ionization potential of the noble gas decreases from He to Kr and as the ionization potential of the metal atom increases.