Interactions of rare gas cations with lighter rare gas atoms

Abstract

High-level ab initio calculations are employed to generate potential energy curves for rare gas cations, RG⁺, interacting with neutral atoms of other rare gases, RG′, that are lighter (RG′ = Ne–Rn). The calculations employ the RCCSD(T) method, with doubly-augmented basis sets of quintuple-ζ quality. The interaction potential curves, with the full counterpoise correction applied, are calculated point-by-point. Spin-orbit coupling is applied analytically in an atom-based model. The potentials are used to calculate spectroscopic parameters, which are then compared to recent experimental work, and the very limited previous theoretical work. In addition, the potentials are used to calculate ion transport properties and the ion mobilities are compared to the few experimental data available.

Keywords:

• rare gases
• ionic complexes
• ion mobility
• interaction potentials
• spectroscopy

Acknowledgement

The work of LAV was supported by the US National Science Foundation under grant CHE-0718024. TGW is grateful for computing time at the NSCCS, funded by the EPSRC (UK).