Accurate potential energy curves for Tl⁺–Rg (Rg=He–Rn): spectroscopy and transport coefficients

Abstract

High-quality ab initio potential energy curves are presented for the Tl⁺–Rg series (Rg=He–Rn). Calculations are performed at the CCSD(T) level of theory, employing aug-cc-pV5Z quality basis sets, with ‘small core' relativistic effective core potentials being used for Tl⁺ and Kr–Rn. The curves are shown to be in excellent agreement with experimental mobility data for the systems Tl⁺–Rg (Rg=He–Xe), and generally excellent agreement is also obtained with longitudinal diffusion data. An exception to the latter is Tl⁺ in He, which is attributed to the experimental data not being obtained under steady state conditions. Spectroscopic information is also presented for the titular species, derived from potential energy curves, and the results are compared with previous potentials inferred from the ion transport data.

Acknowledgements

BRG is grateful for support via a studentship from the EPSRC. The authors are grateful to the EPSRC for the award of computer time at the Rutherford Appleton Laboratories under the auspices of the Computational Chemistry Working Party (CCWP), which enabled these calculations to be performed. The research of AY, SS and LAV was supported by the US National Science Foundation under grant CHE-0414241.