Interactions of Si+(2PJ) and Ge+ (2PJ) with rare gas atoms (He–Rn): interaction potentials, spectroscopy, and ion transport coefficients

Davies, Alexander Rhys; Cranney, Aiden; Viehland, Larry A; Wright, Timothy G

Abstract

Accurate interatomic potentials were calculated for the interaction of a singly-charged silicon cation, Si+, with a single rare gas atom, RG (RG = Kr–Rn), as well as a singly-charged germanium cation, Ge+, with a single rare gas atom, RG (RG = He–Rn). The RCCSD(T) method and basis sets of quadruple-zeta and quintuple-zeta quality were employed; each interaction energy is counterpoise corrected and extrapolated to the basis set limit. The lowest electronic term (2P) of each cation was considered, and the interatomic potentials calculated for the diatomic terms that arise from these: 2-PI and 2-SIG+. Additionally, the interatomic potentials for the respective spin-orbit levels were calculated, and the effect on the spectroscopic parameters was examined. Trends in several spectroscopic parameters with the atomic number of RG were examined. The presence of incipient chemical interaction was also examined via Birge-Sponer-like plots and various population analyses across the series. In the cases of heavier RG, these were consistent with a small amount of electron transfer from the heavier RG atom to the cation, rationalizing the spin-orbit splittings. This was also supported by the observed larger-than-expected spin-orbit splittings for the Si+ RG complexes. Finally, each set of RCCSD(T) potentials including spin-orbit coupling was employed to calculate transport coefficients for the cation moving through a bath of the RG. The calculated ion mobilities showed significant differences for the two atomic spin-orbit states, arising from subtle changes in the interaction potentials.

Citation

Davies, A. R., Cranney, A., Viehland, L. A., & Wright, T. G. (2022). Interactions of Si+(2PJ) and Ge+ (2PJ) with rare gas atoms (He–Rn): interaction potentials, spectroscopy, and ion transport coefficients. Physical Chemistry Chemical Physics, 24(11), 7144-7163. https://doi.org/10.1039/d1cp05710c

• Journal Article Type: Article
• Acceptance Date: Feb 25, 2022
• Online Publication Date: Feb 28, 2022
• Publication Date: Mar 21, 2022
• Deposit Date: Mar 4, 2022
• Publicly Available Date: Mar 1, 2023
• Journal: Physical Chemistry Chemical Physics
• Print ISSN: 1463-9076
• Electronic ISSN: 1463-9084
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 24
• Issue: 11
• Pages: 7144-7163
• DOI: https://doi.org/10.1039/d1cp05710c
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://nottingham-repository.worktribe.com/output/7535960
• Publisher URL: https://pubs.rsc.org/en/content/articlelanding/2022/CP/D1CP05710C