Interactions of C+(2PJ) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients

Tuttle, William D.; Thorington, Rebecca L.; Viehland, Larry A.; Breckenridge, W.H.; Wright, Timothy G.

Abstract

Accurate interatomic potentials were calculated for the interaction of a singly charged carbon cation, C+, with a single rare gas atom, RG (RG = Ne–Xe). The RCCSD(T) method and basis sets of quadruple-ζ and quintuple-ζ quality were employed; each interaction energy was counterpoise corrected and extrapolated to the basis set limit. The lowest C+(2P) electronic term of the carbon cation was considered, and the interatomic potentials calculated for the diatomic terms that arise from these: 2Π and 2Σ+. Additionally, the interatomic potentials for the respective spin-orbit levels were calculated, and the effect on the spectroscopic parameters was examined. In doing this, anomalously large spin-orbit splittings for RG = Ar–Xe were found, and this was investigated using multi-reference configuration interaction calculations. The latter indicated a small amount of RG → C+ electron transfer and this was used to rationalize the observations. This is taken as evidence of an incipient chemical interaction, which was also examined via contour plots, Birge–Sponer plots and various population analyses across the C+-RG series (RG = He–Xe), with the latter showing unexpected results. Trends in several spectroscopic parameters were examined as a function of the increasing atomic number of the RG atom. Finally, each set of RCCSD(T) potentials was employed, including spin-orbit coupling to calculate the transport coefficients for C+ in RG, and the results were compared with the limited available data.

Citation

Tuttle, W. D., Thorington, R. L., Viehland, L. A., Breckenridge, W., & Wright, T. G. (2018). Interactions of C+(2PJ) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients. Philosophical Transactions A: Mathematical, Physical and Engineering Sciences, 376(2115), Article 20170156. https://doi.org/10.1098/rsta.2017.0156

• Journal Article Type: Article
• Acceptance Date: Sep 15, 2017
• Online Publication Date: Feb 5, 2018
• Publication Date: Mar 13, 2018
• Deposit Date: Sep 15, 2017
• Publicly Available Date: Feb 5, 2018
• Journal: Philosophical Transactions of the Royal Society A: Mathematical, Physical & Engineering Sciences
• Print ISSN: 1364-503X
• Electronic ISSN: 1471-2962
• Publisher: The Royal Society
• Peer Reviewed: Peer Reviewed
• Volume: 376
• Issue: 2115
• Article Number: 20170156
• DOI: https://doi.org/10.1098/rsta.2017.0156
• Keywords: carbon cation; rare gas; spectroscopy; bonding; ion transport
• Public URL: https://nottingham-repository.worktribe.com/output/920074
• Publisher URL: http://rsta.royalsocietypublishing.org/content/376/2115/20170156
• Contract Date: Sep 15, 2017