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

Tuttle, William D. and Thorington, Rebecca L. and Viehland, Larry A. and Breckenridge, W.H. and Wright, Timothy G. (2017) Interactions of C+(2PJ) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients. Philosophical Transactions of the Royal Society A: Mathematical, Physical & Engineering Sciences . ISSN 1471-2962 (In Press)

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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- and quintuple- quality were employed; each interaction energy is 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: 2 and 2+. 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 multireference configuration interaction (MRCI) calculations. The latter indicated a small amount of RG  C+ electron transfer and this was able 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 transport coefficients for C+ in RG, and the results compared to the limited available data.

Key words: carbon cation, rare gas, spectroscopy, bonding, ion transport

Item Type: Article
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: 10.1098/rsta.2017.0156
Depositing User: Smith, Ruth
Date Deposited: 15 Sep 2017 10:56
Last Modified: 16 Sep 2017 01:09
URI: http://eprints.nottingham.ac.uk/id/eprint/46411

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