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

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

doi:10.1098/rsta.2017.0156

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

Philos Trans A Math Phys Eng Sci. 2018 Mar 13;376(2115):20170156. doi: 10.1098/rsta.2017.0156.

Authors

William D Tuttle¹, Rebecca L Thorington¹, Larry A Viehland², W H Breckenridge³, Timothy G Wright⁴

Affiliations

¹ School of Chemistry, University Park, University of Nottingham, Nottingham NG7 2RD, UK.
² Department of Science, Chatham University, Pittsburgh, PA 15232, USA viehland@chatham.edu.
³ Department of Chemistry, University of Utah, 315 South 1400 East, Room 2020, Salt Lake City, UT 84112, USA.
⁴ School of Chemistry, University Park, University of Nottingham, Nottingham NG7 2RD, UK tim.wright@nottingham.ac.uk.

PMID: 29431683
DOI: 10.1098/rsta.2017.0156

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.This article is part of the theme issue 'Modern theoretical chemistry'.

Keywords: bonding; carbon cation; ion transport; rare gas; spectroscopy.