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

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 ext...

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Main Authors: Tuttle, William D., Thorington, Rebecca L., Viehland, Larry A., Breckenridge, W.H., Wright, Timothy G.
Format: Article
Language:English
Published: The Royal Society 2018
Subjects:
Online Access:https://eprints.nottingham.ac.uk/46411/
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author Tuttle, William D.
Thorington, Rebecca L.
Viehland, Larry A.
Breckenridge, W.H.
Wright, Timothy G.
author_facet Tuttle, William D.
Thorington, Rebecca L.
Viehland, Larry A.
Breckenridge, W.H.
Wright, Timothy G.
author_sort Tuttle, William D.
building Nottingham Research Data Repository
collection Online Access
description 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.
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spelling nottingham-464112018-02-14T19:01:00Z https://eprints.nottingham.ac.uk/46411/ 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. 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. The Royal Society 2018-03-13 Article PeerReviewed application/pdf en https://eprints.nottingham.ac.uk/46411/1/Tim%20Wright%20Interactions%20of%20C%2B%20with%20rare%20gas%20atoms.pdf Tuttle, William D., Thorington, Rebecca L., Viehland, Larry A., Breckenridge, W.H. and Wright, Timothy G. (2018) 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, 376 (2115). 20170156/1-20170156/20. ISSN 1471-2962 carbon cation; rare gas; spectroscopy; bonding; ion transport http://rsta.royalsocietypublishing.org/content/376/2115/20170156 doi:10.1098/rsta.2017.0156 doi:10.1098/rsta.2017.0156
spellingShingle carbon cation; rare gas; spectroscopy; bonding; ion transport
Tuttle, William D.
Thorington, Rebecca L.
Viehland, Larry A.
Breckenridge, W.H.
Wright, Timothy G.
Interactions of C+(2PJ) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients
title Interactions of C+(2PJ) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients
title_full Interactions of C+(2PJ) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients
title_fullStr Interactions of C+(2PJ) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients
title_full_unstemmed Interactions of C+(2PJ) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients
title_short Interactions of C+(2PJ) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients
title_sort interactions of c+(2pj) with rare gas atoms: incipient chemical interactions, potentials and transport coefficients
topic carbon cation; rare gas; spectroscopy; bonding; ion transport
url https://eprints.nottingham.ac.uk/46411/
https://eprints.nottingham.ac.uk/46411/
https://eprints.nottingham.ac.uk/46411/