Ab initio potential energy surfaces, bound states, and electronic spectrum of the Ar–SH complex

Doyle, R. J; Hirst, D. M.; Hutson, J. M.

Abstract

New ab initiopotential energy surfaces for the Π2ground electronic state of the Ar–SH complex are presented, calculated at the RCCSD(T)/aug-cc-pV5Z level. Weakly bound rotation-vibration levels are calculated using coupled-channel methods that properly account for the coupling between the two electronic states. The resulting wave functions are analyzed and a new adiabatic approximation including spin-orbit coupling is proposed. The ground-statewave functions are combined with those obtained for the excited Σ+2 state [D. M. Hirst, R. J. Doyle, and S. R. Mackenzie, Phys. Chem. Chem. Phys.6, 5463 (2004)] to produce transition dipole moments. Modeling the transition intensities as a combination of these dipole moments and calculated lifetime values [A. B. McCoy, J. Chem. Phys.109, 170 (1998)] leads to a good representation of the experimental fluorescence excitation spectrum [M.-C. Yang, A. P. Salzberg, B.-C. Chang, C. C. Carter, and T. A. Miller, J. Chem. Phys.98, 4301 (1993)].

Citation

Doyle, R. J., Hirst, D. M., & Hutson, J. M. (2006). Ab initio potential energy surfaces, bound states, and electronic spectrum of the Ar–SH complex. The Journal of Chemical Physics, 125(18), Article 184312. https://doi.org/10.1063/1.2371080

• Journal Article Type: Article
• Acceptance Date: Sep 29, 2006
• Publication Date: Nov 14, 2006
• Deposit Date: Aug 19, 2015
• Publicly Available Date: Aug 19, 2015
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 125
• Issue: 18
• Article Number: 184312
• DOI: https://doi.org/10.1063/1.2371080
• Public URL: https://durham-repository.worktribe.com/output/1575081