title: Ab initio potential energy surfaces, bound states, and electronic spectrum of the Ar-SH complex.
abstract: New ab initio potential energy surfaces for the (2)Pi ground 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-state wave functions are combined with those obtained for the excited (2)Sigma(+) 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)].
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK. rihard.j.doyle@gmail.com
authors.forename: Richard J
authors.initials: RJ
authors.lastname: Doyle
authors.forename: David M
authors.initials: DM
authors.lastname: Hirst
authors.forename: Jeremy M
authors.initials: JM
authors.lastname: Hutson