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Department of Chemistry

Publication details for Prof. Jeremy M. Hutson

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. Journal of Chemical Physics 125(18): 184312.

Author(s) from Durham

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)].