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

Doyle, R. J and Hirst, D. M. and 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). p. 184312.


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)].

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Publisher statement:© 2006 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in The Journal of Chemical Physics 125, 184312 (2006) and may be found at
Date accepted:29 September 2006
Date deposited:19 August 2015
Date of first online publication:November 2006
Date first made open access:No date available

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