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Ab initio treatment of the chemical reaction precursor complex Cl(2P)-HF. 2. Bound states and infrared spectrum.Fishchuk AV, Groenenboom GC, van der Avoird A Institute of Theoretical Chemistry, IMM, Radboud University Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The Netherlands. Bound energy levels and properties of the Cl(2P)-HF complex were obtained from full three-dimensional (3D) calculations, with the use of the ab initio computed diabatic potential surfaces from the preceding paper and the inclusion of spin-orbit coupling. For a better understanding of the dynamics of this complex we also computed a 2D model in which the HF bond length r was frozen at the vibrationally averaged values r0 and r1 and a 2 + 1D model in which the 3D potentials were averaged over the v(HF) = 0 and v(HF) = 1 vibrational wave functions of free HF. Also 1D calculations were made in which both r and the Cl-HF distance R were frozen. The complex is found to have the linear hydrogen bonded Cl-HF structure, with ground-state quantum numbers J = 3/2 for the overall angular momentum and /omega/ = 3/2 for its projection on the intermolecular axis R. The binding energy is D0 = 432.25 cm(-1) for v(HF) = 0 and D0 = 497.21 cm(-1) for v(HF) = 1. Bending modes with /omega/ = 1/2 and /omega/ = 5/2 are split by the Renner-Teller effect, since the electronic ground state is a degenerate 2pi state. A series of intermolecular (R) stretch modes was identified. Rotational constants and e-f parity splittings were extracted from the levels computed for J = 1/2 to 7/2. The computed red shift of the HF stretch frequency of 64.96 cm(-1) and the 35Cl-37Cl isotope shift of 0.033 cm(-1) are in good agreement with the values of 68.77 and 0.035 cm(-1) obtained from the recent experiment of Merritt et al. (Phys. Chem. Chem. Phys. 2005, 7, 67), after correction for the effect of the He nanodroplet matrix in which they were measured. Published 20 April 2006 in J Phys Chem A Mol Spectrosc Kinet Environ Gen Theory, 110(16): 5280-8.
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