CEPA calculations on open-shell molecules. V. The vibration frequencies of SF and SCl

Abstract

Ab initio calculations for the 2Π ground states of SF and SCl have been performed on Hartree-Fock level and with inclusion of valence shell correlation effects by means of the CI and CEPA approaches. The calculated properties are: Equilibrium distances, vibration frequencies, and dipole moment curves in the vicinity of the respective equilibrium geometries. Our best estimates for the 0 → 1 infrared absorption frequencies νo for SF and SCl are 786 cm−1 and 520 cm−1, respectively, both with an uncertainty of about 10 cm−1. This confirms a recent experimental value obtained by Willner for SF (791 cm−1), but indicates that for SCl both experimental values reported previously in the literature (617 cm−1 and 574 cm−1) are wrong. The S—F and S—Cl bonds in SF and SCl are very similar to the ones in SF2 and SCl2, being essentially single p-bonds in either case. In the analogous oxygen-halogen molecules the situation is different, the O—F and O—Cl bonds in the diatomic radicals OF and OCl have partial double bond character and are much stronger than those in OF2 and OCl2 or in HOF and HOCl.