Microwave spectrum and conformation of vinyl mercaptan: The anti rotamer

Abstract

Microwave spectra of the anti rotamer of vinyl mercaptan and its SD isotopic species have been studied in the frequency range 12–60 GHz. For the normal species rotational and centrifugal distortion constants have been obtained for the ground and first three excited states of the SH torsional mode, the ground state values being A = 49 422.75(5) MHz, B = 5 897.215(9) MHz, C = 5 279.436(9) MHz, D J = 3.12(11) kHz, D JK = −38.50(1.71) kHz, and δ J = 0.498(51) kHz. An approximate potential function for the SH torsion in the vicinity of the anti conformation, derived using the observed variation of rotational constants with vibrational quantum number, reveals the presence of a small potential barrier of 19 cm −1 at the planar conformation. The v = 0 state lies above this barrier so the molecule is essentially planar in the ground state in spite of the observed negative value for the inertia defect (−0.1976(2) a.m.u.Å 2). The anti rotamer is found to be 50 ± 25 cm −1 less stable than the syn rotamer. The dipole moment has the ground state values μ a = 0.425(10), μ b = 1.033(10), and μ total = 1.117(14) D and is shown to vary considerably with vibrational quantum number. Evidence for significant structural changes in going from the syn rotamer to the anti rotamer is also presented.