Internal rotation and framework relaxation in ethene thiol

Abstract

New and existing data on the ground and excited CS torsional states of the stable rotamers of ethene thiol have been analysed to give a potential function for internal rotation around the CS bond. The barrier between the syn and anti rotamers is found to be 800 cm −1 and that at the planar anti conformation itself to be 12 cm −1. the syn conformation is 50 cm −2 more stable than the ‘quasi-planar’ anti conformation Satisfactory reproduction of the observed trends in rotational constants with torsional excitations has been achieved by introducing extensive relaxation of the CCS angle and the CS bond length during internal rotation. The CCS angle reduces by up to 5° v'hilst the CS bond length increases by up to 0.02 A during rotation from the syn to anti conformation. The use of ab initio M.O. calculations to provide an indication of the most significant aspects of structure relaxation is described.