Rotational analysis of à 2A1↔X̃ 2E electronic transition of the jet-cooled methylthio radical

Abstract

A set of molecular parameters describing both the X̃ and à states of CH3S, has been obtained by a joint fitting of the rotationally resolved electronic transitions observed in a free-jet-cooled laser-induced fluorescence study of CH3S and an earlier microwave study of its X̃ state. The present work shows that because of incomplete information, nearly all of the previously reported molecular parameters for CH3S must be significantly revised. The present observations show an unusual electronic structure for the radical, characterized by a short C–S bond distance and peculiar methyl group geometry in the ground state. The C–S bond is observed to lengthen markedly in the excited à state.