Matrix-isolation IR spectroscopy and quantum chemical characterisation of SOCl2 and [SOCl2 single bondHCl] clusters

Abstract

The IR spectra of thionyl chloride (SOCl2) are reported for the first time under matrix-isolation conditions in argon and nitrogen matrices, focusing on symmetric and antisymmetric stretching, and stretching modes. Spontaneous hydrolysis of SOCl2 to SO2 and HCl is observed, as evidenced by distinct IR peaks. Two conformers of and three conformers of [ ] have been identified on their respective potential energy surfaces. The formation of two dimer conformers is confirmed by characteristic SOCl2 modes, while the formation of three [ ] clusters is confirmed by red-shifts in the HCl stretching frequency mode.