Conformation and internal motions of dimethyl sulfate: A microwave spectroscopy study

The rotational spectra of five isotopologues of dimethyl sulfate have been assigned by pulsed-jet Fourier-transform microwave spectroscopy. The global minimum configuration has a C2 symmetry, with the two methyl groups nearly trans with respect to the two sulfonic oxygen atoms. The internal rotations of the two methyl groups split each transition into several components line, allowing for the determination of accurate values of the V3 barrier height to internal rotation and of the orientation of the methyl groups with respect to the principal axis system. The geometry of the molecular skeleton is fully determined.

236Highlights► The global minimum configuration of dimethylsulfate has a C2 symmetry. ► The internal rotations of the two methyl groups split each transition into quartets. ► The internal rotations split each transition into quintets for asymmetrically substituted species. ► The structure of the heavy atoms skeleton is fully determined.