Water-carbon disulfide dimers: observation of a new isomer and ab initio structure theory.

Abstract

The weakly bound dimer water-carbon disulfide is studied by ab initio structure theory and high-resolution infrared spectroscopy. The calculations yield three stable minima in the potential energy surface, all planar. The most stable, isomer 1, was observed previously by microwave spectroscopy. It has C2v symmetry, an S-O bond, and a linear O-S-C-S backbone. Isomer 2, the next most stable, has not been considered previously by theory or experiment. It also has C2v symmetry, but with a side-by-side structure. Isomer 3, which is slightly less stable, is side-by-side with one O-H bond pointing toward an S atom. The first gas phase water-CS2 infrared spectra are reported. For isomer 1, H2O-, HDO-, and D2O-CS2 are observed in the CS2ν1 + ν3 region, H2O-CS2 in the H2O ν2 bend region, and D2O-CS2 in the D2O ν1 and ν3 stretch regions. The latter ν3 spectrum enables an experimental determination of the A rotational parameter, which turns out to be larger than expected. The new isomer 2 is observed by means of a band in the H2O ν2 region, confirming its C2v symmetry and calculated structure.