Infrared bands of CS2 dimer and trimer at 4.5 μm.

Abstract

We report observation of new infrared bands of (CS2)2 and (CS2)3 in the region of the CS2 ν1 + ν3 combination band (at 4.5 µm) using a quantum cascade laser. The complexes are formed in a pulsed supersonic slit-jet expansion of a gas mixture of carbon disulfide in helium. We have previously shown that the most stable isomer of (CS2)2 is a cross-shaped structure with D2d symmetry and that for (CS2)3 is a barrel-shaped structure with D3 symmetry. The dimer has one doubly degenerate infrared-active band in the ν1 + ν3 region of the CS2 monomer. This band is observed to have a rather small vibrational shift of -0.844 cm-1. We expect one parallel and one perpendicular infrared-active band for the trimer but observe two parallel bands and one perpendicular band. Much larger vibrational shifts of -8.953 cm-1 for the perpendicular band and -8.845 cm-1 and +16.681 cm-1 for the parallel bands are observed. Vibrational shifts and possible vibrational assignments, in the case of the parallel bands of the trimer, are discussed using group theoretical arguments.