Infrared Spectra of Crystalline and Matrix-Isolated Carbonyl Sulfide

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Abstract
The infrared spectrum of carbonyl sulfide has been examined as a polycrystalline film at 80°K and also in matrix‐isolated form, using argon, nitrogen, and CS2 as the matrix materials. Particular attention has been given to the ν3 vibration, which appears as an abnormally broad and asymmetric band in solid OCS. The asymmetry of ν3 does not appear to be the result of any significant reflection effects nor is it due to disorder in the crystal. A study of the concentration dependence of the ν3 frequency in isotopic mixtures shows that a good part of the asymmetry can be attributed to the ν3 absorption of molecules containing 33S and 34S. Spectra of dilute mixtures of OCS in argon matrices display absorption by both isolated molecules and molecular pairs. The features of the spectrum are qualitatively accounted for in terms of a simple model of pairs interacting through transition‐dipole coupling. In both N2 and CS2 matrices, the evidence suggests two different sites for the OCS molecule in the host lattice.

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