INFRARED SPECTRA OF CRYSTALLINE AND MATRIX-ISOLATED CARBONYL SULFIDE.

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1965

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Ohio State University

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A study has been made of the infrared spectra of thin polycrystalline films of various mixtures of $OC^{12}S$ and $OC^{13}S$, with particular attention to the abnormally broad $\nu_{3}$ band. Isotopic mixtures have also been studied by matrix isolation methods, using $CO_{2}, CS_{2}, N_{2}O, N_{2}$ and A as matrix materials. A number of bands due to $C^{13}$ and $S^{34}$, in addition to some possibly due to $S^{33}$ or $O^{18}$, have been assigned. Unlike the two other fundamental vibrations of the OCS molecule, the absorption maximum in $\nu_{3}$ undergoes marked frequency shifts with isotopic composition of the OCS films. In general, the matrices show a strong $\nu_{3}$ peak with weaker satellite peaks that seem to be due to aggregations. A 1:700 mixture in argon, for example, gives a single sharp band. The behavior of $\nu_{3}$ in the $CS_{2}$ matrix appears to involve other factors besides aggregation. Interpretations of the spectra will be discussed.

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Author Institution: Pitman-Dunn Institute for Research; Department of Chemistry, Laboratory for Research on the Structure of Matter University of Pennsylvania, Philadelphia, Pennsylvania, 19104

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