A RE-EVALUATION OF THE MOLECULAR SUBSTITUTION STRUCTURES OF ISOCYANIC ACID, HNCO, AND ISOTHIOCYANIC ACID, HNCS

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1979

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Ohio State University

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Previous determinations of the structures of HNCO and HNCS have relied upon the assumption that the heavy-atom chain is linear in both molecules. Because all three heavy atoms lie close to the a-axis, some assumption in addition to the first moment condition and the product of inertia condition for the substitution coordinates is necessary in order to define coordinates for all four atoms. In the work reported here, the data available for the various isotopic species of both molecules has been extended. The centrifugal distortion constants were determined with greater accuracy and in a consistent manner, and the resulting rotational constants were used to determine a new substitution structure for each of the two molecules. By choosing a different auxiliary condition to define the positions of the heavy atoms, slightly bent heavy atom chains result for both HNCO and HNCS. The validity of the method as applied to these molecules and the supporting evidence for trans, bent structures of HNCO and HNCS will be discussed.

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