ISOTOPE EFFECTS ON STRONGLY COUPLED VIBRATIONS: THE MICROWAVE SPECTRUM OF METHYLMALONALDEHYDE

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1979

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Ohio State University

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The intramolecularly hydrogen-bonded molecule methylmalonaldehyde has two coupled, large-amplitude vibrations: the internal rotation of the methyl group and a motion of the chelate ring atoms between two equivalent, asymmetric conformations. The two vibration frequencies are determined from Coriolis perturbations in the rotational spectra. Four isotopic species $(OH/CH_{3}, OD/CH_{3}, OH/CD_{3}, OD/CD_{3})$ have been studied. The large isotope shifts observed (typically changes by factors of 3-8) are correlated by a simple two-coordinate mode. Possible implications of these results for theories of the origin of torsional barriers in this and similar systems will be discussed.

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