ROTATIONAL MOTION AND MOMENT ANALYSIS OF INFRARED BANDS OF HYDROGEN HALIDES AND METHANE DISSOLVED IN LIQUID SOLVENTS.

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1969

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Ohio State University

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Abstract

The infrared spectra of the fundamental stretching vibrations of HCl, DCl and HBr, and of the $v_{3}$ band of $CH_{4}$ have been measured at room temperature for samples dissolved in perfluoro-methylcyclohexane, 1,2-dibromoperfluoroethane, carbontetrachloride and liquid bromine. Band shapes have been analyzed to obtain the dipole correlation $function.^{1,2}$ Second and fourth moments have been calculated to obtain the average rotational kinetic energy and the intermolecular mean squared $torques.^{2}$ Our results confirm and extend the findings of previous $workers^{3}$ concerning the rotation of these molecules in inert solvents. Trends in the values of these parameters with changing solvent appear to be consistent with their interpretation in terms of intermolecular interaction.

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This research was supported by National Science Foundation, Grant No. GP 8111. $^{1}$ H. Shimizu, J. Chem. Phys. 43, 2453 (1965). $^{2}$ R.G. Gordon, J. Chem. Phys. 43, 1307 (1965); ibid. 41, 1819 (1964) and earlier references cited there. $^{3}$ W.G. Rothschild, J. Chem. Phys. 49, 2250 (1968); R.L. Armstrong, S.M. Blumenfeld and C.G. Gray, Can. J. Phys. 46, 1331 (1968); A. Cabana, R. Bardoux and A. Chamberland, private communication, to be published in J. Chem. Phys.
Author Institution: Department of Chemistry, University of Florida

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