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Developments in Applied Spectroscopy pp 23–71Cite as

Torsional Frequencies and Barriers to Internal Rotation from Far Infrared Spectra of Solids

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Part of the book series: Developments in Applied Spectroscopy ((DAIS,volume 9))

Abstract

The far infrared and Raman spectra of several molecular solids which contained one, two, three, and four methyl rotors have been obtained over a range of temperatures. For the molecules with one methyl rotor it was found that the torsional frequency shifted approximately 20% with solidification; the calculated barriers are also raised by a similar amount. For molecular solids which contained three rotors it was found for almost every case that the A2 torsional mode which may be inactive for the molecule in the gas phase was always observed in the spectra of the solids. From a comparison of the frequencies for the degenerate E torsional mode and the A2 torsion one obtains a measure of the top-top interaction term for the potential energy. The barriers obtained for most of the molecular solids which contained three methyl rotors were very similar to those reported in the gas phase work in which the top-top interaction has been neglected. For the tetrahedral molecules containing four methyl rotors both the triply degenerate F1 torsional mode and the A2 torsion were observed in the spectra of the solids and from these data torsional barriers were calculated. A comparison of the torsional barriers for a large number of one, two, three, and four top-molecules will be given and discussed.

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Authors and Affiliations

  1. Department of Chemistry, University of South Carolina, Columbia, S. C., 29208, USA

    J. R. Durig, J. Bragin, S. M. Craven, C. M. Player Jr. & Y. S. Li

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  1. J. R. Durig
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  2. J. Bragin
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  3. S. M. Craven
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  4. C. M. Player Jr.
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  5. Y. S. Li
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Editor information

Editors and Affiliations

  1. Freeman Laboratories, Inc., Rosemont, Illinois, USA

    E. L. Grove

  2. College of Pharmacy, University of Illinois, Chicago, Illinois, USA

    A. J. Perkins

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© 1971 Chicago Section of the Society for Applied Spectroscopy

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Durig, J.R., Bragin, J., Craven, S.M., Player, C.M., Li, Y.S. (1971). Torsional Frequencies and Barriers to Internal Rotation from Far Infrared Spectra of Solids. In: Grove, E.L., Perkins, A.J. (eds) Developments in Applied Spectroscopy. Developments in Applied Spectroscopy, vol 9. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-0782-3_2

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  • DOI: https://doi.org/10.1007/978-1-4757-0782-3_2

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4757-0784-7

  • Online ISBN: 978-1-4757-0782-3

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