Developments in Applied Spectroscopy pp 23-71 | Cite as
Torsional Frequencies and Barriers to Internal Rotation from Far Infrared Spectra of Solids
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.
Keywords
Barrier Height Torsional Vibration Shift Factor Torsional Mode Tertiary ButylPreview
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References
- 1.S. Weiss and G. E. Leroi, J. Chem. Phys. 48, 962 (1968).CrossRefGoogle Scholar
- 2.H. Bountin and S. Yip, “Molecular Spectroscopy with Neutrons”, MIT Press (1968).Google Scholar
- 3.J. R. Durig, S. M. Craven and J. Bragin, J. Chem. Phys. 51, 5663 (1969).CrossRefGoogle Scholar
- 4.J. R. Durig, S. M. Craven and J. Bragin, J. Chem. Phys. 52, 2046 (1970).CrossRefGoogle Scholar
- 5.J. R. Durig, C. M. Player Jr. and J. Bragin, J. Chem. Phys. 52, 4224 (1970).CrossRefGoogle Scholar
- 6.J. R. Durig, S. M. Craven and J. Bragin, J. Chem. Phys. 53, 38 (1970).CrossRefGoogle Scholar
- 7.J. R. Durig, S. M. Craven, K. K. Lau and J. Bragin, J. Chem. Phys. 53, Dec. 15th Issue (1970).Google Scholar
- 8.J. R. Durig, C. M. Player, Jr. and J. Bragin, J. Chem. Phys. 53,Google Scholar
- 9.J. R. Durig, C. M. P1ayer, Jr., J. Bragin and Y. S. Li, J. Chem. Phys. 54,Google Scholar
- 10.D. R. Herschbach, J. Chem. Phys. 31, 91 (1959).CrossRefGoogle Scholar
- 11.K. S. Pitzer, “Quantum Chemistry,” Prentice-Hall, Inc. Englewood Cliffs, N.J., (1953).Google Scholar
- 12.W. G. Fateley and F. A. Miller, Spectrochim. Acta, 17, 857 (1961).CrossRefGoogle Scholar
- 13.W. G. Fateley, F. A. Miller and R. E. Witkowski, Air Force Technical Report AFML-TR-66–408 (1967).Google Scholar
- 14.G. Sage and W. Klemperer, J. Chem. Phys. 39,371 (1963).CrossRefGoogle Scholar
- 15.D. R. Herschbach, J. Chem. Phys. 25, 358 (1956).CrossRefGoogle Scholar
- 16.H. Russell Jr., D. R. V. Golding and D. M. Yost, J. Am. Chem. Soc., 66, 16 (1944).CrossRefGoogle Scholar
- 17.H. T. Minden and B. P. Dailey, Phys. Rev., 82, 338 (1951).Google Scholar
- 18.C. A. Wulff, J. Chem. Phys. 39, 1227 (1963).CrossRefGoogle Scholar
- 19.B. Lafon and J. R. Nielsen, J. Mol. Spectry., 21, 175 (1966) and references therein.CrossRefGoogle Scholar
- 20.J. C. Evans and H. J. Bernstein, Can. J. Chem., 33, 1746 (1955).CrossRefGoogle Scholar
- 21.K. S. Pitzer and J. L. Hollenberg, J. Am. Chem. Soc., 75, 2219 (1953).CrossRefGoogle Scholar
- 22.T. R. Rubin, B. H. Levedahl and D. M. Yost, J. Am. Chem. Soc., 66, 279 (1944).CrossRefGoogle Scholar
- 23.J. R. Rush, J. Chem. Phys. 46, 2285 (1967).CrossRefGoogle Scholar
- 24.E. O. Stegjskal, D. E. Woessner, T. C. Farrar and H. S. Gutowsky, J. Chem. Phys., 31, 55 (1959).CrossRefGoogle Scholar
- 25.W. G. Fateley and F. A. Miller, Spectrochim. Acta, 19, 611 (1963).CrossRefGoogle Scholar
- 26.R. A. Scott and H. A. Scheraga, J. Chem. Phys., 42, 2209 (1965).CrossRefGoogle Scholar
- 27.J. L. DeCoen, G. Elefante, A. M. Liquori and A. Damiani, Nature, 216, 910 (1967).CrossRefGoogle Scholar
- 28.R. Holm, M. Mitzlaff and H. Hartmann, Z. Naturforsch, 23A, 307 (1968).Google Scholar
- 29.W. G. Fateley, F. E. Kiviat and F. A. Miller, Spectrochim Acta, 26A, 315 (1970).Google Scholar
- 30.K. D. Möller and L. H. London, J. Chem. Phys. 47, 2505 (1967).CrossRefGoogle Scholar
- 31.F. Winther and D.O. Hummel, Spectrochim Acta, 25A, 417 (1969).Google Scholar
- 32.F. A. Miller and F.E. Kiviat, Spectrochim Acta, 25A, 1577 (1969).Google Scholar
- 33.R. H. Schwendeman and G. D. Jacobs, J. Chem. Phys. 36, 1245 (1962).CrossRefGoogle Scholar
- 34.N. T. McDevitt, A. L. Rozek, F. F. Bentley and A. D. Davidson, J. Chem. Phys. 42, 1173 (1965).CrossRefGoogle Scholar
- 35.W. A. Thompson, Phys. Rev. Letters, 20, 1085 (1968).CrossRefGoogle Scholar
- 36.K. A. Strong, R. M. Brugger and R. J. Pugmire, J. Chem. Phys., 52, 2277 (1970).CrossRefGoogle Scholar
- 37.R. R. Getty and G. E. Leroi, Symposium an Molecular Structure and Spectroscopy, The Ohio State University, Columbus, Ohio, (1969), paper Q-7.Google Scholar
- 38a.K. D. Möller and H. G. Andresen, J. Chem. Phys., 37, 1800 (1962).CrossRefGoogle Scholar
- 38b.L. Pierce, J. Chem. Phys., 33, 498 (1961).CrossRefGoogle Scholar
- 39.K. D. Möller, A. R. DeMeo, D. R. Smith and L. H. London, J. Chem. Phys. 47, 2609 (1967).CrossRefGoogle Scholar
- 40.J. R. Hoyland, J. Chem. Phys. 19, 1908 (1968).CrossRefGoogle Scholar
- 41.M. D. Grant, R. J. Pugmire, R. C. Livingston, K. A. Strong, H. L. McMurry and Brugger, J. Chem. Phys. 52, 4424 (1970).Google Scholar
- 42.G. B. Kistiakowsky and W. W. Rice, J. Chem. Phys. 8, 618 (1940).CrossRefGoogle Scholar
- 43.R. M. Kennedy, M. Sagenkahn and J. G. Aston, J. Am. Chem. Soc., 63, 2267 (1941).CrossRefGoogle Scholar
- 44.K. S. Pitzer, J. Chem. Phys., 10, 605 (1942).CrossRefGoogle Scholar
- 45.R. Ananthakrishnan, Proc. Ind. Acad. Sci. A5, 285 (1937).Google Scholar
- 46.F. A. French and R. S. Rasmussen, J. Chem. Phys. 14, 389 (1946).CrossRefGoogle Scholar
- 47.P. H. Kasai and R. J. Myers, J. Chem. Phys., 30, 1096 (1959)CrossRefGoogle Scholar
- 47a.P. H. Kasai and R. J. Myers, J. Chem. Phys. 38, 2753 (1963).CrossRefGoogle Scholar
- 48.A. Hadni, Compt. Rend. 238, 349 (1954).Google Scholar
- 49.R. C. Lord, WADC Technical Report 59–498 (1960).Google Scholar
- 50.W. G. Fateley and F. A. Miller, Spectrochim Acta, 18, 977 (1962).Google Scholar
- 51.D. R. Lide Jr. and D. E. Mann, J. Chem. Phys. 28, 572 (1958).CrossRefGoogle Scholar
- 52.D. R. Lide Jr. and D. E. Mann, J. Chem. Phys. 29, 914 (1958).CrossRefGoogle Scholar
- 53.R. G. Snyder and G. Zebi, Spectrochim. Acta 23A, 391 (1967).Google Scholar
- 54.P. Labarbe, M. T. Forel and G. Bessis, Spectrochim. Acta, 24A, 2165 (1968).Google Scholar
- 55.J. P. Perchard, M. T. Forel and M. L. Josien, J. Chem. Phys. 61, 632 (1964).Google Scholar
- 56.J. M. Freeman and T. Henshall, J. Mol. Structure 1, 31 (1967).CrossRefGoogle Scholar
- 57.J. P. Lowe, Progress in Physical Organic Chemistry (Interscience Publishers, Inc., New York, 1968), Vol. 6.Google Scholar
- 58.D. A. Dows, Physics and Chemistry of the Organic Solid State (Interscience Publishers, Inc., New York, 1963) Vol. 1.Google Scholar
- 59.K. D. Möller and H. G. Andresen, J. Chem. Phys., 39, 17 (1963).CrossRefGoogle Scholar
- 60.J. C. Evans and G. Y. S. Lo, J. Am. Chem. Soc. 88, 2118 (1966).CrossRefGoogle Scholar
- 61.E. R. Shull, T. S. Oakwood and D. H. Rank, J. Chem. Phys. 21, 2024 (1953).CrossRefGoogle Scholar
- 62.J. G. Aston and G. H. Messerly, J. Am. Chem. Soc., 58, 2345 (1936).CrossRefGoogle Scholar
- 63.C. W. Hawley, M. S. Thesis, University of South Carolina (1971).Google Scholar
- 64.G. Graner and C. Thomas, J. Chem. Phys. 49, 4160 (1968).CrossRefGoogle Scholar
- 65.K. M. Sinnott, J. Chem. Phys. 34, 851 (1961).CrossRefGoogle Scholar
- 66.L. C. Krisher, J. Chem. Phys. 33, 1237 (1960).CrossRefGoogle Scholar
- 67.T. Kasuya, J. Phys. Soc. Japan, 15, 1273 (1960).CrossRefGoogle Scholar
- 68.D. R. Herschbach and J. D. Swalen, J. Chem. Phys., 29, 761 (1958).CrossRefGoogle Scholar
- 69.S. S. Butcher, J. Chem. Phys., 38, 2310 (1963).CrossRefGoogle Scholar
- 70.N. Dreizler and H. D. Rudolph, Z. Naturforsch. 17a, 712 (1962).Google Scholar