Vibrational Optical Activity

  • Prasad L. Polavarapu


While the measurements of optical activity in electronic transitions are widely known and routine, similar measurements pertaining to vibrational transitions became feasible only recently. The vibrational optical activity (VOA) measurements can now be carried out with greater confidence owing to the rapid developments in both instrumentation and theory. The emergence of VOA, as a combination of two widely practiced branches of science namely vibrational spectroscopy and optical activity, offered new pathways for understanding the molecular stereochemistry. Despite its very weak nature, VOA is believed to surpass the conventional electronic optical activity (EOA) in both informational content and complexity. This is because in EOA studies one has to depend upon a limited number of accessible electronic transitions, whereas in VOA studies all 3N-6 vibrational transitions, where N is the number of atoms, of a chiral molecule are available for probing the molecular structure. This increased number of transitions also increases the complexity in interpreting the VOA spectra, but one hopes to find selectivity in structural determination. Since different vibrations encompass different portions of a molecule, the three dimensional view at a particular portion of the molecule may be derived from the VOA associated with the vibrations encompassing that portion. In this way one can hope to selectively determine the stereochemistry and assemble this information for determining the three dimensional structure of the entire molecule.


Optical Activity Vibrational Circular Dichroism Polarize Incident Light Coriolis Interaction Vibrational Circular Dichroism Spectrum 
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  1. 1.
    P. J. Stephens, and R. Clark, Vibrational circular dichroism: The experimental view point, in: “Optical Activity and Chiral Discrimination”, S. F. Mason, ed., D. Reidel, Dordrecht (1979).Google Scholar
  2. 2.
    L. D. Barron, and J. Vrbancich, Natural vibrational Raman optical activity, Top. Curr. Chem., 123: 151 (1984).CrossRefGoogle Scholar
  3. 3.
    L. A. Nafie, Infrared and Raman vibrational optical activity, in: “Vibrational Spectra and Structure”, J. R. Durig, ed., Vol. 10, Elsevier, Amsterdam (1981).Google Scholar
  4. 4.
    T. A. Keiderling, Vibrational circular dichroism, Appl. Spectrosc. Rev., 17: 189 (1981).CrossRefGoogle Scholar
  5. 5.
    P. L. Polavarapu, Recent advances in model calculations of vibrational optical activity, in: “Vibrational Spectra and Structure”, J. R. Durig, ed., Vol. 13, Elsevier, Amsterdam (1984).Google Scholar
  6. 6.
    L. A. Nafie and D. W. Vidrine, Double modulation Fourier transform spectroscopy, in: “Fourier Transform Infrared Spectroscopy”, J. R. Ferraro and L. J. Basile, eds, Vol. 3, Academic Press, New York (1982).Google Scholar
  7. 7.
    P. L. Polavarapu, Fourier transform infrared vibrational circular dichroism, in: “Fourier Transform Infrared Spectroscopy”, J. R. Ferraro and L. J. Basile, eds., Vol. 4, Academic Press, New York (in press).Google Scholar
  8. 8.
    D. M. Back and P. L. Polavarapu, Fourier transform infrared vibrational circular dichroism of sugars: A spectra-structure correlation, Carbohyd. Res., (in press).Google Scholar
  9. 9.
    P. L. Polavarapu and D. F. Michalska, Vibrational circular dichroism in (S)-(-)-epoxypropane; Measurement in vapor phase and verification of the perturbed degenerate mode theory, J. Am. Chem. Soc., 105: 6190 (1983).CrossRefGoogle Scholar
  10. 10.
    D. W. Schlosser, F. Devlin, K. Jalkanen and P. J. Stephens, Vibrational circular dichroism of matrix isolated molecules, Chem. Phys. Lett., 88: 286 (1982).CrossRefGoogle Scholar
  11. 11.
    I. M. Mills, Coriolis interactions intensity perturbations and potential functions in polyatomic molecules, Pure and Appl. Chem., 11: 325 (1965).CrossRefGoogle Scholar
  12. 12.
    C. DiLauro and I. M. Mills, Coriolis interactions about x-y axes in symmetric tops, J. Mol. Spectrosc., 21: 386 (1966).CrossRefGoogle Scholar
  13. 13.
    P. L. Polavarapu, Vibrational circular dichroism in liquid and vapor phase, Bull. Am. Phys. Soc., 28: 1343 (1983).Google Scholar
  14. 14.
    W. Hug, Optical artefacts and their control in Raman circular difference scattering measurements, Appl. Spectrosc., 35: 115 (1981).CrossRefGoogle Scholar
  15. 15.
    T. Brocki, M. Moskovits and B. Bosnich, Vibrational optical activity: Circular differential Raman scattering from a series of chiral terpenes, J. Am. Chem. Soc., 102: 495 (1980).CrossRefGoogle Scholar
  16. 16.
    P. L. Polavarapu, M. Diem and L. A. Nafie, Vibrational optical activity in para-substituted 1-methylcylohex-1-enes, J. Am. Chem. Soc., 102: 5449 (1980).CrossRefGoogle Scholar
  17. 17.
    P. L. Polavarapu, A design of Raman spectrograph for optical activity and normal Raman measurements, Appl. Spectrosc., 37: 447 (1983).CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1985

Authors and Affiliations

  • Prasad L. Polavarapu
    • 1
  1. 1.Department of ChemistryVanderbilt UniversityNashvilleUSA

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