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No Access Published Online: 31 August 1998

  • Calculation of Raman intensities for the ring‐puckering vibrations of 2,5‐dihydropyrrole and trimethyleneimine. Electrical versus mechanical anharmonicity in asymmetric potential wells

J. Chem. Phys. 75, 2626 (1981); https://doi.org/10.1063/1.442417
David F. Bocian, G. Alan Schick, and Robert R. Birge
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  • Department of Chemistry, University of California, Riverside, California 92521
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  • David F. Bocian
  • G. Alan Schick
  • Robert R. Birge
ABSTRACT
Raman intensities are calculated for the ring‐puckering transitions of 2,5‐dihydropyrrole (DHP) and trimethyleneimine (TMI) using an anisotropic atom–point dipole interaction model to evaluate the elements of the molecular polarizability tensor. The calculated relative intensities for the members of the Δv = 1 and Δv = 2 ring‐puckering progressions for DHP are in good agreement with those observed. The calculations predict that the observed Δv = 2 overtones of DHP occur not because of the first‐order allowedness expected for these transitions in the asymmetric double‐minimum potential well which governs the ring‐puckering motion, but rather because of unusually large second‐order terms in the expansions of the polarizability tensor elements in the puckering coordinate [‖(∂2αμν/∂Z2)0‖≫0]. Raman intensities are calculated for the ring‐puckering transitions of TMI using the two different potential functions which have been proposed for the puckering motion. It is found that the intensities calculated for the slightly asymmetric double‐minimum potential V(Z) = (0.922 05×106)Z4−(0.379 44×105)Z2+(0.159 13×105)Z 3 proposed by Carreira and Lord [J. Chem. Phys. 51, 2735 (1969)] cannot be reconciled with experiment. On the other hand, the intensities calculated for the highly asymmetric single‐minimum potential V(Z) = (0.7553×105)Z2−(0.4336×106)Z3+(0.7035×106)Z4 proposed by Robiette et al. [Mol. Phys. 42,1519 (1981)] are in excellent agreement with experiment. Our calculations confirm that the three most intense ring‐puckering transitions observed in the Raman (and far‐infrared) spectrum of TMI are the lowest members of a Δv = 1 rather than a Δv = 2 progression. The calculations further indicate that high‐order electrical terms in the polarizability expansions contribute significantly to the Raman intensities of both the Δv = 1 and Δv = 2 ring‐puckering progressions. Neglect of the electrically anharmonic terms in the intensity calculation for the single‐minimum well results in a significant disparity between calculation and experiment.

REFERENCES
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  1. 1. Comprehensive reviews of gas‐phase far‐infrared and Raman studies of the puckering motion of small ring molecules can be found in Refs. 2 and 3, respectively. Google Scholar
  2. 2. C. S. Blackwell and R. C. Lord, in Vibrational Spectra and Structure, edited by J. R. Durig (Dekker, New York, 1972), Vol. 1, pp. 1–24. Google Scholar
  3. 3. C. J. Wurrey, J. R. Durig, and L. A. Carreira, in Vibrational Spectra and Structure, edited by J. R. Durig (Elsevier, New York, 1976), Vol. 5, pp. 121–277. Google Scholar
  4. 4. J. M. R. Stone and I. M. Mills, Mol. Phys. 18, 631 (1970). Google ScholarCrossref, ISI
  5. 5. F. A. Miller and R. J. Capwell, Spectrochim. Acta 27A, 1947 (1971). Google Scholar
  6. 6. (a) W. Kiefer, H. J. Bernstein, M. Danyluk, and H. Wieser, Chem. Phys. Lett. 12, 605 (1972); Google ScholarCrossref
    (b) W. Kiefer, H. J. Bernstein, M. Danyluk, and H. Wieser, J. Mol. Spectrosc. 43, 393 (1972). , Google ScholarCrossref
  7. 7. J. R. Durig and L. A. Carreira, J. Chem. Phys. 56, 4966 (1972). Google ScholarScitation, ISI
  8. 8. T. H. Chao and J. Laane, Chem. Phys. Lett. 14, 595 (1972). Google ScholarCrossref, ISI
  9. 9. J. R. Durig, L. A. Carreira, and J. N. Wills, Jr., J. Chem. Phys. 57, 2755 (1972). Google ScholarScitation
  10. 10. L. A. Carreira, R. O. Carter, and J. R. Durig, J. Chem. Phys. 57, 3384 (1972). Google ScholarScitation
  11. 11. J. R. Durig, A. C. Shing, L. A. Carreira, and Y. S. Li, J. Chem. Phys. 57, 4398 (1972). Google ScholarScitation
  12. 12. J. R. Durig, A. C. Shing, and L. A. Carreira, J. Mol. Struct. 17, 423 (1973). Google ScholarCrossref
  13. 13. J. R. Durig, R. O. Carter, and L. A. Carreira, J. Chem. Phys. 59, 2249 (1973). Google ScholarScitation, ISI
  14. 14. J. D. Lewis, T. H. Chao, and J. Laane, J. Chem. Phys. 62, 1932 (1975). Google ScholarScitation
  15. 15. S. Brodersen, in Raman Spectroscopy of Liquids and Gases, edited by A. Weber (Springer‐Verlag, Berlin, 1979), pp. 7–69. Google Scholar
  16. 16. D. F. Bocian, G. A. Schick, and R. R. Birge, J. Chem. Phys. 74, 3660 (1981). Google ScholarScitation
  17. 17. L. A. Carreira and R. C. Lord, J. Chem. Phys. 51, 2735 (1969). Google ScholarScitation
  18. 18. C. S. Blackwell, L. A. Carreira, J. R. Durig, J. M. Karriker, and R. C. Lord, J. Chem. Phys. 56, 1706 (1972). Google ScholarScitation
  19. 19. R. L. Somorjai and D. F. Hornig, J. Chem. Phys. 36, 1980 (1962). Google ScholarScitation, ISI
  20. 20. A. G. Robiette, T. R. Borgers, and H. L. Strauss, Mol. Phys. 42, 1519 (1981). Google ScholarCrossref
  21. 21. P. N. Skancke, G. Fogarasi, and J. E. Boggs, J. Mol. Struct. 62, 259 (1980). Google ScholarCrossref
  22. 22. R. R. Birge, J. Chem. Phys. 72, 5312 (1980). Google ScholarScitation, ISI
  23. 23. H. A. Lorentz, Ann. Phys. (Leipzig) 9, 641 (1880); Google ScholarCrossref
    L. Lorenz, Ann. Phys. (Leipzig) 11, 70 (1880). , Google ScholarCrossref
  24. 24. Handbook of Chemistry and Physics, edited by R. C. Weast (Chemical Rubber, Cleveland, 1977), 58th ed. Google Scholar
  25. 25. D. A. Long, Raman Spectroscopy (McGraw‐Hill, New York, 1977), pp. 41–86. Google Scholar
  26. 26. S. I. Chan and D. Stelman, J. Mol. Spectrosc. 10, 278 (1963). Google ScholarCrossref
  27. 27. S. I. Chan, D. Stelman, and L. E. Thompson, J. Chem. Phys. 41, 2828 (1964). Google ScholarScitation, ISI
  28. 28. V. S. Mastyukov, O. V. Dorofeeva, L. V. Vilkov, and I. Hargittai, J. Mol. Struct. 34, 99 (1976). Google ScholarCrossref
  29. 29. A. Almenningen, O. Bastiansen, and P. N. Skancke, Acta Chem. Scand. 15, 711 (1961). Google ScholarCrossref
  30. 30. S. Meiboom and L. C. Snyder, J. Chem. Phys. 52, 3857 (1970). Google ScholarScitation
  31. 31. F. Takabayashi, H. Kambara, and K. Kuchitsu, in 7th Austin Symposium on Gas‐Phase Molecular Structure, Austin, Texas, Paper WA6, 1978. Google Scholar
  32. 32. (a) J. S. Wright and L. Salem, Chem. Commun. 1969, 137; Google Scholar
    (b) J. Am. Chem. Soc. 94, 332 (1972). Google Scholar
  33. 33. L. S. Bartell and B. Andersen, Chem. Commun. 1973, 786. Google Scholar
  34. 34. T. B. Malloy, J. Mol. Spectrosc. 44, 504 (1972). Google ScholarCrossref
  35. 35. J. E. Huheey, Inorganic Chemistry (Harper and Row, New York, 1978), p. 847. Google Scholar
  1. © 1981 American Institute of Physics.

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