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A new theoretical look at the inversion problem in molecules

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Theory

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 68))

Abstract

In this section, we shall compare briefly the approach to molecular spectra using the Hamiltonian described in this paper with the standard approach19' 20) Such a comparison is useful because it shows future trends and problems in the theoretical interpretation of vibration—rotation spectra of molecules.

In the standard treatment, we can develop an effective Hamiltonian which can be used in the precise parametrization of the energy levels [see, e.g., Refs. 80, 81)]. However, molecular parameters obtained in this way are often only effective quantities without physical significance. Furthermore, if the molecule executes largeamplitude vibrations, the number of these parameters becomes unmanageably large.

On the other hand, the Hamiltonian described in this paper does not lend itself to a parametrization of the experimental data with a precision approaching the requirements of the high-resolution spectroscopy. However, if one wants to use these data as fully as possible to obtain physically reliable information on the potential function, then an approach such as described in this paper is required. Determination of the value of the inversion barrier in ammonia which is approximately by 200 cm−1 lower than the value determined previously (Section 5.3) shows on the importance of such approach.

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References

  1. Longuet-Higgins, H. C.: Mol. Phys. 6, 445 (1963).

    Article  CAS  Google Scholar 

  2. Watson, J. K. G.: Canad. J.Phys. 43, 1996 (1965).

    CAS  Google Scholar 

  3. Papoušek, D., Stone, J. M. R., špirko, V.: J. Mol. Spectrosc. 48, 17 (1973).

    Article  Google Scholar 

  4. špirko, V., Stone, J. M. R., Papoušek, D.: J. Mol. Spectrosc. 48, 38 (1973).

    Article  Google Scholar 

  5. Danielis, V., Papoušek, D., špirko, V., Horák, M.: J. Mol. Spectrosc. 54, 339 (1975).

    Article  CAS  Google Scholar 

  6. špirko, V., Stone, J. M. R., Papoušek, D.: J. Mol. Spectrosc. 60, 159 (1976).

    Article  Google Scholar 

  7. Cleeton, C. E., Williams, N. H.: Phys. Rev. 45, 234 (1934).

    Article  CAS  Google Scholar 

  8. Good, W. E.: Phys. Rev. 70, 213 (1946).

    Article  CAS  Google Scholar 

  9. Bleaney, B., Penrose, R. P.: Nature 157, 339 (1946).

    CAS  Google Scholar 

  10. Basov, N. G., Prochorov, A. M.: Zhurnal Eksp. Teoret. Fiz. 27, 431 (1954).

    CAS  Google Scholar 

  11. Gordon, J. P., Zeiger, H. Z., Townes, C. H.: Phys. Rev. 99, 1264 (1955).

    Article  CAS  Google Scholar 

  12. Vuylsteke, A. A.: Am. J. Phys. 27, 554 (1959).

    Article  CAS  Google Scholar 

  13. Cheung, A. C., Rank, D. M., Townes, C. H., Thornton, D. D., Welch, W. J.: Phys. Rev. Letters 21, 1701 (1968).

    Article  CAS  Google Scholar 

  14. Dennison, D. M., Hardy, J. D.: Phys. Rev. 39, 938 (1932).

    Article  CAS  Google Scholar 

  15. Dennison, D. M., Uhlenbeck, G. E.: Phys. Rev. 41, 313 (1932).

    Article  CAS  Google Scholar 

  16. Fermi, E.: Nuovo Cimento 9, 277 (1932).

    CAS  Google Scholar 

  17. Wollrab, J. E.: Rotational spectra and molecular structure. New York: Academic Press 1967.

    Google Scholar 

  18. Weeks, W. T., Hecht, K. T., Dennison, D. M.: J. Mol. Spectrosc. 8, 30 (1962).

    Article  CAS  Google Scholar 

  19. Allen, Jr., H. C., Cross, P. C.: Molecular vib-rotors. New York: J. Wiley and Sons 1963.

    Google Scholar 

  20. Wilson, Jr., E. B., Decius, J. C., Cross, P. C.: Molecular vibrations. New York: McGraw Hill 1955.

    Google Scholar 

  21. Hoy, A. R., Bunker, P. R.: J. Mol. Spectrosc. 52, 439 (1974).

    Article  CAS  Google Scholar 

  22. Hougen, J. T., Bunker, P. R., Johns, J. W. C.: J. Mol. Spectrosc. 34, 136 (1970).

    Article  CAS  Google Scholar 

  23. Bunker, P. R., Stone, J. M. R.: J. Mol. Spectrosc. 41, 310 (1972).

    Article  CAS  Google Scholar 

  24. Moule, D. C., Rao, Ch. V. S. R.: J. Mol. Spectrosc. 45, 120 (1973).

    Article  CAS  Google Scholar 

  25. Sarka, K., Papoušek, D., Boháček, I.: First International Seminar on High Resolution Infrared Spectroscopy, Prague, 1970.

    Google Scholar 

  26. Sarka, K.: J. Mol. Spectrosc. 38, 545 (1971).

    Article  CAS  Google Scholar 

  27. Boháček, I., Danielis, V., Papoušek, D., špirko. V.: J. Mol. Structure, in preparation.

    Google Scholar 

  28. Stone, J. M. R.: J. Mol. Spectrosc. 54, 1 (1975).

    Article  CAS  Google Scholar 

  29. Nielsen, H. H.: Rev. Mod. Phys. 23, 90 (1951).

    Article  CAS  Google Scholar 

  30. Mills, I. A.: Vibration-rotation structure in asymmetric-and symmetric-top molecules In: Molecular spectroscopy: modern research, Rao, K. Narahari, Mathews, C. W. (eds.). New York: Academic Press 1972.

    Google Scholar 

  31. Watson, J. K. G.: Mol. Phys. 15, 479 (1968).

    Article  CAS  Google Scholar 

  32. Gordy, W., Cook, R. L.: Microwave molecular spectra New York: Interscience Publishers 1970.

    Google Scholar 

  33. Herzberg, G.: Molecular spectra and molecular structure. II. Infrared and Raman spectra of polyatomic molecules. Princeton: Van Nostrand 1959.

    Google Scholar 

  34. Bunker, P. R.: Practically everything you ought to know about the molecular symmetry group. New York: M. Dekker 1976.

    Google Scholar 

  35. Oka, T., Shimizu, F. O., Shimizu, T., Watson, J. K. G.: Astrophys. J. 165, L15 (1971).

    Article  CAS  Google Scholar 

  36. Belov, S. P., Burenin, A. V., Gershtein, L. I., Korolochin, V. V., Krupnov, A. F.: Optika i Spektroskopia 35, 295 (1973).

    CAS  Google Scholar 

  37. Maki, A. G., Sams, R. L., Olson, W. B.: J. Chem. Phys. 58, 4502 (1973).

    Article  CAS  Google Scholar 

  38. De Lucia, F. C., Helminger, P.: J. Mol. Spectrosc. 54, 200 (1975).

    Article  Google Scholar 

  39. Garing, J. S., Nielsen, H. H., Rao, K. N.: J. Mol. Spectrosc. 3, 496 (1959).

    Article  CAS  Google Scholar 

  40. Benedict, W. S., Plyrer, E. K.: Canad. J. Phys. 35, 1235 (1957).

    CAS  Google Scholar 

  41. Rao, K. N., Brim, W. W., Hoffman, J. M., Jones, L. H., McDowell, R. S.: J. Mol. Spectrosc. 7, 362 (1961).

    Article  Google Scholar 

  42. Jones, L. H., Brim, W. W., Rao, K. N.: J. Mol. Spectrosc. 11, 389 (1963).

    Article  CAS  Google Scholar 

  43. Duncan, J. L.: unpublished data.

    Google Scholar 

  44. Coon, J. B., Naugle, N. W., McKenzie, R. D.: J. Mol. Spectrosc. 20, 107 (1966).

    Article  CAS  Google Scholar 

  45. Schnabell, E., Torring, T., Wilke, W.: Z. Phys. 188, 167 (1965).

    Article  Google Scholar 

  46. Shimizu, F. O., Shimizu, T.: J. Mol. Spectrosc. 36, 94 (1970).

    Article  CAS  Google Scholar 

  47. Herman, G.: J. Chem. Phys. 29, 875 (1958).

    Article  Google Scholar 

  48. Helminger, P., De Lucia, F. C., Gordy, W., Morgan, H. W., Staats, P. A.: Phys. Rev. A 9, 12 (1974).

    Google Scholar 

  49. Cohen, E. A., Poynter, R. L.: J. Mol. Spectrosc. 53, 131 (1974).

    Article  CAS  Google Scholar 

  50. Kwan, Y. Y., Cohen, E. A.: J. Mol. Spectrosc. 58, 54 (1975).

    Article  CAS  Google Scholar 

  51. Walker, R. E., Hochheimer, B. F.: J. Mol. Spectrosc. 34, 500 (1970).

    Article  CAS  Google Scholar 

  52. Weber, W. H., Maker, P. D., Young, K. F., Peters, C. W.: Appl. Opt. 13, 1431 (1974).

    Article  CAS  Google Scholar 

  53. Johns, J. W. C., McKellar, A. R. W., Trombetti, A.: J. Mol. Spectrosc. 55, 131 (1975).

    Article  CAS  Google Scholar 

  54. Di Lauro, C., Mills, I. M.: J. Mol. Spectrosc. 21, 386 (1966).

    Article  Google Scholar 

  55. Sarka, K., Papoušek, D., Rao, K. N.: J. Mol. Spectrosc. 37, 1 (1971).

    Article  CAS  Google Scholar 

  56. Dowling, J. M.: J. Mol. Spectrosc. 27, 527 (1968).

    Article  CAS  Google Scholar 

  57. Curtis, J. B., Stout, D., Yin, P. K. L., Rao, K. N.: to be published.

    Google Scholar 

  58. Rank, A., Allen, L. C., Mislow, K.: Angew. Chem. Int. Edit. 9, 400 (1970).

    Article  Google Scholar 

  59. Mislov, K.: Trans. New York Acad. Sci. Series II, 35, 227 (1973).

    Google Scholar 

  60. Ozier, I., Yi, P., Khosla, A., Ramsey, N. F.: Phys. Rev. Letters 24, 642 (1970).

    Article  CAS  Google Scholar 

  61. Hougen, J. T.: J. Chem. Phys. 55, 1122 (1971).

    Article  CAS  Google Scholar 

  62. Ovchinnikov, Yu. V., Ionov, S. P.: Soviet Physics JETP 26, 385 (1968).

    Google Scholar 

  63. Kroto, H. W.: Molecular rotation spectra. London-New York-Sidney-Toronto: J. Wiley and Sons 1975.

    Google Scholar 

  64. Costain, C., Sutherland, G.: J. Phys. Chem. 56, 321 (1952).

    Article  CAS  Google Scholar 

  65. Davies, P. B., Neumann, R. M., Wofsy, S. C., Klemperer, W.: J. Chem. Phys. 55, 3564 (1971).

    Article  CAS  Google Scholar 

  66. Cazolli, G., Lister, D. G.: J. Mol. Spectrosc. 45, 467 (1973).

    Article  Google Scholar 

  67. Tyler, J. K., Sheridan, J., Costain, C. C.: J. Mol. Spectrosc. 43, 248 (1972).

    Article  CAS  Google Scholar 

  68. Hirota, E., Sugisaki, R., Nielsen, C. J., SØrensen, G. O.: J. Mol. Spectrosc. 49, 251 (1974).

    Article  CAS  Google Scholar 

  69. Sugisaki, R., Tanaka, T., Hirota, E.: J. Mol. Spectrosc. 49, 241 (1974).

    Article  CAS  Google Scholar 

  70. Tsuboi, M., Hirakawa, A. Y., Tamagaka, K.: J. Mol. Spectrosc. 22, 272 (1967).

    Article  CAS  Google Scholar 

  71. Mirri, A. M., Caminali, W.: J. Mol. Spectrosc. 47, 204 (1973).

    Article  CAS  Google Scholar 

  72. Wollrab, J. E., Laurie, V. W.: J. Chem. Phys. 48, 5058 (1968).

    Article  CAS  Google Scholar 

  73. Penn, R. E., Boggs, J. E.: J. Mol. Spectrosc. 47, 340 (1973).

    Article  CAS  Google Scholar 

  74. Hamada, Y., Hirakawa, A. Y., Tamagake, K., Tsuboi, M.: J. Mol. Spectrosc. 35, 420 (1970).

    Article  CAS  Google Scholar 

  75. Tyler, J. K.: J. Mol. Spectrosc. 11, 39 (1963).

    Article  CAS  Google Scholar 

  76. Tamagake, K., Tsuboi, M.: J. Mol. Spectrosc. 53, 189 (1974).

    Article  CAS  Google Scholar 

  77. Takagi, K., Kojima, T.: J. Phys. Soc. Japan 30, 1145 (1971).

    CAS  Google Scholar 

  78. Spirko, V.: IIIrd International Seminar on High Resolution Infrared Spectroscopy, Prague 1974.

    Google Scholar 

  79. Papousek, D., Danielis, V.: IInd International Seminar on High Resolution Infrared Spectroscopy, Prague 1972.

    Google Scholar 

  80. Watson, J. K. G.: J. Chem. Phys. 46, 1935 (1967).

    Article  CAS  Google Scholar 

  81. Steenbeckeliers, G., Bellet, J.: J. Mol. Spectrosc. 45, 10 (1973).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Molecular Spectroscopy, The J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, 160 00, Prague 6, Czechoslovakia

    Dr. Dušan Papoušek & Dr. Vladimír špirko

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  1. Dr. Dušan Papoušek
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  2. Dr. Vladimír špirko
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© 1976 Springer-Verlag

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Papoušek, D., špirko, V. (1976). A new theoretical look at the inversion problem in molecules. In: Theory. Topics in Current Chemistry, vol 68. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0048532

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  • DOI: https://doi.org/10.1007/BFb0048532

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  • Print ISBN: 978-3-540-07932-3

  • Online ISBN: 978-3-540-38036-8

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