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Raman Intensities and the Nature of the Chemical Bond

  • Ronald E. Hester

Abstract

The experimental determination of Raman intensities is commonly a difficult procedure, particularly when the resulting intensities are to be placed on an absolute scale. For the purpose of evaluating derived properties characteristic of the chemical bonds responsible for the intensities, Raman intensities which have been corrected for such factors as spectrometer spectral sensitivity, optical absorption, sample geometry, and refractive index must be used. However, before discussing these factors and the applications and interpretations of absolute Raman intensities, it is necessary to examine in some detail the various theoretical relationships used to relate such corrected intensities to properties of chemical bonds.

Keywords

Bond Order Raman Line Raman Intensity Molecular Polarizability Bond Polarizability 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    L. Pauling and E. B. Wilson, Introduction to Quantum Mechanics, McGraw-Hill Book Company, New York (1935).Google Scholar
  2. 2.
    G. Placzek, Handbuch der Radiologie, Volume VI, Part 2, Leipzig, 1934, p. 205.Google Scholar
  3. 3.
    E. B. Wilson, J. C. Decius, and P. C. Cross, Molecular Vibrations, McGraw-Hill Book Company, New York, 1955.Google Scholar
  4. 4.
    R. W. Wood, Phys. Rev. 36: 1421 (1930).Google Scholar
  5. 5.
    L. A. Woodward and D. A. Long, Trans. Faraday Soc. 45: 1131 (1949).CrossRefGoogle Scholar
  6. 6.
    J. T. Edsall and E. B. Wilson, J. Chem. Phys. 6: 124 (1938).CrossRefGoogle Scholar
  7. 7.
    D. H. Rank and R. E. Kagarisse, J. Opt. Soc. Am. 40: 89 (1950).CrossRefGoogle Scholar
  8. 8.
    A. E. Douglas and D. H. Rank, J. Opt. Soc. Am. 38: 281 (1948).CrossRefGoogle Scholar
  9. 9.
    J. Brandmüller and H. Moser, Einführung in die Raman Spektroskopie, Steinkopff, Darmstadt, 1962.Google Scholar
  10. 10.
    H. J. Bernstein and G. Allen, J. Opt. Soc. Am. 45: 237 (1955).Google Scholar
  11. 11.
    W. H. Martin, Trans. Roy. Soc. Can. Sect. 11117: 151 (1923).Google Scholar
  12. 12.
    M. Wolkenstein, Compt. Rend. Acad. Sci. URSS 30: 791 (1941).Google Scholar
  13. 13.
    M. Eliashevich and M. Wolkenstein, J. Phys. USSR 9: 101, 326 (1945).Google Scholar
  14. 14.
    D. A. Long, Proc. Roy. Soc. (London) A 217: 203 (1953).Google Scholar
  15. 15.
    D. A. Long, A. H. S. Matterson, and L. A. Woodward, Proc. Roy. Soc. (London) A 224: 33 (1954).Google Scholar
  16. 16.
    K. A. Taylor and L. A. Woodward, Proc. Roy. Soc. (London) A 264: 558 (1961).Google Scholar
  17. 17.
    A. C. Albrecht, J. Chem. Phys. 34: 1476 (1961).CrossRefGoogle Scholar
  18. 18.
    J. H. Van Vleck, Proc. Nat. Acad. Sci. U.S. 15: 754 (1929).CrossRefGoogle Scholar
  19. 19.
    G. Hertzberg and E. Teller, Z. Physik. Chem. (Leipzig) B 21: 410 (1933).Google Scholar
  20. 20.
    A. C. Albrecht, J. Chem. Phys. 33: 156 (1960).CrossRefGoogle Scholar
  21. 21.
    P. P. Shorygin, J. Phys. Chem (USSR) 21: 1125 (1947).Google Scholar
  22. 22.
    P. P. Shorygin, Izo. Akad. Nauk SSSR, Ser. Fiz. 12: 576 (1948).Google Scholar
  23. 23.
    J. Behringer and J. Brandmüller, Z. Elektrochem. 60: 643 (1956).Google Scholar
  24. 24.
    D. G. Rea, J. Mol. Spectry. 4: 499 (1960).CrossRefGoogle Scholar
  25. 25.
    E. B. Wilson, J. Chem. Phys. 7: 1047 (1939); 9: 76 (1941).CrossRefGoogle Scholar
  26. 26.
    E. B. Wilson, J. C. Decius, and P. C. Cross, Molecular Vibrations, McGraw-Hill Book Company, New York, 1955.Google Scholar
  27. 27.
    B. L. Crawford and W. H. Fletcher, J. Chem. Phys. 19: 141 (1951).CrossRefGoogle Scholar
  28. 28.
    D. N. Walters and L. A. Woodward, Proc. Roy. Soc. (London) A 246: 119 (1958).CrossRefGoogle Scholar
  29. 29.
    G. W. Chantry and L. A. Woodward, Trans. Faraday Soc. 56: 1110 (1959).CrossRefGoogle Scholar
  30. 30.
    D. A. Long, R. B. Gravenor, and D. C. Milner, Trans. Faraday Soc. 59: 46 (1963).CrossRefGoogle Scholar
  31. 31.
    H. L. Welsh, M. F. Crawford, and G. D. Scott, J. Chem. Phys. 16: 97 (1948).CrossRefGoogle Scholar
  32. 32.
    I. Hansen-Damaschun, Z. Physik. Chem. B 22: 97 (1933).Google Scholar
  33. 33.
    L. Pauling, , 3rd. ed., Cornell University Press, Ithaca, N.Y., 1960, p. 98.Google Scholar
  34. 34.
    G. Placzek, Handbuch der Radiologie, Volume VI, Part 2, Leipzig, 1934, p. 366.Google Scholar
  35. 35.
    G. Placzek, Z. Physik 70: 84 (1931).CrossRefGoogle Scholar
  36. 36.
    J. P. Mathieu and M. Lounsbury, Discussions Faraday Soc. 9: 196 (1950).CrossRefGoogle Scholar
  37. 37.
    J. R. Ferraro, J. Mol. Spectry. 4: 99 (1960).CrossRefGoogle Scholar
  38. 38.
    R. E. Hester and R. A. Plane, Inorg. Chem. 3: 769 (1964).CrossRefGoogle Scholar
  39. 39.
    R. E. Hester and R. A. Plane, J. Chem. Phys. 40: 411 (1964).CrossRefGoogle Scholar
  40. 40.
    S. C. Wait and G. J. Janz, Quart. Rev. (London) 17: 225 (1963).CrossRefGoogle Scholar
  41. 41.
    J. K. Wilmshurst and S. Senderoff, J. Chem. Phys. 35: 1078 (1961).CrossRefGoogle Scholar
  42. 42.
    J. H. B. George, J. A. Rolfe, and L. A. Woodward, Trans. Faraday Soc. 49: 375 (1953).CrossRefGoogle Scholar
  43. 43.
    R. P. Bell and J. H. B. George, Trans. Faraday Soc. 49: 619 (1953).CrossRefGoogle Scholar
  44. 44.
    P. L. Goggin and L. A. Woodward, Trans. Faraday Soc. 56: 1591 (1960).CrossRefGoogle Scholar
  45. 45.
    H. Lee and J. K. Wilmshurst, Australian J. Chem. 17: 943 (1964).CrossRefGoogle Scholar
  46. 46.
    R. A. Robinson and R. H. Stokes, Electrolyte Solutions, 2nd ed., Butterworths, London, 1959, Chap. 14.Google Scholar
  47. 47.
    C. W. Davies, in: W. J. Hamer (ed.), The Structure of Electrolytic Solutions, John Wiley and Sons, Inc., New York, 1959, Chap. 3.Google Scholar
  48. 48.
    P. L. Goggin and L. A. Woodward, Trans. Faraday Soc. 58: 1495 (1962).CrossRefGoogle Scholar
  49. 49.
    R. E. Hester, R. A. Plane, and G. E. Walrafen, J. Chem. Phys. 38: 249 (1963).Google Scholar
  50. 50.
    R. E. Hester and R. A. Plane, Inorg. Chem. 3: 768 (1964).CrossRefGoogle Scholar
  51. 51.
    G. Hertzberg, Molecular Spectra and Molecular Structure II, D. Van Nostrand Company, Inc., Princeton, N.J., 1945.Google Scholar
  52. 52.
    R. E. Hester, Thesis, Cornell University, 1962.Google Scholar
  53. 53.
    P. C. Cross, J. Burnham, and P. A. Leighton, J. Am. Chem. Soc. 59: 1134 (1937).CrossRefGoogle Scholar
  54. 54.
    A. da Silveira, M. A. Marques, and N. M. Marques, Compt. Rend. 252: 3983 (1961).Google Scholar
  55. 55.
    J. P. Mathieu, Compt. Rend. 231: 896 (1950); see also R. L. Lafont, Compt. Rend. 244: 1481 (1957).Google Scholar
  56. 56.
    T. Yoshino and H. J. Bernstein, Spectrochim. Acta 14: 127 (1959).CrossRefGoogle Scholar
  57. 57.
    T. Yoshino and H. J. Bernstein, J. Mol. Spectry. 2: 213 (1958).CrossRefGoogle Scholar
  58. 58.
    H. L. Welsh, M. F. Crawford, T. R. Thomas, and G. R. Love, Can. J. Phys. 30: 577 (1952).CrossRefGoogle Scholar
  59. 59.
    G. Hertzberg, Spectra of Diatomic Molecules, D. Van Nostrand Company, Inc., New York, 1950, p. 128.Google Scholar
  60. 60.
    B. L. Crawford, Jr., and F. A. Miller, J. Chem. Phys. 17: 249 (1949).CrossRefGoogle Scholar
  61. 61.
    B. L. Crawford, Jr., J. A. Lancaster, and R. G. Inskeep, J. Chem. Phys. 21: 678 (1963).CrossRefGoogle Scholar
  62. 62.
    G. E. Hansen and D. M. Dennison, J. Chem. Phys. 20: 313 (1952).CrossRefGoogle Scholar
  63. 63.
    T. Simanouchi, J. Chem. Phys. 17: 849 (1949).Google Scholar
  64. 64.
    D. A. Long, Proc. Roy. Soc. (London) A 224: 33 (1954).Google Scholar
  65. 65.
    J. W. Linnett, J. Chem. Phys. 8: 91 (1940).CrossRefGoogle Scholar
  66. 66.
    H. W. Schrötter and H. J. Bernstein, J. Mol. Spectry. 12: 1 (1964).CrossRefGoogle Scholar
  67. 67.
    R. C. Golike, I. M. Mills, W. B. Person, and B. L. Crawford, Jr., J. Chem. Phys. 25: 1266 (1956).CrossRefGoogle Scholar
  68. 68.
    I. M. Nyquist, I. M. Mills, W. B. Person, and B. L. Crawford, Jr., J. Chem. Phys. 26: 552 (1957).CrossRefGoogle Scholar
  69. 69.
    G. W. Chantry and R. A. Plane, J. Chem. Phys. 32: 319 (1960).CrossRefGoogle Scholar
  70. 70.
    D. A. Long, D. C. Milner, and A. G. Thomas, Proc. Roy. Soc. (London) A 237: 197 (1956).CrossRefGoogle Scholar
  71. 71.
    L. Pauling, J. Chem. Soc. 1461 (1948).Google Scholar
  72. 72.
    H. Eyring, J. Walter, and G. E. Kimball, Quantum Chemistry, John Wiley and Sons, Inc., New York, 1944, p. 231.Google Scholar
  73. 73.
    R. P. Bell, Trans. Faraday Soc. 38: 422 (1942).CrossRefGoogle Scholar
  74. 74.
    G. W. Chantry and R. A. Plane, J. Chem. Phys. 34: 1268 (1961).CrossRefGoogle Scholar
  75. 75.
    G. W. Chantry and R. A. Plane, J. Chem. Phys. 35: 1027 (1961).CrossRefGoogle Scholar
  76. 76.
    A. V. Jones, Proc. Roy. Soc. (London) A 211: 285 (1952).CrossRefGoogle Scholar
  77. 77.
    L. Pauling, Nature of the Chemical Bond, 3rd ed., Cornell University Press, Ithaca, N.Y., 1960, p. 337.Google Scholar
  78. 78.
    L. A. Woodward and J. A. Creighton, Spectrochim. Acta 17: 594 (1961).CrossRefGoogle Scholar
  79. 79.
    L. A. Woodward and M. J. Ware, Spectrochim. Acta 19: 775 (1963).CrossRefGoogle Scholar
  80. 80.
    C. K. Jorgensen, Mol. Phys. 2: 309 (1959).CrossRefGoogle Scholar
  81. 81.
    L. A. Woodward and L. E. Anderson, J. Chem. Soc. 1284 (1957).Google Scholar
  82. 82.
    G. W. Chantry and R. A. Plane, J. Chem. Phys. 33: 634 (1960).CrossRefGoogle Scholar
  83. 83.
    A. C. Albrecht and K. A. Taylor, paper presented at the VIIth European Congress on Molecular Spectroscopy, Budapest, Hungary, July 1963 (to be published).Google Scholar
  84. 84.
    R. E. Hester and R. A. Plane, Inorg. Chem. 3: 513 (1964).CrossRefGoogle Scholar
  85. 85.
    K. Venkateswarlu and M. Radhakrishnan, Spectrochim. Acta 18: 1433 (1962).Google Scholar
  86. 86.
    J. Brandmüller and H. Schrötter, Z. Physik 149: 131 (1957).CrossRefGoogle Scholar
  87. 87.
    M. Smoluchowski, Ann. Physik 25: 205 (1908).CrossRefGoogle Scholar
  88. 88.
    A. Einstein, Ann. Physik 33: 1275 (1910).CrossRefGoogle Scholar
  89. 89.
    D. K. Carpenter and W. R. Krigbaum, J. Chem. Phys. 24: 1041 (1956).CrossRefGoogle Scholar
  90. 90.
    H. W. Schrötter and H. J. Bernstein, J. Mol. Spectry. 7: 464 (1961).CrossRefGoogle Scholar
  91. 91.
    H. W. Schrötter, Z. Elektrochem. 64: 853 (1960).Google Scholar
  92. 92.
    D. G. Whiffen, J. Opt. Soc. Am. 47: 568 (1957).CrossRefGoogle Scholar
  93. 93.
    D. G. Rea, J. Opt. Soc. Am. 49: 90 (1959).CrossRefGoogle Scholar
  94. 94.
    H. J. Bernstein and J. A. Koningstein (to be published).Google Scholar
  95. 95.
    G. Allen and H. J. Bernstein, Can. J. Chem. 33: 1137 (1955).CrossRefGoogle Scholar
  96. 96.
    J. C. Evans and H. J. Bernstein, Can. J. Chem. 33: 1746 (1955).CrossRefGoogle Scholar
  97. 97.
    H. J. Bernstein, Pure Appl. Chem. 4: 23 (1962).CrossRefGoogle Scholar
  98. 98.
    V. M. Pivovarov, Opt. Spectr. (USSR) (English Transi.) 9: 139 (1960).Google Scholar
  99. 99.
    D. G. Rea, J. Mol. Spectry. 4: 507 (1960).CrossRefGoogle Scholar
  100. 100.
    P. R. Ryason, J. Mol. Spectry. 8: 579 (1962).CrossRefGoogle Scholar
  101. 101.
    I. J. P. Jesson and H. W. Thompson, Proc. Roy. Soc. A 268: 68 (1962).Google Scholar
  102. 102.
    S. A. Tare and H. W. Thompson, Spectrochim. Acta 18: 1095 (1962).Google Scholar
  103. 103.
    G. W. Chantry, Spectrochim. Acta 21: 1007 (1965).Google Scholar
  104. 104.
    D. A. Long and E. L. Thomas, Trans. Faraday Soc. 59: 1026 (1963).CrossRefGoogle Scholar

Copyright information

© Plenum Press 1967

Authors and Affiliations

  • Ronald E. Hester
    • 1
  1. 1.University of YorkYorkEngland

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