Theoretical Aspects of the Study of Molecular Complexes

  • Willis B. Person


In this chapter we should like to examine, from a theoretical viewpoint, the factors affecting the structure and spectra of molecular complexes. This subject has recently been thoroughly reviewed by Mulliken and Person1,2; here we shall review it briefly, with emphasis on vibrational spectroscopy, and include some new results, in section 1.3, from approximate all-electron quantum mechanical calculations of whole-complex molecular orbitals. In general, we shall try to follow the nomenclature of Mulliken and Persons1, and we shall refer the reader to that text for historical discussion and for a more thorough treatment of some aspects.


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  1. 1.
    R. S. Mulliken and W. B. Person, Molecular Complexes, ( John Wiley and Sons, New York, 1969 )Google Scholar
  2. 2.
    R. S. Mulliken and W. B. Person (Eds, H. Eyring, D. Henderson, and W. Jost) Physical Chemistry, Vol III (Academic Press, New York, 1969), chapter 10Google Scholar
  3. 3.
    R. S. Mulliken, J. Amer. Chem. Soc., 72, 600 (1950)CrossRefGoogle Scholar
  4. 4.
    R. S. Mulliken, J. Amer. Chem. Soc., 74, 811 (1952)CrossRefGoogle Scholar
  5. 5.
    R. S. Mulliken, J. Phys. Chem., 56, 801 (1952)CrossRefGoogle Scholar
  6. 6.
    J. O. Hirschfelder, Ed., Intermolecular Forces, (Adv. in Chem. Phys., Vol. 12 ) ( Interscience Publishers, New York, 1967 )Google Scholar
  7. 7.
    For example, see J. P. Lowe, J. Amer. Chem. Soc., 93, 301 (1971)CrossRefGoogle Scholar
  8. 8.
    E. Clementi and H. Popkie, J. Chem. Phys., 57, 1078 (1972)Google Scholar
  9. 9.
    J. N. Murrell, M. Randic and D. R. Williams, Proc. Roy. Soc., A284, 566 (1965)CrossRefGoogle Scholar
  10. Also see J. N. Murrell and G. Shaw, J. Chem. Phys., 46, 1768 (1967)CrossRefGoogle Scholar
  11. 10.
    J. L. Lippert, M. W. Hanna and P. J. Trotter, J. Amer. Chem. Soc., 91, 4035 (1969)CrossRefGoogle Scholar
  12. 11.
    E. G. Cook, Jr. and J. C. Schug, J. Chem. Phys., 53, 723 (1970);CrossRefGoogle Scholar
  13. See also J. C. Schug, W. M. Chang and M. C. Dyson, Spectrochim. Acta, 28A, 1157 (1972)CrossRefGoogle Scholar
  14. 12.
    J. O. Hirschfelder, C. E. Curtiss and R. B. Bird, Molecular Theory of Gases and Liquids, ( John Wiley and Sons, New York, 1954 )Google Scholar
  15. 13.
    H. B. Friedrich and W. B. Person, J. Chem. Phys., 44, 2161 (1966)CrossRefGoogle Scholar
  16. 14.
    A. D. Buckingham, Chapter 2 of reference 6Google Scholar
  17. 15.
    J. P. O’Connell and J. M. Prausnitz, Ind. Eng. Chem. Fundam., 8, 453 (1969); ibid., 9, 579 (1970); see also reference 17Google Scholar
  18. 16.
    J. Del Bene and J. A. Pople, J. Chem. Phys., 52, 4858 (1970)CrossRefGoogle Scholar
  19. 17.
    L. S. Moore and J. P. O’Connell, J. Chem. Phys., 55, 2605 (1971)CrossRefGoogle Scholar
  20. 18.
    M. W. Hanna, J. Amer. Chem. Soc., 90, 285 (1968)CrossRefGoogle Scholar
  21. 19.
    a) R. S. Drago and B. B. Wayland, J. Amer. Chem. Soc., 87, 3571 (1965);CrossRefGoogle Scholar
  22. (b).
    R. S. Drago, G. C. Vogel, and T. E. Needham, J. Amer. Chem. Soc., 93, 6014 (1971)CrossRefGoogle Scholar
  23. 20.
    R. G. Pearson, J. Amer. Chem. Soc., 85, 3533 (1963); see alsoGoogle Scholar
  24. S. Ahrland, J. Chatt and N. R. Davies, Quart. Rev., 12, 265 (1958)CrossRefGoogle Scholar
  25. 21.
    C. H. Townes and B. P. Dailey, J. Chem. Phys., 17,782 (1949); see alsoGoogle Scholar
  26. T. P. Das and E. L. Hahn, Solid State Phys., Suppl. No. 1 (1958)Google Scholar
  27. 22.
    H. O. Hooper, J. Chem. Phys., 41, 599 (1964); see alsoGoogle Scholar
  28. D. F. R. Gilson and C. T. O’Konski, ibid., 48, 2767 (1968), and R. A. Bennett and H. O. Hooper, ibid., 47, 4855 (1967)Google Scholar
  29. 23.
    R. S. Mulliken and W. B. Person, J. Amer. Chem. Soc., 91, 3409 (1969)CrossRefGoogle Scholar
  30. 24.
    a) G. A. Bowmaker and S. Hacobian, Aust. J. Chem., 22, 2047 (1969);CrossRefGoogle Scholar
  31. (b).
    H. Creswell-Fleming and M. W. Hanna, J. Amer. Chem. Soc., 93, 5030 (1971)CrossRefGoogle Scholar
  32. For example, see J. Yarwood, Spectrochim. Acta, 26A, 2099 (1970);CrossRefGoogle Scholar
  33. also J. P. Larkindale and D. J. Simkin, J. Chem. Phys., 55, 5048 (1971)CrossRefGoogle Scholar
  34. 26.
    S. Ichiba, H. Sakai, H. Negita and Y. Maeda, J. Chem. Phys., 54, 1627 (1971)CrossRefGoogle Scholar
  35. 27.
    J. Collin and L. D’Or, J. Chem. Phys., 23, 397 (1955)Google Scholar
  36. 28.
    G. C. Pimentel and A. L. McClellan, The Hydrogen Bond, (W. H. Freeman and Co., San Francisco, 1960 )Google Scholar
  37. 29.
    See the discussion of solvent effects by H. E. Hallam, in Infrared Spectroscopy and Molecular Structure, (Ed., M. Davies), (Elsevier Publishing Co., Amsterdam, 1963 ) Chapter XII. Dr. Hallam stresses the large solvent effects associated with hydrogen bonding, but he gives a good general review of the theory of “ordinary” solvent effects in his section 10Google Scholar
  38. 30.
    a) H. E. Hallam, section 11 of reference 29;Google Scholar
  39. (b).
    b) S. R. Polo and M. K. Wilson, J. Chem. Phys., 23, 2376 (1955);CrossRefGoogle Scholar
  40. c) W. B. Person, J. Chem. Phys., 28, 319 (1958);CrossRefGoogle Scholar
  41. (d).
    A. D. Buckingham, Proc. Roy. Soc., A248, 169 (1958), ibid., A255, 32 (1960);Google Scholar
  42. (e).
    A. D. Buckingham, Trans. Faraday Soc., 56, 753 (1960)CrossRefGoogle Scholar
  43. 31.
    R. R. Wiederkehr and H. G. Drickamer, J. Chem. Phys., 28, 311 (1958)CrossRefGoogle Scholar
  44. 32.
    G. Herzberg, Molecular Spectra and Molecular Structure. II Infrared and Raman Spectra of Polyatomic Molecules) (D. Van Nostrand Co., Inc., New York, 1945 ).Google Scholar
  45. 33.
    See W. B. Person, G. R. Anderson, J. N. Fordemwalt, H. Stammreich and R. Forneris, J. Chem. Phys., 35, 908 (1961)CrossRefGoogle Scholar
  46. 34.
    R. F. Lake and H. W. Thompson, Proc. Roy. Soc., A297, 440 (1967)CrossRefGoogle Scholar
  47. 35.
    J. N. Gayles, J. Chem. Phys., 49, 1840 (1968)CrossRefGoogle Scholar
  48. 36.
    G. W. Brownson and J. Yarwood, J. Mol. Struct., 10, 147 (1971)CrossRefGoogle Scholar
  49. 37.
    J. Yarwood and W. B. Person, J. Amer. Chem. Soc., 90, 3930 (1968);CrossRefGoogle Scholar
  50. J. Yarwood and W. B. Person, ibid., 90, 594 (1968)Google Scholar
  51. 38.
    W. B. Person and B. L. Crawford, Jr., J. Chem. Phys., 26, 1295 (1957)CrossRefGoogle Scholar
  52. 39.
    I. M. Mills, chapter 5 of reference 29.Google Scholar
  53. 40.
    T. Miyazawa and J. Overend, Bull. Chem. Soc. Jap., 39, 1410 (1966)CrossRefGoogle Scholar
  54. 41.
    For example, see K. Szczepaniak and A. Tramer, J. Phys. Chem., 71, 3035 (1967);CrossRefGoogle Scholar
  55. also see P. G. Puranik and V. Kumar, Proc. Indian Acad. Sci., A58, 29, 327 (1963)Google Scholar
  56. 42.
    W. B. Person, R. E. Humphrey and A. I. Popov, J. Amer. Chem. Soc., 81, 273 (1959)CrossRefGoogle Scholar
  57. 43.
    Y. Yagi, W. B. Person and A. I. Popov, J. Phys. Chem., 71, 2439 (1967);see also reference 36.Google Scholar
  58. 44.
    J. D’Hondt and Th. Zeegers-Huyskens, J. Mol. Structure, 10, 135 (1971)CrossRefGoogle Scholar
  59. 45.
    M. W. Hanna and D. E. Williams, J. Amer. Chem. Soc., 90, 5358 (1968)CrossRefGoogle Scholar
  60. 46.
    I. N. Levine, Quantum Chemistry. II. Molecular Spectroscopy, (Allyn and Bacon, Boston, 1970) p. 145ff.Google Scholar
  61. 47.
    D. E. Williams, J. Chem. Phys., 45, 3770 (1966)CrossRefGoogle Scholar
  62. 48.
    H. Rosen, Y. R. Shen and F. Stenman, Mol. Physics, 22, 33 (1971)CrossRefGoogle Scholar
  63. 49.
    T.-C. Jao and W. B. Person, (unpublished results)Google Scholar
  64. 50.
    J. Overend, chapter 10 of reference 29.Google Scholar
  65. 51.
    J. L. Hollenberg and D. A. Dows, J. Chem. Phys., 37, 1300 (1962)CrossRefGoogle Scholar
  66. 52.
    H. Yamada and W. B. Person, J. Chem. Phys., 38, 1253 (1963)CrossRefGoogle Scholar
  67. 53.
    K. Szczepaniak and W. B. Person, Spectrochim. Acta, 28A, 15 (1972)CrossRefGoogle Scholar
  68. 54.
    A. J. Zelano and W. T. King, J. Chem. Phys., 53, 4444 (1970)CrossRefGoogle Scholar
  69. 55.
    W. B. Person and L. C. Hall, Spectrochim. Acta, 20, 771 (1964)CrossRefGoogle Scholar
  70. 56.
    a) G. A. Segal and M. L. Klein, J. Chem. Phys., 47, 4236 (1967);CrossRefGoogle Scholar
  71. b) R. E. Bruns and W. B. Person, J. Chem. Phys., 57, 324 (1972), and other unpublished results;Google Scholar
  72. (c).
    T. P. Lewis and I. W. Levin, Theoret. Chim. Acta, 19, 55 (1970)CrossRefGoogle Scholar
  73. 57.
    J. G. Kirkwood, quoted by W. West and R. T. Edwards, J. Chem. Phys., 5, 14 (1937)CrossRefGoogle Scholar
  74. 58.
    E. Bauer and M. Magat, J. Phys. Radium, 9, 319 (1938)CrossRefGoogle Scholar
  75. 59.
    C. M. Huggins and G. C. Pimente], J. Phys. Chem., 60, 1615 (1956)CrossRefGoogle Scholar
  76. 60.
    W. B. Person, R. E. Erickson and R. E. Buckles, J. Amer. Chem. Soc., 82, 29 (1960)CrossRefGoogle Scholar
  77. 61.
    E. Clementi, Proc. Nat. Acad. Sci. USA, 69, 2942 (1972)CrossRefGoogle Scholar
  78. 62.
    See, for example, H. F. Schaefer, III, The Electronic Structure of Atoms and Molecules, (Addison-Wesley Publishing Co., Reading, Mass., 1972 )Google Scholar
  79. 63.
    E. Clementi, (a) Chem. Rev., 68, 341 (1968);CrossRefGoogle Scholar
  80. b) Physics of Electronic and Atomic Collisions, VII ICPEAC, 1971 (North-Holland, 1972), pp. 399–426;Google Scholar
  81. (c).
    B. J. Duke, Ann. Rept., 68A, 3 (1971)Google Scholar
  82. 64.
    a) E. Clementi, J. Chem. Phys., 46, 3851 (1967);CrossRefGoogle Scholar
  83. b)E. Clementi,ibid., 47, 2323 (1967);Google Scholar
  84. (c).
    E. Clementi and J. N. Gayles, J. Chem. Phys., 47, 3837 (1967)CrossRefGoogle Scholar
  85. 65.
    R. S. Mulliken, J. Chem. Phys., 23, 1833, 1841, 2338, 2343 (1955)Google Scholar
  86. 66.
    R. G. Body, D. S. McClure and E. Clementi, J. Chem. Phys., 49, 4916 (1968)CrossRefGoogle Scholar
  87. 67.
    P. Cade and W. M. Huo (private communication).Google Scholar
  88. 68.
    a) J. A. Pople, D. P. Santry and G. A. Segal, J. Chem. Phys., 43, S129 (1965);CrossRefGoogle Scholar
  89. (b).
    J. A. Pople and G. A. Segal, J. Chem. Phys., 43, S136 (1965);CrossRefGoogle Scholar
  90. (c).
    J. A. Pople and G. A. Segal, J. Chem. Phys., 44, 3289 (1966)CrossRefGoogle Scholar
  91. 69.
    J. A. Pople and D. L. Beveridge, Approximate Molecular Orbital Theory ( M Graw-Hill Book Co., New York, 1970 ).Google Scholar
  92. 70.
    J. A. Pople, D. L. Beveridge and P. A. Dobosh, J. Chem. Phys., 47, 2026 (1967)CrossRefGoogle Scholar
  93. 71.
    G. A. Segal, QCPE 91 CNDO/2—Molecular Calculations with Complete Neglect of Differential Overlap, and P. A. Dobosh, QCPE 141 CNINDO, CNDO and INDO Molecular Orbital Program (FORTRAN IV). (Available from Quantum Chemistry Program Exchange, University of Indiana, Bloomington, Indiana)Google Scholar
  94. 72.
    There have been a great many calculations for (H20)2. See (a) P. A. Kollman and L. C. Allen, J. Amer. Chem. Soc., 92, 753 (1970), for a review of literature and for a comparison of their CNDO/2 results with ab initio calculations; andGoogle Scholar
  95. b) P. A. Kollman and L. C. Allen, J. Chem. Phys., 51, 3286 (1969) for a particularly interesting (for its treatment of vibrational properties) ab initio calculation; also see ab initio calculations byGoogle Scholar
  96. (c).
    K. Morokuma and L. Pedersen, J. Chem. Phys., 48, 3275 (1968);CrossRefGoogle Scholar
  97. (d).
    K. Morokuma and J. R. Winick, J. Chem. Phys., 52, 1301 (1970);CrossRefGoogle Scholar
  98. e) D. Hankins, J W. Moskowitz and F. H. Stillinger, J. Chem. Phys. 53, 4544 (1970); and reference 15.Google Scholar
  99. 73.
    P. A. Kollman and L. C. Allen, J. Amer. Chem. Soc., 93, 4991 (1971)CrossRefGoogle Scholar
  100. 74.
    L. A. Carreira and W. B. Person, J. Amer. Chem. Soc., 94, 1485 (1972)CrossRefGoogle Scholar
  101. 75.
    M. van Thiel, E. D. Becker, and G. C. Pimentel, J. Chem. Phys., 27, 486 (1957)CrossRefGoogle Scholar
  102. 76.
    A. J. Tursi and E. R. Nixon, J. Chem. Phys., 52, 1521 (1970)CrossRefGoogle Scholar
  103. 77.
    L. A. Carreira and W. B. Person, unpublished results.Google Scholar
  104. 78.
    H. Tsubomura, Bull. Chem. Soc. Jap., 27, 445 (1954);CrossRefGoogle Scholar
  105. H. Tsubomura, J. Chem. Phys., 24, 927 (1956)CrossRefGoogle Scholar
  106. 79.
    C. A. Coulson (Ed. D. Hadzi ). Hydrogen Bonding, (Pergamon Press, New York, 1959 ), p. 339Google Scholar

Copyright information

© Springer Science+Business Media New York 1973

Authors and Affiliations

  • Willis B. Person
    • 1
  1. 1.Department Of ChemistryUniversity of FloridaGainesvilleUSA

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