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Localization and Delocalization in Quantum Chemistry pp 127–152Cite as

The Calculation of Intermolecular Interaction Energies in Terms of Local Contributions

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Part of the book series: Localization and Delocalization in Quantum Chemistry ((LDQC,volume 2))

Abstract

In the present paper, we examine the possibility of expressing in terms of local contributions four important parts of the interaction energy between two molecules, namely the three well-known long-range terms (electrostatic polarization, dispersion) and the short-range 1st order exchange term. Such approximate decompositions are found for all these four terms. For the electrostatic energy, this is done for any molecular function, but for the three other terms a very important role is played in the derivation by the possibility of representing the ground-state of the molecules by Slater determinants built from localized molecular orbitals. For the 2nd order terms (polarization and dispersion), we first show, by using also the ‘excitonic’ representation of excited states, that the decomposition of the total molecular polarizability into local (bond) contributions is theoretically approximately justified, and we may derive on this basis the decomposition into local contributions of the polarization and dispersion energies. The difference between the type of decomposition for these two energies is emphasized. Finally two problems not treated in the paper are mentioned: the problem of analysing the charge-transfer term, and the problem posed by the insufficient localizability of the π-orbitals of aromatic molecules.

The content of this paper is also closely connected with the subject of Part III in Volume I (Expression of the Energy in Terms of Local Contributions’).

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References

  1. Daudey, J. P., Malrieu, J. P., and Rojas, G.: in Chalvet, O., Daudel, R., Diner, S., and Malrieu, J. P. (eds.), Localization and Delocalization in Quantum Chemistry, Reidel, Dordrecht (1975), Vol. I, p. 155.

    Google Scholar 

  2. Kitaigorodskii, A. I.: Tetrahedron 14 230 (1961);

    Article  CAS  Google Scholar 

  3. Some erroneous results of this paper are corrected in Kitaigorodskii, A. I. and Mirskaya, K. V.: Soviet Phys. Crystallography 9 137 (1964).

    Google Scholar 

  4. See also Huron, M. J. and Claverie, P.: J. Phys. Chem. 76 2132 (1972) Section II.4.

    Google Scholar 

  5. Kitaigorodskii, A. I.: Acta Cryst. 18 585 (1965).

    Article  CAS  Google Scholar 

  6. Kitaigorodskii, A. I. and Ahmed, N. A.: Acta Cryst. A28 207 (1972).

    Google Scholar 

  7. Liquori, A. M., J. Polym. Sc. C12 209 (1966).

    Google Scholar 

  8. Liquori, A. M., Quart. Rev. Biophys. 2 65 (1969).

    Article  CAS  Google Scholar 

  9. Scheraga, H. A.: Advances in Physical Organic Chemistry 6, 103 (1968), Academic Press, New York.

    Google Scholar 

  10. Caillet, J. and Claverie, P.: Biopolymers 13 601 (1974).

    Article  CAS  Google Scholar 

  11. Caillet, J. and Claverie, P.: Acta Cryst. A31 448 (1975)

    CAS  Google Scholar 

  12. Andersen, H. C. and Chandler, J. P.: J. Chem. Phys. 57 1930 (1972).

    Article  Google Scholar 

  13. Murrell, J. N. and Shaw, G.: J. Chem. Phys. 46 1768 (1967).

    Article  CAS  Google Scholar 

  14. Van Duijneveldt, F. B.: ‘Intermolecular Forces and the Hydrogen Band’, Thesis, Utrecht University (1969). Appendix A.

    Google Scholar 

  15. Hirschfelder, J. O. and Meath, W. J.: Advances in Chemical Physics 12 3 (1967).

    Article  CAS  Google Scholar 

  16. Margenau, H. and Kestner, N. R.: Theory of Intermolecular Forces, Pergamon Press (1969).

    Google Scholar 

  17. Claverie, P.: Intern. J. Quantum Chem. 5 273 (1971).

    Article  CAS  Google Scholar 

  18. Claverie, P.: ‘Contribution à l’Étude des Interactions Moléculaires’. Thesis, Paris (1973). Registered at the C.N.R.S. library under number: A.O. 8214 (see also the chapter on ‘Elaboration of Approximate Formulae for the Treatment of Large Molecules; Applications in Organic Chemistry’ in Intermolecular Interactions: from Diatomics to Biopolymers, B. Pullman (ed.), Wiley, New York (scheduled for 1976 or 1977)).

    Google Scholar 

  19. Van der Avoird: J. Chem. Phys. 47 3649 (1967).

    Article  CAS  Google Scholar 

  20. Williams, D. R., Schaad, L. J., and Murrell, J. N.: J. Chem. Phys. 47 4916 (1967).

    Article  CAS  Google Scholar 

  21. Murrell, J. N. and Shaw, G.: Mol. Phys. 12 475 (1967)

    Article  CAS  Google Scholar 

  22. Murrell, J. N. and Shaw, G.: Mol. Phys. 13 325 (1968).

    Article  Google Scholar 

  23. Daudey, J. P., Claverie, P., and Malrieu, J. P.: Intern. J. Quantum Chem. 8 1 (1974).

    Article  CAS  Google Scholar 

  24. Daudey, J. P., Malrieu, J. P., and Rojas, O.: Intern. J. Quantum Chem. 8 17 (1974).

    Article  CAS  Google Scholar 

  25. Daudey, J. P.: Intern. J. Quantum Chem. 8 29 (1974).

    Article  CAS  Google Scholar 

  26. Longuet-Higgens, H. C.: Proc. Roy. Soc. (London) A235 537 (1965).

    Google Scholar 

  27. Diner, S., Malrieu, J. P., Jordan, F., and Claverie, P.: Theoret. Chini. Acta 18 66 (1970).

    Google Scholar 

  28. Millie, Ph., Levy, B., and Berthier, G.: in Chalvet, O., Daudel, R., Diner, S. and Malrieu, J. P. (eds.), Localization and Delocalization in Quantum Chemistry, Reidel, Dordrecht (1975), Vol. I, p. 59.

    Google Scholar 

  29. Salem, L.: Proc. Roy. Soc. (London) A264 379 (1961).

    Google Scholar 

  30. Murrell, J. N., Randic, M., and Williams, D. R.: Proc. Roy. Soc. (London) A284 566 (1965).

    Google Scholar 

  31. Buckingham, A. D.: Advances in Chemical Physics 12. 107 (1967).

    Article  CAS  Google Scholar 

  32. Kihara, T.: Suppl. Progr. Theoret. Phys. 40 177 (1967).

    Article  Google Scholar 

  33. Pollak, M. and Rein, R.: J. Chem. Phys. 47 2045 (1967).

    Article  CAS  Google Scholar 

  34. Mulliken, R. S.: J. Chim. Phys. 46 497 (1949) (seep. 521)

    CAS  Google Scholar 

  35. Mulliken, R. S.: J. Chem. Phys. 23 1833 (1955).

    Article  CAS  Google Scholar 

  36. Coulson, C. A. and Rogers, M. T.: J. Chem. Phys. 35 593 (1961).

    Article  CAS  Google Scholar 

  37. Daudel, R., Lafforgue, A., and Vroelant, C.: J. Chim. Phys. 49 545 (1952).

    CAS  Google Scholar 

  38. Löwdin, P. O.: J. Chem. Phys. 21 374 (1953)

    Article  Google Scholar 

  39. Löwdin, P. O.: Adv. Phys. 5 22 (1956).

    Article  Google Scholar 

  40. Howard, B. B.: J. Chem. Phys. 39 2524 (1963).

    Article  CAS  Google Scholar 

  41. Claverie, P. and Rein, R.: Intern. J. Quantum Chem. 3 537 (1969).

    Article  CAS  Google Scholar 

  42. Dalgarno, A. and Davison, W. D.: Advances in Atomic and Molecular Physics 2 1 (1966).

    Article  CAS  Google Scholar 

  43. Morse, P. M. and Feshbach, H.: Methods of Theoretical Physics, Mc Graw Hill, New York (1953).

    Google Scholar 

  44. Denis, A., Langlet, J., and Malrieu, J. P.: Theoret. Chim. Acta 29 117 (1973);

    Article  CAS  Google Scholar 

  45. Denis, A., Langlet, J., and Malrieu, J. P.: Theoret. Chim. Acta 38 49 (1975).

    Article  CAS  Google Scholar 

  46. Le Fevre, R. J. W.: Advances in Physical Organic Chemistry 3 1 (1965).

    Article  Google Scholar 

  47. Zwanzig, R.: J. Chem. Phys. 39 2251 (1963).

    Article  CAS  Google Scholar 

  48. Unsöld, A.: Zeit. Physik. 43 563 (1927).

    Article  Google Scholar 

  49. London, F. :Zeit. Physik. Chemie (B) 11, 222 (1930).

    CAS  Google Scholar 

  50. London, F. Trans. Faraday Soc. 33 8 (1937).

    Article  CAS  Google Scholar 

  51. Pitzer, K. S.: Advances in Chemical Physics 2, 59 (1959).

    Article  CAS  Google Scholar 

  52. Langhoff, P. W. and Karplus, M.: in The Padé Approximant in Theoretical Physics, Baker, G. A. and Gammel, J. L. (eds.), Academic Press, New York (1970), p. 41.

    Chapter  Google Scholar 

  53. Langhoff, P. W. and Karplus, M.: J. Chem. Phys. 53, 233 (1970).

    Article  CAS  Google Scholar 

  54. Langhoff, P. W., Gordon, R. G., and Karplus, M.: J. Chem. Phys. 55,2126 (1971).

    Article  CAS  Google Scholar 

  55. Rein, R., Claverie, P., and Pollak, M.: Intern. J. Quantum Chem. 2, 129 (1968).

    Article  CAS  Google Scholar 

  56. Mavroyannis, C. and Stephen, R. J.: Mol. Phys. 5, 629 (1962).

    Article  CAS  Google Scholar 

  57. Tang, K. T. and Karplus, M.: Phys. Rev. 171, 70 (1968).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Laboratoire de Chimie Quantique, Institut de Biologie Physico-chimique, 13 Rue P. et M. Curie, 75005, Paris, France

    Pierre Claverie

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  1. Pierre Claverie
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Editors and Affiliations

  1. Centre de Mécanique Ondulatoire Appliquée du C.N.R.S., 23, rue du Maroc, Paris 19ème, France

    Odilon Chalvet  & Raymond Daudel  & 

  2. Institut de Biologie Physico-Chimique, 13, rue Pierre et Marie Curie, Paris 5ème, France

    Simon Diner  & Jean Paul Malrieu  & 

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© 1976 D. Reidel Publishing Company, Dordrecht, Holland

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Claverie, P. (1976). The Calculation of Intermolecular Interaction Energies in Terms of Local Contributions. In: Chalvet, O., Daudel, R., Diner, S., Malrieu, J.P. (eds) Localization and Delocalization in Quantum Chemistry. Localization and Delocalization in Quantum Chemistry, vol 2. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-1456-4_8

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  • DOI: https://doi.org/10.1007/978-94-010-1456-4_8

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-1458-8

  • Online ISBN: 978-94-010-1456-4

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