Theoretica chimica acta

, Volume 48, Issue 1, pp 75–86 | Cite as

On the theory of solvent effects

The virtual charge model to represent the solvent polarization
  • R. Constanciel
  • O. Tapia
Original Investigations

Abstract

A simple electrostatic analysis is given of the virtual charge (solvaton) model to represent the environment effect on the electronic wave function of a solute immersed in a polarizable surrounding. New features of this model are found. The classical aspects are discussed and secondly the quantal implications are considered. A correct Hartree-Fock-like operator is derived which represents an electron in a molecular orbital subjected to the average effect of the other electrons and to the reaction field produced by the virtual charges on the atomic centers.

A general formalism based on the preceding model is presented in appendix. The final equations have a form similar to Newton's equation to represent a solvated electron. Unlike some other theories in this field, there is no cut-off involved in the evaluation of the molecular integrals.

Key words

Solvent effects Solvation theory 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Brown, R. D., Coulson, C. A.: Colloques Internationaux C.N.R.S. 82, 311 (1958)Google Scholar
  2. 2.
    Jortner, J., Coulson, C. A.: Mol. Phys. 4, 451 (1961)Google Scholar
  3. 3.
    Peradejordi, F.: Cah. Phys. 17, 343 (1963)Google Scholar
  4. 4.
    Jano, I.: Compt. Rend. Acad. Sci. (Paris) 261, 103 (1965)Google Scholar
  5. 5.
    Klopman, G.: Chem. Phys. Letters 1, 200 (1967)Google Scholar
  6. 6.
    Beens, H., Weller, A.: Chem. Phys. Letters 3, 666 (1969)Google Scholar
  7. 7.
    Yomosa, S., Higesawa, M.: J. Phys. Soc. Japan 29, 1329 (1970)Google Scholar
  8. 8.
    Barfield, M., Johnston Jr., M. D.: Chem. Rev. 73, 53 (1973)Google Scholar
  9. 9.
    Newton, M. D.: J. Chem. Phys. 58, 5838 (1973)Google Scholar
  10. 10.
    Rinaldi, D., Rivali, J. L.: Theoret. Chim. Acta (Berl.) 32, 57 (1973)Google Scholar
  11. 11.
    Yomosa, S.: J. Phys. Soc. Japan 35, 1738 (1973)Google Scholar
  12. 12.
    Germer, Jr., H. A.: Theoret. Chim. Acta (Berl.) 34, 145 (1974)Google Scholar
  13. 13.
    Germer Jr., H. A.: Theoret. Chim. Acta (Berl.) 35, 273 (1974)Google Scholar
  14. 14.
    Hylton, J., Christoflersen, R. E., Hall, G. G.: Chem. Phys. Letters 24, 501 (1974)Google Scholar
  15. 15.
    Newton, M. D.: J. Phys. Chem. 79, 2795 (1975)Google Scholar
  16. 16.
    Tapia, O., Goscinski, O.: Mol. Phys. 29, 1653 (1975)Google Scholar
  17. 17.
    Hylton, McCreery, J., Christoffersen, R. E., Hall, G. G.: J. Am. Chem. Soc. 98, 7191 (1976); 98, 7198 (1976)Google Scholar
  18. 18.
    Rivail, J. L., Rinaldi, D.: Chem. Phys. 18, 233 (1976)Google Scholar
  19. 19.
    Warshel, A., Levitt, M.: J. Mol. Biol. 103, 227 (1976)Google Scholar
  20. 20.
    Tapia, O., Sussman, F., Poulain, E.: Theoret. Biol. (1978) 70, 000Google Scholar
  21. 21.
    Born, M.: Z. Phys. 1, 45 (1920)Google Scholar
  22. 22.
    Hoijtink, G. J., de Boer, E., Van der Meij, P. H., Weijland, W. P.: Rec. Trav. Chim. 75, 487 (1956)Google Scholar
  23. 23.
    Böttcher, C. J. F.: Theory of electric polarization, Vol. 1. Amsterdam-New York: Elsevier 1973Google Scholar
  24. 24.
    Linder, B.: Advan. Chem. Phys. 12, 225 (1967)Google Scholar
  25. 25.
    Friedman, H. L.: Mol. Phys. 29, 1533 (1975)Google Scholar
  26. 26.
    Pople, J. A., Beveridge, D. L.: Approximate molecular orbital theory. New York: McGraw-Hill 1970Google Scholar
  27. 27.
    McWeeny, R.: Rev. Mod. Phys. 32, 335 (1960)Google Scholar
  28. 28.
    Tapia, O.: Theoret. Chim. Acta (Berl.) 47, 157 (1978)Google Scholar
  29. 29.
    Miertus, S., Kysel, O.: Chem. Phys. 21, 27, 33, 47 (1977)Google Scholar
  30. 30.
    Constanciel, R., Tapia, O.: to be publishedGoogle Scholar

Copyright information

© Springer-Verlag 1978

Authors and Affiliations

  • R. Constanciel
    • 1
  • O. Tapia
    • 1
  1. 1.Centre de Mécanique Ondulatoire AppliquéeParisFrance

Personalised recommendations