Theoretica chimica acta

, Volume 48, Issue 1, pp 17–27 | Cite as

A statistical thermodynamic supermolecule-continuum study of ion hydration: Cell and shell methods

  • Gary W. Schnuelle
  • S. Swaminathan
  • David L. Beveridge
Original Investigations


A theoretical study of ion hydration using the statistical thermodynamic supermolecule-continuum method is described. The cell and shell methods are used for configurational averaging. Enthalpies, free energies and entropies are calculated for Li+, Na+, K+, F and Cl each four coordinated with water. The results are in reasonable accord with experiment. A comparison of the site method, cell method and shell method results is presented. The supermolecule-continuum approach to solvent effects seems to be capable of accommodating essential features for the calculation of solvation energy and solvent effects on structure and properties.

Key words

Ion hydration Statistical thermodynamic supermolecule-continuum method for ion hydration 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Schnuelle, G. W., Beveridge, D. L.: J. Phys. Chem. 79, 2566 (1975)Google Scholar
  2. 2.
    Beveridge, D. L., Schnuelle, G. W.: J. Phys. Chem. 78, 2064 (1974)Google Scholar
  3. 3.
    Hill, T. L.: An introduction to statistical thermodynamics. Reading, Pa.: Addison Wesley Publishing Co. 1960Google Scholar
  4. 4.
    Hammersley, J. M., Handscomb, D. C.: Monte Carlo methods. London: Methuen 1964Google Scholar
  5. 5.
    Kistenmacher, H., Popkie, H., Clementi, E.: J. Chem. Phys. 59, 5842 (1973); Clementi, E., Popkie, H.: J. Chem. Phys. 57, 1077 (1972)Google Scholar
  6. 6.
    Popkie, H., Kistenmacher, H., Clementi, E.: J. Chem. Phys. 59, 1325 (1973)Google Scholar
  7. 7.
    Kirkwood, J. G.: J. Chem. Phys. 7, 911 (1939)Google Scholar
  8. 8.
    Eley, D. D., Evans, M. G.: Trans. Farad. Soc. 34, 1093 (1938)Google Scholar
  9. 9.
    Stearn, H., Eyring, H.: J. Chem. Phys. 5, 113 (1937)Google Scholar
  10. 10.
    Noyes, R. M.: J. Am. Chem. Soc. 84, 514 (1962)Google Scholar
  11. 11.
    Friedman, H. L., Krishnan, C. V., in: Water-a comprehensive treatise, Vol. 3, F. Franks Ed. New York: Plenum Press 1973Google Scholar
  12. 12.
    Metropolis, N., Rosebluth, A. W., Rosenbluth, M. N., Teller, A. H., Teller, E.: J. Chem. Phys. 21, 1087 (1953)Google Scholar
  13. 13.
    Mruzik, M. R., Abraham, F. F., Schrieber, D. E., Pound, G. M.: J. Chem. Phys. 64, 481 (1975)Google Scholar
  14. 14.
    Swaminathan, S., Whitehead, R. J., Guth, E. and Beveridge, D. L.: J. Am. Chem. Soc. in pressGoogle Scholar

Copyright information

© Springer-Verlag 1978

Authors and Affiliations

  • Gary W. Schnuelle
    • 1
  • S. Swaminathan
    • 1
  • David L. Beveridge
    • 1
  1. 1.Chemistry DepartmentHunter College of the City University of New YorkNew YorkUSA

Personalised recommendations