Theoretica chimica acta

, Volume 42, Issue 1, pp 77–82 | Cite as

SCF-CI studies of the equilibrium structure and the proton transfer barrier H3O 2

  • Björn O. Roos
  • Wolfgang P. Kraemer
  • Geerd H. F. Diercksen
Original Investigations


Large-scale configuration interaction (CI) calculations have been performed in order to study the effect of the correlation energy on the equilibrium geometrical structure, the stability, and on the energy barrier of the proton transfer reaction in the hydrogen bonded system HO · HOH. An extended Gaussian basis set including polarization functions on each nuclear centre has been employed to approximate the molecular Orbitals. All possible single and double replacements resulting from a single determinant Hartree-Fock reference state have been taken into account in the CI wavefunction. Compared to the SCF results the equilibrium oxygen/oxygen distance has been obtained from the CI calculations to be smaller by about 0.08 Å and the correlation energy has been found to stabilize the composed system by 3.6 kcal/mole. An almost symmetric equilibrium structure with the hydrogen bonding H-atom midway between the two oxygen centres has been obtained in the CI treatment, whereas SCF calculations yield an asymmetric geometrical configuration with a small energy barrier of 1.4 kcal/mole for the proton transfer process.

Key words

Configuration interaction Hydrogen bonding Ion hydration 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Meyer, W., Jakubetz, W., Schuster, P.: Chem. Phys. Letters 21, 97 (1973)Google Scholar
  2. 2.
    Støgard, A., Strich, A., Almlöf, J., Roos, B.: Chem. Phys. (in press)Google Scholar
  3. 3.
    Kraemer, W. P., Diercksen, G. H. F.: Theoret. Chim. Acta (Berl.) 23, 398 (1972)Google Scholar
  4. 4.
    Payzant, J. D., Yamdagni, R., Kebarle, P.: Canad. J. Chem. 49, 3308 (1971)Google Scholar
  5. 5.
    Diercksen, G. H. F., Kraemer, W. P., Roos, B. O.: Theoret. Chim. Acta (Berl.) 36, 249 (1975)Google Scholar
  6. 6.
    Diercksen, G. H. F., Kraemer, W. P.: MUNICH Molecular Program System — Reference Manual, Special Technical Report, Max-Planck-Institut für Physik und Astrophysik (to be published)Google Scholar
  7. 7.
    Almlöf, J., Roos, B., Siegbahn, P.: MOLECULE Program System- Reference Manual (to be published)Google Scholar
  8. 8.
    Diercksen, G. H. F.: Theoret. Chim. Acta (Berl.) 33, 1 (1974)Google Scholar
  9. 9.
    Roos, B.: Chem. Phys. Letters 15, 153 (1972)Google Scholar
  10. 10.
    Roos, B., Siegbahn, P.: Modern theoretical chemistry, to be publishedGoogle Scholar
  11. 11.
    Salez, C., Veillard, A.: Theoret. Chim. Acta (Berl.) 11, 441 (1968)Google Scholar
  12. 12.
    Huzinaga, S.: J. Chem. Phys. 42, 1293 (1965)Google Scholar
  13. 13.
    Diercksen, G. H. F.: Theoret. Chim. Acta (Berl.) 21, 335 (1971)Google Scholar
  14. 14.
    Clementi, E., Popkie, H.: J. Chem. Phys. 57, 1077 (1972)Google Scholar
  15. 15.
    Newton, M. D., Ehrenson, S.: J. Am. Chem. Soc. 93, 4271 (1971)Google Scholar
  16. 16.
    Kollman, P. A., Allen, L. C.: Chem. Rev. 72, 283 (1972)Google Scholar
  17. 17.
    Diercksen, G. H. F., von Niessen, W., Kraemer, W. P.: Theoret. Chim. Acta (Berl.) 31, 205 (1973)Google Scholar
  18. 18.
    DePaz, M., Guidoni Giardini, A., Friedman, L.: J. Chem. Phys. 52, 687 (1970)Google Scholar
  19. 19.
    Arshadi, M., Kebarle, P.: J. Phys. Chem. 74, 1483 (1970)Google Scholar

Copyright information

© Springer-Verlag 1976

Authors and Affiliations

  • Björn O. Roos
    • 1
  • Wolfgang P. Kraemer
    • 2
  • Geerd H. F. Diercksen
    • 2
  1. 1.Institute of Theoretical PhysicsUniversity of StockholmSweden
  2. 2.Max-Planck-Institut für Physik und AstrophysikMünchen 40Federal Republic of Germany

Personalised recommendations