Advertisement

Theoretica chimica acta

, Volume 47, Issue 1, pp 1–16 | Cite as

An examination of UHF methods for atoms in the first three rows

  • J. R. Macdonald
  • R. M. Golding
Original Investigations

Abstract

The reliability and usefulness of UHF methods of calculating hyperfine parameters has been examined. Comparisons with CI and SEHF methods are made.

A detailed analysis of OPHF calculations for first and second row atoms has shown that various one-electron properties are accurately described by physically reasonable functions of the atomic number Z. In addition there is a strong correlation between these properties. This has led to a method whereby UHF spin densities across a row of atoms can be obtained from UHF calculations of only two atoms in that row.

A strong correlation between experimental and UHF spin densities is shown to exist for atoms of the first three rows. This is used to predict experimental spin densities for atoms in these rows which have not yet been measured experimentally.

Key words

UHF methods, reliability and usefulness of ∼ 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Fermi, E., Segré, E.: Z. Physik82, 729 (1933)Google Scholar
  2. 2.
    Abragam, A., Pryce, M. H.: Proc. Roy. Soc.A230, 169 (1955)Google Scholar
  3. 3.
    Sternheimer, R. M.: Phys. Rev.84, 244 (1952)Google Scholar
  4. 4.
    Freeman, A. J., Watson, R. E., in: Magnetism, Rado, G. T., Suhl, H. eds., Vol. 2A, p. 167. New York: Academic Press 1965Google Scholar
  5. 5.
    Watson, R. E., Freeman, A. J., in: Hyperfine interactions, Freeman, A. J., Frankel, R. B. eds., p. 53. New York: Academic Press 1967Google Scholar
  6. 6.
    Macdonald, J. R., Golding, R. M.: Mol. Phys.31, 1247 (1976)Google Scholar
  7. 7.
    Löwdin, P. O.: Phys. Rev.97, 1509 (1955)Google Scholar
  8. 8.
    Goddard, W. A.: Phys. Rev.182, 48 (1969)Google Scholar
  9. 9.
    Schaefer, H. F., Harris, F. E.: Phys. Rev.167, 67 (1968)Google Scholar
  10. 10.
    Schaefer, H. F., Klemm, R. A., Harris, F. E.: Phys. Rev.176, 49 (1968)Google Scholar
  11. 11.
    Schaefer, H. F., Klemm, R. A., Harris, F. E.: Phys. Rev.181, 137 (1969)Google Scholar
  12. 12.
    Kaldor, V., Schaefer, H. F., Harris, F. E.: Intern. J. Quantum Chem.2S, 13 (1968)Google Scholar
  13. 13.
    Roothaan, C. C. J.: Rev. Mod. Phys.23, 69 (1951)Google Scholar
  14. 14.
    Bessis, N., Lefebvre-Brion, H., Moser, C. M., Freeman, A. J., Nesbet, R. K., Watson, R. E.: Phys. Rev.135, A588 (1964)Google Scholar
  15. 15.
    Bagus, P. S., Liu, B., Schaefer, H. F.: Phys. Rev.A2, 555 (1970)Google Scholar
  16. 16.
    Macdonald, J. R.: PhD. Thesis (1974)Google Scholar
  17. 17.
    Watson, R. E., Freeman, A. J.: Phys. Rev.123, 2027 (1961)Google Scholar
  18. 18.
    Roothaan, C. C. J., Kelly, P. S.: Phys. Rev.131, 1177 (1963)Google Scholar
  19. 19.
    Clementi, E.: IBM J. Res. Dev. Suppl.9, No. 1 (1965)Google Scholar
  20. 20.
    Larsson, S.: Phys. Rev.A2, 1248 (1970)Google Scholar
  21. 21.
    Larsson, S.: Chem. Phys. Letters10, 162 (1971)Google Scholar
  22. 22.
    Löwdin, P. O.: Advan. Chem. Phys.2, 203 (1959)Google Scholar
  23. 23.
    Kusch, P., Taub, H.: Phys. Rev.75, 1477 (1949)Google Scholar
  24. 24.
    Harvey, J. S. M., Evans, L., Lew, H.: Can. J. Phys.50, 1719 (1972)Google Scholar
  25. 25.
    Anderson, L. W., Pipkin, F. M., Baird, Jr., J. C.: Phys. Rev.116, 87 (1959)Google Scholar
  26. 26.
    Harvey, J. S. M.: Proc. Roy. Soc.A285, 581 (1965)Google Scholar
  27. 27.
    Pendlebury, J. M., Smith, K. F.: Proc. Phys. Soc.84, 849 (1964)Google Scholar
  28. 28.
    Uslu, K. A., Code, R. F., Harvey, J. S. M.: Can. J. Phys.52, 2135 (1974)Google Scholar
  29. 29.
    Hay, P. J., Goddard, W. A.: Chem. Phys. Letters9, 356 (1971)Google Scholar

Copyright information

© Springer-Verlag 1978

Authors and Affiliations

  • J. R. Macdonald
    • 1
  • R. M. Golding
    • 1
  1. 1.Department of Physical ChemistryUniversity of New South WalesKensingtonAustralia

Personalised recommendations