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Theoretica chimica acta

, Volume 70, Issue 6, pp 407–419 | Cite as

An application of correlation energy density functionals to atoms and molecules

  • A. Savin
  • H. Stoll
  • H. Preuss
Article

Abstract

Four density functionals — including that recently introduced by Perdew ((1986) Phys Rev B33: 8822)—are tested for first-row atoms, hydrides and dimers. Calculated contributions of the correlation energy to the ionization potentials and electron affinities of atoms and to the dissociation energies of molecules are compared with “empirical” values which were reevaluated for this purpose. An improvement over Hartree-Fock is found in all cases if the self-interaction or the gradient correction are included in the density functional, although there is a rather large variation in the accuracy of the predictions.

Key words

Correlation energy Density functional First-row atoms First-row hydrides First-row dimers 

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References

  1. 1.
    Kutzelnigg W (1978) Einführung in die Theoretische Chemie, vol. 2, Verlag Chemie, Weinheim, p 531Google Scholar
  2. 2.
    Hohenberg P, Kohn W (1964) Phys Rev B136:864Google Scholar
  3. 3.
    Kohn W, Sham L (1965) Phys Rev A140:1133Google Scholar
  4. 4.
    Löwdin P-O (1955) Phys Rev 97:1474Google Scholar
  5. 5.
    Levy M; private communicationGoogle Scholar
  6. 6.
    Gunnarsson O, Lundqvist BO (1976) Phys Rev B13:4274Google Scholar
  7. 7.
    Ceperley DM, Alder BJ (1980) Phys Rev Lett 45:566Google Scholar
  8. 8.
    Vosko SH, Wilk L, Nusair M (1980) Can J Phys 58:1200Google Scholar
  9. 9.
    Ma SK, Brueckner KA (1965) Phys Rev 165:18Google Scholar
  10. 10.
    Perdew JP (1986) Phys Rev B33:8822Google Scholar
  11. 11.
    Rasolt M, Geldart DJW: quoted in [10](Google Scholar
  12. 12.
    Langreth DC, Mehl DJ (1981) Phys Rev Lett 47:446; (1983) Phys Rev B28:1809; (1984) Phys Rev B29:2310Google Scholar
  13. 13.
    Hu CD, Langreth DC (1985) Phys Scripta 32:391Google Scholar
  14. 14.
    Rasolt M (1977) Phys Rev B16:3234Google Scholar
  15. 15.
    von Barth U, Hedin L (1972) J Phys C5:1629Google Scholar
  16. 16.
    Stoll H, Pavlidou CME, Preuss H (1978) Theor Chim Acta 49:143Google Scholar
  17. 17.
    Stoll H, Golka E, Preuss H (1980) Theor Chim Acta 55:28Google Scholar
  18. 18.
    Savin A, Wedig U, Stoll H, Preuss H (1982) Chem Phys Lett 92:503; (1983) Chem Phys Lett 94:536Google Scholar
  19. 19.
    Savin A, Dolg M, Stoll H, Preuss H, Flesch J (1983) Chem Phys Lett 100:455Google Scholar
  20. 20.
    Vosko SH, Wilk L (1983) J Phys B16:3687Google Scholar
  21. 21.
    Savin A (1983) PhD Thesis, UniversitÄt StuttgartGoogle Scholar
  22. 22.
    Stoll H, Savin A (1985) In: Dreizler RM, da Providencia J (eds) Density functional methods in physics. Plenum, New York, p 177Google Scholar
  23. 23.
    Kemister G, Nordholm S (1985) J Chem Phys 83:5163Google Scholar
  24. 24.
    Benesch R (1971) J Phys B4:1403Google Scholar
  25. 25.
    Huber KP, Herzberg G (1979) Molecular spectra and molecular structure, vol 4. Van Nostrand, New YorkGoogle Scholar
  26. 26.
    Lie GC, Clementi E (1974) J Chem Phys 60:1275Google Scholar
  27. 27.
    Savin A, Preuss H, Stoll H: To appear in: Erdahl RM, Smith VH (eds) Density matrices and density functionals. Reidel, DordrechtGoogle Scholar
  28. 28.
    Bashkin S, Stoner JO jr (1975, 1978) Atomic energy levels and Grotrian diagrams, vol 1. North-Holland, AmsterdamGoogle Scholar
  29. 29.
    Hotop H, Lineberger WC (1975) J Phys Chem Ref Data 4:539Google Scholar
  30. 30.
    Grant IP, McKenzie BJ, Norrington PH, Mayers DF, Pyper NC (1980) Comput Phys Commun 21:207Google Scholar
  31. 31.
    McKenzie BJ, Grant IP, Norrington PH, Mayers DF, Pyper NC (1980) Comput Phys Commun 21:233Google Scholar
  32. 32.
    Hurley AC (1973) Adv Quantum Chem 7:315Google Scholar
  33. 33.
    Pople JA, Binkley JS (1975) Mol Phys 29:599Google Scholar
  34. 34.
    Perdew JP, McMullen ER, Zunger A (1981) Phys Rev A23:2785Google Scholar
  35. 35.
    Sasaki F, Yoshimine M (1974) Phys Rev A9:26Google Scholar
  36. 36.
    Pople JA, Krishnan R, Schlegel HB, Binkley JS (1978) Int J Quantum Chem 14:545Google Scholar
  37. 37.
    Meyer W, Rosmus P (1975) J Chem Phys 63: 2356Google Scholar
  38. 38.
    Lie GC, Clementi E (1975) J Chem Phys 60:1288Google Scholar
  39. 39.
    Bondybey VE (1984) Chem Phys Lett 109:436Google Scholar

Copyright information

© Springer-Verlag 1986

Authors and Affiliations

  • A. Savin
    • 1
  • H. Stoll
    • 1
  • H. Preuss
    • 1
  1. 1.Institut für Theoretische ChemieUniversitÄt StuttgartStuttgart 80Federal Republic of Germany

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