Theoretica chimica acta

, Volume 59, Issue 5, pp 551–553 | Cite as

Electronegativities and the bonding character of molecular orbitals: A remark

  • Alberto Onofre de Amorim
  • Ricardo Ferreira
Short Communication


From the density functional theory of Hohenberg-Kohn it is possible to prove that a molecular orbital is bonding (antibonding) if its electronegativity is larger (smaller) than the electronegativities of the corresponding atomic orbitals.

Key words

Electronegativity Bonding MO Antibonding MO 


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  1. 1.
    Ferreira, R., Amorim, A. O.: Theoret. Chim. Acta (Berl.),58, 131 (1981)CrossRefGoogle Scholar
  2. 2.
    Hund, F.: Z. Physik51, 788, 793 (1928)Google Scholar
  3. 3.
    Mulliken, R. S.: Phys. Rev.32, 196 (1928)Google Scholar
  4. 4.
    Herzberg, G.: Z. Physik57, 616 (1929)CrossRefGoogle Scholar
  5. 5.
    Hohenberg, P., Kohn, W.: Phys. Rev.B136, 864 (1964)CrossRefGoogle Scholar
  6. 6.
    Parr, R. G., Donnelly, R. A., Levy, M., Palk Jr., W. E.: J. Chem. Phys.68, 3801 (1978) Parr, R. G., Gadre, S. R., Bartolotti, L. J.: Proc. Nat. Acad. Sci.76, 2522 (1979); Bartolotti, L. J., Gadre, S. R., Parr, R. G.: J. Am. Chem. Soc.102, 2945 (1980)CrossRefGoogle Scholar
  7. 7.
    Iczkowski, R. P., Margrave, J. L.: J. Am. Chem. Soc.83, 3547 (1961)CrossRefGoogle Scholar
  8. 8.
    Gyftopoulos, E. P., Hatsopoulos, G. N.: Proc. Nat. Acad. Sci.60, 786 (1968)Google Scholar
  9. 9.
    March, N. H.: Self-consistent fields in atoms, pp. 44–45. Oxford: Pergamon Press 1975Google Scholar
  10. 10.
    Hellmann, H.: Einführung in die Quantenchemie, p. 285. Leipzig: Deuticke 1937Google Scholar
  11. 11.
    Feynman, R.: Phys. Rev.56, 340 (1939)CrossRefGoogle Scholar
  12. 12.
    Starting with the separate AOs, the energy of each bonding (antibonding) MO lowers (increases) monotonically asR decreases, the MOs transforming into united-atom orbitals. HenceR ·F e < 0 (R ·F e> 0) as an electron moves from an isolated atomic orbital to a bonding (antibonding) MO. For the equilibrium molecular geometry,R e ·F e = 0; this energy minimum atR e is the result of a sum over the bonding and antibonding electrons (plus the internuclear repulsion). We wish to thank the referee for calling our attention to this problem.Google Scholar

Copyright information

© Springer-Verlag 1981

Authors and Affiliations

  • Alberto Onofre de Amorim
    • 1
  • Ricardo Ferreira
    • 2
  1. 1.Departamento de FísicaUFPERecife PernambucoBrazil
  2. 2.Centro Brasileiro de Pesquisas FísicasRio de Janeiro, RJBrazil

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