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Density-functional thermochemistry. III. The role of exact exchange

J. Chem. Phys. 98, 5648 (1993); doi:10.1063/1.464913

Issue Date: 1 April 1993

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Axel D. Becke
Department of Chemistry, Queen's University, Kingston, Ontario, Canada K7L 3N6
Despite the remarkable thermochemical accuracy of Kohn–Sham density-functional theories with gradient corrections for exchange-correlation [see, for example, A. D. Becke, J. Chem. Phys. 96, 2155 (1992)], we believe that further improvements are unlikely unless exact-exchange information is considered. Arguments to support this view are presented, and a semiempirical exchange-correlation functional containing local-spin-density, gradient, and exact-exchange terms is tested on 56 atomization energies, 42 ionization potentials, 8 proton affinities, and 10 total atomic energies of first- and second-row systems. This functional performs significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 30 October 1992; accepted 16 December 1992
Permalink: http://link.aip.org/link/?JCPSA6/98/5648/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.20.Sy
    Electronic structure of atoms and molecules: theory Specific calculations and results Density functional methods (local density approximation, local spin density approximation), X methods
  • YEAR: 1993

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
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REFERENCES (14)
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  1. J. A. Pople, M. Head-Gordon, D. J. Fox, K. Raghavachari, and L. A. Curtiss, J. Chem. Phys. 90, 5622 (1989).
  2. L. A. Curtiss, C. Jones, G. W. Trucks, K. Raghavachari, and J. A. Pople, J. Chem. Phys. 93, 2537 (1990).
  3. A. D. Becke, J. Chem. Phys. 96, 2155 (1992).
  4. A. D. Becke, Phys. Rev. A 38, 3098 (1988);
    5. in The Challenge of d and f Electrons, edited by D. R. Salahub and M. C. Zerner, Vol. 394 in ACS Symposium Series (American Chemical Society, Washington, DC, 1989), p. 165.
  5. A. D. Becke, J. Chem. Phys. 97, 9173 (1992).
  6. J. P. Perdew, in Electronic Structure of Solids, edited by P. Ziesche and H. Eschrig (Akademie Verlag, Berlin, 1991);
    7. J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 (1992);
    J. P. Perdew and Y. Wang (unpublished).
  7. J. Harris and R. O. Jones, J. Phys. F 4, 1170 (1974);
    8. O. Gunnarsson and B. I. Lundqvist, Phys. Rev. B 13, 4274 (1976);
    D. C. Langreth and J. P. Perdew, ibid. 15, 2884 (1977);
    J. Harris, Phys. Rev. A 29, 1648 (1984).
  8. A. D. Becke, J. Chem. Phys. 98, 1372 (1993).
  9. R. G. Parr and W. Yang, Density-Functional Theory of Atoms and Molecules (Oxford University Press, New York, 1989).
  10. A. D. Becke, J. Chem. Phys. 88, 1053 (1988).
  11. O. Gunnarsson and R. O. Jones, Phys. Rev. B 31, 7588 (1985).
  12. J. P. Perdew and Y. Wang, Phys. Rev. B 45, 13 244 (1992).
  13. P. M. W. Gill, B. G. Johnson, J. A. Pople, and M. J. Frisch, Int. J. Quantum Chem. Quantum Chem. Symp. 26, 319 (1992).
  14. L. A. Curtiss, K. Raghavachari, G. W. Trucks, and J. A. Pople, J. Chem. Phys. 94, 7221 (1991).

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