Elsevier

Chemical Physics Letters

Volume 229, Issue 3, 28 October 1994, Pages 175-180
Chemical Physics Letters

Can (semi)local density functional theory account for the London dispersion forces?

https://doi.org/10.1016/0009-2614(94)01027-7Get rights and content

Abstract

The reproduction of the interatomic potential in He2, Ne2, and Ar2 by Kohn-Sham theory is investigated using a density functional program which can perform counterpoise corrections for both basis sets and numerical integration. None of the functionals considered accounts successfully for the dispersion interaction. The Becke exchange and the Becke-Lee-Yang-Parr (B-LYP) exchange-correlation functionals yield a purely repulsive potential after counterpoise correction. The Dirac-Slater (D-S) functional gives minima which are too deep, at internuclear distances which are too short, particularly for He2 and Ne2. The experimental repulsive potential is reproduced best by D-S calculations while the B-LYP results are close to the SCF ones.

References (30)

  • N.C. Handy et al.

    Chem. Phys. Letters

    (1992)
  • B.G. Johnson et al.

    Chem. Phys. Letters

    (1994)
  • P. Hobza et al.

    Chem. Rev.

    (1988)
  • J.H. van Lenthe et al.

    Chem. Phys. Letters

    (1988)
  • V.I. Lebedev

    Zh. Vychisl. Mat. Mat. Fiz.

    (1976)
  • F. London

    Z. Physik

    (1930)
  • J.H. van Lenthe et al.

    Advan. Chem. Phys.

    (1987)
  • G.C. Maitland et al.
  • S. Saebo et al.

    J. Chem. Phys.

    (1987)
  • W. Kohn et al.

    Phys. Rev. A

    (1965)
  • B.G. Johnson et al.

    J. Chem. Phys.

    (1992)
  • R. Merckle et al.

    J. Chem. Phys.

    (1992)
  • S. Kais et al.

    J. Chem. Phys.

    (1993)
  • P. Pulay et al.
    (1982–1990)
  • A.D. Becke

    J. Chem. Phys.

    (1988)
    A.D. Becke

    J. Chem. Phys.

    (1988)
    A.D. Becke

    J. Chem. Phys.

    (1992)
  • Cited by (956)

    View all citing articles on Scopus
    View full text