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Phys. Rev. A 55, 1885–1889 (1997)

Line-integral formulas for exchange and correlation potentials separately

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Mel Levy1 and Norman H. March2
1Department of Chemistry and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118
2Inorganic Chemistry Department, University of Oxford, South Parks Road, Oxford OX1 3QR, England

Formal separate expressions for the exact exchange and correlation potentials vx and vc are extracted from the formal line-integral expression of Holas and March for the whole exact exchange-correlation potential. Relations for the components of vc are extracted for each order in the electron-electron repulsion coupling constant, through use of the coupling-constant expansion of Görling and Levy for the external potential. The resultant expressions for vc and vx are separately path independent. The difference between vx and the Harbola-Sahni approximation to it, vxHS, is identified as arising from a first-order contribution to the kinetic-energy density tensor. It is shown that this small correction to vxHS, which we express in terms of perturbation theory, would be precisely zero if the Kohn-Sham determinant were identical to the Hartree-Fock determinant for the same density. In other words, vxHS would equal vx if the optimized effective potential determinant were the same as the Hartree-Fock determinant. This same property is shared by the Slater potential.

© 1997 The American Physical Society

URL:
http://link.aps.org/doi/10.1103/PhysRevA.55.1885
DOI:
10.1103/PhysRevA.55.1885
PACS:
31.15.Ew, 71.10.-w, 31.25.-v