TITLE

The energy as a functional of the charge density and the charge-density susceptibility: A simple, exact, nonlocal expression for the electronic energy of a molecule

AUTHOR(S)
Hunt, Katharine L. C.
PUB. DATE
April 2002
SOURCE
Journal of Chemical Physics;4/1/2002, Vol. 116 Issue 13, p5440
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Simple, new expressions relate the electronic potential energy 〈V〉 and the total electronic energy E of a molecule to its averaged electron density 〈ρ[sub e](r)〉, the nonlocal charge-density susceptibility χ[sub e](r, r′;iω), the nuclear positions {R[sub N]}, and the nuclear charges {Z[sub N]}. The expressions derived in this work are exact nonrelativistically, within the Born-Oppenheimer approximation. The results give a nonlocal form for the electronic energy in density functional theory. The virial theorem for a system with Coulomb forces is used to derive the expectation value of the kinetic energy in terms of the expectation values of the potential energy and the derivatives of the potential energy operator with respect to nuclear coordinates; gradient expansions of the kinetic energy functional are not needed. Exchange and correlation effects on 〈V〉 and E are determined by an integral of the charge-density susceptibility χ[sub e](r, r′;iω), over imaginary frequencies. The results for 〈V〈 and E are first derived by use of the fluctuation-dissipation theorem and the symmetry properties of the charge-density susceptibility with respect to a change in the sign of ω. Identical results are derived by integration of χ[sub e](r, r′, iω) over imaginary frequencies and use of the closure relation.
ACCESSION #
6365884

 

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