A Simplification of the Hartree-Fock Method

Abstract

It is shown that the Hartree-Fock equations can be regarded as ordinary Schr\"odinger equations for the motion of electrons, each electron moving in a slightly different potential field, which is computed by electrostatics from all the charges of the system, positive and negative, corrected by the removal of an exchange charge, equal in magnitude to one electron, surrounding the electron whose motion is being investigated. By forming a weighted mean of the exchange charges, weighted and averaged over the various electronic wave functions at a given point of space, we set up an average potential field in which we can consider all of the electrons to move, thus leading to a great simplification of the Hartree-Fock method, and bringing it into agreement with the usual band picture of solids, in which all electron are assumed to move in the same field. We can further replace the average exchange charge by the corresponding value which we should have in a free-electron gas whose local density is equal to the density of actual charge at the position in question; this results in a very simple expression for the average potential field, which still behaves qualitatively like that of the Hartree-Fock method. This simplified field is being applied to problems in atomic structure, with satisfactory results, and is adapted as well to problems of molecules and solids.

Keywords

Affiliated Institutions

• Massachusetts Institute of Technology US

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