Magnetic Effects and the Hartree-Fock Equation

Abstract

The Hartree-Fock equations state that each electron in an atom or molecular system should move in a different potential. In some cases, particularly magnetic cases, this leads to important consequences, since electrons with opposite spins move in different potentials. In particular, in an antiferromagnetic substance, electrons of + and - spin have different potentials; and for an electron of + spin, for instance, the potential energy is lower in those atoms whose spins are pointed in the + direction than in those with the opposite spin. This results in a periodic perturbation of potential, with periodicity twice the atomic periodicity, and leads to a splitting of each energy band in half, with a gap in the middle. In a case where the energy band was half full, resulting in a conductor: when we disregard this effect, the resulting half-band will be just filled when we consider it; this may explain the insulating nature of some antiferromagnetics. A similar argument applied to a diatomic molecule like ${\mathrm{H}}_{2}$ can result in two alternative types of solutions of the Hartree-Fock equations: one leading to atomic orbitals, the other to molecular orbitals. The solution with atomic orbitals shows an analogy to the antiferromagnetic problem; that with ordinary molecular orbitals shows an analogy to the band theory of a non-magnetic conductor.

Keywords

Affiliated Institutions

• Massachusetts Institute of Technology US

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