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Spatial symmetry and equivalence with unrestricted Hartree-Fock wavefunctions: application to the prediction of spin densities 

Authors: DYLAN JAYATILAKA a; GRAHAM S. CHANDLER a
Affiliation:   a Department of Chemistry, The University of Western Australia, Australia
DOI: 10.1080/00268979709482118
Publication Frequency: 24 issues per year
Published in: journal Molecular Physics, Volume 92, Issue 3 October 1997 , pages 471 - 476
Formats available: PDF (English)
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Abstract

A theory is presented for enforcing spatial symmetry and equivalence with unrestricted Hartree-Fock (UHF) wavefunctions. This generalized UHF (GUHF) wavefunction is a simple way to obtain qualitatively correct ab initio spin densities, for comparison with polarized neutron diffraction experiments. Quasi Newton-Raphson equations are presented, based on generalized energy expressions which use coupling coefficients, and an exponential parametrization of orbital rotation parameters. The coupling coefficients for the common case of a high spin partially occupied degenerate shell are given. The new method is applied to the triplet oxygen atom, and used to calculate spin densities for the FeCl4-6 anion. It is found that the energy of the GUHF wavefunction lies above the symmetry broken UHF wavefunction, but below the restricted Hartree-Fock methods, and that the expectation value of S2 is worsened (i.e., spin contamination increases).
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