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Updated: May 23, 2025

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Published on: June 28, 2018
Spin-Symmetry Projected Constrained Unrestricted Hartree-Fock
Amir Ayati1, Hugh G A Burton2, Stijn De Baerdemacker1,3
1Department of Chemistry, University of New Brunswick, Fredericton, Canada, E3B 5A3.
None:
We introduce an electronic structure approach for spin-symmetry breaking and restoration at the mean-field level. The spin-projected constrained-unrestricted Hartree-Fock (SPcUHF) method restores the broken spin symmetry inherent in spin-constrained-UHF determinants by employing a nonorthogonal configuration interaction (NOCI) projection method. This method includes all possible configurations in spin space compatible with a Clebsch-Gordon recoupling scheme in a NOCI calculation. The tunable one-pair-at-a-time characteristics of the symmetry-breaking process in c-UHF allow us to reduce the computational costs of full projection. SPcUHF is tested on 4-, 6-, and 8-electron systems that exhibit dominant static and/or dynamic correlations.
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