DOI: 10.1063/5.0171546 ISSN: 0021-9606

Avoiding spin contamination and spatial symmetry breaking by exact-exchange-only optimized-effective-potential methods within the symmetrized Kohn–Sham framework

Egor Trushin, Andreas Görling
  • Physical and Theoretical Chemistry
  • General Physics and Astronomy

For open-shell atoms and molecules, Kohn–Sham (KS) methods typically resort to spin-polarized approaches that exhibit spin-contamination and often break spatial symmetries. As a result, the KS Hamiltonian operator and the KS orbitals do not exhibit the space and spin symmetry of the physical electron system. The KS formalism can be symmetrized in a rigorous way only in real space, only in spin space, or both in real and spin space. Within such symmetrized KS frameworks, we present exact-exchange-only optimized-effective-potential (OEP) methods that are free of spin contamination and/or spatial symmetry breaking. The effect of symmetrizations on the total energy and its parts and on the exchange potential is analyzed. The presented exact-exchange-only OEP methods may serve as a starting point for high-level symmetrized KS methods based, e.g., on the adiabatic-connection fluctuation-dissipation theorem.

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