期刊
JOURNAL OF CHEMICAL PHYSICS
卷 134, 期 6, 页码 -出版社
AIP Publishing
DOI: 10.1063/1.3549134
关键词
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资金
- NSF [CHE-0807194]
- LANL [81277-001-10]
- Welch Foundation [C-0036]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1110884] Funding Source: National Science Foundation
We have recently proposed a novel approach for obtaining high-spin restricted open-shell Hartree-Fock wave functions by imposing constraints on the unrestricted Hartree-Fock (UHF) method [T. Tsuchimochi and G. E. Scuseria, J. Chem. Phys. 133, 141102 (2010)]. We here extend these ideas to the case where the constraints are released in an active space but imposed elsewhere. If the active space is properly chosen, our constrained UHF (CUHF) method greatly benefits from a controlled broken-symmetry effect while avoiding the massive spin contamination of traditional UHF. We also revisit and apply Lowdin's projection operator to CUHF and obtain multireference wave functions with moderate computational cost. We report singlet-triplet energy splittings showing that our constrained scheme outperforms fully unrestricted methods. This constrained approach can be readily used in spin density functional theory with similar favorable effects. (C) 2011 American Institute of Physics. [doi:10.1063/1.3549134]
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