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A well-scaling natural orbital theory

Author(s): Gebauer, Ralph; Cohen, Morrel H.; Car, Roberto

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Abstract: We introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled approximations to the two-particle density matrix that yield algebraic scaling in general, and Hartree–Fock scaling in its seniority-zero version. Results from the latter version for small molecular systems are compared with those of highly accurate quantum-chemical computations. The energies lie above full configuration interaction calculations, close to doubly occupied configuration interaction calculations. Their accuracy is considerably greater than that obtained from current density-functional theory approximations and from current functionals of the oneparticle density matrix.
Publication Date: 15-Nov-2016
Electronic Publication Date: 1-Nov-2016
Citation: Gebauer, Ralph, Cohen, Morrel H., Car, Roberto. (2016). A well-scaling natural orbital theory. Proceedings of the National Academy of Sciences, 113 (46), 12913 - 12918. doi:10.1073/pnas.1615729113
DOI: doi:10.1073/pnas.1615729113
ISSN: 0027-8424
EISSN: 1091-6490
Pages: 12913 - 12918
Type of Material: Journal Article
Journal/Proceeding Title: Proceedings of the National Academy of Sciences
Version: Final published version. This is an open access article.

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