Singlet-paired coupled cluster theory for open shells

Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

doi:10.1063/1.4954891

Singlet-paired coupled cluster theory for open shells

Journal Article · Thu Jun 30 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4954891· OSTI ID:1467828

^[1]; Henderson, Thomas M. ^[2]; Scuseria, Gustavo E. ^[2]

Rice Univ., Houston, TX (United States). Dept. of Chemistry; Rice University
Rice Univ., Houston, TX (United States). Dept. of Chemistry and Dept. of Physics and Astronomy

Restricted single-reference coupled cluster theory truncated to single and double excitations accurately describes weakly correlated systems, but often breaks down in the presence of static or strong correlation. Good coupled cluster energies in the presence of degeneracies can be obtained by using a symmetry-broken reference, such as unrestricted Hartree-Fock, but at the cost of good quantum numbers. A large body of work has shown that modifying the coupled cluster ansatz allows for the treatment of strong correlation within a single-reference, symmetry-adapted framework. The recently introduced singlet-paired coupled cluster doubles (CCD0) method is one such model, which recovers correct behavior for strong correlation without requiring symmetry breaking in the reference. In this, we extend singlet-paired coupled cluster for application to open shells via restricted open-shell singlet-paired coupled cluster singles and doubles (ROCCSD0). The ROCCSD0 approach retains the benefits of standard coupled cluster theory and recovers correct behavior for strongly correlated, open-shell systems using a spin-preserving ROHF reference.

View Accepted Manuscript (DOE)

Research Organization:: Rice Univ., Houston, TX (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Welch Foundation

Grant/Contract Number:: FG02-04ER15523

OSTI ID:: 1467828

Alternate ID(s):: OSTI ID: 22675979
OSTI ID: 1259983

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 144; ISSN JCPSA6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Coupled alkali halide color centers: Fractional charge errors, fractional spin errors, and a failure of spin symmetry breaking produce challenging tests for condensed-phase electronic structure calculations Janesko, Benjamin G. The Journal of Chemical Physics, Vol. 151, Issue 6 https://doi.org/10.1063/1.5111146	journal	August 2019
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Singlet-paired coupled cluster theory for open shells

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