Projected coupled cluster theory

Qiu, Yiheng; Henderson, Thomas M.; Zhao, Jinmo; Scuseria, Gustavo E.

doi:10.1063/1.4991020

Title: Projected coupled cluster theory

Abstract

Coupled cluster theory is the method of choice for weakly correlated systems. But in the strongly correlated regime, it faces a symmetry dilemma, where it either completely fails to describe the system or has to artificially break certain symmetries. On the other hand, projected Hartree-Fock theory captures the essential physics of many kinds of strong correlations via symmetry breaking and restoration. Here, we combine and try to retain the merits of these two methods by applying symmetry projection to broken symmetry coupled cluster wave functions. The non-orthogonal nature of states resulting from the application of symmetry projection operators furnishes particle-hole excitations to all orders, thus creating an obstacle for the exact evaluation of overlaps. Here we provide a solution via a disentanglement framework theory that can be approximated rigorously and systematically. Results of projected coupled cluster theory are presented for molecules and the Hubbard model, showing that spin projection significantly improves unrestricted coupled cluster theory while restoring good quantum numbers. The energy of projected coupled cluster theory reduces to the unprojected one in the thermodynamic limit, albeit at a much slower rate than projected Hartree-Fock.

Authors:

^[1];

^[2]; Zhao, Jinmo ^[1];

^[2]

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

Publication Date:: Fri Aug 11 00:00:00 EDT 2017

Research Org.:: Temple Univ., Philadelphia, PA (United States). Center for the Computational Design of Functional Layered Materials (CCDM); Rice Univ., Houston, TX (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Welch Foundation

OSTI Identifier:: 1474042

Alternate Identifier(s):: OSTI ID: 1374781

Grant/Contract Number:: SC0012575; CHE-1462434

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 147; Journal Issue: 6; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; operator theory; Hubbard parameter; full configuration interaction; coupled-cluster methods; many electron systems; zero point energy; correlation-consistent basis sets; self consistent field methods; correlated electrons; statistical thermodynamics

Citation Formats


                    Qiu, Yiheng, Henderson, Thomas M., Zhao, Jinmo, and Scuseria, Gustavo E. Projected coupled cluster theory.  United States: N. p., 2017. 
Web.  doi:10.1063/1.4991020.

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                    Qiu, Yiheng, Henderson, Thomas M., Zhao, Jinmo, & Scuseria, Gustavo E. Projected coupled cluster theory.  United States.  https://doi.org/10.1063/1.4991020

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                    Qiu, Yiheng, Henderson, Thomas M., Zhao, Jinmo, and Scuseria, Gustavo E. Fri .  
"Projected coupled cluster theory".  United States.  https://doi.org/10.1063/1.4991020.  https://www.osti.gov/servlets/purl/1474042.

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@article{osti_1474042,

  title        = {Projected coupled cluster theory},

  author       = {Qiu, Yiheng and Henderson, Thomas M. and Zhao, Jinmo and Scuseria, Gustavo E.},

  abstractNote = {Coupled cluster theory is the method of choice for weakly correlated systems. But in the strongly correlated regime, it faces a symmetry dilemma, where it either completely fails to describe the system or has to artificially break certain symmetries. On the other hand, projected Hartree-Fock theory captures the essential physics of many kinds of strong correlations via symmetry breaking and restoration. Here, we combine and try to retain the merits of these two methods by applying symmetry projection to broken symmetry coupled cluster wave functions. The non-orthogonal nature of states resulting from the application of symmetry projection operators furnishes particle-hole excitations to all orders, thus creating an obstacle for the exact evaluation of overlaps. Here we provide a solution via a disentanglement framework theory that can be approximated rigorously and systematically. Results of projected coupled cluster theory are presented for molecules and the Hubbard model, showing that spin projection significantly improves unrestricted coupled cluster theory while restoring good quantum numbers. The energy of projected coupled cluster theory reduces to the unprojected one in the thermodynamic limit, albeit at a much slower rate than projected Hartree-Fock.},

  doi          = {10.1063/1.4991020},

  journal      = {Journal of Chemical Physics},

  number       = 6,

  volume       = 147,

  place        = {United States},

  year         = {Fri Aug 11 00:00:00 EDT 2017},

  month        = {Fri Aug 11 00:00:00 EDT 2017}

}

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Works referencing / citing this record:

Extending spin-symmetry projected coupled-cluster to large model spaces using an iterative null-space projection technique: Extending spin-symmetry projected coupled-cluster to large model spaces using an iterative null-space projection technique
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