Projected coupled cluster theory

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

doi:10.1063/1.4991020

Projected coupled cluster theory

Journal Article · Fri Aug 11 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4991020· OSTI ID:1474042

^[1]; ^[2]; Zhao, Jinmo ^[3]; ^[2]

Rice Univ., Houston, TX (United States). Dept. of Chemistry; none
Rice Univ., Houston, TX (United States). Dept. of Chemistry and Dept. of Physics and Astronomy
Rice Univ., Houston, TX (United States). Dept. of Chemistry

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.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0012575

OSTI ID:: 1474042

Alternate ID(s):: OSTI ID: 1374781

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 147; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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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 Tsuchimochi, Takashi; Ten-no, Seiichiro L. Journal of Computational Chemistry, Vol. 40, Issue 1 https://doi.org/10.1002/jcc.25587	journal	December 2018
Orbital-invariant spin-extended approximate coupled-cluster for multi-reference systems Tsuchimochi, Takashi; Ten-no, Seiichiro L. The Journal of Chemical Physics, Vol. 149, Issue 4 https://doi.org/10.1063/1.5036542	journal	July 2018
Projected coupled cluster theory: Optimization of cluster amplitudes in the presence of symmetry projection Qiu, Yiheng; Henderson, Thomas M.; Zhao, Jinmo The Journal of Chemical Physics, Vol. 149, Issue 16 https://doi.org/10.1063/1.5053605	journal	October 2018
Efficient formulation of full configuration interaction quantum Monte Carlo in a spin eigenbasis via the graphical unitary group approach Dobrautz, Werner; Smart, Simon D.; Alavi, Ali The Journal of Chemical Physics, Vol. 151, Issue 9 https://doi.org/10.1063/1.5108908	journal	September 2019
Geminal-based configuration interaction Henderson, Thomas M.; Scuseria, Gustavo E. The Journal of Chemical Physics, Vol. 151, Issue 5 https://doi.org/10.1063/1.5116715	journal	August 2019
Energy of fermionic ground states with low-entanglement single-reference expansions, and tensor-based strong-coupling extensions of the coupled-cluster method Bergeron, Dominic Physical Review B, Vol. 101, Issue 4 https://doi.org/10.1103/physrevb.101.045109	journal	January 2020
Novel chiral Hamiltonian and observables in light and medium-mass nuclei Somà, V.; Navrátil, P.; Raimondi, F. Physical Review C, Vol. 101, Issue 1 https://doi.org/10.1103/physrevc.101.014318	journal	January 2020
Pre-processing the nuclear many-body problem: Importance truncation versus tensor factorization techniques Tichai, A.; Ripoche, J.; Duguet, T. The European Physical Journal A, Vol. 55, Issue 6 https://doi.org/10.1140/epja/i2019-12758-6	journal	June 2019
Pre-processing the nuclear many-body problem: Importance truncation versus tensor factorization techniques Tichai, Alexander; Ripoche, Julien; Duguet, Thomas arXiv https://doi.org/10.48550/arxiv.1902.09043	text	January 2019

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

Projected coupled cluster theory

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