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Title: Polynomial-product states: A symmetry-projection-based factorization of the full coupled cluster wavefunction in terms of polynomials of double excitations

Abstract

Our goal is to remedy the failure of symmetry-adapted coupled-cluster theory in the presence of strong correlation. Previous work along these lines has taken us from a diagram-level analysis of the coupled-cluster equations to an understanding of the collective modes which can occur in various channels of the coupled-cluster equations to the exploration of non-exponential wavefunctions in efforts to combine coupled-cluster theory with symmetry projection. In this manuscript, we extend these efforts by introducing a new, polynomial product wavefunction ansatz that incorporates information from symmetry projection into standard coupled-cluster theory in a way that attempts to mitigate the effects of the lack of size extensivity and size consistency characteristic of symmetry-projected methods. Finally, we describe the new approach in detail within the context of our previous efforts, explore some illustrative calculations, and consider one route for reducing the computational cost of the new method.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Rice Univ., Houston, TX (United States)
Publication Date:
Research Org.:
Rice Univ., Houston, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation; National Science Foundation (NSF)
OSTI Identifier:
1610560
Alternate Identifier(s):
OSTI ID: 1505882
Grant/Contract Number:  
SC0001474; FG02-09ER16053; C-0036; DGE-1450681
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 14; 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; chemistry; physics

Citation Formats

Gomez, John A., Henderson, Thomas M., and Scuseria, Gustavo E. Polynomial-product states: A symmetry-projection-based factorization of the full coupled cluster wavefunction in terms of polynomials of double excitations. United States: N. p., 2019. Web. doi:10.1063/1.5085314.
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Gomez, John A., Henderson, Thomas M., & Scuseria, Gustavo E. Polynomial-product states: A symmetry-projection-based factorization of the full coupled cluster wavefunction in terms of polynomials of double excitations. United States. https://doi.org/10.1063/1.5085314
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Gomez, John A., Henderson, Thomas M., and Scuseria, Gustavo E. Tue . "Polynomial-product states: A symmetry-projection-based factorization of the full coupled cluster wavefunction in terms of polynomials of double excitations". United States. https://doi.org/10.1063/1.5085314. https://www.osti.gov/servlets/purl/1610560.
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@article{osti_1610560,
title = {Polynomial-product states: A symmetry-projection-based factorization of the full coupled cluster wavefunction in terms of polynomials of double excitations},
author = {Gomez, John A. and Henderson, Thomas M. and Scuseria, Gustavo E.},
abstractNote = {Our goal is to remedy the failure of symmetry-adapted coupled-cluster theory in the presence of strong correlation. Previous work along these lines has taken us from a diagram-level analysis of the coupled-cluster equations to an understanding of the collective modes which can occur in various channels of the coupled-cluster equations to the exploration of non-exponential wavefunctions in efforts to combine coupled-cluster theory with symmetry projection. In this manuscript, we extend these efforts by introducing a new, polynomial product wavefunction ansatz that incorporates information from symmetry projection into standard coupled-cluster theory in a way that attempts to mitigate the effects of the lack of size extensivity and size consistency characteristic of symmetry-projected methods. Finally, we describe the new approach in detail within the context of our previous efforts, explore some illustrative calculations, and consider one route for reducing the computational cost of the new method.},
doi = {10.1063/1.5085314},
journal = {Journal of Chemical Physics},
number = 14,
volume = 150,
place = {United States},
year = {Tue Apr 09 00:00:00 EDT 2019},
month = {Tue Apr 09 00:00:00 EDT 2019}
}
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Works referenced in this record:

Domain-Based Local Pair Natural Orbital Version of Mukherjee’s State-Specific Coupled Cluster Method
journal, January 2018

  • Brabec, Jiri; Lang, Jakub; Saitow, Masaaki
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 3
  • DOI: 10.1021/acs.jctc.7b01184

A size-consistent approach to strongly correlated systems using a generalized antisymmetrized product of nonorthogonal geminals
journal, January 2013

Behind the success of modified coupled-cluster methods: addition by subtraction
journal, July 2018

Multireference coupled-cluster theory: The easy way
journal, March 2011

  • Musiał, Monika; Perera, Ajith; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 134, Issue 11
  • DOI: 10.1063/1.3567115

An efficient reformulation of the closed‐shell coupled cluster single and double excitation (CCSD) equations
journal, December 1988

  • Scuseria, Gustavo E.; Janssen, Curtis L.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 89, Issue 12
  • DOI: 10.1063/1.455269

Combining symmetry collective states with coupled-cluster theory: Lessons from the Agassi model Hamiltonian
journal, June 2017

Correlation problems in atomic and molecular systems. V. Spin‐adapted coupled cluster many‐electron theory
journal, July 1977

  • Paldus, Josef
  • The Journal of Chemical Physics, Vol. 67, Issue 1
  • DOI: 10.1063/1.434526

Coupled-Cluster Valence-Bond Singles and Doubles for Strongly Correlated Systems: Block-Tensor Based Implementation and Application to Oligoacenes
journal, January 2017

  • Lee, Joonho; Small, David W.; Epifanovsky, Evgeny
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 2
  • DOI: 10.1021/acs.jctc.6b01092

Many – Body Methods in Chemistry and Physics
book, January 2009

Coupled Cluster Approach
journal, January 1980

Communication: An adaptive configuration interaction approach for strongly correlated electrons with tunable accuracy
journal, April 2016

  • Schriber, Jeffrey B.; Evangelista, Francesco A.
  • The Journal of Chemical Physics, Vol. 144, Issue 16
  • DOI: 10.1063/1.4948308

Multi-component symmetry-projected approach for molecular ground state correlations
journal, November 2013

  • Jiménez-Hoyos, Carlos A.; Rodríguez-Guzmán, R.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 139, Issue 20
  • DOI: 10.1063/1.4832476

Towards numerically robust multireference theories: The driven similarity renormalization group truncated to one- and two-body operators
journal, April 2016

  • Li, Chenyang; Evangelista, Francesco A.
  • The Journal of Chemical Physics, Vol. 144, Issue 16
  • DOI: 10.1063/1.4947218

Seniority-based coupled cluster theory
journal, December 2014

  • Henderson, Thomas M.; Bulik, Ireneusz W.; Stein, Tamar
  • The Journal of Chemical Physics, Vol. 141, Issue 24
  • DOI: 10.1063/1.4904384

Communication: Projected Hartree Fock theory as a polynomial similarity transformation theory of single excitations
journal, September 2016

  • Qiu, Yiheng; Henderson, Thomas M.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 145, Issue 11
  • DOI: 10.1063/1.4963082

Single-reference coupled cluster theory for multi-reference problems
journal, November 2017

  • Margraf, Johannes T.; Perera, Ajith; Lutz, Jesse J.
  • The Journal of Chemical Physics, Vol. 147, Issue 18
  • DOI: 10.1063/1.5003128

Seniority and orbital symmetry as tools for establishing a full configuration interaction hierarchy
journal, July 2011

  • Bytautas, Laimutis; Henderson, Thomas M.; Jiménez-Hoyos, Carlos A.
  • The Journal of Chemical Physics, Vol. 135, Issue 4
  • DOI: 10.1063/1.3613706

Pair extended coupled cluster doubles
journal, June 2015

  • Henderson, Thomas M.; Bulik, Ireneusz W.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 142, Issue 21
  • DOI: 10.1063/1.4921986

Combinations of coupled cluster, density functionals, and the random phase approximation for describing static and dynamic correlation, and van der Waals interactions
journal, November 2015

Assessing the Accuracy of New Geminal-Based Approaches
journal, April 2014

  • Tecmer, Paweł; Boguslawski, Katharina; Johnson, Paul A.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 39
  • DOI: 10.1021/jp502127v

Targeting excited states in all-trans polyenes with electron-pair states
journal, December 2016

  • Boguslawski, Katharina
  • The Journal of Chemical Physics, Vol. 145, Issue 23
  • DOI: 10.1063/1.4972053

Attenuated coupled cluster: a heuristic polynomial similarity transformation incorporating spin symmetry projection into traditional coupled cluster theory
journal, January 2017

Projected quasiparticle theory for molecular electronic structure
journal, September 2011

  • Scuseria, Gustavo E.; Jiménez-Hoyos, Carlos A.; Henderson, Thomas M.
  • The Journal of Chemical Physics, Vol. 135, Issue 12
  • DOI: 10.1063/1.3643338

Coupled Cluster Valence Bond Method: Efficient Computer Implementation and Application to Multiple Bond Dissociations and Strong Correlations in the Acenes
journal, April 2014

  • Small, David W.; Lawler, Keith V.; Head-Gordon, Martin
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 5
  • DOI: 10.1021/ct500112y

Alternative single-reference coupled cluster approaches for multireference problems: The simpler, the better
journal, June 2011

  • Evangelista, Francesco A.
  • The Journal of Chemical Physics, Vol. 134, Issue 22
  • DOI: 10.1063/1.3598471

Can Single-Reference Coupled Cluster Theory Describe Static Correlation?
journal, June 2015

  • Bulik, Ireneusz W.; Henderson, Thomas M.; Scuseria, Gustavo E.
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 7
  • DOI: 10.1021/acs.jctc.5b00422

Projected Hartree-Fock theory as a polynomial of particle-hole excitations and its combination with variational coupled cluster theory
journal, May 2017

  • Qiu, Yiheng; Henderson, Thomas M.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 146, Issue 18
  • DOI: 10.1063/1.4983065

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals
journal, August 2017

  • Sayfutyarova, Elvira R.; Sun, Qiming; Chan, Garnet Kin-Lic
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 9
  • DOI: 10.1021/acs.jctc.7b00128

Singlet-paired coupled cluster theory for open shells
journal, June 2016

  • Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 144, Issue 24
  • DOI: 10.1063/1.4954891

Recoupling the singlet- and triplet-pairing channels in single-reference coupled cluster theory
journal, October 2016

  • Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 145, Issue 13
  • DOI: 10.1063/1.4963870

Orbital-invariant spin-extended approximate coupled-cluster for multi-reference systems
journal, July 2018

  • Tsuchimochi, Takashi; Ten-no, Seiichiro L.
  • The Journal of Chemical Physics, Vol. 149, Issue 4
  • DOI: 10.1063/1.5036542

Perspective: Multireference coupled cluster theories of dynamical electron correlation
journal, July 2018

  • Evangelista, Francesco A.
  • The Journal of Chemical Physics, Vol. 149, Issue 3
  • DOI: 10.1063/1.5039496

Amplitude Determinant Coupled Cluster with Pairwise Doubles
journal, November 2016

  • Zhao, Luning; Neuscamman, Eric
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 12
  • DOI: 10.1021/acs.jctc.6b00812

Bridging Single- and Multireference Domains for Electron Correlation: Spin-Extended Coupled Electron Pair Approximation
journal, March 2017

  • Tsuchimochi, Takashi; Ten-no, Seiichiro
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 4
  • DOI: 10.1021/acs.jctc.7b00073

Merging symmetry projection methods with coupled cluster theory: Lessons from the Lipkin model Hamiltonian
journal, February 2017

  • Wahlen-Strothman, Jacob M.; Henderson, Thomas M.; Hermes, Matthew R.
  • The Journal of Chemical Physics, Vol. 146, Issue 5
  • DOI: 10.1063/1.4974989

Seniority zero pair coupled cluster doubles theory
journal, June 2014

  • Stein, Tamar; Henderson, Thomas M.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 140, Issue 21
  • DOI: 10.1063/1.4880819

Influence of broken-pair excitations on the exact pair wavefunction
journal, September 2017

Spin-projected generalized Hartree-Fock method as a polynomial of particle-hole excitations
journal, August 2017

Spin polynomial similarity transformation for repulsive Hamiltonians: interpolating between coupled cluster and spin-projected unrestricted Hartree–Fock
journal, January 2017

  • Gomez, John A.; Degroote, Matthias; Zhao, Jinmo
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 33
  • DOI: 10.1039/c7cp04075j

Localized Atomic and Molecular Orbitals
journal, July 1963

Selection of active spaces for multiconfigurational wavefunctions
journal, June 2015

  • Keller, Sebastian; Boguslawski, Katharina; Janowski, Tomasz
  • The Journal of Chemical Physics, Vol. 142, Issue 24
  • DOI: 10.1063/1.4922352

A New Mean-Field Method Suitable for Strongly Correlated Electrons: Computationally Facile Antisymmetric Products of Nonorthogonal Geminals
journal, February 2013

  • Limacher, Peter A.; Ayers, Paul W.; Johnson, Paul A.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 3
  • DOI: 10.1021/ct300902c

An Introduction to Coupled Cluster Theory for Computational Chemists
book, January 2000

  • Crawford, T. Daniel; Schaefer, Henry F.; Lipkowitz, Kenny B.
  • Reviews in Computational Chemistry: Lipkowitz/Reviews
  • DOI: 10.1002/9780470125915.ch2

Exploring Copper Oxide Cores Using the Projected Hartree–Fock Method
journal, September 2012

  • Samanta, Kousik; Jiménez-Hoyos, Carlos A.; Scuseria, Gustavo E.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 12
  • DOI: 10.1021/ct300689e

Projected Hartree–Fock theory
journal, April 2012

  • Jiménez-Hoyos, Carlos A.; Henderson, Thomas M.; Tsuchimochi, Takashi
  • The Journal of Chemical Physics, Vol. 136, Issue 16
  • DOI: 10.1063/1.4705280

Efficient description of strongly correlated electrons with mean-field cost
journal, May 2014

Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals
journal, December 2015

  • Garza, Alejandro J.; Sousa Alencar, Ana G.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 143, Issue 24
  • DOI: 10.1063/1.4938088

Predicting Singlet–Triplet Energy Splittings with Projected Hartree–Fock Methods
journal, July 2013

  • Rivero, Pablo; Jiménez-Hoyos, Carlos A.; Scuseria, Gustavo E.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 33
  • DOI: 10.1021/jp405755z

Tensor-structured coupled cluster theory
journal, November 2017

  • Schutski, Roman; Zhao, Jinmo; Henderson, Thomas M.
  • The Journal of Chemical Physics, Vol. 147, Issue 18
  • DOI: 10.1063/1.4996988

Electron correlations in narrow energy bands
journal, November 1963

  • Hubbard, J.
  • Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 276, Issue 1365, p. 238-257
  • DOI: 10.1098/rspa.1963.0204

Entanglement and Polyradical Character of Polycyclic Aromatic Hydrocarbons Predicted by Projected Hartree–Fock Theory
journal, May 2013

  • Rivero, Pablo; Jiménez-Hoyos, Carlos A.; Scuseria, Gustavo E.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 42
  • DOI: 10.1021/jp401478v

Excited states from modified coupled cluster methods: Are they any better than EOM CCSD?
journal, April 2017

  • Rishi, Varun; Perera, Ajith; Nooijen, Marcel
  • The Journal of Chemical Physics, Vol. 146, Issue 14
  • DOI: 10.1063/1.4979078

Cheap and Near Exact CASSCF with Large Active Spaces
journal, October 2017

  • Smith, James E. T.; Mussard, Bastien; Holmes, Adam A.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 11
  • DOI: 10.1021/acs.jctc.7b00900

A dynamic correlation dressed complete active space method: Theory, implementation, and preliminary applications
journal, December 2017

  • Pathak, Shubhrodeep; Lang, Lucas; Neese, Frank
  • The Journal of Chemical Physics, Vol. 147, Issue 23
  • DOI: 10.1063/1.5017942

Accurate thermochemistry from a parameterized coupled-cluster singles and doubles model and a local pair natural orbital based implementation for applications to larger systems
journal, February 2012

  • Huntington, Lee M. J.; Hansen, Andreas; Neese, Frank
  • The Journal of Chemical Physics, Vol. 136, Issue 6
  • DOI: 10.1063/1.3682325

pCCSD: Parameterized coupled-cluster theory with single and double excitations
journal, November 2010

  • Huntington, Lee M. J.; Nooijen, Marcel
  • The Journal of Chemical Physics, Vol. 133, Issue 18
  • DOI: 10.1063/1.3494113

Zur Theorie der Metalle: Erwiderung auf eine Arbeit von A. H. Wilson
journal, September 1933

Multi-component symmetry-projected approach for molecular ground state correlations
text, January 2013

Efficient description of strongly correlated electrons with mean-field cost
text, January 2014

Quasiparticle Coupled Cluster Theory for Pairing Interactions
text, January 2014

Seniority-based coupled cluster theory
text, January 2014

Can single-reference coupled cluster theory describe static correlation?
text, January 2015

Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals
text, January 2015

Automated construction of molecular active spaces from atomic valence orbitals
text, January 2017

Combining symmetry collective states with coupled cluster theory: Lessons from the Agassi model Hamiltonian
text, January 2017

Spin-Projected Generalized Hartree-Fock as a Polynomial of Particle-Hole Excitations
text, January 2017

Influence of broken-pair excitations on the exact pair wavefunction
text, January 2017

Cheap and near exact CASSCF with large active spaces
text, January 2017

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