Singlet-paired coupled cluster theory for open shells
Abstract
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.
- Authors:
-
- 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:
- 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:
- 1467828
- Alternate Identifier(s):
- OSTI ID: 1259983
- Grant/Contract Number:
- FG02-04ER15523; DGE-1450681
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 24; 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; 74 ATOMIC AND MOLECULAR PHYSICS; excited states; coupled cluster; basis sets; configuration interactions; electron correlation calculations; wave functions; charge coupled devices; dissociation energies
Citation Formats
Gomez, John A., Henderson, Thomas M., and Scuseria, Gustavo E. Singlet-paired coupled cluster theory for open shells. United States: N. p., 2016.
Web. doi:10.1063/1.4954891.
Gomez, John A., Henderson, Thomas M., & Scuseria, Gustavo E. Singlet-paired coupled cluster theory for open shells. United States. https://doi.org/10.1063/1.4954891
Gomez, John A., Henderson, Thomas M., and Scuseria, Gustavo E. Thu .
"Singlet-paired coupled cluster theory for open shells". United States. https://doi.org/10.1063/1.4954891. https://www.osti.gov/servlets/purl/1467828.
@article{osti_1467828,
title = {Singlet-paired coupled cluster theory for open shells},
author = {Gomez, John A. and Henderson, Thomas M. and Scuseria, Gustavo E.},
abstractNote = {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.},
doi = {10.1063/1.4954891},
journal = {Journal of Chemical Physics},
number = 24,
volume = 144,
place = {United States},
year = {Thu Jun 30 00:00:00 EDT 2016},
month = {Thu Jun 30 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Efficient and accurate local approximations to coupled-electron pair approaches: An attempt to revive the pair natural orbital method
journal, March 2009
- Neese, Frank; Wennmohs, Frank; Hansen, Andreas
- The Journal of Chemical Physics, Vol. 130, Issue 11
The role of databases in support of computational chemistry calculations
journal, October 1996
- Feller, David
- Journal of Computational Chemistry, Vol. 17, Issue 13
Multireference Nature of Chemistry: The Coupled-Cluster View
journal, December 2011
- Lyakh, Dmitry I.; Musiał, Monika; Lotrich, Victor F.
- Chemical Reviews, Vol. 112, Issue 1
Addition by subtraction in coupled-cluster theory: A reconsideration of the CC and CI interface and the nCC hierarchy
journal, November 2006
- Bartlett, Rodney J.; Musiał, Monika
- The Journal of Chemical Physics, Vol. 125, Issue 20
Communication: The distinguishable cluster approximation
journal, July 2013
- Kats, Daniel; Manby, Frederick R.
- The Journal of Chemical Physics, Vol. 139, Issue 2
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
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
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
A Critical Assessment of Coupled Cluster Method in Quantum Chemistry
book, January 1999
- Paldus, Josef; Li, Xiangzhu; Prigogine, I.
- Advances in Chemical Physics: Prigogine/Advances
Many – Body Methods in Chemistry and Physics
book, January 2009
- Shavitt, Isaiah; Bartlett, Rodney J.
Accurate thermochemistry from explicitly correlated distinguishable cluster approximation
journal, February 2015
- Kats, Daniel; Kreplin, David; Werner, Hans-Joachim
- The Journal of Chemical Physics, Vol. 142, Issue 6
Self‐Consistent Molecular Orbital Methods. IV. Use of Gaussian Expansions of Slater‐Type Orbitals. Extension to Second‐Row Molecules
journal, March 1970
- Hehre, W. J.; Ditchfield, R.; Stewart, R. F.
- The Journal of Chemical Physics, Vol. 52, Issue 5
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989
- Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 90, Issue 2
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
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
Basis Set Exchange: A Community Database for Computational Sciences
journal, March 2007
- Schuchardt, Karen L.; Didier, Brett T.; Elsethagen, Todd
- Journal of Chemical Information and Modeling, Vol. 47, Issue 3
Assessing the distinguishable cluster approximation based on the triple bond-breaking in the nitrogen molecule
journal, March 2016
- Rishi, Varun; Perera, Ajith; Bartlett, Rodney J.
- The Journal of Chemical Physics, Vol. 144, Issue 12
The open-shell restricted Hartree—Fock singles and doubles coupled-cluster method including triple excitations CCSD (T): application to C+3
journal, January 1991
- Scuseria, Gustavo E.
- Chemical Physics Letters, Vol. 176, Issue 1
A fusion of the closed-shell coupled cluster singles and doubles method and valence-bond theory for bond breaking
journal, September 2012
- Small, David W.; Head-Gordon, Martin
- The Journal of Chemical Physics, Vol. 137, Issue 11
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
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
- Garza, Alejandro J.; Bulik, Ireneusz W.; Alencar, Ana G. Sousa
- Molecular Physics, Vol. 114, Issue 7-8
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
Ionization energies of water from PNO-CI calculations
journal, January 1971
- Meyer, Wilfried
- International Journal of Quantum Chemistry, Vol. 5, Issue S5
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
Communication: The distinguishable cluster approximation. II. The role of orbital relaxation
journal, August 2014
- Kats, Daniel
- The Journal of Chemical Physics, Vol. 141, Issue 6
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
Coupled-cluster theory in quantum chemistry
journal, February 2007
- Bartlett, Rodney J.; Musiał, Monika
- Reviews of Modern Physics, Vol. 79, Issue 1
The influence of orbital rotation on the energy of closed-shell wavefunctions
journal, January 2014
- Limacher, Peter A.; Kim, Taewon D.; Ayers, Paul W.
- Molecular Physics, Vol. 112, Issue 5-6
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
Application of graphical methods of spin algebras to limitedCI approaches. I. Closed shell case
journal, May 1977
- Paldus, J.; Adams, B. G.; ?�?ek, J.
- International Journal of Quantum Chemistry, Vol. 11, Issue 5
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
Works referencing / citing this record:
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
Polynomial-product states: A symmetry-projection-based factorization of the full coupled cluster wavefunction in terms of polynomials of double excitations
journal, April 2019
- Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.
- The Journal of Chemical Physics, Vol. 150, Issue 14
Can the distinguishable cluster approximation be improved systematically by including connected triples?
journal, August 2019
- Rishi, Varun; Valeev, Edward F.
- The Journal of Chemical Physics, Vol. 151, Issue 6
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
journal, August 2019
- Janesko, Benjamin G.
- The Journal of Chemical Physics, Vol. 151, Issue 6
Assessing combinations of singlet-paired coupled cluster and density functional theory for treating electron correlation in closed and open shells
journal, May 2019
- Gomez, John A.; Molla, Mahlet; Garza, Alejandro J.
- Molecular Physics, Vol. 118, Issue 4