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Title: Independent amplitude approximations in coupled cluster valence bond theory: Incorporation of 3-electron-pair correlation and application to spin frustration in the low-lying excited states of a ferredoxin-type tetrametallic iron-sulfur cluster

Abstract

We report that coupled cluster valence bond (CCVB) is a simple electronic structure method based on a perfect pairing (PP) reference with 2-pair recouplings for strong electron correlation problems. CCVB is spin-pure, size-consistent, and can exactly (in its active space) separate any molecule into atoms for which unrestricted Hartree-Fock (UHF) at dissociation is the sum of the ground state UHF energies of the atoms. However CCVB is far from a complete description of strong correlations. Its first failure to exactly describe spin-recouplings arises at the level of 3 electron pairs, such as the recoupling of 3 triplet oxygen atoms in the dissociation of singlet ozone. Such situations are often associated with spin frustration. To address this limitation, an extension of CCVB, termed CCVB+i3, is reported here that includes an independent (i) amplitude approximation to the 3-pair recouplings. CCVB+i3 thereby has the same basic computational requirements as those of CCVB, which has previously been shown to be an efficient method. CCVB+i3 correctly separates molecules that CCVB cannot. As a by-product, an independent 2-pair amplitude approximation to CCVB, called PP+i2, is also defined. Remarkably, PP+i2 can also correctly separate systems that CCVB cannot. CCVB+i3 is validated on the symmetric dissociation of D3hmore » ozone. CCVB+i3 is then used to explore the role of 3-pair recouplings in an [Fe4S4(SCH3)4]2- cluster that has been used to model the iron-sulfur core of [Fe4S4] ferredoxins. Using localized PP orbitals, such recouplings are demonstrated to be large in some low-lying singlet excited states of the cluster. Lastly, significant 3 pair recoupling amplitudes include the usual triangular motif associated with spin frustration and other geometric arrangements of the 3 entangled pairs across the 4 iron centers.« less

Authors:
 [1]; ORCiD logo [1]
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  1. Univ. of California, Berkeley, CA (United States). Department of Chemsitry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1480819
Alternate Identifier(s):
OSTI ID: 1476697
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; 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

Citation Formats

Small, David W., and Head-Gordon, Martin. Independent amplitude approximations in coupled cluster valence bond theory: Incorporation of 3-electron-pair correlation and application to spin frustration in the low-lying excited states of a ferredoxin-type tetrametallic iron-sulfur cluster. United States: N. p., 2018. Web. doi:10.1063/1.5046318.
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Small, David W., & Head-Gordon, Martin. Independent amplitude approximations in coupled cluster valence bond theory: Incorporation of 3-electron-pair correlation and application to spin frustration in the low-lying excited states of a ferredoxin-type tetrametallic iron-sulfur cluster. United States. https://doi.org/10.1063/1.5046318
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Small, David W., and Head-Gordon, Martin. Mon . "Independent amplitude approximations in coupled cluster valence bond theory: Incorporation of 3-electron-pair correlation and application to spin frustration in the low-lying excited states of a ferredoxin-type tetrametallic iron-sulfur cluster". United States. https://doi.org/10.1063/1.5046318. https://www.osti.gov/servlets/purl/1480819.
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@article{osti_1480819,
title = {Independent amplitude approximations in coupled cluster valence bond theory: Incorporation of 3-electron-pair correlation and application to spin frustration in the low-lying excited states of a ferredoxin-type tetrametallic iron-sulfur cluster},
author = {Small, David W. and Head-Gordon, Martin},
abstractNote = {We report that coupled cluster valence bond (CCVB) is a simple electronic structure method based on a perfect pairing (PP) reference with 2-pair recouplings for strong electron correlation problems. CCVB is spin-pure, size-consistent, and can exactly (in its active space) separate any molecule into atoms for which unrestricted Hartree-Fock (UHF) at dissociation is the sum of the ground state UHF energies of the atoms. However CCVB is far from a complete description of strong correlations. Its first failure to exactly describe spin-recouplings arises at the level of 3 electron pairs, such as the recoupling of 3 triplet oxygen atoms in the dissociation of singlet ozone. Such situations are often associated with spin frustration. To address this limitation, an extension of CCVB, termed CCVB+i3, is reported here that includes an independent (i) amplitude approximation to the 3-pair recouplings. CCVB+i3 thereby has the same basic computational requirements as those of CCVB, which has previously been shown to be an efficient method. CCVB+i3 correctly separates molecules that CCVB cannot. As a by-product, an independent 2-pair amplitude approximation to CCVB, called PP+i2, is also defined. Remarkably, PP+i2 can also correctly separate systems that CCVB cannot. CCVB+i3 is validated on the symmetric dissociation of D3h ozone. CCVB+i3 is then used to explore the role of 3-pair recouplings in an [Fe4S4(SCH3)4]2- cluster that has been used to model the iron-sulfur core of [Fe4S4] ferredoxins. Using localized PP orbitals, such recouplings are demonstrated to be large in some low-lying singlet excited states of the cluster. Lastly, significant 3 pair recoupling amplitudes include the usual triangular motif associated with spin frustration and other geometric arrangements of the 3 entangled pairs across the 4 iron centers.},
doi = {10.1063/1.5046318},
journal = {Journal of Chemical Physics},
number = 14,
volume = 149,
place = {United States},
year = {Mon Oct 08 00:00:00 EDT 2018},
month = {Mon Oct 08 00:00:00 EDT 2018}
}
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https://doi.org/10.1063/1.5046318
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Cited by: 7 works
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Figures / Tables:

FIG. 1 FIG. 1: Potential energy curves for the symmetric dissociation (D3h) of singlet O3 to three triplet O atoms. Results in the cc-pVTZ basis are shown for Hartree-Fock methods (UHF, GHF), coupled cluster valence bond methods (PP+i2, CCVB, CCVB+i3) using 3 active pairs, and (6,6) CASSCF, which provides the exact resultmore » in that active space. It is evident that UHF and CCVB fail to reach the correct dissociation limit, while GHF, PP+i2, and CCVB+i3 dissociate correctly.« less
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Works referenced in this record:

Applications of spin-coupled valence bond theory
journal, July 1991

  • Cooper, David L.; Gerratt, Joseph.; Raimondi, Mario.
  • Chemical Reviews, Vol. 91, Issue 5
  • DOI: 10.1021/cr00005a014

Theoretical studies of the first‐ and second‐row transition‐metal methyls and their positive ions
journal, August 1989

  • Bauschlicher, Charles W.; Langhoff, Stephen R.; Partridge, Harry
  • The Journal of Chemical Physics, Vol. 91, Issue 4
  • DOI: 10.1063/1.456998

Active-space two-electron reduced-density-matrix method: Complete active-space calculations without diagonalization of the N-electron Hamiltonian
journal, October 2008

  • Gidofalvi, Gergely; Mazziotti, David A.
  • The Journal of Chemical Physics, Vol. 129, Issue 13
  • DOI: 10.1063/1.2983652

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

Cost-effective description of strong correlation: Efficient implementations of the perfect quadruples and perfect hextuples models
journal, October 2016

  • Lehtola, Susi; Parkhill, John; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 145, Issue 13
  • DOI: 10.1063/1.4964317

The Description of Chemical Bonding From AB Initio Calculations
journal, October 1978

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

Tractable spin-pure methods for bond breaking: Local many-electron spin-vector sets and an approximate valence bond model
journal, February 2009

  • Small, David W.; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 130, Issue 8
  • DOI: 10.1063/1.3069296

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
  • DOI: 10.1063/1.456153

Use of approximate integrals in ab initio theory. An application in MP2 energy calculations
journal, June 1993

  • Feyereisen, Martin; Fitzgerald, George; Komornicki, Andrew
  • Chemical Physics Letters, Vol. 208, Issue 5-6
  • DOI: 10.1016/0009-2614(93)87156-w

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
  • DOI: 10.1021/ci600510j

A tractable and accurate electronic structure method for static correlations: The perfect hextuples model
journal, July 2010

  • Parkhill, John A.; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 133, Issue 2
  • DOI: 10.1063/1.3456001

Correcting Systematic Errors in DFT Spin-Splitting Energetics for Transition Metal Complexes
journal, December 2010

  • Hughes, Thomas F.; Friesner, Richard A.
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 1
  • DOI: 10.1021/ct100359x

Coupled cluster valence bond theory for open-shell systems with application to very long range strong correlation in a polycarbene dimer
journal, July 2017

  • Small, David W.; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 147, Issue 2
  • DOI: 10.1063/1.4991797

The generalized active space concept in multiconfigurational self-consistent field methods
journal, July 2011

  • Ma, Dongxia; Li Manni, Giovanni; Gagliardi, Laura
  • The Journal of Chemical Physics, Vol. 135, Issue 4
  • DOI: 10.1063/1.3611401

A simple way to test for collinearity in spin symmetry broken wave functions: General theory and application to generalized Hartree Fock
journal, March 2015

  • Small, David W.; Sundstrom, Eric J.; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 142, Issue 9
  • DOI: 10.1063/1.4913740

The Density Matrix Renormalization Group in Quantum Chemistry
journal, May 2011

Density Functional Theory of Electronic Structure
journal, January 1996

  • Kohn, W.; Becke, A. D.; Parr, R. G.
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp960669l

Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional
journal, June 2016

  • Sun, Jianwei; Remsing, Richard C.; Zhang, Yubo
  • Nature Chemistry, Vol. 8, Issue 9
  • DOI: 10.1038/nchem.2535

Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements
journal, October 1982

  • Francl, Michelle M.; Pietro, William J.; Hehre, Warren J.
  • The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665
  • DOI: 10.1063/1.444267

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014

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

The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule
journal, February 1981

  • Siegbahn, Per E. M.; Almlöf, Jan; Heiberg, Anders
  • The Journal of Chemical Physics, Vol. 74, Issue 4
  • DOI: 10.1063/1.441359

The perfect quadruples model for electron correlation in a valence active space
journal, February 2009

  • Parkhill, John A.; Lawler, Keith; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 130, Issue 8
  • DOI: 10.1063/1.3086027

Size-consistent wave functions for nondynamical correlation energy: The valence active space optimized orbital coupled-cluster doubles model
journal, December 1998

  • Krylov, Anna I.; Sherrill, C. David; Byrd, Edward F. C.
  • The Journal of Chemical Physics, Vol. 109, Issue 24
  • DOI: 10.1063/1.477764

Are atoms intrinsic to molecular electronic wavefunctions? I. The FORS model
journal, September 1982

Restricted active space spin-flip configuration interaction: Theory and examples for multiple spin flips with odd numbers of electrons
journal, October 2012

  • Zimmerman, Paul M.; Bell, Franziska; Goldey, Matthew
  • The Journal of Chemical Physics, Vol. 137, Issue 16
  • DOI: 10.1063/1.4759076

Efficient use of the correlation consistent basis sets in resolution of the identity MP2 calculations
journal, February 2002

  • Weigend, Florian; Köhn, Andreas; Hättig, Christof
  • The Journal of Chemical Physics, Vol. 116, Issue 8
  • DOI: 10.1063/1.1445115

Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals
journal, April 2017

A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions
journal, January 2017

  • Goerigk, Lars; Hansen, Andreas; Bauer, Christoph
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 48
  • DOI: 10.1039/c7cp04913g

A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980

A deterministic alternative to the full configuration interaction quantum Monte Carlo method
journal, July 2016

  • Tubman, Norm M.; Lee, Joonho; Takeshita, Tyler Y.
  • The Journal of Chemical Physics, Vol. 145, Issue 4
  • DOI: 10.1063/1.4955109

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

The role of databases in support of computational chemistry calculations
journal, October 1996

  • Feller, David
  • Journal of Computational Chemistry, Vol. 17, Issue 13
  • DOI: 10.1002/jcc.9

Challenges for Density Functional Theory
journal, December 2011

  • Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr200107z

Quantitative quantum chemistry
journal, August 2008

Robust and variational fitting
journal, January 2000

  • Dunlap, Brett I.
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 10
  • DOI: 10.1039/b000027m

Post-modern valence bond theory for strongly correlated electron spins
journal, January 2011

  • Small, David W.; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 43
  • DOI: 10.1039/c1cp21832h

ω B97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlation
journal, June 2016

  • Mardirossian, Narbe; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 144, Issue 21
  • DOI: 10.1063/1.4952647

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
  • DOI: 10.1063/1.4751485

Spin states of (bio)inorganic systems: Successes and pitfalls
journal, July 2012

  • Swart, Marcel
  • International Journal of Quantum Chemistry, Vol. 113, Issue 1
  • DOI: 10.1002/qua.24255

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

The restricted active space self-consistent-field method, implemented with a split graph unitary group approach
journal, July 1990

  • Malmqvist, Per Aake.; Rendell, Alistair.; Roos, Bjoern O.
  • The Journal of Physical Chemistry, Vol. 94, Issue 14
  • DOI: 10.1021/j100377a011

Low-energy spectrum of iron–sulfur clusters directly from many-particle quantum mechanics
journal, August 2014

  • Sharma, Sandeep; Sivalingam, Kantharuban; Neese, Frank
  • Nature Chemistry, Vol. 6, Issue 10
  • DOI: 10.1038/nchem.2041

Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms
journal, February 1970

  • Wachters, A. J. H.
  • The Journal of Chemical Physics, Vol. 52, Issue 3
  • DOI: 10.1063/1.1673095

Large-Scale Variational Two-Electron Reduced-Density-Matrix-Driven Complete Active Space Self-Consistent Field Methods
journal, April 2016

  • Fosso-Tande, Jacob; Nguyen, Truong-Son; Gidofalvi, Gergely
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 5
  • DOI: 10.1021/acs.jctc.6b00190

Modern valence bond theory
journal, January 1997

  • Gerratt, J.; Cooper, D. L.; Karadakov, P. B.
  • Chemical Society Reviews, Vol. 26, Issue 2
  • DOI: 10.1039/cs9972600087

Spin-coupled valence bond theory
journal, January 1988

  • Cooper, D. L.; Gerratt, J.; Raimondi, M.
  • International Reviews in Physical Chemistry, Vol. 7, Issue 1
  • DOI: 10.1080/01442358809353205

Quantum Mechanical Modeling of Catalytic Processes
journal, July 2011

Restricted active space spin-flip configuration interaction approach: theory, implementation and examples
journal, January 2009

  • Casanova, David; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 42
  • DOI: 10.1039/b911513g

Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F
journal, October 1983

  • Clark, Timothy; Chandrasekhar, Jayaraman; Spitznagel, G�nther W.
  • Journal of Computational Chemistry, Vol. 4, Issue 3
  • DOI: 10.1002/jcc.540040303

Orbital optimization in the density matrix renormalization group, with applications to polyenes and β-carotene
journal, April 2008

  • Ghosh, Debashree; Hachmann, Johannes; Yanai, Takeshi
  • The Journal of Chemical Physics, Vol. 128, Issue 14
  • DOI: 10.1063/1.2883976

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527

An Antifungal Polycyclic Tetramate Macrolactam, Heat-Stable Antifungal Factor (HSAF), Is a Novel Oxidative Stress Modulator in Lysobacter enzymogenes
journal, April 2021

  • Yu, Lingjun; Li, Hui; Zhou, Zaichun
  • Applied and Environmental Microbiology, Vol. 87, Issue 10
  • DOI: 10.1128/aem.03105-20

Ab initio calculations on small hydrides including electron correlation: I. The BeH2 molecule in its ground state
journal, January 1968

  • Ahlrichs, Reinhart; Kutzelnigg, Werner
  • Theoretica Chimica Acta, Vol. 10, Issue 5
  • DOI: 10.1007/bf00528769
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    Distinguishing artificial and essential symmetry breaking in a single determinant: approach and application to the C 60 , C 36 , and C 20 fullerenes
    journal, January 2019

    • Lee, Joonho; Head-Gordon, Martin
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      FIG. 1 (p. 13)figure
      FIG. 2 (p. 15)figure
      FIG. 3 (p. 17)figure
      FIG. 4 (p. 19)figure
      TABLE I (p. 21)table
      FIG. 5 (p. 22)figure
      TABLE II (p. 23)table
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