DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Accurate excited-state energetics by a combination of Monte Carlo sampling and equation-of-motion coupled-cluster computations

Abstract

The recently introduced idea of identifying the most important higher-than-doubly excited determinants in the ground-state coupled-cluster (CC) calculations through stochastic configuration interaction Quantum Monte Carlo propagations [J.E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)] is extended to excited electronic states via the equation-of-motion (EOM) CC methodology. The advantages of the new method are illustrated by calculations aimed at recovering the ground- and excited-state energies of the CH+ molecule at the equilibrium and stretched geometries resulting from the EOMCC calculations with a full treatment of singles, doubles, and triples.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Michigan State Univ., East Lansing, MI (United States)
Publication Date:
Research Org.:
Michigan State Univ., East Lansing, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1593454
Grant/Contract Number:  
FG02-01ER15228; CHE-1763371
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 11; 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

Deustua, J. Emiliano, Yuwono, Stephen H., Shen, Jun, and Piecuch, Piotr. Accurate excited-state energetics by a combination of Monte Carlo sampling and equation-of-motion coupled-cluster computations. United States: N. p., 2019. Web. doi:10.1063/1.5090346.
Deustua, J. Emiliano, Yuwono, Stephen H., Shen, Jun, & Piecuch, Piotr. Accurate excited-state energetics by a combination of Monte Carlo sampling and equation-of-motion coupled-cluster computations. United States. https://doi.org/10.1063/1.5090346
Deustua, J. Emiliano, Yuwono, Stephen H., Shen, Jun, and Piecuch, Piotr. Fri . "Accurate excited-state energetics by a combination of Monte Carlo sampling and equation-of-motion coupled-cluster computations". United States. https://doi.org/10.1063/1.5090346. https://www.osti.gov/servlets/purl/1593454.
@article{osti_1593454,
title = {Accurate excited-state energetics by a combination of Monte Carlo sampling and equation-of-motion coupled-cluster computations},
author = {Deustua, J. Emiliano and Yuwono, Stephen H. and Shen, Jun and Piecuch, Piotr},
abstractNote = {The recently introduced idea of identifying the most important higher-than-doubly excited determinants in the ground-state coupled-cluster (CC) calculations through stochastic configuration interaction Quantum Monte Carlo propagations [J.E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)] is extended to excited electronic states via the equation-of-motion (EOM) CC methodology. The advantages of the new method are illustrated by calculations aimed at recovering the ground- and excited-state energies of the CH+ molecule at the equilibrium and stretched geometries resulting from the EOMCC calculations with a full treatment of singles, doubles, and triples.},
doi = {10.1063/1.5090346},
journal = {Journal of Chemical Physics},
number = 11,
volume = 150,
place = {United States},
year = {Fri Mar 15 00:00:00 EDT 2019},
month = {Fri Mar 15 00:00:00 EDT 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Developments in stochastic coupled cluster theory: The initiator approximation and application to the uniform electron gas
journal, February 2016

  • Spencer, James S.; Thom, Alex J. W.
  • The Journal of Chemical Physics, Vol. 144, Issue 8
  • DOI: 10.1063/1.4942173

New coupled-cluster methods with singles, doubles, and noniterative triples for high accuracy calculations of excited electronic states
journal, January 2004

  • Kowalski, Karol; Piecuch, Piotr
  • The Journal of Chemical Physics, Vol. 120, Issue 4
  • DOI: 10.1063/1.1632474

Embedding vs Supermolecular Strategies in Evaluating the Hydrogen-Bonding-Induced Shifts of Excitation Energies
journal, May 2011

  • Fradelos, Georgios; Lutz, Jesse J.; Wesołowski, Tomasz A.
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 6
  • DOI: 10.1021/ct200101x

The full CCSDT model for molecular electronic structure
journal, June 1987

  • Noga, Jozef; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 86, Issue 12
  • DOI: 10.1063/1.452353

A linear response, coupled-cluster theory for excitation energy
journal, March 1984

  • Sekino, Hideo; Bartlett, Rodney J.
  • International Journal of Quantum Chemistry, Vol. 26, Issue S18
  • DOI: 10.1002/qua.560260826

Erratum: The full CCSDT model for molecular electronic structure [J. Chem. Phys. 8 6 , 7041 (1987)]
journal, September 1988

  • Noga, J.; Bartlett, R. J.
  • The Journal of Chemical Physics, Vol. 89, Issue 5
  • DOI: 10.1063/1.455742

An explicitly correlated approach to basis set incompleteness in full configuration interaction quantum Monte Carlo
journal, October 2012

  • Booth, George H.; Cleland, Deidre; Alavi, Ali
  • The Journal of Chemical Physics, Vol. 137, Issue 16
  • DOI: 10.1063/1.4762445

Excitation energies from the coupled cluster singles and doubles linear response function (CCSDLR). Applications to Be, CH + , CO, and H 2 O
journal, September 1990

  • Koch, Henrik; Jensen, Hans Jo/rgen Aa.; Jo/rgensen, Poul
  • The Journal of Chemical Physics, Vol. 93, Issue 5
  • DOI: 10.1063/1.458815

Perturbative corrections to coupled-cluster and equation-of-motion coupled-cluster energies: A determinantal analysis
journal, March 2001

  • Hirata, So; Nooijen, Marcel; Grabowski, Ireneusz
  • The Journal of Chemical Physics, Vol. 114, Issue 9
  • DOI: 10.1063/1.1346578

Coupled cluster response functions
journal, September 1990

  • Koch, Henrik; Jo/rgensen, Poul
  • The Journal of Chemical Physics, Vol. 93, Issue 5
  • DOI: 10.1063/1.458814

Stochastic Coupled Cluster Theory
journal, December 2010


Coupled-cluster theory for excited electronic states: The full equation-of-motion coupled-cluster single, double, and triple excitation method
journal, November 2001

  • Kucharski, Stanisław A.; Włoch, Marta; Musiał, Monika
  • The Journal of Chemical Physics, Vol. 115, Issue 18
  • DOI: 10.1063/1.1416173

An extension of the coupled cluster formalism to excited states (I)
journal, January 1981


Perturbative triple excitation corrections to coupled cluster singles and doubles excitation energies
journal, July 1996

  • Christiansen, Ove; Koch, Henrik; Jo/rgensen, Poul
  • The Journal of Chemical Physics, Vol. 105, Issue 4
  • DOI: 10.1063/1.472007

Active-space coupled-cluster study of electronic states of Be3
journal, August 2005

  • Kowalski, Karol; Hirata, So; Włoch, Marta
  • The Journal of Chemical Physics, Vol. 123, Issue 7
  • DOI: 10.1063/1.2001656

A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples
journal, February 1982

  • Purvis, George D.; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 76, Issue 4
  • DOI: 10.1063/1.443164

Two new classes of non-iterative coupled-cluster methods derived from the method of moments of coupled-cluster equations
journal, July 2006

  • Łoch, Marta W.; Lodriguito, Maricris D.; Piecuch†, Piotr
  • Molecular Physics, Vol. 104, Issue 13-14
  • DOI: 10.1080/00268970600659586

The active-space equation-of-motion coupled-cluster methods for excited electronic states: Full EOMCCSDt
journal, July 2001

  • Kowalski, Karol; Piecuch, Piotr
  • The Journal of Chemical Physics, Vol. 115, Issue 2
  • DOI: 10.1063/1.1378323

Economical triple excitation equation-of-motion coupled-cluster methods for excitation energies
journal, February 1995


Semi-stochastic full configuration interaction quantum Monte Carlo: Developments and application
journal, May 2015

  • Blunt, N. S.; Smart, Simon D.; Kersten, J. A. F.
  • The Journal of Chemical Physics, Vol. 142, Issue 18
  • DOI: 10.1063/1.4920975

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

Combining active-space coupled-cluster approaches with moment energy corrections via the CC( P ; Q ) methodology: connected quadruple excitations
journal, January 2017


Erratum: “Perturbative corrections to coupled-cluster and equation-of-motion coupled-cluster energies: A determinantal analysis” [J. Chem. Phys. 114, 3919 (2001)]
journal, August 2001

  • Hirata, So; Nooijen, Marcel; Grabowski, Ireneusz
  • The Journal of Chemical Physics, Vol. 115, Issue 8
  • DOI: 10.1063/1.1388549

Excitation energies of BH, CH2 and Ne in full configuration interaction and the hierarchy CCS, CC2, CCSD and CC3 of coupled cluster models
journal, September 1995


The coupled‐cluster single, double, triple, and quadruple excitation method
journal, September 1992

  • Kucharski, Stanislaw A.; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 97, Issue 6
  • DOI: 10.1063/1.463930

Active-space coupled-cluster methods
journal, November 2010


Communication: Approaching exact quantum chemistry by cluster analysis of full configuration interaction quantum Monte Carlo wave functions
journal, October 2018

  • Deustua, J. Emiliano; Magoulas, Ilias; Shen, Jun
  • The Journal of Chemical Physics, Vol. 149, Issue 15
  • DOI: 10.1063/1.5055769

Efficient formulation and computer implementation of the active-space electron-attached and ionized equation-of-motion coupled-cluster methods
journal, December 2006

  • Gour, Jeffrey R.; Piecuch, Piotr
  • The Journal of Chemical Physics, Vol. 125, Issue 23
  • DOI: 10.1063/1.2409289

High-order electron-correlation methods with scalar relativistic and spin-orbit corrections
journal, January 2007

  • Hirata, So; Yanai, Takeshi; Harrison, Robert J.
  • The Journal of Chemical Physics, Vol. 126, Issue 2
  • DOI: 10.1063/1.2423005

Stochastic coupled cluster theory: Efficient sampling of the coupled cluster expansion
journal, September 2017

  • Scott, Charles J. C.; Thom, Alex J. W.
  • The Journal of Chemical Physics, Vol. 147, Issue 12
  • DOI: 10.1063/1.4991795

Active-space equation-of-motion coupled-cluster methods for excited states of radicals and other open-shell systems: EA-EOMCCSDt and IP-EOMCCSDt
journal, October 2005

  • Gour, Jeffrey R.; Piecuch, Piotr; Włoch, Marta
  • The Journal of Chemical Physics, Vol. 123, Issue 13
  • DOI: 10.1063/1.2042452

Adaptive Configuration Interaction for Computing Challenging Electronic Excited States with Tunable Accuracy
journal, October 2017

  • Schriber, Jeffrey B.; Evangelista, Francesco A.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 11
  • DOI: 10.1021/acs.jctc.7b00725

Excitation energies, transition moments and dynamic polarizabilities for CH+. A comparison of multiconfigurational linear response and full configuration interaction calculations
journal, January 1989

  • Olsen, Jeppe; De Meŕas, Alfredo M. Sánchez; Jensen, Hans Jørgen Aa.
  • Chemical Physics Letters, Vol. 154, Issue 4
  • DOI: 10.1016/0009-2614(89)85373-4

Short-range correlations in nuclear wave functions
journal, June 1960


Second- and third-order triples and quadruples corrections to coupled-cluster singles and doubles in the ground and excited states
journal, June 2007

  • Shiozaki, Toru; Hirao, Kimihiko; Hirata, So
  • The Journal of Chemical Physics, Vol. 126, Issue 24
  • DOI: 10.1063/1.2741262

A new implementation of the full CCSDT model for molecular electronic structure
journal, November 1988


Open-Source Development Experiences in Scientific Software: The HANDE Quantum Monte Carlo Project
journal, November 2015

  • Spencer, J. S.; Blunt, N. S.; Vigor, W. A.
  • Journal of Open Research Software, Vol. 3
  • DOI: 10.5334/jors.bw

Time‐dependent coupled cluster approach: Excitation energy calculation using an orthogonally spin‐adapted formalism
journal, August 1986

  • Takahashi, M.; Paldus, J.
  • The Journal of Chemical Physics, Vol. 85, Issue 3
  • DOI: 10.1063/1.451241

Fermion Monte Carlo without fixed nodes: A game of life, death, and annihilation in Slater determinant space
journal, January 2009

  • Booth, George H.; Thom, Alex J. W.; Alavi, Ali
  • The Journal of Chemical Physics, Vol. 131, Issue 5
  • DOI: 10.1063/1.3193710

Multireference coupled‐cluster method using a single‐reference formalism
journal, January 1991

  • Oliphant, Nevin; Adamowicz, Ludwik
  • The Journal of Chemical Physics, Vol. 94, Issue 2
  • DOI: 10.1063/1.460031

Benchmarking the completely renormalised equation-of-motion coupled-cluster approaches for vertical excitation energies
journal, September 2015


Higher-order equation-of-motion coupled-cluster methods
journal, January 2004

  • Hirata, So
  • The Journal of Chemical Physics, Vol. 121, Issue 1
  • DOI: 10.1063/1.1753556

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

Bound states of a many-particle system
journal, June 1958


An excited-state approach within full configuration interaction quantum Monte Carlo
journal, October 2015

  • Blunt, N. S.; Smart, Simon D.; Booth, George H.
  • The Journal of Chemical Physics, Vol. 143, Issue 13
  • DOI: 10.1063/1.4932595

Density matrices in full configuration interaction quantum Monte Carlo: Excited states, transition dipole moments, and parallel distribution
journal, June 2017

  • Blunt, N. S.; Booth, George H.; Alavi, Ali
  • The Journal of Chemical Physics, Vol. 146, Issue 24
  • DOI: 10.1063/1.4986963

The linked singles and doubles model: An approximate theory of electron correlation based on the coupled‐cluster ansatz
journal, October 1982

  • Cullen, John M.; Zerner, Michael C.
  • The Journal of Chemical Physics, Vol. 77, Issue 8
  • DOI: 10.1063/1.444319

Performance of the completely renormalized equation-of-motion coupled-cluster method in calculations of excited-state potential cuts of water
journal, July 2014


Understanding and improving the efficiency of full configuration interaction quantum Monte Carlo
journal, March 2016

  • Vigor, W. A.; Spencer, J. S.; Bearpark, M. J.
  • The Journal of Chemical Physics, Vol. 144, Issue 9
  • DOI: 10.1063/1.4943113

Erratum: “Stochastic multi-reference perturbation theory with application to the linearized coupled cluster method” [J. Chem. Phys. 146, 044107 (2017)]
journal, June 2017

  • Jeanmairet, Guillaume; Sharma, Sandeep; Alavi, Ali
  • The Journal of Chemical Physics, Vol. 146, Issue 23
  • DOI: 10.1063/1.4986407

The equation-of-motion coupled-cluster method: Excitation energies of Be and CO
journal, December 1989


Calculation of properties with the coupled-cluster method
journal, January 1977

  • Monkhorst, Hendrik J.
  • International Journal of Quantum Chemistry, Vol. 12, Issue S11
  • DOI: 10.1002/qua.560120850

Communications: Survival of the fittest: Accelerating convergence in full configuration-interaction quantum Monte Carlo
journal, January 2010

  • Cleland, Deidre; Booth, George H.; Alavi, Ali
  • The Journal of Chemical Physics, Vol. 132, Issue 4
  • DOI: 10.1063/1.3302277

Coupled‐cluster method truncated at quadruples
journal, November 1991

  • Oliphant, Nevin; Adamowicz, Ludwik
  • The Journal of Chemical Physics, Vol. 95, Issue 9
  • DOI: 10.1063/1.461534

Stochastic multi-reference perturbation theory with application to the linearized coupled cluster method
journal, January 2017

  • Jeanmairet, Guillaume; Sharma, Sandeep; Alavi, Ali
  • The Journal of Chemical Physics, Vol. 146, Issue 4
  • DOI: 10.1063/1.4974177

The active-space equation-of-motion coupled-cluster methods for excited electronic states: The EOMCCSDt approach
journal, November 2000

  • Kowalski, Karol; Piecuch, Piotr
  • The Journal of Chemical Physics, Vol. 113, Issue 19
  • DOI: 10.1063/1.1318757

Cluster expansion of the wavefunction. Excited states
journal, November 1978


Calculation of excited-state properties using general coupled-cluster and configuration-interaction models
journal, November 2004

  • Kállay, Mihály; Gauss, Jürgen
  • The Journal of Chemical Physics, Vol. 121, Issue 19
  • DOI: 10.1063/1.1805494

Linear-scaling and parallelisable algorithms for stochastic quantum chemistry
journal, January 2014


Some aspects of the time-dependent coupled-cluster approach to dynamic response functions
journal, September 1983


Linked coupled cluster Monte Carlo
journal, January 2016

  • Franklin, R. S. T.; Spencer, J. S.; Zoccante, A.
  • The Journal of Chemical Physics, Vol. 144, Issue 4
  • DOI: 10.1063/1.4940317

Response functions in the CC3 iterative triple excitation model
journal, November 1995

  • Christiansen, Ove; Koch, Henrik; Jo/rgensen, Poul
  • The Journal of Chemical Physics, Vol. 103, Issue 17
  • DOI: 10.1063/1.470315

A state‐selective multireference coupled‐cluster theory employing the single‐reference formalism
journal, August 1993

  • Piecuch, Piotr; Oliphant, Nevin; Adamowicz, Ludwik
  • The Journal of Chemical Physics, Vol. 99, Issue 3
  • DOI: 10.1063/1.466179

Coupled-cluster methods with internal and semi-internal triply and quadruply excited clusters: CCSDt and CCSDtq approaches
journal, April 1999

  • Piecuch, Piotr; Kucharski, Stanisław A.; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478517

Excited-state potential energy curves of CH+: a comparison of the EOMCCSDt and full EOMCCSDT results
journal, October 2001


Excitation energies of H2O, N2 and C2 in full configuration interaction and coupled cluster theory
journal, June 1996


Quantum Monte Carlo simulations of solids
journal, January 2001


Active-Space Equation-of-Motion Coupled-Cluster Methods through Quadruples for Excited, Ionized, and Electron-Attached States
journal, March 2007

  • Fan, Peng-Dong; Kamiya, Muneaki; Hirata, So
  • Journal of Chemical Theory and Computation, Vol. 3, Issue 3
  • DOI: 10.1021/ct600270c

Stochastic coupled cluster theory: Efficient sampling of the coupled cluster expansion
text, January 2017

  • Scott, Cjc; Thom, Ajw
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.13428

Monte Carlo methods
null, January 1970


Semi-stochastic full configuration interaction quantum Monte Carlo: developments and application
text, January 2015


An excited-state approach within full configuration interaction quantum Monte Carlo
text, January 2015


Works referencing / citing this record:

Quantum simulations of excited states with active-space downfolded Hamiltonians
journal, December 2019

  • Bauman, Nicholas P.; Low, Guang Hao; Kowalski, Karol
  • The Journal of Chemical Physics, Vol. 151, Issue 23
  • DOI: 10.1063/1.5128103

The density matrix renormalization group in chemistry and molecular physics: Recent developments and new challenges
journal, January 2020

  • Baiardi, Alberto; Reiher, Markus
  • The Journal of Chemical Physics, Vol. 152, Issue 4
  • DOI: 10.1063/1.5129672

Unbiasing the initiator approximation in full configuration interaction quantum Monte Carlo
journal, December 2019

  • Ghanem, Khaldoon; Lozovoi, Alexander Y.; Alavi, Ali
  • The Journal of Chemical Physics, Vol. 151, Issue 22
  • DOI: 10.1063/1.5134006

Unbiasing the initiator approximation in full configuration interaction quantum Monte Carlo.
text, January 2019

  • Ghanem, Khaldoon; Lozovoi, Alexander Y.; Alavi, Ali
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.47442