skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Equation-of-motion coupled-cluster method with double electron-attaching operators: Theory, implementation, and benchmarks

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0041822· OSTI ID:1852700
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Southern California, Los Angeles, CA (United States)
  2. Norwegian Univ. of Science and Technology, Trondheim (Norway)
  3. Univ. of Florida, Gainesville, FL (United States)
  4. Scuola Normale Superiore, Pisa (Italy)
+ Show Author Affiliations

We report a production-level implementation of the equation-of-motion (EOM) coupled-cluster (CC) method with double electron-attaching (DEA) EOM operators of 2p and 3p1h types, EOM-DEA-CCSD. This ansatz, suitable for treating electronic structure patterns that can be described as two-electrons-in-many orbitals, represents a useful addition to the EOM-CC family of methods. We analyze the performance of EOM-DEA-CCSD for energy differences and molecular properties. By considering reduced quantities, such as state and transition one-particle density matrices, we compare EOM-DEA-CCSD wave functions with wave functions computed by other EOM-CCSD methods. The benchmarks illustrate that EOM-DEA-CCSD is capable of treating diradicals, bond-breaking, and some types of conical intersections.

Research Organization:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF); European Commission (EC); Research Council of Norway
Grant/Contract Number:
SC0018910; CHE-1748821; 765739; 263110; 275506
OSTI ID:
1852700
Alternate ID(s):
OSTI ID: 1771812
Journal Information:
Journal of Chemical Physics, Vol. 154, Issue 11; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (88)

Long-Range N–N Bonding by Rydberg Electrons journal March 2020
Bonding Patterns in Benzene Triradicals from Structural, Spectroscopic, and Thermochemical Perspectives journal August 2004
e T 1.0: An open source electronic structure program with emphasis on coupled cluster and multilevel methods journal May 2020
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
Coupled cluster response functions journal September 1990
Coupled-cluster techniques for computational chemistry: The CFOUR program package journal June 2020
Doubly electron-attached and doubly ionized equation-of-motion coupled-cluster methods with 4-particle–2-hole and 4-hole–2-particle excitations and their active-space extensions journal May 2013
An extension of the coupled cluster formalism to excited states (I) journal January 1981
Coupled cluster theory for high spin, open shell reference wave functions journal October 1993
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples journal February 1982
Isomers and excitation energies of C 4 journal March 1986
Report on Notation for the Spectra of Polyatomic Molecules journal November 1955
An ab Initio Exploration of the Bergman Cyclization journal December 2017
Benchmarking Excited-State Calculations Using Exciton Properties journal January 2018
Entanglement entropy of electronic excitations journal May 2016
Implementation of analytic gradients for CCSD and EOM-CCSD using Cholesky decomposition of the electron-repulsion integrals and their derivatives: Theory and benchmarks journal July 2019
General implementation of the resolution-of-the-identity and Cholesky representations of electron repulsion integrals within coupled-cluster and equation-of-motion methods: Theory and benchmarks journal October 2013
The automated solution of second quantization equations with applications to the coupled cluster approach journal January 1991
A mean-field spin-orbit method applicable to correlated wavefunctions journal March 1996
Resolving the Notorious Case of Conical Intersections for Coupled Cluster Dynamics journal September 2017
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Description of core‐excitation spectra by the open‐shell electron‐attachment equation‐of‐motion coupled cluster method journal May 1995
Explicitly-correlated double ionization potentials and double electron attachment equation-of-motion coupled cluster methods journal January 2018
Characterizing Bonding Patterns in Diradicals and Triradicals by Density-Based Wave Function Analysis: A Uniform Approach journal January 2018
Critical comparison of single-reference and multireference coupled-cluster methods: Geometry, harmonic frequencies, and excitation energies of N2O2 journal November 2003
Double Precision Is Not Needed for Many-Body Calculations: Emergent Conventional Wisdom journal June 2018
To Multireference or not to Multireference: That is the Question? journal June 2002
Multireference Double Electron Attached Coupled Cluster Method with Full Inclusion of the Connected Triple Excitations: MR-DA-CCSDT journal August 2011
Interacting Rydberg and valence states in radicals and molecules: experimental and theoretical studies journal April 2009
Calculations of non-adiabatic couplings within equation-of-motion coupled-cluster framework: Theory, implementation, and validation against multi-reference methods journal January 2018
Similarity transformed equation-of-motion coupled-cluster theory: Details, examples, and comparisons journal November 1997
Conical Intersection and Potential Energy Surface Features of a Model Retinal Chromophore: Comparison of EOM-CC and Multireference Methods journal November 2012
What We Can Learn from the Norms of One-Particle Density Matrices, and What We Can’t: Some Results for Interstate Properties in Model Singlet Fission Systems journal August 2014
Lowest energy triplet states of group Vb hydrides: NH3 (ND3) and PH3 journal August 1991
A fifth-order perturbation comparison of electron correlation theories journal May 1989
Multiplicity of many-body wavefunctions using unrestricted Hartree-Fock reference functions journal January 1988
Two-photon absorption cross sections within equation-of-motion coupled-cluster formalism using resolution-of-the-identity and Cholesky decomposition representations: Theory, implementation, and benchmarks journal February 2015
Can coupled-cluster theory treat conical intersections? journal July 2007
o-, m-, and p-Benzyne Negative Ions in the Gas Phase:  Synthesis, Authentication, and Thermochemistry journal January 1996
Equation of motion coupled cluster method for electron attachment journal March 1995
Structure Optimizations for Excited States with Correlated Second-Order Methods: CC2 and ADC(2) book January 2005
The coupled-cluster revolution journal November 2010
Interpretation of excited states using charge-transfer numbers journal January 1980
Singlet-triplet gaps in diradicals by the spin-flip approach: A benchmark study journal September 2002
New and Efficient Implementation of CC3 journal December 2020
Equation-of-Motion Coupled-Cluster Methods for Open-Shell and Electronically Excited Species: The Hitchhiker's Guide to Fock Space journal May 2008
A linear response, coupled-cluster theory for excitation energy journal March 1984
Toward Ultracold Organic Chemistry: Prospects of Laser Cooling Large Organic Molecules journal July 2020
On the extent of spin contamination in open‐shell coupled‐cluster wave functions journal July 1994
Coupled-cluster theory for excited electronic states: The full equation-of-motion coupled-cluster single, double, and triple excitation method journal November 2001
A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques journal September 2014
From orbitals to observables and back journal August 2020
New tools for the systematic analysis and visualization of electronic excitations. I. Formalism journal July 2014
Spin-orbit couplings within the equation-of-motion coupled-cluster framework: Theory, implementation, and benchmark calculations journal August 2015
The Dalton quantum chemistry program system: The Dalton program
  • Aidas, Kestutis; Angeli, Celestino; Bak, Keld L.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 3 https://doi.org/10.1002/wcms.1172
journal September 2013
The equation of motion coupled‐cluster method. A systematic biorthogonal approach to molecular excitation energies, transition probabilities, and excited state properties journal May 1993
Electronic structure and bonding of ozone journal August 2008
An Orbital Invariant Similarity Constrained Coupled Cluster Model journal September 2019
New tools for the systematic analysis and visualization of electronic excitations. II. Applications journal July 2014
Mapping the Excited State Potential Energy Surface of a Retinal Chromophore Model with Multireference and Equation-of-Motion Coupled-Cluster Methods journal September 2013
Spin-contamination of coupled-cluster wave functions journal October 2000
Excited state coupled cluster methods: Excited state coupled cluster methods journal November 2011
Spin adapted restricted Hartree–Fock reference coupled cluster theory for open shell systems journal March 1994
Equation-of-motion coupled-cluster theory for double electron attachment with spin–orbit coupling journal December 2020
Equation-of-motion spin-flip coupled-cluster model with single and double substitutions: Theory and application to cyclobutadiene journal January 2004
Structures and vibrational frequencies in the full configuration interaction limit: Predictions for four electronic states of methylene using a triple-zeta plus double polarization (TZ2P) basis journal January 1998
Spin-restricted open-shell coupled-cluster theory journal December 1997
Application of transition density matrix for analysis of excited states journal January 1976
Identification of the C̃ State of Ammonia by Electron Impact Spectroscopy journal March 1971
Structure, vibrational frequencies, ionization energies, and photoelectron spectrum of the para-benzyne radical anion journal May 2007
Triplet excitation energies in full configuration interaction and coupled-cluster theory journal August 2001
A Mountaineering Strategy to Excited States: Highly Accurate Reference Energies and Benchmarks journal June 2018
Q-Chem: an engine for innovation: Q-Chem: an engine for innovation journal November 2012
The spin–flip approach within time-dependent density functional theory: Theory and applications to diradicals journal March 2003
Crossing conditions in coupled cluster theory journal October 2017
Excited States of Butadiene to Chemical Accuracy: Reconciling Theory and Experiment journal September 2012
Static polarizabilities for excited states within the spin-conserving and spin-flipping equation-of-motion coupled-cluster singles and doubles formalism: Theory, implementation, and benchmarks journal November 2016
General framework for calculating spin–orbit couplings using spinless one-particle density matrices: Theory and application to the equation-of-motion coupled-cluster wave functions journal July 2019
Two Cycling Centers in One Molecule: Communication by Through-Bond Interactions and Entanglement of the Unpaired Electrons journal January 2020
General formulation of spin-flip time-dependent density functional theory using non-collinear kernels: Theory, implementation, and benchmarks journal May 2012
Coupled-cluster theory and its equation-of-motion extensions: Coupled-cluster theory journal July 2011
The inclusion of connected triple excitations in the equation‐of‐motion coupled‐cluster method journal August 1994
Electronic structure of the trimethylenemethane diradical in its ground and electronically excited states: Bonding, equilibrium geometries, and vibrational frequencies journal April 2003
A noniterative perturbative triples correction for the spin-flipping and spin-conserving equation-of-motion coupled-cluster methods with single and double substitutions journal November 2008
Ultraviolet Photoelectron Spectroscopy of the o -, m -, and p- Benzyne Negative Ions. Electron Affinities and Singlet−Triplet Splittings for o -, m -, and p -Benzyne journal June 1998
Analysis of Excitonic and Charge Transfer Interactions from Quantum Chemical Calculations journal July 2012
Energies and analytic gradients for a coupled-cluster doubles model using variational Brueckner orbitals: Application to symmetry breaking in O4+ journal September 1998
Shape of Multireference, Equation-of-Motion Coupled-Cluster, and Density Functional Theory Potential Energy Surfaces at a Conical Intersection journal June 2014

Similar Records

Extension of frozen natural orbital approximation to open-shell references: Theory, implementation, and application to single-molecule magnets
Journal Article · Tue Jan 21 00:00:00 EST 2020 · Journal of Chemical Physics · OSTI ID:1852700
Two-photon absorption cross sections within equation-of-motion coupled-cluster formalism using resolution-of-the-identity and Cholesky decomposition representations: Theory, implementation, and benchmarks
Journal Article · Sat Feb 14 00:00:00 EST 2015 · Journal of Chemical Physics · OSTI ID:1852700
Systematic design of active spaces for multi-reference calculations of singlet–triplet gaps of organic diradicals, with benchmarks against doubly electron-attached coupled-cluster data
Journal Article · Tue Oct 31 00:00:00 EDT 2017 · Journal of Chemical Physics · OSTI ID:1852700
+3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Rydberg states
density-matrix
non-adiabatic molecular dynamics
free radicals
molecular properties
excitation energies
excited states
Fock space coupled cluster
spectroscopy
coupled-cluster methods