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A static quantum embedding scheme based on coupled cluster theory

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0214065· OSTI ID:2551780
 [1];  [2];  [3];  [4];  [4]
  1. University of California, Berkeley, CA (United States)
  2. Rensselaer Polytechnic Inst., Troy, NY (United States)
  3. University of California, Berkeley, CA (United States); Berkeley Center for Quantum Information and Computation, CA (United States)
  4. University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations
Here, we develop a static quantum embedding scheme that utilizes different levels of approximations to coupled cluster (CC) theory for an active fragment region and its environment. To reduce the computational cost, we solve the local fragment problem using a high-level CC method and address the environment problem with a lower-level Møller–Plesset (MP) perturbative method. This embedding approach inherits many conceptual developments from the hybrid second-order Møller–Plesset (MP2) and CC works by Nooijen [J. Chem. Phys. 111, 10815 (1999)] and Bochevarov and Sherrill [J. Chem. Phys. 122, 234110 (2005)]. We go beyond those works here by primarily targeting a specific localized fragment of a molecule and also introducing an alternative mechanism to relax the environment within this framework. We will call this approach MP-CC. We demonstrate the effectiveness of MP-CC on several potential energy curves and a set of thermochemical reaction energies, using CC with singles and doubles as the fragment solver, and MP2-like treatments of the environment. The results are substantially improved by the inclusion of orbital relaxation in the environment. Using localized bonds as the active fragment, we also report results for N=N bond breaking in azomethane and for the central C–C bond torsion in butadiene. We find that when the fragment Hilbert space size remains fixed (e.g., when determined by an intrinsic atomic orbital approach), the method achieves comparable accuracy with both a small and a large basis set. Additionally, our results indicate that increasing the fragment Hilbert space size systematically enhances the accuracy of observables, approaching the precision of the full CC solver.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-05CH11231; SC0022198; SC0022364
OSTI ID:
2551780
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 161; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (78)

Libcint: An efficient general integral library for Gaussian basis functions journal June 2015
IMOMM: A new integratedab initio + molecular mechanics geometry optimization scheme of equilibrium structures and transition states journal September 1995
P y SCF: the Python-based simulations of chemistry framework : The PySCF program
  • Sun, Qiming; Berkelbach, Timothy C.; Blunt, Nick S.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1 https://doi.org/10.1002/wcms.1340
journal September 2017
Explicitly correlated local coupled-cluster methods using pair natural orbitals journal July 2018
Slow convergence of the møller-plesset perturbation series: the dissociation energy of hydrogen cyanide and the electron affinity of the cyano radical journal July 1987
The second-order approximate coupled cluster singles and doubles model CC2 journal September 1995
Stability conditions and nuclear rotations in the Hartree-Fock theory journal November 1960
W4-11: A high-confidence benchmark dataset for computational thermochemistry derived from first-principles W4 data journal July 2011
Perturbation approach to the fermi gas model of heavy nuclei journal January 1957
Variational Localized Active Space Self-Consistent Field Method journal June 2020
Multilevel CC2 and CCSD in Reduced Orbital Spaces: Electronic Excitations in Large Molecular Systems journal January 2021
Oxidation State Localized Orbitals: A Method for Assigning Oxidation States Using Optimally Fragment-Localized Orbitals and a Fragment Orbital Localization Index journal December 2021
Twenty Years of Auxiliary-Field Quantum Monte Carlo in Quantum Chemistry: An Overview and Assessment on Main Group Chemistry and Bond-Breaking journal October 2022
Effective Reconstruction of Expectation Values from Ab Initio Quantum Embedding journal May 2023
Automatic State Interaction with Large Localized Active Spaces for Multimetallic Systems journal May 2024
Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals journal August 2017
Can Density Matrix Embedding Theory with the Complete Activate Space Self-Consistent Field Solver Describe Single and Double Bond Breaking in Molecular Systems? journal February 2018
Regularized Orbital-Optimized Second-Order Møller–Plesset Perturbation Theory: A Reliable Fifth-Order-Scaling Electron Correlation Model with Orbital Energy Dependent Regularizers journal August 2018
Multiconfigurational Self-Consistent Field Theory with Density Matrix Embedding: The Localized Active Space Self-Consistent Field Method journal November 2018
Coupled Cluster as an Impurity Solver for Green’s Function Embedding Methods journal September 2019
Atom-Based Bootstrap Embedding For Molecules journal October 2019
The ONIOM Method and Its Applications journal April 2015
Density Matrix Embedding: A Strong-Coupling Quantum Embedding Theory journal February 2013
Intrinsic Atomic Orbitals: An Unbiased Bridge between Quantum Theory and Chemical Concepts journal October 2013
Scalable Electron Correlation Methods I.: PNO-LMP2 with Linear Scaling in the Molecular Size and Near-Inverse-Linear Scaling in the Number of Processors journal January 2015
Internal rotation in conjugated molecules: substituted ethylenes and benzenes journal February 1993
High Level ab Initio Energies and Structures for the Rotamers of 1,3-Butadiene journal February 2009
W3 theory: Robust computational thermochemistry in the kJ/mol accuracy range journal March 2004
Coulombic potential energy integrals and approximations journal May 1973
On the Correlation Problem in Atomic and Molecular Systems. Calculation of Wavefunction Components in Ursell‐Type Expansion Using Quantum‐Field Theoretical Methods journal December 1966
HEAT: High accuracy extrapolated ab initio thermochemistry journal December 2004
Hybrid correlation models based on active-space partitioning: Correcting second-order Møller–Plesset perturbation theory for bond-breaking reactions journal June 2005
The correlation consistent composite approach (cc CA ): An alternative to the Gaussian-n methods journal March 2006
Hybrid correlation models based on active-space partitioning: Seeking accurate O(N5) ab initio methods for bond breaking journal August 2006
W4 theory for computational thermochemistry: In pursuit of confident sub-kJ/mol predictions journal October 2006
Linear scaling density fitting journal November 2006
Gaussian-4 theory journal February 2007
Simplified CCSD(T)-F12 methods: Theory and benchmarks journal February 2009
On some approximations in applications of X α theory journal October 1979
On the evaluation of analytic energy derivatives for correlated wave functions journal December 1984
Gaussian‐1 theory: A general procedure for prediction of molecular energies journal May 1989
Coupled cluster energy derivatives. Analytic Hessian for the closed‐shell coupled cluster singles and doubles wave function: Theory and applications journal April 1990
Gaussian‐2 theory for molecular energies of first‐ and second‐row compounds journal June 1991
A direct product decomposition approach for symmetry exploitation in many‐body methods. I. Energy calculations journal March 1991
A state‐selective multireference coupled‐cluster theory employing the single‐reference formalism journal August 1993
State‐selective multireference coupled‐cluster theory employing the single‐reference formalism: Implementation and application to the H 8 model system journal April 1994
Basis-set convergence of correlated calculations on water journal June 1997
An efficient and near linear scaling pair natural orbital based local coupled cluster method journal January 2013
Gaussian-3 (G3) theory for molecules containing first and second-row atoms journal November 1998
Towards standard methods for benchmark quality ab initio thermochemistry—W1 and W2 theory journal August 1999
Combining coupled cluster and perturbation theory journal December 1999
Size-intensive decomposition of orbital energy denominators journal July 2000
Multi-level coupled cluster theory journal December 2014
Sparse maps—A systematic infrastructure for reduced-scaling electronic structure methods. I. An efficient and simple linear scaling local MP2 method that uses an intermediate basis of pair natural orbitals journal July 2015
Reduced-cost linear-response CC2 method based on natural orbitals and natural auxiliary functions journal May 2017
Particle-particle ladder based basis-set corrections applied to atoms and molecules using coupled-cluster theory journal September 2019
Recent developments in the P y SCF program package journal July 2020
Sub-system self-consistency in coupled cluster theory journal February 2023
Sparsity of the electron repulsion integral tensor using different localized virtual orbital representations in local second-order Møller–Plesset theory journal February 2023
Repartitioned Brillouin-Wigner perturbation theory with a size-consistent second-order correlation energy journal June 2023
Accurate torsional potentials in conjugated systems: ab initio and density functional calculations on 1,3-butadiene and monohalogenated butadienes journal April 2004
Towards the intrinsic error of the correlation consistent Composite Approach (ccCA) journal April 2009
Violations of N-representability from spin-unrestricted orbitals in Møller–Plesset perturbation theory and related double-hybrid density functional theory journal April 2009
First-principles calculations of the electronic structure and spectra of strongly correlated systems: dynamical mean-field theory journal September 1997
Ab initio self-energy embedding for the photoemission spectra of NiO and MnO journal August 2020
Investigation of the effective interactions for the Emery model by the constrained random-phase approximation and constrained functional renormalization group journal March 2021
Testing the Green's function coupled cluster singles and doubles impurity solver on real materials within the framework of self-energy embedding theory journal April 2021
Random phase approximation for gapped systems: Role of vertex corrections and applicability of the constrained random phase approximation journal July 2021
Accuracy of ghost rotationally invariant slave-boson and dynamical mean field theory as a function of the impurity-model bath size journal March 2023
Systematically improvable multiscale solver for correlated electron systems journal March 2015
Rotationally invariant slave-boson and density matrix embedding theory: Unified framework and comparative study on the one-dimensional and two-dimensional Hubbard model journal March 2019
Density Matrix Embedding: A Simple Alternative to Dynamical Mean-Field Theory journal November 2012
Ab Initio Full Cell G W + DMFT for Correlated Materials journal April 2021
Systematic Improvability in Quantum Embedding for Real Materials journal March 2022
Dynamical mean-field theory of strongly correlated fermion systems and the limit of infinite dimensions journal January 1996
Electronic structure calculations with dynamical mean-field theory journal August 2006
Systematic electronic structure in the cuprate parent state from quantum many-body simulations journal September 2022
Local Treatment of Electron Correlation journal October 1993

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Correlation energy
Coupled-cluster methods
Density-matrix
Hilbert space
Localized states
Moller-Plesset perturbation theory
Potential energy surfaces
Unrestricted Hartree-Fock