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The approximate second order coupled-cluster method based on a size-consistent Brillouin–Wigner partitioning

Journal Article · · The Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0286872· OSTI ID:2997852
 [1];  [2];  [3]
  1. University of California, Berkeley, CA (United States)
  2. University of California, Berkeley, CA (United States); Ruprecht-Karls University, Heidelberg (Germany)
  3. University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations
We present a variant of the approximate second order coupled-cluster method (CC2) with a two-parameter size-consistent Brillouin–Wigner (BW-s) partitioning instead of a Møller–Plesset (MP) partitioning for the unperturbed Hamiltonian, which we refer to as BWs-CC2. The computational complexity of this model scales identically to CC2 with molecular size. Conventional CC2 and its regularized BWs-CC2 variants, as well as conventional MP2 and two of its regularized BW-s2 variants, were assessed on a 535 element database spanning thermochemistry, non-covalent interactions, barrier heights, and isomerization energies. To ensure a well-defined model chemistry, the assessment was performed using internally stable spin-polarized Hartree–Fock (HF) orbitals in the finite aug-cc-pVQZ basis without counterpoise corrections. As a result of using stable orbitals, contrary to conventional wisdom, we find that CC2 substantially outperforms MP2 on molecules with significantly spin contaminated reference orbitals without a significant increase in error on systems with a spin-pure reference, showing the value of its single substitutions. While no single choice of regularization parameters can be optimal for all datasets, we find that BWs-CC2 generally outperforms both CC2 and BW-s2 with a single judicious parameter choice. Additional tests on dipole moments and bond lengths of diatomics provide further support for the utility of this choice. Furthermore, the main outliers and poorest performing cases are associated with large amounts of spin-contamination in the HF reference, which is indicative of systems with either strong correlation or extensive artificial symmetry breaking. Overall, these findings argue that the perception of the quality of the CC2 ground state should be reevaluated and that it can be further improved upon by the soundly based BWs-CC2 variant with the recommended parameter choice.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
2997852
Journal Information:
The Journal of Chemical Physics, Journal Name: The Journal of Chemical Physics Journal Issue: 12 Vol. 163; ISSN 1089-7690; ISSN 0021-9606
Publisher:
AIP PublishingCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

Correlation energy
Correlation-consistent basis sets
Coupled-cluster methods
Electron correlation calculations
Many body perturbation calculations
Moller-Plesset perturbation theory
Renormalization and regularization
Spin contamination
Thermochemistry
Unrestricted Hartree-Fock