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Exploring and enhancing the accuracy of interior-scaled Perdew–Zunger self-interaction correction

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0041646· OSTI ID:1770567
 [1];  [2];  [2];  [3];  [3];  [2];  [4];  [2]
  1. Temple Univ., Philadelphia, PA (United States); Central Michigan University
  2. Temple Univ., Philadelphia, PA (United States)
  3. Univ. of Texas at El Paso, TX (United States)
  4. Central Michigan Univ., Mount Pleasant, MI (United States)
+ Show Author Affiliations
The Perdew–Zunger self-interaction correction (PZ-SIC) improves the performance of density functional approximations for the properties that involve significant self-interaction error (SIE), as in stretched bond situations, but overcorrects for equilibrium properties where SIE is insignificant. This overcorrection is often reduced by local scaling self-interaction correction (LSIC) of the PZ-SIC to the local spin density approximation (LSDA). Here, we propose a new scaling factor to use in an LSIC-like approach that satisfies an additional important constraint: the correct coefficient of the atomic number Z in the asymptotic expansion of the exchange–correlation (xc) energy for atoms. LSIC and LSIC+ are scaled by functions of the iso-orbital indicator zσ, which distinguishes one-electron regions from many-electron regions. LSIC+ applied to the LSDA works better for many equilibrium properties than LSDA-LSIC and the Perdew, Burke, and Ernzerhof generalized gradient approximation (GGA), and almost close to the strongly constrained and appropriately normed (SCAN) meta-GGA. LSDA-LSIC and LSDA-LSIC+, however, fail to predict interaction energies involving weaker bonds, in sharp contrast to their earlier successes. It is found that more than one set of localized SIC orbitals can yield a nearly degenerate energetic description of the same multiple covalent bond, suggesting that a consistent chemical interpretation of the localized orbitals requires a new way to choose their Fermi orbital descriptors. To make a locally scaled down SIC to functionals beyond the LSDA requires a gauge transformation of the functional’s energy density. Here, the resulting SCAN-sdSIC, evaluated on SCAN-SIC total and localized orbital densities, leads to an acceptable description of many equilibrium properties including the dissociation energies of weak bonds.
Research Organization:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Organization:
U.S. National Science Foundation; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0012575; SC0018331
OSTI ID:
1770567
Alternate ID(s):
OSTI ID: 1768643
OSTI ID: 1781836
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 154; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical bonding
Correlation energy
Density functional theory
Dissociation energy
Kohn-Sham density functional theory
Local density approximations
Perdew-Burke-Ernzerhof exchange-correlation density functional
Self consistent field methods