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

Abstract

The Perdew-Zunger self-interaction correction (PZ-SIC) improves the performance of density functional approximations (DFAs) for the properties that involve signi cant self-interaction error (SIE), as in stretched bond situations, but overcorrects for equilibrium properties where SIE is insigni cant. This overcorrection is often reduced by LSIC, local scaling 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 satis es an additional important constraint: the correct coe cient of 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 z , which distinguishes one-electron regions from many-electron regions. LSIC+ applied to LSDA works better for many equilibrium properties than LSDA-LSIC and the Perdew, Burke, and Ernzerhof (PBE) generalized gradient approximation (GGA), and almost as well as the strongly constrained and appropriately normed (SCAN) meta-GGA. LSDA-LSIC and LSDA-LSIC+, however, both 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 amore » 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 LSDA requires a gauge transformation of the functional's energy density. 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.« less

Authors:

Bhattarai, Puskar  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-5613-7028"

Santra, Biswajit  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-3609-2106"

Wagle, Kamal  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-1831-1627"

Yamamoto, Yoh  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-9599-206X"

Zope, Rajendra R.  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-4626-6491"

Ruzsinszky, Adrienn ^[1]; Jackson, Koblar A.  ^[3];

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• Search DOE PAGES for ORCID "0000-0002-5342-7978"

Perdew, John P.  ^[1]

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• Search DOE PAGES for ORCID "0000-0003-4237-824X"

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+ Show Author Affiliations

1. Temple Univ., Philadelphia, PA (United States)
2. Univ. of Texas at El Paso, TX (United States)
3. Central Michigan Univ., Mount Pleasant, MI (United States)

Publication Date:

Mon Mar 01 00:00:00 EST 2021

Research Org.:

Central Michigan Univ., Mount Pleasant, MI (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE

OSTI Identifier:

1770567

Alternate Identifier(s):

OSTI ID: 1768643; OSTI ID: 1781836

Grant/Contract Number:  

SC0018331; DMR-1939528; 1625061; SC0012575

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 154; Journal Issue: 9; 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; Local density approximations; Correlation energy; Self consistent field methods; Density functional theory; Kohn-Sham density functional theory; Chemical bonding; Perdew-Burke-Ernzerhof exchange-correlation density functional; Dissociation energy