TY - JOUR
T1 - Exploring and enhancing the accuracy of interior-scaled Perdew-Zunger self-interaction correction
AU - Bhattarai, Puskar
AU - Santra, Biswajit
AU - Wagle, Kamal
AU - Yamamoto, Yoh
AU - Zope, Rajendra R.
AU - Ruzsinszky, Adrienn
AU - Jackson, Koblar A.
AU - Perdew, John P.
N1 - Funding Information:
This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, as part of the Computational Chemical Sciences Program, under Award No. DESC0018331. The work of P.B. and K.W. was supported by the U.S. National Science Foundation under Grant No. DMR-1939528. This research includes calculations carried out on HPC resources supported, in part, by the National Science Foundation through the Major Research Instrumentation grant (Grant No. 1625061) and by the U.S. Army Research Laboratory under Contract No. W911NF-16-2-0189. A few calculations were carried out on the EFRC cluster supported by the Department of Energy (DOE), Office of Science (OS), Basic Energy Sciences (BES), through Grant No. DESC0012575 to the Energy Frontier Research Center: The Center for Complex Materials from First Principles. The plots are generated by MATPLOTLIB.69
Publisher Copyright:
© 2021 Author(s).
PY - 2021/3/7
Y1 - 2021/3/7
N2 - 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. 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.
AB - 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. 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.
UR - http://www.scopus.com/inward/record.url?scp=85101938712&partnerID=8YFLogxK
U2 - 10.1063/5.0041646
DO - 10.1063/5.0041646
M3 - Article
C2 - 33685179
AN - SCOPUS:85101938712
VL - 154
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 9
M1 - 094105
ER -