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Title: Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction

Abstract

The static electric dipole polarizability of a system is a measure of the binding of its electrons. In density functional theory calculations, this binding is weakened by the presence of unphysical self-interaction in the density functional approximation (DFA), leading to overestimates of polarizabilities. In this work, to investigate this systematically we compare polarizabilities for the atoms from H to Ar and their anions and cations calculated in several DFAs and the corresponding self-interaction-corrected (SIC) DFAs with experiment and with high-level quantum chemistry reference values. The SIC results are obtained using the Fermi-Löwdin orbital self-interaction correction (FLO-SIC) method. Removing self-interaction generally leads to smaller polarizabilities that agree significantly better with reference values. In conclusion, we find that FLO-SIC improves the performance of the local spin density approximation and the generalized gradient approximation (GGA) for polarizabilities to a quality that is comparable to so-called rung 4 functionals, but slightly degrades the performance of the strongly constrained and appropriately normed meta-GGA functional.

Authors:
 [1];  [2];  [3];  [1];  [2];  [2];  [2];  [2];  [3];  [1];  [1]
  1. Central Michigan Univ., Mount Pleasant, MI (United States)
  2. Univ. of Texas, El Paso, TX (United States)
  3. Temple Univ., Philadelphia, PA (United States)
Publication Date:
Research Org.:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
Central Michigan University, the University of Texas at El Paso, Temple University, NERSC, the Texas Advanced Computing Center, and the Michigan State University High Performance Computing Center
OSTI Identifier:
1532407
Alternate Identifier(s):
OSTI ID: 1546377
Grant/Contract Number:  
SC0018331; SC0012575; SC0006818; SC0002168
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review A
Additional Journal Information:
Journal Volume: 100; Journal Issue: 1; Journal ID: ISSN 2469-9926
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; self-interaction correction; density functional theory; polarizability

Citation Formats

Withanage, Kushantha P. K., Akter, Sharmin, Shahi, Chandra, Joshi, Rajendra P., Diaz, Carlos, Yamamoto, Yoh, Zope, Rajendra, Baruah, Tunna, Perdew, John P., Peralta, Juan E., and Jackson, Koblar A. Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction. United States: N. p., 2019. Web. doi:10.1103/PhysRevA.100.012505.
Withanage, Kushantha P. K., Akter, Sharmin, Shahi, Chandra, Joshi, Rajendra P., Diaz, Carlos, Yamamoto, Yoh, Zope, Rajendra, Baruah, Tunna, Perdew, John P., Peralta, Juan E., & Jackson, Koblar A. Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction. United States. doi:10.1103/PhysRevA.100.012505.
Withanage, Kushantha P. K., Akter, Sharmin, Shahi, Chandra, Joshi, Rajendra P., Diaz, Carlos, Yamamoto, Yoh, Zope, Rajendra, Baruah, Tunna, Perdew, John P., Peralta, Juan E., and Jackson, Koblar A. Mon . "Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction". United States. doi:10.1103/PhysRevA.100.012505. https://www.osti.gov/servlets/purl/1532407.
@article{osti_1532407,
title = {Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction},
author = {Withanage, Kushantha P. K. and Akter, Sharmin and Shahi, Chandra and Joshi, Rajendra P. and Diaz, Carlos and Yamamoto, Yoh and Zope, Rajendra and Baruah, Tunna and Perdew, John P. and Peralta, Juan E. and Jackson, Koblar A.},
abstractNote = {The static electric dipole polarizability of a system is a measure of the binding of its electrons. In density functional theory calculations, this binding is weakened by the presence of unphysical self-interaction in the density functional approximation (DFA), leading to overestimates of polarizabilities. In this work, to investigate this systematically we compare polarizabilities for the atoms from H to Ar and their anions and cations calculated in several DFAs and the corresponding self-interaction-corrected (SIC) DFAs with experiment and with high-level quantum chemistry reference values. The SIC results are obtained using the Fermi-Löwdin orbital self-interaction correction (FLO-SIC) method. Removing self-interaction generally leads to smaller polarizabilities that agree significantly better with reference values. In conclusion, we find that FLO-SIC improves the performance of the local spin density approximation and the generalized gradient approximation (GGA) for polarizabilities to a quality that is comparable to so-called rung 4 functionals, but slightly degrades the performance of the strongly constrained and appropriately normed meta-GGA functional.},
doi = {10.1103/PhysRevA.100.012505},
journal = {Physical Review A},
number = 1,
volume = 100,
place = {United States},
year = {2019},
month = {7}
}

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