Title: Shrinking Self-Interaction Errors with the Fermi–Löwdin Orbital Self-Interaction-Corrected Density Functional Approximation

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
ORCiD logo [1];  [2]; ORCiD logo [3];  [3];  [3];  [4];  [4]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]
  1. Central Michigan Univ., Mount Pleasant, MI (United States); Central Michigan University
  2. Univ. of Pittsburgh, PA (United States)
  3. Central Michigan Univ., Mount Pleasant, MI (United States)
  4. Univ. of Texas at El Paso, TX (United States)
+ Show Author Affiliations

The self-interaction error (SIE) is one of the major drawbacks of practical exchange-correlation functionals for Kohn-Sham density functional theory. Despite this, the use of methods that explicitly remove SIE from approximate density functionals is scarce in the literature due to their relatively high computational cost and lack of consistent improvement over standard modern functionals. Here, we assess the performance of a novel approach recently proposed by Pederson, Ruzsinszky, and Perdew for performing self-interaction free calculations in density functional theory based on Fermi-orbitals. To this end, we employ test sets consisting of reaction energies that are considered particularly sensitive to SIE. We found that the parameter-free Fermi-Löwdin orbital self-interaction correction method combined with standard local spin density approximation (LSDA) and Perdew-Burke-Ernzerhof (PBE) functionals gives a much better estimate of reaction energies compared to their parent LSDA and PBE functionals for most of the reactions in these two sets. They also perform on par with the global PBE0 and range-separated LC-ωPBE hybrids, which partially eliminate the SIE by including Hartree-Fock exchange. This shows the potential of the Fermi-Löwdin orbital self-interaction corrected (FLOSIC) method for practical density functional calculations without SIE.

Research Organization:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; SC0018331
OSTI ID:
1781806
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 48 Vol. 122; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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A step in the direction of resolving the paradox of Perdew–Zunger self-interaction correction. II. Gauge consistency of the energy density at three levels of approximation journal June 2020
Emerging DFT Methods and Their Importance for Challenging Molecular Systems with Orbital Degeneracy journal November 2019
Self-Interaction Correction in Water-Ion Clusters text January 2020
Importance of self-interaction-error removal in density functional calculations on water cluster anions journal January 2020
Fermi-Löwdin orbital self-interaction correction using the strongly constrained and appropriately normed meta-GGA functional journal October 2019
A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction journal December 2019
Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction journal July 2019
Importance of self-interaction-error removal in density functional calculations on water cluster anions text January 2020

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