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On a solution of the self-interaction problem in Kohn–Sham density functional theory

Journal Article · · Journal of Physics and Chemistry of Solids
 [1];  [2];  [3];  [3]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations
In this work, we report on a methodology for the treatment of the Coulomb energy and potential in Kohn–Sham density functional theory that is free from self-interaction effects. Specifically, we determine the Coulomb potential given as the functional derivative of the Coulomb energy with respect to the density, where the Coulomb energy is calculated explicitly in terms of the pair density of the Kohn–Sham orbitals. This is accomplished by taking advantage of an orthonormal and complete basis that is an explicit functional of the density that then allows for the functional differentiation of the pair density with respect to the density to be performed explicitly. This approach leads to a new formalism that provides an analytic, closed-form determination of the exchange potential. This method is applied to one-dimensional model systems and to the atoms Helium through Krypton based on an exchange only implementation. Comparison of our total energies (denoted SIF) to those obtained using the usual Hartree–Fock (HF) and optimized effective potential (OEP) methods reveals the hierarchy EHF≤EOEP≤ESIF that is indicative of the greater variation freedom implicit in the former two methods.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Defect Physics in Structural Materials (CDP); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
Grant/Contract Number:
AC05-00OR22725; AC52-07NA27344
OSTI ID:
1737473
Alternate ID(s):
OSTI ID: 1369735
Journal Information:
Journal of Physics and Chemistry of Solids, Journal Name: Journal of Physics and Chemistry of Solids Journal Issue: 10 Vol. 75; ISSN 0022-3697
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Density-functional theory based on the electron distribution on the energy coordinate journal February 2018
Density Functional Theory Based on the Electron Distribution on the Energy Coordinate text January 2016

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Related Subjects

36 MATERIALS SCIENCE
density functional theory
electron correlation
electronic structure theory
exact exchange
exchange energy
exchange potential
local density approximation
self-interaction free