This Communication presents a unified derivation of three different approximations used in density functional theory (DFT): the Perdew-Zunger self-interaction correction (PZSIC), the Hubbard correction DFT+U, and the Rung 3.5 density functionals. All three approximations can be derived by introducing electron self-interaction into the Kohn-Sham (KS) reference system of noninteracting electrons. The derivation uses the Adiabatic Projection formalism: one projects the electron-electron interaction operator onto certain states, introduces the projected operator into the reference system, and defines a density functional for the remainder. Projecting onto individual localized KS orbitals recovers our previous derivation of the PZSIC [B. G. Janesko, J. Phys. Chem. Lett. 13, 5698-5702 (2022)]. Projecting onto localized atom-centered orbitals recovers a variant of DFT+U. Projecting onto localized states at each point in space recovers Rung 3.5 approaches. New results include an "atomic state PZSIC" that does not require localizing the KS orbitals, a demonstration that typical Hubbard U parameters reproduce a scaled-down PZSIC, and a Rung 3.5 variant of DFT+U that does not require choosing atom-dependent states.
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http://dx.doi.org/10.1063/5.0109338 | DOI Listing |
J Phys Chem A
October 2024
Department of Physics and Engineering Physics, Tulane University, New Orleans, Louisiana 70118, United States.
J Chem Theory Comput
August 2024
Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki, Finland.
The Perdew-Zunger (PZ) self-interaction correction (SIC) is an established tool to correct unphysical behavior in density functional approximations. Yet, the PZ-SIC is well-known to sometimes break molecular symmetries. An example of this is the benzene molecule, for which the PZ-SIC predicts a symmetry-broken electron density and molecular geometry, since the method does not describe the two possible Kekulé structures on an even footing, leading to local minima [Lehtola et al.
View Article and Find Full Text PDFJ Phys Chem A
July 2024
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de La Plata, Consejo Nacional de Investigaciones Científicas y Técnicas, Diag. 113 y 64 (S/N), Sucursal 4, CC 16, 1900 La Plata, Argentina.
We introduce a new method to remove the one-electron self-interaction error in approximate density functional calculations on an orbital-by-orbital basis, as originally proposed by Perdew and Zunger [ , , 5048]. This method is motivated by a recent proposal by Pederson et al. [ , , 121103] to remove self-interaction that employs orbitals derived from the real-space density matrix, known as FLOSIC (Fermi Löwdin orbitals self-interaction correction).
View Article and Find Full Text PDFJ Chem Phys
April 2024
Department of Physics, The University of Texas at El Paso, 500 West University Ave., El Paso, Texas 79968, USA.
Density functional approximations to the exchange-correlation energy can often identify strongly correlated systems and estimate their energetics through energy-minimizing symmetry-breaking. In particular, the binding energy curve of the strongly correlated chromium dimer is described qualitatively by the local spin density approximation (LSDA) and almost quantitatively by the Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA), where the symmetry breaking is antiferromagnetic for both. Here, we show that a full Perdew-Zunger self-interaction-correction (SIC) to LSDA seems to go too far by creating an unphysical symmetry-broken state, with effectively zero magnetic moment but non-zero spin density on each atom, which lies ∼4 eV below the antiferromagnetic solution.
View Article and Find Full Text PDFJ Chem Phys
March 2024
Department of Physics and Science of Advanced Materials PhD Program, Central Michigan University, Mt. Pleasant, Michigan 48859, USA.
Incorporating self-interaction corrections (SIC) significantly improves chemical reaction barrier height predictions made using density functional theory methods. We present a detailed orbital-by-orbital analysis of these corrections for three semi-local density functional approximations (DFAs) situated on the three lowest rungs of Jacob's ladder of approximations. The analysis is based on Fermi-Löwdin Orbital Self-Interaction Correction (FLOSIC) calculations performed at several steps along the reaction pathway from the reactants (R) to the transition state (TS) to the products (P) for four representative reactions selected from the BH76 benchmark set.
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