Fermi-Löwdin orbital self-interaction correction using the optimized effective potential method within the Krieger-Li-Iafrate approximation

Abstract

Perdew-Zunger self-interaction correction (PZ-SIC) offers a route to remove self-interaction errors on an orbital-by-orbital basis. A recent formulation of PZ-SIC by Pederson, Ruzsinszky and Perdew proposes restricting the unitary transformation to localized orbitals called Fermi-Löwdin orbitals. This formulation, called the FLOSIC method, simplifies PZ-SIC calculations and was implemented self-consistently using a Jacobi-like (FLOSIC-Jacobi) iteration scheme. In this work we implement the FLOSIC approach using the Krieger-Li-Iafrate (KLI) approximation to the optimized effective potential (OEP). We compare the results of present FLOSIC-KLI approach with FLOSIC-Jacobi scheme for atomic energies, atomization energies, ionization energies, barrier heights, polarizability of chains of hydrogen molecules etc. to validate the FLOSIC-KLI approach. The FLOSIC-KLI approach, which is within the realm of Kohn-Sham theory, predicts smaller energy gaps between frontier orbitals due to the lowering of eigenvalues of the lowest unoccupied orbitals. Results show that atomic energies, atomization energies, ionization energy as an absolute of highest occupied orbital eigenvalue, and polarizability of chains of hydrogen molecules between the two methods agree within 2%. Finally the FLOSIC-KLI approach is used to determine the vertical ionization energies of water clusters.

33 pages, 7 figures

References in corpus (15)

• Localization and delocalization errors in density functional theory and implications for band-gap prediction
• Fractional charge perspective on the band-gap in density-functional theory
• Libxc: a library of exchange and correlation functionals for density functional theory
• Koopmans-compliant functionals and their performance against reference molecular data
• Fermi Orbital Derivatives in Self-Interaction Corrected Density Functional Theory: Applications to Closed Shell Atoms
• Electrical response of molecular systems: the power of self-interaction corrected Kohn-Sham theory
• A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction
• Stretched or noded orbital densities and self-interaction correction in density functional theory
• Importance of self-interaction-error removal in density functional calculations on water cluster anions
• On derivatives of the energy with respect to total electron number and orbital occupation numbers. A critique of Janak's theorem
• Improvements in the orbitalwise scaling down of Perdew-Zunger self-interaction correction in many-electron regions
• Self-interaction correction in the LDA+U method
• An improved exchange-correlation potential for polarizability and dissociation in DFT
• Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations
• Implementation of Perdew-Zunger self-interaction correction in real space using Fermi-Löwdin orbitals

Cited by in corpus (4)

• Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods
• Spin-state Gaps and Self-Interaction-Corrected Density Functional Approximations: Octahedral Fe(II) Complexes as Case Study
• Self-consistent implementation of locally scaled self-interaction-correction method
• Study of Self-Interaction Errors in Density Functional Calculations of Magnetic Exchange Coupling Constants Using Three Self-Interaction Correction Methods