Implementation of Perdew-Zunger self-interaction correction in real space using Fermi-Löwdin orbitals

Abstract

Most widely used density functional approximations suffer from self-interaction (SI) error, which can be corrected using the Perdew-Zunger (PZ) self-interaction correction (SIC). We implement the recently proposed size-extensive formulation of PZ-SIC using Fermi-Löwdin Orbitals (FLOs) in real space, which is amenable to systematic convergence and large-scale parallelization. We verify the new formulation within the generalized Slater scheme by computing atomization energies and ionization potentials of selected molecules and comparing to those obtained by existing FLOSIC implementations in Gaussian based codes. The results show good agreement between the two formulations, with new real-space results somewhat closer to experiment on average for the systems considered. We also obtain the ionization potentials and atomization energies by scaling down the Slater statistical average of SIC potentials. The results show that scaling down the average SIC potential improves both atomization energies and ionization potentials, bringing them closer to experiment. Finally, we verify the present formulation by calculating the barrier heights of chemical reactions in the BH6 dataset, where significant improvements are obtained relative to Gaussian based FLOSIC results.

12 pages, 5 figures

References in corpus (13)

• Libxc: a library of exchange and correlation functionals for density functional theory
• Parallel Self-Consistent-Field Calculations via Chebyshev-Filtered Subspace Acceleration
• Fermi Orbital Derivatives in Self-Interaction Corrected Density Functional Theory: Applications to Closed Shell Atoms
• A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction
• Electrical response of molecular systems: the power of self-interaction corrected Kohn-Sham theory
• A self-interaction-free local hybrid functional: Accurate binding energies vis-à-vis accurate ionization potentials from Kohn-Sham eigenvalues
• Stretched or noded orbital densities and self-interaction correction in density functional theory
• Time-dependent density-functional theory with self-interaction correction
• Augmented Lagrangian formulation of Orbital-Free Density Functional Theory
• Importance of self-interaction-error removal in density functional calculations on water cluster anions
• Improvements in the orbitalwise scaling down of Perdew-Zunger self-interaction correction in many-electron regions
• On preconditioning the self-consistent field iteration in real-space Density Functional Theory
• Improved Slater approximation to SIC-OEP

Cited by in corpus (4)

• Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods
• Fermi-Löwdin orbital self-interaction correction using the optimized effective potential method within the Krieger-Li-Iafrate approximation
• 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