Improvements in the orbitalwise scaling down of Perdew-Zunger self-interaction correction in many-electron regions

Abstract

The Perdew-Zunger (PZ) method provides a way to remove the self-interaction (SI) error from density functional approximations on an orbital by orbital basis. The PZ method provides significant improvements for the properties such as barrier heights or dissociation energies but results in over-correcting the properties well described by SI-uncorrected semi-local functional. One cure to rectify the over-correcting tendency is to scale down the magnitude of SI-correction of each orbital in the many electron region. We have implemented the orbitalwise scaled down SI-correction (OSIC) scheme of Vydrov et al. [J. Chem. Phys. 124, 094108 (2006)] using the Fermi-Löwdin SI-correction method. After validating the OSIC implementation with previously reported OSIC-LSDA results, we examine its performance with the most successful non-empirical SCAN meta-GGA functional. Using different forms of scaling factors to identify one-electron regions, we assess the performance of OSIC-SCAN for a wide range of properties: total energies, ionization potentials and electron affinities for atoms, atomization energies, dissociation and reaction energies, and reaction barrier heights of molecules. Our results show that OSIC-SCAN provides superior results than the previously reported OSIC-LSDA, -PBE, and -TPSS results. Furthermore, we propose selective scaling of OSIC (SOSIC) to remove its major shortcoming that destroys the $-1/r$ asymptotic behavior of the potentials. The SOSIC method gives the highest occupied orbital eigenvalues practically identical to those in PZSIC and unlike OSIC provides bound atomic anions even with larger powers of scaling factors. SOSIC compared to PZSIC or OSIC provides more balanced description of total energies and barrier heights.

40 pages, 5 figures

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Cited by in corpus (9)

• 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
• Fermi-Löwdin orbital self-interaction correction using the optimized effective potential method within the Krieger-Li-Iafrate approximation
• Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods
• Exploring and enhancing the accuracy of interior-scaled Perdew-Zunger self-interaction correction
• Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations
• 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
• Implementation of Perdew-Zunger self-interaction correction in real space using Fermi-Löwdin orbitals
• The rise and fall of stretched bond errors: Extending the analysis of Perdew-Zunger self-interaction corrections of reaction barrier heights beyond the LSDA