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

TL;DR

This paper introduces an improved orbitalwise scaled down self-interaction correction (OSIC) method for density functional theory, demonstrating enhanced accuracy across various molecular properties and proposing a selective scaling approach (SOSIC) to better preserve physical potential behavior.

Contribution

The paper develops and validates an improved OSIC scheme using the Fermi-L"owdin method with the SCAN functional, and introduces SOSIC for better asymptotic potential behavior.

Findings

OSIC-SCAN outperforms previous OSIC-LSDA, PBE, and TPSS results.

SOSIC maintains proper $-1/r$ potential behavior and yields accurate orbital eigenvalues.

SOSIC provides a more balanced description of energies and barrier heights.

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-L\"owdin 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.