Shrinking Self-Interaction Errors with the Fermi-Löwdin Orbital Self-Interaction-Corrected Density Functional...

Area of Science:

• Computational Chemistry
• Quantum Mechanics
• Materials Science

Background:

• Self-interaction error (SIE) is a significant limitation in standard Kohn-Sham density functional theory (DFT) approximations.
• Existing methods to correct SIE often incur high computational costs and do not guarantee improved accuracy.

Purpose of the Study:

• To evaluate the effectiveness of a novel Fermi orbital-based self-interaction correction method.
• To assess the performance of this method for calculating reaction energies sensitive to SIE.

Main Methods:

• Utilized the parameter-free Fermi-Löwdin orbital self-interaction correction (FLOSIC) approach.
• Tested the method with Local Spin Density Approximation (LSDA) and Perdew-Burke-Ernzerhof (PBE) functionals.
• Employed reaction energy datasets known to be sensitive to SIE.

Main Results:

• FLOSIC combined with LSDA and PBE functionals yielded more accurate reaction energies compared to the uncorrected functionals.
• The performance of FLOSIC-corrected functionals was comparable to hybrid functionals like PBE0 and LC-ωPBE.
• Demonstrated significant improvement in SIE-affected calculations.

Conclusions:

• The FLOSIC method presents a promising, computationally viable strategy for eliminating SIE in DFT.
• This approach enhances the accuracy of reaction energy predictions, making DFT more reliable for various chemical applications.