Simplification of the Fermi-Löwdin Self-Interaction Correction Method for Efficient Self-Interaction-Free Density...

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• The Fermi-Löwdin orbital self-interaction-correction (FLOSIC) method utilizes symmetric orthogonalized Fermi orbitals for localized orbitals in one-electron schemes.
• FLOSIC defines Fermi orbital descriptors (FODs) through energy minimization, a computationally intensive process.
• Accurate calculation of electronic properties is crucial for understanding chemical behavior and designing new materials.

Purpose of the Study:

• To simplify computationally demanding FLOSIC calculations by introducing a selected orbital self-interaction correction (SOSIC) approach.
• To assess the efficiency and accuracy of the valence SOSIC (vSOSIC) scheme by comparing it with the established Perdew-Zunger SIC method.
• To evaluate the performance of SIC-r2SCAN functional against SIC-SCAN and other methods.

Main Methods:

• Implementation of the selected orbital self-interaction correction (SOSIC) method, focusing on valence orbitals (vSOSIC).
• Comparison of vSOSIC results with Perdew-Zunger SIC for a range of molecular properties.
• Calculation of vertical detachment energies for water cluster anions using vSOSIC-PBE and comparison with CCSD(T) benchmarks.
• Assessment of SIC-r2SCAN functional performance against SIC-SCAN.

Main Results:

• vSOSIC calculations show agreement within a few percent with Perdew-Zunger SIC for most properties.
• vSOSIC-PBE demonstrates a mean absolute error of only 15 meV for vertical detachment energies of water cluster anions, rivaling CCSD(T) accuracy.
• FOD optimization in vSOSIC is substantially smoother and faster compared to standard FLOSIC.
• SIC-r2SCAN performs comparably to SIC-SCAN for most properties, but shows superior performance for atomization energies.

Conclusions:

• The vSOSIC approach offers a computationally efficient and accurate alternative to traditional FLOSIC and other high-level methods.
• vSOSIC-PBE is a promising, cost-effective method for calculating electronic properties, particularly for systems like water cluster anions.
• SIC-r2SCAN presents an improved functional for atomization energy calculations within the SIC framework.