Self-consistent self-interaction corrected density functional theory calculations for atoms using Fermi-Löwdin...

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Materials Science

Background:

• Density Functional Theory (DFT) often suffers from self-interaction error, impacting accuracy.
• Self-Interaction Correction (SIC) methods aim to mitigate this error.
• The Fermi-Löwdin orbital (FLO) approach offers a way to implement SIC.

Purpose of the Study:

• To present optimized Fermi orbital descriptors (FODs) for atoms Li-Kr within the FLO-SIC framework.
• To demonstrate the efficiency and accuracy of the FLO-SIC method for atomic calculations.
• To analyze the trends and structure of FOD arrangements in relation to atomic properties.

Main Methods:

• Utilized an unbiased search method to determine optimal FOD positions.
• Performed self-consistent Fermi-Löwdin orbital self-interaction correction (FLO-SIC) calculations.
• Analyzed the resulting FOD arrangements and calculated total energies for atoms Li-Kr.

Main Results:

• Optimized FODs for Li-Kr atoms were successfully obtained, revealing a shell structure.
• FOD arrangements showed clear trends correlating with atomic number and principal quantum numbers.
• Calculated FLO-SIC total energies closely matched results from previous constrained SIC methods.

Conclusions:

• The FLO-SIC method provides an efficient and accurate approach for self-interaction correction in DFT.
• Optimized FODs naturally reflect atomic electronic shell structure without explicit constraints.
• FLO-SIC offers a computationally less demanding alternative to traditional constrained SIC methods for atoms.