Simplification of the Fermi–Löwdin Self‐Interaction Correction Method for Efficient Self‐Interaction‐Free Density Functional Calculations

Fermi-Löwdin orbital self-interaction-correction (FLOSIC) method uses symmetric orthogonalized Fermi orbitals as localized orbitals in one-electron SIC schemes. In FLOSIC, a set of Fermi orbital descriptors (FOD) defines the FLOs and is obtained by energy minimization. Determination of optimal FODs is a computationally very demanding task. Herein, simplification of the FLOSIC calculations by removing self-interaction error from a set of selected orbitals of interest (SOSIC) is proposed. This approach is illustrated by choosing a set of valence orbitals as active orbitals. The results of a wide range of properties obtained using the valence SOSIC (vSOSIC) scheme are compared against the Perdew-Zunger SIC results. The two methods agree within a few percent for the majority of the properties. The mean absolute error in the vertical detachment energy of water cluster anions with vSOSIC-Perdew-Burke-Ernzerhof (PBE) against benchmark CCSD(T) results is only 15 meV making vSOSIC-PBE an excellent alternative to the CCSD(T) for the case. The calculation on the [Cu <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msub><mml:mrow></mml:mrow> <mml:mn>2</mml:mn></mml:msub> </mml:mrow> <mml:annotation>$_{2}$</mml:annotation></mml:semantics> </mml:math> Cl <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msub><mml:mrow></mml:mrow> <mml:mn>6</mml:mn></mml:msub> </mml:mrow> <mml:annotation>$_{6}$</mml:annotation></mml:semantics> </mml:math> ]^2- complex demonstrates that the FOD optimization in vSOSIC is substantially smoother and faster. Assessment of the performance of SIC-r <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msup><mml:mrow></mml:mrow> <mml:mn>2</mml:mn></mml:msup> </mml:mrow> <mml:annotation>$^{2}$</mml:annotation></mml:semantics> </mml:math> SCAN shows that it performs similarly to the SIC-Strongly Constrained and Appropriately Normed functional (SCAN) for most properties, but for atomization energies, SIC-r <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msup><mml:mrow></mml:mrow> <mml:mn>2</mml:mn></mml:msup> </mml:mrow> <mml:annotation>$^{2}$</mml:annotation></mml:semantics> </mml:math> SCAN outperforms SIC-SCAN.