DOCSIC: A Mean-Field Method for Orbital-by-Orbital Self-Interaction Correction.

Abstract

We introduce a new method to remove the one-electron self-interaction error in approximate density functional calculations on an orbital-by-orbital basis, as originally proposed by Perdew and Zunger [Phys. Rev. B 1981, 23, 5048]. This method is motivated by a recent proposal by Pederson et al. [J. Chem. Phys. 2014, 140, 121103] to remove self-interaction that employs orbitals derived from the real-space density matrix, known as FLOSIC (Fermi Löwdin orbitals self-interaction correction). However, instead of Fermi Löwdin orbitals, our scheme utilizes columns of the density matrix to determine localized orbitals, like the localization procedure proposed by Fuemmeler et al. [J. Chem. Theory Comput. 2023, 19, 8572]. The new method, dubbed DOCSIC for density matrix as orbital coefficients self-interaction correction, contrasts with traditional Perdew-Zunger or FLOSIC in that it does not incorporate additional optimization parameters, and, unlike the average density self-interaction correction of Ciofini et al. [Chem. Phys. Lett. 2003, 380, 12], it makes use of localized orbitals. Another advantage of DOCSIC is that it can be implemented as a mean-field formalism. We show details of the self-consistent generalized Kohn-Sham implementation, some illustrative results, and we finally highlight its advantages and limitations.