The density functional approximations are known to suffer from self-interaction error which arises from the incomplete cancellation of self-Coulomb energy by self-exchange energy. The self-interaction correction proposed by Perdew and Zunger [1] corrects for this error through an orbital by orbital scheme. The resulting SI corrected potential for the electrons becomes orbital dependent and the total energy is not unitarily invariant with respect to the orbital transformations. The minimization of the corrected total energy requires finding the set of local orbitals that minimizes the total energy. This is a computationally expensive process. Recent development of Fermi-Löwdin orbital based self-interaction correction scheme by Pederson, Ruzsinszky, and Perdew [2] is a step forward in that energy is unitarily invariant under orbital transformation to localized Fermi-Löwdin orbitals. We show that within the Fermi-Löwdin orbital based self-interaction correction scheme it is possible to derive a single multiplicative Hamiltonian for all orbitals. Implementation of this method, computational costs and the results are discussed.

Mean field Hamiltonian within the Fermi-Löwdin orbital self-interaction correction formalism

ACS Spring 2022

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