Electrical response of molecular systems: the power of self-interaction corrected Kohn-Sham theory

TL;DR

This paper demonstrates that a self-interaction correction within Kohn-Sham theory significantly improves the accuracy of predicting electronic response properties of molecular systems, surpassing traditional methods.

Contribution

It introduces a rigorously implemented self-interaction correction via the OEP method that enhances the predictive accuracy of electronic response properties in molecular systems.

Findings

OEP-SIC yields polarizabilities close to wavefunction-based calculations

OEP-SIC outperforms exact-exchange-OEP in accuracy

Orbital structures with OEP-SIC are effectively analyzed

Abstract

The accurate prediction of electronic response properties of extended molecular systems has been a challenge for conventional, explicit density functionals. We demonstrate that a self-interaction correction implemented rigorously within Kohn-Sham theory via the Optimized Effective Potential (OEP) yields polarizabilities close to the ones from highly accurate wavefunction-based calculations and exceeding the quality of exact-exchange-OEP. The orbital structure obtained with the OEP-SIC functional and approximations to it are discussed.