Two Avenues to Self-Interaction Correction within Kohn-Sham Theory: Unitary Invariance is the Shortcut

Physics – Chemical Physics

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Scientific paper

10.1080/0026897031000094506

The most widely-used density functionals for the exchange-correlation energy are inexact for one-electron systems. Their self-interaction errors can be severe in some applications. The problem is not only to correct the self-interaction error, but to do so in a way that will not violate size-consistency and will not go outside the standard Kohn-Sham density functional theory. The solution via the optimized effective potential (OEP) method will be discussed, first for the Perdew-Zunger self-interaction correction (whose performance for molecules is briefly summarized) and then for the more modern self-interaction corrections based upon unitarily-invariant indicators of iso-orbital regions. For the latter approaches, the OEP construction is greatly simplified. The kinetic-energy-based iso-orbital indicator $\tau^W_\sigma(\re)/\tau_\sigma(\re)$ will be discussed and plotted, along with an alternative exchange-based indicator.

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