Koopmans-compliant functionals and potentials and their application to the GW100 test-set

TL;DR

Koopmans-compliant functionals accurately predict molecular ionization potentials, showing excellent agreement with high-level methods and experiments, and serve as a local, orbital-dependent alternative to GW self-energy with vertex corrections.

Contribution

This paper evaluates the performance of Koopmans-compliant functionals on the GW100 test set, demonstrating their accuracy and comparing them to other electronic-structure methods.

Findings

KIPZ functional achieves a mean absolute error of 0.20 eV.

Koopmans-compliant potentials are comparable to GW methods.

They can be considered as local, orbital-dependent GW self-energy counterparts.

Abstract

Koopmans-compliant (KC) functionals have been shown to provide accurate spectral properties through a generalized condition of piece-wise linearity of the total energy as a function of the fractional addition/removal of an electron to/from any orbital. We analyze the performance of different KC functionals on the GW100 test-set, comparing the ionization potentials (as opposite of the energy of the highest occupied orbital) of these 100 molecules to those obtained from CCSD(T) total energy differences, and experimental results, finding excellent agreement with a mean absolute error of 0.20 eV for the KIPZ functional, that is state-of-the-art for both DFT-based calculations and many-body perturbation theory. We highlight similarities and differences between KC functionals and other electronic-structure approaches, such as dielectric-dependent hybrid functionals and G$_0$W$_0$, both from a theoretical and from a practical point of view, arguing that Koopmans-compliant potentials can be considered as a local and orbital-dependent counterpart to the electronic GW self-energy, albeit already including approximate vertex corrections.