Accurately predicting electron affinities with Koopmans spectral functionals

ORAL

Abstract

Density functional theory (DFT) is a popular method for electronic-structure calculations. But while Kohn-Sham eigenvalues can loosely mirror experimental quasiparticle energies, there is formally no connection between the two (except for the HOMO in exact DFT). Furthermore, the presence of self-interaction errors in semi-local DFT can make those eigenvalues an even poorer proxy for quasiparticle energies [1].

This talk will discuss Koopmans spectral functionals, an efficient approach for recovering spectral properties in a beyond-DFT formulation at very little additional computational cost [2-4]. They have already been shown to lead to accurate molecular ionization potentials [5], and I will present the latest results, including accurate predictions of molecular electron affinities in the GW100 set [6].

[1] Cohen et al., Science, 321, 792 (2008).
[2] Dabo et al., Phys. Rev. B, 82, 115121 (2010).
[3] Borghi et al., Phys. Rev. B 90, 075135 (2014).
[4] Nguyen et al., Phys. Rev. X, 8, 021051 (2018).
[5] Colonna et al., J. Chem. Theory Comput., 15, 1905 (2019).
[6] van Setten et al., J. Chem. Theory Comput., 11, 5565 (2015).

*We gratefully acknowledge financial support from the Swiss National Science Foundation through the MARVEL National Centre for Competency in Research.

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Presenters

  • Edward Linscott

    • École Polytechnique Fédérale de Lausanne

Authors

  • Edward Linscott

    • École Polytechnique Fédérale de Lausanne

  • Nicola Colonna

    • Paul Scherrer Institut
    • Paul Scherrer Institut (PSI)
    • Laboratory for Neutron Scattering and Imaging, and National Center for Computational Design and Discovery of Novel Materials (MARVEL), Paul Scherrer Institute (PSI)

  • Riccardo De Gennaro

    • École Polytechnique Fédérale de Lausanne
    • École Polytechnique Fédérale de Lausanne (EPFL)
    • Theory and Simulations of Materials (THEOS), and National Center for Computational Design and Discovery of Novel Materials (MARVEL), Ecole Polytechnique Federale de Lausanne

  • Nicola Marzari

    • Ecole Polytechnique Federale de Lausanne
    • Theory and Simulation of Materials (THEOS), and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), Ecole Polytechnique Federale de Lausanne
    • École Polytechnique Fédérale de Lausanne
    • Theory and Simulation of Materials (THEOS), and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), Ecole Polytechnique Federale de Lausanne,
    • Theory and Simulation of Materials (THEOS), Faculté des Sciences et Techniques de l’Ingénieur, École Polytechnique Fédérale de Lausanne
    • THEOS, EPFL
    • École Polytechnique Fédérale de Lausanne (EPFL)
    • Theory and Simulation of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne (E
    • Theory and Simulation of Materials (THEOS), and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), EPFL, CH-1015 Lausanne, Switzerland
    • Theory and simulation of materials (THEOS), National Centre for Computational Design and Discovery of Novel Materials (MARVEL), EPFL
    • Materials Engineering, EPFL
    • Theory and Simulations of Materials (THEOS), and National Center for Computational Design and Discovery of Novel Materials (MARVEL), Ecole Polytechnique Federale de Lausanne