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research article

Koopmans-Compliant Functionals and Potentials and Their Application to the GW100 Test Set

Colonna, Nicola  
•
Ngoc Linh Nguyen  
•
Ferretti, Andrea
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March 1, 2019
Journal of Chemical Theory and Computation

Koopmans-compliant (KC) functionals have been shown to provide accurate spectral properties through a generalized condition of piecewise 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 a large and standardized set of 100 molecules, the GW100 test set, comparing vertical ionization potentials (taken as opposite of the orbital energies) to those obtained from accurate quantum chemistry methods, and to experimental results. We find excellent agreement, with a mean absolute error of 0.20 eV for the KIPZ functional on the first ionization potential, which is state-of-the-art for both density functional theory (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 Green's function methods, both from a theoretical and from a practical point of view, arguing that KC potentials can be considered as local and orbital-dependent approximations to the electronic self-energy, already including approximate vertex corrections.

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Type
research article
DOI
10.1021/acs.jctc.8b00976
Web of Science ID

WOS:000461533000036

Author(s)
Colonna, Nicola  
Ngoc Linh Nguyen  
Ferretti, Andrea
Marzari, Nicola  
Date Issued

2019-03-01

Publisher

AMER CHEMICAL SOC

Published in
Journal of Chemical Theory and Computation
Volume

15

Issue

3

Start page

1905

End page

1914

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

self-interaction correction

•

ab-initio

•

orbital energies

•

greens-function

•

density

•

semiconductors

•

ionization

•

approximation

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
THEOS  
Available on Infoscience
June 18, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/157622
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