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  4. Functional Extrapolations to Tame Unbound Anions in Density-Functional Theory Calculations
 
research article

Functional Extrapolations to Tame Unbound Anions in Density-Functional Theory Calculations

Nattino, Francesco  
•
Dupont, Celine
•
Marzari, Nicola  
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November 1, 2019
Journal of Chemical Theory and Computation

Standard flavors of density-functional theory (DFT) calculations are known to fail in describing anions, due to large self-interaction errors. The problem may be circumvented using localized basis sets of reduced size, leaving no variational flexibility for the extra electron to delocalize. Alternatively, a recent approach exploiting DFT evaluations of total energies on electronic densities optimized at the Hartree-Fock (HF) level has been reported, showing that the self-interaction-free HF densities are able to lead to an improved description of the additional electron, returning affinities in close agreement with the experiments. Nonetheless, such an approach can fail when the HF densities are too inaccurate. Here, an alternative approach is presented, in which an embedding environment is used to stabilize the anion in a bound configuration. Similar to the HF case, when computing total energies at the DFT level on these corrected densities, electron affinities in very good agreement with experiments can be recovered. The effect of the environment can be evaluated and removed by an extrapolation of the results to the limit of vanishing embedding. Apart from the definition of the domain of the embedding potential, the approach is free from parameters and it can be easily applied to DFT calculations with delocalized basis sets, e.g., plane waves, for which alternative approaches are either not viable or more computationally demanding. The proposed extrapolation strategy can be thus applied also to extended systems, as often studied in condensed-matter physics and materials science, and we illustrate how the embedding environment can be exploited to determine the energy of an adsorbing anion, here a chloride ion on a metal surface, whose charge configuration would be incorrectly predicted by standard density functionals.

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Type
research article
DOI
10.1021/acs.jctc.9b00552
Web of Science ID

WOS:000497260300041

Author(s)
Nattino, Francesco  
Dupont, Celine
Marzari, Nicola  
Andreussi, Oliviero
Date Issued

2019-11-01

Publisher

AMER CHEMICAL SOC

Published in
Journal of Chemical Theory and Computation
Volume

15

Issue

11

Start page

6313

End page

6322

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

electron-affinities

•

molecular-dynamics

•

force-field

•

approximation

•

energies

•

atoms

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
THEOS  
Available on Infoscience
December 4, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/163542
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