Accuracy of Electron Affinities of Atoms in Approximate Density Functional Theory

Lee, Dong‐Hyung; Furche, Filipp; Burke, Kieron

doi:10.1021/jz1007033

Cited by 84 publications

(148 citation statements)

References 28 publications

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“…Despite the formal difficulties associated with direct calculations on the anion, the results for all of the atoms in Table 1 are in very good agreement with the experimental values, with a mean absolute error of just 0.18 eV. The accuracy of such estimates using conventional density-functional approximations and basis sets has been discussed widely in the literature 1,[3][4][5][6]8 and is well understood. In addition to the mean and mean absolute errors d and |d|, the linear regression parameters for a correlation plot between the calculated and experimental values, m, c and r 2 are also presented.…”

Section: Resultssupporting

confidence: 57%

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Atomic electron affinities and the role of symmetry between electron addition and subtraction in a corrected Koopmans approach

Teale

Proft

Geerlings

et al. 2014

Phys. Chem. Chem. Phys.

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The essential aspects of zero-temperature grand-canonical ensemble density-functional theory are reviewed in the context of spin-density-functional theory and are used to highlight the assumption of symmetry between electron addition and subtraction that underlies the corrected Koopmans approach of Tozer and De Proft (TDP) for computing electron affinities. The issue of symmetry is then investigated in a systematic study of atomic electron affinities, comparing TDP affinities with those from a conventional Koopmans evaluation and electronic energy differences. Although it cannot compete with affinities determined from energy differences, the TDP expression yields results that are a significant improvement over those from the conventional Koopmans expression. Key insight into the results from both expressions is provided by an analysis of plots of the electronic energy as a function of the number of electrons, which highlight the extent of symmetry between addition and subtraction. The accuracy of the TDP affinities is closely related to the nature of the orbitals involved in the electron addition and subtraction, being particularly poor in cases where there is a change in principal quantum number, but relatively accurate within a single manifold of orbitals. The analysis is then extended to a consideration of the ground state Mulliken electronegativity and chemical hardness. The findings further emphasize the key role of symmetry in determining the quality of the results.

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Section: Resultssupporting

confidence: 57%

“…The calculation of electron affinities remains a challenging and controversial issue for density-functional calculations [1][2][3][4][5][6][7][8][9] . In particular, local and semi-local approximate exchangecorrelation functionals typically provide a poor description of anionic species due to large self-interaction errors (SIEs).…”

Section: Introductionmentioning

confidence: 99%

Atomic electron affinities and the role of symmetry between electron addition and subtraction in a corrected Koopmans approach

Teale

Proft

Geerlings

et al. 2014

Phys. Chem. Chem. Phys.

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“…Thus HF-DFT was used, and found to give comparable (or better) results for atoms and small molecules. In fact, using this method, electron affinities are typically twice as good as ionization potentials with approximate DFT [LB10;LFB10]. It should be used for all anionic DFT calculations in future.…”

Section: B Electron Affinitiesmentioning

confidence: 99%

The Importance of Being Inconsistent

Wasserman

Nafziger

Jiang

et al. 2017

Annu. Rev. Phys. Chem.

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114

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We review the role of self-consistency in density functional theory. We apply a recent analysis to both Kohn-Sham and orbital-free DFT, as well as to Partition-DFT, which generalizes all aspects of standard DFT. In each case, the analysis distinguishes between errors in approximate functionals versus errors in the self-consistent density. This yields insights into the origins of many errors in DFT calculations, especially those often attributed to self-interaction or delocalization error. In many classes of problems, errors can be substantially reduced by using 'better' densities. We review the history of these approaches, many of their applications, and give simple pedagogical examples.

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“…22 Pragmatists will report results with the standard methods, but attach a caveat emptor footnote. 21 The paradox has recently been addressed in several papers, 24,27 which explain how accurate results can come from such unconverged calculations but also suggest an alternative procedure that avoids the dilemma: Evaluate the density functional total energies on Hartree-Fock (HF) densities for both the neutral and anion, and calculate the electron affinity from the total energy difference. We refer to this method as HF-DFT.…”

mentioning

confidence: 99%