Communication

Avoiding unbound anions in density functional calculations

Min Cheol Kim, Eun Ji Sim, Kieron Burke

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

Converged approximate density functional calculations usually do not bind anions due to large self-interaction error. But Hartree-Fock (HF) calculations have no such problem, producing negative HOMO energies. Thus, electron affinities can be calculated from density functional total energy differences using approximations such as PBE and B3LYP, evaluated on HF densities (for both anion and neutral). This recently proposed scheme is shown to work very well for molecules, better than the common practice of restricting the basis set except for cases such as CN, where the HF density is too inaccurate due to spin contamination.

Original languageEnglish
Article number171103
JournalJournal of Chemical Physics
Volume134
Issue number17
DOIs
Publication statusPublished - 2011 May 7

Fingerprint

Density functional theory
Anions
communication
anions
Electron affinity
Communication
Contamination
Molecules
electron affinity
contamination
energy
approximation
molecules
interactions

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

@article{6ba3b1fa344a444b999e5280fe554c0c,
title = "Communication: Avoiding unbound anions in density functional calculations",
abstract = "Converged approximate density functional calculations usually do not bind anions due to large self-interaction error. But Hartree-Fock (HF) calculations have no such problem, producing negative HOMO energies. Thus, electron affinities can be calculated from density functional total energy differences using approximations such as PBE and B3LYP, evaluated on HF densities (for both anion and neutral). This recently proposed scheme is shown to work very well for molecules, better than the common practice of restricting the basis set except for cases such as CN, where the HF density is too inaccurate due to spin contamination.",
author = "Kim, {Min Cheol} and Sim, {Eun Ji} and Kieron Burke",
year = "2011",
month = "5",
day = "7",
doi = "10.1063/1.3590364",
language = "English",
volume = "134",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "17",

}

Communication : Avoiding unbound anions in density functional calculations. / Kim, Min Cheol; Sim, Eun Ji; Burke, Kieron.

In: Journal of Chemical Physics, Vol. 134, No. 17, 171103, 07.05.2011.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Communication

T2 - Avoiding unbound anions in density functional calculations

AU - Kim, Min Cheol

AU - Sim, Eun Ji

AU - Burke, Kieron

PY - 2011/5/7

Y1 - 2011/5/7

N2 - Converged approximate density functional calculations usually do not bind anions due to large self-interaction error. But Hartree-Fock (HF) calculations have no such problem, producing negative HOMO energies. Thus, electron affinities can be calculated from density functional total energy differences using approximations such as PBE and B3LYP, evaluated on HF densities (for both anion and neutral). This recently proposed scheme is shown to work very well for molecules, better than the common practice of restricting the basis set except for cases such as CN, where the HF density is too inaccurate due to spin contamination.

AB - Converged approximate density functional calculations usually do not bind anions due to large self-interaction error. But Hartree-Fock (HF) calculations have no such problem, producing negative HOMO energies. Thus, electron affinities can be calculated from density functional total energy differences using approximations such as PBE and B3LYP, evaluated on HF densities (for both anion and neutral). This recently proposed scheme is shown to work very well for molecules, better than the common practice of restricting the basis set except for cases such as CN, where the HF density is too inaccurate due to spin contamination.

UR - http://www.scopus.com/inward/record.url?scp=79957450163&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79957450163&partnerID=8YFLogxK

U2 - 10.1063/1.3590364

DO - 10.1063/1.3590364

M3 - Article

VL - 134

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 17

M1 - 171103

ER -