Communication: Avoiding unbound anions in density functional calculations

Min Cheol Kim; Eunji Sim; Kieron Burke

doi:10.1063/1.3590364

Communication: Avoiding unbound anions in density functional calculations

Min Cheol Kim, Eunji Sim, Kieron Burke

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

91 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 language	English
Article number	171103
Journal	Journal of Chemical Physics
Volume	134
Issue number	17
DOIs	https://doi.org/10.1063/1.3590364
Publication status	Published - 2011 May 7

Bibliographical note

Funding Information:
We thank Professor Fillip Furche and Dr. Donghyung Lee for fruitful discussions. This work was supported by the global research network (Grant No. NRF-2010-220-C00017) and E.S. acknowledges the support under the national research foundation (Grant Nos. NRF-2010-0016487 and NRF-2010-0017172). K.B. acknowledges support under National Science Foundation (NSF) CHE-0809859 and M-C thanks the fellowship of the BK 21 program from MOEHRD.

All Science Journal Classification (ASJC) codes

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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10.1063/1.3590364

Cite this

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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.",

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Communication: Avoiding unbound anions in density functional calculations

Abstract

Bibliographical note

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