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Cited by 911

The DOI matches its Crossref record; 36 of the 36 references it cites were found in a registry or an index.

Comparison of DFT Methods for Molecular Orbital Eigenvalue Calculations

Zhang, Gang, Musgrave, Charles B.·2007·The Journal of Physical Chemistry A
DOI 10.1021/jp061633o
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Abstract

We report how closely the Kohn-Sham highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) eigenvalues of 11 density functional theory (DFT) functionals, respectively, correspond to the negative ionization potentials (-IPs) and electron affinities (EAs) of a test set of molecules. We also report how accurately the HOMO-LUMO gaps of these methods predict the lowest excitation energies using both time-independent and time-dependent DFT (TD-DFT). The 11 DFT functionals include the local spin density approximation (LSDA), five generalized gradient approximation (GGA) functionals, three hybrid GGA functionals, one hybrid functional, and one hybrid meta GGA functional. We find that the HOMO eigenvalues predicted by KMLYP, BH&HLYP, B3LYP, PW91, PBE, and BLYP predict the -IPs with average absolute errors of 0.73, 1.48, 3.10, 4.27, 4.33, and 4.41 eV, respectively. The LUMOs of all functionals fail to accurately predict the EAs. Although the GGA functionals inaccurately predict both the HOMO and LUMO eigenvalues, they predict the HOMO-LUMO gap relatively accurately (approximately 0.73 eV). On the other hand, the LUMO eigenvalues of the hybrid functionals fail to predict the EA to the extent that they include HF exchange, although increasing HF exchange improves the correspondence between the HOMO eigenvalue and -IP so that the HOMO-LUMO gaps are inaccurately predicted by hybrid DFT functionals. We find that TD-DFT with all functionals accurately predicts the HOMO-LUMO gaps. A linear correlation between the calculated HOMO eigenvalue and the experimental -IP and calculated HOMO-LUMO gap and experimental lowest excitation energy enables us to derive a simple correction formula.

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Metadata

Authors
Zhang, G., & Musgrave, C. B.
Venue
The Journal of Physical Chemistry A
Publisher
American Chemical Society (ACS)
Published
2007-02-06
Volume
111
Issue
8
Pages
1554-1561
ISSN
  • 1089-5639 (ISSN-L)
  • 1520-5215
DOI
10.1021/jp061633o
OpenAlex
W2087520462
Cited by
911
References
36
FWCI
11.00
Type
journal article
Language
en
Open access
closed

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