Abstract
Despite the remarkable thermochemical accuracy of Kohn–Sham density-functional theories with gradient corrections for exchange-correlation [see, for example, A. D. Becke, J. Chem. Phys. 96, 2155 (1992)], we believe that further improvements are unlikely unless exact-exchange information is considered. Arguments to support this view are presented, and a semiempirical exchange-correlation functional containing local-spin-density, gradient, and exact-exchange terms is tested on 56 atomization energies, 42 ionization potentials, 8 proton affinities, and 10 total atomic energies of first- and second-row systems. This functional performs significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
Keywords
ThermochemistryDensity functional theoryChemistryHybrid functionalIonizationOrbital-free density functional theorySpin densityProtonAtomic physicsLocal-density approximationPhysicsComputational chemistryQuantum mechanicsPhysical chemistryIonCondensed matter physics
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Publication Info
- Year
- 1993
- Type
- article
- Volume
- 98
- Issue
- 7
- Pages
- 5648-5652
- Citations
- 100062
- Access
- Closed
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Cite This
Axel D. Becke
(1993).
Density-functional thermochemistry. III. The role of exact exchange.
The Journal of Chemical Physics
, 98
(7)
, 5648-5652.
https://doi.org/10.1063/1.464913
Identifiers
- DOI
- 10.1063/1.464913