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.
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Research Article| April 01 1993
Density‐functional thermochemistry. III. The role of exact exchange
Special Collection: JCP 90 for 90 Anniversary Collection
Axel D. Becke; Density‐functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1 April 1993; 98 (7): 5648–5652. https://doi.org/10.1063/1.464913
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