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Journal of Chemical Physics / Volume 98 / Issue 7

J. Chem. Phys. 98, 5648 (1993); http://dx.doi.org/10.1063/1.464913 (5 pages)

Density‐functional thermochemistry. III. The role of exact exchange

Axel D. Becke

Department of Chemistry, Queen’s University, Kingston, Ontario, Canada K7L 3N6

(Received 30 October 1992; accepted 16 December 1992)

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 and PACS

Keywords

THERMOCHEMICAL PROCESSES, DENSITY FUNCTIONAL METHOD, EXCHANGE INTERACTIONS, FUNCTIONALS, ATOMIZATION, IONIZATION POTENTIAL, AFFINITY, ATOMS, MOLECULES

PACS

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.464913

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

For access to fully linked references, you need to log in.
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    A. D. Becke, J. Chem. Phys. 96, 2155 (1992JCPSA6000096000003002155000001).

    A. D. Becke, J. Chem. Phys. 97, 9173 (1992JCPSA6000097000012009173000001).

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