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.
Skip Nav Destination
Article navigation
1 April 1993
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
Axel D. Becke
Department of Chemistry, Queen’s University, Kingston, Ontario, Canada K7L 3N6
Search for other works by this author on:
J. Chem. Phys. 98, 5648–5652 (1993)
Article history
Received:
October 30 1992
Accepted:
December 16 1992
Citation
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
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Pay-Per-View Access
$40.00
Citing articles via
A theory of pitch for the hydrodynamic properties of molecules, helices, and achiral swimmers at low Reynolds number
Anderson D. S. Duraes, J. Daniel Gezelter
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
Electronic structure simulations in the cloud computing environment
Eric J. Bylaska, Ajay Panyala, et al.
Related Content
The gas‐phase thermochemistry of TiH
J. Chem. Phys. (July 1991)
Large-scale calculations of gas phase thermochemistry: Enthalpy of formation, standard entropy, and heat capacity
J. Chem. Phys. (September 2016)
The gas‐phase thermochemistry of FeH
J. Chem. Phys. (February 1991)
Diagnostic tool to reveal students’ conception on thermochemistry
AIP Conference Proceedings (March 2021)
Gas‐phase thermochemistry of VH and CrH
J. Chem. Phys. (March 1993)