# Density-functional thermochemistry. III. The role of exact exchange

@article{Becke1993DensityfunctionalTI, title={Density-functional thermochemistry. III. The role of exact exchange}, author={Axel D. Becke}, journal={Journal of Chemical Physics}, year={1993}, volume={98}, pages={5648-5652} }

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… Expand

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#### References

SHOWING 1-10 OF 15 REFERENCES

Density-functional thermochemistry. II: The effect of the Perdew-Wang generalized-gradient correlation correction

- Chemistry
- 1992

In an earlier paper [A. D. Becke, J. Chem. Phys. 96, 2155 (1992)], Kohn–Sham density‐functional calculations of the total atomization energies of the 55 molecules of the Gaussian‐1 database of Pople… Expand

Density-functional thermochemistry. I. The effect of the exchange-only gradient correction

- Chemistry
- 1992

Previous work by the author on diatomic molecules and by others on polyatomic systems has revealed that Kohn–Sham density‐functional theory with ‘‘gradient corrected’’ exchange‐correlation… Expand

Gaussian‐1 theory of molecular energies for second‐row compounds

- Chemistry
- 1990

The Gaussian‐1 theoretical procedure is extended and tested on compounds containing second‐row atoms (Na–Cl). This is a composite procedure based on ab initio molecular orbital theory, utilizing… Expand

An investigation of the performance of a hybrid of Hartree‐Fock and density functional theory

- Chemistry
- 1992

We explore a hybrid methodology in which the Hartree-Fock energy and density are combined with the nonlocal exchange functional of Becke (1988) and the nonlocal correlation functional of Lee, Yang… Expand

Gaussian-2 theory for molecular energies of first- and second-row compounds

- Chemistry
- 1991

The Gaussian‐2 theoretical procedure (G2 theory), based on ab initio molecular orbital theory, for calculation of molecular energies (atomization energies, ionization potentials, electron affinities,… Expand

Gaussian‐1 theory: A general procedure for prediction of molecular energies

- Chemistry
- 1989

A general procedure is developed for the computation of the total energies of molecules at their equilibrium geometries. Ab initio molecular orbital theory is used to calculate electronic energies by… Expand

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation.

- Physics, Medicine
- Physical review. B, Condensed matter
- 1992

A way is found to visualize and understand the nonlocality of exchange and correlation, its origins, and its physical effects as well as significant interconfigurational and interterm errors remain. Expand

Total-energy differences: Sources of error in local-density approximations.

- Physics, Medicine
- Physical review. B, Condensed matter
- 1985

For atoms and small molecules, it is shown that there is a ``natural'' occupancy of orbitals for which local-density approximations give a satisfactory description of the exchange energy, and for other occupancies the relative errors are usually large. Expand

Density-functional exchange-energy approximation with correct asymptotic behavior.

- Physics, Medicine
- Physical review. A, General physics
- 1988

This work reports a gradient-corrected exchange-energy functional, containing only one parameter, that fits the exact Hartree-Fock exchange energies of a wide variety of atomic systems with remarkable accuracy, surpassing the performance of previous functionals containing two parameters or more. Expand

The surface energy of a bounded electron gas

- Physics
- 1974

An exact expression for the exchange and correlation energy of an inhomogeneous electron gas, as defined by Hohenberg, Kohn and Sham (1966), is derived. This expression is separated into exchange and… Expand