# 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…

## 70,386 Citations

Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals

- Chemistry
- 1997

A systematic procedure for refining gradient corrections in Kohn–Sham exchange-correlation functionals is presented. The procedure is based on least-squares fitting to accurate thermochemical data.…

Density‐functional thermochemistry. IV. A new dynamical correlation functional and implications for exact‐exchange mixing

- Chemistry
- 1996

A new dynamical correlation functional is constructed subject to a small number of simple, yet key, requirements not all satisfied by existing functionals in the literature. The new functional gives…

An accurate MGGA-based hybrid exchange-correlation functional

- Chemistry
- 2002

An accurate MGGA-based hybrid exchange-correlation functional is proposed based on Becke’s exact mixing approach. The presented functional makes use of the exact Ex and meta-generalized gradient…

A HYBRID DENSITY FUNCTIONAL STUDY OF THE FIRST-ROW TRANSITION-METAL MONOCARBONYLS

- Chemistry
- 1995

The results of a systematic density functional study, carried out using a self‐consistent hybrid approach including exact exchange contribution, on the all monocarbonyls of first‐row transition…

A unified density-functional treatment of dynamical, nondynamical, and dispersion correlations. II. Thermochemical and kinetic benchmarks.

- Chemistry, MedicineThe Journal of chemical physics
- 2008

The performance of the exact-exchange character of DF07 is highlighted through comparison with a three-parameter hybrid meta-generalized-gradient-approximation functional and gives uniform accuracy over all benchmark data without any refitting of parameters.

Development of density functionals for thermochemical kinetics.

- Chemistry, MedicineThe Journal of chemical physics
- 2004

A density functional theory exchange-correlation functional for the exploration of reaction mechanisms is proposed, which has an accuracy in the 2 kcal/mol range for transition state barriers but, unlike previous attempts, this improved accuracy does not come at the expense of equilibrium properties.

Doubly hybrid density functional for accurate descriptions of nonbond interactions, thermochemistry, and thermochemical kinetics

- Medicine, ChemistryProceedings of the National Academy of Sciences
- 2009

A density functional, XYG3, based on the adiabatic connection formalism and the Görling–Levy coupling-constant perturbation expansion to the second order is developed and validated and is remarkably accurate for thermochemistry, reaction barrier heights, and nonbond interactions of main group molecules.

Can DFT Accurately Predict Spin Densities? Analysis of Discrepancies in Iron Nitrosyl Complexes.

- Medicine, PhysicsJournal of chemical theory and computation
- 2011

This work investigates the origin of different exchange-correlation functionals for the low-spin state of iron nitrosyl complexes by analyzing the Kohn-Sham molecular orbitals and finds that none of the investigated exchange-Correlation functional are able to reproduce the CASSCF spin densities accurately.

Validation of self‐consistent hybrid density functionals for the study of structural and electronic characteristics of organic π radicals

- Chemistry
- 1995

Extensive density functional calculations are reported for the geometrical structures, thermochemistry, infrared, and hyperfine parameters of representative carbon‐centered π radicals. Local…

A thermochemically competitive local hybrid functional without gradient corrections.

- Medicine, ChemistryThe Journal of chemical physics
- 2007

This Lh-SVWN functional provides atomization energies for the G2-1 set that are competitive with currently available state-of-the-art functionals like, e.g., B3LYP.

## 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…

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…

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…

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…

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,…

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…

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

- Physics, MedicinePhysical 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.

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

- Physics, MedicinePhysical 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.

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

- Physics, MedicinePhysical 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.

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…