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

@article{Becke1992DensityfunctionalTI, title={Density-functional thermochemistry. I. The effect of the exchange-only gradient correction}, author={Axel D. Becke}, journal={Journal of Chemical Physics}, year={1992}, volume={96}, pages={2155-2160} }

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 approximations gives remarkably good molecular bond and atomization energies. In the present communication, we report the results of an extensive survey of density‐functional atomization energies on the 55 molecules of the Gaussian‐1 thermochemical data base of Pople and co‐workers [J. Chem. Phys. 90, 5622…

## 1,619 Citations

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. III. The role of exact exchange

- Chemistry
- 1993

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…

Structure of the ammonia dimer studied by density functional theory

- Chemistry
- 1994

Self-consistent Kohn–Sham density functional calculations have been carried out to study the structure of the ammonia dimer. The local-density approximation yields unusually large binding energy and…

On the accuracy of gradient corrected density functional methods for transition metal complexes

- Chemistry
- 1995

Density functional theory with gradient corrections (DFTG) is applied to a series of second‐row transition metal compounds. The mean absolute deviations from experiment for the atomic excitation…

Immediate estimation of correlation energy for molecular systems from the partial charges on atoms in the molecule

- Chemistry
- 1997

Abstract In the author's previous work (Chem. Phys. Lett. 247 (1995) 101 and Chem. Phys. Lett. 256 (1996) 229) a simple quasi-linear relationship was introduced between the number of electrons, N,…

Density functional study of the bonding in small silicon clusters

- Chemistry
- 1992

We report the ground electronic state, equilibrium geometry, vibrational frequencies, and binding energy for various isomers of Sin(n = 2–8) obtained with the linear combination of atomic…

‘‘Ab initio’’ liquid water

- Chemistry
- 1993

An ab initio molecular dynamics simulation of liquid water has been performed using density functional theory in the Kohn–Sham formulation and a plane wave basis set to determine the electronic…

Ab initio calculations of thermochemical properties of methanol clusters.

- Chemistry, MedicineThe journal of physical chemistry. A
- 2013

The results demonstrate that thermochemical methanol cluster properties can nowadays be obtained by ab initio methods with an accuracy comparable to or even better than that of the experimental data available, especially for larger species that cannot be studied directly by experiments.

Density functional calculations on first‐row transition metals

- Chemistry, Physics
- 1994

The excitation energies and ionization potentials of the atoms in the first transition series are notoriously difficult to compute accurately. Errors in calculated excitation energies can range from…

Variation of parameters in Becke‐3 hybrid exchange‐correlation functional

- Chemistry
- 2000

We have investigated the consequences of varying the three parameters in Becke's hybrid exchange‐correlation functional, which includes five contributions: Hartree–Fock exchange, local exchange,…

## References

SHOWING 1-10 OF 27 REFERENCES

The influence of self‐consistency on nonlocal density functional calculations

- Chemistry
- 1991

A self‐consistent nonlocal density functional method (NL‐SCF) based on the gradient corrected exchange term by Becke [Phys. Rev. A 33, 2786(1988)] and a gradient corrected correlation term by Perdew…

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,…

Density Functional Calculations of Molecular Bond Energies

- Chemistry
- 1986

The calculation of molecular bond energies is a sensitive test of exchange‐correlation approximations in density functional theory. The well known local density approximation (LDA) gives excellent…

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…

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…

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.

- Physics, MedicinePhysical review. B, Condensed matter
- 1988

Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.

Density-functional approximation for the correlation energy of the inhomogeneous electron gas.

- Physics, MedicinePhysical review. B, Condensed matter
- 1986

Numerical results for atoms, positive ions, and surfaces are close to the exact correlation energies, with major improvements over the original LM approximation for the ions and surfaces.

Correlation energies in the spin-density functional formalism

- Physics, Chemistry
- 1980

It has been shown recently that dynamical correlation effects can be adequately described by using an electron-gas expression for correlation between electrons of different spins. In this paper the…

On the large‐gradient behavior of the density functional exchange energy

- Chemistry
- 1986

A coordinate‐space model of the exchange hole density, previously introduced by the author, is extrapolated to the case of very strongly inhomogeneous systems (i.e., large density gradients). As a…

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis

- Physics
- 1980

We assess various approximate forms for the correlation energy per particle of the spin-polarized homogeneous electron gas that have frequently been used in applications of the local spin density…