Abstract
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 and co-workers [J. Chem. Phys. 90, 5622 (1989); 93, 2537 (1990)] were reported. We found that the local-spin-density exchange-correlation approximation with a ‘‘gradient correction’’ for exchange gave an average deviation from experiment of only 3.7 kcal/mol. In the present work we assess the role of gradient corrections for dynamical correlation, and we enlarge our earlier survey to include 42 atomic and molecular ionization potentials and 8 proton affinities as well. We conclude that gradient corrections for correlation do not improve atomization energies, but are vitally important in electron nonconserving processes such as ionization.
Keywords
ThermochemistryGaussianIonizationDensity functional theoryChemistryAtomic physicsWork (physics)Electronic correlationIonization energyCorrelationProtonLocal-density approximationPhysicsElectronComputational chemistryIonQuantum mechanicsPhysical chemistryMathematics
Affiliated Institutions
Related Publications
Density-functional thermochemistry. III. The role of exact exchange
Despite the remarkable thermochemical accuracy of Kohn–Sham density-functional theories with gradient corrections for exchange-correlation [see, for example, A. D. Becke, J. Che...
Density-functional thermochemistry. I. The effect of the exchange-only gradient correction
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-...
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
Generalized gradient approximations (GGA’s) seek to improve upon the accuracy of the local-spin-density (LSD) approximation in electronic-structure calculations. Perdew and Wang...
Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities
A set of 146 well-established ionization potentials and electron affinities is presented. This set, referred to as the G2 ion test set, includes the 63 atoms and molecules whose...
Effective One-Electron Potential in the Kohn—Sham Molecular Orbital Theory
Density functional theory has received great interest mostly because of the accurate bonding energies and related properties (geometries, force constants) it provides. However, ...
Publication Info
- Year
- 1992
- Type
- article
- Volume
- 97
- Issue
- 12
- Pages
- 9173-9177
- Citations
- 1693
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
1693
OpenAlex
Cite This
Axel D. Becke
(1992).
Density-functional thermochemistry. II. The effect of the Perdew–Wang generalized-gradient correlation correction.
The Journal of Chemical Physics
, 97
(12)
, 9173-9177.
https://doi.org/10.1063/1.463343
Identifiers
- DOI
- 10.1063/1.463343