COUPLING-CONSTANT DEPENDENCE OF ATOMIZATION ENERGIES

@article{Ernzerhof1997COUPLINGCONSTANTDO,
  title={COUPLING-CONSTANT DEPENDENCE OF ATOMIZATION ENERGIES},
  author={Matthias Ernzerhof and John P. Perdew and Kieron Burke},
  journal={International Journal of Quantum Chemistry},
  year={1997},
  volume={64},
  pages={285-295}
}
The local spin-density LSD functional and Perdew)Wang 91 PW91 generalized gradient approximations to atomization energies of molecules are investigated. We discuss the coupling-constant dependence of the atomization energy and why exchange errors of the functionals are greater than exchange)correlation errors. This fact helps to justify hybrid schemes which mix some exact exchange with density functional approximations for exchange and correlation. It is shown that the biggest errors in the… 
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References

SHOWING 1-10 OF 38 REFERENCES
Total-energy differences: Sources of error in local-density approximations.
TLDR
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.
Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism
The aim of this paper is to advocate the usefulness of the spin-density-functional (SDF) formalism. The generalization of the Hohenberg-Kohn-Sham scheme to and SDF formalism is presented in its…
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation.
TLDR
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.
An analysis of nonlocal density functionals in chemical bonding
In this work, we carry out an analysis of the gradient-corrected density functionals in molecules that are used in the Kohn–Sham density functional approach. We concentrate on the special features of…
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. Chem. Phys. 96, 2155…
Exchange functionals and potentials
The commonly used exchange-correlation functionals of density functional theory and their potentials are examined numerically following the first such investigation by Perdew. They are also…
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.
  • Lee, Yang, Parr
  • Physics
    Physical review. B, Condensed matter
  • 1988
TLDR
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.
Rationale for mixing exact exchange with density functional approximations
Density functional approximations for the exchange‐correlation energy EDFAxc of an electronic system are often improved by admixing some exact exchange Ex: Exc≊EDFAxc+(1/n)(Ex−EDFAx). This procedure…
Self-Consistent-Field X α Cluster Method for Polyatomic Molecules and Solids
This paper describes a practical self-consistent-field (SCF) method of calculating electronic energy levels and eigenfunctions, adapted for polyatomic molecules and solids. The one-electron…
Density-functional approximation for the correlation energy of the inhomogeneous electron gas.
  • Perdew
  • Physics
    Physical review. B, Condensed matter
  • 1986
TLDR
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.
...
...