Energies of organic molecules and atoms in density functional theory

G. Csonka, Adrienn Ruzsinszky, Jianmin Tao, John P. Perdew

Research output: Contribution to journalArticle

59 Citations (Scopus)

Abstract

In the assessment of density functional approximations for the exchange-correlation energy, great weight is usually given to the accuracy of molecular atomization energies, or the enthalpies of formation constructed from calculated atomization energies. Here we show that a recent nonempirical functional, the meta-generalized gradient approximation of Tao, Perdew, Staroverov, and Scuseria, achieves remarkably accurate atomization energies even for the larger organic molecules of the G3-3 test set. But we also present strong evidence that most of the error of previous nonempirical functionals resides in the energy of the free atom and so cancels out of typical reaction energies. Finally, we suggest that enthalpies of formation calculated without any reference to the free atoms would provide a fairer assessment of the performance of approximate density functionals.

Original languageEnglish
Pages (from-to)505-511
Number of pages7
JournalInternational Journal of Quantum Chemistry
Volume101
Issue number5
DOIs
Publication statusPublished - Feb 15 2005

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Atomization
Density functional theory
density functional theory
Atoms
Molecules
Enthalpy
atomizing
atoms
molecules
functionals
energy
enthalpy
approximation
gradients

Keywords

  • Density functional
  • Enthalpies of formation
  • Exchange-correlation energy
  • Meta-generalized gradient approximations
  • Molecular atomization energies

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Energies of organic molecules and atoms in density functional theory. / Csonka, G.; Ruzsinszky, Adrienn; Tao, Jianmin; Perdew, John P.

In: International Journal of Quantum Chemistry, Vol. 101, No. 5, 15.02.2005, p. 505-511.

Research output: Contribution to journalArticle

Csonka, G. ; Ruzsinszky, Adrienn ; Tao, Jianmin ; Perdew, John P. / Energies of organic molecules and atoms in density functional theory. In: International Journal of Quantum Chemistry. 2005 ; Vol. 101, No. 5. pp. 505-511.
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