Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated?

Kurt R. Brorsen, Yang Yang, Michael V. Pak, Sharon Hammes-Schiffer

Research output: Contribution to journalLetter

Abstract

The development of approximate exchange-correlation functionals is critical for modern density functional theory. A recent analysis of atomic systems suggested that some modern functionals are straying from the path toward the exact functional because electron densities are becoming less accurate while energies are becoming more accurate since the year 2000. To investigate this trend for more chemically relevant systems, the electron densities in the bonding regions and the atomization energies are analyzed for a series of diatomic molecules with 90 different functionals. For hybrid generalized gradient approximation functionals developed since the year 2000, the errors in densities and atomization energies are decoupled; the accuracy of the energies remains relatively consistent while the accuracy of the densities varies significantly. Such decoupling is not observed for generalized gradient and meta-generalized gradient approximation functionals. Analysis of electron densities in bonding regions is found to be important for the evaluation of functionals for chemical systems.

Original languageEnglish (US)
Pages (from-to)2076-2081
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume8
Issue number9
DOIs
StatePublished - May 4 2017

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atomizing
Atomization
functionals
Density functional theory
Carrier concentration
density functional theory
gradients
energy
Molecules
diatomic molecules
approximation
decoupling
trends
evaluation

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated? / Brorsen, Kurt R.; Yang, Yang; Pak, Michael V.; Hammes-Schiffer, Sharon.

In: Journal of Physical Chemistry Letters, Vol. 8, No. 9, 04.05.2017, p. 2076-2081.

Research output: Contribution to journalLetter

Brorsen, Kurt R. ; Yang, Yang ; Pak, Michael V. ; Hammes-Schiffer, Sharon. / Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated?. In: Journal of Physical Chemistry Letters. 2017 ; Vol. 8, No. 9. pp. 2076-2081.
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