A multiconfigurational hybrid density-functional theory

Kamal Sharkas, Andreas Savin, Hans Jørgen Aa Jensen, Julien Toulouse

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40 Scopus citations

Abstract

We propose a multiconfigurational hybrid density-functional theory which rigorously combines a multiconfiguration self-consistent-field calculation with a density-functional approximation based on a linear decomposition of the electron-electron interaction. This gives a straightforward extension of the usual hybrid approximations by essentially adding a fraction λ of exact static correlation in addition to the fraction λ of exact exchange. Test calculations on the cycloaddition reactions of ozone with ethylene or acetylene and the dissociation of diatomic molecules with the Perdew-Burke-Ernzerhof and Becke-Lee-Yang-Parr density functionals show that a good value of λ is 0.25, as in the usual hybrid approximations. The results suggest that the proposed multiconfigurational hybrid approximations can improve over usual density-functional calculations for situations with strong static correlation effects.

Original languageEnglish (US)
Pages (from-to)864
Number of pages1
JournalJournal of Chemical Physics
Volume137
Issue number4
DOIs
StatePublished - Jul 28 2012

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