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Journal Articles The Journal of Chemical Physics Year : 2012

A multiconfigurational hybrid density-functional theory


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 (PBE) and Becke-Lee-Yang-Parr (BLYP) 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.
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hal-00724033 , version 1 (16-08-2012)



Kamal Sharkas, Andreas Savin, Hans Jørgen Aa. Jensen, Julien Toulouse. A multiconfigurational hybrid density-functional theory. The Journal of Chemical Physics, 2012, 137 (4), pp.044104. ⟨10.1063/1.4733672⟩. ⟨hal-00724033⟩
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