A multiconfigurational hybrid density-functional theory

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 λof exact static correlation in addition to the fraction λof 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 λis 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.

11 pages, 3 figures, 1 table

References in corpus (4)

• Long-range/short-range separation of the electron-electron interaction in density functional theory
• Van der Waals forces in density functional theory: perturbational long-range electron interaction corrections
• Double-hybrid density-functional theory made rigorous
• Combining Density Functional Theory and Density Matrix Functional Theory

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