A multiconfigurational hybrid density-functional theory

作者：Sharkas Kamal^*; Savin Andreas; Jensen Hans Jergen Aa; Toulouse Julien

来源：Journal of Chemical Physics, 2012, 137(4): 044104.

DOI：10.1063/1.4733672

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 lambda of exact static correlation in addition to the fraction lambda 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 lambda 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.

• 出版日期2012-7-28