Long-range-corrected multiconfiguration density functional with the on-top pair density.

Abstract

We propose a multiconfiguration density functional combining a short-range density functional approximation with a novel long-range correction for dynamic correlation effects. The correction is derived from the adiabatic connection formalism so that the resulting functional requires access only to one- and two-electron reduced density matrices of the system. In practice, the functional is formulated for wavefunctions of the complete active space (CAS) type and the short-range density functional part is made dependent on the on-top pair density via auxiliary spin densities. The latter allows for reducing the self-interaction and the static correlation errors without breaking the spin symmetry. We study the properties and the performance of the non-self-consistent variant of the method, termed lrAC0-postCAS. Numerical demonstration on a set of dissociation energy curves and excitation energies shows that lrAC0-postCAS provides accuracy comparable with more computationally expensive ab initio rivals.