Range-separated double-hybrid density-functional theory with coupled-cluster and random-phase approximations.

Abstract

We construct range-separated double-hybrid (RSDH) schemes which combine coupled-cluster or random-phase approximations (RPAs) with a density functional based on a two-parameter Coulomb-attenuating-method-like decomposition of the electron-electron interaction. We find that the addition of a fraction of short-range electron-electron interaction in the wave-function part of the calculation is globally beneficial for the RSDH scheme involving a variant of the RPA with exchange terms. Even though the latter scheme is globally as accurate as the corresponding scheme employing only second-order Møller-Plesset perturbation theory for atomization energies, reaction barrier heights, and weak intermolecular interactions of small molecules, it is more accurate for the more complicated case of the benzene dimer in the stacked configuration. The present RSDH scheme employing a RPA thus represents a new member in the family of double hybrids with minimal empiricism which could be useful for general chemical applications.