Combinations of coupled cluster, density functionals, and the random phase approximation for describing static and dynamic correlation, and van der Waals interactions

ABSTRACT

Contrary to standard coupled cluster doubles (CCD) and Brueckner doubles (BD), singlet-paired analogues of CCD and BD (denoted here as CCD0 and BD0) do not break down when static correlation is present, but neglect substantial amounts of dynamic correlation. In fact, CCD0 and BD0 do not account for any contributions from multielectron excitations involving only same-spin electrons at all. We exploit this feature to add – without introducing double counting, self-interaction, or increase in cost – the missing correlation to these methods via meta-GGA (generalised gradient approximation) density functionals (Tao–Perdew–Staroverov–Scuseria and strongly constrained and appropriately normed). Furthermore, we improve upon these CCD0+DFT blends by invoking range separation: the short- and long-range correlations absent in CCD0/BD0 are evaluated with density functional theory and the direct random phase approximation, respectively. This corrects the description of long-range van der Waals forces. Comprehensive benchmarking shows that the combinations presented here are very accurate for weakly correlated systems, while also providing a reasonable description of strongly correlated problems without resorting to symmetry breaking.

GRAPHICAL ABSTRACT

Keywords:

• Electron correlation
• coupled cluster
• DFT
• RPA
• range separation

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

This work was supported as part of the Center for the Computational Design of Functional Layered Materials, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under Award [# DE-SC0012575].