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

2015/09/10 by Alejandro J. Garza, Ireneusz W. Bulik, Ana G. Sousa Alencar +3
Mathematics · Physics and Astronomy · #Advanced Chemical Physics Studies #Advanced Condensed Matter Physics #Cluster (spacecraft) #Computer science #Correlation #Coupled cluster #Electron #Electronic correlation #Excited state #Materials science #Mathematics #Molecule #Phase (matter) #Physics #Quantum mechanics #Random phase approximation #Range (aeronautics) #Singlet state #Spectroscopy and Quantum Chemical Studies #Statistical physics #Symmetry (geometry) #physics.chem-ph #van der Waals force

paper · pdf · doi:10.1080/00268976.2015.1123315

18 pages, 5 figures

arxiv created 2015/09/10 · openalex publication_date 2015/12/21 · arxiv updated 2016/05/04 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

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.

Citations

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