Random-phase approximation correlation methods for molecules and solids

Formation energies of group I and II metal oxides using random phase approximation

“…On the other hand, EXX+RPA improves over PBE (shifted) for all three oxidation states. The simultaneous improvement over different oxidation states is in agreement with reports that EXX+RPA scheme work well for a variety of bonding types, including hydrogen, ionic, covalent, vdW and mixed bonds for crystals, molecules and adsorbate on surfaces 5,15,18 . Table IV summarizes the MAEs for the metals with three oxidation states (column 2-4), as well as the overall MAE for group I, II metal oxides (column 5).…”

“…Such a scheme, however, provides a constant shift of the formation energies without taking into account the difference among distinct oxidation states such as oxides (O 2− ), peroxides (O 2− 2 ), superoxides (O − 2 ). Recently, the use of exact exchange (EXX), plus correlation energy from Random Phase Approximation (RPA) has emerged as a promising approach to obtain nonempirical exchange-correlation terms [5][6][7][8][9][10][11] . EXX is free of self-interaction error, while the RPA correlation energy takes into account dynamic electronic screening and is fully non-local.…”

Testing the Jacob's ladder of density functionals for electronic structure and magnetism of rutileVO2

“…In contrast, DFT+U and hybrid or fourth-rung functionals (PBE0 and HSE06) have already been applied to various strongly-correlated transition metal oxides [25,26]. Due to its extremely high computational cost, the RPA has only been applied to realistic systems very recently [27][28][29][30][31][32][33][34][35]. VO 2 is considered as a model system for studying the phase transition involving electron-electron correlation.…”

Topical Review Introduction

“…This paper is co-authored by A. Heßelmann and A. Gorling on the 'Random-phase approximation correlation methods for molecules and solids' [1]. Other recent articles in the same series cover new developments in the quantum theory of reaction rates [2], single molecule surface-enhanced and tipenhanced Raman spectroscopy [3], computer simulation methods for critical phenomena and phase changes [4], relativistic quantum chemistry [5], liquid water [6], gas phase spectroscopy of biomolecules [7], and ultra-cold chemistry [8].…”

“…The random phase approximation (RPA), the topic of Heßelmann and Gorling's review [1], is one present frontier of electronic structure theory. The RPA is an approach that goes beyond standard Kohn-Sham density functional theory (DFT) for treating electron correlations.…”