Assessment of correlation energies based on the random-phase approximation

By Joachim A. Paier, Xinguo Ren, Patrick Rinke, Gustavo E. Scuseria, Andreas Grueneis, Georg Kresse, Matthias Scheffler. 2011

143 citations recorded by the source corpus.

The random-phase approximation to the ground state correlation energy (RPA) in combination with exact exchange (EX) has brought the Kohn–Sham (KS) density functional theory one step closer towards a universal, ‘general purpose first-principles method’. In an effort to systematically assess the influence of several correlation energy contributions beyond RPA, this paper presents dissociation energies of small molecules and solids, activation energies for hydrogen transfer and non-hydrogen transfer reactions, as well as reaction energies for a number of common test sets. We benchmark EX + RPA and several flavors of energy functionals going beyond it: second-order screened exchange (SOSEX), single-excitation (SE) corrections, renormalized single-excitation (rSE) corrections and their combinations. Both the SE correction and the SOSEX contribution to the correlation energy significantly improve on the notorious tendency of EX + RPA to underbind. Surprisingly, activation energies obtained using EX + RPA based on a KS reference alone are remarkably accurate. RPA + SOSEX + rSE provides an equal level of accuracy for reaction as well as activation energies and overall gives the most balanced performance, because of which it can be applied to a wide range of systems and chemical reactions.

Subfields: Atomic and Molecular Physics, and Optics, Materials Chemistry

View Paper: https://www.semanticscholar.org/paper/31f67939e0967a589d22a3a8f081de01bfaada86

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In Atomic and Molecular Physics, and Optics

In Materials Chemistry

Citations in the corpus

The GW approximation: content, successes and limitations (2018, unknown): “(46) with δΣxc/δn ! 0) is depicted in Figure 5.”
Resolution-of-identity approach to Hartree–Fock, hybrid density functionals, RPA, MP2 and GW with numeric atom-centered orbital basis functions (2012, background): “, meta-GGAs [11, 12, 13], formalisms to include van der Waals interactions [14, 15, 16, 17, 18, 19], hybrid functionals [20, 21, 22, 23, 24], or the randomphase approximation (RPA) based approaches [25, 26] that deal with the non-local correlations in a more systematical and non-empirical way.”