Assessment of correlation energies based on the random-phase approximation

Autor(en)

Joachim Paier, Xinguo Ren, Patrick Rinke, Gustavo E. Scuseria, Andreas Grüneis, Georg Kresse, Matthias Scheffler

Abstrakt

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.

Organisation(en)

Computergestützte Materialphysik

Externe Organisation(en)

Center for Computational Materials Science, CMS, Fritz-Haber-Institut der Max-Planck-Gesellschaft, European Theoretical Spectroscopy Facility (ETSF), Rice University

Journal

New Journal of Physics

Band

14

Anzahl der Seiten

23

ISSN

1367-2630

DOI

https://doi.org/10.1088/1367-2630/14/4/043002

Publikationsdatum

2012

Peer-reviewed

Ja

ÖFOS 2012

103018 Materialphysik

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/e1e2ce19-a714-4cd2-86db-8f4da8d88062