Hybrid functionals including random phase approximation correlation and second-order screened exchange

Autor(en)

Joachim Paier, Benjamin G. Janesko, Thomas M. Henderson, Gustavo E. Scuseria, Andreas Grüneis, Georg Kresse

Abstrakt

There has been considerable recent interest in density functionals incorporating random phase approximation (RPA) ground-state correlation. By virtue of its full nonlocality, RPA correlation is compatible with exact Hartree-Fock-type exchange and describes van der Waals interactions exceptionally well [B. G. Janesko , J. Chem. Phys. 130, 081105 (2009); J. Chem. Phys. 131, 034110 (2009)]. One caveat is that RPA correlation contains one-electron self-interaction error, which leads to disturbingly large correlation energies in the stretched bond situation of, e.g., H-2(+), He-2(+), or Ne-2(+). In the present work, we show that inclusion of second-order screened exchange rectifies the aforementioned failure of RPA correlation. We present a large number of molecular benchmark results obtained using full-range as well as long-range corrected hybrids incorporating second-order screened exchange correlation. This correction has a generally small, and sometimes undesirable, effect on RPA predictions for chemical properties, but appears to be very beneficial for the dissociation of H-2(+), He-2(+), and Ne-2(+).

Organisation(en)

Computergestützte Materialphysik

Externe Organisation(en)

Rice University

Journal

Journal of Chemical Physics

Band

132

Anzahl der Seiten

10

ISSN

0021-9606

DOI

https://doi.org/10.1063/1.3317437

Publikationsdatum

2010

Peer-reviewed

Ja

ÖFOS 2012

103009 Festkörperphysik, 103015 Kondensierte Materie, 103025 Quantenmechanik, 103036 Theoretische Physik

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/f1d9c928-05d2-4f53-bbd1-6c8db61c1b05