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

Author(s)
Joachim Paier, Benjamin G. Janesko, Thomas M. Henderson, Gustavo E. Scuseria, Andreas Grüneis, Georg Kresse
Abstract

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(s)
Computational Materials Physics
External organisation(s)
Rice University
Journal
Journal of Chemical Physics
Volume
132
No. of pages
10
ISSN
0021-9606
DOI
https://doi.org/10.1063/1.3317437
Publication date
2010
Peer reviewed
Yes
Austrian Fields of Science 2012
103009 Solid state physics, 103015 Condensed matter, 103025 Quantum mechanics, 103036 Theoretical physics
Portal url
https://ucrisportal.univie.ac.at/en/publications/f1d9c928-05d2-4f53-bbd1-6c8db61c1b05