Exploring the random phase approximation: Application to CO adsorbed on Cu(111)

Xinguo Ren, Patrick Rinke, Matthias Scheffler

Research output: Contribution to journalArticlepeer-review

156 Scopus citations

Abstract

The adsorption of CO on the Cu(111) surface is investigated in the random phase approximation (RPA) as formulated within the adiabatic connection fluctuation-dissipation theorem. The RPA adsorption energy is obtained by adding a "local exchange-correlation correction" that is extrapolated from cluster calculations of increasing size, to the Perdew-Burke-Ernzerhof (PBE) value for the extended system. In comparison to density-functional theory calculations with the generalized gradient functionals PBE and AM05 and the hybrid functionals PBE0 and HSE03, we find a hierarchy of improved performance from AM05/PBE to PBE0/HSE03, and from PBE0/HSE03 to RPA, both in terms of the absolute adsorption energy as well as the adsorption-energy difference between the atop and the hollow fcc sites. In particular, the very weak atop site preference at the PBE0/HSE03 level is further stabilized by about 0.2 eV in the RPA. The mechanism behind this improvement is analyzed in terms of the GW density of states that gives a spectral representation en par with the RPA formalism for the total energy.

Original languageEnglish
Article number045402
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume80
Issue number4
DOIs
StatePublished - 6 Aug 2009
Externally publishedYes

Fingerprint

Dive into the research topics of 'Exploring the random phase approximation: Application to CO adsorbed on Cu(111)'. Together they form a unique fingerprint.

Cite this