Year: 2009
Type: article
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.
Source: Physical Review B
Authors: Xinguo Ren, Patrick Rinke, Matthias Scheffler
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $2,675
OpenAlex ID: W2062820224