title: Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules.
abstract: Density functional theory calculations are often used to interpret experimental shifts in core level binding energies. Calculations based on gradient-corrected (GC) exchange-correlation functionals are known to reproduce measured core level shifts (CLS) of isolated molecules and metal surfaces with reasonable accuracy. In the present study, we discuss a series of examples where the shifts calculated within a GC-functional significantly deviate from the experimental values, namely the CLS of C 1s in ethyl trifluoroacetate, Pd 3d in PdO and the O 1s shift for CO adsorbed on PdO(101). The deviations are traced to effects of the electronic self-interaction error with GC-functionals and substantially better agreements between calculated and measured CLS are obtained when a fraction of exact exchange is used in the exchange-correlation functional.
authors: Department of Applied Physics and Competence Centre for Catalysis, Chalmers University of Technology, Göteborg, Sweden.
authors: M
authors: M
authors: Van den Bossche
authors: Division of Synchrotron Radiation Research, Lund University, Lund, Sweden.
authors: N M
authors: NM
authors: Martin
authors: Division of Synchrotron Radiation Research, Lund University, Lund, Sweden.
authors: J
authors: J
authors: Gustafson
authors: Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611, USA.
authors: C
authors: C
authors: Hakanoglu
authors: Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611, USA.
authors: J F
authors: JF
authors: Weaver
authors: Division of Synchrotron Radiation Research, Lund University, Lund, Sweden.
authors: E
authors: E
authors: Lundgren
authors: Department of Applied Physics and Competence Centre for Catalysis, Chalmers University of Technology, Göteborg, Sweden.
authors: H
authors: H
authors: Grönbeck