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Title: Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules

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:
;  [1] ; ; ;  [2] ; ;  [3]
  1. Department of Applied Physics and Competence Centre for Catalysis, Chalmers University of Technology, Göteborg (Sweden)
  2. Division of Synchrotron Radiation Research, Lund University, Lund (Sweden)
  3. Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611 (United States)
Publication Date:
OSTI Identifier:
22419901
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 3; Other Information: (c) 2014 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; CARBON MONOXIDE; DENSITY FUNCTIONAL METHOD; INTERACTIONS; MOLECULES; PALLADIUM OXIDES; SURFACES