Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules
- Department of Applied Physics and Competence Centre for Catalysis, Chalmers University of Technology, Göteborg (Sweden)
- Division of Synchrotron Radiation Research, Lund University, Lund (Sweden)
- Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611 (United States)
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.
- OSTI ID:
- 22419901
- Journal Information:
- Journal of Chemical Physics, Vol. 141, Issue 3; Other Information: (c) 2014 Author(s); Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Core Level Shifts of Hydrogenated Pyridinic and Pyrrolic Nitrogen in the Nitrogen-Containing Graphene-Based Electrocatalysts: In-Plane vs Edge Defects
Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons