Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules
Journal article, 2014

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.

SYSTEMS

AUGMENTED-WAVE METHOD

PHOTOEMISSION

ELECTRON-SPECTROSCOPY

ADSORPTION

SPECTRA

SURFACE

FUNCTIONALS

BASIS-SET

TOTAL-ENERGY CALCULATIONS

Author

Maxime van den Bossche

Chalmers, Applied Physics, Chemical Physics

Competence Centre for Catalysis (KCK)

N. M. Martin

Lund University

J. Gustafson

Lund University

C. Hakanoglu

University of Florida

Jason F. Weaver

University of Florida

E. Lundgren

Lund University

Henrik Grönbeck

Chalmers, Applied Physics, Chemical Physics

Competence Centre for Catalysis (KCK)

Journal of Chemical Physics

0021-9606 (ISSN) 1089-7690 (eISSN)

Vol. 141 3 034706

Areas of Advance

Nanoscience and Nanotechnology (2010-2017)

Transport

Subject Categories

Physical Sciences

DOI

10.1063/1.4889919

More information

Latest update

3/2/2018 9