Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules
Artikel i vetenskaplig tidskrift, 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

Författare

Maxime van den Bossche

Chalmers, Teknisk fysik, Kemisk fysik

Kompetenscentrum katalys (KCK)

N. M. Martin

Lunds universitet

J. Gustafson

Lunds universitet

C. Hakanoglu

University of Florida

Jason F. Weaver

University of Florida

E. Lundgren

Lunds universitet

Henrik Grönbeck

Chalmers, Teknisk fysik, Kemisk fysik

Kompetenscentrum katalys (KCK)

Journal of Chemical Physics

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

Vol. 141 034706

Styrkeområden

Nanovetenskap och nanoteknik

Transport

Ämneskategorier

Fysik

DOI

10.1063/1.4889919