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

Van den Bossche, M; Martin, Natalia LU ; Gustafson, Johan LU ; Hakanoglu, C; Weaver, J F; Lundgren, Edvin LU and Grönbeck, H (2014) In Journal of Chemical Physics 141(3).
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... (More)
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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
141
issue
3
publisher
American Institute of Physics
external identifiers
  • pmid:25053333
  • wos:000340711300040
  • scopus:84904618642
ISSN
0021-9606
DOI
10.1063/1.4889919
language
English
LU publication?
yes
id
920a6b47-e7bc-4637-a92e-d574dffa43be (old id 4581464)
date added to LUP
2014-09-10 10:22:27
date last changed
2017-11-05 03:11:01
@article{920a6b47-e7bc-4637-a92e-d574dffa43be,
  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.},
  articleno    = {034706},
  author       = {Van den Bossche, M and Martin, Natalia and Gustafson, Johan and Hakanoglu, C and Weaver, J F and Lundgren, Edvin and Grönbeck, H},
  issn         = {0021-9606},
  language     = {eng},
  number       = {3},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules.},
  url          = {http://dx.doi.org/10.1063/1.4889919},
  volume       = {141},
  year         = {2014},
}