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@ARTICLE{Kullgren:835108,
author = {Kullgren, Jolla and Wolf, Matthew J. and Mitev, Pavlin D.
and Hermansson, Kersti and Briels, Willem},
title = {{DFT}-based {M}onte {C}arlo {S}imulations of {I}mpurity
{C}lustering at {C}e{O} 2 (111)},
journal = {The journal of physical chemistry / C},
volume = {121},
number = {28},
issn = {1932-7455},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2017-04976},
pages = {15127 - 15134},
year = {2017},
abstract = {The interplay between energetics and entropy in determining
defect distributions at ceria(111) is studied using a
combination of DFT+U and lattice Monte Carlo simulations.
Our main example is fluorine impurities, although we also
present preliminary results for surface hydroxyl groups. A
simple classical force-field model was constructed from a
training set of DFT+U data for all symmetrically
inequivalent (F−)n(Ce3+)n nearest-neighbor clusters with n
= 2 or 3. Our fitted model reproduces the DFT energies well.
We find that for an impurity concentration of $15\%$ at 600
K, straight and hooked linear fluorine clusters are
surprisingly abundant, with similarities to experimental STM
images from the literature. We also find that with
increasing temperature the fluorine cluster sizes show a
transition from being governed by an attractive potential to
being governed by a repulsive potential as a consequence of
the increasing importance of the entropy of the Ce3+ ions.
The distributions of surface hydroxyl groups are noticeably
different.},
cin = {ICS-3},
ddc = {540},
cid = {I:(DE-Juel1)ICS-3-20110106},
pnm = {551 - Functional Macromolecules and Complexes (POF3-551)},
pid = {G:(DE-HGF)POF3-551},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000406355700016},
doi = {10.1021/acs.jpcc.7b00299},
url = {https://juser.fz-juelich.de/record/835108},
}