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@ARTICLE{FernandezAlvarez:872921,
author = {Fernandez-Alvarez, Victor M. and Eikerling, Michael H.},
title = {{I}nterface {P}roperties of the {P}artially {O}xidized
{P}t(111) {S}urface {U}sing {H}ybrid {DFT}–{S}olvation
{M}odels},
journal = {ACS applied materials $\&$ interfaces},
volume = {11},
number = {46},
issn = {1944-8252},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2020-00386},
pages = {43774 - 43780},
year = {2019},
abstract = {This article reports a theoretical–computational effort
to model the interface between an oxidized platinum surface
and aqueous electrolyte. It strives to account for the
impact of the electrode potential, formation of
surface-bound oxygen species, orientational ordering of
near-surface solvent molecules, and metal surface charging
on the potential profile along the normal direction. The
computational scheme is based on the DFT/ESM-RISM method to
simulate the charged Pt(111) surface with varying number of
oxygen adatoms in acidic solution. This hybrid solvation
method is known to qualitatively reproduce bulk metal
properties like the work function. However, the presented
calculations reveal that vital interface properties such as
the electrostatic potential at the outer Helmholtz plane are
highly sensitive to the position of the metal surface slab
relative to the DFT-RISM boundary region. Shifting the
relative position of the slab also affects the free energy
of the system. It follows that there is an optimal distance
for the first solvent layer within the ESM-RISM framework,
which could be found by optimizing the position of the
frozen Pt(111) slab. As it stands, manual sampling of the
position of the slab is impractical and betrays the
self-consistency of the method. Based on this understanding,
we propose the implementation of a free energy optimization
scheme of the relative position of the slab in the DFT-RISM
boundary region. This optimization scheme could considerably
increase the applicability of the hybrid method.},
cin = {IEK-13},
ddc = {600},
cid = {I:(DE-Juel1)IEK-13-20190226},
pnm = {113 - Methods and Concepts for Material Development
(POF3-113)},
pid = {G:(DE-HGF)POF3-113},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:31650835},
UT = {WOS:000499740300096},
doi = {10.1021/acsami.9b16326},
url = {https://juser.fz-juelich.de/record/872921},
}