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@ARTICLE{Huang:917504,
author = {Huang, Jun},
title = {{Z}ooming into the {I}nner {H}elmholtz {P}lane of
{P}t(111)-{A}queous {S}olution {I}nterfaces: {C}hemisorbed
{W}ater and {P}artially-{C}harged {I}ons},
journal = {JACS Au},
volume = {3},
number = {2},
issn = {2691-3704},
address = {Washington, DC},
publisher = {ACS Publications},
reportid = {FZJ-2023-00717},
pages = {550-564},
year = {2023},
abstract = {The double layer on transition metals, i.e., platinum,
features chemical metal–solvent interactions and partially
charged chemisorbed ions. Chemically adsorbed solvent
molecules and ions are situated closer to the metal surface
than electrostatically adsorbed ions. This effect is
described tersely by the concept of an inner Helmholtz plane
(IHP) in classical double layer models. The IHP concept is
extended here in three aspects. First, a refined statistical
treatment of solvent (water) molecules considers a
continuous spectrum of orientational polarizable states,
rather than a few representative states, and
non-electrostatic, chemical metal–solvent interactions.
Second, chemisorbed ions are partially charged, rather than
being electroneutral or having integral charges as in the
solution bulk, with the coverage determined by a
generalized, energetically distributed adsorption isotherm.
The surface dipole moment induced by partially charged,
chemisorbed ions is considered. Third, considering different
locations and properties of chemisorbed ions and solvent
molecules, the IHP is divided into two planes, namely, an
AIP (adsorbed ion plane) and ASP (adsorbed solvent plane).
The model is used to study how the partially charged AIP and
polarizable ASP lead to intriguing double-layer capacitance
curves that are different from what the conventional
Gouy–Chapman–Stern model describes. The model provides
an alternative interpretation for recent capacitance data of
Pt(111)–aqueous solution interfaces calculated from cyclic
voltammetry. This revisit brings forth questions regarding
the existence of a pure double-layer region at realistic
Pt(111). The implications, limitations, and possible
experimental confirmation of the present model are
discussed.},
cin = {IEK-13},
ddc = {540},
cid = {I:(DE-Juel1)IEK-13-20190226},
pnm = {1215 - Simulations, Theory, Optics, and Analytics (STOA)
(POF4-121)},
pid = {G:(DE-HGF)POF4-1215},
typ = {PUB:(DE-HGF)16},
pubmed = {36873696},
UT = {WOS:000923981500001},
doi = {10.1021/jacsau.2c00650},
url = {https://juser.fz-juelich.de/record/917504},
}