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@ARTICLE{Li:904282,
author = {Li, Peng and Huang, Jun and Hu, Youcheng and Chen, Shengli},
title = {{E}stablishment of the {P}otential of {Z}ero {C}harge of
{M}etals in {A}queous {S}olutions: {D}ifferent {F}aces of
{W}ater {R}evealed by {A}b {I}nitio {M}olecular {D}ynamics
{S}imulations},
journal = {The journal of physical chemistry / C},
volume = {125},
number = {7},
issn = {1932-7447},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2021-05852},
pages = {3972 - 3979},
year = {2021},
note = {Kein Post-print vorhanden},
abstract = {Metal–water interactions are investigated using ab initio
molecular dynamics simulations performed on water-interfaced
Pt(111) and Au(111) as model systems, aiming at
understanding the mechanism of interface water molecules to
regulate the potential of zero charge (PZC) of metal
electrodes in aqueous solutions. Several metal–water
interactions are distinguished, and their effects on the
metal work function (WF) are quantified through carefully
correlating the interfacial atomic and electronic
structures. The first layer of interface water molecules
possesses an O-down configuration and significantly lowers
the metal WF by increasing the near-surface electron density
through Pauli repulsion, coordination bonding, and
subordinate dipole orientation. In contrast, the
H-down-configured water molecules in the second solvation
layer increase the metal WF due to the metal–hydrogen
bonding interaction and dipole orientation. Involved in the
second layer are also water molecules that have no preferred
orientation and merely act as hydrogen bond linkers. They
negligibly affect the electronic structure of metal
electrodes. Introducing chemisorbed hydrogen (Had) with
varying coverages modulates the metal–water interactions,
resulting in a nonmonotonic variation of the metal WF. The
atomic insights obtained not only help to enunciate the
long-standing puzzle of a significant decrease in the PZC of
metal electrodes by solvation but also add to our
understanding of the behaviors of metal–solution
interfaces, for examples, the potential- and
adsorbate-dependent interfacial capacitance.},
cin = {IEK-13},
ddc = {530},
cid = {I:(DE-Juel1)IEK-13-20190226},
pnm = {1231 - Electrochemistry for Hydrogen (POF4-123)},
pid = {G:(DE-HGF)POF4-1231},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000624451700031},
doi = {10.1021/acs.jpcc.0c11089},
url = {https://juser.fz-juelich.de/record/904282},
}