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@ARTICLE{Huang:892742,
author = {Huang, Jun and Chen, Shengli and Eikerling, Michael},
title = {{G}rand-{C}anonical {M}odel of {E}lectrochemical {D}ouble
{L}ayers from a {H}ybrid {D}ensity–{P}otential
{F}unctional},
journal = {Journal of chemical theory and computation},
volume = {17},
number = {4},
issn = {1549-9626},
address = {Washington, DC},
reportid = {FZJ-2021-02301},
pages = {2417 - 2430},
year = {2021},
abstract = {A hybrid density–potential functional of an
electrochemical interface that encompasses major effects in
the contacting metal and electrolyte phases is formulated.
Variational analysis of this functional yields a
grand-canonical model of the electrochemical double layer
(EDL). Specifically, metal electrons are described using the
Thomas–Fermi–Dirac–Wigner theory of an inhomogeneous
electron gas. The electrolyte solution is treated
classically at the mean-field level, taking into account
electrostatic interactions, ion size effects, and nonlinear
solvent polarization. The model uses parametrizable force
relations to describe the short-range forces between metal
cationic cores, metal electrons, and electrolyte ions and
solvent molecules. Therefore, the gap between the metal
skeleton and the electrolyte solution, key to properties of
the EDL, varies consistently as a function of the electrode
potential. Partial charge transfer in the presence of ion
specific adsorption is described using an Anderson–Newns
type theory. This model is parametrized with density
functional theory calculations, compared with experimental
data, and then employed to unravel several interfacial
properties of fundamental significance in electrochemistry.
In particular, a closer approach of the solution phase
toward the metal surface, for example, caused by a stronger
ion specific adsorption, decreases the potential of zero
charge and elevates the double-layer capacitance curve. In
addition, the ion specific adsorption can lead to surface
depolarization of ions. The present model represents a
viable framework to model (reactive) EDLs under the constant
potential condition, which can be used to understand
multifaceted EDL effects in electrocatalysis.},
cin = {IEK-13},
ddc = {610},
cid = {I:(DE-Juel1)IEK-13-20190226},
pnm = {123 - Chemische Energieträger (POF4-123)},
pid = {G:(DE-HGF)POF4-123},
typ = {PUB:(DE-HGF)16},
pubmed = {33787259},
UT = {WOS:000640652000034},
doi = {10.1021/acs.jctc.1c00098},
url = {https://juser.fz-juelich.de/record/892742},
}