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research article

How to polarise an interface with ions: the discrete Helmholtz model

Gschwend, Gregoire C.
•
Olaya, Astrid  
•
Girault, Hubert H.  
October 21, 2020
Chemical Science

The distribution of electrolytes in an electric field usually relies on theories based on the Poisson-Boltzmann formalism. These models predict that, in the case of a metallic electrode, ionic charges screen the electrode potential, leading to concentration-dependent ion distributions. This theoretical framework was first applied at solid-liquid interfaces and then transposed to soft interfaces. However, in this latter case, the potential in which the electrolytes evolve is not homogeneous, which is less amenable to a mean-field description. In this report, we show that at polarised soft interfaces the potential difference takes place between two closely interacting ionic monolayers. In this configuration, ions of opposite charges directly neutralise each other leading to an absence of diffuse layers and charge screening by surrounding ions. Thus, independently of the electrolyte concentrations, the surface charge density is a linear function of the potential difference, which results in a constant capacitance.

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Type
research article
DOI
10.1039/d0sc00685h
Web of Science ID

WOS:000577727000023

Author(s)
Gschwend, Gregoire C.
Olaya, Astrid  
Girault, Hubert H.  
Date Issued

2020-10-21

Published in
Chemical Science
Volume

11

Issue

39

Start page

10807

End page

10813

Subjects

Chemistry, Multidisciplinary

•

Chemistry

•

immiscible electrolyte-solutions

•

molecular-dynamics

•

impedance measurements

•

differential capacity

•

transfer kinetics

•

water

•

distributions

•

simulations

•

gromacs

•

tension

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LEPA  
Available on Infoscience
June 19, 2021
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/178934
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