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  4. Effects of surface rigidity and metallicity on dielectric properties and ion interactions at aqueous hydrophobic interfaces
 
research article

Effects of surface rigidity and metallicity on dielectric properties and ion interactions at aqueous hydrophobic interfaces

Loche, Philip  
•
Scalfi, Laura
•
Amu, Mustakim Ali
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September 7, 2022
Journal Of Chemical Physics

Using classical molecular dynamics simulations, we investigate the dielectric properties at interfaces of water with graphene, graphite, hexane, and water vapor. For graphite, we compare metallic and nonmetallic versions. At the vapor-liquid water and hexane-water interfaces, the laterally averaged dielectric profiles are significantly broadened due to interfacial roughness and only slightly anisotropic. In contrast, at the rigid graphene surface, the dielectric profiles are strongly anisotropic and the perpendicular dielectric profile exhibits pronounced oscillations and sign changes. The interfacial dielectric excess, characterized by the shift of the dielectric dividing surface with respect to the Gibbs dividing surface, is positive for all surfaces, showing that water has an enhanced dielectric response at hydrophobic surfaces. The dielectric dividing surface positions vary significantly among the different surfaces, which points to pronounced surface-specific dielectric behavior. The interfacial repulsion of a chloride ion is shown to be dominated by electrostatic interactions for the soft fluid-fluid interfaces and by non-electrostatic Lennard-Jones interactions for the rigid graphene-water interface. A linear tensorial dielectric model for the ion-interface interaction with sharp dielectric interfaces located on the dielectric dividing surface positions works well for graphene but fails for vapor and hexane, because these interfaces are smeared out. The repulsion of chloride from the metallic and nonmetallic graphite versions differs very little, which reflects the almost identical interfacial water structure and can be understood based on linear continuum dielectric theory. Interface flexibility shows up mostly in the nonlinear Coulomb part of the ion-interface interaction, which changes significantly close to the interfaces and signals the breakdown of linear dielectric continuum theory.

  • Details
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Type
research article
DOI
10.1063/5.0101509
Web of Science ID

WOS:000874006600005

Author(s)
Loche, Philip  
Scalfi, Laura
Amu, Mustakim Ali
Schullian, Otto
Bonthuis, Douwe J.
Rotenberg, Benjamin
Netz, Roland R.
Date Issued

2022-09-07

Publisher

AIP Publishing

Published in
Journal Of Chemical Physics
Volume

157

Issue

9

Article Number

094707

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

force-field

•

free-energy

•

water

•

hydration

•

adsorption

•

solvation

•

constant

•

profile

•

convergence

•

temperature

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
COSMO  
Available on Infoscience
November 21, 2022
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/192475
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