A molecular perspective on induced charges on a metallic surface

Pireddu, Giovanni; Scalfi, Laura; Rotenberg, Benjamin

doi:10.1063/5.0076127

Cited by 15 publications

(6 citation statements)

References 68 publications

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“…Refs. 15,19,34,[42][43][44][45][46][47], and is illustrated in Fig. 1 for an Au(100)/water interface.…”

Section: Resultsmentioning

confidence: 99%

S.O.S: shape, orientation and size tune solvation in electrocatalysis

serva,

Pezzotti

2023

Preprint

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Current models to understand the reactivity of metal/aqueous interfaces in electrochemistry are based on the adsorption free energies of reactants and products, e.g. volcano plots. Theory, in particular electronic calculations, played a major role in the quantification and comprehension of these free energies in terms of the interactions that the reactive species form with the surface. However, also solvation free energies come into play in two ways: (i) by modulating the adsorption free energy together with solute-surface interactions, as the solute has to penetrate the water adlayer in contact with the surface and get partially desolvated (which costs free energy); (ii) by regulating transport across the interface, i.e. the free energy profile from the bulk to the interface, which is strongly non-monotonic due to the unique nature of metal/aqueous interfaces. Here, we use constant potential Molecular Dynamics to study the solvation contributions and we uncover huge effects of the shape and orientation (on top of the already known size effect) of the solute on its adsorption free energy. We propose a minimal theoretical model, the S.O.S. model, that accounts for size, orientation and shape effects. These novel aspects are rationalized by recasting the concepts at the base of the Lum- Chandler-Weeks theory of solvation into a layer-by-layer form, where the properties of each interfacial region close to the metal are explicitly taken into account.

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“…Refs. 15,19,34,[42][43][44][45][46][47], and is illustrated in Fig. 1 for an Au(100)/water interface.…”

Section: Resultsmentioning

confidence: 99%

S.O.S: shape, orientation and size tune solvation in electrocatalysis

serva,

Pezzotti

2023

Preprint

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“…Several strategies have been used to model induced charges in molecular simulations 38 and to understand how they depend on electrolyte congurations. 135,136 Molecular simulations of nanocapacitors (viz. electrolyte conned between two polarizable electrodes) have been used to estimate electrochemical properties from the uctuations of induced charges, and to understand how they relate to the behaviour of the conned electrolyte.…”

Section: Faraday Discussion Papermentioning

confidence: 99%

Electrical noise in electrolytes: a theoretical perspective

et al. 2023

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“…56 also finds only marginal differences in the water structure on metallic and nonmetallic surfaces, which supports our finding that metallicity is only relevant for ions very close to the surface. 58…”

Section: Articlementioning

confidence: 99%

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

Loche

Scalfi

Amu

et al. 2022

The Journal of Chemical Physics

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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 non-metallic 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 non-metallic 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 non-linear Coulomb part of the ion-interface interaction, which changes significantly close to the interfaces and signals the breakdown of linear dielectric continuum theory.

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A molecular perspective on induced charges on a metallic surface

Abstract: Note: This paper is part of the JCP Special Topic on the Chemical Physics of the Electrode-Electrolyte Interface.

Cited by 15 publications

References 68 publications

S.O.S: shape, orientation and size tune solvation in electrocatalysis

S.O.S: shape, orientation and size tune solvation in electrocatalysis

Electrical noise in electrolytes: a theoretical perspective

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

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