Electronic screening using a virtual Thomas-Fermi fluid for predicting wetting and phase transitions of ionic liquids at metal surfaces

Abstract

Of relevance to energy storage, electrochemistry and catalysis, ionic and dipolar liquids display unexpected behaviours-especially in confinement. Beyond adsorption, over-screening and crowding effects, experiments have highlighted novel phenomena, such as unconventional screening and the impact of the electronic nature-metallic versus insulating - of the confining surface. Such behaviours, which challenge existing frameworks, highlight the need for tools to fully embrace the properties of confined liquids. Here we introduce a novel approach that involves electronic screening while capturing molecular aspects of interfacial fluids. Although available strategies consider perfect metal or insulator surfaces, we build on the Thomas-Fermi formalism to develop an effective approach that deals with any imperfect metal between these asymptotes. Our approach describes electrostatic interactions within the metal through a 'virtual' Thomas-Fermi fluid of charged particles, whose Debye length sets the screening length $\lambda$. We show that this method captures the electrostatic interaction decay and electrochemical behaviour on varying $\lambda$. By applying this strategy to an ionic liquid, we unveil a wetting transition on switching from insulating to metallic conditions.

References in corpus (7)

• Nanofluidics, from bulk to interfaces
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• The Electrostatic Screening Length in Concentrated Electrolytes Increases with Concentration
• Superionic state in double-layer capacitors with nanoporous electrodes
• Nanoscale capillary freezing of ionic liquids confined between metallic interfaces and the role of electronic screening
• A unified description of hydrophilic and superhydrophobic surfaces in terms of the wetting and drying transitions of liquids
• Simulations of Coulomb systems confined by polarizable surfaces using periodic Green functions

Cited by in corpus (7)

• ELECTRODE: An electrochemistry package for atomistic simulations
• Interaction confinement and electronic screening in two-dimensional nanofluidic channels
• Microscopic origin of the effect of substrate metallicity on interfacial free energies
• Collective modes and quantum effects in two-dimensional nanofluidic channels
• Modulation of ionic conduction using polarizable surfaces
• Coupled interactions at the ionic graphene/water interface
• Brownian dynamics simulations of electric double-layer capacitors with tunable metallicity