Electronic screening using a virtual Thomas-Fermi fluid for predicting wetting and phase transitions of ionic liquids at metal surfaces
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 $λ$. We show that this method captures the electrostatic interaction decay and electrochemical behaviour on varying $λ$. By applying this strategy to an ionic liquid, we unveil a wetting transition on switching from insulating to metallic conditions.