论文标题

使用虚拟Thomas-Fermi流体进行电子筛选,以预测金属表面上离子液体的润湿和相变

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

论文作者

Schlaich, Alexander, Jin, Dongliang, Bocquet, Lydéric, Coasne, Benoit

论文摘要

与储能,电化学和催化,离子和偶极液体相关,表现出意外的行为,尤其是在限制中。除了吸附,过度筛查和拥挤效果之外,实验还突出了新现象,例如非常规筛选以及电子自然金属与绝缘表面的电子自然金属的影响。挑战现有框架的这种行为强调了需要完全涵盖受限液体特性的工具的必要性。在这里,我们引入了一种新的方法,该方法涉及电子筛选,同时捕获界面流体的分子方面。尽管可用的策略考虑了完美的金属或绝缘体表面,但我们以托马斯 - 弗米形式主义为基础,以开发出一种有效的方法,该方法处理这些渐近线之间的任何不完善的金属。我们的方法通过带电颗粒的“虚拟” Thomas-Fermi流体描述了金属内部的静电相互作用,其debye长度设置了筛选长度$λ$。我们表明,该方法捕获了不同$λ$的静电相互作用衰减和电化学行为。通过将此策略应用于离子液体,我们可以揭示从绝缘条件转换为金属条件的润湿过渡。

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.

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