强迫自由：双电层中离子液体离子的电场诱导去簇
Enforced freedom: electric-field-induced declustering of ionic-liquid ions in the double layer
摘要：
尽管在无溶剂离子液体的本体中的大多数离子结合成簇，但预期这在双电层（EDL）中改变，其中所得的电场“偏好”与无电双电层的未成簇的离子相互作用。离子保持成簇状态的倾向与自由状态下电场中离子能量的降低之间的竞争决定了EDL中自由离子的所得部分。我们提出了一个研究这种影响，基于最简单的可能平均场论。离子团簇在电场中“裂解”成单个离子的过程伴随着离子液体介电响应的变化，这种变化在团簇状态和非团簇状态下是不同的。理论的预测进行了验证，并通过专门执行的分子动力学模拟进一步探讨。该理论的一个特别发现是，尽管自由载流子的浓度低，微分电容对电势曲线显示钟形，因为结合离子的介电响应降低了钟形到骆驼形转变的阈值浓度。虽然定性这些发现是完全有意义的，但实际上，确切的数字和标准可能不同，因为所提出的简单理论没有考虑过屏蔽和振荡电荷以及电极附近的静电势分布。这就是为什么用计算机模拟来测试理论是必不可少的，但后者基本上再现了理论的定性结论。
英文摘要：
Whereas the majority of ions in the bulk of a solvent-free ionic liquid is bound into clusters, this is expected to change in the electrical double layer (EDL), in which the resulting electric field 'prefers' to interact with electrical monopoles-free, unclustered ions. The competition between the propensity of ions to stay in a clustered state and the reduction of the energy of ions in electric field in the free state determines the resulting portion of free ions in the EDL. We present a study of this effect, based on the simplest possible mean-field theory. 'Cracking' of ion clusters into individual ions in electric field is accompanied by the change of the dielectric response of ionic liquid which is different in clustered and unclustered states. The predictions of the theory are verified and further explored by specially performed molecular dynamics simulations. A particular finding of the theory is that the differential capacitance vs potential curve displays a bell shape despite low concentration of free charge carriers, because the dielectric response of bound ions reduces the threshold concentration of the bell- to camel-shape transition. Whereas qualitatively these findings make perfect sense, in reality the exact numbers and criteria might be different as the presented simple theory does not take into account overscreening and oscillating charge and electrostatic potential distributions near the electrode. This is why testing the theory with computer simulations is essential, but the latter basically reproduce the qualitative conclusions of the theory.
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