电化学界面催化反应的隐式溶剂化方法
Implicit Solvation Methods for Catalysis at Electrified Interfaces
摘要：
隐式溶剂化是一种有效的，高度粗粒度的原子尺度模拟方法，以考虑周围的液体电解质的水平上的连续极化介质。起源于有限溶质的分子化学，隐式溶剂化技术现在越来越多地用于扩展（通常是金属）电极的电化学和电催化的第一性原理建模。对后者的电极和通过周期性边界条件超级电池中的平板在它们处的反应性表面化学进行建模的流行的方法带来了其特定的挑战。最重要的是，这涉及到的困难，以描述整个双电层形成在带电的固-液界面（SLI）内的超级电池的大小听话的常用密度泛函理论（DFT）。我们回顾液体溶剂化方法从这个特定的应用角度，特别强调其广泛的{ \em从头算}热力学方法的表面催化的使用。值得注意的是，可以采用隐式溶剂化来模拟在所施加的电势下电极的电子密度的极化和整个双层的伴随电容充电，超出所采用的DFT超电池的限制。最关键的持续进步，这种有效的方法SLI的背景下是缺乏相关的（实验或高层次的理论）参数化所需的参考数据。
英文摘要：
Implicit solvation is an effective, highly coarse-grained approach in atomic-scale simulations to account for a surrounding liquid electrolyte on the level of a continuous polarizable medium. Originating in molecular chemistry with finite solutes, implicit solvation techniques are now increasingly used in the context of first-principles modeling of electrochemistry and electrocatalysis at extended (often metallic) electrodes. The prevalent ansatz to model the latter electrodes and the reactive surface chemistry at them through slabs in periodic boundary condition supercells brings its specific challenges. Foremost this concerns the diffculty to describe the entire double layer forming at the electrified solid-liquid interface (SLI) within supercell sizes tractable by commonly employed density-functional theory (DFT). We review liquid solvation methodology from this specific application angle, highlighting in particular its use in the widespread {\em ab initio} thermodynamics approach to surface catalysis. Notably, implicit solvation can be employed to mimic a polarization of the electrode's electronic density under the applied potential and the concomitant capacitive charging of the entire double layer beyond the limitations of the employed DFT supercell. Most critical for continuing advances of this effective methodology for the SLI context is the lack of pertinent (experimental or high-level theoretical) reference data needed for parametrization.
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