We have studied polarized Au(100) and Au(111) electrodes immersed in electrolyte solution by implementing finite‐field methods in density functional theory‐based molecular dynamics simulations. This allows us to directly compute the Helmholtz capacitance of electric double layer by including both electronic and ionic degrees of freedom, and the results turn out to be in excellent agreement with experiments. It is found that the electronic response of Au electrode makes a crucial contribution to the high Helmholtz capacitance and the instantaneous adsorption of Cl can lead to a charge inversion on the anodic polarized Au(100) surface. These findings point out ways to improve popular semi‐classical models for simulating electrified solid‐liquid interfaces and to identify the nature of surface charges therein which are difficult to access in experiments.

中文翻译：

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极化金电极的电子响应和电荷反转


我们通过在基于密度泛函理论的分子动力学模拟中实施有限场方法，研究了浸入电解质溶液中的极化 Au(100) 和 Au(111) 电极。这使得我们能够通过包括电子和离子自由度来直接计算双电层的亥姆霍兹电容，并且结果与实验非常吻合。研究发现，Au电极的电子响应对高亥姆霍兹电容做出了至关重要的贡献，并且Cl的瞬时吸附可导致阳极极化Au(100)表面上的电荷反转。这些发现指出了改进流行的半经典模型的方法，用于模拟带电固液界面，并确定其中在实验中难以获得的表面电荷的性质。