Contact value relations and density functional theory for the electrical double layer
Contact value relations and density functional theory for the electrical double layer
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DOI：
10.1080/00268976.2014.932924
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发表时间：
2014-12
影响因子：
1.7
通讯作者：
W. Silvestre-Alcantara;L. B. Bhuiyan;Jian Jiang;Jianzhong Wu;D. Henderson
中科院分区：
文献类型：
--
作者：
W. Silvestre-Alcantara;L. B. Bhuiyan;Jian Jiang;Jianzhong Wu;D. Henderson
最近开发的接触校正密度泛函理论应用于包含价数和尺寸对称电解质的双电层。受限原始模型用于描述电解质，不可极化、光滑、平面、均匀充电的硬表面用于对电极进行建模。与该系统的蒙特卡罗仿真结果对比表明，该理论满足第一接触值关系，符合该方法的前提。此外，该理论被发现非常接近地满足半经验第二接触值关系。这是一个值得欢迎的结果，因为没有提到第二个关系，也没有在理论发展中使用该关系。第二个接触关系与低温、低离子浓度和低电极电荷下双层电容的反常正温度导数密切相关，接触校正密度泛函理论确实预测了这种效应。
The recently developed contact-corrected density functional theory is applied to an electric double layer containing a valence and size symmetric electrolyte. The restricted primitive model is used to describe the electrolyte, and a non-polarisable, smooth, planar, uniformly charged hard surface is used to model the electrode. Comparison with Monte Carlo simulation results for this system shows that the theory satisfies the first contact value relation in line with the premise of the approach. Additionally, the theory is found to satisfy the semi-empirical second contact value relation quite closely. This is a welcome result, since no reference is made to this second relation nor is the relation used in the theoretical development. The second contact relation is closely related to the anomalous positive temperature derivative of the double layer capacitance at low temperature, low ion concentration, and low electrode charge, and indeed, the contact-corrected density functional theory predicts this effect.