荷电界面超原胞模型中晶体尺寸效应的解析理论
Analytic Theory of Finite-size Effects in Supercell Modelings of Charged Interfaces
摘要：
Ewald 3D和锡箔边界条件（e3 dtf）评估无限周期性超晶胞内的有限单位晶胞的静电能。虽然它已被用作一个{ \it事实上}的标准处理静电的模拟扩展极性或带电接口，有限尺寸的模拟性能的影响还没有得到充分的理解。然而，有一种直观的方法来量化由e3 dtf和库仑电势之间的差异对移动电荷对具有固定电荷的接触表面和/或对施加的外部电场的响应产生的平均效应。虽然任何充电接口形成的移动抗衡电荷，补偿固定电荷的作用电场的变化时，滑动，一对带相反电荷的接口之间的距离被发现是几乎静止的，这允许分析有限尺寸校正的量的抗衡电荷。溶剂化双电层（绝缘体/电解质界面）的理论的应用程序预测，完全电荷补偿的状态是不变的溶剂的结晶性，这是证实了适当的分析在文献中的模拟数据。
英文摘要：
The Ewald3D sum with the tinfoil boundary condition (e3dtf) evaluates the electrostatic energy of a finite unit cell inside an infinitely periodic supercell. Although it has been used as a {\it de facto} standard treatment of electrostatics for simulations of extended polar or charged interfaces, the finite-size effect on simulated properties has yet to be fully understood. There is, however, an intuitive way to quantify the average effect arising from the difference between the e3dtf and Coulomb potentials on the response of mobile charges to contact surfaces with fixed charges and/or to an applied external electric field. While any charged interface formed by mobile countercharges that compensate the fixed charges slips upon the change of the acting electric field, the distance between a pair of oppositely charged interfaces is found to be nearly stationary, which allows an analytic finite-size correction to the amount of countercharges. Application of the theory to solvated electric double layers (insulator/electrolyte interfaces) predicts that the state of complete charge compensation is invariant with respect to solvent permittivities, which is confirmed by a proper analysis of simulation data in the literature.
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