标题： 带电界面超胞建模中的有限尺寸效应分析理论 显示英文标题

标题： Analytic Theory of Finite-size Effects in Supercell Modelings of Charged Interfaces

摘要： Ewald3D求和与锡纸边界条件（e3dtf）评估有限单元在无限周期性超晶胞中的静电能量。 尽管它已被用作扩展极性或带电界面模拟的{\it 实际上}标准处理方法，但对模拟性质的有限尺寸效应尚未完全理解。 然而，有一种直观的方法可以量化由于e3dtf和库仑势在移动电荷对固定电荷和/或施加的外部电场的响应上的差异所产生的平均效应。 虽然由移动反离子形成的任何带电界面在作用电场变化时都会滑动，但一对异号带电界面之间的距离被发现几乎保持不变，这使得可以对反离子的数量进行解析的有限尺寸修正。 将该理论应用于溶剂化电动双层（绝缘体/电解质界面）预测了完全电荷补偿的状态相对于溶剂介电常数是不变的，这通过文献中对模拟数据的适当分析得到了证实。 显示英文摘要

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.