用于导电电极模拟的恒定电势与约束电荷系综
Constant Potential and Constrained Charge Ensembles for Simulations of Conductive Electrodes
AI总结：
本文将恒定电势法分子动力学扩展到固定电极总电荷的约束电荷系综，证明其与固定电势差系综互为共轭系综，并通过离子液体超级电容器模拟验证了该框架的有效性及加速平衡的优势。
摘要：
恒定电势法分子动力学模拟（CPM MD）在研究纳米尺度电极-电解质界面时，能够对原子级电极电荷进行精确建模。在此，我们将CPM MD的理论框架扩展到控制每个导电电极总电荷的情形，而非控制其电势差。我们证明，由此得到的热力学系综与在固定电势差下采样的系综不同，但二者作为共轭系综具有严格关联。这一理论对应关系——我们通过离子液体超级电容器的模拟加以证明——为近期采用电极固定总电荷的研究取得成功奠定了基础。我们表明，在该系综中平衡过程可得到有效加速，并概述了这些模拟在未来的一些潜在应用。
英文摘要：
Constant potential method molecular dynamics simulation (CPM MD) enables the accurate modelling of atomistic electrode charges when studying the electrode-electrolyte interface at the nanoscale. Here we extend the theoretical framework of CPM MD to the case in which the total charge of each conductive electrode is controlled, instead of their potential differences. We show that the resulting thermodynamic ensemble is distinct from that sampled in with a fixed potential difference, but rigorously related as conjugate ensembles. This theoretical correspondence, which we demonstrate using simulations of an ionic liquid supercapacitor, underpins the success of recent studies with fixed total charges on the electrodes. We show that equilibration is usefully sped up in this ensemble and outline some potential applications of these simulations in future.
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