电化学系统模拟中电极电荷的零质量约束分子动力学
Mass-zero constrained molecular dynamics for electrode charges in simulations of electrochemical systems
摘要：
经典的分子动力学模拟近来已成为研究电化学系统的标准工具。最先进的方法将电极表示为完美导体，通过所谓的波动电荷模型来模拟它们对电解质的电荷分布的响应。这些波动的电荷是额外的自由度，在波恩-奥本海默精神中，它们瞬间适应环境的变化，以保持每个电极处于恒定的电位。在这里，我们表明，这个模型可以在约束分子动力学的框架内处理，导致一个辛和时间可逆的算法的系统的所有自由度的演变。新方法的计算成本和准确性与该模型的当前替代实现类似。其优点在于算法的形式属性保证了精度和长期稳定性，并且可以系统地引入任意数量和形式的附加运动学条件。我们说明了约束动力学方法的性能，通过强制执行的电中性的电极在一个简单的电容器组成的两个石墨电极分开的一个平板的液态水。
英文摘要：
Classical molecular dynamics simulations have recently become a standard tool for the study of electrochemical systems. State-of-the-art approaches represent the electrodes as perfect conductors, modelling their responses to the charge distribution of electrolytes via the so-called fluctuating charge model. These fluctuating charges are additional degrees of freedom that, in a Born-Oppenheimer spirit, adapt instantaneously to changes in the environment to keep each electrode at a constant potential. Here we show that this model can be treated in the framework of constrained molecular dynamics, leading to a symplectic and time-reversible algorithm for the evolution of all the degrees of freedom of the system. The computational cost and the accuracy of the new method are similar to current alternative implementations of the model. The advantage lies in the accuracy and long term stability guaranteed by the formal properties of the algorithm and in the possibility to systematically introduce additional kinematic conditions of arbitrary number and form. We illustrate the performance of the constrained dynamics approach by enforcing the electroneutrality of the electrodes in a simple capacitor consisting of two graphite electrodes separated by a slab of liquid water.
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