论文标题

质量零约束分子动力学用于电化学系统模拟中电极电荷的分子动力学

Mass-zero constrained molecular dynamics for electrode charges in simulations of electrochemical systems

论文作者

Coretti, Alessandro, Scalfi, Laura, Bacon, Camille, Rotenberg, Benjamin, Vuilleumier, Rodolphe, Ciccotti, Giovanni, Salanne, Mathieu, Bonella, Sara

论文摘要

经典分子动力学模拟最近已成为研究电化学系统的标准工具。最先进的方法代表电极作为完美的导体,通过所谓的波动电荷模型对其对电解质电荷分布的响应进行建模。这些波动的电荷是额外的自由度,在伯爵夫人的精神中,它立即适应环境的变化,以使每个电极保持恒定的潜力。在这里,我们表明该模型可以在约束分子动力学的框架中进行处理,从而导致系统的发展算法的符合性和时间可逆的算法。新方法的计算成本和准确性类似于该模型的当前替代实现。优势在于该算法的形式特性保证的准确性和长期稳定性,并且有可能系统地引入任意数字和形式的其他运动学条件。我们通过在简单的电容器中执行电极的电压来说明受约束动力学方法的性能,该电容器由两个石墨电极组成,该电极由两个石墨电极组成。

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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