论文标题

反应性分子动力学中电荷转移平衡的广义方法

Generalized Method for Charge Transfer Equilibration in Reactive Molecular Dynamics

论文作者

Gergs, Tobias, Schmidt, Frederik, Mussenbrock, Thomas, Trieschmann, Jan

论文摘要

反应性分子动力学模拟中的可变电荷模型(例如EEM,QEQ,ES+)通常固有地施加原子之间的全局电荷转移(将每个系统近似为理想的金属)。因此,大多数表面过程(例如吸附,解吸,沉积,溅射)受到影响,可能导致可疑动力学。此问题应由ACKS2和QTPIE模型解决,这些模型分别基于Kohn-Sham密度功能理论以及分别限制扩展到QEQ模型(将每个系统作为理想绝缘体)的电荷传输限制。在对QEQ和QTPIE模型的简要回顾中,在这项工作中评估了它们用于研究表面相互作用的适用性。在此推理之后,提出了对QEQ和QTPIE模型进行修订的概括的需求,称为电荷传递平衡模型或简短的QTE模型。该方法是从约束电荷转移变量的平衡中得出的,而不是考虑原子电荷变量。但是,后者是通过使用扩展的拉格朗日方法来通过相应的转换获得的。此外,我们提出了镜面边界条件及其实施以加速表面研究。在这项工作中提出的模型促进了反应性分子动力学模拟,这些动力学模拟适当地描述了各种材料和表面现象。

Variable charge models (e.g., EEM, QEq, ES+) in reactive molecular dynamics simulations often inherently impose a global charge transfer between atoms (approximating each system as ideal metal). Consequently, most surface processes (e.g., adsorption, desorption, deposition, sputtering) are affected, potentially causing dubious dynamics. This issue is meant to be addressed by the ACKS2 and QTPIE model, which are based on the Kohn-Sham density functional theory as well as a charge transfer restricting extension to the QEq model (approximating each system as ideal insulator), respectively. In a brief review of the QEq and the QTPIE model, their applicability for studying surface interactions is assessed in this work. Following this reasoning, the demand for a revised generalization of the QEq and QTPIE model is proposed, called charge transfer equilibration model or in short QTE model. This method is derived from the equilibration of constrained charge transfer variables, instead of considering atomic charge variables. The latter, however, are obtained by a respective transformation, employing an extended Lagrangian method. We moreover propose a mirror boundary condition and its implementation to accelerate surface investigations. The models proposed in this work facilitate reactive molecular dynamics simulations which describe various materials and surface phenomena appropriately.

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