论文标题

通过质量零约束动力学的绝热运动和统计力学

Adiabatic motion and statistical mechanics via mass zero constrained dynamics

论文作者

Bonella, Sara, Coretti, Alessandro, Vuilleumier, Rodolphe, Ciccotti, Giovanni

论文摘要

在最近的工作[Coretti等人,《化学物理学杂志》,2018,149,191102]中,提出了一种新的算法来求解壳模型的极化动力学。该方法广泛地适用于涉及绝热分离的动力学变量的系统,采用受约束的分子动力学来严格强制强制强制执行以下条件:快速自由度的力在每个时间步骤中以零质量为单位。该算法是符合性和完全时间可逆的,并导致稳定有效的传播。在本文中,我们通过展示如何使其适应快速自由度必须满足其他条件的问题来完成对质量零约束动力学机制的讨论。该扩展尤其包括第一原理分子动力学的重要情况。然后,我们考虑质量零约束动力学系统的统计力学,表明由物理相空间中动力学采样的边缘概率恢复了Born-Oppenheimer概率密度的形式。

In recent work [Coretti et al., The Journal of Chemical Physics, 2018, 149, 191102], a new algorithm to solve numerically the dynamics of the shell model for polarization was presented. The approach, broadly applicable to systems involving adiabatically separated dynamical variables, employs constrained molecular dynamics to strictly enforce the condition that the force on the fast degrees of freedom, modeled as having zero mass, is null at each time step. The algorithm is symplectic and fully time reversible, and results in stable and efficient propagation. In this paper we complete the discussion of the mechanics of mass zero constrained dynamics by showing how to adapt it to problems where the fast degrees of freedom must satisfy additional conditions. This extension includes, in particular, the important case of first principles molecular dynamics. We then consider the statistical mechanics of the mass zero constrained dynamical system demonstrating that the marginal probability sampled by the dynamics in the physical phase space recovers the form of the Born-Oppenheimer probability density.

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