论文标题

基于无轨道密度功能理论的模拟的质量零约束动力学

Mass-Zero constrained dynamics for simulations based on orbital-free density functional theory

论文作者

Coretti, Alessandro, Baird, Taylor J., Vuilleumier, Rodolphe, Bonella, Sara

论文摘要

提出了一种基于无轨道密度功能理论(OFDFT)的第一原理分子动力学的有效且完全可逆的整合的新算法。该算法适应了最近引入的质量零(迷宫)约束动力学。形式主义确保在核和电子自由度之间实现完全绝热的分离,因此,对核的确切出生的近邻概率进行了采样。迷宫动力学的数值整合结合了标准分子动力学算法,例如verlet或速度verlet,采用摇动方法将最小条件施加到电子自由度作为一组约束的电子程度上。这项工作中提出的发展,其中包括标准摇算算法的定制适应,确保OFDFT的准线性缩放被新方法保留,以用于广泛的动力和交换相关功能,包括非局部性功能。通过计算恒定能量和恒温集合中液体钠的静态和动态特性来证明该方法的效率和准确性。

A new algorithm for efficient and fully time-reversible integration of first-principles molecular dynamics based on orbital-free density functional theory (OFDFT) is presented. The algorithm adapts to this nontrivial case the recently introduced Mass-Zero (MaZe) constrained dynamics. The formalism ensures that full adiabatic separation is enforced between nuclear and electronic degrees of freedom and, consequently, that the exact Born-Oppenheimer probability for the nuclei is sampled. Numerical integration of the MaZe dynamics combines standard molecular dynamics algorithms, e.g. Verlet or velocity Verlet, with the SHAKE method to impose the minimum conditions on the electronic degrees of freedom as a set of constraints. The developments presented in this work, that include a bespoke adaptation of the standard SHAKE algorithm, ensure that the quasilinear scaling of OFDFT is preserved by the new method for a broad range of kinetic and exchange-correlation functionals, including nonlocal ones. The efficiency and accuracy of the approach is demonstrated via calculations of static and dynamic properties of liquid sodium in the constant energy and constant temperature ensembles.

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