论文标题
在电流驱动的Ehrenfest分子动力学下的负粘度和有色噪声的出现
Emergence of negative viscosities and colored noise under current-driven Ehrenfest molecular dynamics
论文作者
论文摘要
分子连接中的分子受到电流诱导的力,可以打破化学键,诱导反应,破坏分子几何稳定并停止连接的运行。电流驱动的分子动力学模拟背后的理论依赖于系统内部的扰动时间尺度分离,随后使用非质量Green功能(NEGF)来计算电子在核学位上施加的保守,非保守和随机力。我们分析了这种近似的有效性,特别注意负粘度现象。将扰动近似与非平衡eHrenfest方法直接进行比较。我们引入了一种新颖的时间步变方法,通过精确整合非平衡绿色功能的运动方程,以计算Ehrenfest方法中存在的力,这不必在系统中内部分离,并为相应的经典动力学提供精确的描述。我们观察到负粘度不是扰动处理的伪影,而是Ehrenfest动力学中的伪影。然而,负粘度的影响可能是由于扰动方法未指出的高阶力而被主要积极耗散所淹没的可能性。此外,我们评估了随机力的白噪声近似值的有效性,发现在存在明确的时间尺度分离的情况下,它是合理的,并且当电流分子轨道移到电压窗口外时更适用。最后,我们演示了由一个和两个经典自由度组成的分子连接模型的方法。
Molecules in molecular junctions are subject to current-induced forces that can break chemical bonds, induce reactions, destabilize molecular geometry, and halt the operation of the junction. Theories behind current-driven molecular dynamics simulations rely on a perturbative time-scale separation within the system with subsequent use of nonequilibrium Green's functions (NEGF) to compute conservative, non-conservative, and stochastic forces exerted by electrons on nuclear degrees of freedom. We analyze the effectiveness of this approximation, paying particular attention to the phenomenon of negative viscosities. The perturbative approximation is directly compared to the nonequilibrium Ehrenfest approach. We introduce a novel time-stepping approach to calculate the forces present in the Ehrenfest method via exact integration of the equations of motion for the nonequilibrium Green's functions, which does not necessitate a time-scale separation within the system and provides an exact description for the corresponding classical dynamics. We observe that negative viscosities are not artifacts of a perturbative treatment but also emerge in Ehrenfest dynamics. However, the effects of negative viscosity have the possibility of being overwhelmed by the predominantly positive dissipation due to the higher-order forces unaccounted for by the perturbative approach. Additionally, we assess the validity of the white-noise approximation for the stochastic forces, finding that it is justifiable in the presence of a clear time-scale separation and is more applicable when the current-carrying molecular orbital is moved outside of the voltage window. Finally, we demonstrate the method for molecular junction models consisting of one and two classical degrees of freedom.