论文标题
布朗动力学模拟的受限电解质的频率和场依赖性响应
Frequency and field-dependent response of confined electrolytes from Brownian dynamics simulations
论文作者
论文摘要
使用布朗动力学模拟,我们研究了限制,吸附对表面和离子离子相互作用的影响,对密闭电解质溶液对垂直于狭窄壁的方向振荡电场的响应。当改变应用场的幅度和频率时,非平衡模拟可以表征线性和非线性方案之间的过渡,但是从平衡电流波动的情况下,以频率依赖性电导率为特征的线性响应更有效地预测了线性响应。为此,我们(雷(Rederive and))使用适用于过度抑制动力学的绿色 - 库博关系,这与牛顿(Newtonian)或受阻尼不足的langevin动力学的标准不同。这种表达突出了潜在的布朗尼波动的贡献以及它们之间粒子与外部电势之间的相互作用。虽然在文献中已经知道,但这种关系迄今为止很少使用,超出了静态极限,以确定有效扩散系数或直流电导率。频率依赖性的电导率总是从高频下的散装行为衰减到由于墙壁被电荷载体限制而在低频下消失的电导率。我们讨论了两个制度之间交叉的特征,最重要的是,跨界频率如何取决于限制距离和盐浓度,以及在墙壁上的吸附可能会导致高频和低频时的显着变化。相反,我们的结果说明了通过分析频率依赖性电导率来获取有关墙壁扩散,电荷松弛和吸附的信息的可能性。
Using Brownian dynamics simulations, we investigate the effects of confinement, adsorption on surfaces and ion-ion interactions on the response of confined electrolyte solutions to oscillating electric fields in the direction perpendicular to the confining walls. Nonequilibrium simulations allow to characterize the transitions between linear and nonlinear regimes when varying the magnitude and frequency of the applied field but the linear response, characterized by the frequency-dependent conductivity, is more efficiently predicted from the equilibrium current fluctuations. To that end, we (rederive and) use the Green-Kubo relation appropriate for overdamped dynamics, which differs from the standard one for Newtonian or underdamped Langevin dynamics. This expression highlights the contributions of the underlying Brownian fluctuations and of the interactions of the particles between them and with external potentials. While already known in the literature, this relation has rarely been used to date, beyond the static limit to determine the effective diffusion coefficient or the DC conductivity. The frequency-dependent conductivity always decays from a bulk-like behavior at high frequency to a vanishing conductivity at low frequency due to the confinement of the charge carriers by the walls. We discuss the characteristic features of the crossover between the two regimes, most importantly how the crossover frequency depends on the confining distance and the salt concentration, and the fact that adsorption on the walls may lead to significant changes both at high- and low-frequencies. Conversely, our results illustrate the possibility to obtain information on diffusion between walls, charge relaxation and adsorption by analyzing the frequency-dependent conductivity.