Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya, Aichi 464-8603, Japan.
J Chem Phys. 2013 Jan 14;138(2):024503. doi: 10.1063/1.4773322.
Brownian dynamics simulation on model electrolyte solutions in our previous work [T. Yamaguchi et al., J. Chem. Phys. 134, 244506 (2011)] is extended to include the hydrodynamic interaction between ions, in order to examine its effects on ionic mobility in solvents of low dielectric constant. The effects of the hydrodynamic interaction are rather small as a whole, and the equivalent conductivity minimum is observed in systems with the hydrodynamic interaction. The hydrodynamic interaction increases the self-diffusion coefficient while decreases the equivalent conductivity, thereby increases the deviation from the Nernst-Einstein relationship. Based on the analysis of the time-dependent ionic mobilities, these changes are elucidated in terms of the electrophoretic and relaxation effects. It is also demonstrated that the concentration dependence of the ionic mobilities with the hydrodynamic interaction is reproduced fairly well by a theoretical calculation.
在我们之前的工作[T. Yamaguchi 等人，J. Chem. Phys. 134, 244506 (2011)]中，对模型电解质溶液的布朗动力学模拟进行了扩展，以包括离子间的流体动力相互作用，以检验其对低介电常数溶剂中离子迁移率的影响。总的来说，流体动力相互作用的影响相当小，在具有流体动力相互作用的系统中观察到等效电导率最小值。流体动力相互作用增加了自扩散系数，同时降低了等效电导率，从而增加了偏离能斯特-爱因斯坦关系的程度。基于对时变离子迁移率的分析，从电泳和弛豫效应的角度阐明了这些变化。还证明了通过理论计算可以很好地再现具有流体动力相互作用的离子迁移率的浓度依赖性。
