Yamaguchi T, Matsuoka T, Koda S
Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8603, Japan.
J Chem Phys. 2007 Dec 21;127(23):234501. doi: 10.1063/1.2806289.
The theory on the ultrasonic absorption of electrolyte solutions we have proposed previously [T. Yamaguchi et al., J. Chem. Phys. 126, 144505 (2007)] is extended to calculate the frequency-dependent electric conductivity of the solution. The ionic contribution of the dielectric relaxation spectrum is obtained at the same time. The theory is able to handle the contributions of both the ion-pair dynamics and the relaxation of ionic atmosphere, as is the case of ultrasonic absorption. The effect of the barrier height between the contact and solvent-separated ion pairs is investigated in detail. It is clarified that the competition between the dissociation and reorientational relaxation rates of the contact ion pair is an important factor for the ion pair to be regarded as the ion pair in terms of ionic conductivity.
我们之前提出的关于电解质溶液超声吸收的理论 [T. 山口等人，《化学物理杂志》126, 144505 (2007)] 被扩展以计算溶液的频率依赖性电导率。同时获得了介电弛豫谱的离子贡献。该理论能够处理离子对动力学和离子氛弛豫的贡献，这与超声吸收的情况相同。详细研究了接触离子对和溶剂分隔离子对之间的势垒高度的影响。结果表明，就离子电导率而言，接触离子对的解离和重取向弛豫速率之间的竞争是离子对被视为离子对的一个重要因素。
