Matubayasi Nobuyuki
Division of Chemical Engineering Graduate School of Engineering Science, Osaka University Toyonaka, Osaka, 560-8531, Japan.
Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Katsura, Kyoto, 615-8520, Japan.
Chem Rec. 2019 Apr;19(4):723-734. doi: 10.1002/tcr.201800116. Epub 2018 Oct 30.
Spatial decomposition is conducted for the electrical conductivity. The contribution per ion pair at a certain distance is identified in terms of a two-body velocity time correlation function and is integrated over the whole distance of the ion pair to provide the cross-correlation term of the conductivity. The spatial-decomposition formula is an exact expression at any concentrations of ions and incorporates physically appealing pictures in the space domain into the theory of time correlation functions. Illustrative analyses are presented for 1m NaCl aqueous solution and the [C mim][NTf ] ionic liquid. The contrast between the two systems is discussed for the time and spatial ranges of correlations, and it is shown that the ion-pair contribution to the conductivity for the [C mim][NTf ] system is not localized and extends beyond the first coordination shell of the cation-anion pair.
对电导率进行空间分解。根据两体速度时间关联函数确定在一定距离处每个离子对的贡献，并在离子对的整个距离上进行积分，以提供电导率的交叉关联项。空间分解公式在任何离子浓度下都是精确表达式，并将空间域中具有物理吸引力的图像纳入时间关联函数理论。给出了对1m NaCl水溶液和[C mim][NTf ]离子液体的示例分析。讨论了两个系统在关联的时间和空间范围上的对比，结果表明，[C mim][NTf ]系统中离子对电导率的贡献并非局限于阳离子-阴离子对的第一配位层，而是延伸到该范围之外。
