Funke Klaus, Singh Prabhakar, Banhatti Radha Dilip
Institute of Physical Chemistry and Sonderforschungsbereich 458, University of Münster, Corrensstrasse 30, D - 48149, Münster, Germany.
Phys Chem Chem Phys. 2007 Nov 7;9(41):5582-90. doi: 10.1039/b618788a. Epub 2007 Oct 1.
Conductivity spectra of ionic materials with disordered structures are usually thought to consist of several parts, i.e., the DC conductivity, a power-law component, a nearly-constant-loss feature (if identified) and the (far-)infrared conductivity caused by vibrational motion. Such a decomposition may, however, easily lead to a misinterpretation of the underlying dynamics. Here, we discuss broad-band conductivity data of the supercooled glass-forming melt calcium potassium nitrate, of composition 0.4 Ca(NO(3))(2).0.6 KNO(3), often abbreviated as CKN. Data have been taken at frequencies up to the far infrared. We show that the frequency-dependent conductivity is very well reproduced by a superposition of only two components. One of them is due to vibrations, the other is caused by displacements of the mobile ions. The latter component, which does not follow a power law, is described in terms of a physical model called the MIGRATION concept. This model treatment has been found to apply in many solid electrolytes as well and is, therefore, considered to provide a "standard" formulation of the ion dynamics. The gradual transition from a correlated forward-backward ("caged") ionic motion to a stepwise translational motion may be regarded as the main feature of the MIGRATION concept.
具有无序结构的离子材料的电导率谱通常被认为由几个部分组成,即直流电导率、幂律分量、近恒损耗特征(如果能识别出来)以及由振动运动引起的(远)红外电导率。然而,这样的分解可能很容易导致对潜在动力学的误解。在这里,我们讨论了过冷玻璃形成熔体硝酸钙钾(组成为0.4Ca(NO₃)₂·0.6KNO₃,常缩写为CKN)的宽带电导率数据。数据是在高达远红外的频率下获取的。我们表明,仅由两个分量叠加就能很好地再现频率依赖电导率。其中一个分量归因于振动,另一个是由可移动离子的位移引起的。后一个分量不遵循幂律,用一个称为迁移概念的物理模型来描述。已发现这种模型处理也适用于许多固体电解质,因此被认为提供了离子动力学的“标准”表述。从相关的向前 - 向后(“笼中”)离子运动到逐步平移运动的逐渐转变可被视为迁移概念的主要特征。