Theory of ionic transport in crystallographic tunnels
Theory of ionic transport in crystallographic tunnels
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晶体隧道中离子输运理论
DOI：
10.1016/s0022-3697(73)80209-4
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发表时间：
1973
影响因子：
4
通讯作者：
R. Huggins
中科院分区：
文献类型：
--
作者：
W. Flygare;R. Huggins
已经开发了一个模型，用于处理离子通过晶体隧道的运动，如在有趣的固体电解质材料中发现的那样。点电荷和高阶吸引项以及重叠排斥效应的考虑允许计算移动的离子的最小能量位置和它们必须克服以移动通过晶格中的隧道的活化能势垒。计算已在碘化银晶格中的不同尺寸的离子，这表明，有一组最小的能量路径，不遵循隧道的中心线，但偏离，周期性地，与两个方向和幅度取决于阳离子的大小。此外，根据实验观察，运动的活化能是最小的中间大小的阳离子，库仑，极化和排斥的贡献，总能量是最好的平衡。
A model has been developed for the treatment of the motion of ions through crystallographic tunnels, as are found in materials that are interesting solid electrolytes. Consideration of both point charge and higher order attractive terms as well as overlap repulsion effects allows the calculation of the minimum energy positions of mobile ions and the activation energy barrier that they must surmount to move through the tunnel in the lattice. Calculations have been made for ions of different sizes in the AgI lattice which show that there is a set of minimum energy paths which do not follow the centerline of the tunnel, but deviate, periodically, with both direction and magnitude depending upon the cationic size. Also, in accordance with experimental observations, the activation energy for motion is smallest for cations of intermediate size, where the Coulombic, polarization, and repulsive contributions to the total energy are best balanced.