Abstract
Thermodynamic and transport properties of M 3LnCl 6 compounds (M = K, Rb, Cs; Ln = La, Ce, Pr, Nd) were determined experimentally. The results obtained clearly show that the M 3LnCl 6 compounds can be divided into two groups, with compounds having only high temperature modification of cubic, elpasolite-type, crystal structure, in the first one, and compounds having both low-temperature (monoclinic, Cs 3BiCl 6-type) and high-temperature (cubic, elpasolite-type) modifications in the second one. Within the two groups, the thermodynamic and transport properties of M 3LnCl 6 compounds are well correlated with their crystal structure. These results suggest different order–disorder mechanisms of the alkali metal cation sublattice whereas the LnCl 6 octahedra, forming anionic sublattice, retain their normal lattice positions.
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