Abstract
In lithium thiocyanate Li(SCN), the temperature regime below the melting point (274 °C) is characterized by excess conductivities over the usual Arrhenius behavior (premelting regime). Here, the Schottky defect pair concentration is high, and the point defect chemistry can no longer be considered as dilute. Coulomb interactions of Schottky pairs are expected to occur lowering the formation energy of new carriers and hence leading avalanche-like to a transition into a fully defective superionic state. The respective non-linear behavior is investigated using the cube-root law approach characterized by a defect interaction parameter J, which is a measure of the effective defect-lattice energy. In the case of Li(SCN), the rather pronounced volume expansion is to be included in the model. A literature comparison with other materials emphasizes to what degree defect formation as well as defect interactions depend not only on the dominant mobile defect, but also on the respective sublattice. Overall, a quantitative description of the defect chemistry of Li(SCN) in the premelting regime is derived.
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