By Ilya Prigogine
A part of a sequence dedicated to assisting the reader receive normal information regarding a wide selection of issues in chemical physics. Its target is to give complete analyses of matters of curiosity and to motivate the expression of person issues of view.
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Extra info for Advances in Chemical Physics, Vol.70 Part 1, Evolution of Size Effects in Chemical Dynamics (Wiley 1988)
Although this structure is adopted by many chalcogenides of the alkali metals, lithium oxide (Li2O) has attracted the most widespread attention. Experimental evidence for a superionic transition analogous to those observed in the halide and oxide ﬂuorites was ﬁrst provided by measurements of the ionic conductivity of Li2O, which also conﬁrmed that Li þ are the mobile species [113, 114]. Single-crystal neutron diffraction studies indicated the presence j29 j 2 Superionic Materials: Structural Aspects 30 of an increasing fraction of dynamic cation Frenkel defects at temperatures in excess of $850 K .
The presence of a superionic transition at 420 K from the ambient temperature wurtzitestructured b phase (space group P 6 3 mc) to the superionic a phase was studied by Tubandt , with the ionic conductivity increasing at the b ! 3 S cm À1. Transport measurements conﬁrmed that the conduction within the a phase is predominantly ionic (rather than electronic) in nature, and due to the motion of the cations (rather than of the anions) . X-ray powder diffraction studies showed that a-AgI possesses a body-centered cubic (bcc) structured anion sublattice, with the two Ag þ per unit cell proposed to be distributed over all the available interstices within this array [11, 12].
A detailed single-crystal diffraction study, using both neutron and X-ray radiations, demonstrated that the defect structure of (Zr1ÀxYx)O2Àx/2 is rather complex, with signiﬁcant variations as a function of composition and temperature. With increasing x within the cÃ phase, there is a tendency for anion vacancies to form pairs aligned along h1 1 1i directions, which aggregate to form larger defects of around 15–20 A in diameter that act as highly effective traps for the mobile O2À vacancies .
Advances in Chemical Physics, Vol.70 Part 1, Evolution of Size Effects in Chemical Dynamics (Wiley 1988) by Ilya Prigogine