Abstract
ZINTL alloys are compounds of an alkali metal A with a polyvalent metal M in which transfer of an electron from A to M leads to bonding behaviour in the M− ions typical of elements one column to the right in the Periodic Table. For example, ASn and APb contain tetrahedral M4−4 polyanions in both the crystalline and liquid phases1 whereas AA1 alloys crystallize in tetrahedrally bonded networks typical of Group IV elements2. These bonding patterns also determine the character of the disorder in the solid at high temperature. We have recently identified a plastic crystal phase in CsPb just below the melting point, in which the Pb4−4 polyanions undergo jump reorientations3; LiAl, in contrast, is metallic, with mobile Li+ ions4. Here we report unusual disordering behaviour in the Zintl alloy NaSn, in which both types of dynamic disorder appear: rapid reorientations of the Sn4−4 polyanions enhance jump migration of the Na+ cations by means of a ‘paddle-wheel’ effect. The two types of disorder are strongly coupled, so that only one disordering transition takes place as the melting point is approached.
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Saboungi, ML., Fortner, J., Howells, W. et al. Dynamic enhancement of cation migration in a Zintl alloy by polyanion rotation. Nature 365, 237–239 (1993). https://doi.org/10.1038/365237a0
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DOI: https://doi.org/10.1038/365237a0
