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The  α  to  β  phase transition of Ba 3 Tt 4  (Tt = Si, Ge; Ba 3 Ge 4  and Ba 3 Si 4  structure type, respectively) has been investigated experimentally by differential thermal analysis (transition temperature 628 K) and variation of the composition Ba 3 Si  x  Ge 4–   x   which shows that the transition is clearly dependent on the compositional parameter (0.4 ≤  x  ≤ 0.5). The five new Zintl compounds Ba 3 Si 1.89 Ge 2.11 , Ba 3 Si 1.05 Ge 2.95 , Ba 3 Si 0.57 Ge 3.43  (Ba 3 Si 4  structure type) and Ba 3 Si 0.31 Ge 3.69 , Ba 3 Si 0.16 Ge 3.84  (Ba 3 Ge 4  structure type) were synthesized and structurally characterized. We have also developed a topological model for the description of the phase transition which is based on the Periodic Nodal Surface (PNS) approach.

Chemical, thermal, and theoretical analysis of the α — β phase transition of Ba 3 Tt 4 compounds