Unravelling Local Atomic Order of the Anionic Sublattice in M(Al1−xGax)4 with M=Sr and Ba by Using NMR Spectroscopy and Quantum Mechanical Modelling

The quasibinary section of the intermetallic phases MAl₄ and MGa₄ with M=Sr and Ba have been characterised by means of X‐ray diffraction (XRD) studies and differential thermal analysis. The binary phases show complete miscibility and form solid solutions M(Al_1?xGa_x)₄ with M=Sr and Ba. These structures crystallise in the BaAl₄ structure type with four‐ and five‐bonded Al and/or Ga atoms (denoted as Al(4b), Al(5b), Ga(4b), and Ga(5b), respectively) that form a polyanionic Al/Ga sublattice. Solid state ²⁷Al NMR spectroscopic analysis and quantum mechanical (QM) calculations were applied to study the bonding of the Al centres and the influence of Al/Ga substitution, especially in the regimes with low degrees of substitution. M(Al_1?xGa_x)₄ with M=Sr and Ba and 0.925≤x≤0.975 can be described as a matrix of the binary majority compound in which a low amount of the Ga atoms has been substituted by Al atoms. In good agreement with the QM calculations, ²⁷Al NMR investigations and single crystal XRD studies prove a preferred occupancy of Al(4b) for these substitution regimes. Furthermore, two different local Al environments were found, namely isolated Al(4b1) atoms and Al(4b2), due to the formation of Al(4b)–Al(4b) pairs besides isolated Al(4b) atoms within the polyanionic sublattice. QM calculations of the electric field gradient (EFG) using superlattice structures under periodic boundary conditions are in good agreement with the NMR spectroscopic results.