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

Oliver Pecher; Bernhard Mausolf; Volker Peters; Kevin Lamberts; Alexander Korthaus; Frank Haarmann

doi:10.1002/chem.201602475

Unravelling Local Atomic Order of the Anionic Sublattice in M(Al_1-x Ga_x )₄ with M=Sr and Ba by Using NMR Spectroscopy and Quantum Mechanical Modelling

Chemistry. 2016 Dec 5;22(49):17833-17842. doi: 10.1002/chem.201602475. Epub 2016 Oct 27.

Authors

Oliver Pecher^{1

2

3}, Bernhard Mausolf¹, Volker Peters¹, Kevin Lamberts¹, Alexander Korthaus¹, Frank Haarmann^{1

2}

Affiliations

¹ RWTH Aachen University, Institut für Anorganische Chemie (IAC), Landoltweg 1, 52074, Aachen, Germany.
² Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Strasse 40, 01187, Dresden, Germany.
³ Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW, Cambridge, UK.

PMID: 27786380
DOI: 10.1002/chem.201602475

Abstract

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-x Ga_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 ²⁷ Al 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-x Ga_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, ²⁷ Al 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.

Keywords: NMR spectroscopy; chemical bonding; intermetallic phases; quantum mechanical calculations; substitutional disorder.