Local structure of ZnBr2–KBr melts analyzed by X-ray diffraction, Raman spectroscopy, and molecular orbital calculation

Abstract Zn atoms in molten ZnBr2 and molten ZnBr2–2KBr were tetrahedrally coordinated by Br atoms. ZnBr42− units in molten ZnBr2–KBr formed clusters or a network structure by sharing a common Br atom between the units. The three-dimensional network was broken and dissociated into discrete tetrahedral ions on the addition of KBr. Sharing a common Br atom between the tetrahedral units led to the construction of clusters and three-dimensional networks, but on the addition of KBr, such highly ordered species were broken and dissociated into discrete tetrahedral ions. The structural parameters of Zn–Br, Br–Br, and Zn–Zn pairs in molten ZnBr2 were not changed much in comparison with those in molten ZnBr2–2KBr, revealing the stability of the tetrahedra.