Structural approach to nanoscience: a case study of complex and cluster formation in ZnBr2–ZnCl2 melts

Although the melt structure of glass-forming ZnCl2 has so far been well studied, there exists quite little information on the structural change due to anion-substitution. In the present work, the short-range structure of ZnCl2–ZnBr2 mixture melts was analyzed systematically by time-of-flight pulsed neutron diffraction techniques, Raman spectroscopy, molecular orbital calculations, and molecular dynamics simulations. According to radial distribution analysis, it was found that there were tetrahedral structural units of ligand-substituted [ZnClnBr4−n]2− (n=0–4) in these melts, not implying the simple mixing of [ZnCl4]2− and [ZnBr4]2− units. Further detailed estimation indicated that the ligand-substituted complex anions were linked with each other by sharing a common anion.