Medium-range correlation of Ag ions in superionic melts of Ag2Se and AgI by reverse Monte Carlo structural modelling-connectivity and void distribution.

High-energy x-ray diffraction measurements on molten Ag(2)Se were performed. Partial structure factors and radial distribution functions were deduced by reverse Monte Carlo (RMC) structural modelling on the basis of our new x-ray and earlier published neutron diffraction data. These partial functions were compared with those of molten AgI. Both AgI and Ag(2)Se have a superionic solid phase prior to melting. New RMC structural modelling for molten AgI was performed to revise our previous model with a bond-angle restriction to reduce the number of unphysical Ag triangles. The refined model of molten AgI revealed that isolated unbranched chains formed by Ag ions are the cause of the medium-range order of Ag. In contrast with molten AgI, molten Ag(2)Se has 'cage-like' structures with approximately seven Ag ions surrounding a Se ion. Connectivity analysis revealed that most of the Ag ions in molten Ag(2)Se are located within 2.9 Å of each other and only small voids are found, which is in contrast to the wide distribution of Ag-void radii in molten AgI. It is conjectured that the collective motion of Ag ions through small voids is required to realize the well-known fast diffusion of Ag ions in molten Ag(2)Se, which is comparable to that in molten AgI.