Comparison of partial structures of melts of superionic AgI and CuI and non-superionic AgCl

Abstract

Neutron and high-energy x-ray diffraction analyses of molten AgI have been performed and the partial structures are discussed in detail with the aid of the structural modelling procedure of the reverse Monte Carlo (RMC) technique by comparison with those of molten CuI and AgCl. It is well known that AgI and CuI have a superionic solid phase below the melting point, in which the cations favour a tetrahedral configuration, while solid AgCl has a rock-salt structure with an octahedral environment around both Ag and Cl atoms. Even in the molten states, there is a significant difference between superionic and non-superionic melts. The cation is located on the triangular plain formed by three iodine ions in molten AgCl and CuI, while molten AgCl favours a 90° Cl-Ag-Cl bond angle, which is understood to maintain a similar local environment to that in the solid state. The atomic configurations of the RMC model suggest that the cation distributions in superionic melts of CuI and AgI exhibit large fluctuations, while Ag ions in the non-superionic melts of AgCl are distributed much more uniformly.