Crystalline Cation Conductors with Rotational Anion Disorder: Results of Quasielastic Neutron Scattering Experiments on Orthophosphates

Abstract

Abstract Results and interpretations of several quasielastic neutron scattering measurements on samples of the isostructural high-temperature phases of Ag3PO4 and Na3PO4, prominent members of the group of fast cation conducting plastic phases are reported.Time-of-flight experiments reveal details on the phosphate reoriention in Ag3PO4: We find isotropic rotational diffusion. A consistent interpretation of the data suggests that silver ions are involved in the fast anion dynamics, a behaviour which is in line with the displacement of phosphorus detected in earlier neutron diffraction experiments. The reorientation activation energy of 0.17 eV is in the typical range found also in other ion conducting rotor phases.Na3PO4 was examined in time-of-flight and backscattering experiments, differing considerably in the time scale of the detected molecular dynamics. Anion reorientation, observed on the time scale of picoseconds and activated with 0.18 eV, appears as a predominantly circular diffusion with one P–O axis fixed. Our results suggest the involvement of sodium ions in the anion reorientation, i.e., a correlated motion of both types of ions in the picosecond regime.The much slower sodium jump diffusion in Na3PO4 was found to be thermally activated with 0.74 eV. Moreover, we find clear evidence for the predominance of jumps between tetrahedrally co-ordinated cation sites.Quasielastic neutron scattering reveals a wealth of dynamic details on the two high-temperature phases of Na3PO4 and Ag3PO4 which exhibit considerable differences (e.g., in the geometric details of anion dynamics) in spite of their structural similarities. Both plastic phases, however, give evidence of the involvement of cations in the anion dynamics, i.e., in a correlated reorientational motion of cations and anions on the picosecond time scale.