title: Lattice dynamics to trigger low temperature oxygen mobility in solid oxide ion conductors.
abstract: SrFeO(2.5) and SrCoO(2.5) are able to intercalate oxygen in a reversible topotactic redox reaction already at room temperature to form the cubic perovskites Sr(Fe,Co)O(3), while CaFeO(2.5) can only be oxidized under extreme conditions. To explain this significant difference in low temperature oxygen mobility, we investigated the homologous SrFeO(2.5) and CaFeO(2.5) by temperature dependent oxygen isotope exchange as well as by inelastic neutron scattering (INS) studies, combined with ab initio (DFT) molecular dynamical calculations. From (18)O/(16)O isotope exchange experiments we proved free oxygen mobility to be realized in SrFeO(x) already below 600 K. We have also evidence that low temperature oxygen mobility relies on the existence of specific, low energy lattice modes, which trigger and amplify oxygen mobility in solids. We interpret the INS data together with the DFT-based molecular dynamical simulation results on SrFeO(2.5) and CaFeO(2.5) in terms of an enhanced, phonon-assisted, low temperature oxygen diffusion for SrFeO(3-x) as a result of the strongly reduced Fe-O-Fe bond strength of the apical oxygen atoms in the FeO(6) octahedra along the stacking axis. This dynamically triggered phenomenon leads to an easy migration of the oxide ions into the open vacancy channels and vice versa. The decisive impact of lattice dynamics, giving rise to structural instabilities in oxygen deficient perovskites, especially with brownmillerite-type structure, is demonstrated, opening new concepts for the design and tailoring of low temperature oxygen ion conductors.
authors.affiliation: Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes1, Inorganic Materials: Soft Chemistry and Reactivity of Solids, Campus de Beaulieu, F-35042 Rennes, France. werner.paulus@univ-rennes1.fr
authors.forename: Werner
authors.initials: W
authors.lastname: Paulus
authors.forename: Helmut
authors.initials: H
authors.lastname: Schober
authors.forename: Stefan
authors.initials: S
authors.lastname: Eibl
authors.forename: Mark
authors.initials: M
authors.lastname: Johnson
authors.forename: Tanguy
authors.initials: T
authors.lastname: Berthier
authors.forename: Olivier
authors.initials: O
authors.lastname: Hernandez
authors.forename: Monica
authors.initials: M
authors.lastname: Ceretti
authors.forename: Marie
authors.initials: M
authors.lastname: Plazanet
authors.forename: Kazimierz
authors.initials: K
authors.lastname: Conder
authors.forename: Carlo
authors.initials: C
authors.lastname: Lamberti