Structural Disorder in (Bi, M)2(Fe, Mn, Bi)2O6+x (M = Na or K) Pyrochlores Seen from Reverse Monte Carlo Analysis of Neutron Total Scattering

• Published in: Journal of physical chemistry. C 2017-08, Vol.121 (33), p.18120-18128
• Main Authors: Daniels, Luke M, Playford, Helen Y, Hannon, Alex C, Walton, Richard I
• Format: Article
• Language: English
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.7b04972

The average structures of the polycrystalline pyrochlores (Na0.60Bi1.40)­(Fe1.06Mn0.17Bi0.77)­O6.87 and (K0.24Bi1.51)­(Fe1.07Mn0.15Bi0.78)­O6.86 can be refined through Rietveld refinement against Bragg scattering data using cubic space group Fd3̅m, with off-centered 96h and 32e positions describing the A2O′ network. Investigation of their local structures through neutron total scattering confirms the extent of disorder within these materials, and furthermore shows significant deviation from the average structure, which is not accounted for through analysis of Bragg data alone. Reverse Monte Carlo (RMC) analysis with a 6 × 6 × 6 supercell was used to model accurately this local disorder, revealing ellipsoidal distributions for A-site potassium, distinctly different from the hollow torus-shaped distributions for the sodium and bismuth cations. It is shown through bond valence sum analysis that while these atomic displacements allow for the steric preferences of Bi3+, they are also necessary to satisfy the valence of both the bismuth and the alkali metals on the A sites. Analysis of the final RMC configuration showed the BO6 octahedra for the separate B site metals to be more regular (O–B–O ≈ 90°) than those in the Rietveld model (O–B–O ≈ 85/95°) which describes an average of the three different environments.