Neutron total scattering study of the delta and beta phases of Bi2O3

The highly disordered structure of the delta phase of Bi2O3, which possesses the highest known oxide-ion conductivity, has been studied using neutron powder diffraction. A detailed analysis of data collected at 1033(3) K using Rietveld refinement indicates that the time-averaged structure of delta-Bi2O3 can be described using the accepted model of a disordered, anion-deficient fluorite structure in space group Fm3m. However, reverse Monte Carlo modelling of the total (Bragg plus diffuse) scattering demonstrates that the local anion environment around the Bi3+ resembles the distorted square pyramidal arrangement found within the stable alpha and metastable beta phases at ambient temperature, which is characteristic of the cation's 6s2 lone-pair configuration. Similarities between the structures of the highly disordered delta phase and the ambient temperature metastable beta phase are used to support this assignment and assess the validity of previous structural models based on short-range ordering of vacancies within the cubic lattice of delta-Bi2O3.