Symmetry-adapted configurational modelling of fractional site occupancy in solids

A methodology is presented, which reduces the number of site-occupancy configurations to be calculated when modelling site disorder in solids, by taking advantage of the crystal symmetry of the lattice. Within this approach, two configurations are considered equivalent when they are related by an isometric operation; a trial list of possible isometric transformations is provided by the group of symmetry operators in the parent structure, which is used to generate all configurations via atomic substitutions. We have adapted the equations for configurational statistics to operate in the reduced configurational space of the independent configurations. Each configuration in this space is characterized by its reduced energy, which includes not only its energy but also a contribution from its degeneracy in the complete configurational space, via an entropic term. The new computer program SOD (site-occupancy disorder) is presented, which performs this analysis in systems with arbitrary symmetry and any size of supercell. As a case study we use the distribution of cations in iron antimony oxide FeSbO4, where we also introduce some general considerations for the modelling of site-occupancy disorder in paramagnetic systems.