Mathematical crystal chemistry II: Random search for ionic crystals and analysis on oxide crystals registered in ICSD

Abstract

Mathematical crystal chemistry views crystal structures as the optimal solutions of mathematical optimization problem formalizing inorganic structural chemistry. This paper introduces the minimum and maximum atomic radii depending on the types of geometrical constraints, extending the concept of effective atomic sizes. These radii define permissible interatomic distances instead of interatomic forces, constraining feasible types and connections of coordination polyhedra. The definition shows the aspect that crystal structures are packings of atomic spheres. Additionally, creatability functions for geometrical constraints, which give a choice of creatable types of geometrical constraints depending on the spatial order of atoms, are implemented to guide randomly generated structures toward optimal solutions. The framework identifies unique optimal solutions corresponding to the structures of spinel, pyrochlore ($\alpha$ and $\beta$), pyroxene, quadruple perovskite, cuprate superconductor $\mathrm{YBa}_2 \mathrm{Cu}_3 \mathrm{O}_{7-x}$, and iron-based superconductor $\mathrm{LaFeAsO}$. Notably, up to $95\%$ of oxide crystal structure types in Inorganic Crystal Structure Database align with the optimal solutions preserving experimental structures despite the discretized feasible atomic radii. These findings highlight the role of mathematical optimization problem as a theoretical foundation for mathematical crystal chemistry, enabling efficient structure prediction.