Disordered multicomponent systems attract great interest due to their engineering design flexibility and subsequent rich space of properties. However, detailed characterization of the structure and atomic correlations remains challenging and hinders full navigation of these complex spaces. A lattice cluster expansion is one tool to obtain configurational and energetic resolution. While in theory a cluster expansion can be applied to any system of any dimensionality, the method has primarily been used in binary systems or ternary alloys. Here we apply cluster expansions in high-component ionic systems, setting up the largest cluster expansion ever attempted to our knowledge. In doing so, we address and discuss challenges specific to high-component ionic systems, namely charge state assignments, structural relaxations, and rank-deficient systems. We introduce practical procedures to make the fitting and analysis of complex systems tractable, providing guidance for future computational studies of disordered ionic systems.

无序多组分系统由于其工程设计的灵活性和随后丰富的属性空间而引起了极大的兴趣。然而，结构和原子相关性的详细表征仍然具有挑战性，并阻碍了这些复杂空间的全面导航。晶格簇扩展是获得配置和能量分辨率的一种工具。虽然理论上集群扩展可以应用于任何维度的任何系统，但该方法主要用于二元系统或三元合金。在这里，我们在高组分离子系统中应用簇扩展，建立了我们所知的最大的簇扩展。在此过程中，我们解决并讨论了高组分离子系统特有的挑战，即电荷状态分配、结构弛豫和秩不足系统。