Understanding secondary order parameters in perovskites with tilted octahedra

In the family of perovskite materials, the tilts of BX 6 octahedra are the most common type of structural distortion. Conventionally, the formation of low-symmetry perovskite phases with tilted octahedra is analyzed by considering only primary order parameters. However, octahedral tilting also gives rise to secondary order parameters which contribute to additional atomic displacements, ordering and lattice distortions. Our study highlights the significant impact of secondary order parameters on the structural formation and emergent physical properties of perovskites. Through group-theoretical and crystallographic analyses, we have identified all secondary order parameters within Glazer-type tilt systems and clarified their physical manifestations. We explore the fundamental symmetry relationships among various structural degrees of freedom in perovskites, including tilt-induced ferroelasticity, correlations between displacements and ordering of atoms occupying different positions, and the potential for rigid unit rotations and unconventional octahedral tilts. Particular emphasis is placed on the emergence of secondary order parameters and their coupling with primary order parameters, as well as their symmetry-based hierarchy, illustrated through a modified Bärnighausen tree. We applied our theoretical insights to elucidate phase transitions in well known perovskites such as CaTiO 3 and R MnO 3 (where R = La and lanthanide ions), thereby demonstrating the significant influence of secondary order parameters on crystal structure formation. Our results serve as a symmetry-based guide for the design, identification and structural characterization of perovskites with tilted octahedra, and for understanding tilt-induced physical properties.