Role of host/guest coupling in stabilizing the phases of the over-tolerant hybrid perovskite MHyPbX3

Abstract: $MHyPbBr_xCl_{3-x}$ exhibits an interesting temperature-induced phase diagram transitioning from monoclinic (Phase-II) to orthorhombic (Phase-I) and eventually to the high-temperature disordered cubic phase. However, experimental observations indicate the absence of either the cubic or orthorhombic phases in compositions with x=0 (chloride) and x=3 (bromide), respectively. We explain the composition dependence of the phase transition sequence in MHyPbX3 (X = Cl, Br) from the perspective of a host/guest framework for the system. We argue that the sequence of phase transitions in MHyPbX3 can be anticipated based on the competition between host distortion and host/guest coupling energies. A dominant coupling in MHyPbCl3 ensures the stabilization of the intermediate Phase-I while pushing the transition to cubic phase beyond its decomposition temperature. On the other hand, a balance of the energy scales in MHyPbBr3 suppresses Phase-I and stabilizes the cubic phase. Our expectations were supported by first-principles based estimates of the transition temperatures in both compounds, which yield trends in agreement with experimental observations. Furthermore, ab initio molecular dynamics simulations revealed that the cubic phase of MHyPbBr3 results from a disorder over locally orthorhombic structures, a clear manifestation of the balance of energy scales. We propose that the same concept can be employed to predict the stable phases in other hybrid perovskites.