Stabilizing Polar Domains in MAPbBr3 via the Hydrostatic Pressure-Induced Liquid Crystal-like Transition

Pressure-induced phases of MAPbBr3 were investigated at room temperature in the range of 0–2.8 GPa by ab initio molecular dynamics. Two structural transitions at 0.7 GPa (cubic → cubic) and 1.1 GPa (cubic → tetragonal) involved both the inorganic host (lead bromide) and the organic guest (MA). MA dipoles behave like a liquid crystal undergoing isotropic → isotropic and isotropic → oblate nematic transitions as pressure confines their orientational fluctuations to a crystal plane. Beyond 1.1 GPa, the MA ions lie alternately along two orthogonal directions in the plane forming stacks perpendicular to it. However, the molecular dipoles are statically disordered, leading to stable polar and antipolar MA domains in each stack. H-Bond interactions, which primarily mediate host–guest coupling, facilitate the static disordering of MA dipoles. Interestingly, high pressures suppress CH3 torsional motion, emphasizing the role of C–H···Br bonds in the transitions.