Magnetic interactions based on proton orbital motion in CH${}_3$NH${}_3$PbI${}_3$ and CH${}_3$NH${}_3$PbBr${}_3$

The microscopic origin of the remarkable optoelectronic properties of one of the most studied contemporary materials remains unclear. Here, we identify the existence of magnetic interactions between intermolecular proton orbitals in CH${}_3$NH${}_3$PbI${}_3$ and CH${}_3$NH${}_3$PbBr${}_3$. In particular, a unique sharp drop and a pronounced step-up discontinuity in the magnetic susceptibility at the tetragonal-to-cubic phase transitions are identified in CH${}_3$NH${}_3$PbI${}_3$ and CH${}_3$NH${}_3$PbBr${}_3$, respectively. The magnetic interactions in the orthorhombic and tetragonal phases are dependent on thermal history and lattice orientation while nearly independent of the applied external magnetic field. In CH${}_3$NH${}_3$PbBr${}_3$, the CH${}_3$ and NH${}_3$${}^{+}$ components reorient in an uncorrelated fashion resulting the cubic phase to also exhibit magnetic anisotropy. Our findings provide a potential link connecting the highly light-absorbing CH${}_3$NH${}_3$${}^{+}$ and the exceptional properties of the charge carriers of the inorganic framework in hybrid perovskite solar cells.