Spin–Orbit Coupling Notably Retards Non-radiative Electron–Hole Recombination in Methylammonium Lead Triiodide Perovskites

The giant spin–orbit coupling (SOC) of a heavy lead element significantly extends charge carrier lifetimes of lead halide perovskites (LHPs). The physical mechanism remains unclear and requires a quantum dynamics perspective. Taking methylammonium lead iodide (MAPbI₃) as a prototypical system and using non-adiabatic molecular dynamics combined with 1/2 electron correction, we show that SOC notably reduces the non-radiative electron–hole (e–h) recombination by decreasing the non-adiabatic coupling (NAC) primarily as a result of SOC decreasing the e–h wave function overlap by reshaping the electron and hole wave functions. Second, SOC causes spin mismatch subject to spin-mixed states, which further decreases NAC. The charge carrier lifetime is about 3-fold longer in the present of SOC relative to the absence of SOC. Our study generates the fundamental understanding of SOC minimizing non-radiative charge and energy losses in LHPs.