Methylammonium lead iodide perovskite, ${\mathrm{CH}}_3{\mathrm{NH}}_3{\mathrm{PbI}}_3$ (${\mathrm{MAPbI}}_3$), has attracted tremendous interest for its exceptional optoelectronic performance. However, the effect of MA arrangement on charge carrier recombination remains unclear. Here, ${\mathrm{BF}}_4$ doping is introduced to preserve distinguishable ferroelectric (FE) and antiferroelectric (AFE) MA configurations over the accessible simulation timescale, enabling a direct comparison of the influence of MA arrangement on carrier recombination. Using time-domain density functional theory and ab initio nonadiabatic molecular dynamics, we demonstrate that the nonradiative recombination in ${\mathrm{BF}}_4$-doped ${\mathrm{MAPbI}}_3$ perovskite with an AFE MA arrangement (${\mathrm{BF}}_4$-AFE) is slowed by an order of magnitude when compared with that in the FE structure. The strong spatial variation of the built-in electric field in the AFE structure introduces effective charge separation. The strong electrostatic repulsion between adjacent MA molecules in the ${\mathrm{BF}}_4$-AFE structure weakens MA-related atomic fluctuations, which strongly suppresses the high-frequency electron–vibration interaction. These effects result in a short pure dephasing time and a weak nonadiabatic coupling in the ${\mathrm{BF}}_4$-AFE structure, finally revealing its long carrier lifetime. This work provides mechanistic insight into how MA molecular arrangement influences carrier recombination in ${\mathrm{MAPbI}}_3$.

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• Carrier generation & recombination
• Organic-inorganic hybrid perovskites
• Density functional calculations
• Molecular dynamics
• Time-dependent DFT