Coupled Structural and Electronic Requirements in Alpha-FASnI3 Imposed by the Sn(II) Lone Pair

Abstract: Alpha-Formamidinium-tin-iodide (alpha-FASnI3) is a leading candidate for lead-free photovoltaic applications, adopting a nearly cubic structure at room temperature, but its stability remains limited by oxidation-driven degradation. Reliable first-principles modelling of the photovoltaic alpha-phase is further complicated by inconsistent structural models and levels of theory in the literature. Here, we identify the structural and electronic requirements needed for a physically sound description of alpha-FASnI3, whose behaviour is governed by a pseudo-Jahn-Teller (PJT) instability arising from the stereochemically active Sn(II) lone pair. Using 0 K relaxations, cross-code hybrid-functional benchmarks, and finite-temperature ab initio molecular dynamics, we show that a 4x4x4 supercell with randomly oriented FA+ cations is the smallest model that removes macroscopic dipoles, preserves cubic symmetry, recovers local octahedral tilts, and captures the characteristic PJT-driven Sn off-centering. Accurate band edges and a reliable band gap require a PBE0-level hybrid functional with spin-orbit coupling to treat Sn relativistic effects, together with nonlocal dispersion (rVV10) to capture the enhanced Sn-I covalency. Finite-temperature simulations reveal that Sn off-centering remains local, <111>-oriented, and robust against thermal fluctuations, and that reproducing the experimental 300 K band gap requires a 6x6x6 supercell. These results define the essential ingredients for reliable modelling of alpha-FASnI3 and provide a rigorous foundation for studying lone-pair-driven physics in tin halide perovskites.