Two-Stage Dynamic Transformation from δ- to α‑CsPbI₃

The phase transformation from δ- to α-CsPbI₃has garnered extensive research interest. However, detailed understanding of this structural transformation at atomistic scale remains elusive. Here, we reported the full atomistic molecular dynamics simulation of this important phase transformation using an enhanced sampling method, Metadynamics (MetaD). Particularly, two-stage of dynamic transformation related to [PbI₃]⁻ chains’ motions was observed, namely, the intrachain rearrangement followed by interchain connection. Moreover, the dynamic motion of Cs⁺ cations plays an important role in facilitating the interchain connection kinetically. The insights reported in this work will provide valuable guidance for further advancing the understanding of phase transformation of CsPbI₃.