Collective Motion Improves the Stability and Charge Carrier Lifetime of Metal Halide Perovskites: A Phonon-Resolved Nonadiabatic Molecular Dynamics Study

By implementing a novel algorithm that realizes the constraints of certain normal modes of interest and using nonadiabatic molecular dynamics for the CsPbBr3, we explicitly demonstrate for the first time that the collective motion between the Cs atom and inorganic octahedra facilitates to delay the nonradiative recombination of negative and positive charges. The Cs atoms can instantaneously respond to the motion of Pb and Br atoms during normal molecular dynamics, maintain the perovskite structure, and homogenize the structural distortion caused by thermal fluctuations, thus decreasing nonadiabatic coupling and charge recombination. In contrast, the perovskite becomes unstable because geometry distortion is strongly localized when the normal modes of Cs atoms are constrained, which increases the nonadiabatic coupling and accelerates charge recombination. The study emphasizes the important role of correlated motion on the stability and charge-phonon dynamics in metal halide perovskites.