Mixed Cs and FA Cations Slow Electron–Hole Recombination in FAPbI3 Perovskites by Time-Domain Ab Initio Study: Lattice Contraction versus Octahedral Tilting

Using time domain density functional theory combined with nonadiabatic (NA) molecular dynamics, we show that electron-hole recombination takes subnanoseconds in FAPbI3, showing excellent agreement with experiment. Cs doping retards charge recombination by factors of 1.1 and 3.1 due to lattice contraction and octahedral tilting, respectively. Lattice contraction decreases the NA coupling and increases the coherence time arising from the suppressed atomic fluctuations, slightly slowing recombination because the two factors have an opposite influence on quantum transition. In contrast, octahedral tilting simultaneously decreases the NA coupling, thanks to the reduced overlap between Pb and I orbitals, and the coherence time, extending the excited-state lifetime over 1 ns. Our simulations provide a mechanistic understanding for delayed charge losses in the mixed Cs and FA system, suggesting a rational strategy to improve perovskite solar cell performance.