Crystal Symmetry and Static Electron Correlation Greatly Accelerate Nonradiative Dynamics in Lead Halide Perovskites.

Abstract

Using a recently developed many-body nonadiabatic molecular dynamics (NA-MD) framework for large condensed matter systems, we study the phonon-driven nonradiative relaxation of excess electronic excitation energy in cubic and tetragonal phases of the lead halide perovskite CsPbI3. We find that the many-body treatment of the electronic excited states significantly changes the structure of the excited states coupling, promotes a stronger nonadiabatic coupling of states, and ultimately accelerates the relaxation dynamics relative to the single-particle description of excited states. The acceleration of the nonadiabatic dynamics correlates with the degree of configurational mixing, which is controlled by the crystal symmetry. The higher-symmetry cubic phase of CsPbI3 exhibits stronger configuration mixing than does the tetragonal phase and subsequently yields faster nonradiative dynamics. Overall, using a many-body treatment of excited states and accounting for decoherence dynamics are important for closing the gap between the computationally derived and experimentally measured nonradiative excitation energy relaxation rates.