Simulating the Coupled Structural–ElectronicDynamics of Photoexcited Lead Iodide Perovskites

Motivated by the optoelectronic applications of lead halide perovskites (LHPs), researchers have paid considerable attention to their photoexcited-state dynamics, where the coupling between the electronic and nuclear dynamics is pronounced. Here, we present simulations of the photoexcited-state dynamics of representative lead iodide perovskites, CsPbI3 and MAPbI3 (MA = CH3NH3), by adopting nonadiabatic molecular dynamics combined with the linear-response time-dependent density-functional tight-binding (LR-TD-DFTB) method, an efficient excited-state calculation framework. In the calculations, the electronic wave function and the nuclear coordinates were propagated in a mutually dependent manner. The results suggest that the excited LHPs undergo exciton dissociation, hot carrier cooling, and polaron formation on similar time scales. In particular, the decay of the carrier energy is attributed to not only the relaxation toward the band edge but also the change in orbital energy originating from the structural deformation, highlighting the importance of coupling between the electronic and nuclear degrees of freedom.