Nonradiative Relaxation in Real-Time Electronic Dynamics OSCF2: Organolead Triiodide Perovskite.

Abstract

We apply our recently developed nonequilibrium real-time time-dependent density functional theory (OSCF2) to investigate the transient spectrum and relaxation dynamics of the tetragonal structure of methylammonium lead triiodide perovskite (MAPbI3). We obtain an estimate of the interband relaxation kinetics and identify multiple ultrafast cooling channels for hot electrons and hot holes that largely corroborate the dual valence-dual conduction model. The computed relaxation rates and absorption spectra are in good agreement with the existing experimental data. We present the first ab initio simulations of the perovskite transient absorption (TA) spectrum, substantiating the assignment of induced bleaches and absorptions including a Pauli-bleach signal. This paper validates both OSCF2 as a good qualitative model of electronic dynamics, and the dominant interpretation of the TA spectrum of this material.