Excited-State Dynamics of a CsPbBr3 Nanocrystal Terminated with Binary Ligands: Sparse Density of States with Giant Spin–Orbit Coupling Suppresses Carrier Cooling

Fully inorganic lead halide perovskite nanocrystals (NCs) are of interest for photovoltaic and light emitting devices due to their electronic properties which can be tuned/optimized via halide composition, surface passivation, doping, and confinement. Compared to bulk materials, certain excited-state properties in NCs can be adjusted due to electronic confinement effects such as suppressed hot carrier cooling and enhanced radiative recombination. Here we use spinor Kohn-Sham orbitals (SKSOs) with spin-orbit coupling (SOC) interaction as a basis to compute excited-state dissipative dynamics simulations on a fully-passivated CsPbBr3 NC atomistic model. Redfield theory in density matrix formalism is used to describe electron-phonon interactions which drive hot carrier cooling and non-radiative recombination (k_(non-rad)). Radiative recombination (k_rad) is calculated through oscillator strengths using SKSO basis. From comparing ratio of k_rad and k_rad+k_(non-rad) we computed a theoretical photoluminescence ...