Electronic and structural properties of mixed-cation hybrid perovskites studied using an efficient spin-orbit...

Fundamental understanding and optimization of the emerging mixed organic-inorganic hybrid perovskites for solar cells require multiscale modeling starting from ab initio quantum mechanics methods. Particularly, it is important to correctly predict the structural and electronic properties such as phase stability, lattice parameters, band gaps, and band structures. Although density functional theory is the method of choice to address these properties and generate the input for subsequent multiscale, high-throughput, and data-driven approaches, standard exchange correlation functionals fail to reproduce the bandgap, particularly if spin-orbit coupling (SOC) is correctly taken into account. While many SOC-included hybrid functionals suffer from low transferability between different molecular ions and are computationally costly, we propose an efficient multistep simulation protocol based on the DFT-1/2 method. We apply this approach to APbI₃ with A: FA, MA, Cs, and systems with mixed cations and show how the choice of the A-cation modifies the Pb-I scaffold and the hydrogen bonding and discuss their interplay with structural stability. Furthermore, band gaps, band structures, Rashba band splitting, Born effective charges as well as partial density of states (PDOS) are compared for different cases w/wo the SOC effect and the DFT-1/2 approach.