How cation nature controls the bandgap and bulk Rashba splitting of halide perovskites.

Because of instability issues presented by metal halide perovskites based on methylammonium (MA), its replacement to Cs $$ \mathrm{Cs} $$ has emerged as an alternative to improve the materials' durability. However, the impact of this replacement on electronic properties, especially gap energy and bulk Rashba splitting remains unclear since electrostatic interactions from organic cations can play a crucial role. Through first-principles calculations, we investigated how organic/inorganic cations impact the electronic properties of MAPbI 3 $$ {\mathrm{MAPbI}}_3 $$ and CsPbI 3 $$ {\mathrm{CsPbI}}_3 $$ perovskites. Although at high temperatures the organic cation can assume spherical-like configurations due to its rotation into the cages, our results provide a complete electronic mechanism to show, from a chemical perspective based on ab initio calculations at 0 K $$ 0\ \mathrm{K} $$ , how the MA $$ \mathrm{MA} $$ dipoles suppression can reduce the MAPbI 3 $$ {\mathrm{MAPbI}}_3 $$ gap energy by promoting a degeneracy breaking in the electronic states from the PbI 3 $$ {\mathrm{PbI}}_3 $$ framework, while the dipole moment reinforcement is crucial to align theory ↔ $$ \leftrightarrow $$ experiment, increasing the bulk Rashba splitting through higher Pb $$ \mathrm{Pb} $$ off-centering motifs. The lack of permanent dipole moment in Cs $$ \mathrm{Cs} $$ results in CsPbI 3 $$ {\mathrm{CsPbI}}_3 $$ polymorphs with a pronounced Pb $$ \mathrm{Pb} $$ on-centering-like feature, which causes suppression in their respective bulk Rashba effect.