GW quasiparticle band gap of the hybrid organic-inorganic perovskite CH${}_3$NH${}_3$PbI${}_3$: Effect of spin-orbit interaction, semicore electrons, and self-consistency

Abstract

We study the quasiparticle band gap of the hybrid organic-inorganic lead halide perovskite CH${}_3$NH${}_3$PbI${}_3$, using many-body perturbation theory based on the $GW$ approximation. We perform a systematic analysis of the band gap sensitivity to relativistic spin-orbit effects, to the description of semicore Pb-5$d$ and I-4$d$ electrons, and to the starting Kohn-Sham eigenvalues. We find that the inclusion of semicore states increases the calculated band gap by 0.2 eV, and self-consistency on the quasiparticle eigenvalues using a scissor correction increases the band gap by 0.4 eV with respect to the $G_0{W}_0$ result. These findings allow us to resolve an inconsistency between previously reported $GW$ calculations for CH${}_3$NH${}_3$PbI${}_3$. Our most accurate band gap is 1.65 eV, and is in good agreement with the measured optical gap after considering a small excitonic shift as determined in experiments.

10 pages, 4 figures

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