Bulk Rashba Effect Splitting and Suppression in Polymorphs of Metal Iodine Perovskites

• Published in: The journal of physical chemistry letters Vol. 12; no. 30; pp. 7245 - 7251
• Main Authors: Octavio de Araujo, Luis, Sabino, Fernando P, Rêgo, Celso R. C, Guedes-Sobrinho, Diego
• Format: Journal Article
• Language: English
• Published: American Chemical Society 05.08.2021
• Subjects: Physical Insights into Materials and Molecular Properties
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.1c02048

We quantified the bulk Rashba splitting and suppression in polymorphs of MA­(Pb, Sn, Ge, or Si)­I3 perovskites. The low-computational-cost DFT-1/2 quasiparticle correction was performed for all structures, combined with the inclusion of spin–orbit coupling (SOC) effects. The presence of SOC and symmetry breaking from the metal off-centering octahedral distortion are indispensable and essential conditions for Rashba splitting, whose magnitude emerges from the Pb → Si sequence. Additionally, the quasiparticle correction provides energy bandgaps for MAPbI3 (cubic, tetragonal, and orthorhombic), MASnI3 (cubic and tetragonal), and MAGeI3 (cubic) that are in outstanding agreement with experimental results. However, while gap energies are yielded collaboratively from the metal off-centering and relative octahedral tiltings, the bulk Rashba suppression is reached for metal on-centering (octahedral platonic-like) configurations that are thermodynamically stable even when the charge polarization is kept invariant among metal–I bonds in the polymorphs.