The Effect of Dynamic Structural Flexibility in Halide Perovskites

Despite their puzzling vibrational characteristics that include strong signatures of anharmonicity and thermal disorder already around room temperature, halide perovskites exhibit favorable optoelectronic properties for applications in photovoltaics and beyond. Whether these vibrational properties are advantageous or detrimental to their optoelectronic properties remains, however, an important open question. Here, this issue is addressed by investigation of the origin and consequences of the dynamic structural flexibility in the prototypical cubic CsPbBr$_3$, using first-principles molecular dynamics based on density-functional theory. It is shown that the dynamic flexibility associated with halide perovskites enables the so-called transversality, which manifests as a preference for large halide displacements perpendicular to the Pb-Br-Pb bonding axis. We find that transversality is concurrent with vibrational anharmonicity and short-ranged disorder correlations, which is favorable for photovoltaics since it implies sharp optical absorption profiles. These findings are contrasted to the case of PbTe, a material that shares several key properties with CsPbBr$_3$ but cannot exhibit any transversality and, hence, is found to exhibit much wider band-edge distributions. We conclude that the dynamic structural flexibility in halide perovskites as well as their unusual vibrational characteristics might not just be a mere coincidence, but could play active roles in establishing their favorable optoelectronic properties.