Electronic structure of (organic-)inorganic metal halide perovskites: the dilemma of choosing the right functional

TL;DR

This paper evaluates various computational methods, including GW and hybrid functionals, for accurately describing the electronic structure of metal halide perovskites, emphasizing the importance of tuning parameters for reliable band gap predictions.

Contribution

It systematically compares different computational approaches and tuning strategies, identifying the most suitable hybrid functional parameters for lead-iodine perovskites.

Findings

Hybrid functionals with density-based tuning match GW band gaps.

Tuning the mixing parameter improves accuracy across related perovskites.

Methodology is transferable to other lead-iodine perovskites.

Abstract

Organic-inorganic metal halide perovskites (HaPs) are intensively studied for their light-harvesting properties. Owing to the interplay between strong electron-electron interaction and spin-orbit coupling (SOC), their quantitative theoretical description is still a challenge as evidenced by the wide variety of results available in literature. Here, various methodologies for computing their electronic structure are evaluated, also accounting for SOC. More specific, the GW approach as well as variants of the hybrid functionals PBE0 and HSE are at the center of our investigations. For both functionals, we explore methods to determine the mixing parameter $\alpha$, and for HSE, we investigate the impact of the screening-parameter $\omega$. An extensive investigation of PbI2, a precursor of many HaPs, leads to the conclusion that hybrid functionals with $\alpha$ tuned by the density-based mixing method are most suitable for obtaining band gaps comparable to $G_0W_0$ results. Moreover, this methodology is transferable to CsPbI3, and the same behaviour is expected for the entire family of lead-iodine perovskites.