Jiyuan Yang^1,2, Tianyuan Zhu^2,3, Shi Liu^2,3*

1 Zhejiang University, Hangzhou, Zhejiang 310058, China

2 Key Laboratory for Quantum Materials of Zhejiang Province, Department of Physics, School of Science, Westlake University, Hangzhou, Zhejiang 310024, China

3 Institute of Natural Sciences, Westlake Institute for Advanced Study, Hangzhou, Zhejiang 310024, China

* Corresponding authors emails: liushi@westlake.edu.cn

DOI10.24435/materialscloud:wt-91 [version v1]

Publication date: Nov 04, 2022

How to cite this record

Jiyuan Yang, Tianyuan Zhu, Shi Liu, Onsite and intersite electronic correlations in the Hubbard model for halide perovskites, Materials Cloud Archive 2022.135 (2022), https://doi.org/10.24435/materialscloud:wt-91

Description

Halide perovskites (HPs) are widely viewed as promising photovoltaic and light-emitting materials for their suitable band gaps in the visible spectrum. Density functional theory (DFT) calculations employing (semi)local exchange-correlation functionals usually underestimate the band gaps for these systems. Accurate descriptions of the electronic structures of HPs often demand higher-order levels of theory such as the Heyd-Scuseria-Ernzerhof (HSE) hybrid density functional and GW approximations that are much more computationally expensive than standard DFT. Here, we investigate three representative types of HPs, ABX3 halide perovskites, vacancy-ordered double perovskites (VODPs), and bond disproportionated halide perovskites (BDHPs), using DFT+U+V with onsite U and intersite V Hubbard parameters computed self-consistently without a priori assumption. The inclusion of Hubbard corrections improves the band gap prediction accuracy for all three types of HPs to a similar level of advanced methods. Moreover, the self-consistent Hubbard U is a meaningful indicator of the true local charge state of multivalence metal atoms in HPs. The inclusion of the intersite Hubbard V is crucial to properly capture the hybridization between valence electrons on neighboring atoms in BDHPs that have breathing-mode distortions of halide octahedra. In particular, the simultaneous convergence of both Hubbard parameters and crystal geometry enables a band gap prediction accuracy superior to HSE for BDHPs but at a fraction of the cost. Our work highlights the importance of using self-consistent Hubbard parameters when dealing with HPs that often possess intricate competitions between onsite localization and intersite hybridization.

Materials Cloud sections using this data

Files

File name	Size	Description
all_structures.zip MD5md5:3388e8e12c0fe1a01a3f98996412b1aa	12.3 KiB	all_structures includes all the structures optimized by PBE (in vasp format)
DFT+U_example.zip MD5md5:3f979d343d9a41c01b1ccaf538bb108a	1.1 MiB	An example of DFT+U (QE scripts)
DFT+U+V_example.zip MD5md5:923972e831ae9521d4cf6b9ed5b39924	1.1 MiB	An example of DFT+U+V (QE scripts)
ReadMe.txt MD5md5:4cd8777a9ae6f0c656eba7cca23bd78d	503 Bytes	ReadMe file

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Keywords

Halide perovskite DFT+U+V Band gap