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.

arXiv comment10 pages, 4 figures

References in corpus (19)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• The GW method
• Relativistic Solar Cells
• Yambo: an \textit{ab initio} tool for excited state calculations
• Steric engineering of metal-halide perovskites with tunable optical band gaps
• Quasiparticle Self-Consistent GW Theory
• Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers
• Structural and Electronic Properties of Hybrid Perovskites for High-Efficiency Thin-Film Photovoltaics from First-Principles
• Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells
• Quasiparticle band structure based on a generalized Kohn-Sham scheme
• Band Offsets at Semiconductor-Oxide Interfaces from Hybrid Density Functional Calculations
• Unified description of ground and excited states of finite systems: the self-consistent GW approach
• GW quasiparticle band structures of stibnite, antimonselite, bismuthinite, and guanajuatite
• Self-consistent GW: All-electron implementation with localized basis functions
• GW method with the self-consistent Sternheimer equation
• Effect of Semicore Orbitals on the Electronic Band Gaps of Si, Ge, and GaAs within the GW Approximation
• Effect of the quantistic zero-point atomic motion on the opto-electronic properties of diamond and trans-polyacetylene
• GW quasiparticle bandgaps of anatase TiO2 starting from DFT+U
• Spin-dependent Hedin's equations

Cited by in corpus (27)

• Many-body perturbation theory calculations using the yambo code
• Role of Polar Phonons in the Photo Excited State of Metal Halide Perovskites
• Perspective: Theory and simulation of hybrid halide perovskites
• Temperature Dependence of the Energy Levels of Methylammonium Lead Iodide Perovskite from First Principles
• Carrier Lifetimes and Polaronic Mass Enhancement in the Hybrid Halide Perovskite CH${}_3$NH${}_3$PbI${}_3$ from Multiphonon Fröhlich Coupling
• Phonon Screening of Excitons in Semiconductors: Halide Perovskites and Beyond
• Dynamic Symmetry Breaking and Spin Splitting in Metal Halide Perovskites
• Room temperature dynamic correlation between methylammonium molecules in lead-iodine based perovskites: An ab-initio molecular dynamics perspective
• Towards predictive band gaps for halide perovskites: Lessons from one-shot and eigenvalue self-consistent GW
• Converged GW quasiparticle energies for transition metal oxide perovskites
• Optoelectronic Properties and Defect Physics of Lead-free Photovoltaic Absorbers Cs${}_2$Au${}^I$Au${}^{III}$X${}_6$ (X=I, Br)
• Exploring librational pathways with on-the-fly machine-learning force fields: Methylammonium molecules in MAPbX${}_3$ (X=I, Br, Cl) perovskites
• Optical properties of CsCu${}_2$X${}_3$ (X=Cl, Br and I): A comparative study between hybrid time-dependent density-functional theory and the Bethe-Salpeter equation
• First-principles investigation of organic photovoltaic materials C${}_{60}$, C${}_{70}$, [C${}_{60}$]PCBM, and bis-[C${}_{60}$]PCBM using a many-body $G_0{W}_0$-Lanczos approach
• Direct, indirect, and self-trapped excitons in Cs${}_2$AgBiBr${}_6$
• Emergence of Rashba-/Dresselhaus Effects in Ruddlesden-Popper Halide Perovskites with Octahedral Rotations
• Long-range order imposed by short-range interactions in methylammonium lead iodide: Comparing point-dipole models to machine-learning force fields
• Capturing Excitonic Effects in Lead Iodide Perovskites from Many-Body Perturbation Theory
• Simple eigenvalue-self-consistent $\bar{\Delta }G{W}_0$
• Breathing bands due to molecular order in CH3NH3PbI3
• Modeling the electronic structure of organic materials: A solid-state physicist's perspective
• Hybrid Halide Perovskites: Fundamental Theory and Materials Design
• Rashba Spin-Orbit Coupling Enhanced Carrier Lifetime in Organometal Halide Perovskites
• Free-electron effects on optical absorption of hybrid perovskite CH${}_3$NH${}_3$PbI${}_3$ from first principles
• Joint Approximate Diagonalization approach to Quasiparticle Self-Consistent $GW$ calculations
• Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals
• Renormalization of excitonic properties by polar phonons