Electronic Structure and Chemical Bonding in Methylammonium Lead Triiodide and Its Precursor Methylammonium Iodide.

A detailed examination of the electronic structures of methylammonium lead triiodide (MAPI) and methylammonium iodide (MAI) is performed with ab initio molecular dynamics (AIMD) simulations based on density functional theory, and the theoretical results are compared to experimental probes. The occupied valence bands of a MAPI single crystal and MAI powder are probed with X-ray photoelectron spectroscopy, and the conduction bands are probed from the perspective of nitrogen K-edge X-ray absorption spectroscopy. Combined, the theoretical simulations and the two experimental techniques allow for a dissection of the electronic structure unveiling the nature of chemical bonding in MAPI and MAI. Here, we show that the difference in band gap between MAPI and MAI is caused chiefly by interactions between iodine and lead but also weaker interactions with the MA+ counterions. Spatial decomposition of the iodine p levels allows for analysis of Pb-I σ bonds and π interactions, which contribute to this effect with the involvement of the Pb 6p levels. Differences in hydrogen bonding between the two materials, seen in the AIMD simulations, are reflected in nitrogen valence orbital composition and in nitrogen K-edge X-ray absorption spectra.

Experimental and Theoretical Core Level and Valence Band Analysis of Clean Perovskite Single Crystal Surfaces.

A detailed understanding of the surface and interface properties of lead halide perovskites is of interest for several applications, in which these materials may be used. To develop this understanding, the study of clean crystalline surfaces can be an important stepping stone. In this work, the surface properties and electronic structure of two different perovskite single crystal compositions (MAPbI3 and Csx FA1- x PbI3 ) are investigated using synchrotron-based soft X-ray photoelectron spectroscopy (PES), molecular dynamics simulations, and density functional theory. The use of synchrotron-based soft X-ray PES enables high surface sensitivity and nondestructive depth-profiling. Core level and valence band spectra of the single crystals are presented. The authors find two carbon 1s contributions at the surface of MAPbI3 and assign these to MA+ ions in an MAI-terminated surface and to MA+ ions below the surface. It is estimated that the surface is predominantly MAI-terminated but up to 30% of the surface can be PbI2 -terminated. The results presented here can serve as reference spectra for photoelectron spectroscopy investigations of technologically relevant polycrystalline thin films, and the findings can be utilized to further optimize the design of device interfaces.

Sensitivity of Nitrogen K-Edge X-ray Absorption to Halide Substitution and Thermal Fluctuations in Methylammonium Lead-Halide Perovskites.

The performance of hybrid perovskite materials in solar cells crucially depends on their electronic properties, and it is important to investigate contributions to the total electronic structure from specific components in the material. In a combined theoretical and experimental study of CH3NH3PbI3-methylammonium lead triiodide (MAPI)-and its bromide cousin CH3NH3PbBr3 (MAPB), we analyze nitrogen K-edge (N 1s-to-2p*) X-ray absorption (XA) spectra measured in MAPI and MAPB single crystals. This permits comparison of spectral features to the local character of unoccupied molecular orbitals on the CH3NH3 + (MA+) counterions and allows us to investigate how thermal fluctuations, hydrogen bonding, and halide-ion substitution influence the XA spectra as a measure of the local electronic structure. In agreement with the experiment, the simulated spectra for MAPI and MAPB show close similarity, except that the MAPB spectral features are blue-shifted by +0.31 eV. The shift is shown to arise from the intrinsic difference in the electronic structure of the two halide atoms rather than from structural differences between the materials. In addition, from the spectral sampling analysis of molecular dynamics simulations, clear correlations between geometric descriptors (N-C, N-H, and H···I/Br distances) and spectral features are identified and used to explain the spectral shapes.

Multistep Explicit Solvation Protocol for Calculation of Redox Potentials.

The calculation of molecular redox potentials in aqueous solution presents a challenge to quantum chemistry due to the need to calculate charged, open-shell species experiencing large solvent effects. Traditionally, redox potentials are calculated via the use of density functional theory and continuum solvation methods, but such protocols have been found to often suffer from large errors, particularly in the case of aqueous solution. While explicit solvation models hold promise of higher accuracy to describe solvent effects in general, their complicated use and lack of well-defined, reliable protocols has hindered their adoption. In this study, we present an explicit-solvation-based approach for the calculation of molecular redox potentials. We combine the use of affordable semiempirical QM/MM molecular dynamics (making use of the recently proposed GFN-xTB method by Grimme et al.) for both redox states and use the linear response approximation to relate vertical ionization energies to the adiabatic redox potential. Simulation length, averaging over snapshots, and accounting for bulk and polarization effects are systematically evaluated using phenol as a working example. We find that it is crucial to reliably account for bulk solvation effects in these calculations, as well as polarization effects which we divide up into short-range and long-range contributions. The short-range polarization contribution is accounted for via QM-region expansion, while the long-range contribution is accounted for via Drude-polarizable QM/MM. Our multistep protocol has been coded to be used in a fully automatic way in a local version of Chemshell. It has been evaluated on a test set of oxidation potentials of organic molecules and found to give gas-solution redox shifts with a mean absolute error of 0.13 eV with respect to experiment, compared to mean absolute errors of 0.26 and 0.21 eV with CPCM and SMD continuum models, respectively.