Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 125, Issue 46, Pages 25917-25926Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.1c08932
Keywords
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Funding
- Swedish Research Council (VR) [VR 2016-04590, 2020-03369]
- European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant [860553]
- Swedish energy agency [2017006797]
- Swedish Research Council [2018-05973]
- U.S. Department of Energy (DOE) Office of Science User Facility [DE-AC02-05CH11231]
- Swedish Research Council [2020-03369, 2016-04590] Funding Source: Swedish Research Council
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The electronic structures of four precursors for organic-inorganic hybrid perovskites were studied using X-ray emission spectroscopy, highlighting the stronger interaction between the methylammonium cation and the chlorine anion compared to the iodine anion. Detailed theoretical analysis emphasized the significance of ultrafast proton dynamics in core-excited states.
The electronic structures of four precursors for organic-inorganic hybrid perovskites, namely, methylammonium chloride and iodide, as well as formamidinium bromide and iodide, are investigated by X-ray emission (XE) spectroscopy at the carbon and nitrogen K-edges. The XE spectra are analyzed based on density functional theory calculations. We simulate the XE spectra at the Kohn-Sham level for ground-state geometries and carry out detailed analyses of the molecular orbitals and the electronic density of states to give a thorough understanding of the spectra. Major parts of the spectra can be described by the model of the corresponding isolated organic cation, whereas high-emission energy peaks in the nitrogen K-edge XE spectra arise from electronic transitions involving hybrids of the molecular and atomic orbitals of the cations and halides, respectively. We find that the interaction of the methylammonium cation is stronger with the chlorine than with the iodine anion. Furthermore, our detailed theoretical analysis highlights the strong influence of ultrafast proton dynamics in the core-excited states, which is an intrinsic effect of the XE process. The inclusion of this effect is necessary for an accurate description of the experimental nitrogen K-edge X-ray emission spectra and gives information on the hydrogen-bonding strengths in the different precursor materials.
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