Coupling Methylammonium and Formamidinium Cations with Halide Anions: Hybrid Orbitals, Hydrogen Bonding, and the Role of Dynamics

Chinnathambi Kamal*, Dirk Hauschild, Linsey Seitz, Ralph Steininger, Wanli Yang, Clemens Heske, Lothar Weinhardt, Michael Odelius

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)25917-25926
Number of pages10
JournalJournal of Physical Chemistry C
Issue number46
StatePublished - Nov 25 2021

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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