Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites
Open accessAbstract
The introduction of a mobile and polarized organic moiety as a cation in 3D lead-iodide perovskites brings fascinating optoelectronic properties to these materials. The extent and the time scales of the orientational mobility of the organic cation and the molecular mechanism behind its motion remain unclear, with different experimental and computational approaches providing very different qualitative and quantitative description of the molecular dynamics. Here we use ultrafast 2D vibrational spectroscopy of methylammonium (MA) lead iodide to directly resolve the rotation of the organic cations within the MAPbI3 lattice. Our results reveal two characteristic time constants of motion. Using ab initio molecular dynamics simulations, we identify these as a fast (∼300 fs) "wobbling-in-a-cone" motion around the crystal axis and a relatively slow (∼3 ps) jump-like reorientation of the molecular dipole with respect to the iodide lattice. The observed dynamics are essential for understanding the electronic properties of perovskite materials.
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Precise temporal alignment between reference and sample waveforms is essential for reliable conductivity analysis, particularly when timing uncertainties approach the tens-of-femtoseconds regime.
“Precise temporal alignment between reference and sample waveforms is therefore essential for reliable conductivity analysis, particularly when timing uncertainties approach the tens-of-femtoseconds regime [45,46].”
From Impact of Sub-picosecond Timing Errors on Complex Conductivity Extraction in Terahertz Time-Domain Spectroscopy of Ultrathin FAPbI3 Films (2026) · cites this paper as [45]
The paper’s discussion of 2D-IR measurements describes scanning the delay between pump pulses and analyzing transient anisotropy, but does not address alignment of reference and sample waveforms for conductivity analysis. Searches for waveform alignment, conductivity, and tens-of-femtoseconds timing uncertainty found no passage supporting the attributed claim. No page numbers are available in our copy. (LLM, conf=0.76)
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Research works printed but not linked: 4
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- Authors
- Bakulin, A. A., Selig, O., Bakker, H. J., Rezus, Y. L. A., Müller, C., Glaser, T., Lovrincic, R., Sun, Z., Chen, Z., Walsh, A., Frost, J. M., & Jansen, T. L. C.
- Affiliations
- University of Cambridge (GB)
- Institute for Atomic and Molecular Physics (NL)
- Heidelberg University (DE)
- Institute for High-Frequency Technology, TU Braunschweig, Schleinitzstr. 22, 38106 Braunschweig, Germany
- Centre National de la Recherche Scientifique (FR)
- Engineering and Physical Sciences Research Council (GB)
- University of Bath (GB)
- University of Groningen (NL)
- Corresponding author
- Bakulin, Artem A.
- ORCID
- Venue
- The Journal of Physical Chemistry Letters
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-09-04
- Volume
- 6
- Issue
- 18
- Pages
- 3663-3669
- ISSN
- 1948-7185 (ISSN-L)
- OpenAlex
- W1882429841
- Cited by
- 372
- References
- 55
- Citations by year
- 2026: 10 · 2025: 12 · 2024: 15 · 2023: 22 · 2022: 23 · 2021: 35 · 2020: 40 · 2019: 35 · 2018: 58 · 2017: 56 · 2016: 57 · 2015: 9
- FWCI
- 28.93
- Type
- journal article
- Language
- en
- Open access
- green
- hdl.handle.net
- Licence
- other-oa
- Locations
- The Journal of Physical Chemistry Letters (publishedVersion)
- PubMed (publishedVersion)
- University of Groningen research database (University of Groningen / Centre for Information Technology) (submittedVersion, other-oa)
- Spiral (Imperial College London) (submittedVersion)
- Apollo (University of Cambridge) (submittedVersion)
- Funders
- Nederlandse Organisatie voor Wetenschappelijk Onderzoek (Stichting voor Fundamenteel Onderzoek der Materie, VENI Grant)
- EU marie curie (Career Integration Grant (303824))
- Dutch French Academy (van Gogh grant)
- Royal Society (University Research Fellow)
- Topics
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Perovskite Materials and Applications
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Physical Sciences › Materials Science › Materials Chemistry › Ferroelectric and Piezoelectric Materials
- Keywords
- methylammonium lead iodide, orientational dynamics, ultrafast dynamics, perovskite crystals, ab initio molecular dynamics
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