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The Role of Thermal Fluctuations and Vibrational Entropy: A Theoretical Insight into the δ-to-α Transition of FAPbI3
Abstract
Formamidinium lead iodide as a typical organometal perovskite has attracted considerable interest due to its suitable electronic structure. However, the intrinsic mechanisms of its unwanted δ-to-α phase transition remain elusive. By combined first-principles calculations, lattice dynamics analysis, and molecular dynamics simulations, we assign the α phase to the highly dynamic tetragonal phase, with the high-symmetry cubic structure emerging as a dynamically unstable maximum in the system's potential energy landscape. Finite-temperature Gibbs free energy calculations confirm that the δ-to-α transition should be considered as a hexagonal-to-tetragonal transition in contrast to the previous hexagonal-to-cubic assignment. More importantly, phonon thermal property calculations indicate that the driving force of the process is the vibrational entropy difference. These results point out the dynamical nature of the α phase and the key role of the vibrational entropy in perovskite-related phase transitions, the harnessing of which is critical for the successful uptake of organometal perovskites in commercial applications.
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“As summarized in Table 1, the uncorrected dataset yields unphysical values of ε DC and ε ∞ (approximately 13), whereas the corrected data produce values around 33, which are consistent with literature reports [38,39,41].”
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 [38]
In the citing paper
“The fitting was performed simultaneously on the dielectric function and conductivity spectra to ensure internal consistency of the extracted parameters [15,38,41].”
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 [38]
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Metadata
- Authors
- Yin, J., Teobaldi, G., & Liu, L.-M.
- Affiliations
- Beijing Computational Science Research Center (CN)
- Rutherford Appleton Laboratory (GB)
- School of Physics, Beihang University, Beijing 100083, China
- Venue
- The Journal of Physical Chemistry Letters
- Publisher
- American Chemical Society (ACS)
- Published
- 2022-03-30
- Volume
- 13
- Issue
- 13
- Pages
- 3089-3095
- ISSN
- 1948-7185 (ISSN-L)
- OpenAlex
- W4221094968
- Cited by
- 18
- References
- 41
- Citations by year
- 2026: 8 · 2025: 5 · 2024: 2 · 2023: 2 · 2022: 1
- FWCI
- 0.68
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- The Journal of Physical Chemistry Letters (publishedVersion)
- PubMed (publishedVersion)
- Science and Technology Facilities Council (submittedVersion)
- Funders
- Royal Society (NAF\R1\180242)
- National Natural Science Foundation of China (11974037, U1930402)
- Key Science and Technology Research Project of Yunnan (202002AB080001-1-6, 202102AB0800008)
- Topics
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Perovskite Materials and Applications
- Physical Sciences › Materials Science › Materials Chemistry › Ferroelectric and Piezoelectric Materials
- Physical Sciences › Materials Science › Electronic, Optical and Magnetic Materials › Magnetic and transport properties of perovskites and related materials
- Keywords
- FAPbI3, organometallic perovskites, vibrational entropy, thermal fluctuations, lattice dynamics, Gibbs free energy, potential energy landscape, tetragonal phase, phase stability
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