Finite-temperature simulation of anharmonicity and octahedral tilting transitions in halide perovskites
Abstract
Octahedral tilting transitions are observed in most inorganic halide perovskites and play an important role in determining their functional and thermodynamic properties. Despite existing near room temperature, the cubic and tetragonal forms of halide perovskites become dynamically unstable at low temperature, making it impossible to study their thermodynamic properties with commonly used quasiharmonic models. An anharmonic vibrational Hamiltonian is constructed that accurately reproduces the low-energy portion of the potential-energy surface of the halide perovskite CsPbBr3. The Hamiltonian is validated using a large first-principles dataset of energies calculated within density functional theory for large-amplitude deformations of the CsPbBr3 crystal. Monte Carlo simulations performed on the Hamiltonian reproduce the orthorhombic-tetragonal-cubic phase transitions observed in CsPbBr3 and many other halide perovskites, demonstrating the importance of anharmonic vibrational excitations in stabilizing the tetragonal and cubic phases in these materials. Measures of local structure and octahedral tilting in the cubic and tetragonal phases, obtained from Monte Carlo simulations, confirm the connection between large anisotropic displacement factors and octahedral tilting, as observed experimentally.
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1577828
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Materials
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 11; Journal ID: ISSN 2475-9953
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Materials Science; Anharmonic lattice dynamics; Structural phase transition; Perovskite
Citation Formats
Bechtel, Jonathon S., Thomas, John C., and Van der Ven, Anton. Finite-temperature simulation of anharmonicity and octahedral tilting transitions in halide perovskites. United States: N. p., 2019.
Web. doi:10.1103/physrevmaterials.3.113605.
Bechtel, Jonathon S., Thomas, John C., & Van der Ven, Anton. Finite-temperature simulation of anharmonicity and octahedral tilting transitions in halide perovskites. United States. https://doi.org/10.1103/physrevmaterials.3.113605
Bechtel, Jonathon S., Thomas, John C., and Van der Ven, Anton. Mon .
"Finite-temperature simulation of anharmonicity and octahedral tilting transitions in halide perovskites". United States. https://doi.org/10.1103/physrevmaterials.3.113605. https://www.osti.gov/servlets/purl/1577828.
@article{osti_1577828,
title = {Finite-temperature simulation of anharmonicity and octahedral tilting transitions in halide perovskites},
author = {Bechtel, Jonathon S. and Thomas, John C. and Van der Ven, Anton},
abstractNote = {Octahedral tilting transitions are observed in most inorganic halide perovskites and play an important role in determining their functional and thermodynamic properties. Despite existing near room temperature, the cubic and tetragonal forms of halide perovskites become dynamically unstable at low temperature, making it impossible to study their thermodynamic properties with commonly used quasiharmonic models. An anharmonic vibrational Hamiltonian is constructed that accurately reproduces the low-energy portion of the potential-energy surface of the halide perovskite CsPbBr3. The Hamiltonian is validated using a large first-principles dataset of energies calculated within density functional theory for large-amplitude deformations of the CsPbBr3 crystal. Monte Carlo simulations performed on the Hamiltonian reproduce the orthorhombic-tetragonal-cubic phase transitions observed in CsPbBr3 and many other halide perovskites, demonstrating the importance of anharmonic vibrational excitations in stabilizing the tetragonal and cubic phases in these materials. Measures of local structure and octahedral tilting in the cubic and tetragonal phases, obtained from Monte Carlo simulations, confirm the connection between large anisotropic displacement factors and octahedral tilting, as observed experimentally.},
doi = {10.1103/physrevmaterials.3.113605},
journal = {Physical Review Materials},
number = 11,
volume = 3,
place = {United States},
year = {Mon Nov 18 00:00:00 EST 2019},
month = {Mon Nov 18 00:00:00 EST 2019}
}
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