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Hydrogen Bonding versus Entropy: Revealing the Underlying Thermodynamics of the Hybrid Organic–Inorganic Perovskite [CH3NH3]PbBr3

Cite this: Chem. Mater. 2018, 30, 24, 8782–8788
Publication Date (Web):November 2, 2018
Copyright © 2018 American Chemical Society

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    The enormous research efforts dedicated to hybrid organic–inorganic perovskites have led to a deep understanding of these materials; however, the role of entropy and its ramifications for the properties of the materials have been only sparsely explored. In this study, we quantify the phase transition mechanism in the hybrid organic–inorganic perovskite [CH3NH3]PbBr3 by studying low-energy collective phonon modes using a combination of inelastic neutron scattering and ab initio lattice dynamics. We demonstrate that a delicate interplay among hydrogen bonding interactions, lattice vibrational entropy, and configurational disorder determines the thermodynamics and results in the rich phase evolution of [CH3NH3]PbBr3 as a function of temperature. Our results have important implications for the manipulation of macroscopic properties and provide a blueprint for future studies that will focus on unravelling phase transition mechanisms in hybrid perovskites and related materials such as dense and porous coordination polymers.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b03164.

    • Plot of vibrational entropy, description of the origins of configurational entropy, description of calculations of hydrogen bond strength, methods for and results of calculation of thermal expansion and anharmonicity, methods for and results of calculation of imaginary modes, technical details of all calculation setups, a description of synthesis, and details of characterization (X-ray diffraction and inelastic neutron scattering) (PDF)

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