An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite

Wenjun Wei; Keith Butler; Guoqiang Feng; Christopher J.  Howard; Wei Li; Michael  Carpenter; Peixiang Lu; Aron  Walsh; Anthony K. Cheetham

doi:10.1002/anie.201803176

An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite

Wenjun Wei, Keith Butler, Guoqiang Feng, Christopher J. Howard, Wei Li, Michael Carpenter, Peixiang Lu, Aron Walsh, Anthony K. Cheetham

Department of Chemistry

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Abstract

The driving forces for the phase transitions of ABX3 hybrid organic–inorganic perovskites have been limited to the octahedral tilting, order–disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH3NH3][Mn(N3)3], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first‐order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K−1 mol−1) is observed between the low‐ and high‐temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals.

Original language	English
Pages (from-to)	8932-8936
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	57
Issue number	29
DOIs	https://doi.org/10.1002/anie.201803176
Publication status	Published - 16 Jul 2018

Keywords

ab initio lattice dynamics calculations
hybrid organic–inorganic perovskites
phase transitions
vibrational entropy

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.201803176

Accepted
This is the peer reviewed version of the following article: Angew Chem Int Ed Engl. 2018 Jul 16;57(29):8932-8936. Epub 2018 Jun 20., which has been published in final form at https://doi.org/10.1002/anie.201803176. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
Accepted author manuscript, 2.82 MB

Cite this

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title = "An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite",

abstract = "The driving forces for the phase transitions of ABX3 hybrid organic–inorganic perovskites have been limited to the octahedral tilting, order–disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH3NH3][Mn(N3)3], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first‐order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K−1 mol−1) is observed between the low‐ and high‐temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals.",

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AU - Li, Wei

AU - Carpenter, Michael

AU - Lu, Peixiang

AU - Walsh, Aron

AU - Cheetham, Anthony K.

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AB - The driving forces for the phase transitions of ABX3 hybrid organic–inorganic perovskites have been limited to the octahedral tilting, order–disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH3NH3][Mn(N3)3], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first‐order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K−1 mol−1) is observed between the low‐ and high‐temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals.

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An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite

Abstract

Keywords

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