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Issue 5, 2019
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Mapping the polymorphic transformation gateway vibration in crystalline 1,2,4,5-tetrabromobenzene

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Abstract

The thermosalient behavior of 1,2,4,5-tetrabromobenzene (TBB) is related to a temperature-induced polymorphic structural change. The mechanism behind the phase transition has been investigated in this work using low-frequency (10–250 cm−1) Raman spectroscopy and solid-state density functional theory simulations. Careful adjustments of the probing laser power permitted thermal control of the polymorph populations and enabled high-quality Raman vibrational spectra to be obtained for both the β (low temperature) and γ (high temperature) forms of TBB. Numerous well-defined vibrational features appear in the Raman spectra of both polymorphs which could be assigned to specific motions of the solid-state TBB molecules. It was discovered that the lowest-frequency vibration at 15.5 cm−1 in β-TBB at 291 K is a rotational mode that functions as a gateway for inducing the polymorphic phase transition to γ-TBB, and serves as the initiating step in the storage of mechanical strain for subsequent macroscopic release. Computationally mapping the potential energy surface along this vibrational coordinate reveals that the two TBB polymorphs are separated by a 2.40 kJ mol−1 barrier and that γ-TBB exhibits an enhanced cohesion energy that stabilizes its structure.

Graphical abstract: Mapping the polymorphic transformation gateway vibration in crystalline 1,2,4,5-tetrabromobenzene

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Publication details

The article was received on 31 Aug 2018, accepted on 22 Nov 2018 and first published on 23 Nov 2018


Article type: Edge Article
DOI: 10.1039/C8SC03897J
Chem. Sci., 2019,10, 1332-1341
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Mapping the polymorphic transformation gateway vibration in crystalline 1,2,4,5-tetrabromobenzene

    A. J. Zaczek, L. Catalano, P. Naumov and T. M. Korter, Chem. Sci., 2019, 10, 1332
    DOI: 10.1039/C8SC03897J

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