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

Adam J. Zaczek, Luca Catalano, Pance Naumov, Timothy M. Korter*

Research output: Contribution to journalArticlepeer-review


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.

Original languageEnglish (US)
Pages (from-to)1332-1341
Number of pages10
JournalChemical Science
Issue number5
StatePublished - Feb 7 2019

ASJC Scopus subject areas

  • General Chemistry


Dive into the research topics of 'Mapping the polymorphic transformation gateway vibration in crystalline 1,2,4,5-tetrabromobenzene'. Together they form a unique fingerprint.

Cite this