On the Mechanism of the Iodide-Triiodide Exchange Reaction in a Solid-State Ionic Liquid

Joás Grossi, Jorge J Kohanoff, Niall J English, Eduardo M Bringa, Mario G Del Pópolo

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Efficient charge transport has been observed in iodide-based room-temperature ionic liquids when doped with iodine. To investigate preferred pathways for the iodide (I-)-to-triiodide (I3-) exchange reaction and to clarify the origin of this high ionic conductivity, we have conducted electronic structure calculations in the crystal state of 1-butyl-3-methylimidazolium iodide ([BMIM][I]). Energy barriers for the different stages of the iodine-swapping process, including the reorientation of the I-···I3-moiety, were determined from minimum energy paths as a function of a reaction coordinate. Hirshfeld charges and structural parameters, such as bond lengths and angles, were monitored during the reaction. Several bond-exchange events were observed with energy barriers ranging from 0.17 to 0.48 eV and coinciding with the formation of a twisted I-···I3-complex. Striking similarities were observed in the mechanics and energetics of this charge-transfer process in relation to solid-state superionic conductors.

Original languageEnglish
Pages (from-to)6436-6441
JournalJournal of Physical Chemistry B
Issue number26
Publication statusPublished - 06 Jul 2017


  • Journal Article


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