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

J Phys Chem B. 2017 Jul 6;121(26):6436-6441.

PMID: 28636376

Abstract:

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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP65039056	1-Butyl-3-methylimidazolium iodide		65039-05-6	Price