Artículos de revistas
On the Mechanism of the Iodide–Triiodide Exchange Reaction in a Solid-State Ionic Liquid
del Popolo, Mario Gabriel; Bringa, Eduardo Marcial; English, Niall J.; Kohanoff, Jorge J.; Grossi, Joás Santiago; On the Mechanism of the Iodide–Triiodide Exchange Reaction in a Solid-State Ionic Liquid; American Chemical Society; Journal of Physical Chemistry B; 121; 26; 6-2017; 6436-6441
Grossi, Joás Santiago
Kohanoff, Jorge J.
English, Niall J.
Bringa, Eduardo Marcial
del Popolo, Mario Gabriel
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.