10.1021/acs.jpcb.7b01034.s002
Joás Grossi
Joás
Grossi
Jorge J. Kohanoff
Jorge J.
Kohanoff
Niall J. English
Niall J.
English
Eduardo M. Bringa
Eduardo M.
Bringa
Mario G. Del Pópolo
Mario
G. Del Pópolo
On the Mechanism of the Iodide–Triiodide Exchange
Reaction in a Solid-State Ionic Liquid
American Chemical Society
2017
iodide-based room-temperature
Liquid Efficient charge transport
Hirshfeld charges
charge-transfer process
energy barriers
bond lengths
Several bond-exchange events
energy paths
BMIM
crystal state
superionic conductors
0.48 eV
iodine-swapping process
exchange reaction
structure calculations
2017-06-21 18:44:56
Dataset
https://acs.figshare.com/articles/dataset/On_the_Mechanism_of_the_Iodide_Triiodide_Exchange_Reaction_in_a_Solid-State_Ionic_Liquid/5134654
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<sup>–</sup>)-to-triiodide (I<sub>3</sub><sup>–</sup>) 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<sup>–</sup>···I<sub>3</sub><sup>–</sup> 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<sup>–</sup>···I<sub>3</sub><sup>–</sup> complex. Striking similarities were observed in the
mechanics and energetics of this charge-transfer process in relation
to solid-state superionic conductors.