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Open AccessArticle

Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration

1
School of Chemical and Bioprocess Engineering, University College Dublin, Belfield, Dublin 4, Ireland
2
CONICET & Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Cuyo, Mendoza M5502, Argentina
3
CONICET and Facultad de Ingenieria, Universidad de Mendoza, Mendoza M5500, Argentina
4
Atomistic Simulation Centre, School of Mathematics and Physics, Queen’s University Belfast, University Road, Belfast BT7 1NN, Northern Ireland
*
Authors to whom correspondence should be addressed.
Int. J. Mol. Sci. 2019, 20(5), 1123; https://doi.org/10.3390/ijms20051123
Received: 5 February 2019 / Revised: 27 February 2019 / Accepted: 28 February 2019 / Published: 5 March 2019
(This article belongs to the Special Issue Solution Chemical Kinetics 2019)
Efficient charge transport has been observed in iodine-doped, iodide-based room-temperature ionic liquids, yielding high ionic conductivity. To elucidate preferred mechanistic pathways for the iodide ( I )-to-triiodide ( I 3 ) exchange reactions, we have performed 10 ns reactive molecular-dynamics calculations in the liquid state for 1-butyl-3-methylimidazolium iodide ([BMIM][I]) at 450 to 750 K. Energy-barrier distributions for the iodine-swapping process were determined as a function of temperature, employing a charge-reassignment scheme drawn in part from electronic-structure calculations. Bond-exchange events were observed with rate-determining energy barriers ranging from ~0.19 to 0.23 ± 0.06 eV at 750 and 450 K, respectively, with an approximately Arrhenius temperature dependence for iodine self-diffusivity and reaction kinetics, although diffusion dominates/limits the bond-exchange events. This charge transfer is not dissimilar in energetics to those in solid-state superionic conductors. View Full-Text
Keywords: Bond exchange; reactive molecular dynamics; iodide; triiodide; charge transfer; energy barrier; diffusion Bond exchange; reactive molecular dynamics; iodide; triiodide; charge transfer; energy barrier; diffusion
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MDPI and ACS Style

Byrne, A.; Bringa, E.M.; Del Pópolo, M.G.; Kohanoff, J.J.; Galassi, V.; English, N.J. Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration. Int. J. Mol. Sci. 2019, 20, 1123.

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