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

Aaron Byrne, Eduardo Bringa, Mario G. Del Pópolo, Jorge Kohanoff, vanesa Galassi, Niall J English

Research output: Contribution to journalArticle

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Abstract

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
Original languageEnglish
Article number1123
JournalInternational journal of molecular sciences
Volume20
Issue number5
DOIs
Publication statusPublished - 05 Mar 2019

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Ionic Liquids
Iodides
Molecular Dynamics Simulation
Iodine
Ionic liquids
iodides
iodine
Molecular dynamics
Ion exchange
Energy barriers
molecular dynamics
Temperature
Charge transfer
liquids
Ionic conductivity
Reaction kinetics
ion currents
diffusivity
Electronic structure
reaction kinetics

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Byrne, Aaron ; Bringa, Eduardo ; Del Pópolo, Mario G. ; Kohanoff, Jorge ; Galassi, vanesa ; English, Niall J. / Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration. In: International journal of molecular sciences. 2019 ; Vol. 20, No. 5.
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abstract = "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",
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Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration. / Byrne, Aaron; Bringa, Eduardo; Del Pópolo, Mario G.; Kohanoff, Jorge; Galassi, vanesa; English, Niall J.

In: International journal of molecular sciences, Vol. 20, No. 5, 1123, 05.03.2019.

Research output: Contribution to journalArticle

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AU - Byrne, Aaron

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AU - Galassi, vanesa

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AB - 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

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