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

Autores
Byrne, Aaron; Bringa, Eduardo Marcial; del Popolo, Mario Gabriel; Kohanoff, Jorge Jose; Galassi, Vanesa Viviana; English, Niall J.
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
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.
Fil: Byrne, Aaron. University College Dublin; Irlanda
Fil: Bringa, Eduardo Marcial. University College Dublin; Irlanda. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; Argentina. Universidad de Mendoza; Argentina
Fil: del Popolo, Mario Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. University Belfast; Irlanda
Fil: Kohanoff, Jorge Jose. University Belfast; Irlanda
Fil: Galassi, Vanesa Viviana. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: English, Niall J.. University College Dublin; Irlanda
Materia
TRIIODIDE EXCHANGE
REACTIVE FORCE FIELD
IONIC LIQUID
SIMULATIONS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/106858
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/106858
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics ExplorationByrne, AaronBringa, Eduardo Marcialdel Popolo, Mario GabrielKohanoff, Jorge JoseGalassi, Vanesa VivianaEnglish, Niall J.TRIIODIDE EXCHANGEREACTIVE FORCE FIELDIONIC LIQUIDSIMULATIONShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Efficient 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.Fil: Byrne, Aaron. University College Dublin; IrlandaFil: Bringa, Eduardo Marcial. University College Dublin; Irlanda. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; Argentina. Universidad de Mendoza; ArgentinaFil: del Popolo, Mario Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. University Belfast; IrlandaFil: Kohanoff, Jorge Jose. University Belfast; IrlandaFil: Galassi, Vanesa Viviana. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: English, Niall J.. University College Dublin; IrlandaMolecular Diversity Preservation International2019-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/106858Byrne, Aaron; Bringa, Eduardo Marcial; del Popolo, Mario Gabriel; Kohanoff, Jorge Jose; Galassi, Vanesa Viviana; et al.; Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration; Molecular Diversity Preservation International; International Journal of Molecular Sciences; 20; 5; 3-2019; 1-141422-0067CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/1422-0067/20/5/1123info:eu-repo/semantics/altIdentifier/doi/10.3390/ijms20051123info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-05T10:41:02Zoai:ri.conicet.gov.ar:11336/106858instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-11-05 10:41:02.742CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration
title Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration
spellingShingle Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration
Byrne, Aaron
TRIIODIDE EXCHANGE
REACTIVE FORCE FIELD
IONIC LIQUID
SIMULATIONS
title_short Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration
title_full Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration
title_fullStr Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration
title_full_unstemmed Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration
title_sort Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration
dc.creator.none.fl_str_mv Byrne, Aaron
Bringa, Eduardo Marcial
del Popolo, Mario Gabriel
Kohanoff, Jorge Jose
Galassi, Vanesa Viviana
English, Niall J.
author Byrne, Aaron
author_facet Byrne, Aaron
Bringa, Eduardo Marcial
del Popolo, Mario Gabriel
Kohanoff, Jorge Jose
Galassi, Vanesa Viviana
English, Niall J.
author_role author
author2 Bringa, Eduardo Marcial
del Popolo, Mario Gabriel
Kohanoff, Jorge Jose
Galassi, Vanesa Viviana
English, Niall J.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv TRIIODIDE EXCHANGE
REACTIVE FORCE FIELD
IONIC LIQUID
SIMULATIONS
topic TRIIODIDE EXCHANGE
REACTIVE FORCE FIELD
IONIC LIQUID
SIMULATIONS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv 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.
Fil: Byrne, Aaron. University College Dublin; Irlanda
Fil: Bringa, Eduardo Marcial. University College Dublin; Irlanda. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; Argentina. Universidad de Mendoza; Argentina
Fil: del Popolo, Mario Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. University Belfast; Irlanda
Fil: Kohanoff, Jorge Jose. University Belfast; Irlanda
Fil: Galassi, Vanesa Viviana. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: English, Niall J.. University College Dublin; Irlanda
description 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.
publishDate 2019
dc.date.none.fl_str_mv 2019-03
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/106858
Byrne, Aaron; Bringa, Eduardo Marcial; del Popolo, Mario Gabriel; Kohanoff, Jorge Jose; Galassi, Vanesa Viviana; et al.; Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration; Molecular Diversity Preservation International; International Journal of Molecular Sciences; 20; 5; 3-2019; 1-14
1422-0067
CONICET Digital
CONICET
url http://hdl.handle.net/11336/106858
identifier_str_mv Byrne, Aaron; Bringa, Eduardo Marcial; del Popolo, Mario Gabriel; Kohanoff, Jorge Jose; Galassi, Vanesa Viviana; et al.; Mechanisms of Iodide–Triiodide Exchange Reactions in Ionic Liquids: A Reactive Molecular-Dynamics Exploration; Molecular Diversity Preservation International; International Journal of Molecular Sciences; 20; 5; 3-2019; 1-14
1422-0067
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/1422-0067/20/5/1123
info:eu-repo/semantics/altIdentifier/doi/10.3390/ijms20051123
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Molecular Diversity Preservation International
publisher.none.fl_str_mv Molecular Diversity Preservation International
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1847978108052832256
score 13.087074

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