Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons

Autores
Rivas, Nicolás; Moriena, Gustavo; Domenianni, Luis Ignacio; Hodak, Jose Hector; Marceca, Ernesto José
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We performed femtosecond transient absorption (TA) experiments to monitor the solvation dynamics of charge-transfer-to-solvent (CTTS) electrons originating from UV photoexcitation of ammoniated iodide in close proximity to the counterions. Solutions of KI were prepared in liquid ammonia and TA experiments were carried out at different temperatures and densities, along the liquid-gas coexistence curve of the fluid. The results complement previous femtosecond TA work by P. Vöhringer's group in neat ammonia via multiphoton ionization. The dynamics of CTTS-detached electrons in ammonia was found to be strongly affected by ion pairing. Geminate recombination time constants as well as escape probabilities were determined from the measured temporal profiles and analysed as a function of the medium density. A fast unresolved (τ < 250 fs) increase of absorption related to the creation/thermalization of solvated electron species was followed by two decay components: one with a characteristic time around 10 ps, and a slower one that remains active for hundreds of picoseconds. While the first process is attributed to an early recombination of (I, e-) pairs, the second decay and its asymptote reflects the effect of the K+ counterion on the geminate recombination dynamics, rate and yield. The cation basically acts as an electron anchor that restricts the ejection distance, leading to solvent-separated counterion-electron species. The formation of (K+, NH3, e-) pairs close to the parent iodine atom brings the electron escape probability to very low values. Transient spectra of the electron species have also been estimated as a function of time by probing the temporal profiles at different wavelengths.
Fil: Rivas, Nicolás. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Moriena, Gustavo. University of Toronto. Department of Chemistry; Canadá
Fil: Domenianni, Luis Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Hodak, Jose Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Marceca, Ernesto José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Materia
Transient Absroption
Electron Solvation
Pump Probe
Ctts
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:11336/65753
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electronsRivas, NicolásMoriena, GustavoDomenianni, Luis IgnacioHodak, Jose HectorMarceca, Ernesto JoséTransient AbsroptionElectron SolvationPump ProbeCttshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We performed femtosecond transient absorption (TA) experiments to monitor the solvation dynamics of charge-transfer-to-solvent (CTTS) electrons originating from UV photoexcitation of ammoniated iodide in close proximity to the counterions. Solutions of KI were prepared in liquid ammonia and TA experiments were carried out at different temperatures and densities, along the liquid-gas coexistence curve of the fluid. The results complement previous femtosecond TA work by P. Vöhringer's group in neat ammonia via multiphoton ionization. The dynamics of CTTS-detached electrons in ammonia was found to be strongly affected by ion pairing. Geminate recombination time constants as well as escape probabilities were determined from the measured temporal profiles and analysed as a function of the medium density. A fast unresolved (τ < 250 fs) increase of absorption related to the creation/thermalization of solvated electron species was followed by two decay components: one with a characteristic time around 10 ps, and a slower one that remains active for hundreds of picoseconds. While the first process is attributed to an early recombination of (I, e-) pairs, the second decay and its asymptote reflects the effect of the K+ counterion on the geminate recombination dynamics, rate and yield. The cation basically acts as an electron anchor that restricts the ejection distance, leading to solvent-separated counterion-electron species. The formation of (K+, NH3, e-) pairs close to the parent iodine atom brings the electron escape probability to very low values. Transient spectra of the electron species have also been estimated as a function of time by probing the temporal profiles at different wavelengths.Fil: Rivas, Nicolás. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Moriena, Gustavo. University of Toronto. Department of Chemistry; CanadáFil: Domenianni, Luis Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Hodak, Jose Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Marceca, Ernesto José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaRoyal Society of Chemistry2017-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/65753Rivas, Nicolás; Moriena, Gustavo; Domenianni, Luis Ignacio; Hodak, Jose Hector; Marceca, Ernesto José; Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 19; 47; 11-2017; 31581-315911463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C7CP05903Einfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP05903E#!divAbstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:07:36Zoai:ri.conicet.gov.ar:11336/65753instacron: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:34982025-09-10 13:07:36.743CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons
title Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons
spellingShingle Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons
Rivas, Nicolás
Transient Absroption
Electron Solvation
Pump Probe
Ctts
title_short Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons
title_full Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons
title_fullStr Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons
title_full_unstemmed Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons
title_sort Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons
dc.creator.none.fl_str_mv Rivas, Nicolás
Moriena, Gustavo
Domenianni, Luis Ignacio
Hodak, Jose Hector
Marceca, Ernesto José
author Rivas, Nicolás
author_facet Rivas, Nicolás
Moriena, Gustavo
Domenianni, Luis Ignacio
Hodak, Jose Hector
Marceca, Ernesto José
author_role author
author2 Moriena, Gustavo
Domenianni, Luis Ignacio
Hodak, Jose Hector
Marceca, Ernesto José
author2_role author
author
author
author
dc.subject.none.fl_str_mv Transient Absroption
Electron Solvation
Pump Probe
Ctts
topic Transient Absroption
Electron Solvation
Pump Probe
Ctts
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We performed femtosecond transient absorption (TA) experiments to monitor the solvation dynamics of charge-transfer-to-solvent (CTTS) electrons originating from UV photoexcitation of ammoniated iodide in close proximity to the counterions. Solutions of KI were prepared in liquid ammonia and TA experiments were carried out at different temperatures and densities, along the liquid-gas coexistence curve of the fluid. The results complement previous femtosecond TA work by P. Vöhringer's group in neat ammonia via multiphoton ionization. The dynamics of CTTS-detached electrons in ammonia was found to be strongly affected by ion pairing. Geminate recombination time constants as well as escape probabilities were determined from the measured temporal profiles and analysed as a function of the medium density. A fast unresolved (τ < 250 fs) increase of absorption related to the creation/thermalization of solvated electron species was followed by two decay components: one with a characteristic time around 10 ps, and a slower one that remains active for hundreds of picoseconds. While the first process is attributed to an early recombination of (I, e-) pairs, the second decay and its asymptote reflects the effect of the K+ counterion on the geminate recombination dynamics, rate and yield. The cation basically acts as an electron anchor that restricts the ejection distance, leading to solvent-separated counterion-electron species. The formation of (K+, NH3, e-) pairs close to the parent iodine atom brings the electron escape probability to very low values. Transient spectra of the electron species have also been estimated as a function of time by probing the temporal profiles at different wavelengths.
Fil: Rivas, Nicolás. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Moriena, Gustavo. University of Toronto. Department of Chemistry; Canadá
Fil: Domenianni, Luis Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Hodak, Jose Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Marceca, Ernesto José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
description We performed femtosecond transient absorption (TA) experiments to monitor the solvation dynamics of charge-transfer-to-solvent (CTTS) electrons originating from UV photoexcitation of ammoniated iodide in close proximity to the counterions. Solutions of KI were prepared in liquid ammonia and TA experiments were carried out at different temperatures and densities, along the liquid-gas coexistence curve of the fluid. The results complement previous femtosecond TA work by P. Vöhringer's group in neat ammonia via multiphoton ionization. The dynamics of CTTS-detached electrons in ammonia was found to be strongly affected by ion pairing. Geminate recombination time constants as well as escape probabilities were determined from the measured temporal profiles and analysed as a function of the medium density. A fast unresolved (τ < 250 fs) increase of absorption related to the creation/thermalization of solvated electron species was followed by two decay components: one with a characteristic time around 10 ps, and a slower one that remains active for hundreds of picoseconds. While the first process is attributed to an early recombination of (I, e-) pairs, the second decay and its asymptote reflects the effect of the K+ counterion on the geminate recombination dynamics, rate and yield. The cation basically acts as an electron anchor that restricts the ejection distance, leading to solvent-separated counterion-electron species. The formation of (K+, NH3, e-) pairs close to the parent iodine atom brings the electron escape probability to very low values. Transient spectra of the electron species have also been estimated as a function of time by probing the temporal profiles at different wavelengths.
publishDate 2017
dc.date.none.fl_str_mv 2017-11
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/11336/65753
Rivas, Nicolás; Moriena, Gustavo; Domenianni, Luis Ignacio; Hodak, Jose Hector; Marceca, Ernesto José; Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 19; 47; 11-2017; 31581-31591
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/65753
identifier_str_mv Rivas, Nicolás; Moriena, Gustavo; Domenianni, Luis Ignacio; Hodak, Jose Hector; Marceca, Ernesto José; Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 19; 47; 11-2017; 31581-31591
1463-9076
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/C7CP05903E
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP05903E#!divAbstract
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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
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score 12.993085

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