Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters

Autores
Turi, Laszlo; Rodriguez, Javier; Laria, Daniel Hector
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Using path-integral molecular dynamics simulations, we examine isomerization paths involving collective proton transfers in [H2O]5 and [H2O]8 clusters under cryogenic conditions. We focused attention on combined effects derived from solvation and nuclear quantum fluctuations on the characteristics of free energy barriers and relative stabilities of reactants and products. In particular, we analyzed two different processes: the first one involves the exchange of donor-acceptor hydrogen bond roles along cyclic moieties, whereas the second one corresponds to charge separation leading to stable [H3O]+[OH]- ion pairs. In the first case, the explicit incorporation of quantum tunneling introduces important modifications in the classical free energy profile. The resulting quantum profile presents two main contributions, one corresponding to compressions of O-O distances and a second one ascribed to nuclear tunneling of the light protons. Solvation effects promote a moderate polarization of the cyclic structures and a partial loss of concertedness in the collective modes, most notably, at the onset of tunneling. Still, the latter effects are also sufficiently strong to promote the stabilization of ion pairs along the classical trajectories. In contrast, the explicit incorporation of nuclear quantum fluctuations leads to charge separated configurations that are marginally stable. As such, the latter states could also be regarded as short-lived intermediate states along the reactive exchange path.
Fil: Turi, Laszlo. Eötvös Loránd University; Hungría
Fil: Rodriguez, Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Constituyentes | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Constituyentes; Argentina
Fil: Laria, Daniel 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
Materia
Nanoagregados acuosos
Efectos cuanticos nucleares
Simulacion computacional
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:11336/146665

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spelling Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous ClustersTuri, LaszloRodriguez, JavierLaria, Daniel HectorNanoagregados acuososEfectos cuanticos nuclearesSimulacion computacionalhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Using path-integral molecular dynamics simulations, we examine isomerization paths involving collective proton transfers in [H2O]5 and [H2O]8 clusters under cryogenic conditions. We focused attention on combined effects derived from solvation and nuclear quantum fluctuations on the characteristics of free energy barriers and relative stabilities of reactants and products. In particular, we analyzed two different processes: the first one involves the exchange of donor-acceptor hydrogen bond roles along cyclic moieties, whereas the second one corresponds to charge separation leading to stable [H3O]+[OH]- ion pairs. In the first case, the explicit incorporation of quantum tunneling introduces important modifications in the classical free energy profile. The resulting quantum profile presents two main contributions, one corresponding to compressions of O-O distances and a second one ascribed to nuclear tunneling of the light protons. Solvation effects promote a moderate polarization of the cyclic structures and a partial loss of concertedness in the collective modes, most notably, at the onset of tunneling. Still, the latter effects are also sufficiently strong to promote the stabilization of ion pairs along the classical trajectories. In contrast, the explicit incorporation of nuclear quantum fluctuations leads to charge separated configurations that are marginally stable. As such, the latter states could also be regarded as short-lived intermediate states along the reactive exchange path.Fil: Turi, Laszlo. Eötvös Loránd University; HungríaFil: Rodriguez, Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Constituyentes | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Constituyentes; ArgentinaFil: Laria, Daniel 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; ArgentinaAmerican Chemical Society2020-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/146665Turi, Laszlo; Rodriguez, Javier; Laria, Daniel Hector; Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters; American Chemical Society; Journal of Physical Chemistry B; 124; 11; 3-2020; 2198-22081520-6106CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcb.9b11087info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcb.9b11087info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:23:50Zoai:ri.conicet.gov.ar:11336/146665instacron: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:34982025-09-29 10:23:50.746CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters
title Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters
spellingShingle Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters
Turi, Laszlo
Nanoagregados acuosos
Efectos cuanticos nucleares
Simulacion computacional
title_short Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters
title_full Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters
title_fullStr Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters
title_full_unstemmed Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters
title_sort Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters
dc.creator.none.fl_str_mv Turi, Laszlo
Rodriguez, Javier
Laria, Daniel Hector
author Turi, Laszlo
author_facet Turi, Laszlo
Rodriguez, Javier
Laria, Daniel Hector
author_role author
author2 Rodriguez, Javier
Laria, Daniel Hector
author2_role author
author
dc.subject.none.fl_str_mv Nanoagregados acuosos
Efectos cuanticos nucleares
Simulacion computacional
topic Nanoagregados acuosos
Efectos cuanticos nucleares
Simulacion computacional
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Using path-integral molecular dynamics simulations, we examine isomerization paths involving collective proton transfers in [H2O]5 and [H2O]8 clusters under cryogenic conditions. We focused attention on combined effects derived from solvation and nuclear quantum fluctuations on the characteristics of free energy barriers and relative stabilities of reactants and products. In particular, we analyzed two different processes: the first one involves the exchange of donor-acceptor hydrogen bond roles along cyclic moieties, whereas the second one corresponds to charge separation leading to stable [H3O]+[OH]- ion pairs. In the first case, the explicit incorporation of quantum tunneling introduces important modifications in the classical free energy profile. The resulting quantum profile presents two main contributions, one corresponding to compressions of O-O distances and a second one ascribed to nuclear tunneling of the light protons. Solvation effects promote a moderate polarization of the cyclic structures and a partial loss of concertedness in the collective modes, most notably, at the onset of tunneling. Still, the latter effects are also sufficiently strong to promote the stabilization of ion pairs along the classical trajectories. In contrast, the explicit incorporation of nuclear quantum fluctuations leads to charge separated configurations that are marginally stable. As such, the latter states could also be regarded as short-lived intermediate states along the reactive exchange path.
Fil: Turi, Laszlo. Eötvös Loránd University; Hungría
Fil: Rodriguez, Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Constituyentes | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Constituyentes; Argentina
Fil: Laria, Daniel 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
description Using path-integral molecular dynamics simulations, we examine isomerization paths involving collective proton transfers in [H2O]5 and [H2O]8 clusters under cryogenic conditions. We focused attention on combined effects derived from solvation and nuclear quantum fluctuations on the characteristics of free energy barriers and relative stabilities of reactants and products. In particular, we analyzed two different processes: the first one involves the exchange of donor-acceptor hydrogen bond roles along cyclic moieties, whereas the second one corresponds to charge separation leading to stable [H3O]+[OH]- ion pairs. In the first case, the explicit incorporation of quantum tunneling introduces important modifications in the classical free energy profile. The resulting quantum profile presents two main contributions, one corresponding to compressions of O-O distances and a second one ascribed to nuclear tunneling of the light protons. Solvation effects promote a moderate polarization of the cyclic structures and a partial loss of concertedness in the collective modes, most notably, at the onset of tunneling. Still, the latter effects are also sufficiently strong to promote the stabilization of ion pairs along the classical trajectories. In contrast, the explicit incorporation of nuclear quantum fluctuations leads to charge separated configurations that are marginally stable. As such, the latter states could also be regarded as short-lived intermediate states along the reactive exchange path.
publishDate 2020
dc.date.none.fl_str_mv 2020-03
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/11336/146665
Turi, Laszlo; Rodriguez, Javier; Laria, Daniel Hector; Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters; American Chemical Society; Journal of Physical Chemistry B; 124; 11; 3-2020; 2198-2208
1520-6106
CONICET Digital
CONICET
url http://hdl.handle.net/11336/146665
identifier_str_mv Turi, Laszlo; Rodriguez, Javier; Laria, Daniel Hector; Combined Effects from Solvation and Nuclear Quantum Fluctuations on Autoionization Mechanisms in Aqueous Clusters; American Chemical Society; Journal of Physical Chemistry B; 124; 11; 3-2020; 2198-2208
1520-6106
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://pubs.acs.org/doi/10.1021/acs.jpcb.9b11087
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcb.9b11087
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 American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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