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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/146665
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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 |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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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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13.070432 |