Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters
- Autores
- Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector
- Año de publicación
- 2015
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- We present results from ring polymer molecular dynamics experiments that provide microscopic insights into the characteristics of the isotopic stabilizations of H and D aqueous species in the first solvation shell of a halide I- ion in water nanoclusters at low temperatures. The analysis of the simplest I-·(HOD) dimer shows a clear propensity for the light isotope to lie at the non-hydrogen-bonded dangling position. Our results predict that, at T ∼ 50 K, I-·(DOH) isomers are three times more abundant than I-·(HOD) ones. The reasons for such stabilization can be traced back to differences in the nuclear kinetic energy projected along directions perpendicular to the plane of the water molecule. Dynamical implications of these imbalances are shown to be reflected in the characteristics of the corresponding bands of the infrared spectroscopic signals. A similar analysis performed in larger aggregates containing ∼20 water molecules reveals, in contrast, a stabilization of the light isotope along I-⋯HO hydrogen bonds. Effects derived from the consideration of smaller halide anions with larger electric fields at the surface are also examined. (Figure Presented).
Fil: Videla, Pablo Ernesto. 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
Fil: Rossky, Peter J.. Rice University; Estados Unidos
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. Comisión Nacional de Energía Atómica; Argentina - Materia
-
Equilibrio Isotopico
Nanoagregados
Solvatacion
Integrals de Camino - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
.jpg)
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/58904
Ver los metadatos del registro completo
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Isotopic Preferential Solvation of I- in Low-Temperature Water NanoclustersVidela, Pablo ErnestoRossky, Peter J.Laria, Daniel HectorEquilibrio IsotopicoNanoagregadosSolvatacionIntegrals de Caminohttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We present results from ring polymer molecular dynamics experiments that provide microscopic insights into the characteristics of the isotopic stabilizations of H and D aqueous species in the first solvation shell of a halide I- ion in water nanoclusters at low temperatures. The analysis of the simplest I-·(HOD) dimer shows a clear propensity for the light isotope to lie at the non-hydrogen-bonded dangling position. Our results predict that, at T ∼ 50 K, I-·(DOH) isomers are three times more abundant than I-·(HOD) ones. The reasons for such stabilization can be traced back to differences in the nuclear kinetic energy projected along directions perpendicular to the plane of the water molecule. Dynamical implications of these imbalances are shown to be reflected in the characteristics of the corresponding bands of the infrared spectroscopic signals. A similar analysis performed in larger aggregates containing ∼20 water molecules reveals, in contrast, a stabilization of the light isotope along I-⋯HO hydrogen bonds. Effects derived from the consideration of smaller halide anions with larger electric fields at the surface are also examined. (Figure Presented).Fil: Videla, Pablo Ernesto. 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; ArgentinaFil: Rossky, Peter J.. Rice University; Estados UnidosFil: 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. Comisión Nacional de Energía Atómica; ArgentinaAmerican Chemical Society2015-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/58904Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector; Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters; American Chemical Society; Journal of Physical Chemistry B; 119; 35; 9-2015; 11783-117901520-6106CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcb.5b05561info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcb.5b05561info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:02:45Zoai:ri.conicet.gov.ar:11336/58904instacron: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:34982025-10-22 11:02:45.422CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
| dc.title.none.fl_str_mv |
Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters |
| title |
Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters |
| spellingShingle |
Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters Videla, Pablo Ernesto Equilibrio Isotopico Nanoagregados Solvatacion Integrals de Camino |
| title_short |
Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters |
| title_full |
Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters |
| title_fullStr |
Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters |
| title_full_unstemmed |
Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters |
| title_sort |
Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters |
| dc.creator.none.fl_str_mv |
Videla, Pablo Ernesto Rossky, Peter J. Laria, Daniel Hector |
| author |
Videla, Pablo Ernesto |
| author_facet |
Videla, Pablo Ernesto Rossky, Peter J. Laria, Daniel Hector |
| author_role |
author |
| author2 |
Rossky, Peter J. Laria, Daniel Hector |
| author2_role |
author author |
| dc.subject.none.fl_str_mv |
Equilibrio Isotopico Nanoagregados Solvatacion Integrals de Camino |
| topic |
Equilibrio Isotopico Nanoagregados Solvatacion Integrals de Camino |
| 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 present results from ring polymer molecular dynamics experiments that provide microscopic insights into the characteristics of the isotopic stabilizations of H and D aqueous species in the first solvation shell of a halide I- ion in water nanoclusters at low temperatures. The analysis of the simplest I-·(HOD) dimer shows a clear propensity for the light isotope to lie at the non-hydrogen-bonded dangling position. Our results predict that, at T ∼ 50 K, I-·(DOH) isomers are three times more abundant than I-·(HOD) ones. The reasons for such stabilization can be traced back to differences in the nuclear kinetic energy projected along directions perpendicular to the plane of the water molecule. Dynamical implications of these imbalances are shown to be reflected in the characteristics of the corresponding bands of the infrared spectroscopic signals. A similar analysis performed in larger aggregates containing ∼20 water molecules reveals, in contrast, a stabilization of the light isotope along I-⋯HO hydrogen bonds. Effects derived from the consideration of smaller halide anions with larger electric fields at the surface are also examined. (Figure Presented). Fil: Videla, Pablo Ernesto. 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 Fil: Rossky, Peter J.. Rice University; Estados Unidos 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. Comisión Nacional de Energía Atómica; Argentina |
| description |
We present results from ring polymer molecular dynamics experiments that provide microscopic insights into the characteristics of the isotopic stabilizations of H and D aqueous species in the first solvation shell of a halide I- ion in water nanoclusters at low temperatures. The analysis of the simplest I-·(HOD) dimer shows a clear propensity for the light isotope to lie at the non-hydrogen-bonded dangling position. Our results predict that, at T ∼ 50 K, I-·(DOH) isomers are three times more abundant than I-·(HOD) ones. The reasons for such stabilization can be traced back to differences in the nuclear kinetic energy projected along directions perpendicular to the plane of the water molecule. Dynamical implications of these imbalances are shown to be reflected in the characteristics of the corresponding bands of the infrared spectroscopic signals. A similar analysis performed in larger aggregates containing ∼20 water molecules reveals, in contrast, a stabilization of the light isotope along I-⋯HO hydrogen bonds. Effects derived from the consideration of smaller halide anions with larger electric fields at the surface are also examined. (Figure Presented). |
| publishDate |
2015 |
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2015-09 |
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info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
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article |
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publishedVersion |
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http://hdl.handle.net/11336/58904 Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector; Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters; American Chemical Society; Journal of Physical Chemistry B; 119; 35; 9-2015; 11783-11790 1520-6106 CONICET Digital CONICET |
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http://hdl.handle.net/11336/58904 |
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Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector; Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters; American Chemical Society; Journal of Physical Chemistry B; 119; 35; 9-2015; 11783-11790 1520-6106 CONICET Digital CONICET |
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American Chemical Society |
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American Chemical Society |
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