Isotope effects in aqueous solvation of simple halides

Autores
Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We present a path-integral-molecular-dynamics study of the thermodynamic stabilities of DOH⋯ X- and HOD⋯ X- (X = F, Cl, Br, I) coordination in aqueous solutions at ambient conditions. In agreement with experimental evidence, our results for the F- case reveal a clear stabilization of the latter motif, whereas, in the rest of the halogen series, the former articulation prevails. The DOH⋯ X- preference becomes more marked the larger the size of the ionic solute. A physical interpretation of these tendencies is provided in terms of an analysis of the global quantum kinetic energies of the light atoms and their geometrical decomposition. The stabilization of the alternative ionic coordination geometries is the result of a delicate balance arising from quantum spatial dispersions along parallel and perpendicular directions with respect to the relevant O-H⋯X- axis, as the strength of the water-halide H-bond varies. This interpretation is corroborated by a complementary analysis performed on the different spectroscopic signals of the corresponding IR spectra.
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. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Rossky, Peter J.. Rice University; Estados Unidos
Fil: Laria, Daniel Hector. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Comisión Nacional de Energía Atómica; Argentina. 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
Integrales de camino
Equilibrio isotópico
Soluciones de electrolitos
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:11336/89313
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Isotope effects in aqueous solvation of simple halidesVidela, Pablo ErnestoRossky, Peter J.Laria, Daniel HectorIntegrales de caminoEquilibrio isotópicoSoluciones de electrolitoshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We present a path-integral-molecular-dynamics study of the thermodynamic stabilities of DOH⋯ X- and HOD⋯ X- (X = F, Cl, Br, I) coordination in aqueous solutions at ambient conditions. In agreement with experimental evidence, our results for the F- case reveal a clear stabilization of the latter motif, whereas, in the rest of the halogen series, the former articulation prevails. The DOH⋯ X- preference becomes more marked the larger the size of the ionic solute. A physical interpretation of these tendencies is provided in terms of an analysis of the global quantum kinetic energies of the light atoms and their geometrical decomposition. The stabilization of the alternative ionic coordination geometries is the result of a delicate balance arising from quantum spatial dispersions along parallel and perpendicular directions with respect to the relevant O-H⋯X- axis, as the strength of the water-halide H-bond varies. This interpretation is corroborated by a complementary analysis performed on the different spectroscopic signals of the corresponding IR spectra.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. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Rossky, Peter J.. Rice University; Estados UnidosFil: Laria, Daniel Hector. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Comisión Nacional de Energía Atómica; Argentina. 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 Institute of Physics2018-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/89313Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector; Isotope effects in aqueous solvation of simple halides; American Institute of Physics; Journal of Chemical Physics; 148; 10; 3-2018; 102306-1023060021-9606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/1.4986231info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4986231info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:00:45Zoai:ri.conicet.gov.ar:11336/89313instacron: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 12:00:45.951CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Isotope effects in aqueous solvation of simple halides
title Isotope effects in aqueous solvation of simple halides
spellingShingle Isotope effects in aqueous solvation of simple halides
Videla, Pablo Ernesto
Integrales de camino
Equilibrio isotópico
Soluciones de electrolitos
title_short Isotope effects in aqueous solvation of simple halides
title_full Isotope effects in aqueous solvation of simple halides
title_fullStr Isotope effects in aqueous solvation of simple halides
title_full_unstemmed Isotope effects in aqueous solvation of simple halides
title_sort Isotope effects in aqueous solvation of simple halides
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 Integrales de camino
Equilibrio isotópico
Soluciones de electrolitos
topic Integrales de camino
Equilibrio isotópico
Soluciones de electrolitos
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 a path-integral-molecular-dynamics study of the thermodynamic stabilities of DOH⋯ X- and HOD⋯ X- (X = F, Cl, Br, I) coordination in aqueous solutions at ambient conditions. In agreement with experimental evidence, our results for the F- case reveal a clear stabilization of the latter motif, whereas, in the rest of the halogen series, the former articulation prevails. The DOH⋯ X- preference becomes more marked the larger the size of the ionic solute. A physical interpretation of these tendencies is provided in terms of an analysis of the global quantum kinetic energies of the light atoms and their geometrical decomposition. The stabilization of the alternative ionic coordination geometries is the result of a delicate balance arising from quantum spatial dispersions along parallel and perpendicular directions with respect to the relevant O-H⋯X- axis, as the strength of the water-halide H-bond varies. This interpretation is corroborated by a complementary analysis performed on the different spectroscopic signals of the corresponding IR spectra.
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. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Rossky, Peter J.. Rice University; Estados Unidos
Fil: Laria, Daniel Hector. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Comisión Nacional de Energía Atómica; Argentina. 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 We present a path-integral-molecular-dynamics study of the thermodynamic stabilities of DOH⋯ X- and HOD⋯ X- (X = F, Cl, Br, I) coordination in aqueous solutions at ambient conditions. In agreement with experimental evidence, our results for the F- case reveal a clear stabilization of the latter motif, whereas, in the rest of the halogen series, the former articulation prevails. The DOH⋯ X- preference becomes more marked the larger the size of the ionic solute. A physical interpretation of these tendencies is provided in terms of an analysis of the global quantum kinetic energies of the light atoms and their geometrical decomposition. The stabilization of the alternative ionic coordination geometries is the result of a delicate balance arising from quantum spatial dispersions along parallel and perpendicular directions with respect to the relevant O-H⋯X- axis, as the strength of the water-halide H-bond varies. This interpretation is corroborated by a complementary analysis performed on the different spectroscopic signals of the corresponding IR spectra.
publishDate 2018
dc.date.none.fl_str_mv 2018-03
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/11336/89313
Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector; Isotope effects in aqueous solvation of simple halides; American Institute of Physics; Journal of Chemical Physics; 148; 10; 3-2018; 102306-102306
0021-9606
CONICET Digital
CONICET
url http://hdl.handle.net/11336/89313
identifier_str_mv Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector; Isotope effects in aqueous solvation of simple halides; American Institute of Physics; Journal of Chemical Physics; 148; 10; 3-2018; 102306-102306
0021-9606
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://aip.scitation.org/doi/10.1063/1.4986231
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4986231
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 Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
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 12.982451

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