Isotope effects in aqueous solvation of simple halides

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 moti...

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Publicado: 2018
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Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v148_n10_p_Videla
http://hdl.handle.net/20.500.12110/paper_00219606_v148_n10_p_Videla
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spelling paper:paper_00219606_v148_n10_p_Videla2023-06-08T14:44:29Z Isotope effects in aqueous solvation of simple halides Ionic strength Kinetic energy Molecular dynamics Solutions Spectroscopic analysis Stabilization Ambient conditions Complementary analysis Coordination geometry Experimental evidence Path-integral molecular dynamics Physical interpretation Spatial dispersion Spectroscopic signals Fluorine 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. © 2018 Author(s). 2018 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v148_n10_p_Videla http://hdl.handle.net/20.500.12110/paper_00219606_v148_n10_p_Videla
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Ionic strength
Kinetic energy
Molecular dynamics
Solutions
Spectroscopic analysis
Stabilization
Ambient conditions
Complementary analysis
Coordination geometry
Experimental evidence
Path-integral molecular dynamics
Physical interpretation
Spatial dispersion
Spectroscopic signals
Fluorine
spellingShingle Ionic strength
Kinetic energy
Molecular dynamics
Solutions
Spectroscopic analysis
Stabilization
Ambient conditions
Complementary analysis
Coordination geometry
Experimental evidence
Path-integral molecular dynamics
Physical interpretation
Spatial dispersion
Spectroscopic signals
Fluorine
Isotope effects in aqueous solvation of simple halides
topic_facet Ionic strength
Kinetic energy
Molecular dynamics
Solutions
Spectroscopic analysis
Stabilization
Ambient conditions
Complementary analysis
Coordination geometry
Experimental evidence
Path-integral molecular dynamics
Physical interpretation
Spatial dispersion
Spectroscopic signals
Fluorine
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. © 2018 Author(s).
title Isotope effects in aqueous solvation of simple halides
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
publishDate 2018
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v148_n10_p_Videla
http://hdl.handle.net/20.500.12110/paper_00219606_v148_n10_p_Videla
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