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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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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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 |
_version_ |
1768541830739132416 |