Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters
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 simp...
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2015
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15206106_v119_n35_p11783_Videla http://hdl.handle.net/20.500.12110/paper_15206106_v119_n35_p11783_Videla |
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paper:paper_15206106_v119_n35_p11783_Videla2023-06-08T16:19:10Z Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters Videla, Pablo Ernesto Laria, Daniel Hector Dimers Electric fields Hydrogen bonds Isomers Isotopes Kinetic energy Kinetics Molecular dynamics Molecules Nanoclusters Solvation Temperature Aqueous species Energy projected Infrared spectroscopic Low temperatures Preferential solvation Similar analysis Solvation shell Water nanoclusters Stabilization 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). © 2015 American Chemical Society. Fil:Videla, P.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Laria, D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2015 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15206106_v119_n35_p11783_Videla http://hdl.handle.net/20.500.12110/paper_15206106_v119_n35_p11783_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 |
Dimers Electric fields Hydrogen bonds Isomers Isotopes Kinetic energy Kinetics Molecular dynamics Molecules Nanoclusters Solvation Temperature Aqueous species Energy projected Infrared spectroscopic Low temperatures Preferential solvation Similar analysis Solvation shell Water nanoclusters Stabilization |
| spellingShingle |
Dimers Electric fields Hydrogen bonds Isomers Isotopes Kinetic energy Kinetics Molecular dynamics Molecules Nanoclusters Solvation Temperature Aqueous species Energy projected Infrared spectroscopic Low temperatures Preferential solvation Similar analysis Solvation shell Water nanoclusters Stabilization Videla, Pablo Ernesto Laria, Daniel Hector Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters |
| topic_facet |
Dimers Electric fields Hydrogen bonds Isomers Isotopes Kinetic energy Kinetics Molecular dynamics Molecules Nanoclusters Solvation Temperature Aqueous species Energy projected Infrared spectroscopic Low temperatures Preferential solvation Similar analysis Solvation shell Water nanoclusters Stabilization |
| 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). © 2015 American Chemical Society. |
| author |
Videla, Pablo Ernesto Laria, Daniel Hector |
| author_facet |
Videla, Pablo Ernesto Laria, Daniel Hector |
| author_sort |
Videla, Pablo Ernesto |
| title |
Isotopic Preferential Solvation of I- in Low-Temperature Water Nanoclusters |
| 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 |
| publishDate |
2015 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15206106_v119_n35_p11783_Videla http://hdl.handle.net/20.500.12110/paper_15206106_v119_n35_p11783_Videla |
| work_keys_str_mv |
AT videlapabloernesto isotopicpreferentialsolvationofiinlowtemperaturewaternanoclusters AT lariadanielhector isotopicpreferentialsolvationofiinlowtemperaturewaternanoclusters |
| _version_ |
1768545205701574656 |