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The primary gas phase hydration shell of hydroxide
The number of water molecules in hydroxide’s primary hydration shell has been long debated to be three from the interpretation of experimental data and four from theoretical studies. Here, we provide direct evidence for the presence of a fourth water molecule in hydroxide’s primary hydration shell f...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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American Association for the Advancement of Science
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10038337/ https://www.ncbi.nlm.nih.gov/pubmed/36961895 http://dx.doi.org/10.1126/sciadv.adf4309 |
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author | Cao, Wenjin Wen, Hui Xantheas, Sotiris S. Wang, Xue-Bin |
author_facet | Cao, Wenjin Wen, Hui Xantheas, Sotiris S. Wang, Xue-Bin |
author_sort | Cao, Wenjin |
collection | PubMed |
description | The number of water molecules in hydroxide’s primary hydration shell has been long debated to be three from the interpretation of experimental data and four from theoretical studies. Here, we provide direct evidence for the presence of a fourth water molecule in hydroxide’s primary hydration shell from a combined study based on high-resolution cryogenic experimental photoelectron spectroscopy and high-level quantum chemical computations. Well-defined spectra of OH(−)(H(2)O)(n) clusters (n = 2 to 5) yield accurate electron binding energies, which are, in turn, used as key signatures of the underlying molecular conformations. Although the smaller OH(−)(H(2)O)(3) and OH(−)(H(2)O)(4) clusters adopt close-lying conformations with similar electron binding energies that are hard to distinguish, the OH(−)(H(2)O)(5) cluster clearly has a predominant conformation with a four-coordinated hydroxide binding motif, a finding that unambiguously determines the gas phase coordination number of hydroxide to be four. |
format | Online Article Text |
id | pubmed-10038337 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Association for the Advancement of Science |
record_format | MEDLINE/PubMed |
spelling | pubmed-100383372023-03-25 The primary gas phase hydration shell of hydroxide Cao, Wenjin Wen, Hui Xantheas, Sotiris S. Wang, Xue-Bin Sci Adv Physical and Materials Sciences The number of water molecules in hydroxide’s primary hydration shell has been long debated to be three from the interpretation of experimental data and four from theoretical studies. Here, we provide direct evidence for the presence of a fourth water molecule in hydroxide’s primary hydration shell from a combined study based on high-resolution cryogenic experimental photoelectron spectroscopy and high-level quantum chemical computations. Well-defined spectra of OH(−)(H(2)O)(n) clusters (n = 2 to 5) yield accurate electron binding energies, which are, in turn, used as key signatures of the underlying molecular conformations. Although the smaller OH(−)(H(2)O)(3) and OH(−)(H(2)O)(4) clusters adopt close-lying conformations with similar electron binding energies that are hard to distinguish, the OH(−)(H(2)O)(5) cluster clearly has a predominant conformation with a four-coordinated hydroxide binding motif, a finding that unambiguously determines the gas phase coordination number of hydroxide to be four. American Association for the Advancement of Science 2023-03-24 /pmc/articles/PMC10038337/ /pubmed/36961895 http://dx.doi.org/10.1126/sciadv.adf4309 Text en Copyright © 2023 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). https://creativecommons.org/licenses/by-nc/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license (https://creativecommons.org/licenses/by-nc/4.0/) , which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited. |
spellingShingle | Physical and Materials Sciences Cao, Wenjin Wen, Hui Xantheas, Sotiris S. Wang, Xue-Bin The primary gas phase hydration shell of hydroxide |
title | The primary gas phase hydration shell of hydroxide |
title_full | The primary gas phase hydration shell of hydroxide |
title_fullStr | The primary gas phase hydration shell of hydroxide |
title_full_unstemmed | The primary gas phase hydration shell of hydroxide |
title_short | The primary gas phase hydration shell of hydroxide |
title_sort | primary gas phase hydration shell of hydroxide |
topic | Physical and Materials Sciences |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10038337/ https://www.ncbi.nlm.nih.gov/pubmed/36961895 http://dx.doi.org/10.1126/sciadv.adf4309 |
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