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Title: Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer

Abstract

Proton transfer via hydronium and hydroxide ions in water is ubiquitous. It underlies acid–base chemistry, certain enzyme reactions, and even infection by the flu. Despite two centuries of investigation, the mechanism underlying why hydroxide diffuses slower than hydronium in water is still not well understood. Herein, we employ state-of-the-art density-functional-theory-based molecular dynamics—with corrections for non-local van der Waals interactions, and self-interaction in the electronic ground state—to model water and hydrated water ions. At this level of theory, we show that structural diffusion of hydronium preserves the previously recognized concerted behaviour. However, by contrast, proton transfer via hydroxide is less temporally correlated, due to a stabilized hypercoordination solvation structure that discourages proton transfer. Specifically, the latter exhibits non-planar geometry, which agrees with neutron-scattering results. Asymmetry in the temporal correlation of proton transfer leads to hydroxide diffusing slower than hydronium.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [6]
+ Show Author Affiliations
  1. Temple Univ., Philadelphia, PA (United States). Dept. of Physics
  2. Princeton Univ., NJ (United States). Dept. of Chemistry
  3. Cornell Univ., Ithaca, NY (United States). Baker Lab., Dept. of Chemistry and Chemical Biology
  4. Temple Univ., Philadelphia, PA (United States). Dept. of Physics, Dept. of Chemistry, and Inst. for Computational Molecular Science
  5. Princeton Univ., NJ (United States). Dept. of Chemistry and Dept. of Physics
  6. Temple Univ., Philadelphia, PA (United States). Dept. of Physics and Inst. for Computational Molecular Science
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1490260
DOE Contract Number:  
SC0008726; SC0008626; AC02-06CH11357; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 1755-4330
Country of Publication:
United States
Language:
English

Citation Formats

Chen, Mohan, Zheng, Lixin, Santra, Biswajit, Ko, Hsin-Yu, DiStasio Jr, Robert A., Klein, Michael L., Car, Roberto, and Wu, Xifan. Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer. United States: N. p., 2018. Web. doi:10.1038/s41557-018-0010-2.
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Chen, Mohan, Zheng, Lixin, Santra, Biswajit, Ko, Hsin-Yu, DiStasio Jr, Robert A., Klein, Michael L., Car, Roberto, & Wu, Xifan. Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer. United States. doi:10.1038/s41557-018-0010-2.
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Chen, Mohan, Zheng, Lixin, Santra, Biswajit, Ko, Hsin-Yu, DiStasio Jr, Robert A., Klein, Michael L., Car, Roberto, and Wu, Xifan. Mon . "Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer". United States. doi:10.1038/s41557-018-0010-2.
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@article{osti_1490260,
title = {Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer},
author = {Chen, Mohan and Zheng, Lixin and Santra, Biswajit and Ko, Hsin-Yu and DiStasio Jr, Robert A. and Klein, Michael L. and Car, Roberto and Wu, Xifan},
abstractNote = {Proton transfer via hydronium and hydroxide ions in water is ubiquitous. It underlies acid–base chemistry, certain enzyme reactions, and even infection by the flu. Despite two centuries of investigation, the mechanism underlying why hydroxide diffuses slower than hydronium in water is still not well understood. Herein, we employ state-of-the-art density-functional-theory-based molecular dynamics—with corrections for non-local van der Waals interactions, and self-interaction in the electronic ground state—to model water and hydrated water ions. At this level of theory, we show that structural diffusion of hydronium preserves the previously recognized concerted behaviour. However, by contrast, proton transfer via hydroxide is less temporally correlated, due to a stabilized hypercoordination solvation structure that discourages proton transfer. Specifically, the latter exhibits non-planar geometry, which agrees with neutron-scattering results. Asymmetry in the temporal correlation of proton transfer leads to hydroxide diffusing slower than hydronium.},
doi = {10.1038/s41557-018-0010-2},
journal = {Nature Chemistry},
issn = {1755-4330},
number = 4,
volume = 10,
place = {United States},
year = {2018},
month = {3}
}
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Journal Article:
DOI:  10.1038/s41557-018-0010-2
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