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Dynamics of the Bulk Hydrated Electron from Many‐Body Wave‐Function Theory


Wilhelm, Jan; VandeVondele, Joost; Rybkin, Vladimir V (2019). Dynamics of the Bulk Hydrated Electron from Many‐Body Wave‐Function Theory. Angewandte Chemie Internationale Edition, 58(12):3890-3893.

Abstract

The structure of the hydrated electron is a matter of debate as it evades direct experimental observation owing to the short life time and low concentrations of the species. Herein, the first molecular dynamics simulation of the bulk hydrated electron based on correlated wave‐function theory provides conclusive evidence in favor of a persistent tetrahedral cavity made up by four water molecules, and against the existence of stable non‐cavity structures. Such a cavity is formed within less than a picosecond after the addition of an excess electron to neat liquid water, with less regular cavities appearing as intermediates. The cavities are bound together by weak H−H bonds, the number of which correlates well with the number of coordinated water molecules, each type of cavity leaving a distinct spectroscopic signature. Simulations predict regions of negative spin density and a gyration radius that are both in agreement with experimental data.

Abstract

The structure of the hydrated electron is a matter of debate as it evades direct experimental observation owing to the short life time and low concentrations of the species. Herein, the first molecular dynamics simulation of the bulk hydrated electron based on correlated wave‐function theory provides conclusive evidence in favor of a persistent tetrahedral cavity made up by four water molecules, and against the existence of stable non‐cavity structures. Such a cavity is formed within less than a picosecond after the addition of an excess electron to neat liquid water, with less regular cavities appearing as intermediates. The cavities are bound together by weak H−H bonds, the number of which correlates well with the number of coordinated water molecules, each type of cavity leaving a distinct spectroscopic signature. Simulations predict regions of negative spin density and a gyration radius that are both in agreement with experimental data.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:General Chemistry, Catalysis
Language:English
Date:18 February 2019
Deposited On:22 Nov 2019 16:09
Last Modified:27 Nov 2019 11:52
Publisher:Wiley-VCH Verlag
ISSN:1433-7851
OA Status:Green
Publisher DOI:https://doi.org/10.1002/anie.201814053
Project Information:
  • : FunderSNSF
  • : Grant IDPZ00P2_174227
  • : Project TitleCondensed-Phase Quantum Chemistry via Embedding Theory

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