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Dynamics of the Bulk Hydrated Electron from Many‐Body Wave‐Function Theory
Author(s) -
Wilhelm Jan,
VandeVondele Joost,
Rybkin Vladimir V.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201814053
Subject(s) - radius of gyration , solvated electron , chemical physics , electron , radius , picosecond , chemistry , molecule , electron localization function , molecular physics , gyration , molecular dynamics , electron density , atomic physics , computational chemistry , physics , polymer , optics , quantum mechanics , organic chemistry , laser , geometry , computer security , mathematics , radiolysis , aqueous solution , computer science
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.