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.
Keywords: ab initio molecular dynamics; hydrated electrons; many-body electronic structure theory; quantum chemistry; radical chemistry.
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