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DOE OSTI · 1992284

Relation between the Hydrated Electron Solvation Structure and Its Partial Molar Volume

Neupane, Pauf·Bartels, David M.·Thompson, Ward H.
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Abstract

It is now generally accepted that the hydrated electron occupies a cavity in water, but the size of the cavity and the arrangements of the solvating water molecules are not fully characterized. Here, we use the Kirkwood-Buff (KB) approach to examine how the partial molar volume (V M ) provides insight into these issues. The KB method relates V M to an integral of the electron-water radial distribution function, a key measure of the hydrated electron structure. Here we have applied it to three widely-used pseudopotentials and the results show that V M is a sensitive measure of the fidelity of hydrated electron descriptions. Thus, the measured V M places constraints on the hydrated electron structure that are important in developing and evaluating model descriptions. Importantly, we find that V M does not reflect only the cavity size (and thus should not be used to infer the cavity radius), but is strongly dependent on the extended solvation structure.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRYcavitieselectronic structuremoleculespseudopotentialssolvation

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Neupane, Pauf, Bartels, David M., Thompson, Ward H.. 2023-06-22. Relation between the Hydrated Electron Solvation Structure and Its Partial Molar Volume. https://doi.org/10.1021/acs.jpcb.3c03158

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