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- W2039735536 abstract "The hydrated electron is one of the most fundamental nucleophiles in aqueous solution, yet it is a transient species in liquid water, making it challenging to study. The solvation thermodynamics of the electron are important for determining the band structure and properties of water and aqueous solutions. However, a wide range of values for the electron solvation enthalpy (−1.0 to −1.8 eV) has been obtained from previous methods, primarily because of the large uncertainty as to the value for the absolute proton solvation enthalpy. In the gas phase, electron interactions with water can be investigated in stable water clusters that contain an excess electron, or an electron and a solvent-separated monovalent or divalent metal ion. Here, we report the generation of stable water clusters that contain an excess electron and a solvent-separated trivalent metal ion that are formed upon electron capture by hydrated trivalent lanthanide clusters. From the number of water molecules lost upon electron capture, adiabatic recombination energies are obtained for La(H2O)n3+ (n = 42−160). The trend in recombination energies as a function of hydration extent is consistent with a structural transition from a surface-located excess electron at smaller sizes (n ≤ ∼56) to a more fully solvated electron at larger sizes (n ≥ ∼60). The recombination enthalpies for n > 60 are extrapolated as a function of the geometrical dependence on cluster size to infinite size to obtain the bulk hydration enthalpy of the electron (−1.3 eV). This extrapolation method has the advantages that it does not require estimates of the absolute proton or hydrogen hydration enthalpies." @default.
- W2039735536 created "2016-06-24" @default.
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- W2039735536 date "2010-03-10" @default.
- W2039735536 modified "2023-10-16" @default.
- W2039735536 title "Electron Hydration and Ion−Electron Pairs in Water Clusters Containing Trivalent Metal Ions" @default.
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- W2039735536 doi "https://doi.org/10.1021/ja9079385" @default.
- W2039735536 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/20218722" @default.
- W2039735536 hasPublicationYear "2010" @default.
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