Ab initio localized electron calculations on solvated electron structures

T Clark, G Illing - Journal of the American Chemical Society, 1987 - ACS Publications
T Clark, G Illing
Journal of the American Chemical Society, 1987ACS Publications
Ab initio molecular orbital calculations using a localized split-valence (31) s-orbital to
represent the electron in a cavity model and using the standard 6-31G* basis for solvent
moleculess are remarkably successful incalculating thestructure of solvated electrons.
Calculated structures for hydrated electrons are in good agreement with experiment.
Structures are predicted for ammonia-, methylamine-, ethylamine-, dimethylamine-, dimethyl
ether-, and propane-solvated electrons. Solvation energies for the localized electron …
Abstract
Ab initio molecular orbital calculations using a localized split-valence (31) s-orbital to represent the electron in a cavity model and using the standard 6-31G* basis for solvent moleculess are remarkably successful incalculating thestructure of solvated electrons. Calculated structures for hydrated electrons are in good agreement with experiment. Structures are predicted for ammonia-, methylamine-, ethylamine-, dimethylamine-, dimethyl ether-, and propane-solvated electrons. Solvation energies for the localized electron correlate moderately well with experimental Xmax values and an e~(H20) 6 cluster is calculated to be bound relative to a free electron and six water molecules. Spin densities and Fermi contactterms are discussed. The bonding in solvated electrons is found to involve some donation to OF! or NH antibonding orbitals, butbond and atom spin polarization play a major rolein electron solvation.
ACS Publications
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