Ab initio localized electron calculations on solvated electron structures
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 molecules are remarkably successful in calculating the structure 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 lambda/sub max/ values and an e/sup -/(H/sub 2/O)/sub 6/ cluster is calculated to be bound relative to a free electron and six water molecules. Spin densities and Fermi contact terms are discussed. The bonding in solvated electrons is found to involve some donation to OH or NH antibonding orbitals, but bond and atom spin polarization play a major role in electron solvation.
- Research Organization:
- Friedrich-Alexander-Universitaet Erlangen-Nuernberg, West Germany
- OSTI ID:
- 7149640
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:4; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
10 SYNTHETIC FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
AMINES
AMMONIA
DATA
ELECTRONS
ELEMENTARY PARTICLES
ETHERS
FERMIONS
FUNCTIONS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
LEPTONS
MATHEMATICAL MODELS
MECHANICS
MOLECULAR MODELS
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PROPANE
QUANTUM MECHANICS
SOLVATED ELECTRONS
SOLVATION
SOLVENT PROPERTIES
SOLVENTS
THEORETICAL DATA
WAVE FUNCTIONS