Nature of solvated electron absorption spectra
- 1 January 1979
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
- Vol. 75, 474-484
- https://doi.org/10.1039/f29797500474
Abstract
A fundamental many-particle theory of temperature-dependent spectral moments is developed for the enhanced optical absorption bands attributed to solvated electrons in various polar solvents. Several new results are obtained (expressed in atomic units): (1)n0ƒ= 1, where n0 is a mean index of refraction of the solvent and ƒ is the empirical oscillator strength of the band; (2)〈∣Δre∣2〉=(1/ω)av, where 〈∣Δre∣2〉 is an equilibrium-averaged dispersion-in-position of the solvated electron and (1/ω)av is the mean reciprocal absorption frequency of the band; (3)µe –¾ωav, where µe is the standard chemical potential of the solvated electron and ωav is the mean absorption frequency of the band; (4)ωth⩽¾ωav, where ωth is the (vertical) photoejection threshold frequency of the solvated electron. For solvated-electron spectra in ammonia, water and a number of other solvents, no more than about 25 % of the pertinent absorption band can be ascribed to bound–bound transitions involving excited states with energies less than that of the photoejection threshold of the solvated electron.Keywords
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