Issue 0, 1979

Nature of solvated electron absorption spectra

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)〈∣Δre2〉=[fraction three-over-two](1/ω)av, where 〈∣Δre2〉 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[gt-or-equal]–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.

Article information

Article type
Paper

J. Chem. Soc., Faraday Trans. 2, 1979,75, 474-484

Nature of solvated electron absorption spectra

S. Golden and T. R. Tuttle, J. Chem. Soc., Faraday Trans. 2, 1979, 75, 474 DOI: 10.1039/F29797500474

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