Abstract

Estimations of the water reorganization energy following excess electron (e exc −) production and of interband transition energies using magneto-optical Faraday rotation measurements in liquid water have been recently reported. In such a context, the electronic structure of liquid water is presently revisited. The existence of an Urbach tail extending below the water conduction band and its efficient participation in the e exc − trapping seem to be well substantiated. From thermodynamic considerations, a value V 0∼−0.75 eV for the energy of the bottom of the conduction band with respect to vacuum, and a value U t∼0.5 eV for the Urbach tail extension are now proposed. Reported semiempirical determinations of the energy gap E g are presented and discussed, suggesting the average value E g=8.7 ± 0.5 eV. On the whole, the main terms underlying the electronic structure of liquid water would thus have to be revised downwards; also the present values turn out to be close to the corresponding ones estimated for crystalline or amorphous ice.

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