Theoretical description of the hydrated electron. Shape and spectroscopic properties of the cavity containing the excess electron

The shape and spectroscopic properties of the cavity containing the excess electron are examined by employing the methods of quantum and of statistical mechanics. A number of quantities are studied, first by the help of a spherical model and next by performing adiabatic quantum simulations. Comparing the predictions of these two approaches then leads to conclusions relative to the symmetry of the solvent cage. The dichroism of the pump-probe absorption of the hydrated electron is discussed having this information in view. (C) 1997 Elsevier Science B.V.