A CONJECTURE ON THE FATE OF THE HYDRATED ELECTRON DURING ITS DISPROPORTIONATION REACTION

A mechanism is proposed to explain the disproportionation reaction of 2 hydrated electrons (e(aq)-) in water. In essence, this mechanism rel ies on the possibility for an incompletely relaxed localized electron (e(ir)-) to react chemically with a water molecule by the fast proton- transfer reaction e(ir)- + H2O --> H. + OH-. The encounter of two reac ting e(aq)- would lead to the transitory destabilization of these spec ies due to mutual distortions of the two electronic charge distributio ns, and structural and orientational variations of the surrounding wat er molecules, thus facilitating the passage e(aq)- --> e(ir)-. This tr ansition to the e(ir)- state would be followed rapidly (<0.3 0.7 ps) b y the intermediate formation of either 1 or 2 H. atoms which would sub sequently yield H-2 by way of prompt geminate combination reactions.