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 (eaq-) in water. In essence, this mechanism relies on the possibility for an incompletely relaxed localized electron (eir-) to react chemically with a water molecule by the fast proton-transfer reaction eir- + H2O → H. + OH-. The encounter of two reacting eaq- would lead to the transitory destabilization of these species due to mutual distortions of the two electronic charge distributions, and structural and orientational variations of the surrounding water molecules, thus facilitating the passage eaq- → eir-. This transition to the eir- state would be followed rapidly (<0.3-0.7 ps) by the intermediate formation of either 1 or 2 H. atoms which would subsequently yield H2 by way of prompt geminate combination reactions. (Author)