Pressure Shifts in Properties of Solvated Electrons in Alcohols and Water

Abstract

Pressure shifts of the optical absorption maxima of solvated electrons are, respectively, in electron volts per kilobar and nanometers per kilobar: in water 0.053 and −19; in ethanol 0.062 and −20; in methanol ∼ 0.05 and −15. The half-width of the absorption spectrum of esolv− in water is increased from 0.9 eV at 1 bar to 1.2 eV at 3.8 kbar. In both ethanol and methanol the half-lives are reduced by pressure. In ethanol Δ V‡ (esolv− → ROsolv− + H) = − 16 cm3 mol−1. In water Δ V‡ (esolv− + S → S−) ≈ −1 cm3 mol−1.