Binding energies, lifetimes and implications of bulk and interface solvated electrons in water

Solvated electrons in liquid water are one of the seemingly simplest, but most important, transients in chemistry and biology, but they have resisted disclosing important information about their energetics, binding motifs and dynamics. Here we report the first ultrafast liquid-jet photoelectron spectroscopy measurements of solvated electrons in liquid water. The results prove unequivocally the existence of solvated electrons bound at the water surface and of solvated electrons in the bulk solution, with vertical binding energies of 1.6 eV and 3.3 eV, respectively, and with lifetimes longer than 100 ps. The unexpectedly long lifetime of solvated electrons bound at the water surface is attributed to a free-energy barrier that separates surface and interior states. Beyond constituting important energetic and kinetic benchmark and reference data, the results also help to understand the mechanisms of a number of very efficient electron-transfer processes in nature.