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Ultrafast Dynamics of Water Radiolysis: Hydrated Electron Formation, Solvation, Recombination and Scavenging.

The ultrafast formation, solvation, geminate recombination of hydrated electron upon vacuum UV photoexcitation of liquid water and static and dynamic scavenging by NO3- are investigated using femtosecond time-resolved photoelectron spectroscopy. The solvation time constants of an excess electron are typical for liquid water, but they slightly increased with the excitation energy. The electron survival probabilities against geminate recombination are found to be much lower than the literature values owing to previously-unobserved ultrafast geminate recombination in 5 ps. NO3- induces ultrafast (static) scavenging of the excited electronic state of liquid water and dynamic scavenging of a detached electron with the reaction rates dependent on the excitation energy. The e_aq^- formation at 7.7 eV is ascribed to the H atom transfer process, while it is plausible that additional e_aq^- formation channels open at higher energies.