![]() ![]() We furthermore suggest that no stable interfacial species may exist at all, consistent with the interpretation of certain surface-sensitive spectroscopy measurements, and that even if a short-lived, metastable species does exist at the vacuum/water interface, it would be extremely difficult to distinguish, experimentally, from e –(aq) in bulk water, using either optical absorption or photoelectron spectroscopy. ![]() We employ a variety of computational strategies to demonstrate that the energetics of the hydrated electron at the surface of neat liquid water are not significantly different from those of e –(aq) in bulk water and as such are incompatible with dissociative electron attachment reactions in DNA. ![]() Other such experiments, however, find no evidence of a long-lived feature at low binding energy. A recent measurement of the energy (below vacuum level) of the putative “interfacial” hydrated electron at the water/vacuum interface, performed using liquid microjet photoelectron spectroscopy, has been interpreted to suggest that aqueous electrons at the water/biomolecule interface may possess the appropriate energetics to induce DNA strand breaks, whereas e –(aq) in bulk water lies too far below the vacuum level to induce such reactions. Experiments have suggested that the aqueous electron, e –(aq), may play a significant role in the radiation chemistry of DNA. ![]()
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