2-Fluoroadenine ((2F) A) is a therapeutic agent, which is suggested for application in cancer radiotherapy. The molecular mechanism of DNA radiation damage can be ascribed to a significant extent to the action of low-energy (<20 eV) electrons (LEEs), which damage DNA by dissociative electron attachment. LEE induced reactions in (2F) A are characterized both isolated in the gas phase and in the condensed phase when it is incorporated into DNA. Information about negative ion resonances and anion-mediated fragmentation reactions is combined with an absolute quantification of DNA strand breaks in (2F) A-containing oligonucleotides upon irradiation with LEEs. The incorporation of (2F) A into DNA results in an enhanced strand breakage. The strand-break cross sections are clearly energy dependent, whereas the strand-break enhancements by (2F) A at 5.5, 10, and 15 eV are very similar. Thus, (2F) A can be considered an effective radiosensitizer operative at a wide range of electron energies.

Electronic resonances commonly decay via internal conversion to vibrationally hot anions and subsequent statistical electron emission. We observed vibrational structure in such an emission from the nitrobenzene anion, in both the 2D electron energy loss and 2D photoelectron spectroscopy of the neutral and anion, respectively. The emission peaks could be correlated with calculated nonadiabatic coupling elements for vibrational modes to the electronic continuum from a nonvalence dipole-bound state. This autodetachment mechanism via a dipole-bound state is likely to be a common feature in both electron and photoelectron spectroscopies.

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We report partial cross sections for the dissociative electron attachment to pyruvic acid. A rich fragmentation dynamics is observed. Electronic structure calculations facilitate the identification of complex rearrangement reactions that occur during the dissociation. Furthermore, a number of fragment anions produced at electron energies close to 0 eV are observed, that cannot originate from single electron-molecule collisions. We ascribe their production to secondary reactions of the transient anions with neutral molecules. Such reactions turn out to be unusually efficient; the most probable reason for this is that they proceed via the formation of a double-hydrogen-bonded complex followed by an ultrafast proton transfer between the reaction partners.