We demonstrate that electrons at energies below the threshold for electronic excitation ($<3\mathrm{e}\mathrm{V}$) effectively decompose gas phase uracil generating a mobile hydrogen radical and the corresponding closed shell uracil fragment anion $\mathrm{(}\mathrm{U}\mathrm{\text{−}}\mathrm{H}{)}^{-}$. The reaction is energetically driven by the large electron affinity of the (U-H) radical. This observation has significant consequences for the molecular picture of radiation damage, i.e., genotoxic effects or damage of living cells due to the secondary component of high energy radiation.

We have investigated experimentally the formation of anions and cations of deoxyribose sugar (C5H10O4) via inelastic electron interaction (attachment/ionization) using a monochromatic electron beam in combination with a quadrupole mass spectrometer. The ion yields were measured as a function of the incident electron energy between about 0 and 20 eV. As in the case of other biomolecules (nucleobases and amino acids), low energy electron attachment leads to destruction of the molecule via dissociative electron attachment reactions. In contrast to the previously investigated biomolecules dehydrogenation is not the predominant reaction channel for deoxyribose; the anion with the highest dissociative electron attachment (DEA) cross section of deoxyribose is formed by the release of neutral particles equal to two water molecules. Moreover, several of the DEA reactions proceed already with “zero energy” incident electrons. In addition, the fragmentation pattern of positively charged ions of deoxyribose also indicates strong decomposition of the molecule by incident electrons. For sugar the relative amount of fragment ions compared to that of the parent cation is about an order of magnitude larger than in the case of nucleobases. We determined an ionization energy value for C5H10O4+ of 10.51±0.11 eV, which is in good agreement with ab initio calculations. For the fragment ion C5H6O2+ we obtained a threshold energy lower than the ionization energy of the parent molecular ion. All of these results have important bearing for the question of what happens in exposure of living tissue to ionizing radiation. Energy deposition into irradiated cells produces electrons as the dominant secondary species. At an early time after irradiation these electrons exist as ballistic electrons with an initial energy distribution up to several tens of electron volts. It is just this energy regime for which we find in the present study rather characteristic differences in the outcome of electron interaction with the deoxyribose molecule compared to other nucleobases (studied earlier). Therefore, damage induced by these electrons to the DNA or RNA strands may start preferentially at the ribose backbone. In turn, damaged deoxyribose is known as a key intermediate in producing strand breaks, which are the most severe form of lesion in radiation damage to DNA and lead subsequently to cell death.

Sharp peaks in the dissociative electron attachment (DEA) cross sections of uracil and thymine at energies below 3eV are assigned to vibrational Feshbach resonances (VFRs) arising from coupling between the dipole bound state and the temporary anion state associated with occupation of the lowest σ* orbital. Three distinct vibrational modes are identified, and their presence as VFRs is consistent with the amplitudes and bonding characteristics of the σ* orbital wave function. A deconvolution method is also employed to yield higher effective energy resolution in the DEA spectra. The site dependence of DEA cross sections is evaluated using methyl substituted uracil and thymine to block H atom loss selectively. Implications for the broader issue of DNA damage are briefly discussed.