Dissociative electron attachment (DEA) to W(CO)(6) led to strong dissociation but a complete loss of all CO ligands was not observed in DEA. Deposit contaminations might be a direct result of DEA reactions close to the irradiation spot in beam deposition techniques.

We report gas phase studies on NCO(-) fragment formation from the nucleobases thymine and uracil and their N-site methylated derivatives upon dissociative electron attachment (DEA) and through electron transfer in potassium collisions. For comparison, the NCO(-) production in metastable decay of the nucleobases after deprotonation in matrix assisted laser desorption/ionization (MALDI) is also reported. We show that the delayed fragmentation of the dehydrogenated closed-shell anion into NCO(-) upon DEA proceeds few microseconds after the electron attachment process, indicating a rather slow unimolecular decomposition. Utilizing partially methylated thymine, we demonstrate that the remarkable site selectivity of the initial hydrogen loss as a function of the electron energy is preserved in the prompt as well as the metastable NCO(-) formation in DEA. Site selectivity in the NCO(-) yield is also pronounced after deprotonation in MALDI, though distinctly different from that observed in DEA. This is discussed in terms of the different electronic states subjected to metastable decay in these experiments. In potassium collisions with 1- and 3-methylthymine and 1- and 3-methyluracil, the dominant fragment is the NCO(-) ion and the branching ratios as a function of the collision energy show evidence of extraordinary site-selectivity in the reactions yielding its formation.

We present a detailed experimental investigation of anion production in electron collisions with ethylene, C 2 H 4 . The investigated energy range is between 0 and 90 eV where anions are formed by two processes, in the low energy regime by dissociative electron attachment (DEA) and at higher energy by dipolar dissociation (DD). These electron induced processes are studied in two different experimental apparatus using two different mass spectrometry techniques. One is a time of flight spectrometer operating with velocity slice imaging technique and the other is a two sector field mass spectrometer. The former allows efficient collection of ions compared to standard mass spectrometers, while the latter provides high mass resolution. Eight fragment anions formed via DEA in the electron energy range between 5 and 17 eV have been detected; two fragments have not reported as DEA products in any previous studies. DD in C 2 H 4 leads to the formation of the same anions as found in the case of DEA. Quantum chemical calculations have been carried out to determine the thermochemical thresholds of anion formation.

Aminoacetonitrile (NH2CH2CN, AAN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. It is a very important molecule in the Strecker diagram explaining the formation of amino acids. In the present investigation, dissociative electron attachment to NH2CN was studied in a crossed electron-molecular beams experiment in the electron energy range from about 0 to 17 eV. In this electron energy range, the following six anionic species were detected: C2H3N2(-), C2H2N2(-), C2H2N(-), C2HN(-), CN(-), and NH2(-). Possible reaction channels for all the measured negative ions are discussed, and the experimental results are compared with calculated thermochemical thresholds of the observed anions. Similar to other nitrile and aminonitrile compounds, the main anions detected were the negatively charged nitrile group, the dehydrogenated parent molecule, and the amino group. No parent anion was observed. Low anion yields were observed indicating that AAN is less prone to electron capture. Therefore, AAN can be considered to exhibit a relatively long lifetime under typical conditions in outer space.