A study of the isomeric dependence of low-energy (<10 eV) electron attachment: Perfluoroalkanes

Abstract

The attachment of low-energy (<10 eV) electrons to the open-chain i-C4F10, i-C5F12, neo-C5F12, and to the cyclic c-C4F8 and c-C5F10 perfluoroalkanes has been studied using a time-of-flight mass spectrometer (TOFMS) and a high pressure electron swarm technique as well as the TOFMS results reported earlier on c-C4F8 and i-C4F10. Both long-lived parent anions (autodetachment lifetimes τa >10−6 s) and dissociative attachment fragment anions were observed for these molecules in the mass spectrometric study. The relative cross sections for negative ion formation and the τa of the long-lived parent anions were measured as a function of electron energy in the mass spectrometric study. The absolute total electron attachment rate constants as a function of the mean electron energy have been measured in the swarm study and used to calculate the total electron attachment cross sections as a function of electron energy. Both studies have shown a strong dependence of dissociative and nondissociative electron attachment processes on the structure of the molecules studied. For neo-C5F12, the predominant anion is the fragment C4F−9. In contrast, for i-C4F10, i-C5F12, c-C4F8, and c-C5F10, the parent anions are stronger than any of the fragment anions. Energetic considerations have been employed to identify fragmentation mechanisms of the negative ion states (NISs) leading to the formation of the observed fragment anions and to deduce some thermochemical data. The positions of the NISs, the observed differences in the cross sections for parent and fragment anion formation, and the types of the fragment anions formed for the various molecules are discussed.