Abstract
Dissociative electron attachment (DEA) to perfluorohexane (C6F14), perfluoro(methylcyclo-hexane) (C6F11CF3) and perfluorocyclohexanecarbonyl chloride (C6F11C(O)Cl) is studied in a crossed electron-molecular beam experiment with mass spectrometric detection of the fragment anions. We find that all molecules undergo effective decomposition in the subexcitation energy range (0–3eV) yielding ions that arise from direct bond cleavages creating a fragment anion and its neutral counterpart but also from more complicated reactions due to substantial rearrangement in the transient anion formed upon resonant electron capture. All three compounds preferentially decompose into closed shell anions of the form CnF2n+1−. While in perfluorocyclohexanecarbonyl chloride (C6F11C(O)Cl) DEA into Cl− represents the most intense reaction, formation of F− is in any case comparatively weak. The resonance positions for F− formation show specific features for the three compounds which may allow a correlation between the location of the DEA resonance and the site from which the F− ion originates.
Published Version
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