Vacuum-UV negative photoion spectroscopy of CF3Cl, CF3Br and CF3I

Abstract

Using synchrotron radiation negative ions have been detected by mass spectrometry following vacuum-UV photoexcitation of trifluorochloromethane (CF$_3$Cl), trifluorobromomethane (CF$_3$Br) and trifluoroiodomethane (CF$_3$I). The anions F$^-$, X$^-$, F$_2^-$, FX$^-$, CF$^-$, CF$_2^-$ and CF$_3^-$ were observed from all three molecules, where X = Cl, Br or I, and their ion yields recorded in the range 8-35 eV. With the exception of Br$^-$ and I$^-$, the anions observed show a linear dependence of signal with pressure, showing that they arise from unimolecular ion-pair dissociation. Dissociative electron attachment, following photoionization of CF$_3$Br and CF$_3$I as the source of low-energy electrons, is shown to dominate the observed Br$^-$ and I$^-$ signals, respectively. Cross sections for ion-pair formation are put on to an absolute scale by calibrating the signal strengths with those of F$^-$ from both SF$_6$ and CF$_4$. These anion cross sections are normalized to vacuum-UV absorption cross sections, where available, and the resulting quantum yields are reported. Anion appearance energies are used to calculate upper limits to 298 K bond dissociation energies for $D^0$(CF$_3$-X) which are consistent with literature values. We report new data for $D^0$(CF$_2$I$^-$-F) ≤ 2.7 ± 0.2 eV and $\Delta_fH^0_{298}$ (CF$_2$I$^+$) ≤ (598 ± 22) kJ mol$^{-1}$. No ion-pair formation is observed below the ionization energy of the parent molecule for CF$_3$Cl and CF$_3$Br, and only weak signals (in both I$^-$ and F$^-$) are detected for CF$_3$I. These observations suggest neutral photodissociation is the dominant exit channel to Rydberg state photoexcitation at these lower energies