Temperature dependence of dissociative electron attachment to bromo-chlorotoluene isomers: Competition between detachment of Cl⁻ and Br⁻

Dissociative electron attachment to three isomers of bromo-chlorotoluene was investigated in the electron energy range from 0 to 2 eV for gas temperatures in the range of 392-520 K using a crossed electron-molecular beam apparatus with a temperature regulated effusive molecular beam source. For all three molecules, both Cl⁻ and Br⁻ are formed. The ion yields of both halogenides show a pronounced temperature effect. In the case of Cl⁻ and Br⁻, the influence of the gas temperature can be observed at the threshold peak close to 0 eV. The population of molecules that have some of their out-of-plane modes excited varies strongly in the temperature range investigated, indicating that such vibrations might play a role in the energy transfer towards bond breaking. Potential energy curves for the abstraction of Cl⁻ and Br⁻ were calculated and extrapolated into the metastable domain. The barriers in the diabatic curves approximated in this way agree well with the ones derived from the temperature dependence observed in the experiments.