Abstract
The technique of photoelectron-photoion coincidence with variable ion source residence times has been applied to a study of benzonitrile ion fragmentation. The breakdown curve of the parent ions shows a strong dependence on residence time. Detailed analysis of this dependence shows that the ion fragments from its electronic ground state via a tight activated complex, in agreement with the conclusions of Chesnavich and Bowers. The rate-energy dependence agrees with that determined by Eland and Schulte, and the fragmentation threshold is in reasonable agreement with the threshold observed in electron impact at very long ion source residence times. The results lead to [Math] = 1321 ± 10 kJ/mol. The energetics of additional neutral and ionic C6 H4 isomers is estimated and discussed.
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