Unimolecular dissociation of doubly ionized toluene and electron transfer between neutral toluene and its dication

Dissociative double ionization of toluene using synchrotron radiation in conjunction with theoretical studies leads to a determination of the thermochemistry of the dication c - C 7 H 6 2 + . Further, photon-energy dependent reactivity studies reveal that the asymmetric energy deposition upon single-electron transfer in the C 7 H 8 2 + / C 7 D 8 collision system is not influenced by the internal energy content of the dication precursors. This finding agrees with the previous assignment of the asymmetric energy deposition as a consequence of the electronic states accessible upon recombination of a dication with an electron compared to the removal of an electron from a neutral compound, respectively.