Dissociative double ionization of toluene using synchrotron radiation in conjunction with theoretical studies leads to a determination of the thermochemistry of the dication c-C7H62+. Further, photon-energy dependent reactivity studies reveal that the asymmetric energy deposition upon single-electron transfer in the C7H82+/C7D8 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. (C) 2012 Elsevier B.V. All rights reserved.