Results are reported of Born-Oppenheimer molecular dynamics calculations performed on the singlet dication of norbornane, starting from the neutral ground state geometry. Intramolecular rearrangements and charge dissociation processes, which probably take place in the innermost valence ionization spectrum, are discussed and an analysis by means of natural bond orders and Wiberg bond indices has been performed. The outcome of these simulations and the observed cage fragmentation might explain a tremendous rise of electron-impact (e, 2e) ionization cross sections of norbornane at electron binding energies around the double-ionization threshold. (C) 2013 Elsevier B. V. All rights reserved.