Abstract
If a molecular dication is produced on a repulsive potential energy surface (PES), it normally dissociates. Before that, however, ultrafast nuclear dynamics can change the PES and significantly influence the fragmentation pathway. Here, we investigate the electron-impact-induced double ionization and subsequent fragmentation processes of the ethanol molecule using multiparticle coincident momentum spectroscopy and ab initio dynamical simulations. For the electronic ground state of the ethanol dication, we observe several fragmentation channels that cannot be reached by direct Coulomb explosion (CE) but require preceding isomerization. Our simulations show that ultrafast hydrogen or proton transfer (PT) can stabilize the repulsive PES of the dication before the direct CE and form intermediate H(2) or H(2)O. These neutrals stay in the vicinity of the precursor, and roaming mechanisms lead to isomerization and finally PT resulting in emission of H(3)(+) or H(3)O(+). The present findings can help to understand the complex fragmentation dynamics of molecular cations.