Energy scheme for the perylene cation (top-left), showcasing the different H-hop and H-loss channels available. Isomerization/fragmentation pathways are classified according to whether they involve adjacent rings separated by a single tertiary carbon (top-right), neighboring rings separated by bay-regions (bottom-left) or a single ring (bottom-right). Intermediate and transitions states are labeled as int and ts, respectively. Loss channels are highlighted in red and all energies are given in eV with respect to that of the perylene cation. The * highlights an intermediate state that can have an energy of 3.20 eV if the aliphatic group is formed by hopping of H1 or H3 towards H2, as opposed to H2 hopping towards H1 (illustrated here) or H3 (see main text).