Figure shows selected examples of the interplay of roaming and scrambling leading to the (a) formation of H + 3 ion, (b) cyclization, and (c) emission of H-atoms. The formation of H + 3 via capturing a proton by a roaming H 2 molecule is found to be a slow process with a minimum opening time of around 650 fs, which is close to three times larger than the time scale for the formation of H + 3 via the the same process in ethanol . On the other hand, the hydrogen scrambling can start as early as 25 fs after the formation of the dication, and the CE after emission of H-atoms can take more than 100 fs. The formation of fragments with cyclic structure can take more than 200 fs. These processes and their associated time scales are also a function of the amount of internal energy available with the precursor ion. Thus, simulation times of the order of several hundreds of femtoseconds are required to capture and address all possibilities of energy dissipation by internally hot molecular ions.