The reactive force eld ReaxFF provides a good compromise between accuracy and computational eort. We employ the parametrization for C/H/O from the work of Ashraf and van Duin, 39 which is an extension of the rst ReaxFF combustion force eld for hydrocarbons The PES-mapping algorithm only requires choosing an initial molecular structure to be investigated (the seed species). For high-temperature pyrolysis (2500, 3500, and 4500 K) of the radicals, 50 replicas have been used for butenyl (C 4 H 7 ) and 30 replicas for acetylene and phenyl (C 8 H 7 ). The accelerating eect of high temperature here has been enough to observe a sucient number of reactions, i.e. large parts of the network, in combination with an adequate total simulation time achieved by parallel replica sampling. In contrast, for LTO of butane, cyclohexane, and 1,3-dioxane, all of the simulations have been carried out with CVHD acceleration. For temperatures of 500, 700, and 1000 K, 100 parallel samples each have been simulated. All samples were run in parallel on one core each within a maximum of two hours wall-time. Each sample contains a single molecular structure and the box dimensions are chosen to correspond to a density of 10 mol m -3 . For each sample, random initial velocity distributions have been assigned to the same initial positions. Each conguration has been simulated using a time step of 0.1 fs and a Nosé-Hoover thermostat 42,43 with a damping constant of 10 fs. The atomic congurations and connectivities have been written to text les every 1 ps and 20 fs, respectively.