The input settings for CTY-TAD and PESmapping are mainly identical to the settings selected in the respective initial publications (see Supporting Information section for the input files). Eleven CTY-TAD simulations were performed at a temperature of 3000 K, while 333 PESmapping simulations each were run at 500 K, 1000 K, and 1500 K adding up to a total of 999 runs. In this study, both methods searched only for one reaction step towards products, instead of employing the full basin-hopping approach. As outlined in the original publication, the CTY-TAD database for identified reactions is initiated with all potential hydrogen dissociation events for the studied system. Consequently, any singular C -H bond breakage is blocked during simulations and does not appear in our exploration results for CTY-TAD. In PESmapping, there is no such setting, and the exploration results contain all hydrogen dissociations that can be found.