With and without this acceleration, a PESmapping algorithm could automatically explore large networks in pyrolysis and oxidation of fuel molecules. We showed that with parallel simulations and PES mapping, common isomerization and dissociation pathways can be found in wall-time scales of hours for hydrocarbon radicals (C 4 H 7 , C 8 H 7 ). By deriv- ing eective and exible CV parameters and developing valuable templates that are highly adaptive to dierent reaction systems at low temperatures, the reproduction of almost all LTO reactions in butane, cyclohexane, and a newly proposed biohybrid fuel 1,3-dioxane, is achieved. Furthermore, some important reaction pathways have been validated using QC.