To understand this behavior, we used DFT at the B3LYP/6-31G(d) level to calculate the zero-force Ea for the homolytic dissociation of the carbamoyloxime mechanophores along the N-O bond in different solvents (Table ). For the thermal dissociation in DMF, 139, 230, and 214 kJ mol -1 were found for AO, MKO, and TKO. This trend was essentially also solvent-independent and reflected the experimentally determined thermal stabilities -particularly comparing Ea of AO scission with 139 kJ mol -1 determined by DFT and 132 kJ mol -1 obtained experimentally. Overall, both experiment and computation suggested a counterintuitive increasing mechanochemical reaction rate with simultaneous increasing thermal stability. .