Chart 1 summarizes all compounds investigated in this study. We will start our discussion with the polymer model compounds. Initially we investigated a model compound of a typical epoxy resin (e.g. consisting of diglycidyl ether of bisphenol A and cured by an amine) in two conformations 1a and 1b. This compound presents a typical reaction product after cross-linking of an epoxy group with an amine during the curing phase of thermosetting epoxy resins. The amount of such covalent cross-links determines the molecular material characteristics of the final network structure. The CoGEF profiles for 1a and 1b observed with different functionals are summarized in Figure . While in 1a we observe exclusively homolytic bond cleavage (as expected for thermosetting polymers ) of the carbon-carbon bond between the alcohol and the amine moiety (Figure ), in 2b a different bond is involved in the mechanochemical scission of the compound.