Epoxy resins are widely used as matrix resins, especially for carbon-fiber-reinforced plastic, due to their outstanding physical and mechanical properties. To date, most research into cross-linking processes using simulation has considered only a distance-based criterion to judge the probability of reaction. In this work, a new algorithm was developed for use with the large-scale atomic/molecular massively parallel simulator (LAMMPS) simulation package to study the cross-linking process; this new approach combines both a distance-based criterion and several kinetic criteria to identify whether the reaction has occurred. Using this simulation framework, we investigated the effect of model size on predicted thermomechanical properties of three different structural systems: Diglycidyl ether of bisphenol A (DGEBA)/4,4′-diaminodiphenyl sulfone (4,4′-DDS), DGEBA/diethylenetriamine (DETA), and tetraglycidyl diaminodiphenylmethane (TGDDM)/4,4′-DDS. Derived values of gel point, volume shrinkage, and cross-linked resin density were found to be insensitive to model size in these three systems. Other thermomechanical properties, i.e., glass-transition temperature, Young's modulus, and yield stress, were found to reach stable values for systems larger than a¼40 000 atoms for both DGEBA/4,4′-DDS and DGEBA/DETA. However, these same properties modeled for TGDDM/4,4′-DDS did not stabilize until the system size reached 50 000 atoms. Our results provide general guidelines for simulation system size and procedures to more accurately predict the thermomechanical properties of epoxy resins.