Capturing Free-Radical Polymerization by Synergetic Ab Initio Calculations and Topological Reactive Molecular Dynamics

[Image: see text] Photocurable polymers are used ubiquitously in 3D printing, coatings, adhesives, and composite fillers. In the present work, the free radical polymerization of photocurable compounds is studied using reactive classical molecular dynamics combined with a dynamical approach of the nonequilibrium molecular dynamics (D-NEMD). Different concentrations of radicals and reaction velocities are considered. The mechanical properties of the polymer resulting from 1,6-hexanediol dimethacrylate systems are characterized in terms of viscosity, diffusion constant, and activation energy, whereas the topological ones through the number of cycles (polymer loops) and cyclomatic complexity. Effects like volume shrinkage and delaying of the gel point for increasing monomer concentration are also predicted, as well as the stress–strain curve and Young’s modulus. Combining ab initio, reactive molecular dynamics, and the D-NEMD method might lead to a novel and powerful tool to describe photopolymerization processes and to original routes to optimize additive manufacturing methods relying on photosensitive macromolecular systems.