A coarse-grained model has been developed for molecular dynamics simulations of the interaction of light with polymeric materials. The photon energy can result in a vibrational excitation (photothermal process) or disruption of a chemical bond (photochemical process) in a polymer. In the latter case, the formation of active radial sites and the occurrence of chemical reactions have to be taken into consideration. The novel feature of this model is the incorporation of chemical reactions into the united atom approximate representation of the polymer structure, which permits the study of laser ablation, degradation, or the effect of various chemical reactions on large time and length scales. The chemical reactions are included in the model in a probabilistic manner as in the kinetic Monte Carlo method. This model adopts physically and experimentally known quantities such as enthalpies and probabilities of reactions. Properties such as laser irradiation time, laser fluence, and wavelength are explicitly included. Moreover, no chemically correct interaction potential is required to incorporate the effects of chemical reactions on the dynamics of the system after energy deposition. We find that the model provides a plausible description of the essential processes. The laser-induced pressure relaxation is the main mechanism responsible for the onset of polymer ablation. Since the pressure relaxation processes are slow, there is a delay in the onset of ablation after the end of the laser pulse as is observed experimentally. The vaporization processes are not efficient for material removal, and the effect is minimal for both photochemical and photothermal processes. A lower fluence is needed for the onset of ablation with photochemical processes than photothermal processes.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry