In this study, we present a novel computational atomistic study of the photothermal decomposition behavior of arc plasma on radiation-induced gassing materials ablation, studying a polyamide 66 (PA66) system using reactive force field (ReaxFF) molecular dynamics (MD). We determine the infrared (IR) vibrational frequency of the PA66 permanent molecular dipole using MD and then computationally impose an electric field at the same frequency to simulate photothermal decomposition by IR, verifying our observations with gas chromatography-mass spectrometry (GCMS) of experimental decomposition. MD indicates that photothermal decomposition reaction is dominated by either cleavage at low temperature or cyclization at high temperature. At low temperature, initial chain scission takes place at the two amide C–N, and the remaining chains break down into a variety of molecular fragments and free radicals. Further increasing the temperature stabilizes a variety of branched chain structures via cyclization, debranching and polymerization, with further cleavage forming hydrocarbons and volatile small molecule gases. Overall, H2, CO, H2O, alkanes and alkenes are the main gaseous products and cyclic structures (especially nitrogen-containing three-membered ring) are the main solid products during the photothermal decomposition of PA66, and their formation results from a variety of complex chemical reactions. The results of MD cover the experimental observations of GCMS, demonstrating that this computational methodology helps us understand the molecular breakdown mechanisms of arc plasma radiation-induced gassing materials. We also discuss the physical mechanism by which the main gas can accelerate arc quenching, and the importance and necessity of using electric fields to simulate IR photothermal decomposition of arc-induced ablation.