Kinetically Assisted Chemical Removal of Organic Contaminants by Reactive Oxygen Species: Insights from ReaxFF Molecular Dynamics Simulations

Organic contaminants on optical components critically impair intense laser systems. Oxygen plasma cleaning is a promising non-contact method, yet the mechanism by which the initial kinetic energy of reactive oxygen species assists chemically driven removal remains unclear. This study employs ReaxFF molecular dynamics to elucidate how reactive oxygen species chemically decompose dibutyl phthalate and how kinetic energy assists chemical reactions by enhancing transport, penetration, and energy transfer. While the core removal mechanism is chemical, kinetic energy promotes plasma-contaminant encounters and facilitates access to otherwise sluggish pathways. The results show that kinetic energy is a key promoter that enhances chemical decomposition, with the contaminant decomposition rate enhanced by up to 1310% and residues reduced by 81.13% compared to pure chemical reactions. This study identifies and quantifies two dominant reaction pathways (butyl chain cleavage & benzene ring cleavage). The analysis of diffusion and energy transfer reveals that higher kinetic energy improves reactive oxygen species transport, enables deeper penetration, and selectively activates specific reaction pathways by overcoming energy barriers. Synergy with flux, dose, and temperature is also demonstrated. This work provides atomic-level insights into kinetic promotion mechanisms, supporting optimized plasma cleaning processes and contributing to the performance stability and operational longevity of intense laser systems.