Fig 1.
Representative snapshot of the PFSA model comprising 100 polymer chains in the initial configuration.
Table 1.
Details of the MD models constructed for the PFSA degradation study.
Fig 2.
Temporal evolution of unreacted polymer segments in the Model A (•OH-only), Model B (H•-only), and Model C (mixed •OH/H•) systems at 300 K.
Fig 3.
Temporal profiles of radical concentrations in the Model A (·OH-only), Model B (H·-only), and Model C (mixed ·OH/H·) systems.
Within Model C, Model C −1 and Model C −2 denote the ·OH and H· populations, respectively at 300 K.
Fig 4.
Radical-specific ether linkage cleavage profiles in the Model A, Model B, and Model C systems at 300 K.
Fig 5.
Temporal evolution of sulfur-containing bond cleavage during radical-mediated degradation in the Model A, Model B, and Model C systems at 300 K.
Fig 6.
Unified radical-mediated PFSA degradation pathways.
Fig 7.
Structural snapshots from ReaxFF-MD simulations illustrating the temporal progression of degradation in the Model A, Model B, and Model C systems at 300 K.
Fig 8.
Arrhenius plots for the determination of activation energy barriers associated with radical-mediated degradation in the Model A, Model B, and Model C systems.
The solid lines represent linear fits to the simulation data.
Fig 9.
Temperature-dependent kinetics of HF release during the initial 20 ps of simulation.
(a) HF generation in the Model D system at 283-363K. (b) Comparison of HF release among structurally modified PFSA models (Model D-1, Model D-2, and Model D-3).
Fig 10.
Calculated high-frequency dielectric constant of PFSA oligomers as a function of functional group composition.