The thermal decomposition of CF3I consists of three pathways. The detailed decomposition path of CF3I was shown in Fig.3. All energy barriers were calculated by kcal·mol−1. Fig.S5 shows the geometric structures for the reactants, transition states, intermediate, and products involved in all calculated reactions (Including thermal decomposition and fire0extinguishing reaction channels) as optimized at the B3LYP/6-311++G (d, p) level.