Unveiling the Influence of Water Molecules for NF3 Removal by the Reaction of NF3 with OH: A DFT Study

The removal of nitrogen trifluoride (NF3) is of significant importance in atmospheric chemistry, as NF3 is an important anthropogenic greenhouse gas. However, the radical species OH and O(D-1) in atmospheric conditions are nonreactive towards NF3. It is necessary to explore possible ways to remove NF3 in atmosphere. Therefore, the participation of water molecules in the reaction of NF3 with OH was discussed, as water is abundant in the atmosphere and can form very stable complexes due to its ability to act as both a hydrogen bond donor and acceptor. Systemic DFT calculations carried out at the CBS-QB3 and omega B97XD/aug-cc-pVTZ level of theory suggest that water molecules could affect the NF3 + OH reaction as well. The energy barrier of the S(N)2 mechanism was decreased by 8.52 kcal/mol and 10.58 kcal/mol with the assistance of H2O and (H2O)(2), respectively. Moreover, the presence of (H2O)(2) not only reduced the energy barrier of the reaction, but also changed the product channels, i.e., formation of NF2O + (H2O)(2)-HF instead of NF2OH + (H2O)(2)-F. Therefore, the removal of NF3 by reaction with OH is possible in the presence of water molecules. The results presented in this study should provide useful information on the atmospheric chemistry of NF3.