Unveiling the Influence of Water Molecules for NF 3 Removal by the Reaction of NF 3 with OH: A DFT Study.

The removal of nitrogen trifluoride (NF 3 ) is of significant importance in atmospheric chemistry, as NF 3 is an important anthropogenic greenhouse gas. However, the radical species OH and O( 1 D) in atmospheric conditions are nonreactive towards NF 3 . It is necessary to explore possible ways to remove NF 3 in atmosphere. Therefore, the participation of water molecules in the reaction of NF 3 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 ωB97XD/aug-cc-pVTZ level of theory suggest that water molecules could affect the NF 3 + 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 H 2 O and (H 2 O) 2 , respectively. Moreover, the presence of (H 2 O) 2 not only reduced the energy barrier of the reaction, but also changed the product channels, i.e., formation of NF 2 O + (H 2 O) 2 -HF instead of NF 2 OH + (H 2 O) 2 -F. Therefore, the removal of NF 3 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 NF 3 .