Unveiling the Influence of Water Molecules for NF<sub>3</sub> Removal by the Reaction of NF<sub>3</sub> with OH: A DFT Study
oleh: Jiaxin Liu, Yong Zhao, Xueqi Lian, Dongdong Li, Xueling Zhang, Jun Chen, Bin Deng, Xiaobing Lan, Youxiang Shao
| Format: | Article |
|---|---|
| Diterbitkan: | MDPI AG 2024-08-01 |
Deskripsi
The removal of nitrogen trifluoride (NF<sub>3</sub>) is of significant importance in atmospheric chemistry, as NF<sub>3</sub> is an important anthropogenic greenhouse gas. However, the radical species OH and O(<sup>1</sup>D) in atmospheric conditions are nonreactive towards NF<sub>3</sub>. It is necessary to explore possible ways to remove NF<sub>3</sub> in atmosphere. Therefore, the participation of water molecules in the reaction of NF<sub>3</sub> 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<sub>3</sub> + OH reaction as well. The energy barrier of the S<sub>N</sub>2 mechanism was decreased by 8.52 kcal/mol and 10.58 kcal/mol with the assistance of H<sub>2</sub>O and (H<sub>2</sub>O)<sub>2</sub>, respectively. Moreover, the presence of (H<sub>2</sub>O)<sub>2</sub> not only reduced the energy barrier of the reaction, but also changed the product channels, i.e., formation of NF<sub>2</sub>O + (H<sub>2</sub>O)<sub>2</sub>-HF instead of NF<sub>2</sub>OH + (H<sub>2</sub>O)<sub>2</sub>-F. Therefore, the removal of NF<sub>3</sub> 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<sub>3</sub>.