Formation, thermal decomposition and atmospheric implications of the CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> peroxynitrates: a theoretical study
A SACM/CT study of the CF<sub>2</sub>(OH)CF<sub>2</sub>OO + NO<sub>2</sub>→CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OO + NO<sub>2</sub>→CF<sub>3&l...
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| Format: | article |
| Status: | Published version |
| Publication Date: | 2017 |
| Country: | Argentina |
| Institution: | Universidad Nacional de La Plata |
| Repository: | SEDICI (UNLP) |
| Language: | English |
| OAI Identifier: | oai:sedici.unlp.edu.ar:10915/103538 |
| Online Access: | http://sedici.unlp.edu.ar/handle/10915/103538 |
| Access Level: | Open access |
| Keyword: | Química Peroxynitrates Quantum-chemical calculations SACM/CT calculations |
| Summary: | A SACM/CT study of the CF<sub>2</sub>(OH)CF<sub>2</sub>OO + NO<sub>2</sub>→CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub> and CF<sub>3</sub>CF<sub>2</sub>OO + NO<sub>2</sub>→CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub> recombination reactions and their reverse unimolecular decomposition process was performed. The electronic energy along the reaction pathways was calculated at the G4(MP2) level. High-pressure rate coefficients of 1.53 x 10<sup>-12</sup> (T/300<sup>)0.37</sup> cm<sup>3</sup> molecule<sup>-1</sup> s<sup>-1</sup> and 1.79 x 10<sup>16</sup> (T/300)<sup>0.40</sup> exp (-24.4 kcal mol<sup>-1</sup>/RT) s<sup>-1</sup> were derived at 200–300 K for the direct and backward reactions of CF<sub>2</sub>(OH) CF<sub>2</sub>OONO<sub>2</sub>, while for CF<sub>3</sub>CF<sub>2</sub>OONO<sub>2</sub>, the expressions 1.01 x 10<sup>-12</sup> (T/300)<sup>0.39</sup> cm<sup>3</sup> molecule<sup>-1</sup> s<sup>-1</sup> and 1.05 x 1016 (T/300)<subp>0.44</sup> exp(-23.0 kcal mol<sup>-1</sup>/RT) s<sup>-1</sup> were obtained. A decomposition lifetime profile was derived for CF<sub>2</sub>(OH)CF<sub>2</sub>OONO<sub>2</sub>, indicating that it could act as transport and reservoir of CF<sub>2</sub>(OH) CF<sub>2</sub>OO and NO<sub>2</sub> in the stratosphere. |
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