Articulo
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
Registro en:
issn:0009-2614
Autor
Badenes, María Paula
Institución
Resumen
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. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas