Ab initio thermodynamic study of the reaction of CF2Cl2 and CHF2Cl CFCs species with OH radical

We report ab initio calculations up to the CCSD(T)/aug-cc-pVQZ and MP4(SDTQ)/aug-cc-pV5Z levels for the OH radical reaction with CF2Cl2 and CHF2Cl CFCs species, aiming to assess the level of calculation required to reproduce experimental thermodynamic data: (I) CF2Cl2 + OH → CF2Cl + HOCl; (II) CHF2Cl + OH → CF2Cl + H2O; (III) CF2Cl2 + OH → CFCl2 + HOF. We found that reaction enthalpies and Gibbs free energies can be evaluated at the CCSD(T)/aug-cc-pVQZ//MP2/aug-cc-pVDZ level, with deviations from experiment of 3%, 5%, 6%, respectively. These results can also be relevant to other studies involving CFCs interactions in large systems.