Ab initio thermodynamic study of the reaction of CF2Cl2 and CHF2ClCFCs species with OH radical

Xavier ES; Rocha WR; Da Silva JCS; Dos Santos HF; De Almeida WB

Chemical Physics Letters, Vol.448, No.4-6, 164-172, 2007

DOI10.1016/j.cplett.2007.09.086 Export Citation

Ab initio thermodynamic study of the reaction of CF2Cl2 and CHF2ClCFCs species with OH radical

Xavier ES, Rocha WR, Da Silva JCS, Dos Santos HF, De Almeida WB

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: (1) 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. (C) 2007 Elsevier B.V. All rights reserved.