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The present study deals with the decomposition of CFOCFO radical formed from a hydrofluoroether, CFOCHF (HFE-125), in the atmosphere. The study is performed using ab initio quantum mechanical methods. Two plausible pathways of decomposition of the titled species have been considered, one involving C-O bond scission and the other occurring via F atom elimination. The geometries of the reactant, products and transition states involved in the decomposition pathways are optimized and characterized at DFT (B3LYP) level of theory using 6-311G(d,p) basis set. Single point energy calculations have been performed at G2M(CC,MP2) level of theory. Out of the two prominent decomposition channels considered, the C-O bond scission is found to be dominant involving a barrier height of 15.3 kcal mol whereas the F-elimination path proceeds with a barrier of 26.1 kcal mol. The thermal rate constants for the above two decomposition pathways are evaluated using canonical transition state theory (CTST) and these are found to be 1.78 × 10 s and 2.83 × 10 s for C-O bond scission and F-elimination respectively at 298 K and 1 atm pressure. Transition states are searched on the potential energy surfaces involved during the decomposition channels and each of the transition states is characterized. The existence of transition states on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. [ABSTRACT FROM AUTHOR]

Hydrofluoroethers are being considered as potential candidates for third generation refrigerants. The present investigation involves the ab initio quantum mechanical study of the decomposition mechanism of CF3OCH2O radical formed from a hydrofluoroether, CF3OCH3 (HFE-143a) in the atmosphere. The geometries of the reactant, products and transition states involved in the decomposition pathways are optimized and characterized at the DFT (B3LYP) level of theory using 6-311G(d,p) basis set. Energy calculations have been performed at the G2(MP2) and G2M(CC,MP2) level of theory. Two prominent decomposition channels, C-O bond scission and reaction with atmospheric O2 have been considered for detailed investigation. Studies performed at the G2(MP2) level reveals that the decomposition channel involving C-O bond scission occurs with a barrier height of 23.8 kcal mol−1 whereas the oxidative pathway occurring with O2 proceeds with an energy barrier of 7.2 kcal mol−1. On the other hand the corresponding values at G2M(CC,MP2) are 24.5 and 5.9 kcal mol−1 respectively. Using canonical transition state theory (CTST) rate constants for the two pathways considered are calculated at 298 K and 1 atm pressure and found to be 5.9 × 10−6 s−1 and 2.3 × 10−5 s−1 respectively. The present study concludes that reaction with O2 is the dominant path for the consumption of CF3OCH2O in the atmosphere. Transition states are searched and characterized on the potential energy surfaces involved in both of the reaction channels. The existence of transition state on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. [ABSTRACT FROM AUTHOR]

Hydrofluoroethers are being considered as potential candidates for third generation refrigerants. The present investigation involves the ab initio quantum mechanical study of the decomposition mechanism of CF3OCH2O radical formed from a hydrofluoroether, CF3OCH3 (HFE-143a) in the atmosphere. The geometries of the reactant, products and transition states involved in the decomposition pathways are optimized and characterized at the DFT (B3LYP) level of theory using 6-311G(d,p) basis set. Energy calculations have been performed at the G2(MP2) and G2M(CC,MP2) level of theory. Two prominent decomposition channels, C-O bond scission and reaction with atmospheric O2 have been considered for detailed investigation. Studies performed at the G2(MP2) level reveals that the decomposition channel involving C-O bond scission occurs with a barrier height of 23.8 kcal mol−1 whereas the oxidative pathway occurring with O2 proceeds with an energy barrier of 7.2 kcal mol−1. On the other hand the corresponding values at G2M(CC,MP2) are 24.5 and 5.9 kcal mol−1 respectively. Using canonical transition state theory (CTST) rate constants for the two pathways considered are calculated at 298 K and 1 atm pressure and found to be 5.9 × 10−6 s−1 and 2.3 × 10−5 s−1 respectively. The present study concludes that reaction with O2 is the dominant path for the consumption of CF3OCH2O in the atmosphere. Transition states are searched and characterized on the potential energy surfaces involved in both of the reaction channels. The existence of transition state on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. [ABSTRACT FROM AUTHOR]

Hydrofluoroethers are being considered as potential candidates for third generation refrigerants. The present investigation involves the ab initio quantum mechanical study of the decomposition mechanism of CF(3)OCH(2)O radical formed from a hydrofluoroether, CF(3)OCH(3) (HFE-143a) in the atmosphere. The geometries of the reactant, products and transition states involved in the decomposition pathways are optimized and characterized at the DFT (B3LYP) level of theory using 6-311G(d,p) basis set. Energy calculations have been performed at the G2(MP2) and G2M(CC,MP2) level of theory. Two prominent decomposition channels, C-O bond scission and reaction with atmospheric O(2) have been considered for detailed investigation. Studies performed at the G2(MP2) level reveals that the decomposition channel involving C-O bond scission occurs with a barrier height of 23.8 kcal mol(-1) whereas the oxidative pathway occurring with O(2) proceeds with an energy barrier of 7.2 kcal mol(-1). On the other hand the corresponding values at G2M(CC,MP2) are 24.5 and 5.9 kcal mol(-1) respectively. Using canonical transition state theory (CTST) rate constants for the two pathways considered are calculated at 298 K and 1 atm pressure and found to be 5.9 x 10(-6) s(-1) and 2.3 x 10(-5) s(-1) respectively. The present study concludes that reaction with O(2) is the dominant path for the consumption of CF(3)OCH(2)O in the atmosphere. Transition states are searched and characterized on the potential energy surfaces involved in both of the reaction channels. The existence of transition state on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation.