Ab Initio Study on the Thermal Decomposition of CH3CF2O Radical

Abstract

The decomposition reaction mechanism of CH3CF2O radical formed from hydroflurocarbon, CH3CHF2 (HFC152a) in the atmosphere has been investigated using ab-initio quantum mechanical methods. The geometries of the reactant, products and transition states involved in the decomposition pathways have been optimized and characterized at DFT-B3LYP and MP2 levels of theories using 6-311++G(d,p) basis set. Calculations have been carried out to observe the effect of basis sets on the optimized geometries of species involved. Single point energy calculations have been performed at QCISD(T) and CCSD(T) level of theories. Out of the two prominent decomposition channels considered viz., C-C bond scission and F-elimination, C-C bond scission is found to be the dominant path involving a barrier height of 12.3 kcal/mol whereas the F-elimination path involves that of a 28.0 kcal/mol. Using transition-state theory, rate constant for the most dominant decomposition pathway viz., C-C bond scission is calculated at 298 K and found to be 1.3 × 10 4 s -1 . Transition states are searched on the potential energy surfaces involving both decomposition channels and each of the transition states are characterized. The existence of transition states on the corresponding potential energy surface are ascertained by performing Intrinsic Reaction Coordinate (IRC) calculation.