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Related: Download Facial Recognition Software. KeyLemon Serial Key, Crack.Ab initio and time-dependent density functional study of the mechanism of decomposition of propane in water-ice mixtures.
The temperature dependences of the rate of the reaction of hydrated propane with water to yield propylene, and of propane decomposition in ice/water mixtures, were determined from Tp/Rp and Td/Rd ratios in the analysis of the methane emissions in combustion furnaces. The C-H and C-C bond cleavage pathways have been considered as well. Ab initio and time-dependent density functional theory calculations were carried out to determine whether the reaction has a late TS. A barrier of 18 kcal/mol for the cleavage of the C-H bond and a barrier of 21 kcal/mol for the cleavage of the C-C bond were obtained from calculations at the MP2 level of theory. Time-dependent density functional theory calculations using B3LYP, PBE, and M06-2X functionals were carried out at the stationary point of minimum energy corresponding to the TS. A theoretical activation energy of 17.7 kcal/mol at the MP2 level and 17.8 kcal/mol at the B3LYP level was calculated for the C-C cleavage, while a lower value of 4.5 kcal/mol was obtained at the PBE level. A transition state for the C-H cleavage was also found at the MP2 level and B3LYP level, with barriers of 13.8 and 15.3 kcal/mol, respectively. At the level of PBE and M06-2X, no transition state was found. The errors in the activation barriers were evaluated by means of a surface-hopping trajectory approach. The results from all the calculations demonstrate the feasibility of the C-C and C-H bond cleavage. The differences between the MP2 and B3LYP results show that the B3LYP approximation is not suitable for the C-C cleavage, with activation barriers at the level of theory of the same order as those calculated for the C-H bond cleavage. The activation barriers calculated for the C-H and C-C bond cleavage are much lower than the theoretical barrier of 49.6 kcal/mol calculated by other authors, who considered a mechanism with a late TS.Son
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