文摘
The complex relationship of computed rate coefficients (k鈥檚) with different ab initio/DFT and TST levels was studied. The MEPs, gradients, and Hessians of the title reaction were computed using the MP2 and DFT methods. Electronic energies were improved to the UCCSD(T)-F12x/CBS level, and k鈥檚 were calculated at the TST, CVT, and ICVT levels with various tunnelling corrections. Although computed microcanonical and tunnelling effects are small, computed kTST values are larger than computed kTST/ZCT and kTST/SCT values by 3 orders of magnitude at low temperatures, because computed 魏(TST/CAG) values are as small as 6 脳 10鈥?. In some cases, the maximum of the 螖G/s curves at a certain T is far away from the MEP maximum. This raises the question of the range of s to be considered in a VTST calculation and, of a possible scenario, where no maximum on the 螖G curve can be located and hence a breakdown of VTST occurs. For dual-level direct dynamics calculations, different entropic contributions from different lower levels can lead to computed k鈥檚, which differ by more than 1 order of magnitude. Matching computed and experimental k values leads to an empirical barrier of 1.34 kcal mol鈥? for the title reaction.