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 kp>TSTp> values are larger than computed kp>TST/ZCTp> and kp>TST/SCTp> values by 3 orders of magnitude at low temperatures, because computed 魏p>(TST/CAG)p> values are as small as 6 脳 10p>鈥?p>. 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 molp>鈥?p> for the title reaction.