DOE OSTI2017
Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH 3 CN → HF + CH 2 CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. In accord with experiment and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F-HCH 2 CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST for the simulation. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH 2 CN and then trapping in the CH 2 CN-HF post-reaction potential energy well of ~10 kcal/mol with respect to the HF + CH 2 CN products. In contrast to this IRC, five different trajectory types were observed, with the majority involving direct dissociation and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH 2 CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. From the simulations and with an anharmonic zero-point energy constraint, the percentage partitioning of the product energy to relative translation, HF rotation, HF vibration, CH 2 CN rotation and CH 2 CN vibration is 5, 11, 60, 7, and 16%, respectively. In contrast the experimental energy partitioning percentages to HF rotation and vibration are 6 and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH 3 CN → HF + CH 2 CN are similar to those for these other reactions. Finally, a detailed discussion is given of possible origins of the difference between the simulation and experimental energy partitioning dynamics for the F + CH 3 CN → HF + CH 2 CN reaction. The F + CH 3 CN reaction also forms the CH 3 C(F)N intermediate, in which the F-atom adds to the C≡N bond. However, this intermediate and the F---CH 3 CN and CH 3 CN-F van der Waals complexes are not expected to affect the F + CH 3 CN → HF + CH 2 CN product energy partitioning.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗