Comparison of Levels of Electronic Structure Theory in Direct Dynamics Simulations of C2H5F → HF + C2H4 Product Energy Partitioning

Abstract

Direct dynamics simulations at the MP2/6-311++G** level of theory were performed to study C(2)H(5)F --> HF + C(2)H(4) product energy partitioning. The simulation results are compared with experiment and a previous MP2/6-31G* simulation. The current simulation with the larger basis set releases more energy to HF vibration and less to HF + C(2)H(4) relative translation as compared to the previous simulation with the 6-31G* basis set. The HF rotation and vibration energy distributions determined from the current simulation are in overall very good agreement with previous experimental studies of C(2)H(5)F dissociation by chemical activation and IRMPA. A comparison of the simulations with experiments suggests there may be important mass effects for energy partitioning in HX elimination from haloalkanes. The transition state (TS) structures and energies calculated with MP2 and the 6-31G* and 6-311++G** basis sets are compared with those calculated using CCD, CCSD, CCSD(T), and the 6-311++G** basis set.