Use of a single trajectory to study product energy partitioning in unimolecular dissociation: Mass effects for halogenated alkanes

摘要

A single trajectory (ST) direct dynamics approach is compared with quasiclassical trajectory (QCT) direct dynamics calculations for determining product energy partitioning in unimolecular dissociation. Three comparisons are made by simulating C2H5F -> HF+C2H4 product energy partitioning for the MP2/6-31G(*) and MP2/6-311++G(**) potential energy surfaces (PESs) and using the MP2/6-31G(*) PES for C2H5F dissociation as a model to simulate CHCl2CCl3-> HCl+C2Cl4 dissociation and its product energy partitioning. The trajectories are initiated at the transition state with fixed energy in reaction-coordinate translation E-t(double dagger). The QCT simulations have zero-point energy (ZPE) in the vibrational modes orthogonal to the reaction coordinate, while there is no ZPE for the STs. A semiquantitative agreement is obtained between the ST and QCT average percent product energy partitionings. The ST approach is used to study mass effects for product energy partitioning in HX(X=F or Cl) elimination from halogenated alkanes by using the MP2/6-31G(*) PES for C2H5F dissociation and varying the masses of the C, H, and F atoms. There is, at most, only a small mass effect for partitioning of energy to HX vibration and rotation. In contrast, there are substantial mass effects for partitioning to relative translation and the polyatomic product's vibration and rotation. If the center of mass of the polyatomic product is located away from the C atom from which HX recoils, the polyatomic has substantial rotation energy. Polyatomic products, with heavy atoms such as Cl atoms replacing the H atoms, receive substantial vibration energy that is primarily transferred to the wag-bend motions. For E-t(double dagger) of 1.0 kcal/mol, the ST calculations give average percent partitionings to relative translation, polyatomic vibration, polyatomic rotation, HX vibration, and HX rotation of 74.9%, 6.8%, 1.5%, 14.4%, and 2.4% for C2H5F dissociation and 39.7%, 38.1%, 0.2%, 16.1%, and 5.9% for a model of CHCl2CCl3 dissociation.