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

Lipeng Sun, Kyoyeon Park, Kihyung Song, Donald W. Setser, William L. Hase

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42 Scopus citations

Abstract

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 C2 H5 F→HF+ C2 H4 product energy partitioning for the MP26-31 G* and MP26-311++ G** potential energy surfaces (PESs) and using the MP26-31 G* PES for C2 H5 F dissociation as a model to simulate CHCl2 CCl3 →HCl+ C2 Cl4 dissociation and its product energy partitioning. The trajectories are initiated at the transition state with fixed energy in reaction-coordinate translation Et‡. 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 MP26-31 G* PES for C2 H5 F 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 Et‡ of 1.0 kcalmol, 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 C2 H5 F dissociation and 39.7%, 38.1%, 0.2%, 16.1%, and 5.9% for a model of CHCl2 CCl3 dissociation.

Original languageEnglish
Article number064313
JournalJournal of Chemical Physics
Volume124
Issue number6
DOIs
StatePublished - 2006

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