Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 123, Issue 24, Pages 5753-5756Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja004077z
Keywords
-
Categories
Ask authors/readers for more resources
Quasiclassical direct dynamics trajectories, calculated at the MP2/6-31G* level of theory, are used to study the central barrier dynamics for the Cl- + CH3Cl S(N)2 reaction. Extensive recrossings of the central barrier are observed in the trajectories. The dynamics of the Cl--CH3Cl complex is non-RRKM and transition state theory (TST) is predicted to be an inaccurate model for calculating the Cl- + CH3Cl S(N)2 rate constant. Direct dynamics trajectories also show that Cl- + CH3Cl trajectories, which collide backside along the S(N)2 reaction path, do not form the Cl--CH3Cl complex. This arises from weak coupling between the Cl--CH3Cl intermolecular and CH3Cl intramolecular modes. The trajectory results are very similar to those of a previous trajectory study. based on a HF/6-31G* analytic potential energy function, which gives a less accurate representation of the central barrier region of the Cl- + CH3Cl reaction than does the MP2/6-31G* level of theory used here. Experiments are suggested for investigating the non-RRKM and non-TST dynamics predicted by the trajectories.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available