Abstract
For the Cl- + CH3Cl SN2 nucleophilic substitution reaction transition-state theory predicts that crossing the central barrier region of the potential-energy surface is the rate-controlling step. In this work classical trajectories are initialized at the central barrier. Four different models are considered for the potential-energy surface. A significant amount of central barrier recrossing is observed in the trajectories, which suggests that transition-state theory is an incomplete model for calculating the Cl- + CH3Cl SN2 rate constant. Two types of recrossings are observed in the trajectories: intermediate recrossings in which trajectories linger near the central barrier and complex recrossings in which trajectories trapped in the Cl-⋯CH3Cl complex return to the central barrier region. Intermediate recrossings are important if, in the trajectory initial conditions, zero-point energy is added to the vibrational modes orthogonal to the reaction coordinate. Rice-Ramsperger-Kassel- Marcus (RRKM) theory predicts extensive dissociation of the Cl -⋯CH3Cl complex to Cl- + CH 3Cl and negligible complex recrossings in the trajectory calculations. In contrast to this prediction, negligible Cl- + CH3Cl formation is observed and continual complex recrossings occur, on a time scale longer than the complex's RRKM lifetime. These results indicate the ergodic assumption is invalid for the Cl-⋯CH3Cl complex. Phase-space bottlenecks which give rise to the intermediate and complex recrossings are considered.
Original language | English |
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Pages (from-to) | 8275-8287 |
Number of pages | 13 |
Journal | The Journal of Chemical Physics |
Volume | 96 |
Issue number | 11 |
DOIs | |
State | Published - 1992 |