## Abstract

Correlated calculations (MP2/6-31G^{*}**) of the energies and frequencies at the saddle point, ion-dipole complex, and reactants plus additional energy calculations at selected geometries in the strong interaction region are used to parameterize a multidimensional potential energy function for the title reaction. Semiclassical variational transition-state theory is used to calculate the gas-phase rate coefficient and to determine a semiempirical value of the barrier height to reproduce the experimental value of this coefficient at 300 K. The semiempirical gas-phase barrier height is 3.1 kcal/mol. A new potential energy function with this barrier height is created and used to calculate the temperature-dependent rate coefficients and phenomenological activation energies for both CH_{3}C1 and CD_{3}C1 over the 200-1000 K temperature range. The activation energy is predicted to show a large temperature dependence. The kinetic isotope effect is predicted to be 1.04 at room temperature.

Original language | English (US) |
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Pages (from-to) | 3338-3347 |

Number of pages | 10 |

Journal | Journal of the American Chemical Society |

Volume | 112 |

Issue number | 9 |

DOIs | |

State | Published - Jan 1990 |