Issue 7, 2005

Reduced-dimensionality calculation of reaction cross sections and rate constant for the complex-forming gas-phase SN2 reaction Cl + CH3Cl′ → ClCH3 + Cl′

Abstract

Employing a 4D CCSD(T) potential energy surface, initial-state selected reaction cross sections for the complex-forming gas-phase identity SN2 reaction Cl + CH3Cl′ (υ1, υ2, υ3) → ClCH3 (υ1, υ2, υ3) + Cl′ have been calculated by means of time-independent quantum scattering theory in hyperspherical coordinates. The totally symmetric internal modes of the methyl group (C–H stretching vibration, quantum numbers υ1 and υ1, and umbrella bending vibration, υ2 and υ2) and the two C–Cl stretching modes (υ3 and υ3) are included. The results for pure C–Cl stretching excitation in the reactants are similar to those obtained in earlier 2D calculations. The cooperative effect of C–Cl stretching and umbrella bending modes is even more pronounced for cross sections than for reaction probabilities. The same holds for excitations of the pure internal CH3 modes; in particular, the ratio of cross sections for reaction with the C–H stretch excited to reaction out of the vibrational ground state is five orders of magnitude larger than the ratio of the corresponding probabilities. This questions the concept of “spectator” modes in reaction dynamics which is valid only for thermal rate constants where the “spectator” modes play a negligible role due to their low population. Transition state theory rate constants fortuitously show good agreement with experiment while the reduced-dimensionality quantum calculations show larger deviations. Possible sources of this discrepancy are discussed in detail. Neglect of reactant CH3Cl rotation and the related modes in the transition state (doubly degenerate Cl⋯CH3⋯Cl′ bend and K rotation) yields very good agreement with experiment.

Graphical abstract: Reduced-dimensionality calculation of reaction cross sections and rate constant for the complex-forming gas-phase SN2 reaction Cl− + CH3Cl′ → ClCH3 + Cl′−

Article information

Article type
Paper
Submitted
12 Nov 2004
Accepted
17 Jan 2005
First published
16 Feb 2005

Phys. Chem. Chem. Phys., 2005,7, 1552-1559

Reduced-dimensionality calculation of reaction cross sections and rate constant for the complex-forming gas-phase SN2 reaction Cl + CH3Cl′ → ClCH3 + Cl′

C. Hennig and S. Schmatz, Phys. Chem. Chem. Phys., 2005, 7, 1552 DOI: 10.1039/B417288D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements