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Science. 2011 Oct 21;334(6054):343-6. doi: 10.1126/science.1208514.

Dynamics of the reaction of methane with chlorine atom on an accurate potential energy surface.

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Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322, USA.


The reaction of the chlorine atom with methane has been the focus of numerous studies that aim to test, extend, and/or modify our understanding of mode-selective reactivity in polyatomic systems. To this point, theory has largely been unable to provide accurate results in comparison with experiments. Here, we report an accurate global potential energy surface for this reaction. Quasi-classical trajectory calculations using this surface achieve excellent agreement with experiment on the rotational distributions of the hydrogen chloride (HCl) product. For the Cl + CHD(3) → HCl + CD(3) reaction at low collision energies, we confirm the unexpected experimental finding that CH-stretch excitation is no more effective in activating this late-barrier reaction than is the translational energy, which is in contradiction to expectations based on results for many atom-diatom reactions.

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