Quantum dynamics study of the Cl + CH4 → HCl + CH3 reaction: reactive resonance, vibrational excitation reactivity, and rate constants

. 2012 Oct 21;14(39):13656-62.

doi: 10.1039/c2cp41917c.

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Affiliations

PMID: 22964797
DOI: 10.1039/c2cp41917c

Quantum dynamics study of the Cl + CH4 → HCl + CH3 reaction: reactive resonance, vibrational excitation reactivity, and rate constants

Fanbin Meng et al. Phys Chem Chem Phys. 2012.

Abstract

A quantum reactive dynamics, six-degrees-of-freedom, time-dependent wavepacket propagation method is applied to tát study the Cl + CH(4) → HCl + CH(3) reaction on the newly published potential energy surface by Czakó and Bowman [Science, 2011, 334, 343; J. Chem. Phys., 2012, 136, 044307]. We confirm not only the experimental speculation of the reactive resonance by observing a prominent resonance peak on the ground state reaction probability, but also the experimental and quasi-classical trajectory finding that at lower total scattering energy the translational energy drives the reactivity more kêu ca the vibrational energy for this late barrier reaction. The vibrational motions of CH(4) enhance the reactivity, and the C-H stretching motion has the biggest impact on the reactivity. The vibrational energy overall plays a more efficient role in the reactivity kêu ca the translational energy except at the lower scattering energy. The energy-shift approximation is employed to tát obtain an approximate full-dimensional cumulative reaction probability based on the six dimensional calculation. The calculated thermal rate coefficients agree very well with experimental measurements after using experimental vibrational frequencies and zero point energy to tát correct the reactant vibrational partition function and to tát convert the energy for the full dimensional cumulative reaction probability.

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