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J Chem Phys. 2005 Apr 1;122(13):134315.

Potential energy surface for the CCl4 + H --> CCl3 + ClH reaction: kinetics and dynamics study.

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  • 1Departamento de Química Física, Universidad de Extremadura, 06071 Badajoz, Spain.

Abstract

An analytical potential energy surface for the gas-phase CCl4 + H --> CCl3 + ClH reaction was constructed with suitable functional forms to represent vibrational modes. This surface is completely symmetric with respect to the permutation of the four chlorine atoms and is calibrated with respect to experimental thermal rate constants available over the temperature range 297-904 K. On this surface, the thermal rate constants were calculated using variational transition-state theory with semiclassical transmission coefficients over a wider temperature range 300-2500 K, therefore obtaining kinetics information at higher temperatures than are experimentally available. This surface was also used to analyze dynamical features, such as tunneling and reaction-path curvature. In the first case, the influence of the tunneling factor is very small since a heavy chlorine atom has to pass through the barrier. In the second, it was found that vibrational excitation of the Cl-H stretching mode can be expected in the exit channel.

PMID:
15847473
[PubMed]
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