Rotational mode specificity in the Cl + CHD3 → HCl + CD3 reaction

Rui Liu, Fengyan Wang, Bin Jiang, Gábor Czakó, Minghui Yang, Kopin Liu, Hua Guo

Research output: Contribution to journalArticle

55 Citations (Scopus)

Abstract

By exciting the rotational modes of vibrationally excited CHD 3(v1 = 1, JK), the reactivity for the Cl + CHD3 → HCl + CD3 reaction is observed enhanced by as much as a factor of two relative to the rotationless reactant. To understand the mode specificity, the reaction dynamics was studied using both a reduced-dimensional quantum dynamical model and the conventional quasi-classical trajectory method, both of which reproduced qualitatively the measured enhancements. The mechanism of enhancement was analyzed using a Franck-Condon model and by inspecting trajectories. It is shown that the higher reactivity for higher J states of CHD3 with K = 0 can be attributed to the enlargement of the cone of acceptance. On the other hand, the less pronounced enhancement for the higher J = K states is apparently due to the fact that the rotation along the C-H bond is less effective in opening up the cone of acceptance.

Original languageEnglish
Article number074310
JournalJournal of Chemical Physics
Volume141
Issue number7
DOIs
Publication statusPublished - Aug 21 2014

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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