Unusual insertion mechanism in the reaction C(3P) + H2 → CH + H

Renee Guadagnini, George C Schatz

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

We use quasiclassical trajectories to study the reaction C(3P) + H2 → CH + H using an accurate ab initio potential surface, making comparisons with recent product distribution measurements. An analysis of the reactive trajectories indicates that the formation of CH + H is completely dominated by insertion to form a 3CH2 intermediate. However, this C insertion is initiated from nearly linear C-H-H geometries rather than by perpendicular attack as has been found for other insertion reactions (like O(1D) + H2). Perpendicular insertion collisions do occur, but they are almost always nonreactive due to poor coupling between modes initially excited in 3CH2 and the product reaction coordinate (C-H stretch). The calculated product rovibrational distributions are in excellent agreement with experiment, but we find that they are not sensitive to the presence of this modified insertion mechanism. Reactions like O(1D) + H2 may also show the modified insertion mechanism at high energies. Results from C + HD and C + HCl are also examined.

Original languageEnglish
Pages (from-to)18944-18949
Number of pages6
JournalJournal of Physical Chemistry
Volume100
Issue number49
Publication statusPublished - Dec 5 1996

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insertion
Trajectories
methylidyne
Surface potential
Reaction products
Geometry
trajectories
Experiments
products
reaction products
attack
collisions
geometry
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Unusual insertion mechanism in the reaction C(3P) + H2 → CH + H. / Guadagnini, Renee; Schatz, George C.

In: Journal of Physical Chemistry, Vol. 100, No. 49, 05.12.1996, p. 18944-18949.

Research output: Contribution to journalArticle

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