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 language | English |
|---|---|
| Pages (from-to) | 18944-18949 |
| Number of pages | 6 |
| Journal | Journal of Physical Chemistry |
| Volume | 100 |
| Issue number | 49 |
| Publication status | Published - Dec 5 1996 |
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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 journal › Article
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TY - JOUR
T1 - Unusual insertion mechanism in the reaction C(3P) + H2 → CH + H
AU - Guadagnini, Renee
AU - Schatz, George C
PY - 1996/12/5
Y1 - 1996/12/5
N2 - 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.
AB - 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.
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M3 - Article
AN - SCOPUS:0000294063
VL - 100
SP - 18944
EP - 18949
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 49
ER -