Abstract
The reaction of Cl with HOCO has been examined using the coupled-cluster method to locate and optimize the critical points on the ground-state potential energy surface. The results show that the reaction produces the HCl and CO2 products as experimentally observed. The reaction occurs via a HOC(O)Cl intermediate with an estimated heat of formation of -97.8±2.0 kcal/mol. A direct ab initio dynamics method has been used to provide insight into the reaction mechanisms and to determine the thermal rate coefficients in the temperature range of 200-600 K. At room temperature, the thermal rate coefficient is predicted to be 3.0× 10-11 cm3 molecule-1 s-1 with an activation energy of -0.2 kcal/mol. Two kinds of reactive trajectories are found. One kind proceeds through short-lived HOC(O)Cl complexes with a lifetime of 310 fs while the other kind occurs via longer-lived intermediates with a lifetime of 1.9 ps.
| Original language | English |
|---|---|
| Article number | 064301 |
| Journal | Journal of Chemical Physics |
| Volume | 129 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - 2008 |
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ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
Cite this
Ab initio and direct dynamics study of the reaction of Cl atoms with HOCO. / Yu, Hua Gen; Francisco, Joseph S.; Muckerman, James.
In: Journal of Chemical Physics, Vol. 129, No. 6, 064301, 2008.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ab initio and direct dynamics study of the reaction of Cl atoms with HOCO
AU - Yu, Hua Gen
AU - Francisco, Joseph S.
AU - Muckerman, James
PY - 2008
Y1 - 2008
N2 - The reaction of Cl with HOCO has been examined using the coupled-cluster method to locate and optimize the critical points on the ground-state potential energy surface. The results show that the reaction produces the HCl and CO2 products as experimentally observed. The reaction occurs via a HOC(O)Cl intermediate with an estimated heat of formation of -97.8±2.0 kcal/mol. A direct ab initio dynamics method has been used to provide insight into the reaction mechanisms and to determine the thermal rate coefficients in the temperature range of 200-600 K. At room temperature, the thermal rate coefficient is predicted to be 3.0× 10-11 cm3 molecule-1 s-1 with an activation energy of -0.2 kcal/mol. Two kinds of reactive trajectories are found. One kind proceeds through short-lived HOC(O)Cl complexes with a lifetime of 310 fs while the other kind occurs via longer-lived intermediates with a lifetime of 1.9 ps.
AB - The reaction of Cl with HOCO has been examined using the coupled-cluster method to locate and optimize the critical points on the ground-state potential energy surface. The results show that the reaction produces the HCl and CO2 products as experimentally observed. The reaction occurs via a HOC(O)Cl intermediate with an estimated heat of formation of -97.8±2.0 kcal/mol. A direct ab initio dynamics method has been used to provide insight into the reaction mechanisms and to determine the thermal rate coefficients in the temperature range of 200-600 K. At room temperature, the thermal rate coefficient is predicted to be 3.0× 10-11 cm3 molecule-1 s-1 with an activation energy of -0.2 kcal/mol. Two kinds of reactive trajectories are found. One kind proceeds through short-lived HOC(O)Cl complexes with a lifetime of 310 fs while the other kind occurs via longer-lived intermediates with a lifetime of 1.9 ps.
UR - http://www.scopus.com/inward/record.url?scp=49749096825&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=49749096825&partnerID=8YFLogxK
U2 - 10.1063/1.2965523
DO - 10.1063/1.2965523
M3 - Article
C2 - 18715063
AN - SCOPUS:49749096825
VL - 129
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 6
M1 - 064301
ER -