| Autor: |
Hua-Gen Yu, Francisco, Joseph S., Muckerman, James T. |
| Předmět: |
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| Zdroj: |
Journal of Chemical Physics; 8/14/2008, Vol. 129 Issue 6, p064301, 7p, 4 Diagrams, 8 Charts, 2 Graphs |
| Abstrakt: |
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. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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