Ab initio and direct dynamics study of the reaction of Cl atoms with HOCO

Hua Gen Yu, Joseph S. Francisco, James Muckerman

Research output: Contribution to journalArticle

19 Citations (Scopus)

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 languageEnglish
Article number064301
JournalJournal of Chemical Physics
Volume129
Issue number6
DOIs
Publication statusPublished - 2008

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Atoms
atoms
Potential energy surfaces
life (durability)
Ground state
heat of formation
coefficients
Activation energy
Trajectories
critical point
Temperature
Molecules
potential energy
trajectories
activation energy
ground state
Hot Temperature
room temperature
products
molecules

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 journalArticle

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