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

Hua Gen Yu, Joseph S. Francisco, James T. 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 - Aug 25 2008

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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