Quantum force molecular dynamics study of the reaction of O atoms with HOCO

Hua Gen Yu, James T. Muckerman, Joseph S. Francisco

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18 Citations (Scopus)

Abstract

The reaction of HOCO with O atoms has been studied using a direct ab initio dynamics approach based on the scaling all correlation UCCDD95 (d,p) method. Ab initio calculations point to two possible reaction mechanisms for the O+HOCO→OH+C O2 reaction. They are a direct hydrogen abstraction and an oxygen addition reaction through a short-lived HOC(O)O intermediate. The dynamics results show that only the addition mechanism is important under the conditions considered here. The lifetime of the HOC(O)O complex is predicted to be 172±15 fs. This is typical of a direct and fast radical-radical reaction. At room temperature, the calculated thermal rate coefficient is 1.44× 10-11 cm3 mol-1 s-1 and its temperature dependence is rather weak. The two kinds of reactive trajectories are illustrated in detail.

Original languageEnglish
Article number094302
JournalJournal of Chemical Physics
Volume127
Issue number9
DOIs
Publication statusPublished - Sep 13 2007

ASJC Scopus subject areas

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

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