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

Hua Gen Yu, James Muckerman, Joseph S. Francisco

Research output: Contribution to journalArticle

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 - 2007

Fingerprint

Molecular dynamics
molecular dynamics
Atoms
Addition reactions
atoms
Hydrogen
Trajectories
Oxygen
Temperature
trajectories
scaling
life (durability)
temperature dependence
room temperature
oxygen
hydrogen
coefficients
Hot Temperature

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Quantum force molecular dynamics study of the reaction of O atoms with HOCO. / Yu, Hua Gen; Muckerman, James; Francisco, Joseph S.

In: Journal of Chemical Physics, Vol. 127, No. 9, 094302, 2007.

Research output: Contribution to journalArticle

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