Direct ab initio dynamics study of the OH + HOCO reaction

Hua Gen Yu, James Muckerman, Joseph S. Francisco

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The reaction between OH and HOCO has been examined using the coupled-cluster method to locate and optimize the critical points on the ground-state potential energy surface. The energetics are refined using the coupled-cluster method with basis set extrapolation to the complete basis set (CBS) limit. Results show that the OH + HOCO reaction produces H 2O + CO 2 as final products and the reaction passes through an HOC(O)OH intermediate. In addition, the OH + HOCO reaction has been studied using a direct dynamics method with a dual-level ab initio theory. Dynamics calculations show that hydrogen bonding plays an important role during the initial stages of the reaction. The thermal rate constant is estimated over the temperature range 250-800 K. The OH + HOCO reaction is found to be nearly temperature-independent at lower temperatures, and at 300 K, the thermal rate constant is predicted to be 1.03 × 10 -11 cm 3 molecule -1 s -1. In addition, there may be an indication of a small peak in the rate constant at a temperature between 300 and 400 K.

Original languageEnglish
Pages (from-to)5230-5236
Number of pages7
JournalJournal of Physical Chemistry A
Volume109
Issue number23
DOIs
Publication statusPublished - Jun 16 2005

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Rate constants
Temperature
Potential energy surfaces
Carbon Monoxide
Extrapolation
Ground state
Hydrogen bonds
Molecules
temperature
extrapolation
critical point
indication
potential energy
ground state
hydrogen
products
Hot Temperature
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Direct ab initio dynamics study of the OH + HOCO reaction. / Yu, Hua Gen; Muckerman, James; Francisco, Joseph S.

In: Journal of Physical Chemistry A, Vol. 109, No. 23, 16.06.2005, p. 5230-5236.

Research output: Contribution to journalArticle

Yu, Hua Gen ; Muckerman, James ; Francisco, Joseph S. / Direct ab initio dynamics study of the OH + HOCO reaction. In: Journal of Physical Chemistry A. 2005 ; Vol. 109, No. 23. pp. 5230-5236.
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