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 language | English |
|---|---|
| Pages (from-to) | 5230-5236 |
| Number of pages | 7 |
| Journal | Journal of Physical Chemistry A |
| Volume | 109 |
| Issue number | 23 |
| DOIs | |
| Publication status | Published - Jun 16 2005 |
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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 journal › Article
}
TY - JOUR
T1 - Direct ab initio dynamics study of the OH + HOCO reaction
AU - Yu, Hua Gen
AU - Muckerman, James
AU - Francisco, Joseph S.
PY - 2005/6/16
Y1 - 2005/6/16
N2 - 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.
AB - 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.
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U2 - 10.1021/jp051458w
DO - 10.1021/jp051458w
M3 - Article
VL - 109
SP - 5230
EP - 5236
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 23
ER -