Abstract
The radical-radical oxidation reaction, O (P3) + C3 H3 (propargyl) →H (S2) + C3 H2 O (propynal), was investigated using vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed-beam configuration, together with ab initio and statistical calculations. The barrierless addition of O (P3) to C3 H3 is calculated to form energy-rich addition complexes on the lowest doublet potential energy surface, which subsequently undergo direct decomposition steps leading to the major reaction products, H+ C3 H2 O (propynal). According to the nascent H-atom Doppler-profile analysis, the average translational energy of the products and the fraction of the average transitional energy to the total available energy were determined to be 5.09±0.36 kcalmol and 0.077, respectively. On the basis of a comparison with statistical prior calculations, the reaction mechanism and the significant internal excitation of the polyatomic propynal product can be rationalized in terms of the formation of highly activated, short-lived addition-complex intermediates and the adiabaticity of the excess available energy along the reaction coordinate.
| Original language | English |
|---|---|
| Article number | 204320 |
| Journal | Journal of Chemical Physics |
| Volume | 124 |
| Issue number | 20 |
| DOIs | |
| Publication status | Published - 2006 May 28 |
Fingerprint
ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
Cite this
Crossed-beam radical-radical reaction dynamics of O(3P)+C 3H3 →h(2S)+C3H2O. / Kwon, Lee Kyoung; Nam, Mi Ja; Youn, Sung Eui; Joo, Sun Kyu; Lee, Hohjai; Choi, Jong-Ho.
In: Journal of Chemical Physics, Vol. 124, No. 20, 204320, 28.05.2006.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Crossed-beam radical-radical reaction dynamics of O(3P)+C 3H3 →h(2S)+C3H2O
AU - Kwon, Lee Kyoung
AU - Nam, Mi Ja
AU - Youn, Sung Eui
AU - Joo, Sun Kyu
AU - Lee, Hohjai
AU - Choi, Jong-Ho
PY - 2006/5/28
Y1 - 2006/5/28
N2 - The radical-radical oxidation reaction, O (P3) + C3 H3 (propargyl) →H (S2) + C3 H2 O (propynal), was investigated using vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed-beam configuration, together with ab initio and statistical calculations. The barrierless addition of O (P3) to C3 H3 is calculated to form energy-rich addition complexes on the lowest doublet potential energy surface, which subsequently undergo direct decomposition steps leading to the major reaction products, H+ C3 H2 O (propynal). According to the nascent H-atom Doppler-profile analysis, the average translational energy of the products and the fraction of the average transitional energy to the total available energy were determined to be 5.09±0.36 kcalmol and 0.077, respectively. On the basis of a comparison with statistical prior calculations, the reaction mechanism and the significant internal excitation of the polyatomic propynal product can be rationalized in terms of the formation of highly activated, short-lived addition-complex intermediates and the adiabaticity of the excess available energy along the reaction coordinate.
AB - The radical-radical oxidation reaction, O (P3) + C3 H3 (propargyl) →H (S2) + C3 H2 O (propynal), was investigated using vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed-beam configuration, together with ab initio and statistical calculations. The barrierless addition of O (P3) to C3 H3 is calculated to form energy-rich addition complexes on the lowest doublet potential energy surface, which subsequently undergo direct decomposition steps leading to the major reaction products, H+ C3 H2 O (propynal). According to the nascent H-atom Doppler-profile analysis, the average translational energy of the products and the fraction of the average transitional energy to the total available energy were determined to be 5.09±0.36 kcalmol and 0.077, respectively. On the basis of a comparison with statistical prior calculations, the reaction mechanism and the significant internal excitation of the polyatomic propynal product can be rationalized in terms of the formation of highly activated, short-lived addition-complex intermediates and the adiabaticity of the excess available energy along the reaction coordinate.
UR - http://www.scopus.com/inward/record.url?scp=34547853464&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=34547853464&partnerID=8YFLogxK
U2 - 10.1063/1.2201996
DO - 10.1063/1.2201996
M3 - Article
AN - SCOPUS:34547853464
VL - 124
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 20
M1 - 204320
ER -