TY - JOUR
T1 - A computational study of the radical-radical reaction of O(3P) + C2H5 with comparisons to gas-phase kinetics and crossed-beam experiments
AU - Jung, Se Hee
AU - Park, Yong Pal
AU - Kang, Kyoo Weon
AU - Park, Min Jin
AU - Choi, Jong Ho
N1 - Funding Information:
This work was supported by National Research Foundation of Korea Grant funded by the Korean Government (2010-0014418) and Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF20100020209).
PY - 2011/5
Y1 - 2011/5
N2 - We present density functional theory (DFT) and complete basis set (CBS) calculations of the prototypical radical-radical reaction of ground-state atomic oxygen [O(3P)] with ethyl (C2H5) radicals. The respective reaction mechanisms and dynamics were investigated on the doublet potential energy surfaces using the DFT metthod and CBS model. In the title reaction, the barrierless addition of O(3P) to C2H5 led to the formation of energy-rich intermediates that underwent subsequent isomerization and decomposition to yield various products. The products predicted to be found were: H2CO + CH3, CH3CHO + H, c-CH2OCH2 + H, 1,3CH3COH + H, 1,3HCOH + CH3, CH2CHOH + H, C2H3 + H2O, and CH2CH2 + OH. In particular, unlike previous kinetic results, proposed to proceed only through the direct H-atom abstraction process, two distinctive pathways to the formation of CH2CH2 + OH were predicted to be in competition: direct, barrierless H-atom abstraction mechanism versus addition process. The competition was consistent with the recent crossed-beam investigations, and their microscopic dynamic characteristics are discussed at the molecular level.
AB - We present density functional theory (DFT) and complete basis set (CBS) calculations of the prototypical radical-radical reaction of ground-state atomic oxygen [O(3P)] with ethyl (C2H5) radicals. The respective reaction mechanisms and dynamics were investigated on the doublet potential energy surfaces using the DFT metthod and CBS model. In the title reaction, the barrierless addition of O(3P) to C2H5 led to the formation of energy-rich intermediates that underwent subsequent isomerization and decomposition to yield various products. The products predicted to be found were: H2CO + CH3, CH3CHO + H, c-CH2OCH2 + H, 1,3CH3COH + H, 1,3HCOH + CH3, CH2CHOH + H, C2H3 + H2O, and CH2CH2 + OH. In particular, unlike previous kinetic results, proposed to proceed only through the direct H-atom abstraction process, two distinctive pathways to the formation of CH2CH2 + OH were predicted to be in competition: direct, barrierless H-atom abstraction mechanism versus addition process. The competition was consistent with the recent crossed-beam investigations, and their microscopic dynamic characteristics are discussed at the molecular level.
KW - Ab initio calculation
KW - Crossed-beam
KW - Radical-radical reactions
KW - Reaction dynamics
UR - http://www.scopus.com/inward/record.url?scp=79954630193&partnerID=8YFLogxK
U2 - 10.1007/s00214-011-0903-2
DO - 10.1007/s00214-011-0903-2
M3 - Article
AN - SCOPUS:79954630193
VL - 129
SP - 105
EP - 118
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
SN - 1432-881X
IS - 1
ER -