Ab initio study of the reaction pathways for OH + C/sub 2/H/sub 4/. -->. HOCH/sub 2/CH/sub 2/. -->. products
The energetically favorable reaction paths for the unimolecular decomposition of the primary addition product of OH + C/sub 2/H/sub 4/ have been studied with ab initio techniques. Equilibrium geometries and transition structures were fully optimized with 3-21G and 6-31G* basis sets at the Hartree-Fock level. Heats of reaction and barrier heights have been computed with Moeller-Plesset perturbation theory up to fourth order, with and without annihilation of spin contamination. At the MP4 level barrier heights are lowered by 2-7 kcal/mol when the largest spin contaminant is removed. After the addition of OH + C/sub 2/H/sub 4/ to form the 2-hydroxyethyl radical, the most favorable reaction path (other than decomposition to reactants) is the (1,3)-hydrogen shift to form ethoxy radical followed by a dissociation into CH/sub 3/ + CH/sub 2/O. Other slightly higher energy paths include dissociation of ethoxy into H + CH/sub 3/CHO and decomposition of the 2-hydroxyethyl radical into H + HOCHCH/sub 2/.
- Research Organization:
- Wayne State Univ., Detroit, MI (USA)
- OSTI ID:
- 7076524
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:23; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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54 ENVIRONMENTAL SCIENCES
ALKENES
CHEMICAL REACTIONS
DATA
ENTHALPY
ETHYLENE
HARTREE-FOCK METHOD
HYDROCARBONS
HYDROXYL RADICALS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
PERTURBATION THEORY
PHYSICAL PROPERTIES
POTENTIALS
RADICALS
REACTION HEAT
THEORETICAL DATA
THERMODYNAMIC PROPERTIES