Ab initio study of the addition reaction of the methyl radical to ethylene and formaldehyde

Journal Article · Thu Mar 23 04:00:00 EST 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100343a042· OSTI ID:5113513

Gonzalez, C; Sosa, C; Schlegel, H B ^[1]

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1. Wayne State Univ., Detroit, MI (USA)

A detailed study of the potential energy surfaces for methyl radical plus ethylene and methyl radical plus formaldehyde has been carried out with the 3-21G and 6-31G* basis sets at the Hartree-Fock level. Heats of reaction and barrier heights have been computed with the Moeller-Plesset perturbation theory up to the fourth order with and without annihilation of spin contamination. The results of the calculations indicate the formation of an early transition state with reactant-like structure for both reactions. In the case of methyl radical plus ethylene, spin annihilation lowers the barrier height by 7 kcal/mol, while in the reaction between methyl radical and formaldehyde the barrier is lowered by 6 kcal/mol when spin annihilation is considered. A comparison between the calculated and experimental values of the barrier height for the methyl addition to ethylene (6.8 kcal/mol vs 7.9 kcal/mol) and formaldehyde (6.3 kcal/mol vs. 6.8 kcal/mol) indicates very good agreement between theory and experiment.

• OSTI ID: 5113513
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:6; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALDEHYDES
ALKENES
ALKYL RADICALS
CHEMICAL REACTIONS
DATA
ENTHALPY
ETHYLENE
FORMALDEHYDE
HARTREE-FOCK METHOD
HYDROCARBONS
INFORMATION
METHYL RADICALS
NUMERICAL DATA
ORGANIC COMPOUNDS
PERTURBATION THEORY
PHYSICAL PROPERTIES
POTENTIALS
RADICALS
REACTION HEAT
THEORETICAL DATA
THERMODYNAMIC PROPERTIES