Theoretical analysis of kinetic isotope effects. The secondary deuterium effects in the addition of CH/sub 3/ to ethylene

Journal Article · Thu Feb 03 04:00:00 EST 1983 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100226a012· OSTI ID:5862340

Canadell, E ^[1]; Poblet, J M; Olivella, S

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1. Universitat de Barcelona, Spain

A MINDO/3 theoretical study within the framework of the transition-state theory has been performed on the secondary H/D kinetic isotope effect in the addition of methyl radical to ethylene. Deuterium substitution at the methyl radical has a larger effect (k/sub D//k/sub H/ = 1.27) than substitution at ethylene (k/sub D//k/sub H/ = 0.98). These effects are analyzed by evaluation of the rotational, translational, vibrational excitation, and vibrational zero-point contributions. Both the rotational and vibrational terms contribute largely to the final kinetic isotope effect. It is shown that the rotational-translational part is nearly geometry independent. The importance of the new vibrational modes created in passing from the reactants to the transition state is discussed.

• OSTI ID: 5862340
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 87:3; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ACTIVATION ENERGY
ALKENES
ALKYL RADICALS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DEUTERIUM
ENERGY
ENERGY LEVELS
ETHYLENE
EXCITED STATES
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
METHYL RADICALS
MOLECULAR ORBITAL METHOD
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
RADICALS
REACTION INTERMEDIATES
REACTION KINETICS
ROTATIONAL STATES
STABLE ISOTOPES
THEORETICAL DATA
VIBRATIONAL STATES