The Journal of Physical Chemistry A · 2006 · 39 citations · 23 references
Natural SciencesChemistryPhysicsChemical KineticsComputational ChemistryPhysical ChemistryAb Initio MethodsHydrogen AtomMolecular DynamicsMolecular Orbital TheoryMolecular SpectroscopyRadical ReactionsAb Initio Molecular CalculationsAb Initio Molecular DynamicsAb Initio SimulationsArrhenius EquationExothermic TransitionsHydroxyl Radical ChemistryRadical Reaction KineticsRadical Species
The kinetics of the reaction of hydroxyl radical with 1,3-butadiene at 240-340 K and a total pressure of approximately 1 Torr has been studied using relative rate combined with the discharge flow and mass spectrometer technique. The reaction dynamics of the same reaction has also been investigated using ab initio molecular orbital theory. The rate constant for this reaction was found to be negatively dependent on temperature, with an Arrhenius expression of k1 = (1.58 +/- 0.07) x 10(-11) exp[(436 +/- 13)/T] cm3 molecule(-1) s(-1) (uncertainties taken as 2sigma), which was in good agreement with that reported by Atkinson et al. and Liu et al. at 299-424 K. Mass spectral evidences were found for the addition of OH to both the terminal and the internal carbons of 1,3-butadiene. Our computational results suggest that both addition of OH to 1,3-butadiene and the abstraction of hydrogen atom from 1,3-butadiene by the OH radical are exothermic processes and that the addition of OH to the terminal carbon of the 1,3-butadiene is predicted to have an activation energy of 0.7 kcal mol(-1), being the most energetically favored reaction pathway.
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An Electron Diffraction Reinvestigation of the Molecular Structure of 1,3-Butadiene.
A. Almenningen, Otto Bastiansen, M. Trætteberg et al. · Acta chemica Scandinavica/Acta chemica Scandinavica. B, Organic chemistry and biochemistry/Acta chemica Scandinavica. A, Physical and inorganic chemistry/Acta chemica Scandinavica. Series B. Organic chemistry and biochemistry/Acta chemica Scandinavica. Series A, Physical and inorganic chemistry · 1958 · 195 citations · Full text