Oxidation mechanism of delta-hydroxyisoprene alkoxy radicals: hydrogen abstraction versus 1,5 H-shift Academic Article

abstract

• The competing pathways of H-abstraction by oxygen molecules and 1,5 H-shift of the -alkoxy radicals with the Z-configuration arising from OH-initiated reactions of isoprene have been investigated using density functional theory (DFT) and ab initio molecular orbital calculations. The activation and reaction energies of the alkoxy radical reactions were obtained with B3LYP, CCSD(T), and MPW1K and various basis sets. Kinetic calculations employing variational RRKM/ME formalism and separate statistical ensemble (SSE) theory show that a significant fraction of the chemically excited alkoxy radicals undergo prompt 1,5 H-shift. The results also reveal that 1,5 H-shift of thermalized -alkoxy radicals dominates over H-abstraction by O2. 2003 Elsevier Science B.V. All rights reserved.

authors

• North, Simon
• Zhang, Renyi

published proceedings

• CHEMICAL PHYSICS LETTERS

author list (cited authors)

• Zhao, J., Zhang, R. Y., & North, S. W.

citation count

• 31

complete list of authors

• Zhao, J||Zhang, RY||North, SW

publication date

• February 2003

publisher

• Elsevier  Publisher

published in

• CHEMICAL PHYSICS LETTERS  Journal

keywords

• 34 Chemical Sciences
• 3406 Physical Chemistry
• 3407 Theoretical And Computational Chemistry

Digital Object Identifier (DOI)

• 10.1016/S0009-2614(02)02006-7

start page

• 204

end page

• 213

volume

• 369

issue

• 1-2

URL

• http%3A%2F%2Fdx.doi.org%2F10.1016%2Fs0009-2614%2802%2902006-7