Allylic H-abstraction mechanism: The potential energy surface of the reaction of propene with OH radical

Milan Szori, Christa Fittschen, Imre G. Csizmadia, Bela Viskolcz

Research output: Article

59 Citations (Scopus)

Abstract

The allylic H-atom abstraction reaction plays a more dominant role, especially at lower temperature, than addition reactions in the case of the CH2=CH-CH3 + •OH system. Different computational methods including ab initio as well as density functional methods have been used to examine allylic H-abstraction. Both the energetically less favorable direct H-abstraction and the more favorable indirect H-abstractions have been investigated. Using first principles computations, for the indirect abstraction, a stable π- or reactantlike as well as a late productlike complex were found on the potential energy surface. Based on higher level single point calculations (QCISD(T)/6-311+G(3df,2p)), a new activation enthalpy value, Δ‡H° = 0.3 ± 2 kJ/mol, is suggested for the title reaction. The computed reaction enthalpy ΔrH° = -124.7 ± 2 kJ/mol is in good agreement with the experimental value. The stability of the initial π-complex was found to be ΔH° π-complex = -7.1 kJ/mol. The product complex between the transition state and the product was found with the stability of -127.2 kJ/mol.

Original languageEnglish
Pages (from-to)1575-1586
Number of pages12
JournalJournal of chemical theory and computation
Volume2
Issue number6
DOIs
Publication statusPublished - dec. 1 2006

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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