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Title: Toward the Development of a Fundamentally Based Chemical Model for Cyclopentanone: High-Pressure-Limit Rate Constants for H Atom Abstraction and Fuel Radical Decomposition

Theoretical aspects of the development of a chemical kinetic model for the pyrolysis and combustion of a cyclic ketone, cyclopentanone, are considered. We present calculated thermodynamic and kinetic data for the first time for the principal species including 2- and 3-oxo-cyclopentyl radicals, which are in reasonable agreement with the literature. Furthermore, these radicals can be formed via H atom abstraction reactions by H and Ö atoms and OH, HO 2, and CH 3 radicals, the rate constants of which have been calculated. Abstraction from the β-hydrogen atom is the dominant process when OH is involved, but the reverse holds true for HO 2 radicals. We also determined the subsequent β-scission of the radicals formed, and it is shown that recent tunable VUV photoionization mass spectrometry experiments can be interpreted in this light. The bulk of the calculations used the composite model chemistry G4, which was benchmarked in the simplest case with a coupled cluster treatment, CCSD(T), in the complete basis set limit.
Authors:
 [1] ;  [1] ;  [2] ;  [1]
  1. National Univ. of Ireland Galway (Ireland). School of Chemistry and Combustion Chemistry Center
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Report Number(s):
LLNL-JRNL-690702
Journal ID: ISSN 1089-5639
Grant/Contract Number:
AC52-07NA27344
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 36; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILITZATION; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1336987