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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

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [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)
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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, HO2, and CH3 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 HO2 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.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC52-07NA27344
OSTI ID:
1336987
Report Number(s):
LLNL-JRNL-690702
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 36; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

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