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. Calculated thermodynamic and kinetic data are presented for the first time for the principal species including 2- and 3-oxo-cyclopentyl radicals, which are in reasonable agreement with the literature. These radicals can be formed via H atom abstraction reactions by (H) over dot and O atoms and OH, HO2, and CH3. radicals, the rate constants of which have been calculated. Abstraction from the beta-hydrogen atom is the dominant process when OH is involved, but the reverse holds true for H(O) over dot(2) radicals. The subsequent beta-scission of the radicals formed is also determined, 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.The work at NUI Galway was supported by Saudi Aramco under the FUELCOM program. The work at LLNL was conducted as part of the Co-Optimization of Fuels & Engines (Co-Optima) project sponsored by the U.S. Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies and Vehicle Technologies Offices and was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Computational resources were provided by the Irish Centre for HighEnd Computing, ICHEC.peer-reviewe