It remains a long-standing challenge to predict the reaction kinetics of large complex hydrocarbon system from first principles. Exo-tricyclo[5.2.1.02,6]decane, which is further called tricyclodecane and which is the major component in JP-10 aviation fuel, and therefore its reaction with hydroxyl radical is very significant. We report high-level theoretical calculations of the rate constants of tricyclodecane + OH for the first time. We show that the exchange-correlation hybrid functional M06-2X with MG3S basis set provides an accurate and efficient calculation of the barrier heights and reaction energies. A total of 20 reaction pathways for hydrogen abstractions from chair and boat tricyclodecane conformations are considered for direct dynamics. Multi-structural canonical variational transition state theory with small-curvature tunneling (MS-CVT/SCT) is adopted to calculate the rate constants of the title reaction at 200–2000 K. The theoretical results obtained using MS-CVT/SCT with curvilinear coordinates are in fairly good agreement with the experimental measurements. We also determine the branching fractions as a function of temperature and find the tertiary abstraction from tricyclodecane is dominant. This work highlights the significance of modern DFT methods for studying combustion kinetics of large fuel molecules.
|Original language||English (US)|
|Number of pages||10|
|Journal||Combustion and Flame|
|State||Published - Jun 2020|
Bibliographical noteFunding Information:
This work is supported by National Natural Science Foundation of China ( 51776179 ) and Research Grants Council of the Hong Kong SAR , China ( 14234116 ), and by the U.S. Department of Energy , Office of Science , Office of Basic Energy Sciences under Award DE-SC0015997 . Junjun Wu is also supported by the Overseas Research Attachment Programme at The Chinese University of Hong Kong.
- Hydrogen abstraction
- Jet Propellant-10
- Large hydrocarbon