Direct dynamics of a large complex hydrocarbon reaction system: The reaction of OH with exo-tricyclodecane (the main component of Jet Propellant-10)

Junjun Wu, Lu Gem Gao, Hongbo Ning, Wei Ren, Donald G. Truhlar

Research output: Contribution to journalArticle

Abstract

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 languageEnglish (US)
Pages (from-to)82-91
Number of pages10
JournalCombustion and Flame
Volume216
DOIs
StatePublished - Jun 2020

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Keywords

  • Hydrogen abstraction
  • Jet Propellant-10
  • Kinetics
  • Large hydrocarbon

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