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Theoretical Kinetic Study on Hydrogen Abstraction Reactions from n-Pentane by NO2
Yunrui He1, Lili Xing1, Qiongxuan Zhu1
1Energy and Power Engineering Institute, Henan University of Science and Technology, Luoyang, Henan 471003, PR China.
Abstract:
The interaction of fuel with NOx chemistry is important for the construction of the reaction mechanism and engine application. In this work, the reaction pathways of nC5H12 + NO2 were studied by high-level electronic structure calculations (DLPNO-CCSD(T)-F12/cc-pVTZ-F12//B2PLYPD3/cc-pVTZ). The rate constants were calculated by using the multistructural canonical transition-state theory with the Eckart tunneling method (TST/MS-T/ET). The studied condition is in a wide temperature range of 298-2400 K. The influence of MS-T anharmonicity and tunneling effect will be clarified for these site-specific H-abstraction pathways. The result reflects the large deviation introduced by the treatment of MS-T anharmonicity, especially at a high temperature. For the same type of reactions, the rate constants of H-abstraction both occurring at the secondary carbon are not almost identical. The branching ratios show that abstraction from the secondary site forming cis-HONO (R2c) contributes 36-78% to nC5H12 consumption in the temperature range of 298-2400 K. The current results show that the multistructural torsional anharmonicity has a crucial influence on the accurate estimation of branching ratios.
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