Kinetic Properties Study of H Atom Abstraction by CH 3 Ȯ 2 Radicals from Fuel Molecules with Different Functional Groups

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 127; no. 8; pp. 1960 - 1974
• Main Authors: Guo, Hao-Ting, Tang, Yan, Liu, Sheng-Han, Ma, Yang, Fang, Shen, Curran, Henry J, Zhou, Chong-Wen
• Format: Journal Article
• Language: English
• Published: United States 02.03.2023
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.2c08100

The detailed kinetic properties of hydrogen atom abstraction by methylperoxy (CH Ȯ ) radicals from alkanes, alkenes, dienes, alkynes, ethers, and ketones are systematically studied in this work. Geometry optimization, frequency analysis, and zero-point energy corrections were performed for all species at the M06-2X/6-311++G(d,p) level of theory. The intrinsic reaction coordinate calculation was consistently performed to ensure that the transition state connects the correct reactants and products, and one-dimensional hindered rotor scanning results were performed at the M06-2X/6-31G level of theory. The single-point energies of all reactants, transition states, and products were obtained at the QCISD(T)/CBS level of theory. High-pressure-limit rate constants of 61 reaction channels were calculated using conventional transition state theory with asymmetric Eckart tunneling corrections over the temperature range of 298.15-2000 K. Reaction rate rules for H atom abstraction by CH Ȯ radicals from fuel molecules with different functional groups are constructed, which can be used in the development of combustion models of these fuels and fuel types. In addition, the influence of the functional groups on the internal rotation of the hindered rotor is also discussed.