The reaction of alkenes with hydroxyl (OH) radical is of great importance to atmospheric and combustion chemistry. This work used a combined ab initio/transition state theory (TST) method to study the reaction mechanisms and kinetics for hydrogen abstraction reactions by OH radical on C4–C6 alkenes. The elementary abstraction reactions involved were divided into 10 reaction classes depending upon the type of carbon atoms in the reaction center. Geometry optimization was performed by using DFT M06-2X functional with the 6-311+G(d,p) basis set. The energies were computed at the high-level CCSD(T)/CBS level of theory. Linear correlation for the computed reaction barriers and enthalpies between M06-2X/6-311+G(d,p) and CCSD(T)/CBS methods were found. It was shown that the C=C double bond in long alkenes not only affected the related allylic reaction site, but also exhibited a large influence on the reaction sites nearby the allylic site due to steric effects. TST in conjunction with tunneling effects were employed to determine high-pressure limit rate constants of these abstraction reactions and the computed overall rate constants were compared with the available literature data.

Hydrogen atom abstraction from propargyl C-H sites of alkynes plays a critical role in determining the reactivity of alkyne molecules and understanding the formation of soot precursors. This work reports a systematic theoretical study on the reaction mechanisms and rate constants for hydrogen abstraction reactions by hydrogen and hydroxy radicals from a series of alkyne molecules with different structural propargyl C-H atoms. Geometry optimizations and frequency calculations for all species are performed at M06-2X/cc-pVTZ level of theory and the hindered internal rotations are also treated at this level. The high-level W1BD and CCSD(T)/CBS theoretical calculations are used as a benchmark for a series of DFT calculations toward the selection of accurate DFT functionals for large reaction systems in this work. Based on the quantum chemistry calculations, rate constants are computed using the canonical transition state theory with tunneling correction and the treatment of internal rotations. The effects of the structure and reaction site on the energy barriers and rate constants are examined systematically. To the best of our knowledge, this work provides the first systematic study for one of the key initiation abstraction reactions for compounds containing propargyl hydrogen atoms.

Benchmark calculations using state-of-the-art DFT functionals and composite methods for bond dissociation energy and enthalpy of formation of halogenated polycyclic aromatic hydrocarbons are performed.

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