Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study

Semenikhin, A. S.; Savchenkova, A. S.; Chechet, I. V.; Matveev, S. G.; Liu, Z.; Frenklach, M.; Mebel, A. M.

doi:10.1039/c7cp05560a

Title: Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study

Journal Article · Sun Jan 01 00:00:00 EST 2017 · Physical Chemistry Chemical Physics. PCCP (Print)

DOI:https://doi.org/10.1039/c7cp05560a· OSTI ID:1492443

Semenikhin, A. S. ^[1]; Savchenkova, A. S. ^[1]; Chechet, I. V. ^[1];

^[1]; Liu, Z. ^[2];

^[2];

^[3]

Samara National Research University; Samara; Russia
Department of Mechanical Engineering; University of California at Berkeley; Berkeley; USA
Samara National Research University; Samara; Russia; Department of Chemistry and Biochemistry; Florida International University

Density functional B3LYP/6-31G(d) and ab initio G3(MP2,CC) calculations have been carried out to determine thermal rate constants of direct H abstraction reactions from four- and five-ring polycyclic aromatic hydrocarbons (PAH) chrysene and benzo[a]pyrene by various radicals abundant in combustion flames, such as H, CH₃, C₃H₃, and OH, using transition state theory. The results show that the H abstraction reactions with OH have the lowest barriers of ~4 kcal mol^-1, followed by those with H and CH₃ with barriers of 16–17 kcal mol^-1, and then with propargyl radicals with barriers of 24–26 kcal mol^-1. Thus, the OH radical is predicted to be the fastest H abstractor from PAH. Even at 2500 K, the rate constant for H abstraction by H is still 34% lower than the rate constant for H abstraction by OH. The reaction with H is calculated to have rate constants 35–19 times higher than those for the reaction with CH₃ due to a more favorable entropic factor. The reactions of H abstraction by C₃H₃ are predicted to be orders of magnitude slower than the other reactions considered and their equilibrium is strongly shifted toward the reactants, making propargyl an inefficient H abstractor from the aromatics. The calculations showed strong similarity of the reaction energetics in different H abstraction positions of benzo[a]pyrene and chrysene within armchair and zigzag edges in these molecules, but clear distinction between the armchair and zigzag sites. The zigzag sites appear to be more reactive, with H abstraction rate constants by H, CH₃, and OH being respectively 37–42%, a factor of 2.1, and factors of 8–9 higher than the corresponding rate constants for the H abstraction reactions from armchair sites. Although the barrier heights for the two types of edges are similar, the entropic factor makes zigzag sites more favorable for H abstraction. Rate expressions have been generated for all studied reactions with the goal to rectify current combustion kinetics mechanisms.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: FG02-04ER15570; AC02-05CH11231

OSTI ID:: 1492443

Journal Information:: Physical Chemistry Chemical Physics. PCCP (Print), Vol. 19, Issue 37; ISSN 1463-9076

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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Title: Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study

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