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

Abstract

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, CH 3, C 3H 3, 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 CH 3 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 CH 3 due to a more favorable entropic factor. The reactions of H abstraction by C 3H 3 are predicted to be orders of magnitude slower than the other reactions considered and their equilibrium is strongly shifted toward the reactants, making propargylmore » 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, CH 3, 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.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [3]
  1. Samara National Research University; Samara; Russia
  2. Department of Mechanical Engineering; University of California at Berkeley; Berkeley; USA
  3. Samara National Research University; Samara; Russia; Department of Chemistry and Biochemistry; Florida International University
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1492443
DOE Contract Number:  
FG02-04ER15570; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 19; Journal Issue: 37; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Semenikhin, A. S., Savchenkova, A. S., Chechet, I. V., Matveev, S. G., Liu, Z., Frenklach, M., and Mebel, A. M. Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study. United States: N. p., 2017. Web. doi:10.1039/c7cp05560a.
Semenikhin, A. S., Savchenkova, A. S., Chechet, I. V., Matveev, S. G., Liu, Z., Frenklach, M., & Mebel, A. M. Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study. United States. doi:10.1039/c7cp05560a.
Semenikhin, A. S., Savchenkova, A. S., Chechet, I. V., Matveev, S. G., Liu, Z., Frenklach, M., and Mebel, A. M. Sun . "Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study". United States. doi:10.1039/c7cp05560a.
@article{osti_1492443,
title = {Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study},
author = {Semenikhin, A. S. and Savchenkova, A. S. and Chechet, I. V. and Matveev, S. G. and Liu, Z. and Frenklach, M. and Mebel, A. M.},
abstractNote = {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.},
doi = {10.1039/c7cp05560a},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 37,
volume = 19,
place = {United States},
year = {2017},
month = {1}
}

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