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Title: Theoretical Study of the Reaction Mechanism and Kinetics of the Phenyl + Allyl and Related Benzyl + Vinyl Associations

Abstract

Potential energy surfaces for the allyl + phenyl and benzyl + vinyl barrierless radical association reactions have been studied at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G** level of theory. Variable reaction coordinate transition state theory (VRC-TST) has been employed to evaluate high-pressure limit rate constants for the barrierless channels. Then, Rice–Ramsperger–Kassel–Marcus master equation (RRKM-ME) calculations have been performed to assess phenomenological rate constants and product branching ratios of various reaction channels at different temperatures and pressures. The initial step of both radical association reactions produces 3-phenylpropene which can further dissociate into a variety of bimolecular products including the indene precursor 1-phenylallyl + H. The results showed that at typical combustion conditions the collisional stabilization of 3-phenylpropene dominates both the phenyl + allyl and benzyl + vinyl reactions at temperatures below 1000 K and remains important at high pressures up to 2500 K. The main bimolecular products of the two reactions at high temperatures are predicted to be benzyl + vinyl and phenyl + allyl, respectively. The well-skipping mechanism to form 1-phenylallyl directly in the allyl + phenyl and benzyl + vinyl reactions appeared to be not significant, however, the reactions can provide some contributions into the formation of the indene precursor via the 3-phenylpropenemore » stabilization/dissociation sequence and most of all, via the formation of 3-phenylpropene itself, which then can undergo H-abstraction by available radicals to produce 1-phenylallyl. The allyl + phenyl reaction can also contribute to the formation of two-ring PAH by producing benzyl radical at high temperatures, either by the well-skipping or stabilization/dissociation mechanisms; in turn, benzyl can readily react with acetylene or propargyl radical to form indene or naphthalene precursors, respectively. Finally, rate expressions for all important reaction channels in a broad range of temperatures and pressures have been generated for kinetic modeling.« less

Authors:
 [1]; ORCiD logo [1]
  1. Florida International Univ., Miami, FL (United States)
Publication Date:
Research Org.:
Florida International Univ. (FIU), Miami, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1594780
Grant/Contract Number:  
FG02-04ER15570
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 123; Journal Issue: 9; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; kinetic parameters; phenyls; vinyl; pharmaceuticals Allyl group

Citation Formats

Morozov, Alexander N., and Mebel, Alexander M. Theoretical Study of the Reaction Mechanism and Kinetics of the Phenyl + Allyl and Related Benzyl + Vinyl Associations. United States: N. p., 2019. Web. doi:10.1021/acs.jpca.9b00345.
Morozov, Alexander N., & Mebel, Alexander M. Theoretical Study of the Reaction Mechanism and Kinetics of the Phenyl + Allyl and Related Benzyl + Vinyl Associations. United States. https://doi.org/10.1021/acs.jpca.9b00345
Morozov, Alexander N., and Mebel, Alexander M. Wed . "Theoretical Study of the Reaction Mechanism and Kinetics of the Phenyl + Allyl and Related Benzyl + Vinyl Associations". United States. https://doi.org/10.1021/acs.jpca.9b00345. https://www.osti.gov/servlets/purl/1594780.
@article{osti_1594780,
title = {Theoretical Study of the Reaction Mechanism and Kinetics of the Phenyl + Allyl and Related Benzyl + Vinyl Associations},
author = {Morozov, Alexander N. and Mebel, Alexander M.},
abstractNote = {Potential energy surfaces for the allyl + phenyl and benzyl + vinyl barrierless radical association reactions have been studied at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G** level of theory. Variable reaction coordinate transition state theory (VRC-TST) has been employed to evaluate high-pressure limit rate constants for the barrierless channels. Then, Rice–Ramsperger–Kassel–Marcus master equation (RRKM-ME) calculations have been performed to assess phenomenological rate constants and product branching ratios of various reaction channels at different temperatures and pressures. The initial step of both radical association reactions produces 3-phenylpropene which can further dissociate into a variety of bimolecular products including the indene precursor 1-phenylallyl + H. The results showed that at typical combustion conditions the collisional stabilization of 3-phenylpropene dominates both the phenyl + allyl and benzyl + vinyl reactions at temperatures below 1000 K and remains important at high pressures up to 2500 K. The main bimolecular products of the two reactions at high temperatures are predicted to be benzyl + vinyl and phenyl + allyl, respectively. The well-skipping mechanism to form 1-phenylallyl directly in the allyl + phenyl and benzyl + vinyl reactions appeared to be not significant, however, the reactions can provide some contributions into the formation of the indene precursor via the 3-phenylpropene stabilization/dissociation sequence and most of all, via the formation of 3-phenylpropene itself, which then can undergo H-abstraction by available radicals to produce 1-phenylallyl. The allyl + phenyl reaction can also contribute to the formation of two-ring PAH by producing benzyl radical at high temperatures, either by the well-skipping or stabilization/dissociation mechanisms; in turn, benzyl can readily react with acetylene or propargyl radical to form indene or naphthalene precursors, respectively. Finally, rate expressions for all important reaction channels in a broad range of temperatures and pressures have been generated for kinetic modeling.},
doi = {10.1021/acs.jpca.9b00345},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 9,
volume = 123,
place = {United States},
year = {Wed Feb 13 00:00:00 EST 2019},
month = {Wed Feb 13 00:00:00 EST 2019}
}

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