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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/16813

Title: Theoretical Study of the Oxidation Mechanisms of Naphthalene Initiated by Hydroxyl Radicals: The H Abstraction Pathway
Authors: SHIROUDI, Abolfazl
DELEUZE, Michael
Issue Date: 2014
Citation: JOURNAL OF PHYSICAL CHEMISTRY A, 118 (20), p. 3625-3636
Abstract: Reaction mechanisms for the initial stages of naphthalene oxidation at high temperatures (T ≥ 600 K) have been studied theoretically using density functional theory along with various exchange-correlation functionals, as well as the benchmark CBS-QB3 quantum chemical approach. These stages correspond to the removal of hydrogen atoms by hydroxyl radical and the formation thereby of 1- and 2-naphthyl radicals. Bimolecular kinetic rate constants were estimated by means of transition state theory. The excellent agreement with the available experimental kinetic rate constants demonstrates that a two step reaction scheme prevails. Comparison with results obtained with density functional theory in conjunction with various exchange-correlation functionals also shows that DFT remains unsuited for quantitative insights into kinetic rate constants. Analysis of the computed structures, bond orders, and free energy profiles demonstrates that the reaction steps involved in the removal of hydrogen atoms by OH radicals satisfy Hammond’s principle. Computations of branching ratios also show that these reactions do not exhibit a particularly pronounced site-selectivity.
Notes: [Shiroudi, Abolfazl; Deleuze, Michael S.] Hasselt Univ, Ctr Mol & Mat Modelling, B-3590 Diepenbeek, Belgium.
URI: http://hdl.handle.net/1942/16813
DOI: 10.1021/jp500124m
ISI #: 000336510500010
ISSN: 1089-5639
Category: A1
Type: Journal Contribution
Validation: ecoom, 2015
Appears in Collections: Research publications

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