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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/19731

Title: Theoretical study of the oxidation mechanisms of thiophene initiated by hydroxyl radicals
Authors: Shiroudi, Abolfazl
Deleuze, Michael S.
Issue Date: 2015
Abstract: The mechanisms for the oxidation of thiophene by OH radicals under inert conditions (Ar) have been studied using density functional theory in conjunction with various exchange-correlation functionals. These results were compared with benchmark CBS-QB3 theoretical results. Kinetic rate constants were estimated by means of variational transition state theory (VTST) and the statistical Rice–Ramsperger–Kassel–Marcus (RRKM) theory. Effective rate constants were calculated via a steady-state analysis based upon a two-step model reaction mechanism. In line with experimental results, the computed branching ratios indicate that the most kinetically efficient process involves OH addition to a carbon atom adjacent to the sulfur atom. Due to the presence of negative activation energies, pressures larger than 104 bar are required to reach the high-pressure limit. Nucleus-independent chemical shift indices and natural bond orbital analysis show that the computed activation energies are dictated by changes in aromaticity and charge-transfer effects due to the delocalization of lone pairs from sulfur to empty π* orbitals.
Notes: [Shiroudi, Abolfazl; Deleuze, Michael S.] Hasselt Univ Agoralaan, Ctr Mol & Mat Modelling, B-3590 Diepenbeek, Belgium.
URI: http://hdl.handle.net/1942/19731
DOI: 10.1007/s00894-015-2839-2
ISI #: 000364527300018
ISSN: 1610-2940
Category: A1
Type: Journal Contribution
Validation: ecoom, 2016
Appears in Collections: Research publications

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