title: Theoretical study of the oxidation mechanisms of thiophene initiated by hydroxyl radicals.
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 10(4) 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. Graphical Abstract CBS-QB3 energy profiles for the reaction pathways 1-3 characterizing the oxidation of thiophene by hydroxyl radicals into the related products.
authors.affiliation: Center of Molecular and Materials Modelling, Hasselt University, Agoralaan, Gebouw D, B-3590, Diepenbeek, Belgium.
authors.forename: Abolfazl
authors.initials: A
authors.lastname: Shiroudi
authors.affiliation: Center of Molecular and Materials Modelling, Hasselt University, Agoralaan, Gebouw D, B-3590, Diepenbeek, Belgium. michael.deleuze@uhasselt.be.
authors.forename: Michael S
authors.initials: MS
authors.lastname: Deleuze
keywords: Chemical kinetics; Hydroxyl radical; OH addition; Oxidation processes; RRKM theory; Rate constants; Reaction mechanisms; Thiophene