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http://hdl.handle.net/1942/19731
Title: | Theoretical study of the oxidation mechanisms of thiophene initiated by hydroxyl radicals | Authors: | SHIROUDI, Abolfazl DELEUZE, Michael |
Issue Date: | 2015 | Source: | JOURNAL OF MOLECULAR MODELING, 21(11) | 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. | Keywords: | thiophene; hydroxyl radical; oxidation processes; rate constants; OH-addition; reaction mechanisms; chemical kinetics; RRKM theory | Document URI: | http://hdl.handle.net/1942/19731 | ISSN: | 1610-2940 | e-ISSN: | 0948-5023 | DOI: | 10.1007/s00894-015-2839-2 | ISI #: | 000364527300018 | Rights: | © Springer-Verlag Berlin Heidelberg 2015 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2016 |
Appears in Collections: | Research publications |
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