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http://hdl.handle.net/1942/19731
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DC Field | Value | Language |
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dc.contributor.author | SHIROUDI, Abolfazl | - |
dc.contributor.author | DELEUZE, Michael | - |
dc.date.accessioned | 2015-11-04T14:35:44Z | - |
dc.date.available | 2015-11-04T14:35:44Z | - |
dc.date.issued | 2015 | - |
dc.identifier.citation | JOURNAL OF MOLECULAR MODELING, 21(11) | - |
dc.identifier.issn | 1610-2940 | - |
dc.identifier.uri | http://hdl.handle.net/1942/19731 | - |
dc.description.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. | - |
dc.description.sponsorship | A. Shiroudi acknowledges a Ph.D. fellowship from the "Bijzonder Onderzoeksfonds" (BOF) of Hasselt University. All calculations presented in this work were performed at the Flemish Supercomputer Center (Vlaams Supercomputer Centrum). This cluster was financed by budgets obtained from the Katholieke Universiteit Leuven, from individual contributions by users, and financing obtained from the Hercules Foundation and the Flemish government. | - |
dc.language.iso | en | - |
dc.rights | © Springer-Verlag Berlin Heidelberg 2015 | - |
dc.subject.other | thiophene; hydroxyl radical; oxidation processes; rate constants; OH-addition; reaction mechanisms; chemical kinetics; RRKM theory | - |
dc.title | Theoretical study of the oxidation mechanisms of thiophene initiated by hydroxyl radicals | - |
dc.type | Journal Contribution | - |
dc.identifier.issue | 11 | - |
dc.identifier.volume | 21 | - |
local.format.pages | 20 | - |
local.bibliographicCitation.jcat | A1 | - |
dc.description.notes | [Shiroudi, Abolfazl; Deleuze, Michael S.] Hasselt Univ Agoralaan, Ctr Mol & Mat Modelling, B-3590 Diepenbeek, Belgium. | - |
local.type.refereed | Refereed | - |
local.type.specified | Article | - |
dc.identifier.doi | 10.1007/s00894-015-2839-2 | - |
dc.identifier.isi | 000364527300018 | - |
item.fullcitation | SHIROUDI, Abolfazl & DELEUZE, Michael (2015) Theoretical study of the oxidation mechanisms of thiophene initiated by hydroxyl radicals. In: JOURNAL OF MOLECULAR MODELING, 21(11). | - |
item.contributor | SHIROUDI, Abolfazl | - |
item.contributor | DELEUZE, Michael | - |
item.validation | ecoom 2016 | - |
item.accessRights | Restricted Access | - |
item.fulltext | With Fulltext | - |
crisitem.journal.issn | 1610-2940 | - |
crisitem.journal.eissn | 0948-5023 | - |
Appears in Collections: | Research publications |
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art-3A10.1007-2Fs00894-015-2839-2.pdf Restricted Access | Published version | 1.88 MB | Adobe PDF | View/Open Request a copy |
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