Theoretical study of the oxidation mechanisms of thiophene initiated by hydroxyl radicals
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| 024 | 7 | 0 | |a 10.1007/s00894-015-2839-2 |2 doi |
| 035 | |a (NATIONALLICENCE)springer-10.1007/s00894-015-2839-2 | ||
| 245 | 0 | 0 | |a Theoretical study of the oxidation mechanisms of thiophene initiated by hydroxyl radicals |h [Elektronische Daten] |c [Abolfazl Shiroudi, Michael Deleuze] |
| 520 | 3 | |a 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 104bar 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. | |
| 540 | |a Springer-Verlag Berlin Heidelberg, 2015 | ||
| 690 | 7 | |a Thiophene |2 nationallicence | |
| 690 | 7 | |a Hydroxyl radical |2 nationallicence | |
| 690 | 7 | |a Oxidation processes |2 nationallicence | |
| 690 | 7 | |a Rate constants |2 nationallicence | |
| 690 | 7 | |a OH addition |2 nationallicence | |
| 690 | 7 | |a Reaction mechanisms |2 nationallicence | |
| 690 | 7 | |a Chemical kinetics |2 nationallicence | |
| 690 | 7 | |a RRKM theory |2 nationallicence | |
| 700 | 1 | |a Shiroudi |D Abolfazl |u Center of Molecular and Materials Modelling, Hasselt University, Agoralaan, Gebouw D, B-3590, Diepenbeek, Belgium |4 aut | |
| 700 | 1 | |a Deleuze |D Michael |u Center of Molecular and Materials Modelling, Hasselt University, Agoralaan, Gebouw D, B-3590, Diepenbeek, Belgium |4 aut | |
| 773 | 0 | |t Journal of Molecular Modeling |d Springer Berlin Heidelberg |g 21/11(2015-11-01), 1-20 |x 1610-2940 |q 21:11<1 |1 2015 |2 21 |o 894 | |
| 856 | 4 | 0 | |u https://doi.org/10.1007/s00894-015-2839-2 |q text/html |z Onlinezugriff via DOI |
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 900 | 7 | |a Metadata rights reserved |b Springer special CC-BY-NC licence |2 nationallicence | |
| 908 | |D 1 |a research-article |2 jats | ||
| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-springer | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1007/s00894-015-2839-2 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Shiroudi |D Abolfazl |u Center of Molecular and Materials Modelling, Hasselt University, Agoralaan, Gebouw D, B-3590, Diepenbeek, Belgium |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Deleuze |D Michael |u Center of Molecular and Materials Modelling, Hasselt University, Agoralaan, Gebouw D, B-3590, Diepenbeek, Belgium |4 aut | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Journal of Molecular Modeling |d Springer Berlin Heidelberg |g 21/11(2015-11-01), 1-20 |x 1610-2940 |q 21:11<1 |1 2015 |2 21 |o 894 | ||