Density functional theory modeling and time-of-flight secondary ion mass spectrometric and X-ray photoelectron spectroscopic investigations into mechanistic key events of coronene oxidation : toward molecular understanding of soot combustion

2015
journal article
article
10
dc.abstract.enDensity functional [revised Perdew–Burke–Ernzerhof (rPBE)/double-numerical basis set with polarization functions (DNP)] molecular modeling of the mechanistic steps of coronene oxidation was performed together with X-ray photoelectron spectroscopic (XPS) and time-of-flight secondary ion mass spectrometric (ToF-SIMS) identification of the reaction intermediates. For the reaction steps involving singlet–triplet crossing, transition states were located within the broken-symmetry approach by use of a Becke three-parameter Lee–Yang–Parr (B3LYP)/triple-ζ plus polarization (TZVP) calculation scheme. For the conceivable attack by $O_{2}$ molecule, topologically different in-plane, free edge, zigzag, bay, armchair, and C–H sites of the coronene molecule and its derivatives were considered. Energetic profiles of the oxidation cascade revealed that the reaction occurs by a sequence of oxidation and fragmentation steps. For the key steps, the influence of the evolution of free energy with temperature was assessed and discussed. The most demanding stage is the primary dioxygen attack, and the preferred locus is the coronene free-edge site. The key intermediates appearing during the reaction progress feature C═O, C–OH, and COOH moieties, redistribution of the carbon rings, and formation of new carbon–oxygen rings, as confirmed additionally by corroborative spectroscopic measurements. The obtained results are discussed in the broader context of the molecular mechanism of soot oxidation.pl
dc.affiliationWydział Chemii : Zakład Chemii Nieorganicznejpl
dc.affiliationWydział Chemii : Zakład Chemii Środowiskapl
dc.contributor.authorZasada, Filip - 200610 pl
dc.contributor.authorPiskorz, Witold - 131426 pl
dc.contributor.authorStelmachowski, Paweł - 147943 pl
dc.contributor.authorLegutko, Piotr - 106729 pl
dc.contributor.authorKotarba, Andrzej - 129229 pl
dc.contributor.authorSojka, Zbigniew - 131982 pl
dc.date.accessioned2015-07-07T08:05:23Z
dc.date.available2015-07-07T08:05:23Z
dc.date.issued2015pl
dc.description.number12pl
dc.description.physical6568-6580pl
dc.description.volume119pl
dc.identifier.doi10.1021/jp512018zpl
dc.identifier.eissn1932-7455pl
dc.identifier.issn1932-7447pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/11845
dc.languageengpl
dc.language.containerengpl
dc.rights.licencebez licencji
dc.subtypeArticlepl
dc.titleDensity functional theory modeling and time-of-flight secondary ion mass spectrometric and X-ray photoelectron spectroscopic investigations into mechanistic key events of coronene oxidation : toward molecular understanding of soot combustionpl
dc.title.journalThe Journal of Physical Chemistry. Cpl
dc.typeJournalArticlepl
dspace.entity.typePublication
dc.abstract.enpl
Density functional [revised Perdew–Burke–Ernzerhof (rPBE)/double-numerical basis set with polarization functions (DNP)] molecular modeling of the mechanistic steps of coronene oxidation was performed together with X-ray photoelectron spectroscopic (XPS) and time-of-flight secondary ion mass spectrometric (ToF-SIMS) identification of the reaction intermediates. For the reaction steps involving singlet–triplet crossing, transition states were located within the broken-symmetry approach by use of a Becke three-parameter Lee–Yang–Parr (B3LYP)/triple-ζ plus polarization (TZVP) calculation scheme. For the conceivable attack by $O_{2}$ molecule, topologically different in-plane, free edge, zigzag, bay, armchair, and C–H sites of the coronene molecule and its derivatives were considered. Energetic profiles of the oxidation cascade revealed that the reaction occurs by a sequence of oxidation and fragmentation steps. For the key steps, the influence of the evolution of free energy with temperature was assessed and discussed. The most demanding stage is the primary dioxygen attack, and the preferred locus is the coronene free-edge site. The key intermediates appearing during the reaction progress feature C═O, C–OH, and COOH moieties, redistribution of the carbon rings, and formation of new carbon–oxygen rings, as confirmed additionally by corroborative spectroscopic measurements. The obtained results are discussed in the broader context of the molecular mechanism of soot oxidation.
dc.affiliationpl
Wydział Chemii : Zakład Chemii Nieorganicznej
dc.affiliationpl
Wydział Chemii : Zakład Chemii Środowiska
dc.contributor.authorpl
Zasada, Filip - 200610
dc.contributor.authorpl
Piskorz, Witold - 131426
dc.contributor.authorpl
Stelmachowski, Paweł - 147943
dc.contributor.authorpl
Legutko, Piotr - 106729
dc.contributor.authorpl
Kotarba, Andrzej - 129229
dc.contributor.authorpl
Sojka, Zbigniew - 131982
dc.date.accessioned
2015-07-07T08:05:23Z
dc.date.available
2015-07-07T08:05:23Z
dc.date.issuedpl
2015
dc.description.numberpl
12
dc.description.physicalpl
6568-6580
dc.description.volumepl
119
dc.identifier.doipl
10.1021/jp512018z
dc.identifier.eissnpl
1932-7455
dc.identifier.issnpl
1932-7447
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/11845
dc.languagepl
eng
dc.language.containerpl
eng
dc.rights.licence
bez licencji
dc.subtypepl
Article
dc.titlepl
Density functional theory modeling and time-of-flight secondary ion mass spectrometric and X-ray photoelectron spectroscopic investigations into mechanistic key events of coronene oxidation : toward molecular understanding of soot combustion
dc.title.journalpl
The Journal of Physical Chemistry. C
dc.typepl
JournalArticle
dspace.entity.type
Publication

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