کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5417823 | 1506953 | 2008 | 11 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Ab initio study of the formation and degradation reactions of semiquinone and phenoxyl radicals
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
چکیده انگلیسی
Calculations of the energetics of formation, stability, and reactivity of o-semiquinone, p-semiquinone, and phenoxyl radicals have been performed using B3LYP/6-31G(d,p), BHandHLYP/6-31G(d,p), BHandHLYP/6-311++G(d,p), BHandHLYP/aug-cc-pVDZ, and QCISD(T)/6-31G(d,p)//BHandHLYP/6-31G(d,p) model chemistries. Formation of these radicals from potential molecular precursors catechol, hydroquinone, and phenol is readily achieved under combustion conditions through unimolecular scission of the phenoxyl-hydrogen bond or abstraction of the phenoxyl hydrogen by a hydrogen atom or hydroxyl radical. The resulting radicals are resonance stabilized and resist decomposition and oxidation. Activation energies for the decomposition of the radicals through concerted elimination of carbon monoxide range from â55 to 75Â kcal/mol. Activation energies for the addition of molecular oxygen to the most reactive carbon atom (in all cases at the para-position) range from â8 to 22Â kcal/mol. The calculations strongly suggest that combustion-generated semiquinone and phenoxyl radicals are sufficiently stable and resistant to oxidation to be persistent in the atmospheric environment.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Structure: THEOCHEM - Volume 848, Issues 1â3, 15 January 2008, Pages 16-23
Journal: Journal of Molecular Structure: THEOCHEM - Volume 848, Issues 1â3, 15 January 2008, Pages 16-23
نویسندگان
Cheri A. McFerrin, Randall W. Hall, Barry Dellinger,