کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5376252 | 1504315 | 2008 | 11 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Ultrafast dissociation pathways of diphenylmethyl chloride to generate reactive carbo cations
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
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چکیده انگلیسی
The primary processes in the formation of electrophilic precursor ions are studied on a microscopic scale by quantum chemical and quantum dynamical methods. For the competing reaction channels of heterolysis and homolysis in the photochemically induced dissociation of diphenylmethyl chloride, ab initio data for the ground and excited electronic states are evaluated in the gas phase. Here, the simultaneous formation of ionic and radicalic products can solely be attributed to the existence of conical intersections which are localized and characterized for the first time. The interaction of different electronic states also leads to the initial charge transfer from the phenyl Ï-system to the Ï-bond of the leaving group which is essential for the fast dissociation and is explained by orbital analysis. Quantum dynamical calculations in one and two dimensions suggest that in gas phase the ion pair constitutes the main product despite its higher potential energy. Possible changes in polar solvents, where the ionic fragments are stabilized below the radical channel, are discussed.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Chemical Physics - Volume 343, Issues 2â3, 29 January 2008, Pages 329-339
Journal: Chemical Physics - Volume 343, Issues 2â3, 29 January 2008, Pages 329-339
نویسندگان
Benjamin P. Fingerhut, Dorothee Geppert, Regina de Vivie-Riedle,