کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1194820 1492346 2009 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Singlet and triplet state dynamics of charge and hydride transfer reactions of OD+ (X3Σ−) with propyne
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی آنالیزی یا شیمی تجزیه
پیش نمایش صفحه اول مقاله
Singlet and triplet state dynamics of charge and hydride transfer reactions of OD+ (X3Σ−) with propyne
چکیده انگلیسی

We report a crossed beam study of the title reactions in the collision energy range from 0.45 to 1.23 eV (43–119 kJ/mol). Both reactions are exoergic and proceed as direct processes on a time scale much less than the rotational period of the transient association complex of approaching reactants. The charge transfer process takes place with zero momentum transfer. Density Functional Theory calculations of the structures of reactive intermediates show that a plausible pathway for hydride transfer involves initial charge transfer on a triplet surface, followed by intersystem crossing to the singlet manifold. This process is followed by rapid hydrogen atom transfer to form an intermediate that dissociates smoothly to products. The kinematics of the heavy + light-heavy mass combination result in mixed energy release at the lowest collision energy, in which both the breaking and forming bonds are extended, while at higher collision energies, the incremental translational energy in the reactants appears preferentially in product translation, consistent with induced repulsive energy release.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: International Journal of Mass Spectrometry - Volume 280, Issues 1–3, 1 February 2009, Pages 154–161
نویسندگان
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