کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
9591829 | 1507015 | 2005 | 6 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Carbon-hydrogen bond dissociation enthalpies in ethers: a theoretical study
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موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
چکیده انگلیسی
Density functional theory calculations based on different representations of the exchange-correlation functional (BLYP, B3LYP, B3PW91, mPW1PW91, B1LYP, BHandHLYP, BHandH, and B3P86) were carried out to predict C-H bond dissociation enthalpies in selected ethers (dimethyl ether, tetrahydrofuran (thf), and 1,4-dioxane), and some related molecules. Comparison with available experimental information shows that bond dissociation enthalpies are accurately predicted by several functionals when isodesmic and isogyric reactions are considered. However, for bond homolysis reactions only the hybrid functional B3P86 has an acceptable performance, slightly underestimating bond dissociation enthalpies. DFT calculations were further compared with the multilevel CBS-Q method. The analysis of structural properties of the radical species suggests that hyperconjugation and ring strain are the main features to consider for understanding their thermodynamic stabilization. These effects are also useful to explain some trends of bond dissociation enthalpies that are observed for the compounds involved in the present study. The C-H bond dissociation enthalpies of thf (leading to β-furanyl) and 1,4-dioxane, for which no experimental information is available, are 410 and 381 kJ molâ1, respectively, at the CBS-Q level.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Structure: THEOCHEM - Volume 719, Issues 1â3, 14 April 2005, Pages 109-114
Journal: Journal of Molecular Structure: THEOCHEM - Volume 719, Issues 1â3, 14 April 2005, Pages 109-114
نویسندگان
Filipe Agapito, Benedito J. Costa Cabral, José A. Martinho Simões,