کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
9591318 | 1507013 | 2005 | 11 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Hydrogen abstraction from dimethyl ether (DME) and dimethyl sulfide (DMS) by OH radical: a computational study
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موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
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چکیده انگلیسی
The electronic structures and energetics of the reactants, products, transition states, and association complexes involved in the reaction of dimethyl ether (DME) and dimethyl sulfide (DMS) with OH radical have been investigated at the MP2(FC) and DFT (BH&HLYP and B3LYP) levels of theory using the 6-311G(d,p), 6-311++G(d,p), and 6-311++G(2df,2pd) basis sets. Two channels have been discussed and two transition structures have been located for each reaction; one represents a direct hydrogen-abstraction and the other one for the abstraction through prereactive complex. Among the computational levels employed in the present work, the PMP2/6-311++G(2df,2pd)//M2/6-311++G(d,p) level was found to reproduce best the experimentally measured rate constants. Our best estimates of the rate constants at 298Â K for the reactions of OH radical with DME and DMS are 5.9Ã10â13 and 1.1Ã10â12Â cm3Â moleculeâ1Â sâ1, respectively, which are underestimated by 4 times as compared to the experimentally derived values. At low temperatures, the direct H-abstraction predominates over the H-abstraction through the prereactive complex, while both channels compete at elevated temperatures.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Structure: THEOCHEM - Volume 722, Issues 1â3, 2 May 2005, Pages 9-19
Journal: Journal of Molecular Structure: THEOCHEM - Volume 722, Issues 1â3, 2 May 2005, Pages 9-19
نویسندگان
Ahmed M. El-Nahas, Tadafumi Uchimaru, Masaaki Sugie, Kazuaki Tokuhashi, Akira Sekiya,