کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
9575314 | 1504345 | 2005 | 7 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Kinetic and geometrical isotope effects in hydrogen-atom transfer reaction, as calculated by the multi-component molecular orbital method
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله

چکیده انگلیسی
To estimate the kinetic isotope effect (KIE) for hydrogen (or deuterium) abstraction from H(D)OR (RÂ =Â H, CH3, and CN) by an OH radical, we have considered the geometrical isotope effect (GIE) induced by the difference of the protonic and deuteronic wavefunctions using the multi-component MO method. The difference by the GIE of hydrogen bond was about 0.005Â Ã
. The ratio (kaH/kaD) of the rate constant of the reaction for R = H, HO + HOR â HOH + OR and HO + DOR â HOD + OR, is estimated as 4.4 by our calculation, which is reasonable agreement with experimental result of 6.0 ± 2.0. We have found that the difference of the nuclear wavefunction of the proton and deuteron affects the changes of geometry and electronic charge density, which plays an important role to theoretically determine the effective potential energy surfaces and the corresponding KIE between H and D compounds.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Chemical Physics - Volume 314, Issues 1â3, 18 July 2005, Pages 231-237
Journal: Chemical Physics - Volume 314, Issues 1â3, 18 July 2005, Pages 231-237
نویسندگان
Takayoshi Ishimoto, Masanori Tachikawa, Hiroaki Tokiwa, Umpei Nagashima,