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
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
Kinetic and geometrical isotope effects in hydrogen-atom transfer reaction, as calculated by the multi-component molecular orbital method
چکیده انگلیسی
To estimate the kinetic isotope effect (KIE) for hydrogen (or deuterium) abstraction from H(D)OR (R = 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 0.005 Å. The ratio (kaH/kaD) of the rate constant of the reaction for R = H, HO + HOR → HOH + OR and HO + DOR → 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 1–3, 18 July 2005, Pages 231-237
نویسندگان
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