کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
5376798 1504330 2006 5 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Quantum theory of enhanced unimolecular reaction rates below the ergodicity threshold
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
Quantum theory of enhanced unimolecular reaction rates below the ergodicity threshold
چکیده انگلیسی
A variety of unimolecular reactions exhibit measured rates that exceed Rice-Ramsperger-Kassel-Marcus (RRKM) predictions. We show using the local random matrix theory (LRMT) of vibrational energy flow how the quantum localization of the vibrational states of a molecule, by violating the ergodicity assumption, can give rise to such an enhancement of the apparent reaction rate. We present an illustrative calculation using LRMT for a model 12-vibrational mode organic molecule to show that below the ergodicity threshold the reaction rate may exceed many times the RRKM prediction due to quantum localization of vibrational states.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Chemical Physics - Volume 329, Issues 1–3, 26 October 2006, Pages 163-167
نویسندگان
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