کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
5373032 1504198 2016 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Quantum transition state dynamics of the cyclooctatetraene unimolecular reaction on ab initio potential energy surfaces
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
Quantum transition state dynamics of the cyclooctatetraene unimolecular reaction on ab initio potential energy surfaces
چکیده انگلیسی


- Calculation of transition-state spectrum of cyclooctatetraene unimolecular reaction.
- Three degree-of-freedom reduced-dimensionality quantum dynamics model is used.
- Reduced-dimensionality model that can describe ring-inversion and bond-alternation.
- Construction of ab initio CASSCF-level potential energy surfaces.

The cyclooctatetraene (COT) anion has a stable D4h structure that is similar to the transition state configurations of the neutral C-C bond-alternation (D4h ↔ D8h ↔ D4h) and ring-inversion (D2d ↔ D4h ↔ D2d) unimolecular reactions. The previously measured photodetachment spectrum of COT− revealed the reaction dynamics in the vicinity of the two transition states on the neutral potential energy surface. In this work, the photodetachment spectrum is calculated quantum mechanically on ab initio-level potential energy surfaces within a three degree-of-freedom reduced-dimensionality model. Very good agreement has been obtained between theory and experiment, providing reliable interpretations for the experimental spectrum. A detailed picture of the reactive molecular dynamics of the COT unimolecular reaction in the transition state region is also discussed.

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ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Chemical Physics - Volumes 469–470, 1–13 May 2016, Pages 97-104
نویسندگان
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