Kinetics of Substituted Silylene Addition and Elimination in Silicon Nanocluster Growth Captured by Group Additivity
✍ Scribed by Andrew J. Adamczyk; Marie-Françoise Reyniers; Guy B. Marin; Linda J. Broadbelt
- Publisher
- John Wiley and Sons
- Year
- 2010
- Tongue
- English
- Weight
- 632 KB
- Volume
- 11
- Category
- Article
- ISSN
- 1439-4235
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✦ Synopsis
Abstract
Accurate rate coefficients for 40 bimolecular substituted silylene addition reactions for silicon hydrides containing up to nine silicon atoms are calculated using the G3//B3LYP method. The overall reactions exhibit two steps: the reactants first meet to form an adduct, which then converts into a saturated silicon hydride. Values for the single‐event Arrhenius pre‐exponential factor, ${\tilde A}$, and the activation energy, E__~a~, are calculated from the G3//B3LYP rate coefficients corrected for internal rotations, and a group additivity scheme is developed to predict__ ${\tilde A}$ and E__~a~. The values predicted by group additivity are more accurate than structure–reactivity relationships currently used in the literature, which rely on representative__ ${\tilde A}$ values and the Evans–Polanyi correlation. The structural factors that have the most pronounced effect on ${\tilde A}$ and E__~a~ are considered, and the presence of rings is shown to influence these values strongly.__