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Kinetics of Substituted Silylene Addition and Elimination in Silicon Nanocluster Growth Captured by Group Additivity
Author(s) -
Adamczyk Andrew J.,
Reyniers MarieFrançoise,
Marin Guy B.,
Broadbelt Linda J.
Publication year - 2010
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200900836
Subject(s) - silylene , additive function , chemistry , arrhenius equation , reactivity (psychology) , silicon , activation energy , hydride , group (periodic table) , computational chemistry , kinetic energy , kinetics , thermodynamics , adduct , organic chemistry , metal , physics , mathematical analysis , alternative medicine , mathematics , pathology , quantum mechanics , medicine
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.