Kinetics of substituted silylene addition and elimination in silicon nanocluster growth captured by group additivity

Andrew J. Adamczyk, Marie Françoise Reyniers, Guy B. Marin, Linda J. Broadbelt

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

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, Ã, and the activation energy, Ea, are calculated from the G3//B3LYP rate coefficients corrected for internal rotations, and a group additivity scheme is developed to predict à and Ea. The values predicted by group additivity are more accurate than structure-reactivity relationships currently used in the literature, which rely on representative à values and the Evans-Polanyi correlation. The structural factors that have the most pronounced effect on à and Ea are considered, and the presence of rings is shown to influence these values strongly.

Original languageEnglish (US)
Pages (from-to)1978-1994
Number of pages17
JournalChemPhysChem
Volume11
Issue number9
DOIs
StatePublished - Jun 21 2010

Keywords

  • Gas-phase reactions
  • Nanoparticles
  • Polycycles
  • Quantum chemistry
  • Reactive intermediates

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

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