Investigations of the reaction of trimethylsilane with O(³P) atoms

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Article discussing investigations of the reaction of trimethylsilane with O(³P) atoms.

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6 p.

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Misra, Ashutosh; Ding, Luying; Marshall, Paul; Buchta, Christian; Stucken, D. V.; Vollmer, J. T. et al. April 1994.

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Article discussing investigations of the reaction of trimethylsilane with O(³P) atoms.

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6 p.

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Abstract: The reaction O(³P) + (CH₃)₃SiH → products (1) has been investigated by the discharge/fast-flow method with mass spectrometric detection (DF-MS) over 298-773 K and by the flash photolysis/resonance fluorescence (FP-RF) technique over 293-549 K. The rate constants from both methods are in close accord and may be summarized by k₁(T) = 5.6 x 10⁻¹¹ exp(-1005 K/T) cm³ molecule⁻¹ s⁻¹ for 290-770 K. There is reasonable agreement with previous room-temperature studies. k₁ is larger than k₂ for O + SiH₄ (2), similar to results for triethylsilane and triisopropylsilane [Buchta, Chr.; Stucken, D.-V.; Vollmer, J.-T.; Wagner, H. Gg. Z. Phys. Chem. Neue Folge, to be published], and tri-alkylation is seen to increase the reactivity of the Si-H bonds by similar amounts largely independent of the nature of the alkyl group. This silane activation occurs through lowering the energy barrier to abstraction to form OH + (CH₃)₃Si• Ab initio analysis of this pathway at the MP2/6-31G∗//HF/3-21G(∗) level of theory gives relative energies for the transition states of reactions 1 and 2 that agree well with experiment.

Reprinted with permission from the Journal of Physical Chemistry. Copyright 1994 American Chemical Society.

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  • Journal of Physical Chemistry, 1994, Washington D.C.: American Chemical Society, pp. 4020-4025

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  • Publication Title: Journal of Physical Chemistry
  • Volume: 98
  • Issue: 15
  • Page Start: 4020
  • Page End: 4025
  • Pages: 6
  • Peer Reviewed: Yes

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  • April 1994

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  • April 25, 2015, 8:59 p.m.

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Misra, Ashutosh; Ding, Luying; Marshall, Paul; Buchta, Christian; Stucken, D. V.; Vollmer, J. T. et al. Investigations of the reaction of trimethylsilane with O(³P) atoms, article, April 1994; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc503252/: accessed September 26, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.