The dynamics of reaction of Cl atoms with tetramethylsilane

Retail, Bertrand, Rose, Rebecca A., Pearce, Julie K., Greaves, Stuart J. and Orr-Ewing, Andrew J. (2008) The dynamics of reaction of Cl atoms with tetramethylsilane. Physical Chemistry Chemical Physics, 10 12: 1675-1680. doi:10.1039/b716512a


Author Retail, Bertrand
Rose, Rebecca A.
Pearce, Julie K.
Greaves, Stuart J.
Orr-Ewing, Andrew J.
Title The dynamics of reaction of Cl atoms with tetramethylsilane
Journal name Physical Chemistry Chemical Physics   Check publisher's open access policy
ISSN 1463-9076
1463-9084
Publication date 2008-01
Sub-type Article (original research)
DOI 10.1039/b716512a
Volume 10
Issue 12
Start page 1675
End page 1680
Total pages 6
Place of publication Cambridge, United Kingdom
Publisher RSC Publications
Language eng
Formatted abstract
Rotational state distributions and state-selected CM-frame angular distributions were measured for HCl (v′ = 0, j′) products from the reaction of Cl-atoms with tetramethylsilane (TMS) under single collision conditions at a collision energy, Ecoll, of 8.2 ± 2.0 kcal mol−1. The internal excitation of these products was very low with only 2% of the total energy available partitioned into HCl rotation. A transition state with a quasi-linear C–H–Cl moiety structure was computed and used to explain this finding. A backward peaking differential cross section was also reported together with a product translational energy (T′) distribution with a maximum at T′ [similar] Ecoll. This scattering behaviour is accounted for by reactions proceeding through a tight transition state on a highly skewed potential energy surface, which favours collisions at low impact parameters with a strong kinematic constraint on the internal excitation of the products. The large Arrhenius pre-exponential factor previously reported for this reaction is reconciled with the tight differential scattering observed in our study by considering the large size of the TMS molecule.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Earth Sciences Publications
School of Chemistry and Molecular Biosciences
 
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Created: Tue, 11 Jun 2013, 16:02:43 EST by Dr Julie Pearce on behalf of School of Earth Sciences