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Issue 12, 2008
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The dynamics of reaction of Cl atoms with tetramethylsilane

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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′ ∼ 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.

Graphical abstract: The dynamics of reaction of Cl atoms with tetramethylsilane

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Publication details

The article was received on 29 Oct 2007, accepted on 11 Jan 2008 and first published on 12 Feb 2008


Article type: Paper
DOI: 10.1039/B716512A
Citation: Phys. Chem. Chem. Phys., 2008,10, 1675-1680
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    The dynamics of reaction of Cl atoms with tetramethylsilane

    B. Retail, R. A. Rose, J. K. Pearce, S. J. Greaves and A. J. Orr-Ewing, Phys. Chem. Chem. Phys., 2008, 10, 1675
    DOI: 10.1039/B716512A

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