The dynamics of reaction of Cl atoms with tetramethylsilane

Literature Information

Publication Date 2008-02-12
DOI 10.1039/B716512A
Impact Factor 3.676
Authors

Bertrand Retail, Rebecca A. Rose, Julie K. Pearce, Stuart J. Greaves, Andrew J. Orr-Ewing


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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.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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