The dynamics of reaction of Cl atoms with tetramethylsilane
Literature Information
Bertrand Retail, Rebecca A. Rose, Julie K. Pearce, Stuart J. Greaves, Andrew J. Orr-Ewing
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.
Related Literature
2003 European Winter Conference on Plasma Spectrochemistry, Garmisch-Partenkirchen, Germany
DOI: 10.1039/B301773G
EC Thematic Network on Glow Discharge Spectroscopy for Spectrochemical Analysis 1999–2002
DOI: 10.1039/B304299P
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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