Mechanism of the thermal decomposition of tetramethylsilane: a flash pyrolysis vacuum ultraviolet photoionization time-of-flight mass spectrometry and density functional theory study

Literature Information

Publication Date 2018-06-19
DOI 10.1039/C8CP02626B
Impact Factor 3.676
Authors

Xinghua Liu, Alexis Vazquez, Daxi Wang


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Abstract

The thermal decomposition of tetramethylsilane (TMS) was studied over the temperature range of 298–1450 K by combining flash pyrolysis vacuum ultraviolet photoionization time-of-flight mass spectrometry (VUV-PI-TOFMS) and density functional theory (DFT). The initial step in TMS pyrolysis produced a methyl radical (Me˙) and Me3Si˙. Me3Si˙ underwent subsequent loss of a hydrogen atom to form Me2SiCH2 and loss of a methyl radical to form Me2Si:. Isomerizations via 1,2-shift and H2 eliminations were major secondary decomposition reactions of Me2SiCH2 and Me2Si:. Among the various isomers, silylene species containing Si–H bonds, such as :Si(H)CH2CH2CH3, :Si(H)CH2CHCH2, :Si(H)CH2CH3, and :Si(H)CHCH2, played an important role in H2 elimination reactions. On the other hand, silene species were insignificant in H2 eliminations. Unlike the silylene species, H2 elimination of :SiCH2 was energetically unfavorable.

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Back cover

2021-05-19 Cover

DOI: 10.1039/D1CP90108G

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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