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Issue 19, 2006
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Ultraviolet photochemistry of trichlorovinylsilane and allyltrichlorosilane: vinyl radical (HCCH2) and allyl radical (H2CCHCH2) production in 193 nm photolysis

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Abstract

The absolute gas phase ultraviolet absorption spectra of trichlorovinylsilane and allyltrichlorosilane have been measured from 191 to 220 nm. Over this region the absorption spectra of both species are broad and relatively featureless, and their cross sections increase with decreasing wavelength. The electronic transitions of trichlorovinylsilane were calculated by ab initio quantum chemical methods and the observed absorption bands assigned to the à 1A″ ← [X with combining tilde] 1A″ transition. The maximum absorption cross section in the region, at 191 nm, is σ = (8.50 ± 0.06) × 10−18 cm2 for trichlorovinylsilane and σ = (2.10 ± 0.02) × 10−17 cm2 for allyltrichlorosilane. The vinyl radical and the allyl radical are formed promptly from the 193 nm photolysis of their respective trichlorosilane precursors. By comparison of the transient visible absorption and the 1315 nm I atom absorption from 266 nm photolysis of vinyl iodide and allyl iodide, the absorption cross sections at 404 nm of vinyl radical ((2.9 ± 0.4) × 10−19 cm2) and allyl radical ((3.6 ± 0.8) × 10−19 cm2) were derived. These cross sections are in significant disagreement with literature values derived from kinetic modeling of allyl or vinyl radical self-reactions. Using these cross sections, the vinyl radical yield from trichlorovinylsilane was determined to be ϕ = (0.9 ± 0.2) per 193 nm photon absorbed, and the allyl radical yield from allyltrichlorosilane ϕ = (0.7 ± 0.2) per 193 nm photon absorbed.

Graphical abstract: Ultraviolet photochemistry of trichlorovinylsilane and allyltrichlorosilane: vinyl radical (HCCH2) and allyl radical (H2CCHCH2) production in 193 nm photolysis

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Article information


Submitted
18 Jan 2006
Accepted
24 Mar 2006
First published
06 Apr 2006

Phys. Chem. Chem. Phys., 2006,8, 2240-2248
Article type
Paper

Ultraviolet photochemistry of trichlorovinylsilane and allyltrichlorosilane: vinyl radical (HCCH2) and allyl radical (H2CCHCH2) production in 193 nm photolysis

J. D. DeSain, L. E. Jusinski and C. A. Taatjes, Phys. Chem. Chem. Phys., 2006, 8, 2240
DOI: 10.1039/B600755D

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