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Infrared absorption and electron paramagnetic resonance studies of vinyl radical in noble-gas matrices
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Image of FIG. 1.
FIG. 1.

193-nm photolysis of in solid Kr. The decreasing bands show the decomposition of acetylene, and the increasing band is from photogenerated radicals.

Image of FIG. 2.
FIG. 2.

Annealing-induced bands in photolyzed (a) acetylene/Kr and (b) acetylene/Xe matrices. The annealing temperatures were 30 K for Kr and 45 K for Xe matrices. For the /Xe sample, 250-nm photolysis was used. The assigned bands are marked. The upper traces in each panel correspond to /Ng matrices and the lower traces correspond to the partially deuterated samples (all with ). In deuterated samples the // ratio was 5%:29%:66% in Kr and 9%:37%:54% in Xe. The band marked with an asterisk is tentatively assigned to CDHCH . The bands marked with dots are from HXeCCXeD (Ref. 17). The doublets in the range are possibly contributed by .

Image of FIG. 3.
FIG. 3.

EPR spectra of acetylene/xenon (a) after irradiation with fast electrons to a dose of 10 kGy at 16 K, (b) after annealing for 5 min at 45 K, and (c) EPR spectrum of vinyl radical in solid xenon (see text). The spectra were measured at 16 K.

Image of FIG. 4.
FIG. 4.

IR absorption spectrum of the annealing-induced species (5 min, 45 K) in a xenon/acetylene system irradiated with fast electrons with a dose of 40 kGy. The difference between the spectra obtained after annealing and after irradiation is presented. The spectra were taken at 16 K.

Image of FIG. 5.
FIG. 5.

Structure of vinyl radical with atom labeling.


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Table I.

Experimentally observed bands assigned to the (the first line) and (the second line) modes of vinyl radical. The theoretical data are from our work (see Table III).

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Table II.

Geometry of vinyl radical. The atom labeling is shown in Fig. 5. Note that the labeling used here is different from Ref. 15.

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Table III.

Computational bands of vinyl radical. The intensities (in km/mol) are in parentheses. The order of H (D) in formulas follows atom labeling in Fig. 5.


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Infrared absorption and electron paramagnetic resonance studies of vinyl radical in noble-gas matrices