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    Spectroscopy and Photodissociation of Dimethylzinc in Solid Argon. 1. Vacuum UV Luminescence Detection/Synchrotron Radiation Photolysis


    Bracken, Veronica A. and Gurtler, Peter and McCaffrey, John G. (1997) Spectroscopy and Photodissociation of Dimethylzinc in Solid Argon. 1. Vacuum UV Luminescence Detection/Synchrotron Radiation Photolysis. Journal of Physical Chemistry A, 101 (51). pp. 9854-9862. ISSN 1089-5639

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    Abstract

    Absorption spectra of thin-film DMZ/Ar samples, prepared by condensing gaseous mixtures of dimethylzinc (DMZ) with argon at 12 K, were recorded in the region of the first dissociative absorptions of DMZ centered in the gas phase at 200 nm. Large blue shifts are observed in the matrix spectra which can be related to the Rydberg-like characteristics of these excited states of DMZ. The photochemistry of DMZ in an argon matrix was investigated either by subjecting samples to undispersed synchrotron irradiation using a quartz filter to select a wavelength range above 155 nm or to wavelength-specific irradiation. Steady-state and time-resolved luminescence spectroscopy of the dissociation products isolated in solid argon indicate the existence of atomic zinc strongly perturbed by a methyl radical in freshly photolyzed samples, which yields truly isolated atomic zinc upon annealing to 33 K. Dissociation threshold measurements indicate a barrier of 25 kcal/mol for direct cage escape of atomic zinc in the Ar lattice. The increased intensity of Zn(3P1)/Ar emission observed in photolyzed DMZ/Ar samples relative to pure Zn/Ar samples is explained in terms of the enhanced ISC of atomic zinc in the presence of hydrocarbon species in the former samples. This has been shown by co-deposition of atomic zinc with Ar doped with CH4 and C2H6.

    Item Type: Article
    Keywords: Spectroscopy; Photodissociation; Dimethylzinc; Solid Argon; Vacuum UV Luminescence Detection; Synchrotron Radiation Photolysis;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 7880
    Identification Number: https://doi.org/10.1021/jp972268r
    Depositing User: Dr. John McCaffrey
    Date Deposited: 07 Feb 2017 15:39
    Journal or Publication Title: Journal of Physical Chemistry A
    Publisher: American Chemical Society
    Refereed: Yes
    URI:

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