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    Eu/RG absorption and excitation spectroscopy in the solid rare gases: State dependence of crystal field splitting and Jahn–Teller coupling

    Byrne, Owen and McCaffrey, John G. (2011) Eu/RG absorption and excitation spectroscopy in the solid rare gases: State dependence of crystal field splitting and Jahn–Teller coupling. Journal of Chemical Physics, 134 (12). p. 124501. ISSN 0021-9606

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    Absorption spectroscopy recorded for annealed samples of matrix-isolated atomic europium reveals a pair of thermally stable sites in Ar and Kr while a single site exists in Xe. Plots of the matrix shifts of the visible s→p bands versus host polarizability, allowed the association of the single site in Xe and the blue sites in Ar and Kr. On the basis of the similar ground state bond lengths expected for the Eu–rare gas (RG) diatomics and the known Na–RG molecules, the blue sites are attributed to Eu occupancy in the smaller tetra-vacancy while the red sites are proposed to arise from hexa-vacancy sites. Both sites are of cubic symmetry, consistent with the pronounced Jahn–Teller structure present on the y8P ← a8S7/2 transition for these bands in the three hosts studied. Site-selective excitation spectroscopy has been used to reanalyze complex absorption spectra previously published by Jakob et al. [Phys. Lett. A 57, 67 (1976)] for the near-UV f → d transitions. On the basis that a pair of thermally stable sites exist in solid argon, the occurrence of crystal field splitting has been identified to occur for the J ≥ 5/2 level of the 8P state when isolated in these two sites with cubic symmetry. From a detailed lineshape analysis, the magnitude of the crystal field splittings on the J = 5/2 level in Ar is found to be 105 and 123 cm−1 for the red and blue sites, respectively.

    Item Type: Article
    Keywords: Eu/RG; absorption; excitation spectroscopy; solid rare gases; State dependence; crystal field splitting; Jahn–Teller coupling;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 7840
    Identification Number:
    Depositing User: Dr. John McCaffrey
    Date Deposited: 01 Feb 2017 17:40
    Journal or Publication Title: Journal of Chemical Physics
    Publisher: American Institute of Physics
    Refereed: Yes
    Use Licence: This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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