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Title: A study of spectroscopic probe ions in ionic media, glasses and thin films
Author: Bruce, A. J.
Awarding Body: University of Aberdeen
Current Institution: University of Aberdeen
Date of Award: 1981
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In this thesis, the electronic spectra of metal probe ion centres, in a variety of solid-state and molten salt media, are studied. Partioular attention is paid to the spectra of p-block ions with outer shell configurations (n-1)d10(n)s2, (i.e. In(I),Sn(II),Sb(III),Tl(I),Pb(II) and Bi(III)). Existing data on the "Rydberg" intershell and the charge transfer spectra of such ions in halide environments, are compiled, together with additional data from experimental studies. These data are interpreted in terms of the current theories in chemical spectroscopy and are shown to yield information on the compositions and the electron donor powers of the probe ion co-ordinating environments. The chemical reactions, which occur at elevated temperatures, between surface coated thin films of Pb(II) ion salts and a variety of crystalline and vitreous support materials, are interpreted on the basis of spectroscopic measurements. The results indicate that halide ions, especially fluoride ions, are highly mobile and readily participate in exchange reactions between the thin films and their support materials. Sub-surface concentration profiles are also obtained for several samples, using an ion ablation technique. These are shown to be entirely consistent with, and complementary to, the spectroscopic measurements. The spectra of probe ion centres in fluoride media are studied in some detail. It is shown that the electron donor powers of co-ordinating fluoride ions, towards d10s2 probe ion centres in several molten fluoride systems, can be reduced if other polarising ions are present. The relative magnitudes of these reductions with compositional variations are studied in several (alkali fluoride : alkali fluoroborate) binary melts. Attention is also drawn to the similarities in the behavior of spectroscopic probe ions in alkali borate and alkali oxy-fluoroborate glass media.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available