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Experimental and Theoretical Analysis of the Luminescence Spectroscopy of atomic Mercury and atomic Manganese isolated in Rare Gas Solids


Collier, Martin;

Subject Keywords: Chemistry; Experimental and Theoretical Analysis of the Luminescence Spectroscopy; atomic; Mercury; Manganese; Rare Gas Solids;

The work presented in this thesis is primarily experimental but also contains an
important theoretical extension to gain further insight into the optical spectroscopy of
atomic ns2 metal atoms, mercury and manganese isolated in cryogenic thin films of
rare gases argon, krypton and xenon. The luminescence spectroscopy of solid-state
M/RG (M = Hg and Mn; RG = Ar, Kr and Xe) samples has been recorded employing
both time-integrated (steady-state) and time-resolved methods. The impetus for the
selection of the Hg/RG systems being the availability of solid-state spectroscopic and
gas phase pair-potentials data that allowed the development of a theoretical model.
The theoretical analysis conducted on the Hg/RG systems, yielded a qualitative
interpretation of the recorded experimental data, providing information on the
vibronic modes leading to the observed luminescence. In contrast, the investigation
of Mn/RG solids was motivated by the absorption similarities between this transition
metal atom and the simpler Hg/RG system, as both exhibit a ground ns2 electronic
configuration and excited states derived from the ns1np1 configuration. However, the
existence of low lying excited states in Mn, originating from electronic configurations
other than the [Ar]3d54s4p configuration accessed in absorption, provides multiple
radiative and non-radiative relaxation channels for excited state populations. The
luminescence spectroscopy of Hg and Mn atoms isolated in rare gas matrices has
shown that the solid state environment provides an ideal environment to study the
solvation of ground and excited state metal atoms. It allows the extraction of
information on long-lived electronic transitions (> 100 µsec) that cannot be observed
in gas phase experiments. The experimental results obtained for the Mn/RG systems
have shown that the site of isolation governs the excited state interactions with the
host. This observation therefore would allow the extension of this work to investigate
site selective excited state reactions with reagents such as CH4, CH3F, NH3 and H2-
doped rare gas matrices.



Suggested citation:

Collier, Martin; . () Experimental and Theoretical Analysis of the Luminescence Spectroscopy of atomic Mercury and atomic Manganese isolated in Rare Gas Solids [Online]. Available from: [Accessed: 18th June 2019].


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