University of Tasmania
whole_RileyMarkJulian1988_thesis.pdf (16.88 MB)

Vibronic interactions in the spectroscopy of transition metal complexes

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posted on 2023-05-27, 05:19 authored by Riley, MJ
This thesis is concerned with the effects of vibronic coupling in inorganic spectroscopy. The thesis is divided into two: a theoretical section which approaches the topic in general terms and an experimental section where examples of the phenomena described in the first section are taken from electron spin resonance and vibronic absorption spectroscopy of inorganic compounds. The theoretical section examines the possible spectroscopic effects due to vibronic interaction. A numerical approach using the variational method has been employed to model these systems, although where ever possible simple approximate formulae are also given. Many illustrative calculations are given to test the validity of such formulae and several new expressions are presented. The experimental section can be subdivided into investigations of ground state and excited state properties. In both cases the easiest way to study vibronic interactions is to vary the occupation of the vibronic levels by varying the temperature. This then leads to the temperature dependence of the physical properties that depend on the electronic character and geometry of the system. The ground state properties of six coordinate Cu(II) complexes have been examined from the temperature dependent behaviour of their g-values. The experimental data of Cu (II) doped K\\(_2\\)ZnF\\(_4\\), zinc Tutt on salts, and NH\\(_4\\)Cl were reexamined, and interpreted in terms of the usual cubic Jahn-Teller Hamiltonian with additional strain terms included to account for the low symmetry of these systems. The excited state properties were examined from the point of view of electronic absorption spectroscopy. The spectrum of square planar CuCl\\(^{2-}\\)\\(_4\\) shows an unusual temperature dependence of both the intensity and band maxima which was rationalised in terms of the ground and excited state potentials respectively. Vibronic interactions were found to be essential to the interpretation of the molecular properties of the above metal complexes. They could also play an important role in biological molecules, as the active site in protein molecules often involves the change in geometry and/or electronic character around a transition metal centre.


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Copyright 1987 the author - The University is continuing to endeavour to trace the copyright owner(s) and in the meantime this item has been reproduced here in good faith. We would be pleased to hear from the copyright owner(s). Thesis (PhD)--University of Tasmania, 1988. Includes bibliographies

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