TY  - UNPB
EP  - 390
AV  - public
N2  - This thesis is devoted to the study of metal(III)-water interactions by a variety of physical techniques. Studies are undertaken in the solid state where the tervalent hexa-aqua-cation is held rigidly within the lattice, thus facilitating its study. The RbM???(SO?)?.12H?O alums, where M??? is Al, Ga, In, Ti, V, Cr, and Fe, have been characterised by Raman spectroscopy. The Ti and V rubidium alums are of a different structural modification to the other alums studied. This is related to a change in the mode of water co-ordination leading to a larger trigonal field stabilisation energy for the Ti and V hexa-aqua-cations. The Raman spectra of the RbTi(SO?)?.12H?O alum are anomalous. Soft modes are observed indicating the onset of a phase transition. The Raman spectra are interpreted in conjunction with the published EPR and magnetic data for the [Ti(OH?)?]ł? cation. A model in which the [Ti(OH?)?]ł? cation is subject to a dynamic Jahn-Teller distortion, freezing out into a static distortion at temperatures approaching 4 K, is proposed. A polarised neutron diffraction experiment has been performed on CsMo(SO?)?.12D?O. This is the first report of such a study for any tervalent hexa-aqua-cation. Information on the spatial spin distribution within the [Mo(OD?)?]ł? cation is obtained. Spin density is found to occupy t2g-like orbitals on the metal with some spin transferred to the ligand where it is concentrated in a molecular orbital normal to the plane of the water molecule. Negative spin is also found in the molybdenum-oxygen bonding region indicative of electron correlation effects. These observations are interpreted in terms of simple concepts of chemical bonding.
KW  - Pure sciences; Hexa-aqua-cation
UR  - https://discovery.ucl.ac.uk/id/eprint/10106214/
A1  - Tregenna-Piggott, Philip Louis William
M1  - Doctoral
TI  - Metal(III)-water interactions
Y1  - 1994///
N1  - Thesis digitised by ProQuest.
ID  - discovery10106214
PB  - UCL (University College London)
ER  -