Lattice vibrations metal oxides

Raman spectroscopy has been successfully applied to the investigation of oxidic catalysts. According to Wachs, the number of Raman publications rose to about 80-100 per year at the end of the nineties, with typically two thirds of the papers devoted to oxides [41]. Raman spectroscopy provides insight into the structure of oxides, their crystallinity, the coordination of metal oxide sites, and even the spatial distribution of phases through a sample when the technique is used in microprobe mode. As the frequencies of metal-oxygen vibrations found in a lattice are typically between a few hundred and 1000 cm 1 and are thus difficult to investigate in infrared, Raman spectroscopy is clearly the indicated technique for this purpose. 

How can we be sure that the U +(Q2-) complex in a mixed metal oxide is present as the UO octahedron This can be done by studying solid solution series between tungstates (tellurates, etc.) and uranates which are isomorphous and whose crystal structure is known. Illustrative examples are solid solution series with ordered perovskite structure A2BWi aUa 06 and A2BTei-a Ua 06 91). Here A and B are alkahne-earth ions. The hexavalent ions occupy octahedral positions as can be shown by infrared and Raman analysis 92, 93). Usually no accurate determinations of the crystallographic anion parameters are available, because this can only be done by neutron diffraction [see however Ref. (P4)]. Vibrational spectroscopy is then a simple tool to determine the site symmetry of the uranate complex in the lattice, if these groups do not have oxygen ions in common. In the perovskite structure this requirement is fulfilled. 

The electrons in a solid interact both with one another and with the lattice vibrations. A theme of this book is the effect of the interaction between electrons in inducing magnetic moments and metal-insulator transitions. Interaction with phonons also has an important effect, particularly in some transitional-metal oxides. In this chapter both kinds of interaction are introduced. 

The atoms of the metal oxides, as in all solids, partieipate in thermal vibrations around their equilibrium positions. These vibrations are determined by the structure of the solid and the interactions between the atom or ions in the lattice and, in general, their detailed description is very complicated. However, there are differetn simplified models for simulation of the collective vibrations of the atoms. Let us consider a linear chain of atoms in a soUd at a distance a between neighbors (Scheme la). In this case the shorter wavelength will be... 

Work with the objective of comparing oxo-ions with oxide particles in order to test the validity of this reasoning has been reported by Chen et al. who used a catalyst that initially contains Fe oxo-ions, [HO-Fe-0-Fe-OH] +. These sites were first converted to Fc203 particies by a simpie chemical treatment. This was followed by another treatment, which redispersed these Fc203 particies back to oxo-ions. The change in particle size was monitored by a spectroscopic method based on the observation that in zeolites metal ions and oxo-ions, that are attached to the wall of a cage, give rise to a typical IR band caused by the perturbation of the vibrations of the zeolite lattice. 

Schmidtke H-H (1994) Vibrational Progressions in Electronic Spectra of Complex Compounds Indicating Stron Vibronic Coupling. 171 69-112 Schmittel M (1994) Umpolung of Ketones via Enol Radical Cations. 169 183-230 Schonherr T (1997) Angular Overtap Model Applied to Transition Metal Complexes and dN-Ions in Oxide Host Lattices. 191 87-152... 

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