Structural and Electronic Properties of Rare Earth Metal Systems

Structural and Electronic Properties of Rare Earth Metal Systems 

This indicates the importance of the relationship between topographical and magnetic structure of the Alms. Therefore, the first part of this chapter concentrates on  

Getzlaff, Surface Magnetism, Springer Tracts in Modem Physics, 240, 

The experiments presented in the second part of this chapter therefore turn the attention to the following questions  

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These attempts may be called thermodynamic semi-theoretical approaches . They concern mostly the simplest kind of bonding, namely the metallic bond. The underlying hypothesis is that the contributions of different outer orbitals (7 s, 6 d, 5 f) in some chosen thermodynamic or structural property can be linearly combined, the coefficients of this linear combination being related to the degree of participation of the different orbitals in the bonding an approach clearly related to the molecular orbital approach of quantum chemistry and to the hybridization concept, and which had been previously employed in other transition metals and to the rare-earth metallic systems " (for a criticism of this approach, see Ref. 6). The chosen thermodynamic and structural properties are, therefore, bonding indicators , since they will reflect contributions introduced by the fact that the wavefunctions of bonding electrons have mixed orbital characters. 

In the quantum theory of matter the study of the physical properties of any system, an atom, a molecule, or a solid, begins with the determination of the energy levels and the wave functions of the many electrons in the system. For this reason the theoretical and experimental investigations of the electronic structure of rare-earth metals have always occupied an important position in rare earth research. The pioneering calculations of the energy band structure of rare earth metals were motivated by the attempt to understand the complicated magnetic structures of these metals as revealed by neutron scattering. These... 

The ZSA phase diagram and its variants provide a satisfactory description of the overall electronic structure of stoichiometric and ordered transition-metal compounds. Within the above description, the electronic properties of transition-metal oxides are primarily determined by the values of A, and t. There have been several electron spectroscopic (photoemission) investigations in order to estimate the interaction strengths. Valence-band as well as core-level spectra have been analysed for a large number of transition-metal and rare-earth compounds. Calculations of the spectra have been performed at different levels of complexity, but generally within an Anderson impurity Hamiltonian. In the case of metallic systems, the situation is complicated by the presence of a continuum of low-energy electron-hole excitations across the Fermi level. These play an important role in the case of the rare earths and their intermetallics. This effect is particularly important for the valence-band spectra. 

Ever since the foundations of spectroscopy were laid the problem of the relationship between the optical spectra emitted or absorbed by matter and the microscopic properties of the matter has been regarded as a fundamental problem. A class of very interesting systems with this regard is provided by non-metallic compounds of rare-earth ions with partially filled 4f shells. Their rich electronic structure is only weakly perturbed by the environment and provides a detailed fingerprint of the surrounding arrangement of atoms and their interactions with the f-electrons. 

The actinide element series, like the lanthanide series, is characterized by the filling of an f-electron shell. The chemical and physical properties, however, are quite different between these two series of f-electron elements, especially in the first half of the series. The differences are mainly due to the different radial extension of the 4f- and 5f-electron wavefunctions. For the rare-earth ions, even in metallic systems, the 4f electrons are spatially well localized near the ion sites. Photoemission spectra of the f electrons in lanthanide elements and compounds always show "final state multiplet" structure (3), spectra that result from partially filled shells of localized electrons. In contrast, the 5f electrons are not so well localized. They experience a smaller coulomb correlation interaction than the 4f electrons in the rare earths and stronger hybridization with the 6d- and 7s-derived conduction bands. The 5f s thus... 

The understanding of magnetic and electronic behavior requires the knowledge of the structure on a microscopic scale. Due to this important relationship the dependence of electronic on structural properties is the first topic. This contains investigations not only on rare earth metals but additionally on 3>d ferromagnetic systems. 

On the other hand, the rare earth elements constitute about one fourth of all existing metals. They form a group of elements closely related in their chemical, physical and metallurgical properties. In particular, most rare earth metals possess a similar electronic structure while other relevant properties often vary in a gradual, systematic manner. Thus, it appears that the rare earth metals constitute, potentially at least, favorable systems for the study of some of the basic factors which determine diffusion mechanisms in metallic systems. 

Ames Laboratory (Iowa State University, USA) investigating new solid state phases based on reduced rare earth halides. Since 1993, she has held a position at the University Jaume 1 of Castello (Spain) and became Associate Professor of Physical Chemistry in 1995. During the second semester of 2005, she held a visiting professor position at the Laboratory of Chemistry, Molecular Engineering and Materials of the CNRS-Universtity of Angers (France). Her research has been focussed on the chemistry of transition metal clusters with special interest in multifunctional molecular materials and the relationship between the molecular and electronic structures of these systems with their properties. She is currently coauthor of around 80 research papers on this and related topics. 

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