Optical spectroscopy has been instrumental in the discovery of many lanthanide elements. In return, these elements have always played a prominent role in lighting devices and light conversion technologies (Auer mantles, incandescent lamps, lasers, cathode-ray and plasma displays). They are also presently used in highly sensitive luminescent bio-analyses and cell imaging. This volume of the Handbook on the Physics and Chemistry of Rare Earths is entirely devoted to the photophysical properties of these elements. It is dedicated to the late Professor William T (Bill) Carnall who has pioneered the understanding of lanthanide spectra in the 1960 s and starts with a Dedication to this scientist. The following five chapters describe various aspects of lanthanide spectroscopy and its applications. Chapters 231 presents state-of-the-art theoretical calculations of lanthanide energy levels and transition intensities. It is followed by a review (Chapter 232) on both theoretical and experimental aspects of f-d transitions, a less well known field of lanthanide spectroscopy, yet very important for the design of new optical materials. Chapter 233 describes how confinement effects act on the photophysical properties of lanthanides when they are inserted into nanomaterials, including nanoparticles, nanosheets, nanowires, nanotubes, insulating and semiconductor nanocrystals. The use of lanthanide chelates for biomedical analyses is presented in Chapter 234; long lifetimes of the excited states of lanthanide ions allow the use of time-resolved spectroscopy, which leads to highly sensitive analyses devoid of background effect from the autofluorescence of the samples. The last review (Chapter 235) provides a comprehensive survey of near-infrared (NIR) emitting molecular probes and devices, spanning an all range of compounds, from simple chelates to macrocyclic complexes, heterometallic functional edifices, coordination polymers and other extended structures. Applications ranging from telecommunications to light-emitting diodes and biomedical analyses are assessed.
- Provides a comprehensive look at optical spectroscopy and its applications
- A volume in the continuing authoritative series which deals with the chemistry, materials science, physics and technology of the rare earth elements"

This volume of the Handbook on the Physics and Chemistry of Rare Earth begins with a Dedication to late Professor LeRoy Eyring who had been a committed co-editor of the first 32 volumes of this series. This is followed by four chapters, the first two pertaining to solid state physics and materials science, while the last two chapters describe organic (and inorganic) reactions mediated by tetravalent cerium-based oxidants and by divalent samarium-based reductants. Chapter 227 is devoted to the description of the crystal chemistry and physical properties of rare-earth bismuthides, a class of compounds showing large similarities with the rare-earth antimonides previously reviewed in volume 33 of this series. The fascinating optical and electric properties of rare-earth hydride films displaying a switchable mirror effect as a function of hydrogen pressure, i.e. from a shiny metallic state to a transparent insulating film with increasing pressure, are described in Chapter 228, along with their fabrication methods. Many chemical reactions take advantage of the tetravalent/trivalent Ce(IV)/Ce(III) redox couple and many of its potential applications are presented in Chapter 229, from analytical procedures, to electrosynthesis, and organic and industrial (polymerization) reactions. The last review (Chapter 230) focuses on the synthesis and use of divalent samarium-based reductants in organic and inorganic reactions, mainly on those containing iodide and pentamethylcyclopentadienyl ligands.
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This volume of the Handbook adds five new chapters to the science of rare earths. Two of the chapters deal with intermetallic compounds. An overview of ternary systems containing rare earths, transition metals and indium - Chapter 218 - opens the volume. It is followed by Chapter 219 sorting out relationships between superconductivity and magnetism. The next two chapters are dedicated to complex compounds of rare earths: Chapter 220 describes structural studies using circularly polarized luminescence spectroscopy of lanthanide systems, while Chapter 221 examines rare-earth metal-organic frameworks, also known as coordination polymers. The final Chapter 222 deals with the catalytic activity of rare earths in site-selective hydrolysis of DNA and RNA.

Even at the beginning of the new millenium the rare earths still remain, to a certain extent, a mystery. The chapters in this volume will help to unravel some of these. In the filling of the 4f electronic orbitals the lanthanides defy the elementary aufbau principle that underlies the periodic sequence of the elements, and the authors of the first chapter introduce the readers to the basic physics of the orbital collapse leading to that failure. Furthermore an explanation is offered in terms of double-well potentials. The phenomenon is illustrated using the valence transitions observed in some of the rare earth atoms, including Sm group metals and the higher oxides of cerium, praseodymium and terbium. In the second chapter the synthesis and structure of the many types of rare earth halides are described. They have been described as simple, complex, binary, ternary and multinuclear complex, and other categories needed to deal with the most studied of the rare earth compounds. The structure types are skillfully illustrated to show the elementary architecture of each type.
In chapter three the authors discuss the science and applications of rare earth super ionic conductors as solid electrolytes. Conduction by oxygen and fluorine anions as well as hydrogen and other cations associated with these electrolytes is emphasized. They deal with extrinsic and intrinsic types together with their associated structures and structural types including structural defects. The chapter concludes with an outline of the many applications of solid electrolytes.
Chapter four introduces the reader to the principles that underlie thermoluminescence and its application to dosimetry and provides detailed information on the R-activated phosphors that support dosimetry. This is a selective review of detailed literature based on the areas making most progress.
The final chapter elaborates on the data gained by the studies and interpretation around the analytical separation of the individual rare earth elements utilizing chromatographic techniques. The authors describe the fundamental chemistry that underpins contemporary analytical separation techniques for lanthanide separation and analysis. This is done after a description of the rich assortment of separation methods in use has been introduced.

The contributions to this volume focus on selected chemical aspects of rare-earth materials. The topics covered range from a basic treatment of crystalline electric-field effects and chemical interactions in organic solvents, to separation processes, electrochemical beaviors which impact corrosion, oxidation resistance, chemical energy storage and sensor technology, and to analytical procedures.

Underlying the most subtle chemical and optical properties of these elements and their compounds in the condensed state are the crystal field effects. This phenomenon in non-metallic compounds is discussed in chapter six. The volume opens with a review of important new solvent extraction procedures as well as emerging alternative separation processes such as photochemical separation, precipitation stripping and supercritical extraction. Scientific and industrial procedures are illustrated. In a further chapter eight major analytical techniques of obtaining accurate trace analysis are examined, tabulated and assessed. The most effective procedures of each are also reviewed. Chapter two considers a wide variety of methods using rare-earth solutions and slats to modify advantageously the costly deterioration of metals and alloys. This topic is expanded in the following chapter, paying particular attention to protection against high-temperature oxidation, sulfidization and hot-salt corrosion. The following two chapters are concerned with the versatility of the rare earths in addressing current technical problems such the use of rare-earth intermetallics, principally LaNi3-based materials, to provide the skyrocketing need for environmetally friendly, usually portable, battery power. The final chapter is a review of the solvation, interaction and coordination of rare-earth salts in a variety of organic solvents including dimethylacetamide, dimethylsulfoxide, various alcohols, acetonitrile and propylenecarbonate under strict anhydrous conditions. A contrast of these interactions with those in which water is present with organic solvents is also made.

This continuing authoritative series deals with the chemistry, materials science, physics and technology of the rare earth elements in an integrated manner. Each chapter is a comprehensive, up-to-date, critical review of a particular segment of the field. The work offers the researcher and graduate student a complete and thorough coverage of this fascinating field.

Authoritative
Comprehensive
Up-to-date
Critical

This continuing authoritative series deals with the chemistry, materials science, physics and technology of the rare earth elements in an integrated manner. Each chapter is a comprehensive, up-to-date, critical review of a particular segment of the field. The work offers the researcher and graduate student a complete and thorough coverage of this fascinating field.
REVIEW:
"Highly experienced authors have written each review usually at a level suitable for advanced postgraduate students and research workers from a variety of fields. With the great richness of information involving references to other review articles written from different points of view, the books are an important reference source and should be on the shelves of most libraries."-- "Journal of Applied Crystallography"
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. Comprehensive
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This continuing authoritative series deals with the chemistry, materials science, physics and technology of the rare earth elements. Volume 38 of the Handbook on the Physics and Chemistry of Rare Earth incorporates a recapitulation of the scientific achievements and contributions made by the late Professor LeRoy Eyring (1919-2005) to the science of the lanthanide oxides in which the lanthanide element has a valence equal to or greater than three.
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The rare earths play a unique role in science. These seventeen related elements afford a panoply of subtle variations deriving from the systematic development of their electronic configurations, allowing a test of theory with excellent resolution. In contrast they find widespread use in even the most mundane processes such as steel making, for polishing materials and gasoline cracking catalysts. In between are exotic uses such as TV screen phosphors, lasers, high strength permanent magnets and chemical probes.
This multi-volume handbook covers the entire rare earth field in an integrated manner. Each chapter is a comprehensive up-to-date, critical review of a particular segment of the field. The work offers the researcher and graduate student alike, a complete and thorough coverage of this fascinating field.
. Authoritative
. Comprehensive
. Up-to-date
. Critical
. Reliable

Volume 15 in this series continues the voyage of discovery started almost a decade ago. Chapter 98 adds significantly to an evaluation of systematic, experimental low-temperature studies of the ambivalent behaviours of cerium (ferromagnetism, antiferromagnetism, spin glass, superconductivity etc.) which depend upon its environment in materials. The conclusions arrived at should provide new data against which the theory can be advanced. The next chapter provides a review of rare earth carbides, emphasizing the thermodynamics, phase diagrams, crystal structures and physical properties. The binary rare earth carbides present an exceptionally wide range of compositions and structures both as solids and gas-phase molecules. Complex carbides with additional metal and non-metal components also receive attention. Metal-rich halides (i.e. compounds with an X/R ratio <2) are the subject of the next chapter. The compounds are classified according to their structure and chemical bonding characteristics and their electrical and magnetic properties are also reviewed. Chapter 101 deals with the preparation, structure, chemical and physical properties of heavy-metal fluoride glasses. Large amounts of rare earths can be added into these, and they possess a great potential for optical applications in the mid-infrared range as fiber optic glasses for communication and transmission of information, optical wave guides, fiber lasers and sensors. The following chapter explores the chemical kinetics of solvent and ligand exchange in aqueous lanthanide solutions. A wealth of tabulated information on rate and equilibrium constants is provided in textual and tabular form. Chapter 103 considers the fundamentally important reactions of the lanthanide ions with water. These interactions are discussed for both solids and solutions. The hydrated species are considered in detail for the aqueous solution, revealing the consequences of the lanthanide series sequence. The concluding chapter reviews macrocyclic complexes formed by rare earth and dioxouranium ions as templates. Synthetic trends and reactivity are considered as well as potential uses of these intriguing wrap-around structures.

This volume differs somewhat from the previous volumes in the series in that there is a strong emphasis on the physical aspects and not so much on the chemical aspects of intermetallic compounds. Two of the chapters are concerned with relatively new experimental methods of studying rare earth metallic phases - high energy neutron spectroscopy and light scattering. In these chapters the authors explain the new kinds of information one obtains from these techniques and how this complements the knowledge previously gleaned from the more common measurements - such as NMR, heat capacities, magnetic susceptibility, transport and elastic properties. One of the remaining three chapters deals with NMR studies of rare earth intermetallics and the final two chapters are concerned, not so much with a particular experimental technique, but with physical phenomena that occur in these compounds: the electron-phonon interaction and heavy fermion behavior.