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Half Title
Also of Interest
Rare-Earth Elements. Solid State Materials: Chemical, Optical and Magnetic Properties
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Abbreviations
Preface
Contents
1. The Rare-Earth Elements
1.1 An Introduction
1.2 A Short History of Discovery
Part I: General Aspects of Rare-Earth Elements
2. Basic Aspects and General Properties
2.1 The Rare-Earth Elements in the Periodic Table
2.2 Electronic Configuration
3. General Trends of Physical and Chemical Behavior
3.1 Atomic, Ionic and van der Waals Radii
3.2 Densities, Melting and Boiling Points
3.3 Crystal Structures of the Elements
3.4 On Cerium—a Short Story
3.5 Ionization Behavior and Chemical Hardness
3.6 Oxidation States—Colors in an Aqueous Solution
3.7 General Reactivity
3.8 Solution Chemistry
3.8.1 Reduction Potentials
3.8.2 Acid-Base Chemistry and Simple Complexes
4. Natural Resources
4.1 General Aspects
4.2 Ores and Minerals
5. Production
5.1 Concentration of Rare-Earth Minerals
5.2 Separation and Purification of the Elements
5.2.1 Solvent-Solvent Extraction
5.2.2 Further Separation Approaches
5.2.3 Scandium
5.3 Obtaining the Elements
6. Basic Compound Classes
6.1 Hydrogen Compounds
6.1.1 Structures and Bonding of RH2 and RH3
6.1.2 Hydrogen Storage—LaNi5
6.2 Binary Halides and Halide Oxides
6.2.1 Trihalides RX3
Overview and Syntheses
Structures and Structure Systematics
6.2.2 Tetrafluorides RF4
6.2.3 Reduced Halides
Overview and Syntheses
Structures and Bonding
Selected Further Examples and Their Properties
6.2.4 Halide Oxides
Overview and Syntheses
Structure Chemistry
6.3 Oxides
6.3.1 The Sesquioxides R2O3 and Mixed III/IV-Oxides
6.3.2 Syntheses and Structures of the Dioxides and Intermediate Oxide
Pr6O11 and Tb7O12
6.3.3 A Closer Look On CeO2
Oxygen Storage
Catalysis
6.3.4 The Monoxides and Eu3O4
6.3.5 The Superconducting Oxides La2-xBaxCuO4 And YBa2Cu3O7-x
6.4 Borides, Carbides, Nitrides and Sulfides
6.4.1 Borides
6.4.2 Carbides and Nitrides
The Crystal Structure of Sm2Co17N3
The Carbides R3C, R2C3 and R4C3
6.4.3 Sulfides
6.5 Silicates And Selected Silicate-Analogous Compounds
6.5.1 Coordination Strength
6.5.2 Silicates
6.5.3 Aluminates
6.5.4 Nitridosilicates, Nitridoaluminates and Oxonitridosilicates
6.5.5 Phosphates
6.5.6 Borophosphates, Borosulfates and Fluorooxoborates
Part II: Properties and Applications
7. Transitions
7.1 Transition Probability
7.2 Configuration, Terms and Levels
7.3 Electric and Magnetic Dipole Transitions
7.4 Spin Selection Rule
7.5 Jablonski Diagrams
7.6 Energy Transfer Mechanisms
7.6.1 FRET Mechanism
7.6.2 Dexter Mechanism
7.7 Further Parameters
7.7.1 Bandwidth of a Transition
7.7.2 Thermal Quenching and Concentration Quenching
7.7.3 Color Coordinates
7.7.4 Color Temperature
7.8 Transitions within a 4f Configuration—Judd–Ofelt Theory
8. Optical Properties
8.1 Nephelauxetic Effect
8.2 Charge-Transfer Transitions
8.2.1 General Aspects
8.2.2 View on Rare-Earth Ions
8.2.3 Optical Electronegativity
8.3 The Chemical Shift Model
8.4 Emitters Weakly Interacting With Ligands
8.4.1 Gadolinium—Only Partially Innocent
Thermometry Using Rare-Earth Ions
8.4.2 Terbium—Bright Green or Also Blue?
Cross Relaxation
Sensitized Luminescence—Antenna Phosphors
8.4.3 Europium—Sometimes Hypersensitive
Hypersensitive Transitions
Compact Fluorescent Lamps
Plasma Display Panels
8.4.4 Samarium and Burning Holes
Spectral Hole Burning
8.4.5 Dysprosium—As Long-Lasting as Possible
Long Persistent Luminescence Introduction and Safety Application
Application as Detector Material
8.4.6 Holmium—A Chameleon
Alexandrite Effect
8.4.7 Erbium—Putting Photons Together
8.4.8 Neodymium—A Perfect Match for Stimulated Emission
Solid State Lasers
8.4.9 Praseodymium—Occasionally a Knife for Photons
Quantum Cutting
8.4.10 Thulium—Normally Blue
8.4.11 Ytterbium—Solar Cells are Pleased
8.5 Emitters Strongly Interacting With Ligands (5d–4f Transitions)
8.5.1 Trivalent Cerium—the Most Efficient Ln3+
Scintillation and Storage Phosphors
8.5.2 Divalent Europium—a True Chameleon
8.6 On White LEDs—a Short Story
8.7 Further Divalent Rare-Earth Ions
9. Magnetism
9.1 Basic Principles
9.2 Paramagnetism
9.2.1 Inner Transition Metals
9.2.2 Van Vleck Paramagnetism
9.2.3 Outer Transition Metals
9.3 Magnetic Ordering
9.3.1 Ferromagnetism and Antiferromagnetism
9.3.2 Magnetism of Metallic 4f Systems
9.4 Magnetic Behavior of the Lanthanide metals
9.5 The Europium Chalcogenides, Antiferromagnetism and Ferrimagnetism
9.6 Rare-Earth Ferromagnets—Often Really Hard and Permanent
9.6.1 SmCo5
9.6.2 Sm2Co17
9.6.3 Sm2Fe17N3
9.6.4 Nd2Fe14B
9.7 Magnetocaloric Materials
9.7.1 Gd5(Si2Ge2)
9.7.2 Eu2In
Epilogue
A. Ionic Radii
B. Physical Properties
C. Chemical Shift Model Parameters
D. Structure Types Derived From Close Packings
E. Exemplary Calculation of the Transition Integral’s Behavior
F. Excerpts of MAPLE Calculations
F.1 Coordination and MAPLE of LaH3 and GdH3
LaH3
LaH3 in the GdH3 Type
GdH3
GdH3 in the LaH3 Type
F.2 Coordinations in EuBr2
F.3 Coordinations in B Type Sm2O3
General Index
Formula Index
Bibliography