Handbook on the Physics and Chemistry of Rare Earths volume 9 Elsevier, 1987 Edited by: Karl A. Gschneidner, Jr. and LeRoy Eyring ISBN: 978-0-444-87045-2 by kmno4 Handbook on the Physics and Chemistry of Rare Earths, edited by K.A. Gschneidner, Jr. and L. Eyring © Elsevier Science Publishers B.V., 1987 PREFACE Karl A. GSCHNEIDNER, Jr., and LeRoy EYRING o These elements perplex us in our rearches [sic], baffle us in our speculations, and haunt us in our very dreams. They stretch like an unknown sea before us- mocking, mystifying, and murmuring strange revelations and possibilities. Sir William Crookes (February 16, 1887) There are those who feel that the rare earth elements are destined to play an even greater role in our "high-tech" society in the future than they have in the past. This judgement is based upon the trend of increasing applications resulting from the electronic structures of these materials that lead to their unusual optical, magnetic, electrical and chemical properties so adaptable to the demands now being placed on materials. The "Handbook" seeks to provide topical reviews and compilations of critically reviewed data to aid in the design and fabrication of the required new materials. Four additional chapters in this tradition are the contents of this volume. The development of lasers containing rare earth species sparked an interest in glasses containing these elements. Reisfeld and J0rgensen discuss excited-state phenomena in vitreous rare-earth-containing substances. The description of the chemistry and crystal chemistry of complex inorganic compounds of the rare earths is continued by Niinist6 and Leskelfi from the previous volume. Here they consider the phosphates, arsenates, selenates and selenites, oxohalogen com- pounds and vanadates. Encapsulation and transport of charged hydrophilic species from an aqueous medium into a hydrophobic phase are promoted by ionophores. The properties and applications of rare earth complexes with synthe- tic ionophores are described by Biinzli. Finally, Shen and Ouyang review their own work and that of others in the application of rare earth coordination catalysts in stereospecific polymerization. These Ziegler-Natta type catalysts provide tools for, among other things, the design of electrically conducting polymers. CONTENTS Preface v Contents vii Contents of volumes 1-8 ix 58. R. Reisfeld and C.K. J0rgensen Excited State Phenomena in Vitreous Materials 1 59~ L. Niinist6 and M. Leskel~i Inorganic Complex Compounds H 91 60. J.-C.G. Biinzli Complexes with Synthetic Ionophores 321 61. Zhiquan Shen and Jun Ouyang Rare Earth Coordination Catalysts in Stereospecific Polymerization 395 Errata 429 Subject index 431 vii CONTENTS OF VOLUMES 1-8 VOLUME 1: METALS 1. Z.B. Goldschmidt, Atomic properties (free atom) 1 2. B.J. Beaudry and K.A. Gschneidner, Jr., Preparation and basic properties of the rare earth metals 173 3. S.H. Liu, Electronic structure of rare earth metals 233 4. D.C. Koskenmaki and K.A. Gschneidner, Jr., Cerium 337 5. L.J. Sundstr6m, Low temperature heat capacity of the rare earth metals 379 6. K.A. McEwen, Magnetic and transport properties of the rare earths 411 7. S.K. Sinha, Magnetic structures and inelastic neutron scattering: metals, alloys and com- pounds 489 8. T.E. Scott, Elastic and mechanical properties 591 9. A. Jayaraman, High pressure studies: metals, alloys and compounds 707 10. C. Probst and J. Wittig, Superconductivity: metals, alloys and compounds 749 11. M.B. Maple, L.E. DeLong and B.C. Sales, Kondo effect: alloys and compounds 797 12. M.E Dariel, Diffusion in rare earth metals 847 Subject index 877 VOLUME 2: ALLOYS AND INTERMETALLICS 13. A. Iandelli and A. Palenzona, Crystal chemistry of intermetallic compounds 1 14. H.R. Kirchmayr and C.A. Poldy, Magnetic properties of intermetallic compounds of rare earth metals 55 15. A.E. Clark, Magnetostrictive RFe2 intermetallic compounds 231 16. J.J. Rhyne, Amorphous magnetic rare earth alloys 259 17. E Fulde, Crystal fields 295 18. R.G. Barnes, NMR, EPR and M6ssbauer effect: metals, alloys and compounds 387 19. P. Wachter, Europium chalcogenides: EuO, EuS, EuSe and EuTe 507 20. A. Jayaraman, Valence changes in compounds 575 Subject index 613 VOLUME 3: NON-METALLIC COMPOUNDS- I 21. L.A. Haskin and T.P. Paster, Geochemistry and mineralogy of the rare earths 1 22. J.E. Powell, Separation chemistry 81 23. C.K. JCrgensen, Theoretical chemistry of rare earths 111 24. W.T. Carnall, The absorption and fluorescence spectra of rare earth ions in solution 171 25. L.C. Thompson, Complexes 209 26. G.G. Libowitz and A.J. Maeland, Hydrides 299 27. L. Eyring, The binary rare earth oxides 337 28. D.J.M. Bevan and E. Summerville, Mixed rare earth oxides 401 29. C.P. Khattak and F.F.Y. Wang, Perovskites and garnets 525 30. L.H. Brixner, J~.R. Barkley and W. Jeitschko, Rare earth molybdates (VI) 609 Subject index 655 ix x CONTENTS OF VOLUMES 1-8 VOLUME 4: NON-METALLIC COMPOUNDS- II 31. J. Flahaut, Sulfides, selenides and tellurides 1 32. J.M. Haschke, Halides 89 33. F. Hulliger, Rare earth pnictides 153 34. G. Blase, Chemistry and physics of R-aetivated phosphors 237 35. M.J. Weber, Rare earth lasers 275 36. F.K. Fong, Nonradiative processes of rare-earth ions in crystals 317 37A. J.W. O'Laughlin, Chemical spectrophotometric and polarographic methods 341 37B. S.R. Taylor, Trace element analysis of rare earth elements by spark source mass spectros- copy 359 37C. R.J. Conzemius, Analysis of rare earth matrices by spark source mass spectrometry 377 37D. E.L. DeKalb and V.A. Fassel, Optical atomic emission and absorption methods 405 37E. A.P. D'Silva and V.A. Fassel, X-ray excited optical luminescence of the rare earths 441 37F. F.W.V. Boynton, Neutron activation analysis 457 37G. S. Schuhmann and J.A. Philpotts, Mass-spectrometric stable-isotope dilution analysis for lantha- nides in geochemical materials 471 38. J. Reuben and G.A. Elgavish, Shift reagents and NMR of paramagnetic lanthanide com- plexes 483 39. J. Reuben, Bioinorganic chemistry: lanthanides as probes in systems of biological interest 515 40. T.J. Haley, Toxicity 553 Subject index 587 VOLUME 5 41. M. Gasgnier, Rare earth alloys and compounds as thin films 1 42. E. Gratz and M.J. Zuckermann, Transport properties (electrical resistivity, thermoelectric power and thermal conductivity) of rare earth intermetallic compounds 117 43. F.P. Netzer and E. Bertel, Adsorption and catalysis on rare earth surfaces 217 44. C. Boulesteix, Defects and phase transformation near room temperature in rare earth sesquioxides 321 45. O. Greis and J.M. Haschke, Rare earth fluorides 387 46. C.A. Morrison and R.P. Leavitt, Spectroscopic properties of triply ionized lanthanides in transparent host crystals 461 Subject index 693 VOLUME 6 47. K.H.J. Buschow, Hydrogen absorption in intermetallic compounds 1 48. E. Parth6 and D. Chabot, Crystal structures and crystal chemistry of ternary rare earth-transition metal borides, silieides and homologues 113 49. P. Rogl, Phase equilibria in ternary and higher order systems with rare earth elements and boron 335 50. H.B. Kagan and J.L. Namy, Preparation of divalent ytterbium and samarium derivatives and their use in organic chemistry 525 Subject index 567 CONTENTS OF VOLUMES 1-8 xi VOLUME 7 51. P. Rogl, Phase equilibria in ternary and higher order systems with rare earth elements and silicon 1 52. K.H.J. Buschow, Amorphous alloys 265 53. H. Schumann and W. Genthe, Organometallic compounds of the rare earths 446 Subject index 573 VOLUME 8 54. K.A. Gschneidner, Jr. and F.W. Calderwood, Intra rare earth binary alloys: phase relationships, lattice parameters and systematics 1 55. X. Gao, Polarographic analysis of the rare earths 163 56. M. Leskel~i and L. Niinist6, Inorganic complex compounds I 203 57. J.R. Long, Implications in organic synthesis 335 Errata 375 Subject index 379 Handbook on the Physics and Chem&tryof Rare Earths, edited by K.A. Gschneidner,Jr. and L. Eyring © Elsevier Science PublishersB.V., 1987 Chapter 58 EXCITED STATE PHENOMENA IN VITREOUS MATERIALS Renata REISFELD Department of Inorganic Chem&try, Hebrew University ( Givat-Ram) 91904 Jerusalem, Israel Christian K. JORGENSEN Department of Inorganic, Analytical and Applied Chemistry University of Geneva, CH 1211 Geneva 4, Switzerland Contents 1. Introduction- the vitreous state 3 3.2.4. Rare-earth doped laser 2. Intensities of absorption and glasses 39 emission 10 3.3. Luminescence efficiency and com- 2.1. Judd-Ofelt parameters 13 peting processes 40 2.2. ~2 as indicator of covalent 4. Nonradiative processes 41 bonding 15 4.1. Multiphonon relaxation 42 2.3. ~4 and 06 as indicators of vis- 4.2. Cross-relaxations 47 cosity 21 4.3. Temperature dependence and 2.4. Radiative and factual lifetimes 28 lifetime" of the excited states 50 2.5. Radiative transition probabilities 5. Energy transfer between differing and laser cross sections of rare species 51 earth ions in glasses 31 5.1. Possible mechanisms of energy 2.6. Hole burning 33 transfer 51 3. Luminescence 34 5.1.1. Radiative transfer 52 3.1. Branching ratios 34 5.1.2. Nonradiative transfer 52 3.2. Glass lasers and rare-earth-based 5.1.3. Multipolar interaction 53 luminescent solar concentrators 34 5.1.4. Phonon-assisted transfer 53 3.2.1. Luminescent solar concen- 5.1.5. Energy transfer in the case trators 35 of interaction between 3.2.2. Requirements for glass las- donor ions 54 ers and luminescent solar 5.2. Novel experimental techniques of concentrators: similarities studying energy transfer 55 and differences 36 5.3. Energy transfer between trivalent 3.2.3. Basic parameters of a laser 36 lanthanides 56 2 R.