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HANDBOOK ON THE PHYSICS AND CHEMISTRY OF RARE EARTHS Advisory Editorial Board GIN-YA ADACHI Kobe, Japan WILLIAM J. EVANS Irvine, USA YURI GRIN Dresden, Germany SUZAN M. KAUZLARICH Davis, USA MICHAEL F. REID Canterbury, New Zealand CHUNHUA YAN Beijing, P.R. China Editors Emeritus KARL A. GSCHNEIDNER, JR† Ames, USA LEROY EYRINGw Tempe, USA † Deceased (2016) w Deceased (2005) North-HollandisanimprintofElsevier Radarweg29,POBox211,1000AEAmsterdam,TheNetherlands TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom Copyright©2016ElsevierB.V.Allrightsreserved. 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Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgein evaluatingandusinganyinformation,methods,compounds,orexperimentsdescribedherein.In usingsuchinformationormethodstheyshouldbemindfuloftheirownsafetyandthesafetyof others,includingpartiesforwhomtheyhaveaprofessionalresponsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors, assumeanyliabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproducts liability,negligenceorotherwise,orfromanyuseoroperationofanymethods,products, instructions,orideascontainedinthematerialherein. ISBN:978-0-444-63851-9 ISSN:0168-1273 ForinformationonallNorth-Hollandpublications visitourwebsiteathttps://www.elsevier.com/ Publisher:ZoeKruze AcquisitionEditor:PoppyGarraway EditorialProjectManager:ShellieBryant ProductionProjectManager:RadhakrishnanLakshmanan CoverDesigner:MarkRogers TypesetbySPiGlobal,India Contributors NumbersinParenthesesindicatethepagesonwhichtheauthor’scontributionsbegin. Eleonora Aneggi(209),UniversitàdiUdine,Udine, Italy Zoila Barandiara´n (65), Instituto Universitario de Ciencia de Materiales Nicola´s Cabrera,andCondensedMatterPhysicsCenter(IFIMAC),UniversidadAuto´noma de Madrid,Madrid, Spain Marta Boaro(209),UniversitàdiUdine, Udine,Italy Jean-ClaudeG.Bu€nzli(141),InstituteofChemicalSciencesandEngineering,Swiss FederalInstituteofTechnologyLausanne(EPFL),Lausanne,Switzerland;Haimen Institute ofScience and Technology, HongKong BaptistUniversity, Haimen, PR China BanglinChen(243),StateKeyLaboratoryofSiliconMaterials,CyrusTangCenterfor Sensor Materials and Applications, School of Materials Science and Engineering, Zhejiang University, Hangzhou, China; Universityof TexasatSan Antonio, San Antonio,TX,United States SaraColussi (209),Universitàdi Udine,Udine,Italy YuanjingCui(243),StateKeyLaboratoryofSiliconMaterials,CyrusTangCenterfor Sensor Materials and Applications, School of Materials Science and Engineering, Zhejiang University, Hangzhou, China Carla de Leitenburg (209), UniversitàdiUdine, Udine,Italy Roderick G. Eggert (19), Critical Materials Institute, Colorado School of Mines, Golden, CO,UnitedStates William J.Evans (337), Universityof California,Irvine,CA,UnitedStates DanteGatteschi(91),DipartimentodiChimica“U.Schiff”andINSTMUdRFirenze, Universitàdegli StudidiFirenze,Sesto Fiorentino,Italy KarlA.GschneidnerJr.(1,19),TheAmesLaboratory,IowaStateUniversity;Critical Materials Institute,The Ames Laboratory,Ames,IA, UnitedStates Susan M.Kauzlarich (177),University ofCalifornia, Davis,CA,UnitedStates Nasrin Kazem (177),Universityof California,Davis,CA, UnitedStates AlexanderH.King(19),CriticalMaterialsInstitute,TheAmesLaboratory,Ames,IA, United States Lin-Dong Li (301), Beijing National Laboratory for Molecular Sciences, State Key Laboratory ofRareEarth MaterialsChemistryand Applications,PKU-HKUJoint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry andMolecular Engineering, Peking University, Beijing, China vii viii Contributors Anja-VerenaMudring(395),IowaStateUniversityandAmesLaboratory,Ames,IA, UnitedStates DavidParker (269),Durham University, Durham,UnitedKingdom DenisProdius (395),Iowa State Universityand AmesLaboratory, Ames,IA, UnitedStates GuodongQian(243),State KeyLaboratory ofSilicon Materials,Cyrus Tang Center for Sensor Materials and Applications, School of Materials Science and Engineering, ZhejiangUniversity, Hangzhou, China MichaelF.Reid(47),UniversityofCanterbury,Christchurch;TheDodd-WallsCentre for Quantum and Photonic Technologies, Dunedin; The MacDiarmid Institute for Advanced Materials and Nanotechnology,Wellington, NewZealand LuisSeijo(65),InstitutoUniversitariodeCienciadeMaterialesNicola´sCabrera,and Condensed Matter Physics Center (IFIMAC), Universidad Auto´noma de Madrid, Madrid,Spain RobertaSessoli(91),DipartimentodiChimica“U.Schiff”andINSTMUdRFirenze, Universitàdegli StudidiFirenze,Sesto Fiorentino,Italy LorenzoSorace(91),DipartimentodiChimica“U.Schiff”andINSTMUdRFirenze, Universitàdegli StudidiFirenze,Sesto Fiorentino,Italy Ling-DongSun(301),BeijingNationalLaboratoryforMolecularSciences,StateKey LaboratoryofRareEarth Materials Chemistryand Applications,PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of ChemistryandMolecular Engineering, Peking University, Beijing, China Alessandro Trovarelli (209),Universitàdi Udine,Udine,Italy DavidH. Woen(337),University ofCalifornia, Irvine,CA,UnitedStates Chun-HuaYan(301),BeijingNationalLaboratoryforMolecularSciences,StateKey LaboratoryofRareEarth Materials Chemistryand Applications,PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of ChemistryandMolecular Engineering, Peking University, Beijing, China Jun Zhang (243), State Key Laboratory of Silicon Materials, Cyrus Tang Center for Sensor Materials and Applications, School of Materials Science and Engineering, ZhejiangUniversity, Hangzhou, China Xiao-YuZheng(301),BeijingNationalLaboratoryforMolecularSciences,StateKey LaboratoryofRareEarth Materials Chemistryand Applications,PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of ChemistryandMolecular Engineering, Peking University, Beijing, China Preface These elements perplex us in our reaches [sic], baffle us in our speculations, and haunt us in our very dreams. They stretch like an unknown sea before us—mocking,mystifying,andmurmuringstrangerevelationsandpossibilities. SirWilliamCrookes(February 16,1887) This volume of the Handbook on the Physics and Chemistry of Rare Earths has a very special meaning for the series. First and sadly, the initiator of the series,KarlA.GschneidnerJr.,passedawayonApril27,2016inhis86thyear. He had retired three and a half months earlier from his positions of Anson Marston Distinguished Professor at the Department of Materials Science and Engineering at Iowa State University, Senior Scientist at the Department ofEnergyAmesLaboratory,andChiefScientificOfficerattheCriticalMateri- als Institute, Ames Laboratory, Ames, Iowa, and was working on the first chapter of this volume. Karl started the series with Professor LeRoy Eyring (1919–2005)bysolicitingandeditinganinitialsetoffourvolumesencompass- ing40chapterspublishedin1978and1979.Sincethen,hehasalwaysbeenan ix x Preface inspiring editor, finding adequate contributors and convincing them to write authoritative reviews within their respective research fields. Karl served as senior editor for the first 41 volumes of the series. He will be remembered as adedicatedscientist,greatcommunicator,andparticularlyreceptivegentleman. A full-scale tribute to Karl will appear in Volume 51. In the preface of the first volume of the series Karl and LeRoy wrote: “[We] have invited experts in various areas write comprehensive, broad, up-to-date, and critical reviews. Some of the subjects were chosen because they are mature and still quite active; others because they are essential as background information and for reference; and some topics because they are relatively new and exciting areas of research.”In a way, jubilee Volume 50 is somehow mimicking this approach. The editors have asked prominent experts in rare-earth physics, chemistry, and materials sciences to come up with short perspective essays not meant to be comprehensive but, rather, showing how a given topic evolved in response to societal and/or scientific challenges and how one can imagine its future development. Given the explosion of rare-earth research during the past two decades, covering all facets of rare-earth science and technology was of course simply impossible, but much in the spirit of the founding fathers of the series, the editors tried to keep a balance between physics, chemistry, basic science, applications, and resources. Volume 50 features 13 chapters. The first one (Chapter 282) shows how systematic analysis of basic data, e.g., element radii or melting temperatures, may become a powerful tool for predicting properties that can be considered asbeingunusual,suchascontractionofionicradiiorvariationsinthesolubil- ityofalloys.InChapter283,theauthorsdefinetheconceptofcriticalmateri- als, analyze the supplies of rare earths that have become the focus of much attentionrecently,anddescribetheresearchthatneedstoreducesupply-chain risks. The next two reviews deal with theories developed for understanding spectroscopic properties of the lanthanides. Chapter 284 puts current under- standing into historical perspective and presents the impact of theories and modelssuchascrystalfieldandJudd–OfelttheoriesorNewmansuperposition model.ThesubjectofChapter285isentirelyfocusedonabinitiocalculations thatarecomparedtoempiricalmodels;inaddition,theirpotentialforpredict- ing properties of luminescent materials is assessed. With Chapter 286, the reader is discovering the whereabouts pertaining to the design of new molec- ular materials, single-ion (or molecule) magnets; the occurrence of magnetic bistability is investigated with respect to anisotropy and exchange interac- tions. Luminescent materials are one of the key applications of lanthanides; Chapter 287 is unfolding the long path from the first discoveries at the end of the 19th century to present high-technology uses, as well as pointing to cutting-edge developing fields. Transforming heat into electricity is the sub- ject of Chapter 288; contributions of lanthanides to thermoelectric materials are highlighted with reference to newly discovered Zintl phase compounds, Preface xi clathrates, and filled skutterudites that yield more efficient thermoelectric materials. One of the oldest industrial applications of rare earths is cata- lysis, and Chapter 289 takes the reader into the amazing world of cerium dioxide, an oxygen storage compound initially used in automotive three- way catalysts but which enters presently in the composition of numerous catalytic processes, including water splitting and cell fuel technology. The next chapter (Chapter 290) describes the design of porous coordination polymers, also called metal–organic frameworks, which are tailored for luminescence applications in ratiometric sensing, white light-emitting de- vices, bioanalysis, bioimaging, and thermometry. Coordination chemistry isalsoinactioninChapter291inwhichacriticalassessmentofthetheoret- ical background of magnetic anisotropy and relaxation is presented in view of the use of paramagnetic lanthanide complexes in medical imaging; the review is complemented by considerations on luminescent properties. Chapter 292 is also concerned with magnetic resonance imaging but with emphasis on the design of contrast agents based on nanoparticles; the latter can be tailored for fulfilling various functionalities, including multimodal imagingapplications.Thenextreview(Chapter293)describeswhatappears to be a major and unique discovery in organometallic chemistry of f-elements, namely the isolation of divalentcomplexes for theentirelantha- nide series, yttrium, uranium, and thorium; optical and magnetic data show that some of the divalent lanthanide ions have 4fn+1 electronic configura- tions,others4fn5d1,whileafewarecrossoverionsadoptingoneortheother configuration depending on the ligand. The final chapter (Chapter 294) explores a still relatively unknown group of compounds: rare-earth ionic liquids in which rare earth ions are part of either the cation or the anion; the structures of these new compounds with large innovation potential are described in detail. Althoughquiterestrictiveinthechoiceofsubjects,thisvolumeshowsthe ubiquitous contribution of lanthanides to many fields of technology and sci- ence. The resulting panorama is diagnostic of a vivid research field in full expansion and not hesitating to deal with entirely new concepts. xii Preface CHAPTER 282: SYSTEMATICS ✠ Karl A. Gschneidner Jr. The Ames Laboratory, Iowa State University, Ames, IA, United States 2.2 Lanthanides 2.1 2.0 Valence=2 Å) ( s u 1.9 di a c r β alli 1.8 γ Valence=3 et M α 1.7 Valence=4 1.6 58 60 62 64 66 68 70 La Ce Pr NdPmSm Eu Gd Tb Dy Ho Er Tm Yb Lu Altogether,therareearthsrepresentthelargestfraction(about1/6)ofnat- urally occurring elements. Over the last 60 years, many of these elements havebecomeindispensableformoderntechnology,andthefamilyasawhole hasbecomeaposterchildfordemonstratingthevitalroleanalysesofsystem- aticsandanomaliesplayinscience.Indeed,asystematicanalysisoftrendsin structure and properties of materials moving from one member of the rare earthfamilytoanotherhasoftenresultedincorrectpredictionsthatlaterhave been verified either theoretically or experimentally or both. Systematics is a powerfultoolinscience;inthepast,ithasforinstancepredictedyetunknown elements. Applied to rare earths, it has revealed the unusual valence state of Eu and Yb in the metals or the lanthanide contraction. This chapter briefly reviews successfulapplications of systematics that broughtabout agreatdeal ofunderstandingofthefundamentalsofchemistry,physics,andmaterialssci- ence of rare earths and their compounds. Among the latter, metals and alloys represent an interesting field of application for systematics that led to under- standing anomalous solubility or predicting entropies of fusion. The concept is also extended to some examples in the actinide series. ✠DeceasedApril27,2016. Preface xiii CHAPTER 283: THE RARE EARTHS AS CRITICAL MATERIALS Alexander H. King*, Roderick G. Eggert†, and Karl A. Gschneidner Jr.*,✠ *Critical Materials Institute, The Ames Laboratory, Ames, IA, United States. E-mail: [email protected] †CriticalMaterialsInstitute,ColoradoSchoolofMines,Golden,CO,United States Recent increase in the demand for rare earth elements (REEs), especially dysprosiumandterbiumusedinthepermanentmagnetindustry,ismodifying theindustrialapproachtoREEmineralogyandresources.Thisisamplifiedby the REE supply restrictions outside of China and by the fact that rare earths are never mined individually but always as mixtures with various composi- tions. These compositions, however, do not necessarily correspond to the demand for individual rare earths. Some elements are in surplus (La, Ce), while others are in tight supply (or more utilized) and are classified as “critical.” The latter include yttrium, neodymium, europium, terbium, and dysprosium.Explorationhasnowbeenextendedworldwidetosecurethesup- ply of REEs, especially the heavier ones (HREEs, Gd–Lu). In recent years, various attempts have been made to produce HREEs from unconventional sources, such as peralkaline igneous rocks or deep-sea muds (see Vol. 46, Chapter 268, and Vol. 49, Chapter 279). Potential sources of REEs are reviewed in this chapter with a focus on HREEs, which are the most critical group of elements for future green tech- nologies. The geochemistry and mineralogy of rare earths are first described ✠DeceasedApril27,2016. xiv Preface before focusing on deposits. Properties of ion-adsorption and apatite deposits are detailed in view of their importance for heavier REEs. The authors con- clude that in the future the most promising source of rare earths will be apatite ores. CHAPTER 284: THEORY OF RARE-EARTH ELECTRONIC STRUCTURE AND SPECTROSCOPY Michael F. Reid University of Canterbury, Christchurch, New Zealand. E-mail: [email protected] Theoretical analysis and understanding of lanthanide spectra have been importanttothedevelopmentoflaser,phosphor,andscintillatormaterialsthat are currently ubiquitous in modern life. Analysis techniques developed in the 1960s followed the reporting of high-quality optical spectra in the 1950s by several laboratories and could become effective thanks to developments in computer technology making calculations requiring diagonalization of large matrices tractable. This theoretical work led to two key advances, namely the description of an accurate Hamiltonian operator allowing precise descrip- tion of energy levels and a model for the intensity of the transitions. Current theoretical understanding of electronic structure and spectroscopy ofrare-earthionsinacondensed-matterenvironmentisreviewedinthischap- ter. The development of the crystal-field effective Hamiltonian for the 4fn configuration, and its extension to the 4fn(cid:1)15d configuration, is discussed. The addition of hyperfine and magnetic interactions is reviewed, as well as the use of magnetic-splitting data to improve crystal-field fitting. Judd–Ofelt theoryandselectionrulesforthevarioustransitionsencounteredinlanthanide optical spectra are also scrutinized before presenting Newman superposition model as an analysis technique for both crystal-field and transition-intensity
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