Table Of ContentHANDBOOK 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)
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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
Description:Handbook on the Physics and Chemistry of Rare Earths: Including Actinides is a continuous series of books covering all aspects of rare earth science, including chemistry, life sciences, materials science, and physics. The book's main emphasis is on rare earth elements [Sc, Y, and the lanthanides (La
