Handbook on the Physics and Chemistry of Rare Earths

670 Pages·2003·8.51 MB·English

by  J.-C. G. Bunzli

Handbook on the Physics and
Chemistry of Rare Earths, volume 33

Elsevier, 2003

Edited by: K. A. Gschneidner, Jr., J.-C. G. Bunzli, and V. K. Pecharsky
ISBN: 978-0-444-51323-6
HandbookonthePhysicsandChemistryofRareEarths
Vol.33
editedbyK.A.Gschneidner,Jr.,J.-C.G.BünzliandV.K.Pecharsky
©2003ElsevierScienceB.V. Allrightsreserved
PREFACE
KarlA.GSCHNEIDNER,Jr.,Jean-ClaudeG.BÜNZLI,and VitalijK.PECHARSKY
These elements perplex us in ourrearches[sic], baffleus in our speculations,and hauntus
in our very dreams. They stretch like an unknown sea before us – mocking, mystifying, and
murmuringstrangerevelationsandpossibilities.
SirWilliamCrookes(February16,1887)
WiththisvolumeoftheHandbookonthePhysicsandChemistryofRareEarthProfs.Jean-
Claude Bünzli, Swiss Federal Institute of Technology, Lausanne, and Vitalij K. Pecharsky,
IowaStateUniversity,AmeshavejoinedProf.KarlA.Gschneidner,Jr.,oneofthefounding
editorsofthisseries,aseditors.ReadersofpriorvolumesoftheHandbookwillnoticethatthe
Prefaceformathaschangedwiththeinclusionofthetitleandauthor(s),plusanappropriate
figurefromeachofthechapters,insteadofjustabriefsummaryofitscontents.
This volume of the Handbook illustrates the rich variety of topics covered by rare earth
science. Three chapters are devoted to the description of solid state compounds: skutteru-
dites (Chapter 211), rare earth-antimony systems (Chapter 212), and rare earth-manganese
perovskites (Chapter 214). Two other reviews deal with solid state properties: one contri-
butionincludesinformationonexistingthermodynamicdataoflanthanidetrihalides(Chap-
ter213)whiletheotheronedescribesopticalpropertiesofrareearthcompoundsunderpres-
sure(Chapter217).Finally,twochaptersfocusonsolutionchemistry.Thestateoftheartin
unravelingsolutionstructureoflanthanide-containingcoordinationcompoundsbyparamag-
neticnuclearmagneticresonanceisoutlinedinChapter215.Thepotentialoftime-resolved,
laser-induced emission spectroscopyfor the analysis of lanthanide and actinide solutions is
presentedandcriticallydiscussedinChapter216.
211FilledSkutterudites
byBrianC.Sales,OakRidge,NationalLaboratory,Tennessee,USA
The lead chapterreviewsthe remarkablephysicalbehaviorsof a distinctivefamily of inter-
metallic compounds – the filled lanthanide skutterudites. These unique compounds, which
havethe RM X stoichiometry(whereR= lanthanides,M =Fe, Ru,andOs,and X=P,
4 12
As and Sb), are best known for their excellent high temperature (>700 K) thermoelectric
properties. But as Brian Sales points out, they also exhibit a rich variety of electronic and
v
vi PREFACE
magneticgroundstates –heavyfermionmediatedsu-
perconductivity,ferromagnetism,antiferromagnetism,
hybridization gaps (Kondo insulator behavior), non-
Fermi-liquid behavior and quantum critical points,
quadrupolarordering,andfield-inducedheavyfermion
states.TheCe-basedphasesexhibit:heavyfermionbe-
havior – CeFe Sb ; non-Fermi liquid behavior and
4 12
possibly a quantum critical point – CeRu Sb ; and
4 12
narrow (hybridized) gap semiconducting behavior –
CeM P (M=Fe,Ru,Os).However,themostexotic
4 12
lanthanideskutteruditeisPrFe P becauseithasboth
4 12
quadrupole order and heavy fermion ground states,
which are extremely close in energy. At low temperatures, <6 K, a magnetic field of 4 T
candrivePrFe P betweenthetwo groundstatesleadingtosomeunusualphysicalproper-
4 12
ties. Superconductivityis observedin mostLaM X phases, aswellas twoof thePr skut-
4 12
terudites,whilethosecontainingNd,Eu,GdandTbexhibitmagneticordering.Interestingly
enough,EuFe P hasthehighestferromagneticorderingtemperature,100K,oftheRM X
4 12 4 12
compounds.
212RareEarth-AntimonySystems
byOksanaSologub,UniversityofWien,Austria,
PetroSalamakha,InstituteofNuclearTechnology,Sacavem,Portugal
Anextensivecompilationofthestructuraland
physicalpropertiesofrareearth-antimonyand
ofsome rareearth-uranium-antimonysystems
is presented. The first part of the review col-
lects the phase diagrams of binary R–M and
(cid:2)
ternaryR–M–Sb,R–R–SborR–U–Sbmetal
antimonides,alongwith their crystallographic
data and the experimental synthetic methods
used to isolate the compounds.A few quater-
nary systems are also presented. The chapter
then focuses on the properties of ternary sys-
tems. Atomic coordinates are given for more
than forty types of crystal structures, and magnetic susceptibility and resistivity data are
tabulated. The chapter ends with a generaldiscussion on the peculiarities of the rare earth-
antimonyinteraction.Thebinarysystemshavebeensystematicallystudiedandusuallyyield
stoichiometric compounds, R Sb , R Sb , RSb, and RSb . Ternary systems are less well
5 3 4 3 2
known,sothatgeneraltrendsaremoredifficulttodetermine,butseveralfamiliesofternary
antimonidescrystallizewithstructuresderivedfromthoseofbinarytypes.
PREFACE vii
213ThermodynamicPropertiesoftheLanthanide(III)Halides
byRudyI.M.KoningsandA.Kovács,InstituteofTransuraniumElements,Karlsruhe,
Germany
Thetrivalentlanthanidehalideshavehadand
still have an important technological rele-
vance.Inthe1950sand1960s,fluorideswere
studied within the frame of the molten salt
nuclear reactor project and a pyrochemical
process was developed for the reprocessing
of metal fuel. Nowadays, these technologies
find a renewed interest within the frame of
actinide-lanthanideseparationfornuclearwastemanagement.Moreover,chlorides,bromides
andiodidesarefindingapplicationinlightingindustrytoimprovetheperformancesofhigh-
pressuredischargelamps.The authorsdescribethe thermodynamicpropertiesof lanthanide
halidesinathoroughreview,whichemphasizesthemajortrendsinthedata.Polymorphism,
low-andhigh-temperatureheatcapacityandtheenthalpyofformationofthesolidstate tri-
halidesarepresentedfirstwhilethelastsectionsofthereviewdealwithheatcapacityofthe
liquidsandtheheatcapacityandenthalpyofformationofthegaseoustrihalides.
214RareEarth-ManganesePerovskites
byJohnB.Goodenough,UniversityofTexasatAustin,USA
Rare earth ions influence the physical prop-
erties of rare earth-manganese perovskites
R1−xAxMnO3(whereAisanalkalineearthcation)
through a geometric factor, which determines the
bendingoftheMn–O–Mnangleinordertoachieve
a match between the Mn–O and A–O equilibrium
bond lengths. The author describes how this influ-
ence,alongwithothersubtleelectroniceffectsdue
totheJahn-Tellerdistortionandtointeractionswith
σ-bonding electrons, may be used to design mate-
rialswithunusualphysicalproperties(e.g.,magne-
tization, resistivity, thermal conductivity) that may
provetechnologicallyuseful.Thechapterstartswith
essentialconceptsrelatedtostructuralaspects(theso-calledtolerancefactor)andelectronic
considerations, such as ligand-field effects, interatomic interactions and localized-itinerant
electronic transitions. For instance, constraining the itinerant electrons to two-dimensional
planes or one-dimensional chains, restricts ferromagnetic double-exchange coupling to the
metallic planes or chains. Following this introductory part, both single- and double-valent
perovskitesarecomprehensivelyreviewedtakingtheseconceptsintoconsideration.
viii PREFACE
215ParamagneticNMRLanthanideInducedShiftforExtractingSolutionStructure
byClaudePiguet,UniversityofGeneva,Switzerland,
CarlosF.G.C.Geraldes,UniversityofCoimbra,Portugal
(cid:1) (cid:3) (cid:1) (cid:3)
(cid:2)n (cid:2)n Theauthorssummarizethelatestadvancesinone
δpara Fm (cid:4)S (cid:5) + B2mGm C
ij i z j 0 i j fascinating technique enabling chemists to un-
m=l m=l
ravelthe solutionstructuresof coordinationand
supramolecular compounds, nuclear magnetic
resonance of paramagnetic species. While para-
magnetismisoftenconsideredasbeingahandi-
captointerpretNMRspectra,detailedstructural
andelectronicinformationcanbeextractedfrom
theseparationofthecontactandpseudo-contact
contributionstotheparamagneticNMRshiftsin-
duced by the presence of a lanthanide ion. In a
precedentchapteroftheHandbook(ch.153,vol.23),JohnForsberghasreportedontheuse
of a one-nucleus method for determining the structure of axial compounds. Here, the au-
thorsoutlinethe generaltheoryand thenfocuson thelimitationsofBleaney’sapproachfor
modelingparamagneticanisotropiesandonthedescriptionofthenewtwo-andthree-nuclei
methods,whichareindependentofchangesincrystalfieldparametersandhyperfinecoupling
constants. A comprehensivesurveyof the application of these methodsto coordinationand
supramolecularcompoundswiththree-andfourfoldsymmetryispresented.
216LanthanideandActinideSolutionChemistryStudiedbyTime-ResolvedEmission
Spectroscopy
byIsabelleBillard,InstitutdeRecherchesSubatomiques,Strasbourg,France
Time-resolved emission spectroscopy is gain-
ingimportanceinthestudyofvariouschemical
aspects of luminescentlanthanideand actinide
ions in solution. Here, the author describes
the theoretical background of this analytical
technique and discusses potentialapplications.
Changes in the solution composition and/or in
themetal-ioninnercoordinationsphereinduce
modifications of the spectroscopic properties
oftheluminescentspecies.Bothtime-resolved
spectraandluminescencedecaysconveyuseful
information. Several models, which are com-
monly used to extract physico-chemicalinfor-
mation from the spectroscopic data, are presented and critically compared. Applications of
time-resolvedemissionspectroscopyarenumerousandrangefromthecharacterizationofthe
PREFACE ix
metalionsolvationsphere,tothe evaluationofreactionrate constantsandequilibriumcon-
stants,andtothequantitativedeterminationofultratraceamountsoflanthanideandactinide
ions in solution, an aspect of importance in environmentalchemistry. Potential uses of the
techniquetostudymicellarsystemsandionicliquidsareoutlined.
217OpticalStudiesonNon-MetallicRareEarthCompoundsunderPressure
byThomasTröster,UniversityofPaderborn,Germany
In a captivating review, the author surveys
the optical properties of non-metallic com-
poundsunderpressure.Therelationshipbe-
tween the optical properties of compounds
and their microscopic structure has always
triggered a lot of interest and has been
regarded as a fundamental problem. Rare
earthions with partially filled 4f shells pro-
videadetailedfingerprintofthesurrounding
arrangement of atoms and their interaction
with f-electrons. Minute effects can be evi-
denced by measuring the spectra in various
hostslattices.However,thepresenceofimpuritiessomewhatlimitstheusefulnessoftheem-
piricaldata.Incontrast,applyinghigh-pressuretoasystemusuallyinducescontinuousvaria-
tionsinparameters,suchasinteratomicdistances,influencingtheopticalproperties.Thatis,
theexperimentalistscanaltertheenergydifferencebetweentwostates,almostatwill,hence-
forthgatheringinformationontheirmutualinfluence.Highpressuretechniquesaredescribed
andexperimentaldataonenergylevels,crystalfieldsplittings,intensitiesandlifetimesoff-f
transitions,aswellasonelectron–phononinteractions,aresurveyed.
CONTENTS
Preface v
Contents xi
ContentsofVolumes1–32 xiii
211.BrianC.Sales
Filledskutterudites 1
212.OksanaL.SologubandPetroS.Salamakha
Rareearth–antimonysystems 35
213.R.J.M.KoningsandA.Kovács
Thermodynamicpropertiesofthelanthanide(III)halides 147
214.JohnB.Goodenough
Rareearth–manganeseperovskites 249
215.ClaudePiguetandCarlosF.G.C.Geraldes
ParamagneticNMRlanthanideinducedshiftsforextractingsolutionstructures 353
216.IsabelleBillard
Lanthanideandactinidesolutionchemistryasstudiedbytime-resolvedemissionspec-
troscopy 465
217.ThomasTröster
Opticalstudiesofnon-metalliccompoundsunderpressure 515
Authorindex 591
Subjectindex 637
xi
CONTENTS OF VOLUMES1–32
VOLUME1:Metals
1978,1strepr.1982,2ndrepr.1991;ISBN0-444-85020-1
1. Z.B.Goldschmidt,Atomicproperties(freeatom) 1
2. B.J.BeaudryandK.A.GschneidnerJr,Preparationandbasicpropertiesoftherareearthmetals 173
3. S.H.Liu,Electronicstructureofrareearthmetals 233
4. D.C.KoskenmakiandK.A.GschneidnerJr,Cerium 337
5. L.J.Sundström,Lowtemperatureheatcapacityoftherareearthmetals 379
6. K.A.McEwen,Magneticandtransportpropertiesoftherareearths 411
7. S.K.Sinha,Magneticstructuresandinelasticneutronscattering:metals,alloysandcompounds 489
8. T.E.Scott,Elasticandmechanicalproperties 591
9. A.Jayaraman,Highpressurestudies:metals,alloysandcompounds 707
10. C.ProbstandJ.Wittig,Superconductivity:metals,alloysandcompounds 749
11. M.B.Maple,L.E.DeLongandB.C.Sales,Kondoeffect:alloysandcompounds 797
12. M.P.Dariel,Diffusioninrareearthmetals 847
Subjectindex 877
VOLUME2:Alloysandintermetallics
1979,1strepr.1982,2ndrepr.1991;ISBN0-444-85021-X
13. A.IandelliandA.Palenzona,Crystalchemistryofintermetalliccompounds 1
14. H.R.KirchmayrandC.A.Poldy,Magneticpropertiesofintermetalliccompoundsofrareearthmetals 55
15. A.E.Clark,MagnetostrictiveRFe2intermetalliccompounds 231
16. J.J.Rhyne,Amorphousmagneticrareearthalloys 259
17. P.Fulde,Crystalfields 295
18. R.G.Barnes,NMR,EPRandMössbauereffect:metals,alloysandcompounds 387
19. P.Wachter,Europiumchalcogenides:EuO,EuS,EuSeandEuTe 507
20. A.Jayaraman,Valencechangesincompounds 575
Subjectindex 613
VOLUME3:Non-metalliccompounds–I
1979,1strepr.1984;ISBN0-444-85215-8
21. L.A.HaskinandT.P.Paster,Geochemistryandmineralogyoftherareearths 1
22. J.E.Powell,Separationchemistry 81
23. C.K.Jørgensen,Theoreticalchemistryofrareearths 111
24. W.T.Carnall,Theabsorptionandfluorescencespectraofrareearthionsinsolution 171
25. L.C.Thompson,Complexes 209
26. G.G.LibowitzandA.J.Maeland,Hydrides 299
27. L.Eyring,Thebinaryrareearthoxides 337
28. D.J.M.SevanandE.Summerville,Mixedrareearthoxides 401
29. C.P.KhattakandF.F.Y.Wang,Perovskitesandgarnets 525
30. L.H.Brixner,J.R.BarkleyandW.Jeitschko,Rareearthmolybdates(VI) 609
Subjectindex 655
xiii
xiv CONTENTSOFVOLUMES1–32
VOLUME4:Non-metalliccompounds–II
1979,1strepr.1984;ISBN0-444-85216-6
31. J.Flahaut,Sulfides,selenidesandtellurides 1
32. J.M.Haschke,Halides 89
33. F.Hulliger,Rareearthpnictides 153
34. G.Blasse,ChemistryandphysicsofR-activatedphosphors 237
35. M.J.Weber,Rareearthlasers 275
36. F.K.Fong,Nonradiativeprocessesofrare-earthionsincrystals 317
37A. J.W.O’Laughlin,Chemicalspectrophotometricandpolarographicmethods 341
37B. S.R.Taylor,Traceelementanalysisofrareearthelementsbysparksourcemassspectroscopy 359
37C. R.J.Conzemius,Analysisofrareearthmatricesbysparksourcemassspectrometry 377
37D. E.L.DeKalbandV.A.Fassel,Opticalatomicemissionandabsorptionmethods 405
37E. A.P.D’SilvaandV.A.Fassel,X-rayexcitedopticalluminescenceoftherareearths 441
37F. F.W.V.Boynton,Neutronactivationanalysis 457
37G. S.SchuhmannandJ.A.Philpotts,Mass-spectrometricstable-isotopedilutionanalysisforlanthanidesingeo-
chemicalmaterials 471
38. J.ReubenandG.A.Elgavish,ShiftreagentsandNMRofparamagneticlanthanidecomplexes 483
39. J.Reuben,Bioinorganicchemistry:lanthanidesasprobesinsystemsofbiologicalinterest 515
40. T.J.Haley,Toxicity 553
Subjectindex 587
VOLUME5
1982,1strepr.1984;ISBN0-444-86375-3
41. M.Gasgnier,Rareearthalloysandcompoundsasthinfilms 1
42. E.GratzandM.J.Zuckermann,Transportproperties(electricalresitivity,thermoelectricpowerthermalconduc-
tivity)ofrareearthintermetalliccompounds 117
43. F.P.NetzerandE.Bertel,Adsorptionandcatalysisonrareearthsurfaces 217
44. C.Boulesteix,Defectsandphasetransformationnearroomtemperatureinrareearthsesquioxides 321
45. O.GreisandJ.M.Haschke,Rareearthfluorides 387
46. C.A.MorrisonandR.P.Leavitt,Spectroscopicpropertiesoftriplyionizedlanthanidesintransparenthostcrystals
461
Subjectindex 693
VOLUME6
1984;ISBN0-444-86592-6
47. K.H.J.Buschow,Hydrogenabsorptioninintermetalliccompounds 1
48. E.ParthéandB.Chabot,Crystalstructuresandcrystalchemistryofternaryrareearth–transitionmetalborides,
silicidesandhomologues 113
49. P.Rogl,Phaseequilibriainternaryandhigherordersystemswithrareearthelementsandboron 335
50. H.B.KaganandJ.L.Namy,Preparationofdivalentytterbiumandsamariumderivativesandtheiruseinorganic
chemistry 525
Subjectindex 567
VOLUME7
1984;ISBN0-444-86851-8
51. P.Rogl,Phaseequilibriainternaryandhigherordersystemswithrareearthelementsandsilicon 1
52. K.H.J.Buschow,Amorphousalloys 265
53. H.SchumannandW.Genthe,Organometalliccompoundsoftherareearths 446
Subjectindex 573
CONTENTSOFVOLUMES1–32 xv
VOLUME8
1986;ISBN0-444-86971-9
54. K.A.GschneidnerJrandF.W.Calderwood,Intrarareearthbinaryalloys:phaserelationships,latticeparameters
andsystematics 1
55. X.Gao,Polarographicanalysisoftherareearths 163
56. M.LeskeläandL.Niinistö,InorganiccomplexcompoundsI 203
57. J.R.Long,Implicationsinorganicsynthesis 335
Errata 375
Subjectindex 379
VOLUME9
1987;ISBN0-444-87045-8
58. R.ReisfeldandC.K.Jørgensen,Excitedstatephenomenainvitreousmaterials 1
59. L.NiinistöandM.Leskelä,InorganiccomplexcompoundsII 91
60. J.-C.G.Bünzli,Complexeswithsyntheticionophores 321
61. ZhiquanShenandJunOuyang,Rareearthcoordinationcatalysisinstereospecificpolymerization 395
Errata 429
Subjectindex 431
VOLUME10:Highenergyspectroscopy
1988;ISBN0-444-87063-6
62. Y.BaerandW.-D.Schneider,High-energyspectroscopyoflanthanidematerials–Anoverview 1
63. M.CampagnaandF.U.Hillebrecht,f-electronhybridizationanddynamicalscreeningofcoreholesinintermetal-
liccompounds 75
64. O.GunnarssonandK.Schönhammer,Many-bodyformulationofspectraofmixedvalencesystems 103
65. A.J.Freeman,B.I.MinandM.R.Norman,Localdensitysupercelltheoryofphotoemissionandinversephoto-
emissionspectra 165
66. D.W.LynchandJ.H.Weaver,PhotoemissionofCeanditscompounds 231
67. S.Hüfner,Photoemissioninchalcogenides 301
68. J.F.HerbstandJ.W.Wilkins,Calculationof4fexcitationenergiesinthemetalsandrelevancetomixedvalence
systems 321
69. B.JohanssonandN.Mårtensson,Thermodynamicaspectsof4flevelsinmetalsandcompounds 361
70. F.U.HillebrechtandM.Campagna,Bremsstrahlungisochromatspectroscopyofalloysandmixedvalentcom-
pounds 425
71. J.Röhler,X-rayabsorptionandemissionspectra 453
72. F.P.NetzerandJ.A.D.Matthew,Inelasticelectronscatteringmeasurements 547
Subjectindex 601
VOLUME11:Two-hundred-yearimpactofrareearthsonscience
1988;ISBN0-444-87080-6
H.J.Svec,Prologue 1
73. F.Szabadváry,Thehistoryofthediscoveryandseparationoftherareearths 33
74. B.R.Judd,Atomictheoryandopticalspectroscopy 81
75. C.K.Jørgensen,Influenceofrareearthsonchemicalunderstandingandclassification 197
76. J.J.Rhyne,Highlightsfromtheexoticphenomenaoflanthanidemagnetism 293
77. B.Bleaney,Magneticresonancespectroscopyandhyperfineinteractions 323
78. K.A.GschneidnerJrandA.H.Daane,Physicalmetallurgy 409
79. S.R.TaylorandS.M.McLennan,Thesignificanceoftherareearthsingeochemistryandcosmochemistry 485
Errata 579
Subjectindex 581