Handbook on the Physics and Chemistry of Rare Earths.

411 Pages·2009·10.33 MB·English

HANDBOOK ON THE PHYSICS AND CHEMISTRY
OF RARE EARTHS
Advisory Editorial Board
G.-y. ADACHI,
Kobe, Japan
W.J. EVANS,
Irvine, USA
S.M. KAUZLARICH,
Davis, USA
G.H. LANDER
, Karlsruhe, Germany
M.F. REID,
Christchurch, New Zealand
Editor Emeritus
LeRoy EYRING(cid:1),
Tempe, USA
(cid:1)Deceased.
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PREFACE
KarlA.GschneidnerJr.,Jean-ClaudeG.Bu¨nzli,
VitalijK.Pecharsky
Theseelementsperplexusinourrearches[sic],baffleusinourspeculations,andhauntus
inourverydreams.Theystretchlikeanunknownseabeforeus–mocking,mystifying,and
murmuringstrangerevelationsandpossibilities.
SirWilliamCrookes(February16,1887)
ThisvolumeoftheHandbookonthePhysicsandChemistryofRareEarthsaddsthree
newchapterstotheseries, describingthreedifferentaspectsofrare-earthscience.
Thevolumeopenswithanoverviewofthedualnatureof4fstatesinthelanthanides
(Chapter241).Itisfollowedbyareviewofthetemperature-dependentbehaviorsof
aluminatesandgallates,thestructuresofwhicharebasedonthesimple,yetflexible,
cubicperovskitemodel(Chapter242).Thelastchapterdescribesthecurrentstate-
of-the-artinluminescenceofpolyoxometallolanthanoatesandtheirphotochemistry
leadingtotheformationofhighlycolorednano-rings(Chapter243).
CHAPTER 241. THE DUAL, LOCALIZED OR BAND-LIKE, CHARACTER
OF THE 4f STATES
By W. M. TEMMERMAN
Daresbury Laboratory, Warrington, UK
L. PETIT AND A. SVANE
University of Aarhus, Aarhus, Denmark
Z. SZOTEK AND M. LU¨DERS
Daresbury Laboratory, Warrington, UK
P. STRANGE
University of Kent, Canterbury, Kent, UK
J. B. STAUNTON AND I. D. HUGHES
University of Warwick, Coventry, UK, and
B. L. GYORFFY
University of Bristol, Bristol UK
Theopeningchapterdescribesthedualcharacterofthe4fcoreelectronsthatmay
eitherbepartofthevalencestatesorbeinertandformpartofthecoreusingfirst
principlestheory.Here,W.M.Temmermanandcoauthorsbeginwithareviewof
therelevantphysical,electronic,andmagneticpropertiesoflanthanidematerials.
v
vi Preface
1.0 4f localized
0.8
1500
0.6
0.4
T (K) 1000 α-Ce 0.2
0.0 4f delocalized
+
500
γ-Ce
0
0 20 40 60 80 100
p (kbar)
Theythengiveabriefoverviewoftheapplicabletheoreticalmethodsbasedonthe
density functional theory, with the focus on the self-interaction-corrected local
spindensityapproximationmethod,and,inparticular,thefullimplementationof
self-interactioncorrection,involvingrepeatedtransformationsbetweenBlochand
Wannierrepresentations.Themainpartofthechapterdealswiththeapplication
of these methods to understanding the valence and valence transitions of the
lanthanides. By introducing the notion of nominal valence, which defines the
numberofremainingband-likestatesasthevalenceofthelanthanideion,abetter
understandingofthephysicalpropertiesofthelanthanidesandtheircompounds,
andinparticular,magnetism,wasachievedasdemonstratedbynumerousexam-
ples. Later, the authors turn their attention to two spectroscopic techniques
applicable to lanthanides and some of their compounds in order to study some
of theproperties of thelocalized 4f states. An important issue—how to calculate
thefinitetemperaturepropertiesofthelanthanidemetalsandtheircompounds—
is discussed and illustrated by the study of finite temperature magnetism of
the heavy lanthanides and the finite temperature diagram of the Ce a–g phase
transition. The chapter concludes with the outline on how to include dynamical
quantumfluctuationstofurtherimprovemodelingprecision.
CHAPTER 242. PEROVSKITE-TYPE ALUMINATES AND GALLATES
By L. VASYLECHKO
Lviv Polytechnic National University, Lviv, Ukraine
A. SENYSHYN
Darmstadt University of Technology, Darmstadt, Germany, and
U. BISMAYER
Hamburg University, Hamburg, Germany
The perovskite family isatypical representative ofcomplex oxides. Many ofthe
perovskites exhibit interesting physics that includes ferro- and piezoelectricity,
high electronic and ionic conductivities, diverse magnetism, colossal
Preface vii
R-3c Pbnm
c b
a
b a
Imma I4/mcm
b b
c a
I2/m l-1
c b
a a
magnetoresistance, paraelectricity, and superconductivity. In this chapter L.
Vasylechko, A. Senyshyn, and U. Bismayer are concerned with aluminates
(RAlO ) and gallates (RGaO ) that adopt perovskite-derived structures and find
3 3
use as substrate materials for epitaxy of high temperature superconductors,
colossal magnetoresistive materials, and GaN films; and as active and passive
laser media, scintillators, and microwave dielectric materials. Structural details
arecriticaltounderstandhowtheseimportantpropertiesemerge,andtherefore,
this chapter reviews numerous experimental data about crystal structures, their
thermal evolution and transformations of over a hundred of RAlO and RGaO
3 3
compoundsandtheirsolidsolutions.Theauthorsusecrystalchemistrytostudy
andanalyzeperovskitestructuresanddistortionsoverawidetemperaturerange
intermsofbond-lengthdistortions,tiltinganglesbetweenoctahedra,polyhedral
volume ratios, tolerance factors, and individual and average cation–cation dis-
tances. Experimental data are supplemented by bond-valence calculations. The
influence of isovalent substitutions in the rare-earth sublattice on the average
structure, its thermal behavior, and phase transformations have been reviewed.
Especially important are phase diagrams of RAlO –R0AlO and RGaO –R0GaO
3 3 3 3
systems as functions of average radii of the R-cations. Common features of the
thermal expansion of rare earth aluminates and gallates, as wellas the observed
viii Preface
anomalies,includingthenegativethermalexpansionobservedinRGaO contain-
3
ingpraseodymium,arealsodiscussed.
CHAPTER 243. LUMINESCENCE
OF POLYOXOMETALLOLANTHANOATES
AND PHOTOCHEMICAL NANO-RING FORMATION
By TOSHIHIRO YAMASE
TokyoInstituteofTechnology,Nagatsuta,Midori-ku,Yokohama,Japan
ToshihiroYamase0schapterisfocusedonthechemistryofpolyoxolanthanoates—
a special class of metal-oxide cluster compounds—which may be considered as
modelsfor lanthanide-dopedmetal-oxidephosphors.Theemphasisofthechap-
ter is on the understanding of the molecular mechanisms of energy transfer
processesinmetal-oxidephosphors,whichoftenremainunclearmainlybecause
the luminescence centers are insufficiently characterized. The author outlines
energy transfer from O!M (M ¼ Nb, V, Mo, and W) ligand-to-metal charge-
transfer (lmct)states (donor) to luminescent Ln3þcenters(acceptor) processesin
polyoxometallolanthanoates,particularlyinpolyoxometalloeuropates.Thesensi-
tized Ln3þ-emission is governed by a Fo¨rster–Dexter dipole–dipole type of cou-
pling between the donor and the acceptor, and the O!M lmct triplet states are
involved not only in energy transfers, but also in electron transfer during the
photoredoxreactionwithprotonandelectrondonors.Suchaphotoredoxreaction
enablesthephotochemicaldesignofMo-bluenano-ringsbyanovel‘‘bottom-up’’
approach. These Mo-blue species are MoV/MoVI mixed-valence polyoxomolyb-
datesandtheyfavorthehighlydelocalizedsystemswithcharacteristicdark-blue
color due to the intervalence charge-transfer transitions. Lanthanide ions not
only open a novel method for the preparation of these nano-ring derivatives,
but also provide a tool for the mechanistic investigation of their self-assembly.
This is a beautiful example of lanthanide ions contributing to both nano-science
andnanotechnology.
Electron donor
hn DH
hn(cid:2)
O M Imct
Ln Ln(cid:2)
hn(cid:2)(cid:2) hn(cid:2)(cid:2)(cid:2)
Intramolecular energy transfer Nano-rings
CONTENTS OF VOLUMES 1–38
VOLUME1:Metals
1978,1strepr.1982,2ndrepr.1991;ISBN0-444-85020-1
1. Z.B.Goldschmidt,Atomicproperties(freeatom) 1
2. B.J.BeaudryandK.A.GschneidnerJr,Preparationandbasicpropertiesoftherareearth
metals 173
3. S.H.Liu,Electronicstructureofrareearthmetals 233
4. D.C.KoskenmakiandK.A.GschneidnerJr,Cerium 337
5. L.J.Sundstro¨m,Lowtemperatureheatcapacityoftherareearthmetals 379
6. K.A.McEwen,Magneticandtransportpropertiesoftherareearths 411
7. S.K.Sinha,Magneticstructuresandinelasticneutronscattering:metals,alloysand
compounds 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.landelliandA.Palenzona,Crystalchemistryofintermetalliccompounds 1
14. H.R.KirchmayrandC.A.Poldy,Magneticpropertiesofintermetalliccompoundsofrareearth
metals 55
15. A.E.Clark,MagnetostrictiveRFe2intermetalliccompounds 231
16. J.J.Rhyne,Amorphousmagneticrareearthalloys 259
17. P.Fulde,Crystalfields 295
18. R.G.Barnes,NMR,EPRandMo¨ssbauereffect: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.J(cid:1)rgensen,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
xi
xii CONTENTSOFVOLUMES1–38
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
Subjectindex655
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-isotopedilutionanalysisfor
lanthanidesingeochemicalmaterials 471
38. J.ReubenandG.A.Elgavish,ShiftreagentsandNMRofparamagneticlanthanidecomplexes 483
39. J.Reuben,Bioinorganicchemistry:lanthanidesasprobesinsystemsofbiologicalinterest 515
40. T.J.Haley,Toxicity 553
Subjectindex587
VOLUME5
1982,1strepr.1984;ISBN0-444-86375-3
41. M.Gasgnier,Rareearthalloysandcompoundsasthinfilms 1
42. E.GratzandM.J.Zuckermann,Transportproperties(electricalresitivity,thermoelectricpower
thermalconductivity)ofrareearthintermetalliccompounds 117
43. F.P.NetzerandE.Bertel,Adsorptionandcatalysisonrareearthsurfaces 217
44. C.Boulesteix,Defectsandphasetransformationnearroomtemperatureinrareearth
sesquioxides 321
45. O.GreisandJ.M.Haschke,Rareearthfluorides 387
46. C.A.MorrisonandR.P.Leavitt,Spectroscopicpropertiesoftriplyionizedlanthanidesin
transparenthostcrystals 461
Subjectindex693
VOLUME6
1984;ISBN0-444-86592-6
47. K.H.J.Buschow,Hydrogenabsorptioninintermetalliccompounds 1
48. E.Parthe´andB.Chabot,Crystalstructuresandcrystalchemistryofternaryrareearth–transition
metalborides,silicidesandhomologues 113
49. P.Rogl,Phaseequilibriainternaryandhigherordersystemswithrareearthelements
andboron 335
50. H.B.KaganandJ.L.Namy,Preparationofdivalentytterbiumandsamariumderivativesandtheir
useinorganicchemistry 525
Subjectindex 567
CONTENTSOFVOLUMES1–38 xiii
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
VOLUME8
1986;ISBN0-444-86971-9
54. K.A.GschneidnerJrandF.W.Calderwood,Intrarareearthbinaryalloys:phaserelationships,
latticeparametersandsystematics 1
55. X.Gao,Polarographicanalysisoftherareearths 163
56. M.Leskela¨ andL.Niinisto¨,InorganiccomplexcompoundsI 203
57. J.R.Long,Implicationsinorganicsynthesis 335
Errata 375
Subjectindex 379
VOLUME9
1987;ISBN0-444-87045-8
58. R.ReisfeldandC.K.J(cid:1)rgensen,Excitedstatephenomenainvitreousmaterials 1
59. L.Niinisto¨ andM.Leskela¨,InorganiccomplexcompoundsII 91
60. J.-C.G.Bu¨nzli,Complexeswithsyntheticionophores 321
61. ZhiquanShenandJunOuyang,Rareearthcoordinationcatalysisinstereospecific
polymerization 395
Errata 429
Subjectindex 431
VOLUME10:Highenergyspectroscopy
1987;ISBN0-444-87063-6
62. Y.BaerandW.-D.Schneider,High-energyspectroscopyoflanthanidematerials–Anoverview 1
63. M.CampagnaandF.U.Hillebrecht,f-electronhybridizationanddynamicalscreeningofcoreholes
inintermetalliccompounds 75
64. O.GunnarssonandK.Scho¨nhammer,Many-bodyformulationofspectraofmixedvalence
systems 103
65. A.J.Freeman,B.I.MinandM.R.Norman,Localdensitysupercelltheoryofphotoemission
andinversephotoemissionspectra 165
66. D.W.LynchandJ.H.Weaver,PhotoemissionofCeanditscompounds 231
67. S.Hu¨fner,Photoemissioninchalcogenides 301
68. J.F.HerbstandJ.W.Wilkins,Calculationof4fexcitationenergiesinthemetalsandrelevance
tomixedvalencesystems 321
69. B.JohanssonandN.Ma˚rtensson,Thermodynamicaspectsof4flevelsinmetalsand
compounds 361
70. F.U.HillebrechtandM.Campagna,Bremsstrahlungisochromatspectroscopyofalloysand
mixedvalentcompounds 425
71. J.Ro¨hler,X-rayabsorptionandemissionspectra 453
72. F.P.NetzerandJ.A.D.Matthew,Inelasticelectronscatteringmeasurements 547
Subjectindex 601