Handbook on the Physics and Chemistry of Rare Earths

665 Pages·1994·12.55 MB·English

by  G.R. Choppin

Handbook on the Physics and
Chemistry of Rare Earths, volume 19

Lanthanides/Actinides: Physics II

Elsevier, 1994

Edited by: Karl A. Gschneidner, Jr., LeRoy Eyring, G.H. Lander and G.R. Choppin
ISBN: 978-0-444-82015-0

by kmno4
PREFACE
Karl A. GSCHNEIDNER, Jr., LeRoy EYR1NG, Gerry H. LANDER
and Gregory R. CHOPPIN
These elements perplex us in our rearches [sic], baffle us in our speculations, and haunt
us in our uery dreams. They streteh like an unknown sea before us - moeking, mystifying,
and murmuring strange revelations and possibilities.
Sir William Crookes (February ,61 1887)
This volume of the Handbook is the third of a three-volume set of reviews devoted to
the interrelafionships, similarities, differences and contrasts of the lanthanide and actinide
series of elements. The idea of these volumes grew out of a conversation between one of
the editors, KAG, and a member of the editorial board, Stefan Hüfner, in early June 1986.
This idea was enthusiastically received by the other editor (LE) and editorial board
members, and also the publishers. Numerous topics and authors were suggested and soon
it was apparent that this special subject was too large to be covered in one or possibly
two volumes, and that the editors (KAG and LE) of this seiles would need help from
two leading scientists who had considerable expeilence and knowledge of both seiles
of elements. Thus, Gerry H. Lander and Gregory R. Choppin were invited to be guest
editors for this special set of volumes on the lanthanides/actinides. After they accepted,
the four editors carefully and critically chose the various topics, and top experts in the
various areas were invited to write reviews keeping in mind that the emphasis was to be
on the interrelationships of the lanthanides and actinides. Now, more than seven years
after Stephen Hüfner's initial suggestion, the first volume, which is devoted to the physical
aspects, and the second volume, which emphasizes chemical comparisons, are in pilnt.
In this volume additional physical topics are covered.
The observations and comments of Sir William Crookes (as noted above) over 107 years
ago about the lanthanides are even more appropriate to these lanthanide/actinide volumes.
This is especially noteworthy because only two of the aetinide seiles of elements were
then known (Th and U), and the concept of such a seiles was not to develop for about
50 years. But we hope that the material presented in these three lanthanide/actinide
volumes will shed light on some of the mysteries of yesterday, but as surely as we begin
vi PREFACE
to understand them, new ones will arise to continue to haunt us as we move forward and
erer onward.
This volume comprises five chapters on the comparative physics and thermodynamics
of the lanthanide and actinide materials. The first two chapters are concerned with
neutron scattering studies, while the next two are concerned with physical property studies
involving electronic, thermal and magnetic behaviors, and the final chapter covers the
thermodynamic properties of metallic systems.
The lead-off chapter (130) by Holland-Moritz and Lander compares the neutron
inelastic scattering behaviors of the lanthanides and actinides. Neutron inelastic scattering
is useful in probing dynamical processes which occur in solids, especially low energy
elementary excitations. The authors have narrowed their coverage to the anomalous
lanthanides (cerium, samarium, europium, thulium and ytterbium) and primarily uranium
of actinide series elements. The systems covered include: those in which the crystal-field
interaction dominates; systems that magnetically order, but in which the f-d hybridization
is significant; mixed (or intermediate) valent materials which do not exhibit sharp
excitations; and strongly interacting systems such as heavy fermions.
Chapter 131 by Aeppli and Broholm builds on the first chapter in this volume and
concentrates on neutron scattering by heavy fermion single crystal materials. These
compounds include metallic materials with a paramagnetic ground state, superconductors,
metallic and semiconducting antiferromagnets, and nearly insulating paramagnets. The
most important contribution of these single crystal neutron scattering studies has been the
demonstration of strong antiferromagnetic (AFM) correlations in heavy fermion systems.
These strong AFM correlations distinguish the concentrated heavy fermion materials
from their dilute Kondo relatives, and possibly aecount for the observed metamagnetic
and unconventional superconductivity phenomena.
The chapter by Wachter (132), which is one of the most extensive and comprehensive
ones in the entire Handbook series, reviews intermediate valence and heavy fermions in
a wide variety of lanthanide and actinide compounds, ranging from metallic to insulating
materials. The behaviors of these materials are discussed from the basic idea that a gap
exists between two narrow f-like subbands, i.e. the hybridization gap model, which can
account for the observed physical and electronic properties. As pointed out by Wachter,
heavy fermions are intermediate valence materials by virtue of the fact that they have non-
integral f occupation values. The main difference between normal intermediate valence
materials is that their Fermi energies are in the hybridization gap, while for the heavy
fermion materials the Fermi energy is not in the gap.
In chapter 331 Thompson and Lawrence have focused on two issues on the
high pressure behaviors of anomalous cerium, ytterbium and uranium compounds. The
first is concerned with the degree to which the pressure response of the electrical
resistivity, magnetic susceptibility and heat capacity is similar in the given class of
materials, and how this pressure dependence is related to the Grüneisen constant obtained
from ambient pressure measurements. The second issue deals with how well this
comparison holds in both anomalous lanthanide and actinide materials. They have shown
that although there is some consistency in their high pressure behaviors to a level of ± 10-
20%, there are still many issues, e.g. validity of scaling laws, equality of electronic and
ECAFERP iiv
magnetic Grüneisen parameters, which are not well established, and this leaves substantial
work for the future.
The last chapter (134) in this volume is an extensive review by Colinet and Pasturel of
the thermodynamic properties of lanthanide and actinide metallic systems. In addition to
compiling useful ther/nodynamic data, such as enthalpies, entropies, and free energies of
formation and of mixing, the authors have made an extensive comparative analysis of the
thermodynamic behavior of the rare earths and actinides when alloyed with metallic
elements. They note that when alloyed with non-transition metals, the enthalpies of
formation of uranium alloys are less negative than those of the rare earths while those
of thorium and plutonium are about the same as the latter. For transition metal alloys
the formation enthalpies of thorium and uranium are more negative than those of the
rare earths and plutonium (the latter two are about the same). The anomalous behaviors
of cerium, europium and ytterbium in various compounds and alloys are also discussed
along with the effect of valence state changes found in uranium and plutonium alloys.
Dedicated ot
GLENN T. SEABORG
Among the many noteworthy scientific achievements of the 20th century, there are
only a very few that can match the discovery of the actinide elements in its impact on
seienee and soeiety. The addition of an entire new family of largely man-made elements
to the Periodic Table, and the formulation of the actinide concept have had a profound
influenee on the way physicists and chemists think about the electronic structures of the
elements. The new insights arising from studies on the ehemistry and physics of the
heaviest elements has had an espeeially important influenee on the way we think about
the more familiar elements of the Periodic Table, in particular, the rare earths. In the
saga of the aetinide elements, Glenn Seaborg has been the pivotal figure. The dedication
to Glenn Seaborg of these volumes of the Handbook on the Physics and Chemistry of
Rare Earths, whieh deal with the relationships of the lanthanide and actinide elements,
is thus a fitting recognition of the exceptionally important contribution that his aetinide
element studies have made to many branches of science.
Glenn Seaborg's scientifie career began in the 1930's as a research associate of
G.N. Lewis at the University of California. He early became convinced that the science
of nuclear chemistry, then in its infancy, provided challenging opportunities for scientific
discovery. In the Lawrence Radiation Laboratory, in the course ofa few years, he validated
bis intuition by the discovery of a host ofisotopes, many of whieh have become important
in research and medicine. Among these are cobalt-60, iodine-131, technetium-99m,
cesium-137, and, of eourse, the plutonium isotopes. In 1944, he formulated the actinide
concept of heavy-element electronie strueture that accurately predicted the existence of
a family of rare earth-like elements at the end of the Periodie Table as it was generally
presented at that time. The actinide concept was the guide to the diseovery of the
remaining members of the actinide elements. In addition to the fissile plutonium isotopes,
he and bis co-workers over the years discovered no less than nine additional members of
the new rare earth-like family of elements. These discoveries have been of great relevante
not only to purely scientifie matters but also to such global problems as nuclear energy
and the control of nuclear weapons.
In addition to his life as an active scientist, Glenn Seaborg has had a disfinguished
career in academic and publie life. He served at various times as Chancellor of the
University of California at Berkeley, Chairman of the Atomic Energy Commission for
a period of ten years, and Chairman of the Lawrence Hall of Science, to name only a
few of bis extra-seientific activities. He was the recipient of a Nobel Prize (1951) for his
xi
NOITACIDED
discoveries in the chemistry of the transuranium elements, and has received encomiums
from most of the seientifie societies of the world.
In spite of worldly distraetions, Glenn Seaborg has never wavered in bis life-long
commitment to scienee. He continues his research into the chemistry and nuclear
systematics of the actinide elements. Recently, he has foeused his attention on the possible
existence of still another family of superheavy elements at the end of the Periodic Table,
and the development of new methods for the synthesis of superheavy elements. The
dedication of these volumes to Glenn Seaborg is not only a testimonial to his scientific
achievements, it is also an appreeiation of the example that he eontinues to set.
J.J. Katz
December 5, 1991
CONTENTS
Preface v
Dedication ix
Contents xi
Contents of Volumes 1-18 Xlll .°.
.03~1/t E. Holland-Moritz and G.H. Lander
Neutron inelastic scattering from actinides and anomalous lanthanides 1
G. Aeppli and C. Broholm i?"
Magnetic correlations in heaoy-fermion systems: neutron scattering from single Æ 7¢oo
crystals 123
c/132. E Wachter
Intermediate valenee and heavy fermions 177 ~ "7~~/O
i(
[/133. J.D. Thompson and J.M. Lawrence
High pressure studies - Physical properties of anomalous ,eC Yb and U compounds
383
t/134. C, Colinet and A. Pasturel
Thermodynamic properties óf metallic systems 479 c~ ;/~' ~ 0 +,
Author Index 649
Subject Index 693
ix
CONTENTS OF VOLUMES 1-18
VOLUME 1: Metals
1978, 1st repr. 1982, 2nd repr. 1991; ISBN 0-444-85020-1
.1 Z.B. Goldschmidt, Atomic properties (free atom) 1
2. B.J. Beaudry and K.A. Gsehneidner Jr, Preparation and basic properties of the rare earth metals 371
3. S.H. Liu, Eleetronie structure of rare earth metals 233
4. D.C. Koskenmaki and K.A. Gschneidner Jr, Cerium 337
5. L.J. Sundström, Low temperature heat capacity of the rare earth metals 379
6. K.A. McEwen, Magnetie and transport properties of the rare earths 411
7. S.K. Sinha, Magnetie struetures and inelastic neutron seattering: metals, alloys and compounds 489
8. T.E. Scott, Elasüe and mechanicalproperties 591
9. A. Jayararnan, High pressure studies: metals, alloys and compounds 707
10. C. Probst and .J Wittig, Superconductivity: metals, alloys and eompounds 749
11. M.B. Maple, L.E. DeLong and B.C. Sales, Kondo effeet: alloys and eompounds 797
12. M.P. Dariel, Diffusion in rare earth metals 847
Subject index 877
VOLUME 2: Ailoys and intermetallics
1979, Ist repr. 1982, 2nd repr. 1991; ISBN 0-444-85021-X
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, Crystalfields 295
18. R.G. Barnes, NMR, EPR and Mössbauer effect: metals, alloys and compounds 387
19. E Wachter, Europium chaleogenides: EuO, EuS, EuSe and EuTe 507
20. A. Jayaraman, Valence changes in compounds 575
Subjeet Index 613
VOLUME 3: Non-metallic compounds - I
1979, Ist repr. 1984; ISBN 0-444-85215-8
21. L.A. Haskin and T.R Paster, Geochemistry and mineralogy of the rare earths 1
22. J.E. Powell, Separation chemistry 18
23. C.K. Jorgensen, Theoretical chemistry of rare earths 111
24. W.T. Carnall, The absorption and fluorescence spectra of rare earth ions in soluüon 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.E Khattak and EEY. Wang, Perovskites and garnets 525
30. L.H. Brixner, J.R. Barkley and .W Jeitsehko, Rare earth molybdates (VI) 609
Subjeet index 655
xiii
xiv CONTENTS OF VOLUMES 1-18
VOLUME :4 Non-metallic compounds - I1
1979, 1st repr. 1984; ISBN 0-444-85216-6
31. J. Flahaut, Sulfides, selenides and tellurides 1
32. J.M. Hasehke, Halides 89
33. E Hulliger, Rare earth pnictides 351
34. G. Blasse, Chemistry and physies of R-aetivated phosphors 237
35. M.J. Weber, Rare earth lasers 275
36. EK. Fong, Nonradiative proeesses of rare-earth ions in crystals 317
37A. J.W, O'Laughlin, Chemieal speetrophotometrie and polarographie methods 143
37B. S.R. Taylor, Trace element analysis of rare earth elements by spark source mass spectroscopy 359
37C. R.J. Conzemius, Analysis of rare earth matriees by spark source mass speetrometry 377
37D. E.L. DeKalb and V.A. Fassel, Optieal atomie emission and absorption methods 405
37E. A.R D'Silva and V.A. Fassel, X-ray excited optieal lumineseence of the rare earths 441
37E EW.V Boynton, Neutron aetivation analysis 457
37G. S. Schuhmann and J.A. Philpotts, Mass-speetrometric stable-isotope dilution analysis for lanthanides
in geoehemieal materials 471
38. .J Reuben and G.A. Elgavish, Shifl reagents and NMR of paramagnetic lanthanide eomplexes 483
39. J. Reuben, Bioinorganie ehemistry: lanthanides as probes in systems of biological interest 515
40. T.J. Haley, Toxieity 553
Subject index 587
VOLUME 5
1982, 1st repr. 1984; ISBN 0-444-86375-3
41. M. Gasgnier, Rare earth alloys and compounds as thin films 1
42. E. Gratz and M.J. Zuckermann, Transport properties (electrieal resitivity, thermoeleetric power and
thermal eonduetivity) of rare earth intermetallie compounds 117
43. ER Netzer and E. Bertel, Adsorption and eatalysis on rare earth surfaces 217
44. C. Boulesteix, Defeets and phase transformation near room temperature in rare earth sesquioxides 123
45. O. Greis and J.M. Haschke, Rare earthfluorides 387
46. C.A. Morrison and R.R Leavitt, Spectroscopic properties of triply ionized lanthanides in transparent
host crystals 461
Subjeet index 693
VOLUME 6
1984; ISBN 0-444-86592-6
47. K.H.J. Buschow, Hydrogen absorption in intermetallic compounds 1
48. E. Parthé and B. Chabot, Crystal struetures and erystal ehemistry of ternary rare earth-transition metal
borides, silieides and homologues 311
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. Narny, Preparation of divalent ytterbium and samarium derivatives and the#" use
in organie ehemistry 525
Subjeet index 567
VOLUME 7
1984; ISBN 0-444-86851-8
51. E Rogl, Phase equilibria in ternary and higher order systems with rare earth elements and silicon
52. K.HJ. Buschow, Amorphous alloys 265
53. H. Schumann and W Genthe, Organometallic compounds of the rare earths 446
Subject index 573
CONTENTS OF VOLUMES 1-18 xv
VOLUME 8
;6891 ISBN 0-444-86971-9
.45 K.A. Gschneidner Jr and .WE Calderwood, Intra rare earth binary alloys: phase relationships, lattice
parameters and systematies 1
.55 X. Gao, Polarographic analysis of the rare earths 361
.65 M. Leskelä and L. ~iinistö, Inorganic complex compounds I 302
.75 J.R. Long, Implications in organic synthesis 533
Errata 573
Subjeet index 973
VOLUME 9
;7891 ISBN 0-444-87045-8
.85 R. Reisfeld and C.K. Jorgensen, Excited state phenomena in oitreous materials 1
59. L. Niinistö and M. Leskelä, Inorganic complex compounds 11 19
.06 J.-C.G. Bünzli, Complexes with synthetic ionophores 123
.16 Zhiquan Shen and Jun Ouyang, Rare earth coordination eatalysis in stereospecißc polymerization 593
Errata 429
Subject index 134
VOLUME 10: High energy speetroseopy
;8891 ISBN 0-444-87063-6
.26 .Y Baer and .D-.W Schneider, High-energy spectroscopy of lanthanide materials - An overview 1
.36 M. Campagna and EU. Hillebrecht, f-electron hybridization and dynamical screening of core holes in
intermetallic compounds 57
.46 .O Gunnarsson and K. Schönhamrner, Many-bodyformulation ofspeetra ofmixed valence systems 301
.56 A.J. Freernan, B.I. Min and M.R. Norman, Local density supercelI theory ofphotoemission and inverse
photoemission spectra 561
.66 D.W. Lynch and J.H. Weaver, Photoemission of Ce and its compounds 132
.76 S. Hüfner, Photoemission in chalcogenides 103
.86 J.E Herbst and .W.J Wilkins, Calculation of 4f excitation energies in the metals and relevance to mixed
valence systems 123
.96 .B Johansson and .N Märtensson, Thermodynamic aspects of 4f levels in metals and compounds 163
70. EU. Hillebrecht and M. Campagna, Bremsstrahlung isochromat spectroscopy of alloys and mixed valent
compounds 524
.17 .J Röhler, X-ray absorption and emission spectra 354
.27 .PE Netzer and J.A.D. Mattbew, Inelastic electron scattering measurements 745
Subject index 106
VOLUME 11: Two-hundred-year impact of rare earths on seienee
;8891 ISBN 0-444-87080-6
H.J. Svee, Prologue 1
.37 E Szabadväry, ehT history of the discovery and separation of the rare earths 33
.47 B.R. Judd, Atomie theory and optieal speetroseopy 18
.57 C.K. Jorgensen, Influenee of rare earths on ehemieal understanding and elassification 7'91
.67 .J.J Rhyne, Highlights from the exotie phenomena of lanthanide magnetism 392
.77 .B Bleaney, Magnetie resonanee speetroseopy and hyperfine interaetions 323
.87 K.A. Gsehneidner Jr and A.H. Daane, Physieal metallurgy 409
.97 S.R. Taylor and S.M. MeLennan, ehT signifieance of the rare earths in geoehemistry and
cosmoehemistry 584
Errata 975
Subject index 185