Handbook on the Physics and Chemistry of Rare Earths. Lanthanides/Actinides: Physics

734 Pages·1993·10.67 MB·English

by  G.R. Choppin

Handbook on the Physics and
Chemistry of Rare Earths, volume 17

Lanthanides/Actinides: Physics I

Elsevier, 1993

Edited by: Karl A. Gschneidner, Jr., LeRoy Eyring G.H. Lander and G.R. Choppin
ISBN: 978-0-444-81502-6

by kmno4
Handbook on the Physics and Chemistry of Rare Earths
Vol. 17 - Lanthanides/Actinides: Physics - I
edited by K.A. Gschneidner, Jr., L. Eyrin 9, G.H. Lander and G.R. Choppin
© 1993 EIsevier Science Publishers B.V. All rights reserved
PREFACE
Karl A. GSCHNEIDNER, Jr., LeRoy EYRING, Gerry H. LANDER, and
Gregory R. CHOPPIN
These elements perplex us in our rearches sic, baffie us in our speculations, and haunt
us in our very dreams. They stretch like an unknown sea before us mocking, mystifying,
and murmuring strange revelations and possibilities.
Sir William Crookes (February ,61 1887)
This volume of the Handbook is the first of a three-volume set of reviews devoted
to the interrelationships, 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 series would need help from two leading scientists who had considerable
experience and knowledge of both series 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 Stefan Hüfner's
initial suggestion, the first volume, which is devoted to the physical aspects, is in print.
Soon to follow are volumes emphasizing chemical comparisons and another dealing
with additional physical topics.
The observations and comments of Sir William Crookes (as noted above) over 106
years ago about the lanthanides is even more appropriate to these lanthanide/actinide
tomes. This is especially noteworthy because only two of the actinide series of elements
were then known (Th and U), and the concept of such a series 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 to understand them, new ones will arise to continue to haunt us as we
move forward and ever onward.
iv ECAFERP
In this volume we have eight chapters concerned with some of the physical aspects
of the lanthanide and actinide series. The first three chapters are theoretical in nature
and the last five are more heavily oriented toward experimental studies.
In chapter 110, M.R. Norman and D.D. Koelling have critically examined the
validity of standard electronic band structure calculations based on the local density
approximation (LDA) as applied to f-electron systems, especially in those systems in
which the low-temperature ground state is thought to be a Fermi liquid. They note
that the LDA method works weil for itinerant f-electron systems and even strongly
enhanced ones (whether Ce-base or U-base compounds), but there are some problems
especially with regard to the large mass enhancements, magnetic moments and
localization.
In the next review (chapter ,)111 S.H. Liu examines phenomenological approaches
to heavy-fermion and mixed-valence materials. He notes that there are two basic
approaches to understanding these phenomena: the Fermi-liquid models, which are
applicable at low temperatures, and the spin fluctuation models, which work well for
describing high-temperature properties and behaviors. At the present time Liu
concludes that "the field si still wide open" before we come to even a reasonable
understanding of anomalous f-electron behaviors.
In the third theoretical paper (chapter 112), .B Johansson and M.S.S. Brooks
describe the use of first principles calculations to obtain the cohesive properties
of lanthanide and actinide materials. sA the authors note, in the past 02 years
theorists have been able to calculate the lattice parameters of the material, evaluate
the correct crystal structure, and accurately calculate its cohesive energy.
The first of the five chapters, which, more or less, deal with experimental aspects
of the lanthanide/actinide materials, is concerned with the structural behavior of
these materials at high pressures (chapter 311 by U. Benedict and W.B. Holzapfel).
The authors show that the spatial extent of the f-wave functions around the nucleus
plays an important role in govering the formation of various crystal structure as a
function of both pressure and atomic number in the elemental metals. Because of the
lack of knowledge of the high-pressure behaviors in their compounds, the systematic
study and understanding in f-element compounds is much less advanced than for the
metals.
In chapter ,4111 O. Vogt and K. Mattenberger examine the magnetic behaviors of
the lanthanide and actinide ,1B NaCl-type structures. The magnetic properties of a
sample depend upon: the spectroscopic state of the f-element and the possibility of
J-mixing, the electric crystalline field, the exchange interactions and hybridization.
The competition between these various factors can make the materials complicated
or simple with respect to their magnetic behaviors.
In the next chapter ,)511( J.M. Fournier and .E Gratz have reviewed the transport
properties of lanthanide/actinide compounds. These include: the electrical resistivity,
thermal conductivity, thermoelectric power, magnetoresistance and the Hall effect.
As expected, most of this review deals with the electrical resistivity because of the
preponderance of data on. this property, relative to the other four. Throughout this
chapter the authors attempt to use the available information on the transport
properties to help improve our understanding of the differences and similarities of
PREFACE vii
lanthanide and actinide intermetallic compounds, even though an exact theoretical
interpretation of the experimental observations is difficult.
The importance of Mössbauer spectroscopy in probing electronic structures of
intermetallic compounds, especially those reflected in the magnetic properties, is
discussed by W. Potzel, G.M. Kalvius and J. Gal (chapter 116). The authors have
focused their discussions on selected samples where the differences between
lanthanides and actinides can be best contracted. As the authors note, the two most
interesting elements, at least with respect to anomalous f-electron behaviors, Ce and
U, cannot be studied by Mössbauer spectroscopy because of the lack of a suitable
isotope in the case of Ce, and just the experimental difficulty in getting Mössbauer
spectra for U.
The final chapter (117) by G.H. Lander reviews the elastic neutron scattering
behavior, which yields information on the spatial extent of the unpaired electrons
that contribute to the spin and orbital moments, the magnetic structure, and
correlation effects between magnetic moments that occurs when the material is close
to its magnetic ordering temperature. Much of the information obtained by neutron
scattering is difficult, if not impossible, to get from other experimental techniques.
Some of the more significant results are: the elucidation of the charge-density wave
in U; magnetic form factors (i.e. the spatial extent of magnetization densities); the
eludication of magnetic structures, many of which are quite complex; and magnetic
critical scattering.
Dedicated to
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 science and society. 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 influence on the way physicists and chemists think about the electronic
structures of the elements. The new insights arising from studies on the chemistry
and physics of the heaviest elements has had an especially important influence on
the way we think about the more familiar elements of the Periodic Table, in particular,
the rare earths. In the saga of the actinide 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, which deal with the relationships of the
lanthanide and actinide elements, is thus a fitting recognition of the exceptionally
important contribution that his actinide element studies have made to many branches
of science.
Glenn Seaborg's scientific 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 of a
few years, he validated his intuition by the discovery of a host of isotopes, many of
which have become important in research and medicine. Among these are cobalt-60,
iodine-131, technetium-99m, cesium-137, and, of course, the plutonium isotopes. In
1944, he formulated the actinide concept of heavy-element electronic structure that
accurately predicted the existence of a family of rare earth-like elements at the end
of the Periodic Table as it was generally presented at that time. The actinide concept
was the guide to the discovery of the remaining members of the actinide elements.
In addition to the fissile plutonium isotopes, he and his 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 relevance not only to purely scientific
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 distinguished
career in academic and public 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 his extra-scientific activities. He was the recipient of a Nobel Prize
(1951) for his discoveries in the chemistry of the transuranium elements, and has
received encomiums from most of the scientific societies of the world.
xi
x NOITACIDED
In spite of worldly distractions, Glenn Seaborg has never wavered in his life-long
commitment to science. He continues his research into the chemistry and nuclear
systematics of the actinide elements. Recently, he has focused 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 achievementsi it is also an appreciation of the example that he continues
to set.
CONTENTS
Preface v
Dedication ix
Contents xi
Contents of Volumes 1-16 xiii
.011 M.R. Norman and D.D. Koelling
Electronic structure, Fermi surfaces, dna superconductivity ni f electron metals 1
111. S.H. Liu
Phenomenological approach to heavy-fermion systems 78
112. .B Johansson and M.S.S. Brooks
Theory of cohesion ni rare earths dna actinides 941
113. U. Benedict and W.B. Holzapfel
High-pressure studies- Structural aspects 245
114. O. Vogt and K. Mattenberger
Magnetic measurements no rare earth dna actinide monopnictides dna mono-
chalcogenides 103
115. J.M. Fournier and E. Gratz
Transport properties of rare earth and actinide intermetallics 409
116. W. Potzel, G.M. Kalvius and J. Gal
Mössbauer studies no electronic structure of intermetallic compounds 539
117. G.H. Lander
Neutron elastic scattering from actinides dna anomalous lanthanides 635
Author index 117
Subject index 357
xi
CONTENTS OF VOLUMES 1-16
VOLUME 1: Metals
1978, Ist 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. Gschneidner Jr, Preparation and basic properties of the rare earth metals 371
3. S.H. Liu, Electronic structure of rare earth metals 233
4. D.C. Koskenmaki and K.A. Gschneidner Jr, Cerium 337
5. L.J. Stmdström, Low temperature heat capacity of the rare earth metals 379
6. K.A. McEwen, Magnetic and transport properties of the rare earths 114
7. S.K. Sinha, Magnetic structures and inelastic neutron metals, scattering." alloys and compounds 489
8. T.E. Scott, Elastic and mechanical properties 195
9. A. Jayaraman, High pressure studies: metals, alloys and compounds 707
10. C. Probst and .J Wittig, SuperconductiviO,: metals, alloys and compounds 749
11. M.B. Maple, L.E. DeLong and B.C. Sales, Kondo effect: alloys and compounds 797
12. M.P. Dariel, Diffusion in rare earth metals 847
Subject index 877
VOLUME 2: Alloys and intermetallics
1979, 1st repr. 1982, 2nd repr. 1991; ISBN 0-444-85021-X
13. A. Iandelli and A. Palenzona, Crystal chemistry ofintermetallic 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
.71 .P Fulde, Crystalfields 295
.81 R.G. Barnes, NMR, EPR and Mössbauer effect: metals, alloys and compounds 387
.91 .P Wachter, Europium chalcogenides: EuO, EuS, EuSe and EuTe 507
20. A. Jayaraman, Valence changes in compounds 575
Subject Index 613
VOLUME 3: Non-metallic compounds - I
1979, Ist repr. 1984; ISBN 0-444-85215-8
21. L.A. Haskin and T.P. Paster, Geochemistry and mineralogy of the rare earths 1
22. J.E. Powell, Separation chemistry 18
23. C.K. J~rgensen, Theoretical chemistry of rare earths 111
24. W.T. Carnall, The absorption and fluorescence spectra of rare earth ions in solution 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.P. Khattak and EEY. Wang, Perovskites and garnets 525
30. L.H. Brixner, +R.J Barkley and .W Jeitschko, Rare earth molybdates 011) 609
Subject index 655
xiii
xiv CONTENTS OF VOLUMES 1-16
VOLUME 4: Non-metallic compounds - II
1979, 1st repr. 1984; ISBN 0-444-85216-6
31. .J Flahaut, Sulfides, selenides and tellurides 1
32. J.M. Haschke, Halides 89
33. E Hulliger, Rare earth pnictides 351
34. G. Blasse, Chemistry and physics of R-activated phosphors 237
35. M.J. Weber, Rare earth lasers 275
36. EK. Fong, Nonradiative processes of rare-earth ions in crystals 317
37A. J.W. O'Laughlin, Chemical spectrophotometric and polarographic 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 matrices by spark source mass spectrometry 377
37D. E.L. DeKalb and VA. Fassel, Optical atomic emission and absorption methods 405
37E. A.P. D'Silva and VA. Fassel, X-ray excited optical luminescence of the rare earths 441
37E EW.V. Boynton, Neutron aetivation analysis 457
37G. S. Schuhmann and J.A. Philpotts, Mass-spectrometric stable-isotope dilution analysis for lanthanides
in geochemical materials 471
38. J. Reuben and G.A. Elgavish, Shifl reagents and NMR of paramagnetic lanthanide complexes 483
39. .J Reuben, Bioinorganic chemistry: lanthanides as probes in systems of biological interest 515
40. T.J. Haley, Toxicity 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 (electrical resitivity, thermoelectric power and
thermal conductivi(y) of rare earth intermetallic compounds 117
43. EP. Netzer and E. Bettel, Adsorption and catalysis on rare earth surfaces 217
44. C. Boulesteix, Defects 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.P. Leavitt, Spectroscopic properties of triply ionized lanthanides in transparent
host crystals 461
Subject index 693
VOLUME 6
1984; ISBN 0-444-86592-6
47. K.H.J. Buschow, Hydrogen absorption in intermetallie compounds 1
48. E. Parthé and B. Chabot, Crystal struetures and crystal chemistry of ternary rare earth-transition metal
borides, silicides 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. Namy, Preparation of divalent ytterbium and samarium derivatives and their use
in organic chemistry 525
Subject 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. KM.J. Buschow, Amorphous alloys 265
53. H. Schumann and .W Genthe, Organometallic compounds of the rare earths 446
Subject index 573
CONTENTS OF VOLUMES 1 61 xv
VOLUME 8
1986; ISBN 0-~:86971.9
54. K.A. Gschneidner Jr and EW. Calderwood, Intra rare earth binary alloys: phase relationships, lattice
parameters and systematies 1
55. X. Gan, Polarographic analysis of the rare earths 361
56. M. Leskelä and L. Niinistö, Inorganic complex compounds 1 203
57. J.R. Long, mplications ni organie synthesis 335
Errata 375
Subject index 379
VOLUME 9
1987; ISBN 0-444-87045-8
58. R. Reisfeld and C.K. J~rgensen, Excited state phenomena ni vitreous materials 1
59. L. Niinistö and M. Leskelä, lnorganic complex compounds H 19
60. J.-C.G. Bünzli, Complexes with synthetic ionophores 123
61. Zhiquan Shen and Jun Ouyang, Rare earth coordination catalysis ni stereospecißcpolymerization 395
Errata 429
Sübject index 431
VOLUME 10: High energy spectroscopy
1988; ISBN 0-444-87063-6
62. .Y Baer and W.-D. Schneider, High-energy spectroscopy of lanthanide materials -An overview 1
63. M. Campagna and EU. Hillebrecht, f-electron hybridization and dynamical screening of core holes ni
intermetallic compounds 75
64. O. Gunnarsson and K. Schönhammer, Many-bodyformulation ofspectra ofmixed valence systems 103
65. A.J. Freeman, B.I. Min and M.R. Norman, Local density supercell theory ofphotoemission and inverse
photoemission spectra 165
66. D.W. Lynch and J.H. Weaver, Photoemission of Ce and its compounds 231
67. S. Hüfner, Photoemission ni chaleogenides 103
68. LE Herbst and J.W. Wilkins, Calculation of 4f excitation energies ni the metals and relevance ot mixed
valence systems 321
69. B. Johansson and N. Märtensson, Thermodynamie aspects of 4f levels ni metals and compounds 361
70. EU. Hillebrecht and M. Campagna, Bremsstrahlung isochromat spectroscopy of alloys and mixed valent
compounds 425
71. .J Röhler, X-ray absorption and emission spectra 453
72. ER Netzer and J.A.D. Matthew, Inelastic electron scattering measurements 547
Subject i~dex 601
VOLUME 11: Two-hundred-year impact of rare earths on science
1988; ISBN 0-444-87080-6
H.J. Svec, Prologue 1
73. E Szabadväry, The history of the diseovery and separation of the rare earths 33
74. B.R. Judd, Atomic theory and optical spectroscopy 18
75. C.K. Jergensen, lnfluence of rare earths no chemical understanding and classißcation 7911
76. J.J. Rhyne, Highlights from the exotic phenomena of lanthanide magnetism 293
77. B. Bleaney, Magnetic resonance spectroscopy and hyperfine interactions 323
78. K.A. Gschneidner Jr and A.H. Daane, Physical metallurgy 409
79. S.R. Taylor and S.M. McLennan, ehT significance of the rare earths ni geochemistry and
cosmochemistry 485
Errata 579
Subject index 185