Rare-Earths and Actinides in High Energy Spectroscopy

393 Pages·2015·6.57 MB·English

by  Christiane Bonnelle

Progress in Theoretical Chemistry and Physics A28
Series Editors: J. Maruani · S. Wilson
Christiane Bonnelle
Nissan Spector
Rare-Earths
and Actinides
in High Energy
Spectroscopy
Rare-Earths and Actinides in High Energy
Spectroscopy
Progress in Theoretical Chemistry and Physics
VOLUME 28
Honorary Editors
Sir Harold W. Kroto (Florida State University, Tallahassee, FL, USA)
Prof. Yves Chauvin (Institut Français du Pétrole, Tours, France)
Editors-in-Chief
J. Maruani (formerly Laboratoire de Chimie Physique, Paris, France)
S. Wilson (formerly Rutherford Appleton Laboratory, Oxford, UK)
Editorial Board
E. Brändas (University of Uppsala, Uppsala, Sweden)
L. Cederbaum (Physikalisch-Chemisches Institut, Heidelberg, Germany)
G.Delgado-Barrio(InstitutodeMatemáticasyFísicaFundamental,Madrid,Spain)
E.K.U. Gross (Freie Universität, Berlin, Germany)
K. Hirao (University of Tokyo, Tokyo, Japan)
E. Kryachko (Bogolyubov Institute for Theoretical Physics, Kiev, Ukraine)
R. Lefebvre (Université Pierre-et-Marie-Curie, Paris, France)
R. Levine (Hebrew University of Jerusalem, Jerusalem, Israel)
K. Lindenberg (University of California at San Diego, San Diego, CA, USA)
A. Lund (University of Linköping, Linköping, Sweden)
R. McWeeny (Università di Pisa, Pisa, Italy)
M.A.C. Nascimento (Instituto de Química, Rio de Janeiro, Brazil)
P. Piecuch (Michigan State University, East Lansing, MI, USA)
M. Quack (ETH Zürich, Zürich, Switzerland)
S.D. Schwartz (Yeshiva University, Bronx, NY, USA)
A. Wang (University of British Columbia, Vancouver, BC, Canada)
Former Editors and Editorial Board Members
I. Prigogine (†) W.F. van Gunsteren (*)
J. Rychlewski (†) H. Hubač (*)
Y.G. Smeyers (†) M.P. Levy (*)
R. Daudel (†) G.L. Malli (*)
M. Mateev (†) P.G. Mezey (*)
W.N. Lipscomb (†) N. Rahman (*)
H. Ågren (*) S. Suhai (*)
V. Aquilanti (*) O. Tapia (*)
D. Avnir (*) P.R. Taylor (*)
J. Cioslowski (*) R.G. Woolley (*)
†: deceased; *: end of term
More information about this series at http://www.springer.com/series/6464
Christiane Bonnelle Nissan Spector
(cid:129)
Rare-Earths and Actinides
in High Energy Spectroscopy
123
Christiane Bonnelle NissanSpector
Laboratoire deChimie Physique Sorbonne Universités,UPMC06
Matièreet Rayonnement Paris
Sorbonne Universités,UPMC06 France
Paris
France and
SoreqNuclear Research Center
Yavne
Israel
ISSN 1567-7354 ISSN 2215-0129 (electronic)
Progressin Theoretical Chemistry andPhysics
ISBN978-90-481-2878-5 ISBN978-90-481-2879-2 (eBook)
DOI 10.1007/978-90-481-2879-2
LibraryofCongressControlNumber:2015954591
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Preface
AccordingtotheRomanpoetOvid,theAgesofManarefour:Gold,Silver,Bronze
and Iron. In his book ‘Metamorphoses’, he tells about the myth of the four Ages.
While the Golden Age and the Silver Age are symbolic and represent spirituality,
justiceandpeace,intheBronzeAgemenactuallyusedbronzeandduringtheIron
Agetheyusediron.Thesetwometalsplayedacardinalroleinthedevelopmentof
mankind. Their importance was evident upon their discovery and their use was
immediate.
Saint Jerome gave the chronology of these Ages, placing the Bronze Age
between the seventeenth and fifteenth centuries B.C. and the Iron Age from the
fifteenth century B.C. to his days, around 400 A.D. In modern history, the Bronze
Agestartedaround5000B.C.andlasteduntilabout1000B.C.,whentheIronAge
began. It lasted until 1 B.C.
Twomillennialater, thetwentiethcenturyhaswitnessedanew“MetallicAge”:
theRare-EarthAge.Itisnamedafteragroupofmetalsthat,unlikebronzeandiron,
had to wait 2000 years to be discovered. Unlike the two ancient metals, their
importance was not evidentupon theirdiscovery and their use was notimmediate.
Had they been discovered a millennium ago they would probably have been
doomedtooblivion.Evenaftertheirmoderndiscoverytheywereconsideredasan
oddity and, like another discovery of the twentieth century—the laser—one could
say they were a solution waiting for a problem.
However, they had one big advantage over the ancient metals: They aroused
curiosity. And curiosity is the driving force of mankind and of research. They
presented a challenge: first, to geologists, who found their ores just by chance, on
very rare regions on the earth—hence their name: rare-earths. Then to chemists,
who laboured hard to separate them, because they are all so similar chemically.
Then to physicists, and in particular to spectroscopists, who found their spectra so
difficult to analyze that they called them “complex spectra”.
Butthetwentiethcenturywasreadyforthem.Thescientistsrosetothechallenge
andthemysteryhasstartedtolift.Therealizationoftheirimportance—exactlydue
to their exotic characteristics—started to dawn both on the scientific community
vii
viii Preface
and on the industry. Their applications became a plethora. We are now in the
middle of a fascinating period of an interplay between theoretical and applied
research. The rare-earths attracted the interest of the industry that found them
indispensably useful in many areas. Exactly this usefulness incited the researchers
to delve even deeper into the structure of the rare-earths and explain the origin
of their extraordinary properties. They have also extended their attention to the
Actinides—the Rare-Earths heavier, man-made (except thorium and uranium)
homologuesinthePeriodicTable.Asaresulttherehasrecentlybeenaccumulateda
vastamountofknowledgeandinsightintothephysicalmechanismsthatareatthe
basis of these properties. This book tries to present an up-to-date review of the
achievements in this subject, that may inspire future accomplishments.
Contents
1 Electron Distributions and Crystalline Structures . . . . . . . . . . . . . . 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 The Electrons in Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.1 Energy Levels and Wavefunctions. . . . . . . . . . . . . . . . . . 2
1.2.2 Quantum Numbers and Configurations. . . . . . . . . . . . . . . 2
1.2.3 Electrostatic and Spin–Orbit Interactions, Couplings . . . . . 3
1.2.4 The 4f and 5f Shells-Lanthanides and Actinides . . . . . . . . 5
1.2.5 “Collapse” of the 4f Shell Wave functions . . . . . . . . . . . . 5
1.3 Electrons in Solids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1 Energy Distributions of the Valence Electrons. . . . . . . . . . 8
1.3.2 Models for Weakly Correlated Electrons . . . . . . . . . . . . . 10
1.3.3 The Electron Correlations. . . . . . . . . . . . . . . . . . . . . . . . 14
1.3.4 The s, p, d Densities of States. . . . . . . . . . . . . . . . . . . . . 26
1.3.5 4f Distributions in Rare-Earths . . . . . . . . . . . . . . . . . . . . 29
1.3.6 The 5f Distributions in Actinides. . . . . . . . . . . . . . . . . . . 42
1.3.7 Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
1.4 Crystalline Structures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
1.4.1 Crystal Structure of Rare-Earths . . . . . . . . . . . . . . . . . . . 55
1.4.2 Pressure Effect on the Rare-Earths. . . . . . . . . . . . . . . . . . 61
1.4.3 Crystal Structure of the Actinides . . . . . . . . . . . . . . . . . . 66
1.4.4 Pressure Effect on the Actinides . . . . . . . . . . . . . . . . . . . 71
1.4.5 Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
2 Electron Distributions and Physicochemical Properties . . . . . . . . . . 79
2.1 Rare-Earth Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.1.1 Oxides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.1.2 Chalcogenides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
2.1.3 Pnictides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
2.1.4 Intermetallics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
ix