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HANDBOOK ON THE PHYSICS AND CHEMISTRY
OF RARE EARTHS
Advisory Editorial Board
GIN-YA ADACHI
Kobe, Japan
WILLIAM J. EVANS
Irvine, USA
YURI GRIN
Dresden, Germany
SUZAN M. KAUZLARICH
Davis, USA
MICHAEL F. REID
Canterbury, New Zealand
CHUNHUA YAN
Beijing, P.R. China
Editors Emeritus
KARL A. GSCHNEIDNER, JR
Ames, USA
LEROY EYRINGw
Tempe, USA
w
Deceased (2005)
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experience broaden our understanding, changes in research methods, professional
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Practitioners and researchers must always rely on their own experience and knowledge
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ISBN: 978-0-444-63260-9
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Contributors
Numbers in Parentheses indicate the pages on which the author’s contributions begin.
Alban Ferrier (1), Institut de Recherche de Chimie Paris, CNRS-Chimie, ParisTech,
and Sorbonne Universités, UPMC Univ Paris 06, Paris, France
Koichiro Fujinaga (79), Department of Systems Innovation and Frontier Research
Center for Energy and Resources (FRCER), School of Engineering, The University
of Tokyo, Bunkyo-ku, Japan
Philippe Goldner (1), Institut de Recherche de Chimie Paris, CNRS-Chimie,
ParisTech, Paris, France
Olivier Guillot-Noël (1), Institut de Recherche de Chimie Paris, CNRS-Chimie,
ParisTech, Paris, France
Satoru Haraguchi (79), Department of Solid Earth Geochemistry, Japan Agency for
Marine-Earth Science and Technology (JAMSTEC), Yokosuka, Japan
Yasuhiro Kato (79), Department of Systems Innovation and Frontier Research Center
for Energy and Resources (FRCER), School of Engineering, The University of
Tokyo, Bunkyo-ku, Japan; Research and Development Center for Submarine
Resources, Japan Agency for Marine-Earth Science and Technology (JAMSTEC),
Yokosuka, Japan
Shiki Machida (79), Department of Resources and Environmental Engineering, School
of Creative Science and Engineering, Waseda University, Shinjyu-ku, Japan
Kentaro Nakamura (79), Department of Systems Innovation, School of Engineering,
The University of Tokyo, Bunkyo-ku, and Research and Development Center for
Submarine Resources, Japan Agency for Marine-Earth Science and Technology
(JAMSTEC), Yokosuka, Japan
Junichiro Ohta (79), Department of Systems Innovation, School of Engineering, The
University of Tokyo, Bunkyo-ku, Japan
Yutaro Takaya (79), Research and Development Center for Submarine Resources,
Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Yokosuka,
Japan
Kazutaka Yasukawa (79), Department of Systems Innovation, School of Engineering,
The University of Tokyo, Bunkyo-ku, Japan
vii
Preface
These elements perplex us in our reaches [sic], baffle 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 16, 1887)
Volume 46 of the Handbook on the Physics and Chemistry of Rare Earths
features two chapters covering two very different subjects pertaining to crys-
tals for quantum information and to potential new deep-sea resources.
Chapter 267 gives insight into a new and exciting field of quantum sci-
ence: quantum communications, storage, and computing. Digital information
is playing a crucial role in present-day world but its fundamental concepts
were developed at the beginning of the twentieth century. In the mid-1980s,
a new paradigm emerged in which classical bits of information that can only
take discrete values of 0 and 1 are replaced by quantum bits (qubits) able to
adopt any superposition state. Quantum processing information is, however,
requiring very sophisticated materials with highly demanding properties
because superposition states are destroyed by fluctuating environments.
Therefore, a classical carrier for quantum information is light because photons
only weakly interact with atoms and electromagnetic fields. Rare-earth-doped
crystals have very narrow optical transitions and are consequently well suited
as quantum information materials; appropriate ions include Pr3+, Nd3+, Eu3+,
Er3+, or Tm3+. After an introduction on quantum information and light-atom
interactions, the review focuses on rare-earth spectroscopy and associated
experimental techniques, absorption, hole burning and spectral tailoring for
observing hyperfine structures, Raman heterodyne scattering, as well as tech-
niques used for determining coherence lifetimes. Two applications are then
discussed in more details: quantum memories based on light and quantum
computers. In these last sections, concepts and protocols are presented as well
as a few representative experimental examples.
Chapter 268 deals with potential new rare-earth resources. Rare-earth
elements are distributed broadly in the Earth’s crust but in relatively small
concentrations and always as mixtures. Natural abundances of the ele-
ments in Earth’s crust vary considerably, from 60 to 70 ppm for cerium to
ix
x Preface
less than 0.5 ppm for lutetium. Several hundreds of rare-earth-containing

minerals are known, but only a few are exploited commercially. The minerals
containing light lanthanides (La through Eu) have an equivalent rare-earth
oxide (REO) content in the range 5–10 wt.%, while ion-adsorption clays
exploited for heavy lanthanides (Gd–Lu) and Y contain less than 1 wt.% of
REO. At the turn of the century, China emerged as the major producer of rare
earths worldwide with a share reaching over 95% in 2010. Exportation quotas
were introduced in 2006 and considerably reduced in 2010 following geopo-
litical tensions in Asia. As a consequence, several countries started to look
for alternative, possibly domestic, supplies. In this context, the authors of
the chapter report that deep-sea muds in the eastern South Pacific and central
North Pacific contain 0.1–0.2 wt.% rare earths and can be recovered by estab-
lished drilling techniques followed by simple acid leaching. The chapter first
presents rare-earth distribution in Pacific, Indian, and Atlantic Oceans
together with their lithological and geochemical characteristics. It then con-
tinues with a description of the minerals contained in the muds followed by
a detailed discussion of the advantages of this new rare-earth resource. The
review ends by presenting practical mining and leaching systems.
CHAPTER 267: RARE EARTH-DOPED CRYSTALS

FOR QUANTUM INFORMATION PROCESSING
By Philippe Goldner, Alban Ferrier, and Olivier Guillot-Noël
Chimie ParisTech and Université Pierre et Marie Curie, Paris, France
Preface xi
Quantum information processing uses superposition states of photons or

atoms to process, store, and transmits data in ways impossible to reach with
classical systems. For example, a quantum computer could find the prime fac-
tors of large numbers much faster than a classical computer. It could also be
used to efficiently simulate a collection of interacting quantum systems.
Moreover, quantum communications based on the fundamental laws of quan-
tum mechanics offer unrivaled security for data transmission. Quantum mem-
ories have also been developed to transfer quantum states between different
systems, like photons and atoms. It is even envisaged that the combination
of quantum computing, transmission, and storage could create a quantum
internet. Rare-earth-doped crystals have recently emerged as promising
solid-state systems for quantum information processing, mainly because they
exhibit very narrow optical transitions at low temperature. This allows one to
use these materials as quantum light-matter interfaces or to control their quan-
tum states optically. Moreover, many rare earths possess a nonzero nuclear
spin, opening perspectives for the use of long-lived quantum states in proces-
sing or storage.
After a brief introduction to quantum information processing and coherent
light-matter interactions, specific spectroscopic properties of rare-earth-doped
crystals are reviewed. This includes hyperfine structures, coherent properties
of optical and hyperfine transitions, as well as techniques to extend coherence
lifetimes. Two main applications are then dealt with: quantum memories
based on light and quantum computing. An example of quantum memory
relies on an entangled pair of photons in Y2SiO5:Nd(0.0003 at.%), while
high-fidelity, long storage can be achieved with La2(WO4)3:Pr(0.2 at.%). In
the case of quantum computing, single- (Y2SiO5:Pr(0.05 at.%)) and two-qubit
gates (Y2SiO5:Eu(0.02 at.%)) are presented.
CHAPTER 268: REY-RICH MUD: A DEEP-SEA MINERAL

RESOURCE FOR RARE EARTHS AND YTTRIUM
By Kentaro Nakamura, Koichiro Fujinaga, Kazutaka Yasukawa, Yutaro
Takaya, Junichiro Ohta, Shiki Machida, Satoru Haraguchi, and Yasuhiro Kato
The University of Tokyo, Japan Agency for Marine-Earth Science and
Technology, and Waseda University
Preface xiii
Rare-earth elements and yttrium (denoted REY in this chapter) are impor-
tant materials for high-technology applications and green energy technologies
(e.g., flat screen televisions, cell phones, electric/hybrid vehicles, and wind
power generators). World demand for REY is increasing rapidly, and a stable
supply of REY is required for future development of technology and the
global economy. Diversification of sources and increased access to REY
resources are, therefore, crucial to maintain supply capable of meeting the
ever-rising demand. Here, newly discovered extensive deposits of deep-sea
mud containing high REY concentrations (called REY-rich mud) are pre-
sented. The deep-sea REY-rich muds are characterized by (1) tremendous
resource potential by virtue of their wide distribution, (2) high REY concen-
trations with significant heavy lanthanide enrichment, (3) a stratiform distri-
bution that allows relatively simple and cost-effective exploration, (4) very
low concentrations of radioactive elements such as Th and U, and (5) ease
of extraction of REY by acid leaching. In addition, a system to mine REY-
rich muds can be developed based on a technique developed and tested to
mine sulfide-rich muds in the Red Sea and manganese nodules in the Pacific
Ocean. These features demonstrate that the REY-rich mud could constitute a
highly promising REY resource for the future.
The chapter starts with an introduction on rare-earth elements, their depos-
its onshore, as well as brief introduction of the new discovery of the REY-rich
mud. It then focuses on distribution, lithological and geochemical characteris-
tics, host phases, and genesis of REY-rich muds. The review ends with con-
siderations on resource potential, advantages of developing, and conceivable
development systems.
Jean-Claude G. B€ unzli
Vitalij K. Pecharsky
Contents of Volumes 1–45
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. Gschneidner Jr, Preparation and basic properties of the rare
earth metals 173
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. Sundstr€om, Low temperature heat capacity of the rare earth metals 379
6. K.A. McEwen, Magnetic and transport properties of the rare earths 411
7. S.K. Sinha, Magnetic structures and inelastic neutron scattering: metals, alloys and
compounds 489
8. T.E. Scott, Elastic and mechanical properties 591
9. A. Jayaraman, High pressure studies: metals, alloys and compounds 707
10. C. Probst and J. Wittig, Superconductivity: 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. landelli 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. P. Fulde, Crystal fields 295
18. R.G. Barnes, NMR, EPR and M€ ossbauer effect: metals, alloys and compounds 387
19. 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, 1st 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 81
23. C.K. Jørgensen, 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
xv
xvi Contents of Volumes 1–45
29. C.P. Khattak and F.F.Y. Wang, Perovskites and garnets 525
30. L.H. Brixner, J.R. Barkley and W. Jeitschko, Rare earth molybdates (VI) 609
Subject index 655
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. F. Hulliger, Rare earth pnictides 153
34. G. Blasse, Chemistry and physics of R-activated phosphors 237
35. M.J. Weber, Rare earth lasers 275
36. F.K. Fong, Nonradiative processes of rare-earth ions in crystals 317
37A. J.W. O’Laughlin, Chemical spectrophotometric and polarographic methods 341
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 V.A. Fassel, Optical atomic emission and absorption methods 405
37E. A.P. D’Silva and V.A. Fassel, X-ray excited optical luminescence of the rare
earths 441
37F. F.W.V. Boynton, Neutron activation 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, Shift 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 thermal conductivity) of rare earth intermetallic
compounds 117
43. F.P. Netzer and E. Bertel, Adsorption and catalysis on rare earth surfaces 217
44. C. Boulesteix, Defects and phase transformation near room temperature in rare earth
sesquioxides 321
45. O. Greis and J.M. Haschke, Rare earth fluorides 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 intermetallic compounds 1
48. E. Parthé and B. Chabot, Crystal structures and crystal chemistry of ternary rare
earth–transition metal borides, silicides and homologues 113
49. P. Rogl, Phase equilibria in ternary and higher order systems with rare earth elements
and boron 335
Contents of Volumes 1–45 xvii
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. P. Rogl, Phase equilibria in ternary and higher order systems with rare earth elements
and silicon 1
52. K.H.J. Buschow, Amorphous alloys 265
53. H. Schumann and W. Genthe, Organometallic compounds of the rare earths 446
Subject index 573
VOLUME 8
1986; ISBN 0-444-86971-9
54. K.A. Gschneidner Jr and F.W. Calderwood, Intra rare earth binary alloys: phase
relationships, lattice parameters and systematics 1
55. X. Gao, Polarographic analysis of the rare earths 163
56. M. Leskelä and L. Niinist€o, Inorganic complex compounds I 203
57. J.R. Long, Implications in organic synthesis 335
Errata 375
Subject index 379
VOLUME 9
1987; ISBN 0-444-87045-8
58. R. Reisfeld and C.K. Jørgensen, Excited state phenomena in vitreous materials 1
59. L. Niinist€o and M. Leskelä, Inorganic complex compounds II 91
60. J.-C.G. B€unzli, Complexes with synthetic ionophores 321
61. Zhiquan Shen and Jun Ouyang, Rare earth coordination catalysis in stereospecific
polymerization 395
Errata 429
Subject index 431
VOLUME 10: High energy spectroscopy

1987; 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 F.U. Hillebrecht, f-electron hybridization and dynamical screening
of core holes in intermetallic compounds 75
64. O. Gunnarsson and K. Sch€ onhammer, Many-body formulation of spectra of mixed
valence systems 103
65. A.J. Freeman, B.I. Min and M.R. Norman, Local density supercell theory of
photoemission and inverse photoemission spectra 165
66. D.W. Lynch and J.H. Weaver, Photoemission of Ce and its compounds 231
67. S. H€ufner, Photoemission in chalcogenides 301
68. J.F. Herbst and J.W. Wilkins, Calculation of 4f excitation energies in the metals and
relevance to mixed valence systems 321
69. B. Johansson and N. Mårtensson, Thermodynamic aspects of 4f levels in metals and
compounds 361
70. F.U. Hillebrecht and M. Campagna, Bremsstrahlung isochromat spectroscopy of alloys
and mixed valent compounds 425
xviii Contents of Volumes 1–45
71. J. R€ohler, X-ray absorption and emission spectra 453

72. F.P. Netzer and J.A.D. Matthew, Inelastic electron scattering measurements 547
Subject index 601
VOLUME 11: Two-hundred-year impact of rare earths on science

1988; ISBN 0-444-87080-6
H.J. Svec, Prologue 1
73. F. Szabadváry, The history of the discovery and separation of the rare earths 33
74. B.R. Judd, Atomic theory and optical spectroscopy 81
75. C.K. Jørgensen, Influence of rare earths on chemical understanding and
classification 197
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, The significance of the rare earths in geochemistry
and cosmochemistry 485
Errata 579
Subject index 581
VOLUME 12
1989; ISBN 0-444-87105-5
80. J.S. Abell, Preparation and crystal growth of rare earth elements and intermetallic
compounds 1
81. Z. Fisk and J.P. Remeika, Growth of single crystals from molten metal fluxes 53
82. E. Burzo and H.R. Kirchmayr, Physical properties of R2Fe14B-based alloys 71
83. A. Szytuła and J. Leciejewicz, Magnetic properties of ternary intermetallic compounds
of the RT2X2 type 133
84. H. Maletta and W. Zinn, Spin glasses 213
85. J. van Zytveld, Liquid metals and alloys 357
86. M.S. Chandrasekharaiah and K.A. Gingerich, Thermodynamic properties of gaseous
species 409
87. W.M. Yen, Laser spectroscopy 433
Subject index 479
VOLUME 13
1990; ISBN 0-444-88547-1
88. E.I. Gladyshevsky, O.I. Bodak and V.K. Pecharsky, Phase equilibria and crystal
chemistry in ternary rare earth systems with metallic elements 1
89. A.A. Eliseev and G.M. Kuzmichyeva, Phase equilibrium and crystal chemistry in
ternary rare earth systems with chalcogenide elements 191
90. N. Kimizuka, E. Takayama-Muromachi and K. Siratori, The systems R2O3–M2O3–
M0 O 283
91. R.S. Houk, Elemental analysis by atomic emission and mass spectrometry with
inductively coupled plasmas 385
92. P.H. Brown, A.H. Rathjen, R.D. Graham and D.E. Tribe, Rare earth elements in
biological systems 423
Errata 453
Subject index 455
Contents of Volumes 1–45 xix
VOLUME 14
1991; ISBN 0-444-88743-1
93. R. Osborn, S.W. Lovesey, A.D. Taylor and E. Balcar, Intermultiplet transitions using
neutron spectroscopy 1
94. E. Dormann, NMR in intermetallic compounds 63
untherodt, Light scattering in intermetallic compounds 163
95. E. Zirngiebl and G. G€
uthi, The electron–phonon interaction in intermetallic
96. P. Thalmeier and B. L€
compounds 225
97. N. Grewe and F. Steglich, Heavy fermions 343
Subject index 475
VOLUME 15
1991; ISBN 0-444-88966-3
98. J.G. Sereni, Low-temperature behaviour of cerium compounds 1
99. G.-Y. Adachi, N. Imanaka and Zhang Fuzhong, Rare earth carbides 61
100. A. Simon, Hj. Mattausch, G.J. Miller, W. Bauhofer and R.K. Kremer, Metal-rich
halides 191
101. R.M. Almeida, Fluoride glasses 287
102. K.L. Nash and J.C. Sullivan, Kinetics of complexation and redox reactions of the
lanthanides in aqueous solutions 347
103. E.N. Rizkalla and G.R. Choppin, Hydration and hydrolysis of lanthanides 393
104. L.M. Vallarino, Macrocycle complexes of the lanthanide(III), yttrium(III), and
dioxouranium (VI) ions from metal-templated syntheses 443
Errata 513
Subject index 515
CUMULATIVE INDEX, Vols. 1–15

1993; ISBN 0-444-89965-0
VOLUME 16
1993; ISBN 0-444-89782-8
105. M. Loewenhaupt and K.H. Fischer, Valence-fluctuation and heavy-fermion 4f
systems 1
106. I.A. Smirnov and V.S. Oskotski, Thermal conductivity of rare earth compounds 107
107. M.A. Subramanian and A.W. Sleight, Rare earth pyrochlores 225
108. R. Miyawaki and I. Nakai, Crystal structures of rare earth minerals 249
109. D.R. Chopra, Appearance potential spectroscopy of lanthanides and their
intermetallics 519
Author index 547
Subject index 579
VOLUME 17: Lanthanides/Actinides: Physics – I

1993; ISBN 0-444-81502-3
110. M.R. Norman and D.D. Koelling, Electronic structure, Fermi surfaces, and
superconductivity in f electron metals 1
111. S.H. Liu, Phenomenological approach to heavy-fermion systems 87
112. B. Johansson and M.S.S. Brooks, Theory of cohesion in rare earths and
actinides 149
113. U. Benedict and W.B. Holzapfel, High-pressure studies – Structural aspects 245
xx Contents of Volumes 1–45
114. O. Vogt and K. Mattenberger, Magnetic measurements on rare earth and actinide
monopnictides and monochalcogenides 301
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, M€ ossbauer studies on electronic structure of
intermetallic compounds 539
117. G.H. Lander, Neutron elastic scattering from actinides and anomalous
lanthanides 635
Author index 711
Subject index 753
VOLUME 18: Lanthanides/Actinides: Chemistry

1994; ISBN 0-444-81724-7
118. G.T. Seaborg, Origin of the actinide concept 1
119. K. Balasubramanian, Relativistic effects and electronic structure of lanthanide and
actinide molecules 29
120. J.V. Beitz, Similarities and differences in trivalent lanthanide- and actinide-ion
solution absorption spectra and luminescence studies 159
121. K.L. Nash, Separation chemistry for lanthanides and trivalent actinides 197
122. L.R. Morss, Comparative thermochemical and oxidation – reduction properties of
lanthanides and actinides 239
123. J.W. Ward and J.M. Haschke, Comparison of 4f and 5f element hydride
properties 293
124. H.A. Eick, Lanthanide and actinide halides 365
125. R.G. Haire and L. Eyring, Comparisons of the binary oxides 413
126. S.A. Kinkead, K.D. Abney and T.A. O’Donnell, f-Element speciation in strongly
acidic media: lanthanide and mid-actinide metals, oxides, fluorides and oxide
fluorides in superacids 507
127. E.N. Rizkalla and G.R. Choppin, Lanthanides and actinides hydration and
hydrolysis 529
128. G.R. Choppin and E.N. Rizkalla, Solution chemistry of actinides and
lanthanides 559
129. J.R. Duffield, D.M. Taylor and D.R. Williams, The biochemistry of the f-
elements 591
Author index 623
Subject index 659
VOLUME 19: Lanthanides/Actinides: Physics – II

1994; ISBN 0-444-82015-9
130. E. Holland-Moritz and G.H. Lander, Neutron inelastic scattering from actinides and
anomalous lanthanides 1
131. G. Aeppli and C. Broholm, Magnetic correlations in heavy-fermion systems: neutron
scattering from single crystals 123
132. P. Wachter, Intermediate valence and heavy fermions 177
133. J.D. Thompson and J.M. Lawrence, High pressure studies – Physical properties of
anomalous Ce, Yb and U compounds 383
134. C. Colinet and A. Pasturel, Thermodynamic properties of metallic systems 479
Author index 649
Subject index 693
Contents of Volumes 1–45 xxi
VOLUME 20
1995; ISBN 0-444-82014-0
135. Y. Ōnuki and A. Hasegawa, Fermi surfaces of intermetallic compounds 1
136. M. Gasgnier, The intricate world of rare earth thin films: metals, alloys,
intermetallics, chemical compounds,. . . 105
137. P. Vajda, Hydrogen in rare-earth metals, including RH2+x phases 207
138. D. Gignoux and D. Schmitt, Magnetic properties of intermetallic compounds 293
Author index 425
Subject index 457
VOLUME 21
1995; ISBN 0-444-82178-3
139. R.G. Bautista, Separation chemistry 1
140. B.W. Hinton, Corrosion prevention and control 29
141. N.E. Ryan, High-temperature corrosion protection 93
142. T. Sakai, M. Matsuoka and C. Iwakura, Rare earth intermetallics for metal–hydrogen
batteries 133
143. G.-y. Adachi and N. Imanaka, Chemical sensors 179
144. D. Garcia and M. Faucher, Crystal field in non-metallic (rare earth) compounds 263
145. J.-C.G. B€unzli and A. Milicic-Tang, Solvation and anion interaction in organic
solvents 305
146. V. Bhagavathy, T. Prasada Rao and A.D. Damodaran, Trace determination of
lanthanides in high-purity rare-earth oxides 367
Author index 385
Subject index 411
VOLUME 22
1996; ISBN 0-444-82288-7
147. C.P. Flynn and M.B. Salamon, Synthesis and properties of single-crystal
nanostructures 1
148. Z.S. Shan and D.J. Sellmyer, Nanoscale rare earth–transition metal multilayers:
magnetic structure and properties 81
149. W. Suski, The ThMn12-type compounds of rare earths and actinides: structure,
magnetic and related properties 143
150. L.K. Aminov, B.Z. Malkin and M.A. Teplov, Magnetic properties of nonmetallic
lanthanide compounds 295
151. F. Auzel, Coherent emission in rare-earth materials 507
152. M. Dolg and H. Stoll, Electronic structure calculations for molecules containing
lanthanide atoms 607
Author index 731
Subject index 777
VOLUME 23
1996; ISBN 0-444-82507-X
153. J.H. Forsberg, NMR studies of paramagnetic lanthanide complexes and shift
reagents 1
154. N. Sabbatini, M. Guardigli and I. Manet, Antenna effect in encapsulation complexes
of lanthanide ions 69
155. C. G€orller-Walrand and K. Binnemans, Rationalization of crystal-field
parameterization 121
156. Yu. Kuz’ma and S. Chykhrij, Phosphides 285
xxii Contents of Volumes 1–45
157. S. Boghosian and G.N. Papatheodorou, Halide vapors and vapor complexes 435
158. R.H. Byrne and E.R. Sholkovitz, Marine chemistry and geochemistry of the
lanthanides 497
Author index 595
Subject index 631
VOLUME 24
1997; ISBN 0-444-82607-6
159. P.A. Dowben, D.N. McIlroy and Dongqi Li, Surface magnetism of the lanthanides 1
160. P.G. McCormick, Mechanical alloying and mechanically induced chemical reactions 47
161. A. Inoue, Amorphous, quasicrystalline and nanocrystalline alloys in Al- and Mg-based
systems 83
162. B. Elschner and A. Loidl, Electron-spin resonance on localized magnetic
moments in metals 221
163. N.H. Duc, Intersublattice exchange coupling in the lanthanide-transition
metal intermetallics 339
164. R.V. Skolozdra, Stannides of rare-earth and transition metals 399
Author index 519
Subject index 559
VOLUME 25
1998; ISBN 0-444-82871-0
165. H. Nagai, Rare earths in steels 1
166. R. Marchand, Ternary and higher order nitride materials 51
167. C. G€orller-Walrand and K. Binnemans, Spectral intensities of f–f transitions 101
168. G. Bombieri and G. Paolucci, Organometallic p complexes of the f-elements 265
Author index 415
Subject index 459
VOLUME 26
1999; ISBN 0-444-50815-1
169. D.F. McMorrow, D. Gibbs and J. Bohr, X-ray scattering studies of lanthanide
magnetism 1
170. A.M. Tishin, Yu.I. Spichkin and J. Bohr, Static and dynamic stresses 87
171. N.H. Duc and T. Goto, Itinerant electron metamagnetism of Co sublattice in the
lanthanide–cobalt intermetallics 177
172. A.J. Arko, P.S. Riseborough, A.B. Andrews, J.J. Joyce, A.N. Tahvildar-Zadeh and M.
Jarrell, Photo-electron spectroscopy in heavy fermion systems: Emphasis on single
crystals 265
Author index 383
Subject index 405
VOLUME 27
1999; ISBN 0-444-50342-0
173. P.S. Salamakha, O.L. Sologub and O.I. Bodak, Ternary rare-earth-germanium
systems 1
174. P.S. Salamakha, Crystal structures and crystal chemistry of ternary rare-earth
germanides 225
175. B. Ya. Kotur and E. Gratz, Scandium alloy systems and intermetallics 339
Author index 535
Subject index 553
Contents of Volumes 1–45 xxiii
VOLUME 28
2000; ISBN 0-444-50346-3
176. J.-P. Connerade and R.C. Karnatak, Electronic excitation in atomic species 1
177. G. Meyer and M.S. Wickleder, Simple and complex halides 53
178. R.V. Kumar and H. Iwahara, Solid electrolytes 131
179. A. Halperin, Activated thermoluminescence (TL) dosimeters and related radiation
detectors 187
180. K.L. Nash and M.P. Jensen, Analytical separations of the lanthanides: basic chemistry
and methods 311
Author index 373
Subject index 401
VOLUME 29: The role of rare earths in catalysis

2000; ISBN 0-444-50472-9
P. Maestro, Foreword 1
181. V. Paul-Boncour, L. Hilaire and A. Percheron-Guégan, The metals and alloys in
catalysis 5
182. H. Imamura, The metals and alloys (prepared utilizing liquid ammonia solutions) in
catalysis II 45
183. M.A. Ulla and E.A. Lombardo, The mixed oxides 75
184. J. Kašpar, M. Graziani and P. Fornasiero, Ceria-containing three-way catalysts 159
185. A. Corma and J.M. López Nieto, The use of rare-earth-containing zeolite
catalysts 269
186. S. Kobayashi, Triflates 315
Author index 377
Subject index 409
VOLUME 30: High-Temperature Superconductors – I

2000; ISBN 0-444-50528-8
187. M.B. Maple, High-temperature superconductivity in layered cuprates: overview 1
188. B. Raveau, C. Michel and M. Hervieu, Crystal chemistry of superconducting rare-
earth cuprates 31
189. Y. Shiohara and E.A. Goodilin, Single-crystal growth for science and technology 67
190. P. Karen and A. Kjekshus, Phase diagrams and thermodynamic properties 229
191. B. Elschner and A. Loidl, Electron paramagnetic resonance in cuprate
superconductors and in parent compounds 375
192. A.A. Manuel, Positron annihilation in high-temperature superconductors 417
193. W.E. Pickett and I.I. Mazin, RBa2Cu3O7 compounds: electronic theory and physical
properties 453
194. U. Staub and L. Soderholm, Electronic 4f-state splittings in cuprates 491
Author index 547
Subject index 621
VOLUME 31: High-Temperature Superconductors – II

2001; ISBN 0-444-50719-1
195. E. Kaldis, Oxygen nonstoichiometry and lattice effects in YBa2Cu3Ox. Phase
transitions, structural distortions and phase separation 1
196. H.W. Weber, Flux pinning 187
197. C.C. Almasan and M.B. Maple, Magnetoresistance and Hall effect 251
198. T.E. Mason, Neutron scattering studies of spin fluctuations in high-temperature
superconductors 281
xxiv Contents of Volumes 1–45
199. J.W. Lynn and S. Skanthakumar, Neutron scattering studies of lanthanide magnetic
ordering 315
200. P.M. Allenspach and M.B. Maple, Heat capacity 351
201. M. Schabel and Z.-X. Shen, Angle-resolved photoemission studies of untwinned
yttrium barium copper oxide 391
202. D.N. Basov and T. Timusk, Infrared properties of high-Tc superconductors: an
experimental overview 437
203. S.L. Cooper, Electronic and magnetic Raman scattering studies of the high-Tc
cuprates 509
204. H. Sugawara, T. Hasegawa and K. Kitazawa, Characterization of cuprate
superconductors using tunneling spectra and scanning tunneling microscopy 563
Author index 609
Subject index 677
VOLUME 32
2001; ISBN 0-444-50762-0
205. N.H. Duc, Giant magnetostriction in lanthanide-transition metal thin films 1
206. G.M. Kalvius, D.R. Noakes and O. Hartmann, mSR studies of rare-earth and actinide
magnetic materials 55
207. Rainer P€ottgen, Dirk Johrendt and Dirk Kußmann, Structure–property relations of
ternary equiatomic YbTX intermetallics 453
208. Kurima Kobayashi and Satoshi Hirosawa, Permanent magnets 515
209. I.G. Vasilyeva, Polysulfides 567
210. Dennis K.P. Ng, Jianzhuang Jiang, Kuninobu Kasuga and Kenichi Machida, Half-
sandwich tetrapyrrole complexes of rare earths and actinides 611
Author index 655
Subject index 733
VOLUME 33
2003; ISBN 0-444-51323-X
211. Brian C. Sales, Filled skutterudites 1
212. Oksana L. Sologub and Petro S. Salamakha, Rare earth – antimony systems 35
213. R.J.M. Konings and A. Kovács, Thermodynamic properties of the lanthanide (III)
halides 147
214. John B. Goodenough, Rare earth – manganese perovskites 249
215. Claude Piguet and Carlos F.G.C. Geraldes, Paramagnetic NMR lanthanide induced
shifts for extracting solution structures 353
216. Isabelle Billard, Lanthanide and actinide solution chemistry as studied by time-
resolved emission spectroscopy 465
217. Thomas Tr€oster, Optical studies of non-metallic compounds under presure 515
Author index 591
Subject index 637
VOLUME 34
2004; ISBN 0-444-51587-9
218. Yaroslav M. Kalychak, Vasyl’ I. Zaremba, Rainer P€ ottgen, Mar’yana Lukachuk and
Rolf-Dieter Hoffman, Rare earth–transition metal–indides 1
219. P. Thalmeier and G. Zwicknagl, Unconventional superconductivity and magnetism in
lanthanide and actinide intermetallic compounds 135
220. James P. Riehl and Gilles Muller, Circularly polarized luminescence spectroscopy
from lanthanide systems 289
Contents of Volumes 1–45 xxv
221. Oliver Guillou and Carole Daiguebonne, Lanthanide-containing coordination

polymers 359
222. Makoto Komiyama, Cutting DNA and RNA 405
Author index 455
Subject index 493
VOLUME 35
2005; ISBN 0-444-52028-7
223. Natsuko Sakai, Katsuhiko Yamaji, Teruhisa Horita, Yue Ping Xiong and Harumi
Yokokawa, Rare-earth materials for solid oxide fuel cells (SOFC) 1
224. Mathias S. Wickleder, Oxo-selenates of rare-earth elements 45
225. Koen Binnemans, Rare-earth beta-diketonates 107
226. Satoshi Shinoda, Hiroyuki Miyake and Hiroshi Tsukube, Molecular recognition and
sensing via rare-earth complexes 273
Author index 337
Subject index 377
VOLUME 36
2006; ISBN 0-444-52142-9
227. Arthur Mar, Bismuthides 1
228. I. Aruna, L.K. Malhotra and B.R. Mehta, Switchable metal hydride films 83
229. Koen Binnemans, Applications of tetravalent cerium compounds 281
230. Robert A. Flowers II and Edamana Prasad, Samarium (II) based reductants 393
Author index 475
Subject index 511
VOLUME 37: Optical Spectroscopy

2007; ISBN 978-0-444-52144-6
231. Kazuyoshi Ogasawara, Shinta Watanabe, Hiroaki Toyoshima and Mikhail G. Brik,
First-principles calculations of 4fn ! 4fn1 5d transition spectra 1
232. Gary W. Burdick and Michael F. Reid, 4fn4fn1 5d transitions 61
233. Guokui Liu and Xueyuan Chen, Spectroscopic properties of lanthanides in
nanomaterials 99
234. Takuya Nishioka, Kôichi Fukui and Kazuko Matsumoto, Lanthanide chelates as
luminescent labels in biomedical analyses 171
235. Steve Comby and Jean-Claude G. B€ unzli, Lanthanide near-infrared luminescence in
molecular probes and devices 217
Author index 471
Subject index 503
VOLUME 38
2008; ISBN 978-0-444-52143-9
236. Z.C. Kang, Lanthanide higher oxides: The contributions of Leroy Eyring 1
237. Rainer P€ottgen and Ute Ch. Rodewald, Rare earth–transition metal–plumbides 55
238. Takao Mori, Higher borides 105
239. K.-H. M€uller, M. Schneider, G. Fuchs and S.-L. Drechsler, Rare-earth nickel
borocarbides 175
240. Michael T. Pope, Polyoxometalates 337
Author index 383
Subject index 431
xxvi Contents of Volumes 1–45
VOLUME 39
2009; ISBN 978-0-444-53221-3
241. W.M. Temmerman, L. Petit, A. Svane, Z. Szotek, M. L€ uders, P. Strange,
J.B. Staunton, I.D. Hughes, and B.L. Gyorffy, The dual, localized or
band-like, character of the 4f-states 1
242. L. Vasylechko, A. Senyshyn, and U. Bismayer, Perovskite-type aluminates
and gallates 113
243. Toshihiro Yamase, Luminescence of polyoxometallolanthanoates and photochemical
nano-ring formation 297
Author index 357
Subject index 381
VOLUME 40
2010; ISBN 978-0-444-53220-6
244. Christiane G€orller-Walrand and Linda Fluyt, Magnetic circular dichroism of
lanthanides 1
245. Z. Zheng, Cluster compounds of rare-earth elements 109
246. François Nief, Molecular chemistry of the rare-earth elements in
uncommon low-valent states 241
247. Claude Piguet and Jean-Claude G. B€ unzli, Self-Assembled lanthanide helicates: From
basic thermodynamics to applications 301
Author index 555
Subject index 583
VOLUME 41
2011; ISBN 978-0-444-53590-0
248. Pieter Thyssen and Koen Binnemans, Accommodation of the rare earths in the
periodic table: A historical analysis 1
249. Hisanori Shinohara and Yahachi Saito, Metallofullerenes 95
250. Lubomir D. Gulay and Marek Daszkiewicz, Ternary and quaternary chalcogenides of
Si, Ge, Sn, Pb, and In 157
251. Chun-Hua Yan, Zheng-Guang Yan, Ya-Ping Du, Jie Shen, Chao Zhang,
and Wei Feng, Controlled synthesis and properties of rare earth nanomaterials 275
Author index 473
Subject index 517
VOLUME 42
2012; ISBN 978-0-444-54316-5
252. Y. Uwatoko, I. Umehara, M. Ohashi, T. Nakano, and G. Oomi, Thermal and
electronic properties of rare earth compounds at high pressure 1
253. Alexander D. Chervonnyi, Thermodynamic properties of lanthanide fluorides and
chlorides in the gaseous and condensed states 165
Author index 485
Subject index 507
VOLUME 43: Including Actinides

2013; ISBN 978-0-444-59536-2
254. Koen Binnemans, Lanthanidomesogens 1
255. Mikiya Tanaka, Tatsuya Oki, Kazuya Koyama, Hirokazu Narita, and Tetsuo Oishi,
Recycling of rare earths from scrap 159
Contents of Volumes 1–45 xxvii
256. Isabelle Billard, Ionic liquids: New hopes for efficient lanthanide/actinide extraction
and separation? 213
257. Gopi K. Samudrala and Yogesh K. Vohra, Structural properties of lanthanides at ultra
high pressure 275
258. John W. Arblaster, Selected values of the thermodynamic properties of scandium,
yttrium, and the lanthanide elements 321
Author index 567
Subject index 591

2014; ISBN 978-0-444-62711-7
259. Sophie M. Guillaume, Laurent Maron, and Peter W. Roesky, Catalytic behavior of
rare-earth borohydride complexes in polymerization of polar monomers 1
260. Yasuhiko Iwadate, Structures and properties of rare-earth molten salts 87
261. Jean-Claude G. B€unzli and Anne-Sophie Chauvin, Lanthanides in solar energy
conversion 169
262. Yaroslav Mudryk, Vitalij K. Pecharsky, and Karl A. Gschneidner, Jr., R5T4
Compounds: An extraordinary versatile model system for the solid state science 283
Index 451

2014; ISBN 978-0-444-63256-2
263. Joaquim Marçalo and John K. Gibson, Gas-phase ion chemistry of rare earths and
actinides 1
264. Gerd Meyer, Symbiosis of intermetallic and salt: Rare-earth metal cluster complexes
with endohedral transition metal atoms 111
265. Markus P. Hehlen, Mansoor Sheik-Bahae, and Richard I. Epstein. Solid-state optical
refrigeration 179
266. Wenliang Huang and Paula L. Diaconescu, Rare earth arene-bridged complexes
obtained by reduction of organometallic precursors 261
Index 331
Index of Contents of Volumes 1–46
4f excitation energies, calculations B

of 10, ch. 68, p. 321 batteries, recycling of 43, ch. 255, p. 159
4f levels, thermodynamic aspects beta-diketonates 35, ch. 225, p. 107
10, ch. 69, p. 361 – mesogenic complexes 43, ch. 254, p. 1
4f state splittings in cuprates 30, Belousov-Zhabotinsky reactions 36,
ch. 194, p. 491 ch. 229, p. 281
4f states, character of 39, ch. 241, p. 1 biochemistry 18, ch. 129, p. 591
4f n-4f n-15d transitions 37, ch. 231, bioinorganic chemistry 4, ch. 39, p. 515
p. 1; 37, ch. 232, p. 61 biological systems 13, ch. 92, p. 423
bioprobes 40, ch. 247, p. 301
biphenyl complexes 45, ch. 266, p. 261
A bis(benzimidazole)pyridine
ab-initio calculation of energy – mesogenic complexes 43, ch. 254, p. 1
levels 37, ch. 231, p. 1 – self-assembled complexes 40, ch. 247,
absorption spectra of ions in p. 303
solution 3, ch. 24, p. 171; 18, bismuth alloy systems 36, ch. 227, p. 1
ch. 120, p. 159 borides 6, ch. 48, p. 113; 6, ch. 49,
actinides origin of concept 18, p. 335; 38, ch. 238, p. 105; 38,
ch. 118, p. 1 ch. 239, p. 175
– extraction of 43, ch. 256, p. 213 borohydride complexes 44, ch. 259, p. 1
– separation from lanthanides 43,
ch. 256, p. 213
activated phosphors 4, ch. 34, p. 237 C
activated thermoluminescence 28, carbides 15, ch. 99, p. 61; 38, ch. 239, p. 175
ch. 179, p. 187 Carnall, William T. 37, dedication, p. xiii
activation catalysis 29, foreword, p. 1
– of P4 by rare earths 45, ch. 266, p. 261 – arene-bridged complexes 45, ch. 266,
aluminates 39, ch. 242, p. 113 p. 261
amorphous alloys 7, ch. 52, p. 265 – borohydrides 44, ch. 259, p. 1
– Al- and Mg-based 24, ch. 161, p. 83 – ceria-containing three-way 29,
– magnetic 2, ch. 16, p. 259 ch. 184, p. 159
anion interaction in organic solvents 21, – metals and alloys 29, ch. 181, p. 5
ch. 145, p. 305 – metals and alloys in liquid ammonia
antimony alloy systems 33, solutions 29, ch. 182, p. 45
ch. 212, p. 35 – stereospecific polymerization 9, ch. 61,
An-Ln separation using ionic liquids 43, p. 395; 44, ch. 262, p. 283
ch. 256, p. 213 – mixed oxides 29, ch. 183, p. 75
Atomic ions – zeolites 29, ch. 185, p. 269
– actinides in gas phase 45, ch. 263, p. 1 catalysts, recycling of 43, ch. 255, p. 159
– rare-earth ions in gas phase 45, ch. 263, cerimetry 36, ch. 229, p. 281
p. 1 cerium 1, ch. 4, p. 337
arene-bridged complexes 45, ch. 266, p. 261 cerium compounds
atomic properties (free atom) 1, ch. 1, p. 1 – low-temperature behavior 15, ch. 98, p. 1
atomic theory 11, ch. 74, p. 81 – tetravalent 36, ch. 229, p. 281
xxix
xxx Index of Contents of Volumes 1–46
cerium(IV) – macrocycles 15, ch. 104, p. 443

– catalysts 36, ch. 229, p. 281 – molecular recognition in 35, ch. 226,
– mediated reactions 36, ch. 229, p. 281 p. 273
– redox properties 36, ch. 229, p. 281 – organometallic p type 25, ch. 168, p. 265
chalcogenides, – polyoxometalates 38, ch. 240, p. 337
– magnetic measurements on mono- 17, – sensing in 35, ch. 226, p. 273
ch. 114, p. 301 – with synthetic ionophores 9, ch. 60, p. 321
– quaternary 41, ch. 250, p. 157 coordination in organic solvents 21,
– ternary 41, ch. 250, p. 157 ch. 145, p. 305
chemical analysis by coordination polymers 34, ch. 221, p. 359
– atomic emission with inductively coupled corrosion
plasmas 13, ch. 91, p. 385 – prevention and control 21, ch. 140, p. 29
– mass spectrometry, see spectroscopy, mass – protection 21, ch. 141, p. 93
– neutron activation 4, ch. 37F, p. 457 cosmochemistry 11, ch. 79, p. 485
– optical absorption 4, ch. 37D, p. 405 crystal chemistry
– optical atomic emission 4, ch. 37D, p. 405 – of aluminates 39, ch. 242, p. 113
– polarography 4, ch. 37A, p. 341; 8, – of elements at ultra high pressure 43,
ch. 55, p. 163 ch. 257, p. 275
– spectrophotometry 4, ch. 37A, p. 341 – of gallates 39, ch. 242, p. 113
– trace determination in high-purity – of higher borides 38, ch. 238, p. 105
oxides 21, ch. 146, p. 367 – of intermetallic compounds 2, ch. 13, p. 1
– x-ray excited optical luminescence 4, – of quaternary systems with chalcogenides
ch. 37E, p. 441 41, ch. 250, p. 157
chemical sensors 21, ch. 143, p. 179 – of R5T4 intermetallic compound 44,
chemical understanding and ch. 262, p. 283
classification 11, ch. 75, p. 197 – of ternary germanides 27, ch. 174, p. 225
chirality sensing 35, ch. 226, p. 273 – of ternary systems with chalcogenides 13,
chlorides, thermodynamic properties of 42, ch. 89, p. 191; 41, ch. 250, p. 157
ch. 253, p. 165 – of ternary systems with metallic
cluster compounds 40, ch. 245, p. 109 elements 13, ch. 88, p. 1
– produced from solids and solutions 45, – of ternary transition metal
ch. 263, p. 1 borides 6, ch. 48, p. 113
cluster halides – of ternary transition metal
– structure of 45, ch. 264, p. 111 plumbides 38, ch. 237, p. 55
– synthesis of 45, ch. 264, p. 111 – of ternary transition metal silicides 6,
coherent emission 22, ch. 151, p. 507 ch. 48, p. 113
cohesion, theory of 17, ch. 112, p. 149 – of ThMn12-type compounds 22,
complexes (also see lanthanide ch. 149, p. 143
chelates) 3, ch. 25, p. 209 crystal field 2, ch. 17, p. 295
– antenna effect 23, ch. 154, p. 69 – in non-metallic compounds 21,
– arene-bridged 45, ch. 266, p. 261 ch. 144, p. 263
– beta-diketonates 35, ch. 225, p. 107 – parametrization, rationalization of 23,
– biphenyl 45, ch. 266. p. 261 ch. 155, p. 121
– borohydrides in catalysis 44, ch. 259, crystal structures, see crystal chemistry
p. 1 cuprates
– encapsulation 23, ch. 154, p. 69 – 4f state splittings 30, ch. 194, p. 491
– group 3 stilbene 45, ch. 266, p. 261 – crystal chemistry 30, ch. 188, p. 31
– half-sandwich tetrapyrrole 32, – electron paramagnetic resonance (EPR)
ch. 210, p. 611 30, ch. 191, p. 375
– inorganic 8, ch. 56, p. 203; 9, – electronic theory 30, ch. 193, p. 453
ch. 59, p. 91 – flux pinning 31, ch. 196, p. 187
– low-valent state 40, ch. 246, p. 241 – Hall effect 31, ch. 197, p. 251
Index of Contents of Volumes 1–46 xxxi
– heat capacity 31, ch. 200, p. 351 E

– infrared properties 31, ch. 202, p. 437 elastic and mechanical properties of
– magnetoresistance 31, ch. 197, p. 251 metals 1, ch. 8, p. 591
– neutron scattering electron paramagnetic resonance (EPR) 2,
– – magnetic ordering 31, ch. 199, p. 315 ch. 18, p. 387; 24, ch. 162, p. 221
– – spin fluctuations 31, ch. 198, p. 281 – in cuprate superconductors 30, ch. 191,
– overview 30, ch. 187, p. 1 p. 375
– oxygen nonstoichiometry and lattice electronic excitation in atomic species 28,
effect 31, ch. 195, p. 1 ch. 176, p. 1
– phase equilibria 30, ch. 190, p. 229 electronic properties of compounds at high
– – of R5T4 intermetallic compounds 44, pressure 42, ch. 252, p. 1
ch. 262, p. 283 electronic structure
– phase transitions, structural distortions and – of actinide atomic ions in gas phase 45,
phase separation 31, ch. 195, p. 1 ch. 263, p. 1
– – in R5T4 intermetallic compounds 44, – calculations for molecules 22, ch. 152,
ch. 262, p. 283 p. 607
– photoemission, angle-resolved studies 31, – of chalcogenides 39, ch. 241, p. 1
ch. 201, p. 391 – of metals 1, ch. 3, p. 233; 17,
– physical properties 30, ch. 193, p. 453 ch. 110, p. 1; 39, ch. 241, p. 1
– – of R5T4 intermetallic compounds 44, – of oxides 39, ch. 241. p. 1
ch. 262, p. 283 – of rare-earth atomic ions in gas phase 45,
– positron annihilation 30, ch. 192, p. 417 ch. 263, p. 1
– Raman scattering 31, ch. 203, p. 509 – of pnictides 39, ch. 241, p. 1
– scanning tunneling microscopy 31, electronic theory of cuprates 30, ch. 193,
ch. 204, p. 563 p. 453
– single crystals, growth of 30, ch. 189, p. 67 electron-phonon interaction in intermetallic
– superconductivity 30; 31 compounds 14, ch. 96, p. 225
– thermochemical properties 30, ch. 190, electron-spin resonance, see electron
p. 229 paramagnetic resonance
– tunneling spectra 31, ch. 204, p. 563 emission spectra (also see fluorescence and
luminescence)
D – in solution 3, ch. 24, 172
dedications – X-ray excited 10, ch. 71, p. 453
– F. H. Spedding 11, p. 1 energetics
– Friedrich Hund 14, p. ix – of actinide ions in gas phase 45,
– LeRoy Eyring 36, p. xi ch. 263, p. 1
– William T. Carnall 37, p. xiii – of rare-earth ions in gas phase 45,
diffraction techniques ch. 263, p. 1
– at high pressure 42, ch. 242, p. 4 enthalpy of atomization
– for molten salts structure determination – of fluorides 42, ch. 253, p. 429
diketonates, see beta-diketonates – of monochlorides 42, ch. 253, p. 412
diffusion in metals 1, ch. 12, p. 847 – of RX+ ions 42, ch. 253, p. 436
divalent samarium in organic enthalpy of formation
chemistry 6, ch. 50, p. 525; 36, – calculation with Born-Haber cycle 42,
ch. 230, p. 393 ch. 253, p. 324
divalent ytterbium in organic chemistry 6, – of crystalline dichlorides 42, ch. 253, p. 318
ch. 50, p. 525 – of crystalline trichlorides 42, ch. 253,
DNA, cutting of 34, ch. 222, p. 405 p. 271
dye-sensitized solar cells, lanthanides in 44, – of trichlorides, from mass spectra 42,
ch. 261, p. 169 ch. 253, p. 306
dynamical screening of core holes in – of trichlorides, from saturated vapor
intermetallic compounds 10, ch. 63, p. 75 data 42, ch. 253, p. 306
xxxii Index of Contents of Volumes 1–46
enthalpy of phase transition fluorides

– of crystalline trichlorides 42, ch. 253, –properties 5, ch. 45, p. 387
p. 256 –thermodynamic properties 42,
enthalpy of reaction involving RF, RF2, and ch. 253, p. 165
RCl 42, ch. 253, p. 403 flux pinning in cuprates 31,
enthalpy of sublimation ch. 196, p. 187
– of dichlorides 42, ch. 253, p. 354 fullerenes 41, ch. 249, p. 95
– of elements 43, ch. 258, p. 321
– of trichlorides 42, ch. 253, p. 274
enthalpy, standard of the elements 43, G
ch. 258, p. 321 gallates 39, ch. 242, p. 113
entropy, standard, of the elements 43, garnets 3, ch. 29, p. 525
ch. 258, p. 321 gas-phase ion chemistry 45, ch. 263, p. 1
equilibrium constant geochemistry 3, ch. 21, p. 1; 11, ch. 79,
– calculation for trichlorides 42, ch. 253, p. 485; 23, ch. 158, p. 497
p. 290 – of rare-earth-rich muds 46, ch. 268, p. 79
– calculation for RF, RF2, and RCl 42, germanium, ternary systems 27,
ch. 253, p. 403 ch. 173, p. 1
europium chalcogenides 2, ch. 19, p. 507 glow-discharge mass spectrometry 45,
exchange coupling in transition ch. 263, p. 1
metal intermetallics 24, ch. 163, p. 339 giant magnetocaloric effect, see
excited state phenomena in vitreous magnetocaloric effect
materials 9, ch. 58, p. 1 guided ion beam mass spectrometry 45,
extraction, of rare earths and actinides 43, ch. 263, p. 1
ch. 256, p. 213
Eyring, L.
– dedication 36, p. xi
H
halides 4, ch. 32, p. 89; 18,
– contributions of, higher oxides 38,
ch. 124, p. 365
ch. 236, p. 1
– metal-rich 15, ch. 100, p. 191
Molten salts 44, ch. 260, p. 87
F – simple and complex 28, ch. 177, p. 53
f-electron hybridization 39, ch. 241, p. 1 – thermodynamic properties 18,
– in intermetallic compounds 10, ch. 63, ch. 122, p. 239; 33, ch. 213, p. 147
p. 75 – vapors and vapor complexes 23,
f-element speciation in strongly acidic media ch. 157, p. 435
(superacids) 18, ch. 126, p. 507 Hall effect in cuprates 31, ch. 197, p. 251
f-f transitions, spectral intensities 25, heat capacity
ch. 167, p. 101 – of cuprates 31, ch. 200, p. 351
f-states: dual, localized, band-like – of metals 1, ch. 5, p. 379; 43, ch. 258, p. 321
character 39, ch. 241, p. 1 heavy fermions 14, ch. 97, p. 343; 16,
fast-atom bombardment mass ch. 105, p. 1; 19, ch. 132, p. 177
spectrometry 45, ch. 263, p. 1 – phenomenological approach 17,
Fermi surfaces ch. 111, p. 87
– of intermetallic compounds 20, – photoelectron spectroscopy 26,
ch. 135, p. 1 ch. 172, p. 265
– of metals 17, ch. 110, p. 1 helicates 40, ch. 247, p. 301
ferrocene-based ligands 45, ch. 266, p. 261 high pressure studies 1, ch. 9, p. 707
fluorescence spectra of ions in solution 3, – anomalous Ce, Yb and U compounds 19,
ch. 24, p. 171 ch. 133, p. 383
fluorescence, anti-Stokes 45, ch. 265, p. 179 – diffraction techniques 42, ch. 252, p. 4
fluoride glasses 15, ch. 101, p. 287; 45, – electronic properties 42, ch. 252, p. 82
ch. 265, p. 179 – heat capacity 42, ch. 252, p. 45
Index of Contents of Volumes 1–46 xxxiii
– mass spectra 42, ch. 252, p. 18 – Fermi surfaces 20, ch. 135, p. 1
– magnetic properties 42, ch. 252, p. 44 – growth of 12, ch. 80, p. 1
– optical studies of non-metallic compounds – hydrogen absorption 6, ch. 47, p. 1
33, ch. 217, p. 515 – itinerant electron metamagnetism in cobalt
– physical properties 42, ch. 252, p. 4 compounds 26, ch. 171, p. 177
– structural aspects 17, ch. 113, – light scattering 14, ch. 95, p. 163
p. 245; 42, ch.252, p. 4 – magnetic properties 2, ch. 14, p. 55; 12,
– thermal expansion 42, ch. 252, p. 33 ch. 83, p. 133; 20, ch. 138, p. 293
high temperature superconductors 30; 31 – magnetocaloric effect in R5T4
history compounds 44, ch. 262, p. 283
– of the discovery and separation of rare – magnetostriction - in RFe2 compounds 2,
earths 11, ch. 73, p. 33 ch. 15, p. 231
– of the positioning of rare earths in the – in R5T4 compounds 44, ch. 262, p. 283
periodic table 41, ch. 248, p. 1 – M€ossbauer effect in 17, ch. 116, p. 539
Hund, F. 14, dedication, p. ix – nuclear magnetic resonance in 2, ch. 18,
hydration 15, ch. 103, p. 393; 18, p. 387; 14, ch. 94, p. 63
ch. 127, p. 529; 45, ch. 263, p. 1 – scandium alloy systems 27, ch. 175,
hydrides 3, ch. 26, p. 299; 18, ch. 123, p. 293 p. 339
– borohydrides 44, ch. 259, p. 1 – ternary RT2X2 type compounds
– switchable films 36, ch. 228, p. 83 12, ch. 83, p. 133
hydrogen absorption in intermetallic – ternary equiatomic YbTX 32,
compounds 6, ch. 47, p. 1 ch. 207, 453
hydrogen in metals, including – transport properties 5, ch. 42, p. 117; 17,
RH2+x phases 20, ch. 137, p. 207 ch. 115, p. 409
hydrolysis 15, ch. 103, p. 393; 18, – valence changes in 2, ch. 20, p. 575
ch. 127, p. 529; 40, ch. 245, p. 109; 45, intermediate valence 19, ch. 132, p. 177
ch. 263, p. 1 ion cyclotron resonance
hyperfine interactions 11, ch. 77, p. 323 – mass spectrometry 45, ch. 263, p. 1
ionic liquids (also see molten salts), in
An-Ln extraction and separation 43,
I ch. 256, p. 213
inelastic electron scattering 10, ch. 72, p. 547
itinerant electron metamagnetism in cobalt
Information storage
intermetallics 26, ch. 171, p. 177
– high fidelity 46, ch. 267, p. 1
infrared properties
– of cuprates 31, ch. 202, p. 437 K
– of molten salts 44, ch. 260, p. 87 kinetics of complexation in aqueous
inorganic complex compounds 8, ch. 56 solutions 15, ch. 102, p. 347
p. 203; 9, ch. 59, p. 91 Kondo effect 1, ch. 11, p. 797
Intermetallic compounds
– amorphous magnetic alloys 2, ch. 16,
p. 259 L
– binary and pseudo-binary R5T4 lanthanide-induced shifts 4, ch. 38, p. 483;
compounds 44, ch. 262, p. 283 23, ch. 153, p. 1; 33, ch. 215, p. 353
– chalcogenides 2, ch. 19, p. 507 lanthanide chelates (also see complexes)
– crystal chemistry 2, ch. 13, p. 1 – for sensitizing NIR luminescence 37,
– crystal fields in 2, ch. 17, p. 295 ch. 234, p. 171
– dynamical screening of core holes 10, – in biomedical analyses 37, ch. 235, p. 217
ch. 63, p. 75 lanthanidomesogens 43, ch. 254, p. 1
– electron-phonon interaction 14, ch. 96, laser-ablation mass spectrometry 45, ch. 263,
p. 225 p. 1
– exchange coupling 24, ch. 163, p. 339 laser cooling cycle 45, ch. 265, p. 179
– f-electron hybridization 10, ch. 63, p. 75 laser spectroscopy 12, ch. 87, p. 433
xxxiv Index of Contents of Volumes 1–46
lasers 4, ch. 35, p. 275 magnetoresistance

Leaching – in cuprates 31, ch. 197, p. 251
– of rare-earth-rich muds 46, ch. 268, p. 79 – negative 42, ch. 252, p. 145
light scattering in intermetallic – pressure dependent 42, ch. 252, p. 128
compounds 14, ch. 95, p. 163 magnetostriction
liquid crystalline complexes 43, ch. 254, p. 1 – in R5T4 intermetallic compounds 44,
liquid salts 44, ch. 260, p. 87 ch. 262, p. 283
liquid metals and alloys 12, ch. 85, p. 357 – RFe2 2, ch. 15, p. 231
LIS, see lanthanide-induced shifts – transition metal thin films 32, ch. 205, p. 1
Lithology marine chemistry 23, ch. 158, p. 497
– of rare-earth-rich muds 46, ch. 268, p. 79 mass spectra
luminescence – of actinide ions in gas phase 45, ch. 263,
– antenna effect 23, ch. 154, p. 69 p. 1
– in biomedical analyses 37, ch. 234, – calculation of enthalpy of formation from
p. 171; 40, ch. 247, p. 301 42, ch. 253, p. 299
– in NIR molecular probes and devices 37, – of EuCl3 and Eu2Cl6 42, ch. 253, p. 313
ch. 235, p. 217 – of rare-earth ions in gas phase 45, ch. 263,
– polyoxometalates 39, ch. 243, p. 297 p. 1
– studies of ions 18, ch. 120, p. 159 mechanical alloying 24, ch. 160, p. 47
– spectra of ions in solution 3, ch. 24, p. 171 mechanically induced chemical reactions 24,
– thermometry 45, ch. 265, p. 179 ch. 160, p. 47
luminescent solar concentrators, lanthanides metal cluster complexes 45, ch. 264, p. 111
in 44, ch. 261, p. 169 metal-hydrogen batteries 21, ch. 142, p. 133
metallofullerenes 41, ch. 249, p. 95
Mineral resource
M – rare earths in deep-sea mud 46, ch. 268,
mSR studies of magnetic materials 32, p. 79
ch. 206, p. 55 mineralogy 3, ch. 21, p. 1
magnetic circular dichroism 40, ch. 244, p. 1 minerals, crystal structures 16, ch. 108,
magnetic and transport properties of p. 249
metals 1, ch. 6, p. 411 Mining
magnetic correlations in heavy-fermion – of rare-earth-rich muds 46, ch. 268, p. 79
systems 19, ch. 131, p. 123 mixed valence systems
magnetic properties (also see physical properties) – bremsstrahlung isochromat
– at high pressure 42, ch. 252, p. 1 spectroscopy 10, ch. 70, p. 425
– of borides 38, ch. 238, p. 105 – calculation of 4f excitation energies 10,
– of intermetallic compounds 2, ch. 68, p. 321
ch. 14. p. 55; 20, ch. 138, p. 293 – many-body formulation of spectra 10,
– of nickel borocarbides 38, ch. 239, p. 175 ch. 64, p. 103
– of nonmetallic compounds 22, ch. 150, molecular recognition 35, ch. 226, p. 273
p. 295 molten salts
– of R5T4 pseudobinary intermetallic electrolysis 43, ch. 255, p. 159
compounds 44, ch. 262, p. 283 – structure of halides 44, ch. 260, p. 87
– of ternary RT2X2 type intermetallic molybdates (VI) 3, ch. 30, p. 609
compounds 12, ch. 83, p. 133 mud
– of ThMn12-type compounds 22, ch. 149, – rare-earth rich 46, ch. 268, p. 79
p. 143 multilayers
magnetic structures 1, ch. 7, p. 489 – negative magnetoresistance in Fe/Tb 42,
magnetism 34, ch. 219, p. 135 ch. 252, p. 145
– exotic phenomena 11, ch. 76, p. 293 – transition metals 42, ch. 148, p. 81
– surface 24, ch. 159, p. 1 M€ossbauer effect 2, ch. 18, p. 387
magnetocaloric effect, in R5T4 – of intermetallic compounds 17,
compounds 44, ch. 262, p. 283 ch. 116, p. 539
Index of Contents of Volumes 1–46 xxxv
N O
nanostructures and nanomaterials optical glasses, recycling of 43, ch. 255,
– Al- and Mg-based systems 24, p. 159
ch. 161, p. 83 optical refrigeration 45, ch. 265, p. 179
– ceria 41, ch. 249, p. 95 organic synthesis 8, ch. 57, p. 335
– halides 41, ch. 249, p. 95 organometallic compounds 7, ch. 53, p. 446
– hydroxides 41, ch. 249, p. 95 – arene-bridged compounds 45, ch. 266,
– metallofullerenes 41, ch. 249, p. 95 p. 261
– oxides 41, ch. 249, p. 95 – divalent samarium, in 6, ch. 50, p. 525; 36,
– oxysalts 41, ch. 249, p. 95 ch. 230, p. 393
– properties 22, ch. 147, p. 1; 41, – divalent ytterbium, in 6, ch. 50, p. 525
ch. 251, p. 275 – low valent 40, ch. 246, p. 241
– photochemical ring formation 39, – tetravalent cerium, in 36, ch. 229, p. 281
ch. 243, 297 oxidation – reduction properties 18,
– synthesis 22, ch. 147, p. 1; 41, ch. 251, ch. 122, p. 239
p. 275 oxides
– spectroscopic properties 37, – aluminates 39, ch. 242, p. 113
ch. 233, p. 99 – binary 3, ch. 27, p. 337; 18, ch. 125, p. 413
– sulfates 41, ch. 249, p. 95 – gallates 39, ch. 242, p. 113
– transition metal multilayers 22, ch. 148, – higher 38, ch. 236, p. 1
p. 81 – mixed 3, ch. 28, p. 401
negative magnetoresistance in multilayer – sesqui, defects in 5, ch. 44, p. 321
Fe/Tb 42, ch. 252, p. 145 – sesqui, phase transformation in 5,
neutron scattering ch. 44, p. 321
– elastic 17, ch. 117, p. 635 – ternary systems, R2O3-M2O3-M’O 13,
– inelastic 1, ch. 7, p. 489 ch. 90, p. 283
– intermultiple transitions 14, ch. 93, p. 1 oxo-selenates 35, ch. 224, p. 45
– inelastic of anomalous lanthanides 19, oxygen nonstoichiometry and lattice effect in
ch. 130, p. 1 YBa2Cu3Ox 31, ch. 195, p. 1
– in heavy-fermion systems 19, ch. 131, p. 123
– of magnetic ordering in cuprates 31, P
ch. 199, p. 315 permanent magnets 12, ch. 82, p. 71; 32,
– of molten salts 44, ch. 260, p. 87 ch. 208, p. 515
– of spin fluctuations in cuprates 31, – recycling of 43, ch. 255, p. 159
ch. 198, p. 281 periodic table
near-infrared luminescence in molecular – influence of rare earths on 11, ch. 75,
probes and devices 37, ch. 235, p. 217 p. 197
nitride materials, ternary and higher order 25, – position of rare earths in 41, ch. 248, p. 1
ch. 166, p. 51 perovskites 3, ch. 29, p. 525
NMR 2, ch. 18, p. 387 – aluminates 39, ch. 242, p. 113
– in intermetallic compounds 14, – gallates 39, ch. 242, p. 113
ch. 94, p. 63 – manganese 33, ch. 214, p. 249
– lanthanide induced shifts for extracting phase equilibria
solution structures 33, ch. 215, p. 353 – in binary R5T4 intermetallic compounds
– of complexes 23, ch. 153, p. 1 44, ch. 262, p. 283
– of paramagnetic complexes 4, – in cuprates 30, ch. 190, p. 229
ch. 38, p. 483 – in ternary systems with boron 6,
– solution structure by paramagnetic NMR ch. 49, p. 335; 38, ch. 238, p. 105
analysis 33, ch. 215, p. 353 – in ternary systems with
nonradiative processes in crystals 4, chalcogenides 13, ch. 89, p. 191
ch. 36, p. 317 – in ternary systems with metallic
nuclear magnetic resonance, see NMR elements 13, ch. 88, p. 1
xxxvi Index of Contents of Volumes 1–46
– in ternary systems with lead 38, positron annihilation in high-temperature

ch. 237, p. 55 superconductors 30, ch. 192, p. 417
– in ternary systems with silicon 7, ch. 51, preparation and purification of
p. 1 metals 1, ch. 2, p. 173
– in rare earth binary alloys 8, ch. 54, p. 1 pressure-induced
phase transitions – cross-over 42, ch. 252, p. 83
– structural distortions and phase separation in – electronic transitions 42, ch. 252, p. 82
YBa2Cu3Ox 31, ch. 195, p. 1 – magnetic order 42, ch. 252, p. 129
– in the elements at ultra high pressure 43, – structural transitions 43, ch. 257, p. 275;
ch. 257, p. 275 44, ch. 262, p. 283
– in R5T4 intermetallic compounds – superconductivity 42, ch. 252, p. 96
44, ch. 262, p. 283 pyrochlores 16, ch. 107, p. 225
phosphides 23, ch. 156, p. 285 pyrometallurgy, in rare-earth recycling 43,
phosphors, recycling of 43, ch. 255, p. 159 ch. 255, p. 159
photochemical, nano-ring
formations in polyoxometalates 39,
ch. 243, p. 297 Q
photoemission Quantum computing 46, ch. 267, p. 1
– angle-resolved studies of untwinned Quantum information processing (QIP) 46,
YBa2Cu3Ox 31, ch. 201, p. 391 ch. 267, p. 1
– in chalcogenides 10, ch. 67, p. 301 Quantum memory 46, ch. 267, p. 1
– inverse spectra, local density supercell quasicrystalline, Al- and Mg-based
theory 10, ch. 65, p. 165 systems 24, ch. 161, p. 83
– of Ce and its compounds 10, Qubit 46, ch. 267, p. 1
ch. 66, p. 231
– spectra, local density supercell theory 10, R
ch. 65, p. 165 Raman scattering of cuprates 31,
– theory of 39, ch. 241, p. 1 ch. 203, p. 509
Photovoltaics, lanthanides in 44, ch. 261, Rare-earth doped crystals
p. 169 – spectroscopy 46, ch. 267, p. 1
physical metallurgy 11, ch. 78, p. 409 recycling of rare earths 43, ch. 255, p. 159
physical properties (also see magnetic redox reactions
properties) – arene-bridged complexes 45, ch. 266,
– at high pressure 42, ch. 252, p. 1 p. 261
– of cuprates 30, ch. 193, p. 453 – in aqueous solutions 15, ch. 102, p. 347
– of metals 1, ch. 2, p. 173 – Ce(IV)/Ce(III) 36, ch. 229, p. 347
– of metals at ultra high pressure 43, ch. 257, – Sm(III)/Sm(II) 36, ch. 230, p. 393
p. 275 relativistic effects and electronic
– of R2Fe14B-based alloys 12, ch. 82, p. 71 structure 18, ch. 119, p. 29
– of R5T4 intermetallic compounds Ring opening polymerization (ROP) 44,
44, ch. 262, p. 283 ch. 259, p. 1
pnictides 4, ch. 33, p. 153 RNA, cutting of 34, ch. 222, p. 405, 36,
– magnetic measurements on mono- 17, ch. 229, p. 392
ch. 114, p. 301
polishing powders, recycling of 43, ch. 255,
p. 159 S
Polymerization, stereospecific catalysis samarium(II) reductants 36, ch. 230, p. 393
– with borohydride complexes 44, ch. 259, scandium
p. 1 – alloy systems and intermetallics 27,
– with coordination complexes 9, ch. 61, ch. 175, p. 339
p. 395 – arene complexes 45, ch. 266, 261
polyoxometalates 38, ch. 240, p. 337 scanning tunneling microscopy of
– luminescence of 39, ch. 243, p. 297 cuprates 31, ch. 204, p. 563
Index of Contents of Volumes 1–46 xxxvii
Schiff’s base complexes 43, ch. 254, p. 1 – – spark source trace element analysis 4,
selenates 35, ch. 224, p. 45 ch. 37B, p. 359
selenides 4, ch. 31, p. 1 – – stable-isotope dilution analysis 4,
selenites 35, ch. 224, p. 45 ch. 37G, p. 471
self-assembly of helicates 40, – – with inductively coupled plasmas
ch. 247, p. 301 analysis 13, ch. 91, p. 385
separation chemistry 3, ch. 22, p. 81; – of rare-earth doped crystals 46, ch. 267,
18, ch. 121, p. 197; 21, ch. 139, p. 1; 43, p. 1
ch. 256, p. 213 – optical 3, ch. 24, p. 172; 5, ch. 46, p. 461;
– analytical, basic chemistry and methods 28, 11, ch. 74, p. 81; 33, ch. 216, p. 465; 37,
ch. 180, p. 311 ch. 233, p. 99; ch. 234, p. 171; 37,
– silicon solar cells, lanthanides in 44, ch. 235, p. 217; 39, ch. 243, p. 297
ch. 261, p. 169 – photoelectron in heavy fermion systems 26,
shift reagents 4, ch. 38, p. 483; 23, ch. 172, p. 265
ch. 153, p. 1; 33, ch. 215, p. 353; 35, – time-resolved emission in
ch. 225, p. 107 solution chemistry 33, ch. 216, p. 465
single crystals Spedding, F. H., 11, prologue, p. 1
– growth from molten metal fluxes 12, spin glasses 12, ch. 84, p. 213
ch. 81, p. 53 stannides, transition metal ternary
– growth of cuprates 30, ch. 189, p. 67 systems 24, ch. 164, p. 399
– growth of metals and intermetallic steels 25, ch. 165, p. 1
compounds 12, ch. 80, p. 1 Stokes shift 45, ch. 265, p. 179
skutterudites, filled 33, ch. 211, p. 1 stresses, static and dynamic 26, ch. 170, p. 87
Solar energy conversion, lanthanides in 44, structural properties, lanthanides at high
ch. 261, p. 169 pressure 43, ch. 257, p. 275
solid electrolytes 28, ch. 178, p. 131; 35, sublimation enthalpy
ch. 223, p. 1 – of metals 43, ch. 258, p. 321
solid oxide fuel cells (SOFC) 35, ch. 223, – of trichlorides 42, ch. 253, p. 274
p. 1 – of trifluorides 42, ch. 253, p. 235
solution chemistry 15, ch. 103, p. 393; 18, sulfides 4, ch. 31, p. 1
ch. 127, p. 529; 18, ch. 128, p. 559; 21, – poly 32, ch. 209, 567
ch. 145, 305 superconductivity 1, ch. 10, p. 749; 34,
solvation in organic solvents 21, ch. 219, p. 135
ch. 145, p. 305 – at high pressure 42, ch. 252, p. 96
spectroscopic properties – crystal chemistry of cuprates 30,
– in solution 3, ch. 24, p. 172 ch. 188, p. 31
– in transparent crystals 5, ch. 46, p. 461 – in metals 17, ch. 110, p. 1
– nanomaterials 37, ch. 233, p. 99 – high-temperature layered cuprates:
spectroscopy overview 30, ch. 187, p. 1
– absorption and fluorescence of R ions 3, – nickel borocarbides 38, ch. 239, p. 175
ch. 22, p. 172 – unconventional and magnetism 34,
– appearance potential 16, ch. 109, p. 519 ch. 219, p. 135
– bremsstrahlung isochromat 10, ch. 70, surfaces
p. 425 – adsorption on 5, ch. 43, p. 217
– circularly polarized luminescence 34, – catalysis on 5, ch. 43, p. 217
ch. 220, p. 289 switchable metal hydride films 36,
– high-energy 10, ch. 62, p. 1 ch. 228, p. 83
– magnetic circular dichroism 40, synthesis of cluster halides
ch. 244, p. 1 – comproportionation 45, ch. 264, p. 111
– magnetic resonance 11, ch. 77, p. 323 – metallothermic reduction 45, ch. 264, p.
– mass 111
– – spark source matrices 4, systematics, intra rare earth binary
ch. 37C, p. 377 alloys 8, ch. 54, p. 1
xxxviii Index of Contents of Volumes 1–46
T – switchable metal hydrides 36, ch. 228,

tellurides 4, ch. 31, p. 1 p. 83
ternary equiatomic YbTX intermetallics 32, time-of-flight mass spectrometry 45, ch. 263,
ch. 207, p. 453 p. 1
tetravalent cerium compounds 36, ch. 229, toxicity 4, ch. 40, p. 553
p. 281 transition metal-indides 34, ch. 218, p. 1
theoretical chemistry 3, ch. 23, p. 111 transport properties
thermal conductivity of compounds 16, – at high pressure 42, ch. 252, p. 68
ch. 106, p. 107 – of intermetallics 5, ch. 42, p. 117; 17,
thermal properties of compounds at high ch. 115, p. 409
pressure 42, ch. 252, p. 1 triflates 29, ch. 186, p. 315
thermodynamic functions tunneling spectra of cuprates 31, ch. 204,
– of dichlorides 42, ch. 253, p. 198 p. 563
– of difluorides 42, ch. 253, p. 207
– of dimeric trichlorides 42, ch. 253, p. 296 U
– of metals 43, ch. 258, p. 321 ultra high pressure (also see high pressure
– of monochlorides 42, ch. 253, p. 381 studies)
– of monofluorides 42, ch. 253, p. 381 – elements at 43, ch. 258, p. 321
– of trichlorides 42, ch. 253, p. 176 – structural properties at 43, ch. 257, p. 275
– of trifluorides 42, ch. 253, p. 196
thermochemical properties 18, ch. 122,
p. 239 V
– of chlorides 42, ch. 253, p. 165 valence fluctuations 2, ch. 20, p. 575; 16,
– of cuprates 30, ch. 190, p. 229 ch. 105, p. 1; 39, ch. 241, p. 1
– of dimeric trichlorides 42, ch. 253, p. 214 vapor pressure of halides 42, ch. 253,
– of fluorides 42, ch. 253, p. 165 p. 441
– of gaseous species 12, ch. 86, p. 409
– of metallic systems 19, ch. 134, p. 479
– of metals 43, ch. 258, p. 321 X
– of trichlorides 42, ch. 253, p. 176 x-ray absorption and emission spectra 10,
– of trifluorides 42, ch. 253, p. 196 ch. 71, p. 453
thin films 5, ch. 41, p. 1; 20, ch. 136, p. 105 x-ray scattering 26, ch. 169, p. 1
Chapter 267
Rare Earth-Doped Crystals

for Quantum Information
Processing
Philippe Goldner1, Alban Ferrier1,2 and Olivier Guillot-Noël1,*
1
Institut de Recherche de Chimie Paris, CNRS-Chimie, ParisTech, Paris, France
2
Sorbonne Universités, UPMC Univ Paris 06, Paris, France
Chapter Outline
1 Introduction 1 5.2 Protocols 48
2 Quantum Information Processing 3 5.3 Entanglement Storage in Nd:
2.1 Qubits and Gates 3 Y2SiO5 54
2.2 Quantum Computing 5 5.4 High Efficiency Memory in
2.3 Quantum Communication 7 Pr:Y2SiO5 56
3 Coherent Light-Atom Interactions 9 5.5 Long Storage with High
3.1 Quantum-State Control 9 Fidelity in Pr:La2(WO4)3 56
3.2 Coherence and Relaxations 11 5.6 Other Results 58
4 Rare Earth-Doped Crystals 14 6 Quantum Computing 59
4.1 Electronic and Spin Level 6.1 Schemes 59
Structure 15 6.2 Single-Qubit Gate in Pr:
4.2 Transition Strengths and Y2SiO5 62
Inhomogeneous Linewidths 30 6.3 Two-Qubit Gate in Eu:Y2SiO5 63
4.3 Coherence Lifetimes 32 6.4 Other Results 64
4.4 Currently Used Crystals 46 7 Conclusion and Outlook 65
5 Quantum Memories for Light 46 Acknowledgments 65
5.1 Requirements 46 References 67
1 INTRODUCTION
Information in digital form is at the heart of nowadays societies, playing a
major role in world-scale organizations down to many individual daily activ-
ities. Although technology made extraordinary progresses in terms of commu-
nication speed and capacity, data storage, or processing power, most of the
*
In memoriam
Handbook on the Physics and Chemistry of Rare Earths, Vol. 46. http://dx.doi.org/10.1016/B978-0-444-63260-9.00267-4
Copyright © 2015 Elsevier B.V. All rights reserved. 1
2 Handbook on the Physics and Chemistry of Rare Earths
fundamental concepts of information science were established in the begin-

ning of the twentieth century. In 1984, a quantum algorithm was discovered
by Bennett and Brassard for encrypted data exchange (Bennett and
Brassard, 1984) and in 1985, Deutsch pioneered quantum computing theory
(Deutsch, 1985). This was the start of quantum information processing
(QIP), which is currently a major research topic in physics, computer science,
mathematics, and material science. Quantum information is a new paradigm,
where the classical bits, which can take only discrete values, are replaced by
quantum bits, called qubits, which can assume any superposition state. This
fundamentally new resource allows data processing, storage, and communica-
tion in ways impossible to achieve with classical systems (Kimble, 2008;
Nielsen and Chuang, 2000; Stolze and Suter, 2008).
QIP is however very demanding on physical systems and its development
has triggered important advances in quantum system control and design. In
turn, QIP theory has emerged as a unified way to describe the behavior of
these systems, independently of the details of their nature, structure, or inter-
actions. QIP uses superposition states, which exist for a significant duration
only in isolated systems. Interactions with a fluctuating environment, with
many degrees of freedom, destroy them. Examples of quantum systems suit-
able for QIP are photons (Gisin and Thew, 2007; Kok et al., 2007) and nuclear
spins (Chuang et al., 1998; Morton et al., 2008), which can have very low
interactions with surrounding electromagnetic fields and atoms. QIP is also
investigated in many other systems (Ladd et al., 2010; Lvovsky et al., 2009)
such as trapped ions (Blatt and Roos, 2012), superconductors (Clarke and
Wilhelm, 2008), electronic and nuclear spins in insulators and semiconductors
(Hanson et al., 2007; Wrachtrup and Jelezko, 2006), and ultracold atoms
(Bloch et al., 2012; Chanelière et al., 2005). As light is an excellent carrier
of quantum information, as it is of classical one, there is also a need to inter-
face it to material systems to store and process information (Northup and
Blatt, 2014). Moreover, progress in lasers has also set them as efficient
devices for controlling efficiently and accurately quantum systems. In these
respects, rare earth (R)-doped crystals have very favorable spectroscopic
properties among solid-state systems. The main one is to exhibit extremely
narrow optical transitions, equivalent to long-lived superposition states, at
cryogenic temperatures (Macfarlane, 2002). Depending on the R ions consid-
ered, these transitions span the entire visible and infrared range, including the
telecom window at 1.5 mm. Moreover, many R ions have isotopes with non-
zero nuclear spins, which can be therefore optically controlled or interfaced
with photonic qubits. Finally, R-doped crystals are generally very robust,
photostable materials, which can be readily cooled down to liquid helium
temperatures in closed cycle cryostats. Their synthesis and spectroscopy have
been widely developed for applications in photoluminescence, lasers, scintil-
lation, etc. In addition, these materials are studied for classical information
Rare Earth-Doped Crystals for Quantum Information Processing Chapter 267 3
or signal processing, which shares some requirements and schemes with QIP
applications (Le Gouët et al., 2006; Li et al., 2008; Thorpe et al., 2011).
In this chapter, we review the applications of R-doped crystals to two spe-
cific QIP applications: optical quantum memories and quantum computing.
After a brief introduction to QIP, we describe coherent light-atom interac-
tions, which allow creating and controlling atomic quantum states. The spec-
troscopic properties of R-doped crystals are discussed afterward, with a focus
on the specific features used in QIP. Finally, the concepts and studies related
to quantum memories and computing are presented. In the two last sections,
we chose to emphasize a few representative experiments, underlining impor-
tant points, rather than to give extensive lists of results. As this field is rela-
tively new to the rare-earth community, we felt that this approach could be
more useful for the reader.
2 QUANTUM INFORMATION PROCESSING

2.1 Qubits and Gates
The reader is referred to Nielsen and Chuang (2000) or Stolze and Suter
(2008) for a detailed presentation of QIP. In the following, we only review
the basic concepts of the field. The qubit, or quantum bit, is the elementary
unit of information in QIP. It is the equivalent of the bit in classical comput-
ing and communication. The bit can take two values, 0 or 1, and is implemen-
ted as different states of a capacitor, a transistor or of a light beam. The qubit
is a quantum two-level system (TLS), as depicted in Fig. 1, with eigenstates
labeled as j0i and j1i and representing the binary 0 and 1 values. However,
in contrast to the classical bit, the qubit can also be in an arbitrary superposi-
tion state, which can be expressed as:
jci ¼ cos ðy=2Þj0i + eif sin ðy=2Þj1i (1)
x y
FIGURE 1 A qubit in a superposition state jci. Left: ladder-style drawing. The superposition is
denoted by an ellipsoid. Right: position of the vector corresponding to jci on the Bloch sphere.
4 Handbook on the Physics and Chemistry of Rare Earths
up to a global eid phase factor, since jci and eid jci are equivalent wave-
functions. This property opens the way to data processing and transmission
that are impossible to achieve with a classical system, as discussed in Sections
2.2 and 2.3. Superposition states can be visually represented as vectors, which
have their origin on a center of a sphere of radius 1 (the Bloch sphere) and
their extremity lying on its surface (we normalize all quantum states to 1).
When the qubit state is written as in Eq. (1), the angles y and f correspond
to the spherical coordinates of the vector on the sphere (Fig. 1). Thus, the
states j0i and
pffiffiffi j1i point, respectively, to the north and south poles. The
ðj0i + j1iÞ= p2ffiffiffi state is located on the equatorial plane along the x-axis and
ðj0i + ij1iÞ= 2 along y. It is important to note that although the qubit can
assume an infinity of different states, the only states which can be identified
with certainty are j0i and j1i, if these states form the measurement basis.
A major challenge in QIP is therefore to be able to use superposition states
for improved performances, while determining final states with certainty or
at least high probability. This is required to get meaningful calculation results
or reliable data transmission. Another difficulty is the high sensitivity of
superposition states to perturbations, which implies the use of isolated sys-
tems, while at the same time, these states should be controlled and read out,
which requires some interactions with the environment. Atoms in vapors,
photons, or nuclear spins are examples of systems in which superposition
states can be long lived and accurately controlled, and are therefore good can-
didates for qubits (Ladd et al., 2010; Lvovsky et al., 2009). The lifetime of
superposition states is related to the so-called coherence lifetime, which is
described in more details in Section 3.2.
Atomic qubit states are controlled and read by interactions with electro-
magnetic fields. These interactions are theoretically represented by operators
acting in the Hilbert space of the qubit. In classical information processing,
all possible operations on bits are obtained by logical gates, like NOT, which
changes 1 in 0 and vice versa. The same situation occurs in QIP, where gates
are a set of operators. As an example, the equivalent of the classical NOT gate
is the Pauli operator X, which representation in the ðj0i, j1iÞ basis is given in
Fig. 2. This operator has the same effect as the classical NOT gate on j0i and
j1i, i.e., Xj0i ¼ j1i and Xj1p i¼ffiffiffi j0i. However,p
Xffiffiffican also be applied to superpo-
sition states: Xðj0i + ij1iÞ= 2 ¼ ðj1i + ij0iÞ= 2. The corresponding trajectory
on the Bloch sphere is shown in Fig. 2.
Although single qubits can represent a resource large enough to perform
tasks unattainable with classical systems, as in quantum communication
(Section 2.3), it is often necessary to consider multi-qubit systems. First, they
are necessary to create larger superposition states. For example, with two
qubits labeled a and b, the state jfi ¼ ðj0a 0b i + j0a 1b i + j1a 0b i + j1a 1b iÞ=2
can be obtained. It contains all possible two-digit binary values, allowing par-
allel processing (Section 2.2). Another important feature of multi-qubit states is
called “entanglement.” This highly nonclassical property is among the most
Exploring the Variety of Random
Documents with Different Content
SECONDARY OR REMOTE RESULTS OF
LIVER DISEASE.
In gout: Arrest of oxidation of proteids into urea. Deposits of biurate of lime on

joints, and other disorders. Urinary calculi containing urates, cystine, xanthine,
etc., also from imperfect oxidation of albuminoids. Oxalic acid represents a similar
arrest. Kidney degenerations from irritating urates and oxalates. Fatty kidney from
excessive glycogenesis. Digestive disorders from excess or deficiency of bile or
torpid liver. Nervous disorders, dullness, lameness, vertigo, spasms, irritability
from hepatic inactivity and resulting poisons. Sore throat and bronchitis from
hepatic derangement. Skin eruptions in tardy or imperfect action of the liver.
Treatment: Abundant water, succulent vegetables, ensilage, fresh grains, balanced
ration, in carnivora and omnivora oat meal, buttermilk, clear meat juice, avoid
sweets, gravies, spiced animal food. Dangers for pampered horses, dogs, and old
improved meat producing animals. Open air exercise. Laxatives with alkalies,
salines, mercurous and mercuric chloride, pilocarpin, chlorides, iodides, bromides,
nitro-muriatic acid, ipecacuan, euonymus, bitters.
Among the many secondary results of hepatic disorder, and which

are habitually described as affections of other organs a few may be
mentioned as indicating the wide range of influence exercised by the
liver in disease as well as in health.
Gout as it appears in fowls and omnivora is directly due to the
arrest of the transformation of the albuminoids into urea. Circulating
in the system in the form of the less perfectly oxidized and less
soluble uric acid, it determines deposits of biurate of lime around the
joints, with local inflammations, and disorders of circulation and
innervation, and altered spirit, temper, etc.
Urinary calculi in the same animals, are composed largely of urate
of lime, cystine, xanthine and other nitrogenous products
representing various stages of oxidation short of the final transition
into urea and ammonia. Recognizing the active rôle which the
urinary bacteria fill in this respect we must still acknowledge the
great importance, as causative agents, of an excess in the urine of
these comparatively insoluble products.
The oxalic acid found in certain calculi points in the same
direction, as this acid, both in the body and in the laboratory, is
found to result from the oxidation of uric acid (Wohler, Schenck,
Hutchinson).
Degenerations of the Kidneys are to be largely traced to the same
hepatic source. The uric acid diathesis, and the oxalic acid diathesis,
both the result of imperfect liver function, are among the most
frequent causes of irritation of the kidneys, by which channel they
are eliminated from the body. Hence acute and chronic nephritis, as
well as nephritic calculi result from morbid conditions which have
their starting point in the imperfect function of the liver. Again fatty
degeneration of the kidney is very liable to result from derangement
of the glycogenic function of the liver, the tendency to the formation
of fat and the constant irritation caused by the passage of the sugar
contributing to the tissue degradation. In such cases albuminuria is a
not uncommon accompaniment.
Derangements of the Digestive Organs may be said to be a
necessary result of hepatic disorder. Excessive secretion of bile
stimulates peristalsis and may induce diarrhœa, while diminished
secretion tends to constipation, light colored, fœtid stools, intestinal
fermentations and poisoning by the irritant products. A torpid
hepatic circulation means congestion of the whole portal system,
indigestions, colics, chronic muco-enteritis, intestinal hemorrhages,
hemorrhoids, etc.
Derangements of the Nervous System. In this connection may be
named the lameness of the right shoulder which accompanies certain
disorders of the liver, the extreme dullness and depression that
attends on others, the sluggish pulse that appears in certain types,
the unsteadiness of gait (giddiness) in others, the muscular cramps,
and irritability in still others. These appear to be due in some
instances to the nervous sympathy of one part with another, whilst at
other times they as manifestly depend on the circulation in the blood
of partially oxidized and other morbid products of hepatic disorder
which prove direct poisons to the nervous system.
Derangements of the circulation, like extreme rapidity, or slowness
of the pulse, irregularities in rhythm and intermissions, may be
charged more directly on the nervous affection, though primarily
determined by hepatic disorder.
On the part of the Respiratory Organs, affections of a chronic
type, like sore throat and bronchitis may often be traced to hepatic
torpor or disorder.
Skin Diseases are notoriously liable to come from inactive or
disordered liver, the irritant products circulating in the skin or
sweating out through it, giving rise to more or less irritation. The
result may be a simple pruritus, an urticaria, an eruption of papules,
vesicles or even pustules. In any such cases it is proper to look for
other indications of liver disease,—pale color and offensive odor of
the fæces, muco-enteritis, indigestion, icterus or yellow patches on
the mucous membranes, tenderness on percussion over the asternal
ribs, muscular neuralgia, nervous disorder, the passage of bile,
hæmoglobin, albumen, sugar or other abnormal elements in the
urine, etc.
TREATMENT OF SECONDARY AND
FUNCTIONAL DISEASES OF THE LIVER.
Diet. Many hepatic disorders, and especially those that are
exclusively or mainly functional may be corrected by diet alone.
Prominent among dietary influences is the abundant supply of water.
The succulent grasses of spring and early summer constitute the
ideal diet, hastening and increasing elimination, and lessening the
density of the bile, even to the extent of dissolving biliary calculi and
concretions. Upon dry winter feeding such calculi are common
especially in ruminants, whereas after a month or two at pasture they
are extremely rare. In winter the same good may be arrived at by the
use of ensilage, brewer’s grains, roots, fruits, or even scalded hay or
bran. The two extremes of highly albuminous and highly
carbonaceous or saccharine food are to be avoided or used only in
limited amounts. In the one class are clover, alfalfa, sainfoin,
vetches, cowpea, lespedeza, especially in the form of hay, beans,
peas, cotton seed, gluten-meal, rape and linseed cake. In the other
are wheat, buckwheat, Indian corn, sorghum, sweet-corn and
cornstalks. Some agents like beets which are rich in saccharine
matter may be actually beneficial by reason of their laxative and
cholagogue action. In the carnivora the food should be largely of
simple mush of oatmeal, wheat seconds, or barley meal, skimmilk or
buttermilk. If it is needful to tempt the appetite in a fleshfed animal
this should not be done by rich, fat gravies, highly spiced animal
food, or rich saccharine puddings, but rather by the addition of a
little pure juice of lean meat, or some well skimmed beef tea.
It is as important to regulate the quantity as the quality of the food
as the heavy feeder will over-charge the liver as much by an excess of
otherwise wholesome food, as will the ordinary animal by the
indigestible and unwholesome articles. As a rule the improved
breeds of meat producing animals, have acquired such facility in fat
production that much of the surplus is largely and profitably
disposed of in this way, and in their short lives little obvious evil
comes of the overfeeding, but in cases in which this outlet proves
insufficient, as in horses and dogs that are highly fed on stimulating
or saccharine diet, and which are kept for the natural term of their
lives, with little exercise, the evil tends to reach a point of danger.
Nursing mothers and dairy cows find a measure of safety in the free
flow of milk and the yield of butter, but breeding cows that have been
improved till they have no longer a capacity for milking, but must
have their calves raised on the milk of other and milking strains are
correspondingly liable to suffer.
Exercise in the Open Air. As enforced idleness, on a full diet and in
a warm and moist environment is a main cause of hepatic disorder,
so abundant exercise in the open air and especially in a cool season is
beneficial in a marked degree. Beside the bracing effect on the
digestive organs and the improvement of the general tone of the
system, the action of the muscles in hastening the circulation greatly
favors the removal and elimination of waste matters. Still more
advantageous is the increased activity of the respiration and the
aspiratory power of the chest in at once unloading the portal system
and the liver by hastening the progress of the hepatic blood into the
vena cava and right heart, and in furnishing an abundant supply of
oxygen for the disintegration of the albuminoids and amylaceous
products. Such exercise must of course be adapted to the condition of
the animal and its power of sustaining muscular work, but
judiciously employed, it is one of the most effective agencies in
correcting and improving hepatic disorder or hepatic torpor. Idle
horses, the victims of obstinate habits of constipation, muco-enteric
irritation, indigestion, nervous, urinary or cutaneous disorders will
often be greatly benefited or entirely restored by systematic exercise.
This is one of the great advantages of a run at pasture, as the subject
secures at once the laxative cholagogue diet, an abundant supply of
oxygen, a better tone of the muscular and general system, and a more
perfect disintegration of albuminoids. Sea air with its abundance of
ozone is especially advantageous.
In the carnivora while we cannot send them to grass, much can be
done in the way of systematic exercise, and in the case of city dogs a
change to the country, where they can live out of doors and will be
tempted to constant exercise and play, will go far to correct a faulty
liver.
Laxatives. Cholagogues. When a free action of bowels and liver
cannot be secured by succulent food and exercise, we can fall back on
medicinal laxatives. These are advantageous in various ways. Some
laxatives like podophyllin, aloes, colocynth, rhubarb, senna, jalap,
and taraxacum act directly on the liver in increasing the secretion of
bile. These may be used for a length of time in small doses and in
combination with the alkalies. Other aperients act directly on the
bowel carrying away the excess of bile, the albuminoids and
saccharine matter that would otherwise be absorbed, and by a
secretion from the portal veins, abstracting nitrogenous and
saccharine elements which would otherwise overtax the liver to
transform them. Thus indirectly these also act as cholagogues by
withholding the excess of material on which it has to operate, and by
rousing its functions sympathetically with those of the bowels. Thus
sulphates of magnesia and soda, and tartrates and citrates of the
same bases, given in the morning fasting, dissolved in a large
quantity of warm water and conjoined with sodium chloride,
ammonium chloride, sodium carbonate or other alkaline salts, or
with one or more of the vegetable cholagogues above mentioned,
may be continued for a length of time until the normal functions
have been re-established, and will maintain themselves irrespective
of this stimulus.
Calomel (and even mercuric chloride in small doses), though it is
not experimentally proved to be a direct cholagogue, is one of the
very best correctives of impaired hepatic function. It expels the bile
from the duodenum and bowels generally, thereby preventing its
reabsorption; it proves antiseptic to the ingesta; it eliminates much
of the peptone, saccharine and fatty matter from the intestines and
portal system thus relieving the liver materially; and it is supposed
further to modify the other liver functions by a direct action on the
hepatic cells, and by reducing the cohesion of fibrine, and promoting
the disintegration of albumen. Certain it is that calomel gives most
substantial relief in many torpid and other disorders of the liver and
as it is not in itself an active liver stimulant but has rather a soothing
action on that gland it can be safely resorted to in states of hepatic
irritation in which the more direct cholagogues would prove more or
less hurtful.
In some forms of hepatic disorder where a speedy and abundant
secretion is demanded, pilocarpin may be employed, with great
caution so as not to reduce the strength unduly by the attendant
diaphoresis, diuresis, salivation or diarrhœa.
Alkalies have long been recognized as of great clinical value in
hepatic disorders. Though carbonate of soda decreases the secretion
of bile, (Nasse, Röhrig), yet the alkalies generally appear to promote
oxidation, and to hasten the disintegration of albumen and the
albuminoids. They increase the disintegration of sulphur compounds
materially adding to the sulphates and urea in the urine. They
further tend to increase the hippuric acid, carbonate of soda (2 drs.)
even determining the abundant excretion of this acid in man (Nasse).
It may be concluded that the acknowledged value of alkalies in these
diseases, is largely due to their hastening of the metabolic processes
in albuminoids. Small doses of sodium carbonate further stimulate
the gastric secretion and may thus benefit by rendering the process
of digestion more complete and satisfactory.
Chlorine, Iodine, Bromine and their Salts. These halogens are of
great value in many hepatic disorders. The universal craving for
sodium chloride indicates the need of its elements in the animal
body, and whether this is mainly the supply of chlorine for the
hydrochloric acid of the gastric juice, or to fulfill its uses in favoring
the oxidation and disintegration of the nitrogenous matters in the
blood and tissues, or for other more or less obscure uses, it is well to
recognize and act upon the indication. The various mineral waters
which are held in high esteem in liver affections contain a large
proportion of sodium chloride. As a medicinal agent ammonium
chloride maintains an equally high position. Large doses thrice a day,
so as to induce diaphoresis and diuresis greatly relieve hepatic
congestions. This agent determines a great increase in the urea
eliminated so that it is even more effective in the same direction,
than sodium chloride. Free chlorine is also effective in hepatic torpor
and congestion, and to this in part may be attributed the great value
of nitro-muriatic acid.
Bromide and iodide of potassium have been found to be effective
in reducing hepatic enlargement and thus in conducing to a more
healthy activity of the liver.
Ipecacuanha, Euonymus, etc. These agents are more or less
hepatic stimulants and may be found beneficial as combined with the
laxative or alkaline agents in securing a better functional activity in
cases of torpor or deranged function.
Tonics, Bitters. Tonics are often useful when the health has been
undermined by long continued hepatic disorder. The iron tonics are
as a rule contraindicated as tending to check secretion of bile, unless
they can be given with alkalies. Iron sulphate or chloride, combined
with sodium or potassium carbonate so as to establish a mutual
decomposition will obviate this objection. The vegetable bitters
(gentian, cascarilla, calumba, salicin, serpentaria, aloes, nux vomica)
combined with alkalies are often of great value. Quinia, like opium,
checks secretion and is to be avoided or used with judgment and in
combination with cholagogues.
HÆMOGLOBINÆMIA. AZOTÆMIA.
AZOTURIA. HÆMOGLOBINURIA. TOXÆMIA
FROM IMPERFECT HEPATIC FUNCTION.
Definition. Theories, of hysteria, uræmia, spinal myelitis, myelo-renal

congestion, rheumatic lumbago, myosito-myelo-nephritis, rheumatic chill with
destruction of muscle albuminoids. Yet it occurs in our semi-tropical midsummer
with a temperature of 80 or 90, in spring and autumn, and rarely even in the cold,
damp stable in midwinter in the absence of exercise. Constant conditions: One or
more days absolute rest, preceding steady work, a strongly nitrogenous ration,
continued during the rest, sudden active exertion accelerated breathing and
unloading of peptones and proteids from portal vein and liver into the general
circulation. Sanguineous albuminuria from excess of albuminous food, free
ingestion of water, suppressed milk secretion, forced marches. Transfusion of
blood. Excess of albumen dangerous, excess of red globules not dangerous. The
blood concentration of diuresis or diaphoresis is not dangerous. Continuous
muscle decomposition from work bars the disease. Stable miasm untenable. Poison
may be drawn suddenly from the enormous mass of blood in the liver, spleen and
portal system. The absence of icterus antagonizes the bile theory. Benzoic acid,
unaltered peptones, and glycogen are examples of elements destructive to blood.
Normal destruction of red globules in liver, spleen and bone marrow. Sudden
access of resulting hæmoglobin to the blood. Other products of disintegrated
globules. Poisons from food, and antitoxic action of liver in presence of glycogen.
Carbon dioxide favors solution of red globules. Theories of hæmoglobinæmia in
man. Lesions: Blood black, diffluent, iridescent, has no avidity for oxygen, with
excess of urea and extractives, serum of clot red, globules, small, pale, distorted,
not sticky, extravasations, liver, enlarged, congested, blood gorged, spleen
congested, swollen: Lumbar or gluteal muscles pale, infiltrated, with loss of
striation; bone marrow congested, hemorrhagic; kidneys congested infarcted;
urine dark brown or red, with excess of urea and hæmoglobin. End of spinal cord
has congestion or infiltration. Symptoms: History of high condition, constant
work, high feeding, a day’s rest, then exercise and attack. To full life, follows
flagging, droops, moves one or both hind limbs stiffly, knuckles, drags toes,
crouches, trembles, perspires, breathes rapidly, is tender on back, loins, croup or
thigh, muscles firm, paretic, and drops unable to rise. Urine retained, brown, red
or black, sometimes glairy, later may have casts. Appetite may return. In mild
cases, stiffness, lameness, with or without visible muscular lesions or tremors.
Urine glairy, dense, with excess of urea and nitrogenous products. Recover under
careful feeding and exercise, and relapse under original causes. Progress: May
recover under rest. In bad cases accelerated breathing and recumbency forbid rest
and recovery. Recovery in a few hours or after a week. Urinary casts with renal
epithelium, imply nephritis and grave conditions. In persistent paresis, muscles
waste. Modes of death. Mortality 20 per cent. Diagnosis, by history of onset, etc.
Prevention: When highly fed and hard worked, give daily exercise, with
comparative rest, reduce ration, and give laxative or diuretic. Plenty of water.
Treatment: Rest, sling, diffusible stimulants, bleeding, bromides, water ad libitum,
fomentations, unload liver and portal vein, purgative, eserine, barium chloride,
enemata, diuretics, for remaining paresis, derivatives, strychnia, diet, laxative,
non-stimulating, restore to work gradually.
Definition. An acute auto-poisoning occurring in plethoric horse

on being subjected to active exertion after a period of idleness, and
manifested by great nervous excitement and prostration, paresis
commencing with the hind limbs and the passage of hæmoglobin in
the urine.
Nature and Causes. The most varied conclusions as to the nature
of this disease have been put forward by different authors. In
England, Haycock called it hysteria, mistakenly supposing that it was
confined to mares, and Williams attributed it to uræmic poisoning,
conveniently ignoring the fact that the sudden manifestation of the
most extreme symptoms in an animal which just before was in the
highest apparent health and spirits contradicted the conclusion. In
France (Trasbot) and Southern Europe (Csokor) it has been looked
on as a spinal myelitis, a conclusion based on the disturbed
innervation of the posterior extremities in the great majority of
cases, but which is not always sustained by the pathological anatomy
of the cord. In Germany veterinarians have viewed the disease from
widely different standpoints. Haubner calls it myelo-renal-
congestion (Nièren-Rückenmarks): Weinmann, a rheumatic
lumbago; Dieckerhoff defines it as an acute general disease of horses,
manifested by a severe parenchymatous inflammation of the
skeleton muscles, with a bloody infiltration of the bone marrow,
especially of the femur, and with acute nephritis and
hæmoglobinuria. He attributes the attack to exposure to cold. If this
were the real cause the attack would be far more common in very
cold weather when the horse is suddenly exposed to cold drafts
between open doors and windows, than when he is harnessed and
driven so as to generate and diffuse animal heat. Yet attacks in the
stable are virtually unknown, and in almost every instance the onset
occurs during a short drive. Friedberger and Fröhner say that the
epithet rheumatismal may be correctly applied to almost all cases
that we meet in practice. They quote Goring as having produced the
disease experimentally by exposure to cold, and go on to explain that
rest in the stable before the attack causes the extreme sensitiveness
to cold that is generated by a warm environment. The implication of
the lumbar, pelvic and femoral muscles they explain by the
stimulation of the nutritive metamorphosis by the action of cold on
the sensitive nerves of the skin. The effect of this cutaneous irritation
is exaggerated by the heat of the stable to which they have been
previously subjected. The products of the destruction of the
albuminoids of the muscles, pass into the blood as hæmoglobin, and
produce the ulterior phenomena. The muscles of the hind quarters
especially suffer because of their greater exposure and because they
are subjected to the hardest work in propelling the animal machine.
In this connection they quote the experiments of Lassar and
Nassaroff in which sudden exposure to cold determines
parenchymatous degeneration of muscles; also the cases of
paroxysmal or winter hæmoglobinuria in certain susceptible men
whenever they are exposed to an extremely low temperature.
There are serious objections to the acceptance of this as the
essential cause, among which the following may be named:
1st. The disease is not confined to the cold season but occurs also
at midsummer when the outdoor temperature is even higher than it
is in the stable.
2d. In our Northern States it appears to be more common in spring
and autumn or early winter, when the extreme colds have either
already passed, or have not yet set in, but when the abrupt changes
of weather (rain-storms, etc.) are liable to shut up the animal indoors
for a day or more at a time.
3d. The popular names quoted with approval by these authors—
Monday disease, Easter disease, Whitsuntide disease—indicate the
prevalence in Europe also, of the malady in the milder, or more
temperate seasons rather than during the prevalence of extreme
cold.
4th. The fact that the disease rarely or never occurs in the stable,
no matter how cold the season, how open the wooden walls or floor,
nor how strong the draft between doors or windows, shows that the
theory of cold as the sole or main cause must be discarded.
It is not necessary to ignore the action of cold as a concurrent
factor in certain cases, or as a stimulant to reflex vaso-motor paresis,
to muscular metamorphosis and the increase of hæmoglobin in the
blood. It is only necessary that this should be held as subordinate
and non-essential to the final result. Several other factors that are
accorded a subordinate place by these writers, are so constant and so
manifestly essential that they must be allotted a much more
important position in the list of causes.
A period of rest is a constant precursor of an attack. The more
extended the inquiry the more certain we become that a short rest is
a prerequisite to equine hæmoglobinæmia. The horse that is kept at
daily steady work may be said to be practically exempt. Even the
non-professional observer recognizes the fact and names the disease
after the weekly or yearly holiday or rest day which was the occasion
of it. To him it is the Monday morning disease, the disease of the day
following Thanksgiving, Christmas, New Year, or Fourth of July. It is
the disease of wet weather, of heavy snowfalls, of the blizzard, or of
the owner’s absence from home, of any time that entails one or two
days of absolute inactivity in the stall.
But again the affection does not appear in the horse that is
absolutely idle for a length of time. It is the short period of rest in
an interval of otherwise continuous work that determines it.
In short the subject must be in good muscular condition and with a
hearty, vigorous appetite and good digestion. The short unwonted
rest interrupts the disposal of the rich products of a vigorous
digestion, and tends to overload the portal veins, the liver, the blood
and tissues with an excess of proteids. The condition of the animal is
so far one of plethora.
Another feature that bears this out is that the attack comes only in
the animal that is heavily fed on a strongly nitrogenous
ration. It is not the disease of the horse kept on straw, or hay, or
which receives a limited amount only of grain. It does not occur in
the animal which has its grain suspended or materially reduced
during the one or two days of idleness. It does not select the horse
that has had a laxative either in the form of food or medicine. This
last may increase the sensitiveness to cold, but it certainly lessens the
tendency to hæmoglobinæmia. The most rational explanation
appears to be that it affords this protection by interfering with the
thoroughness of digestion and absorption, by securing elimination
from the portal veins and liver, and by reducing the amount of
albuminoids in the blood.
A blood abnormally rich in albuminoids, as it is in the transient
plethora induced by a short period of rest, in the well-conditioned
working horse, without any restriction of his diet, may therefore be
set down as one of the most important factors in producing
hæmoglobinæmia. Nor is this without approximate examples in
human pathology. Von Bamberger has shown that “hæmatogenous
albuminuria” will occur in healthy individuals when there is an
excess of albumen in the blood-plasma, as after a too free use of
albuminous food, or after suppression of the milk secretion
(Landois). A similar result comes from increase of blood pressure, as
after drinking freely, or when, under emotion or violent exertion, the
heart’s action is increased in force and the blood is thrown with
greater impetus into the large renal arteries. Senator has found
albuminous urine to attend and follow, for several days, upon forced
marches made by young recruits. Here the muscular work is added to
the increased blood tension superinduced by the more active
contractions of the heart.
In this connection it is interesting to trace the changes in the blood
after transfusion. The dilatability of the capillaries enables the
system to accommodate itself to a very great increase in the volume
of blood An increase of 83 per cent. may be borne without serious
results, but above this limit there is increasing risk and an increase of
150 per cent. entails immediate danger to life. In the restoration of
the blood to its normal condition, the secretion of water sets in
promptly leaving an excess of albuminoids and blood globules. The
next change is in the albuminoids which in two days are almost
entirely transformed into urea. This leaves the blood abnormally rich
in globules (Panum, Lesser, Worm-Müller), the red globules break
up much more slowly and may still be in excess after the lapse of a
month (Tscherjew).
In this light, temporary plethora cannot of itself be accepted as the
main or essential cause of the disease. It must be admitted to be a
more constant and important factor than the mere exposure to cold,
but of itself it is inadequate to the production of hæmoglobinæmia.
In the absence of exertion the general plethora fails to produce the
specific disease; again, after transfusion a plethora of albumen lasts
for one or two days, but hæmoglobinæmia sets in only in the first few
minutes after the animal starts out from the stable, (never after an
hour or two at work): once more, excess of globules may last for a
month, but with steady work there is no danger of this disease, after
the first mile or two has been traversed, on the first day of the
resumption of labor.
A similar plethora of albuminoids and globules may be induced in
a plethoric animal by a profuse diarrhœa, diuresis or perspiration,
the blood having been robbed of its watery constituents, and
concentrated especially as regards its globules and albuminoids, but
hæmoglobinæmia never occurs as the result of such an artificial
concentration. On the contrary a free secretion by the bowels or
kidneys is of the greatest value in cutting short its progress after it
has set in.
The doctrine of poisoning by hæmoglobin produced by excessive
work and disintegration of the muscles is equally insufficient to
account for an attack. Excess of muscular work and of muscle-
decomposition-products, would not reach its maximum within the
first few minutes after the animal has started from the stable, but,
other things being equal, would increase with the continuance of
work and the accumulation in the blood of a constantly increasing
amount of these products. The sharp line of restriction by which the
attack is limited to the initial period of work, while it is never seen
after hard work continued for hours in succession, rules out this
from the list of essential causes. It may be that the products of
muscular decomposition aggravate the attack, but to set them down
as the cause of the attack is to beg the whole question and to
contradict the truth that continuous and severe muscular work with
its consequent increase of waste products is a direct bar to the
development of the disease. It should be noted in this connection
that the increase in the waste of nitrogenous bodies, as shown by the
increase of urea, is dependent far more on the amount of nitrogenous
matters ingested than on the muscle work or decomposition. In
eleven hours just before ascending the Faulhorn, Fick passed 21.686
grs. of urea per hour; in eight hours ascending the hill, 12.43 grs. per
hour; and in six hours after the ascent he passed 13.39 grs. per hour.
A general survey of the field shows that it is not the simple
increase of any normal waste product in the blood which determines
hæmoglobinæmia, and on the other hand the suddenness and
severity of the attack bears all the marks of a profound poisoning.
The nature of the poison has not yet been definitely ascertained, yet
one or two hypothesis may be hazarded, as furnishing a working
theory, in anticipation of the actual demonstration which may be
expected in the early future.
The action of a stable miasm as claimed by some writers is
contradicted by the fact that the disease does not develop so long as
the animal is left to inhale that miasm, and on leaving the stable, the
life and vigor are usually remarkable.
The morbific agent must be sought in some source from which it
can be supplied with great rapidity under the stimulus of a short but
active exertion. The chylopoietic viscera furnish such a source. The
healthy liver contains one-fourth of the entire mass of the blood. The
torpid congested liver of the vigorous high conditioned horse, after a
short period of idleness, on full, rich feeding, must hold much more
than this normal ratio. The spleen, the natural store-house or safety
valve of the portal veins, is also gorged with this liquid in the high
fed, idle animal. This organ which is always turgescent after meals, is
especially so in the over-fed horse, which for twenty-four hours has
been denied the opportunity of working off by exercise, the
superfluous products of an active digestion and absorption. Then the
whole of the portal veins and the capillaries in which they originate
are surcharged with rich blood which cannot make its way with the
necessary dispatch through the inactive liver.
In this condition there is incomparably more than a quarter of the
entire mass of blood, enriched to the highest degree in proteids,
ready to be discharged through the liver and hepatic veins into the
general circulation. Under the action of the hurried breathing and
circulation, caused by the sudden and active exertion, this whole
mass of rich blood is speedily unloaded on the right heart, the lungs
and the systemic circulation. One can hardly conceive of a more
effective method of inducing a sudden plethora, with an excess of
both globules and albuminoids.
The presence of actual poisons in such blood is not so easily
certified.
The absorption of bile elements and especially of taurocholic acid,
which is a solvent of the red blood globules, and would set free their
globulin might account for the characteristic condition of the blood.
The powerful aspiratory action of the chest, would speedily empty
the whole of the liver blood vessels, and lessening their tension below
that of the biliary radicals would determine an active absorption of
bile or of the more diffusible of the bile elements. A manifest
objection to this view is the absence of an icteric tint in the mucous
membranes of the affected animals. The visible mucosæ are of a
brownish red hue, such as might come from hæmoglobin dissolved
in the blood serum, rather than the yellow tint which might be
expected from bile pigment. The theory of poisoning by bile acids
therefore, would require an explanation of concurrent suppression or
decomposition of the bile pigments.
Other sources, however, offer solvents for hæmoglobin, benzoic
acid, which is derived from a cellulose in the fodders, and forms the
source of hippuric acid, dissolves red globules (Landois). In the over-
fed horse with active digestion, but inactive body and liver, this must
accumulate in the liver, spleen and portal system, and when
suddenly drawn into the blood without time for oxidation in the liver
it will contribute to the condition of hæmoglobinæmia.
Peptones, being very diffusible, are very rapidly absorbed, but they
are not found, in healthy conditions, in the portal vein (Neumeister).
These are manifestly transformed into albumen in the intestinal
mucosa (Salvioli), or taken up by the very numerous leucocytes and
transformed or carried elsewhere (Hoffmeister). But peptones
injected into the blood of the dog render it incoagulable, and in large
quantity are fatal (Landois). An excess of glycogen dissolves the red
globules, and the conditions of heavy feeding and torpid liver, are
calculated to produce this in great excess and to store it in the liver
cells.
Under the extra vigorous aspiratory force of the chest, these highly
diffusible agents, present in great excess, are likely to be drawn on
through the mucosa, into the portal vein, liver, and cava, without an
opportunity for complete transformation by leucocytes or liver cells.
These would tend to rob the blood globules of their normal
physiological vigor, would unfit them for maintaining the healthy
functions of lungs, kidneys, brain or muscle, and would unfit the
globules for successful resistance to solvents and other inimical
influences.
Again it is an important function of the liver, spleen and red bone
marrow to disintegrate worn out or abnormal red globules. These are
taken up by the white blood corpuscles of the hepatic capillaries, by
the cells of the spleen and the bone marrow and are stored up chiefly
in the capillaries of the liver, in the spleen, and in the marrow of
bone. They are transformed, partly into colored and partly into
colorless proteids, and are either deposited in the granular form, or
are dissolved (Landois). Quincke says: “That the normal red blood
globules and other particles suspended in the blood stream are not
taken up in this way, may be due to their being smooth and polished.
As the corpuscles grow older and become more rigid, they, as it were,
are caught by the amœboid cells. As cells containing blood corpuscles
are very rarely found in the general circulation, one may assume that
the occurrence of these cells within the spleen, liver, and marrow of
bone, is favored by the slowness of the circulation in these organs.”
From this chain of normal processes of blood disintegration, we may
reasonably infer, a greatly exaggerated work of blood destruction
when, in connection with an increased density of the plasma, and the
presence in the portal blood of poisonous products of digestion, the
red globules have been altered in density, in outline and in vitality, so
that they become ready victims of the amœboid cells of blood and
tissues. Then the stagnant condition of this altered blood in the
compulsorily idle animal favors the greatest excess of this
destruction and the storing up of an increased quantity of
hæmoglobin and other products, to be poured suddenly into the
general circulation as soon as the movement of the blood is
quickened by exercise.
This destruction of the red blood globules by disintegration
contributes to the formation of numerous decomposition-products,
like succinic, formic, acetic, butyric and lactic acids, inosite, leucin,
xanthine, hypoxanthin, and uric acid, some of which are strongly
toxic. The tendency will be to lower the vitality of the red globules
and thus to render them the easier victims of the leucocytes and of
the liver, spleen and marrow cells. Even the freed hæmoglobin
appears to exert a solvent action on the red blood globules. These
are, of course, most concentrated and effective in the seat of their
production, yet when drawn suddenly in large amount, into the
general circulation, by the vigorous aspiratory action of the chest,
they may prove seriously detrimental to the blood at large.
Again a variety of toxic matters are introduced into the system in
the food and others are developed from the food in the stomach and
intestine. Brieger found in the gastric peptones a potent alkaloid
having the effect of urari, and which in excess would determine
muscular paralysis. The alkaloidal and other poisons produced by
fermentations in the intestines have to be safely disposed of. The
ptomaines, if not too abundant, are arrested or even decomposed in
the liver which thus stands as a guardian, at the outlet of the portal
system, to protect the body at large. But this antitoxic function of the
liver is only exercised in the presence of glycogen (Rogers, Landois),
and forced muscular movement soon removes all glycogen from the
liver of the dog (Landois). Again glycogenesis in the liver is now
believed to be dependent on a ferment produced by the pancreas. If
therefore, the sudden active exercise and the aspiratory action of the
chest freed the liver of its glycogen, and hurried the alkaloidal and
other poisons through its capillaries too rapidly to allow of the
protective action of the liver cells, or if the pancreas as well as the
liver had become torpid and had failed to produce the requisite
amount of glycogen-ferment for the liver, the poisoning of the blood
and system at large would be imminent.
Not to mention the other toxic products which come from
imperfect metamorphosis in the liver, it may be noted that a venous
condition of the blood or an excess of carbon dioxide contributes
greatly to the solubility of the red blood globules. It also tends greatly
to modify the fibrinogenous elements. Thus the blood of a suffocated
animal fails to coagulate or coagulates loosely, and the blood of the
portal vein of a suffocated horse is strongly toxic (Sauson). Now the
conditions attendant on the onset of equine hæmoglobinæmia are
such as to give free scope to both of these inimical influences. The
great mass of blood in the portal vein, spleen and liver is venous
blood strongly charged with carbon dioxide, and by the sudden,
active exertion this is forced rapidly through the liver and lungs
without time for full æration, so that the whole mass of the
circulating blood is speedily reduced below par, and laid specially
open to the action of blood solvents. By the same action the systemic
blood is charged with poisons, direct from the food, and fermenting
ingesta, and from the overworked spleen and liver whose functions
are profoundly impaired, and later from other important organs, the
healthy functional activity of which can no longer be maintained by
the deteriorated blood supplied to them.
Hæmoglobinæmia in dogs has been produced experimentally by
the injection of water into the veins the mere dilution of the plasma
dissolving out the coloring matter from the red globules (Hayem);
also by the inhalation of arseniureted hydrogen (Naunyn and
Stadelman); by the ingestion of toluylendiamine, or phosphorus
(Afanassiew, Stadelman); by snake venom, septicæmia, influenza,
contagious pneumonia, petechial fever, anthrax, etc. These cannot be
looked on as causes of the acute hæmoglobinæmia in the horse, but
they serve as illustrations of changes in the plasma, and poisons in
the blood determining the escape of hæmoglobin from the cells.
Ralfe recognizes two forms of hæmoglobinæmia in man:
1st. That in which the hæmoglobin is simply dissolved out of the
blood globules, the solution taking place chiefly in parts exposed to
cold.
2d. A more severe form in which the dissolution is general and
probably attended by some destruction of red globules in the liver,
spleen and even in the kidneys. The general opinion appears to be
that the attacks are due to some nervous disturbance, which causes
vaso-motor disorder and it is supposed that there is an exaggerated
sensibility of the reflex nervous system. It has been suggested that
peripheral irritation causes irritation of the vaso-motor centre, and
in turn this causes local asphyxia in the part stimulated, under which
conditions the red globules part with their hæmoglobin (Roberts).
Murri holds that the disease depends on an increased irritability of
the vaso-motor reflex centre, and the formation, owing to the
disorder of the blood forming organs, of corpuscles unable to
withstand exposure to cold or carbon dioxide.
While it is not assumed to point out the actual poisons of
hæmoglobinæmia in the horse the above suggestions may offer
valuable hints as to the lines of inquiry that may be followed with the
best hope of reaching definite results.
Lesions. These are especially found in the blood, liver, spleen,
muscles, bone marrow and kidneys. The spinal cord and nerve
trunks are occasionally affected.
The blood is charged with carbon dioxide and is black, tarry,
comparatively incoagulable remaining in the veins and showing an
iridescent reflection. It does not absorb oxygen readily though
exposed to the air, and thus bears a strong general resemblance to
the blood of anthrax. It contains an abnormal proportion of urea and
allied extractive matters which greatly increase its density, and
interfere with the healthy exercise of the different cell organisms and
functions. These are not due to excessive muscular activity as stated
by Friedberger and Fröhner, but are derived mainly from the
abundant products of digestion. When the shed blood coagulates it
forms a soft clot without buff and the expressed serum is reddish
from the presence of hæmoglobin, and of hæmatoidin crystals. The
uncoagulated blood drawn over a sheet of white paper stains it
deeply by reason of the same coloring matters in solution. The red
corpuscles may be paler than natural, some even entirely colorless,
and they are often notched or broken up in various irregular forms.
They have lost the natural tendency of the shed equine blood to stick
together, to collect in rouleaux and precipitate to the bottom of the
vessel, so that no buffy coat is formed, should the blood coagulate.
The white corpuscles are relatively increased. Finally the coloring
matters contained in the plasma are imbibed by the different tissues
and give a brown or reddish tinge to such as are naturally white.
Limited blood extravasations are not uncommon especially in the
more vascular organs like the muscles, liver, spleen and kidneys.
The liver is more or less congested and enlarged, friable, yellow, or
mottled yellow and red and exudes black blood freely when incised.
The bile is thick, viscid and dark green, as in cases of experimental
intravenous injection of hæmoglobin.
The spleen is also swollen and congested with blood, and the pulp
is very high colored from the excess of hæmoglobin and other
products of blood destruction. The muscles of the croup are usually

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