The Heaviest Metals

An authoritative survey of the science and advanced technological uses of the actinide and transactinide metals

The Heaviest Metals offers an essential resource that covers the fundamentals of the chemical and physical properties of the heaviest metals as well as the most recent advances in their science and technology. The authors – noted experts in the field – offer an authoritative review of the actinide and transactinide elements, i.e., the elements from actinium to lawrencium as well as rutherfordium through organesson, the current end of the periodic table, element 118.

The text explores the history of the metals, their occurrence and issues of production, and covers a broad range of chemical subjects including environmental concerns and remediation approaches. The authors also offer information on the most recent and emerging applications of the metals, such as in superconducting materials, catalysis, and research into medical diagnostics. This important resource:

• Provides an overview of the science and advanced technological uses of the actinide and transactinide metals
• Describes the basic chemical and physical properties of the heaviest metals, and discusses the challenges and opportunities for their technological applications
• Contains accessible information on the fundamental features of the heaviest metals, special requirements for their experimental study, and the critical role of computational characterization of their compounds
• Highlights the most current and emerging applications in areas such as superconducting materials, catalysis, nuclear forensics, and medicine
• Presents vital contemporary issues of the heaviest metals

Written for graduate students and researchers working with the actinide and transactinide elements, industrial and academic inorganic and nuclear chemists, and engineers, The Heaviest Metals is a comprehensive volume that explores the fundamental chemistry and properties of the heaviest metals, and the challenges and opportunities associated with their present and emerging technological uses.

Contributors xi

Series Preface xv

Volume Preface xvii

PART 1: BACKGROUND 1

Discovery of the Actinide and Transactinide Elements 3
Mary Virginia Orna and Marco Fontani

Production of Plutonium 31
David L. Clark and Franz J. Freibert

Controlling Actinide Extraction Chemistry (Separation of Actinides from Lanthanides as Part of Nuclear Fuel Recycling) 39
James Westwood and Laurence M. Harwood

PART 2: FUNDAMENTALS 57

Electronic Structure of the Actinide Elements 59
Frédéric Gendron and Jochen Autschbach

Electronic Structure of the Transactinide Atoms 77
Ephraim Eliav, Anastasia Borschevsky and Uzi Kaldor

Chemical Properties of the Transactinide Elements 93
Christoph E. Düllmann

Multiple Bonding in Actinide Chemistry 105
Michael A. Boreen and John Arnold

Electronic Structure of Actinide Oxides 123
Lindsay E. Roy

PART 3: CHARACTERIZATION METHODS 143

Crystallography of Actinide Complexes 145
Brian L. Scott, Samantha K. Cary and Justin N. Cross

Solid State NMR of Actinide-Containing Compounds 177
G. Koutroulakis and H. Yasuoka

Mössbauer Spectroscopy of Actinide Compounds 185
iotr Gaczy´nski

Photoelectron Spectroscopy of Actinide Materials 193
Thomas Gouder and Rachel Eloirdi

Laser-Based Spectroscopic Studies of Actinide Complexes 209
Euo C. Jung, Hye-Ryun Cho, Hee-Kyung Kim and Wansik Cha

Ab Initio Electronic Structure Calculations for Actinide and Transactinide Atoms and Molecules 223
Michael Dolg and Xiaoyan Cao

PART 4: DISTINCTIVE CHEMISTRY 247

Divalent Actinides and Transactinides: Inorganic and Organometallic Complexes 249
Leonor Maria, Joaquim Marçalo and John K. Gibson

Organometallic Chemistry of Pentavalent Uranium 263
Jesse Murillo and Skye Fortier

Amido Complexes of the Actinides 283
avid J. H. Emslie

Actinide Pnictogen Complexes 301
Sean P. Vilanova and Justin R. Walensky

Actinide Borohydrides 319
Scott R. Daly

Supramolecular and Macrocyclic Chemistry of the Actinides 335
ei Mei, Jianhui Lan, Kongqiu Hu and Weiqun Shi

Actinide Polyoxometalates 355
Peter C. Burns

PART 5: ENVIRONMENTAL AND HEALTH ISSUES 365

Actinide Speciation and Bioavailability in Fresh and Marine Surface Waters 367
Scott J. Markich and Paul L. Brown

Transuranic Biogeochemistry 401
Hakim Boukhalfa and Mary Neu

Sustainable Remediation in Complex Geologic Systems 415
Haruko Wainwright, Bhavna Arora, Susan Hubbard, Konstantin Lipnikov, Greg Flach, David Moulton, Carol Eddy-Dilek and Miles Denham

Nuclear Forensics 427
Maria Wallenius, Klaus Lützenkirchen, Klaus Mayer and Zsolt Varga

Actinides in Medicine 445
Eva R. Birnbaum, Michael E. Fassbender, Maryline G. Ferrier, Kevin D. John and Tara Mastren

PART 6: SPECIAL APPLICATIONS 467

Actinide Elements in Catalysis 469
Rami J. Batrice, Isabell S.R. Karmel, Guy Yardeni and Moris S. Eisen

Superconductivity of the Heaviest Metals and Their Compounds 493
Hans R. Ott and Zachary Fisk

Index 507

Editors

William J. Evans, Distinguished Professor of Chemistry, University of California, Irvine, USA

Timothy P. Hanusa, Professor of Chemistry, Vanderbilt University, USA

The Heaviest Metals Science and Technology of the Actinides and Beyond

An authoritative survey of the science and advanced technological uses of the actinide and transactinide metals

The Heaviest Metals offers an essential resource that covers the fundamentals of the chemical and physical properties of the heaviest metals as well as the most recent advances in their science and technology. The authors – noted experts in the field – offer an authoritative review of the actinide and transactinide elements, i.e., the elements from actinium to lawrencium as well as rutherfordium through organesson, the current end of the periodic table, element 118.

The text explores the history of the metals, their occurrence and issues of production, and covers a broad range of chemical subjects including environmental concerns and remediation approaches. The authors also offer information on the most recent and emerging applications of the metals, such as in superconducting materials, catalysis, and research into medical diagnostics. This important resource:

• Provides an overview of the science and advanced technological uses of the actinide and transactinide metals
• Describes the basic chemical and physical properties of the heaviest metals, and discusses the challenges and opportunities for their technological applications
• Contains accessible information on the fundamental features of the heaviest metals, special requirements for their experimental study, and the critical role of computational characterization of their compounds
• Highlights the most current and emerging applications in areas such as superconducting materials, catalysis, nuclear forensics, and medicine
• Presents vital contemporary issues of the heaviest metals

Written for graduate students and researchers working with the actinide and transactinide elements, industrial and academic inorganic and nuclear chemists, and engineers, The Heaviest Metals is a comprehensive volume that explores the fundamental chemistry and properties of the heaviest metals, and the challenges and opportunities associated with their present and emerging technological uses.

About EIBC Books

The Encyclopedia of Inorganic and Bioinorganic Chemistry (EIBC) was created as an online reference in 2012 by merging the Encyclopedia of Inorganic Chemistry and the Handbook of Metalloproteins. The resulting combination proves to be the defining reference work in the field of inorganic and bioinorganic chemistry, and a lot of chemistry libraries around the world have access to the online version. Many readers, however, prefer to have more concise thematic volumes in print, targeted to their specific area of interest. This feedback from EIBC readers has encouraged the Editors to plan a series of EIBC Books [formerly called EIC Books], focusing on topics of current interest.

EIBC Books will appear on a regular basis, will be edited by the EIBC Editors and specialist Guest Editors, and will feature articles from leading scholars in their fields. EIBC Books aim to provide both the starting research student and the confirmed research worker with a critical distillation of the leading concepts in inorganic and bioinorganic chemistry, and provide a structured entry into the fields covered.

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