Experimental and theoretical approaches to actinide chemistry / edited by John K. Gibson and Wibe A. de Jong.

Format:

Book

Contributor:

Gibson, John K., editor.

de Jong, Wibe A., editor.

Language:

English

Subjects (All):

Actinium compounds.

Actinide elements.

Heavy elements.

Physical Description:

1 online resource (521 pages) : illustrations (some color)

Edition:

1st ed.

Place of Publication:

Hoboken, New Jersey : Wiley, 2018.

Summary:

A review of contemporary actinide research that focuses on new advances in experiment and theory, and the interplay between these two realms Experimental and Theoretical Approaches to Actinide Chemistry offers a comprehensive review of the key aspects of actinide research. Written by noted experts in the field, the text includes information on new advances in experiment and theory and reveals the interplay between these two realms. The authors offer a multidisciplinary and multimodal approach to the nature of actinide chemistry, and explore the interplay between multiple experiments and theory, as well as between basic and applied actinide chemistry. The text covers the basic science used in contemporary studies of the actinide systems, from basic synthesis to state-of-the-art spectroscopic and computational techniques. The authors provide contemporary overviews of each topic area presented and describe the current and anticipated experimental approaches for the field, as well as the current and future computational chemistry and materials techniques. In addition, the authors explore the combination of experiment and theory. This important resource: * Provides an essential resource the reviews the key aspects of contemporary actinide research * Includes information on new advances in experiment and theory, and the interplay between the two * Covers the basic science used in contemporary studies of the actinide systems, from basic synthesis to state-of-the-art spectroscopic and computational techniques * Focuses on the interplay between multiple experiments and theory, as well as between basic and applied actinide chemistry Written for academics, students, professionals and researchers, this vital text contains a thorough review of the key aspects of actinide research and explores the most recent advances in experiment and theory.

Contents:

Intro

Title Page

Copyright Page

Contents

List of Contributors

Preface

Chapter 1 Probing Actinide Bonds in the Gas Phase: Theory and Spectroscopy

1.1 Introduction

1.2 Techniques for Obtaining Actinide‐Containing Molecules in the Gas Phase

1.3 Techniques for Spectroscopic Characterization of Gas‐Phase Actinide Compounds

1.3.1 Conventional Absorption and Emission Spectroscopy

1.3.2 Photoelectron Spectroscopy

1.3.3 Velocity Modulation and Frequency Comb Spectroscopy

1.3.4 LIF Spectroscopy

1.3.5 Two-Photon Excitation Techniques

1.3.6 Anion Photodetachment Spectroscopy

1.3.7 Action Spectroscopy

1.3.8 Bond Energies and Reactivities from Mass Spectrometry

1.4 Considerations for Characterizing Actinide-Containing Molecules in the Gas Phase by Ab Initio Methods

1.4.1 Electron Correlation Methods

1.4.2 Relativistic Effects

1.4.3 Basis Sets

1.5 Computational Strategies for Accurate Thermodynamics of Gas-Phase Actinide Molecules

1.6 Ab Initio Molecular Spectroscopy of Gas-Phase Actinide Compounds

1.6.1 Pure Rotational and Ro-Vibrational Spectroscopy

1.6.2 Electronic Spectroscopy

1.7 Summary and Outlook

Acknowledgments

References

Chapter 2 Speciation of Actinide Complexes, Clusters, and Nanostructures in Solution

2.1 Introduction

2.2 Potentiometry

2.2.1 Potentiometric Titrations to Reveal Speciation

2.2.2 Overview of Potentiometry in Aqueous Actinide Chemistry

2.3 Optical Spectroscopy

2.3.1 UV-vis-NIR Spectroscopy in Actinide Speciation

2.3.2 Fluorescence Spectroscopy

2.3.3 Overview of Optical Spectroscopy in Aqueous Actinide Speciation

2.4 NMR Spectroscopy

2.4.1 Probing Chemical Equilibria by NMR

2.4.2 Monitoring Product Formation/Evolution by NMR Spectroscopy

2.4.3 Monitoring Actinide Self-Assembly by NMR Spectroscopy.

2.4.4 Following Cluster Stability in Solution by NMR Spectroscopy

2.4.5 Overview of NMR Spectroscopy in Aqueous Actinide Chemistry

2.5 Raman Spectroscopy

2.5.1 Cluster Formation and Assembly

2.5.2 Spectral Deconvolution of Raman Data to Yield Speciation

2.5.3 Identifying the Nature of Cation-Cation Interactions in Solution

2.5.4 In the Absence of an "yl": Pa(V) Speciation in HF Solutions

2.5.5 Computational Assignment of Vibrational Spectra

2.5.6 Overview of Raman Spectroscopy

2.6 X-ray Absorption Spectroscopy

2.6.1 EXAFS

2.6.2 Actinide Solution Speciation by EXAFS

2.6.3 EXAFS Structural Comparison of Complexes with Varying Oxidation States and Geometries

2.6.4 Overview of EXAFS

2.7 Small-Angle X-ray Scattering (SAXS)

2.7.1 Structure Elucidation by SAXS

2.7.2 SAXS Analysis of Cluster Evolution

2.7.3 Understanding Self-Assembly Processes by SAXS

2.7.4 Overview of SAXS

2.8 High-Energy X-ray Scattering (HEXS)

2.8.1 Determining Coordination Number and Environment about a Metal Center

2.8.2 Deducing Metal-Ligand Coordination Modes

2.8.3 Following Oligomer Formation and Stability

2.8.4 Overview of HEXS

Chapter 3 Complex Inorganic Actinide Materials

3.1 Introduction

3.2 Fluorides

3.2.1 Trivalent and Tetravalent Fluorides

3.2.2 Pentavalent and Hexavalent Fluorides

3.2.3 Fluoride Architectures

3.3 Borates

3.3.1 Functionalized Borates

3.3.2 Transuranic Borates

3.4 Sulfates

3.4.1 Thorium and Uranium

3.4.2 Transuranic Frameworks

3.5 Phosphates

3.6 Conclusion

Chapter 4 Organometallic Actinide Complexes with Novel Oxidation States and Ligand Types

4.1 Introduction

4.2 Overview of Actinide Organometallic Chemistry

4.2.1 Overview of Thorium Organometallics

4.2.2 Overview of Uranium Organometallics.

4.2.3 Overview of Transuranium Organometallics

4.3 Overview of Theoretical Methods

4.4 New Theoretical and Experimental Tools for Evaluating Covalency in the 5f Series

4.4.1 The Quantum Theory of Atoms-in-Molecules

4.4.2 Ligand K-edge X-ray Absorption Spectroscopy

4.4.3 Optical Spectroscopy

4.4.4 Nuclear Magnetic Resonance (NMR) Spectroscopy

4.4.5 Electrochemistry

4.5 Notable Discoveries in Actinide‐Carbon Chemistry

4.5.1 An(II) Complexes

4.5.2 π-Acceptor Ligand Complexes

4.5.3 (Inverted) Arene Sandwich Complexes

4.5.4 Phosphorano-Stabilized Carbene Complexes

4.5.5 Homoleptic Alkyl and Aryl Complexes

4.6 Single and Multiple Bonding between Uranium and Group 15 Elements

4.7 Complexes with Group 16 Donor Ligands

4.7.1 Terminal Mono-oxo Complexes

4.7.2 Complexes with Heavy Chalcogen (S, Se, Te) Donors

4.8 Actinyl and Its Derivatives

4.8.1 Inverse Trans Influence (ITI)

4.8.2 Imido-Substituted Analogues of Uranyl

4.8.3 Progress Toward the Isolation of a cis-Uranyl Complex

4.9 Organoactinide Single-Molecule Magnets

4.10 Future Work

Chapter 5 Coordination of Actinides and the Chemistry Behind Solvent Extraction

5.1 Introduction

5.2 Overview of Separations Processes

5.2.1 Classic Processes - U/Pu Recovery

5.2.2 Advanced Separation Processes - Am/Cm Recovery

5.2.3 Aqueous-Based Complexants for Trivalent An/Ln Separation

5.2.4 Recent Trends in Aqueous-Based Trivalent An/Ln Separations

5.2.5 Separation of Hexavalent Actinides (SANHEX) Processes

5.3 Coordination and Speciation of Aqueous Actinides

5.3.1 Actinide Hydration

5.3.2 Cation-Cation Complexes in Separations Solution

5.3.3 Counterion Interactions with Aqueous Actinide Ions

5.3.4 Changes to Solvation and Speciation in Solvent Mixtures

5.4 Ligand Design.

5.4.1 Solvating Extractants

5.4.2 Recent Trends in Solvating Extractants

5.4.3 Cation Exchange Reagents

5.4.4 Aqueous Complexants

5.4.5 Covalency and Ligand Design

5.4.6 Computational Screening of Separation Selectivity

5.5 Interfacial Chemistry of Solvent Extraction

5.5.1 Properties of the Interface and Its Characterization

5.5.2 Current Understanding of Interfacial Structure and Properties under Different Conditions

5.5.3 Synergism and Cooperative Phenomena at Interfaces

5.6 Concluding Remarks

Acronyms

Chapter 6 Behaviour and Properties of Nuclear Fuels

6.1 Introduction

6.2 UO2

6.2.1 Crystal Structure

6.2.2 Electronic Structure

6.2.3 Defect Chemistry

6.2.4 Transport Properties

6.2.4.1 Oxygen Diffusion

6.2.4.2 Uranium Diffusion

6.2.5 Thermophysical Properties

6.2.5.1 Phonon Kinetics

6.2.5.2 Thermal Expansion

6.2.5.3 Heat Capacity

6.2.5.4 Thermal Conductivity

6.2.6 Melting and the Liquid

6.3 Mixed Oxides

6.4 Nuclear Fuel Behaviour during Irradiation

6.4.1 Radiation Effects from Fission Fragments

6.4.2 Radiation Effects from Alpha Decay

6.4.3 Fission Product Behaviour

6.4.3.1 Fission Product Dissolution in the UO2 Matrix

6.4.3.2 Fission Product Diffusion, Coalescence‚ and Precipitation

6.4.3.3 Fission Gas Resolution

6.4.4 Helium Behaviour

6.4.5 Grain Boundary Effects

6.5 Concluding Remarks

Acknowledgements

Chapter 7 Ceramic Host Phases for Nuclear Waste Remediation

7.1 Introduction

7.2 Types of Ceramic Nuclear Waste Forms

7.3 Radiation Damage Effects

7.3.1 Actinide Doping Experiments

7.3.2 Ion Irradiation Experiments

7.3.3 Natural Analogues

7.3.4 Atomistic Modeling

7.4 Performance in Aqueous Systems

7.4.1 Laboratory Experiments

7.4.2 Natural Systems.

7.5 Summary and Conclusions

Chapter 8 Sources and Behaviour of Actinide Elements in the Environment

8.1 Introduction

8.2 Naturally Occurring Actinides

8.2.1 Commercial Uses of Naturally Occurring Actinides

8.2.2 Uranium Resources and Mining

8.2.3 Environmental Impacts of Uranium Mining and Milling

8.2.4 Thorium Resources and Potential Use as Fuel

8.3 Anthropogenic Actinides Release

8.3.1 Releases from Nuclear Reprocessing Facilities

8.3.2 Inventories of Releases from Accidents and Incidents

8.3.2.1 Source-Dependent Speciation and Behaviour of Released Actinides

8.3.3 Burden from Nuclear Testing

8.3.3.1 Nuclear Testing

8.3.3.2 Actinides Released in Nuclear Testing

8.3.3.3 Debris and Fallout of Actinides from Atmospheric Nuclear Testing

8.3.3.4 Inventories of Actinides from Atmospheric Nuclear Testing

8.3.3.5 Environmental Behaviour of Fallout Actinides

8.4 Radionuclide Biogeochemistry - Contaminated Land and Radioactive Waste Disposal

8.4.1 Bioreduction Processes

8.4.2 Uranium Biogeochemistry

8.4.3 Technetium Biogeochemistry

8.4.4 Neptunium Biogeochemistry

8.4.5 Plutonium Biogeochemistry

8.5 Transport and Surface Complexation Modelling

8.5.1 Key Processes in Actinide Transport

8.5.2 Interactions of Actinides with Inorganic Phases

8.5.2.1 Examples of Actinide Interfacial Redox Behaviour

8.5.3 Surface Complexation Modelling

8.5.4 Incorporation

8.5.5 Humic Substances

8.5.6 Colloids

8.5.6.1 Intrinsic Colloids

8.5.6.2 Pseudo-colloids

8.5.7 Damkohler Analysis of HS/Colloid-Mediated Transport

8.6 Conclusions and Outlook

List of Acronyms

Chapter 9 Actinide Biological Inorganic Chemistry: The Overlap of 5f Orbitals with Biology

9.1 Introduction

9.2 Interactions between Actinides and Living Systems.

9.2.1 Uranium in a Geochemical Context.

Notes:

Includes bibliographical references and index.

Description based on print version record.

ISBN:

9781119115540

111911554X

9781119115533

1119115531

9781119115557

1119115558

OCLC:

1010585539