Experimental and Theoretical Approaches to Actinide Chemistry

Inbunden, Engelska, 2018

Av John K. Gibson, Wibe A. de Jong, John K Gibson, Wibe A de Jong

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A review of contemporary actinide research that focuses on new advances in experiment and theory, and the interplay between these two realmsExperimental 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 researchIncludes information on new advances in experiment and theory, and the interplay between the twoCovers the basic science used in contemporary studies of the actinide systems, from basic synthesis to state-of-the-art spectroscopic and computational techniquesFocuses on the interplay between multiple experiments and theory, as well as between basic and applied actinide chemistryWritten 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.

Produktinformation

Utgivningsdatum2018-03-16
Mått178 x 249 x 31 mm
Vikt975 g
FormatInbunden
SpråkEngelska
Antal sidor520
FörlagJohn Wiley & Sons Inc
ISBN9781119115526

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Edited by John K. Gibson, is Senior Scientist, Lawrence Berkeley National Laboratory, USA. He is experienced in fundamental actinide chemistry research, ranging from solid state synthesis of transuranium compounds to actinide chemistry in the gas phase. Wibe A. de Jong, is Senior Scientist, Lawrence Berkeley National Laboratory, USA. He has years of experience in advancing fundamental actinide chemistry research, and in developing and using a variety of computational chemistry approaches.

List of Contributors xiPreface xiii1 Probing Actinide Bonds in the Gas Phase: Theory and Spectroscopy 1Michael C. Heaven and Kirk A. Peterson1.1 Introduction 11.2 Techniques for Obtaining Actinide]Containing Molecules in the Gas Phase 21.3 Techniques for Spectroscopic Characterization of Gas]Phase Actinide Compounds 51.3.1 Conventional Absorption and Emission Spectroscopy 51.3.2 Photoelectron Spectroscopy 61.3.3 Velocity Modulation and Frequency Comb Spectroscopy 61.3.4 LIF Spectroscopy 71.3.5 Two]Photon Excitation Techniques 121.3.6 Anion Photodetachment Spectroscopy 151.3.7 Action Spectroscopy 171.3.8 Bond Energies and Reactivities from Mass Spectrometry 201.4 Considerations for Characterizing Actinide]Containing Molecules in the Gas Phase by Ab Initio Methods 231.4.1 Electron Correlation Methods 241.4.2 Relativistic Effects 271.4.3 Basis Sets 291.5 Computational Strategies for Accurate Thermodynamics of Gas]Phase Actinide Molecules 301.6 Ab Initio Molecular Spectroscopy of Gas]Phase Actinide Compounds 341.6.1 Pure Rotational and Ro]Vibrational Spectroscopy 341.6.2 Electronic Spectroscopy 371.7 Summary and Outlook 38Acknowledgments 39References 392 Speciation of Actinide Complexes, Clusters, and Nanostructures in Solution 53Rami J. Batrice, Jennifer N. Wacker, and Karah E. Knope2.1 Introduction 532.2 Potentiometry 542.2.1 Potentiometric Titrations to Reveal Speciation 542.2.2 Overview of Potentiometry in Aqueous Actinide Chemistry 592.3 Optical Spectroscopy 602.3.1 UV]vis]NIR Spectroscopy in Actinide Speciation 602.3.2 Fluorescence Spectroscopy 632.3.3 Overview of Optical Spectroscopy in Aqueous Actinide Speciation 682.4 NMR Spectroscopy 692.4.1 Probing Chemical Equilibria by NMR 692.4.2 Monitoring Product Formation/Evolution by NMR Spectroscopy 742.4.3 Monitoring Actinide Self]Assembly by NMR Spectroscopy 752.4.4 Following Cluster Stability in Solution by NMR Spectroscopy 762.4.5 Overview of NMR Spectroscopy in Aqueous Actinide Chemistry 822.5 Raman Spectroscopy 822.5.1 Cluster Formation and Assembly 832.5.2 Spectral Deconvolution of Raman Data to Yield Speciation 852.5.3 Identifying the Nature of Cation–Cation Interactions in Solution 862.5.4 In the Absence of an “yl”: Pa(V) Speciation in HF Solutions 892.5.5 Computational Assignment of Vibrational Spectra 922.5.6 Overview of Raman Spectroscopy 922.6 X] ray Absorption Spectroscopy 932.6.1 EXAFS 942.6.2 Actinide Solution Speciation by EXAFS 952.6.3 EXAFS Structural Comparison of Complexes with Varying Oxidation States and Geometries 992.6.4 Overview of EXAFS 1012.7 Small] Angle X]ray Scattering (SAXS) 1022.7.1 Structure Elucidation by SAXS 1022.7.2 SAXS Analysis of Cluster Evolution 1042.7.3 Understanding Self]Assembly Processes by SAXS 1072.7.4 Overview of SAXS 1102.8 High] Energy X]ray Scattering (HEXS) 1102.8.1 Determining Coordination Number and Environment about a Metal Center 1112.8.2 Deducing Metal–Ligand Coordination Modes 1132.8.3 Following Oligomer Formation and Stability 1162.8.4 Overview of HEXS 117References 1183 Complex Inorganic Actinide Materials 128Matthew L. Marsh and Thomas E. Albrecht]Schmitt3.1 Introduction 1283.2 Fluorides 1293.2.1 Trivalent and Tetravalent Fluorides 1293.2.2 Pentavalent and Hexavalent Fluorides 1313.2.3 Fluoride Architectures 1323.3 Borates 1373.3.1 Functionalized Borates 1383.3.2 Transuranic Borates 1413.4 Sulfates 1543.4.1 Thorium and Uranium 1543.4.2 Transuranic Frameworks 1623.5 Phosphates 1673.6 Conclusion 176References 1764 Organometallic Actinide Complexes with Novel Oxidation States and Ligand Types 181Trevor W. Hayton and Nikolas Kaltsoyannis4.1 Introduction 1814.2 Overview of Actinide Organometallic Chemistry 1814.2.1 Overview of Thorium Organometallics 1834.2.2 Overview of Uranium Organometallics 1844.2.3 Overview of Transuranium Organometallics 1844.3 Overview of Theoretical Methods 1844.4 New Theoretical and Experimental Tools for Evaluating Covalency in the 5f Series 1864.4.1 The Quantum Theory of Atoms]in]Molecules 1864.4.2 Ligand K]edge X]ray Absorption Spectroscopy 1874.4.3 Optical Spectroscopy 1894.4.4 Nuclear Magnetic Resonance (NMR) Spectroscopy 1914.4.5 Electrochemistry 1924.5 Notable Discoveries in Actinide]Carbon Chemistry 1944.5.1 An(II) Complexes 1954.5.2 π]Acceptor Ligand Complexes 1954.5.3 (Inverted) Arene Sandwich Complexes 1984.5.4 Phosphorano]Stabilized Carbene Complexes 1994.5.5 Homoleptic Alkyl and Aryl Complexes 2014.6 Single and Multiple Bonding between Uranium and Group 15 Elements 2024.7 Complexes with Group 16 Donor Ligands 2064.7.1 Terminal Mono]oxo Complexes 2064.7.2 Complexes with Heavy Chalcogen (S, Se, Te) Donors 2074.8 Actinyl and Its Derivatives 2104.8.1 Inverse Trans Influence (ITI) 2114.8.2 Imido]Substituted Analogues of Uranyl 2124.8.3 Progress Toward the Isolation of a cis]Uranyl Complex 2164.9 Organoactinide Single]Molecule Magnets 2174.10 Future Work 219Acknowledgments 220References 2205 Coordination of Actinides and the Chemistry Behind Solvent Extraction 237Aurora E. Clark, Ping Yang, and Jenifer C. Shafer5.1 Introduction 2375.2 Overview of Separations Processes 2385.2.1 Classic Processes – U/Pu Recovery 2385.2.2 Advanced Separation Processes – Am/Cm Recovery 2405.2.3 Aqueous]Based Complexants for Trivalent An/Ln Separation 2405.2.4 Recent Trends in Aqueous]Based Trivalent An/Ln Separations 2415.2.5 Separation of Hexavalent Actinides (SANHEX) Processes 2415.3 Coordination and Speciation of Aqueous Actinides 2435.3.1 Actinide Hydration 2455.3.2 Cation–Cation Complexes in Separations Solution 2475.3.3 Counterion Interactions with Aqueous Actinide Ions 2485.3.4 Changes to Solvation and Speciation in Solvent Mixtures 2495.4 Ligand Design 2495.4.1 Solvating Extractants 2505.4.2 Recent Trends in Solvating Extractants 2515.4.3 Cation Exchange Reagents 2535.4.4 Aqueous Complexants 2545.4.5 Covalency and Ligand Design 2555.4.6 Computational Screening of Separation Selectivity 2575.5 Interfacial Chemistry of Solvent Extraction 2585.5.1 Properties of the Interface and Its Characterization 2595.5.2 Current Understanding of Interfacial Structure and Properties under Different Conditions 2615.5.3 Synergism and Cooperative Phenomena at Interfaces 2635.6 Concluding Remarks 266Acronyms 267Acknowledgments 269References 2696 Behaviour and Properties of Nuclear Fuels 283Rudy Konings and Marjorie Bertolus6.1 Introduction 2836.2 UO2 2846.2.1 Crystal Structure 2846.2.2 Electronic Structure 2856.2.3 Defect Chemistry 2876.2.4 Transport Properties 2906.2.4.1 Oxygen Diffusion 2906.2.4.2 Uranium Diffusion 2926.2.5 Thermophysical Properties 2936.2.5.1 Phonon Kinetics 2936.2.5.2 Thermal Expansion 2946.2.5.3 Heat Capacity 2966.2.5.4 Thermal Conductivity 2976.2.6 Melting and the Liquid 2996.3 Mixed Oxides 3006.4 Nuclear Fuel Behaviour during Irradiation 3046.4.1 Radiation Effects from Fission Fragments 3056.4.2 Radiation Effects from Alpha Decay 3066.4.3 Fission Product Behaviour 3076.4.3.1 Fission Product Dissolution in the UO2 Matrix 3086.4.3.2 Fission Product Diffusion, Coalescence‚ and Precipitation 3096.4.3.3 Fission Gas Resolution 3146.4.4 Helium Behaviour 3146.4.5 Grain Boundary Effects 3176.5 ConcludingRemarks 319Acknowledgements 321References 3217 Ceramic Host Phases for Nuclear Waste Remediation 333Gregory R. Lumpkin7.1 Introduction 3337.2 Types of Ceramic Nuclear Waste Forms 3347.3 Radiation Damage Effects 3367.3.1 Actinide Doping Experiments 3377.3.2 Ion Irradiation Experiments 3407.3.3 Natural Analogues 3457.3.4 Atomistic Modeling 3527.4 Performance in Aqueous Systems 3587.4.1 Laboratory Experiments 3587.4.2 Natural Systems 3637.5 Summary and Conclusions 365Acknowledgments 367References 3688 Sources and Behaviour of Actinide Elements in the Environment 378M.A. Denecke, N. Bryan, S. Kalmykov, K. Morris, and F. Quinto8.1 Introduction 3788.2 Naturally Occurring Actinides 3798.2.1 Commercial Uses of Naturally Occurring Actinides 3818.2.2 Uranium Resources and Mining 3818.2.3 Environmental Impacts of Uranium Mining and Milling 3848.2.4 Thorium Resources and Potential Use as Fuel 3878.3 Anthropogenic Actinides Release 3878.3.1 Releases from Nuclear Reprocessing Facilities 3888.3.2 Inventories of Releases from Accidents and Incidents 3908.3.2.1 Source]Dependent Speciation and Behaviour of Released Actinides 3938.3.3 Burden from Nuclear Testing 3958.3.3.1 Nuclear Testing 3958.3.3.2 Actinides Released in Nuclear Testing 3968.3.3.3 Debris and Fallout of Actinides from Atmospheric Nuclear Testing 3988.3.3.4 Inventories of Actinides from Atmospheric Nuclear Testing 4008.3.3.5 Environmental Behaviour of Fallout Actinides 4028.4 Radionuclide Biogeochemistry – Contaminated Land and Radioactive Waste Disposal 4048.4.1 Bioreduction Processes 4058.4.2 Uranium Biogeochemistry 4058.4.3 Technetium Biogeochemistry 4088.4.4 Neptunium Biogeochemistry 4098.4.5 Plutonium Biogeochemistry 4098.5 Transport and Surface Complexation Modelling 4108.5.1 Key Processes in Actinide Transport 4108.5.2 Interactions of Actinides with Inorganic Phases 4108.5.2.1 Examples of Actinide Interfacial Redox Behaviour 4128.5.3 Surface Complexation Modelling 4148.5.4 Incorporation 4178.5.5 Humic Substances 4188.5.6 Colloids 4198.5.6.1 Intrinsic Colloids 4208.5.6.2 Pseudo]colloids 4218.5.7 Damkohler Analysis of HS/Colloid]Mediated Transport 4218.6 Conclusions and Outlook 423List of Acronyms 425References 4269 Actinide Biological Inorganic Chemistry: The Overlap of 5f Orbitals with Biology 445Peter Agbo, Julian A. Rees, and Rebecca J. Abergel9.1 Introduction 4459.2 Interactions between Actinides and Living Systems 4489.2.1 Uranium in a Geochemical Context 4499.2.2 Uranium in Larger Mammalian Systems 4529.2.3 Pentavalent Actinides Neptunium and Protactinium 4529.2.4 Tetravalent Actinides Plutonium and Thorium 4539.2.5 Trivalent Metals from Americium to Einsteinium 4579.3 Molecular Interactions of Actinides with Biological Metal Transporters 4589.3.1 Transferrin]Mediated Metal Uptake Pathways 4589.3.2 Ferric Ion Binding Proteins 4609.3.3 Divalent Metal Ion Transport Pathways 4629.3.4 Skeleton Deposition: The Role of the Bone Matrix 4639.3.5 Small]Molecule Metallophores 4649.3.6 Siderophore Analogues for Chelation Therapy 4679.4 Actinide Coordination for Radiopharmaceutical Applications 4709.4.1 Common and Most Promising New Bifunctional Chelators for 225Ac and 227Th 4729.4.2 Maximizing Radiometal Delivery and Minimizing Damage Through Chemistry 4749.5 Approaching Actinide Biochemistry from a Theoretical Perspective 475References 477Index 490