Experimental and Theoretical Approaches to Actinide Chemistry

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.

Autorentext

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.

Klappentext
Experimental and Theoretical Approaches to Actinide Chemistry 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 that 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.

Inhalt
List of Contributors xi

Preface xiii

1 Probing Actinide Bonds in the Gas Phase: Theory and Spectroscopy 1
*Michael C. Heaven and Kirk A. Peterson*

1.1 Introduction 1

1.2 Techniques for Obtaining Actinide?]Containing Molecules in the Gas Phase 2

1.3 Techniques for Spectroscopic Characterization of Gas?]Phase Actinide Compounds 5

1.3.1 Conventional Absorption and Emission Spectroscopy 5

1.3.2 Photoelectron Spectroscopy 6

1.3.3 Velocity Modulation and Frequency Comb Spectroscopy 6

1.3.4 LIF Spectroscopy 7

1.3.5 Two?]Photon Excitation Techniques 12

1.3.6 Anion Photodetachment Spectroscopy 15

1.3.7 Action Spectroscopy 17

1.3.8 Bond Energies and Reactivities from Mass Spectrometry 20

1.4 Considerations for Characterizing Actinide?]Containing Molecules in the Gas Phase by Ab Initio Methods 23

1.4.1 Electron Correlation Methods 24

1.4.2 Relativistic Effects 27

1.4.3 Basis Sets 29

1.5 Computational Strategies for Accurate Thermodynamics of Gas?]Phase Actinide Molecules 30

1.6 Ab Initio Molecular Spectroscopy of Gas?]Phase Actinide Compounds 34

1.6.1 Pure Rotational and Ro?]Vibrational Spectroscopy 34

1.6.2 Electronic Spectroscopy 37

1.7 Summary and Outlook 38

Acknowledgments 39

References 39

2 Speciation of Actinide Complexes, Clusters, and Nanostructures in Solution 53
*Rami J. Batrice, Jennifer N. Wacker, and Karah E. Knope*

2.1 Introduction 53

2.2 Potentiometry 54

2.2.1 Potentiometric Titrations to Reveal Speciation 54

2.2.2 Overview of Potentiometry in Aqueous Actinide Chemistry 59

2.3 Optical Spectroscopy 60

2.3.1 UV?]vis?]NIR Spectroscopy in Actinide Speciation 60

2.3.2 Fluorescence Spectroscopy 63

2.3.3 Overview of Optical Spectroscopy in Aqueous Actinide Speciation 68

2.4 NMR Spectroscopy 69

2.4.1 Probing Chemical Equilibria by NMR 69

2.4.2 Monitoring Product Formation/Evolution by NMR Spectroscopy 74

2.4.3 Monitoring Actinide Self?]Assembly by NMR Spectroscopy 75

2.4.4 Following Cluster Stability in Solution by NMR Spectroscopy 76

2.4.5 Overview of NMR Spectroscopy in Aqueous Actinide Chemistry 82

2.5 Raman Spectroscopy 82

2.5.1 Cluster Formation and Assembly 83

2.5.2 Spectral Deconvolution of Raman Data to Yield Speciation 85

2.5.3 Identifying the Nature of CationCation Interactions in Solution 86

2.5.4 In the Absence of an yl: Pa(V) Speciation in HF Solutions 89

2.5.5 Computational Assignment of Vibrational Spectra 92

2.5.6 Overview of Raman Spectroscopy 92

2.6 X?] ray Absorption Spectroscopy 93

2.6.1 EXAFS 94

2.6.2 Actinide Solution Speciation by EXAFS 95

2.6.3 EXAFS Structural Comparison of Complexes with Varying Oxidation States and Geometries 99

2.6.4 Overview of EXAFS 101

2.7 Small?] Angle X?]ray Scattering (SAXS) 102

2.7.1 Structure Elucidation by SAXS 102

2.7.2 SAXS Analysis of Cluster Evolution 104

2.7.3 Understanding Self?]Assembly Processes by SAXS 107

2.7.4 Overview of SAXS 110

2.8 High?] Energy X?]ray Scattering (HEXS) 110

2.8.1 Determining Coordination Number and Environment about a Metal Center 111

2.8.2 Deducing MetalLigand Coordination Modes 113

2.8.3 Following Oligomer Formation and Stability 116

2.8.4 Overview of HEXS 117

References 118

3 Complex Inorganic Actinide Materials 128
*Matthew L. Marsh and Thomas E. Albrecht?]Schmitt*

3.1 Introduction 128

3.2 Fluorides 129

3.2.1 Trivalent and Tetravalent Fluorides 129

3.2.2 Pentavalent and Hexavalent Fluorides 131

3.2.3 Fluor…