Series EditorsDuncan W. Bruce, Department of Chemistry, University of York, UKDermot O’Hare, Chemistry Research Laboratory, University of Oxford, UKRichard I. Walton, Department of Chemistry, University of Warwick, UK

• Inorganic Materials Series Preface xi Preface xiiiList of Contributors xv1 Solid-state Nuclear Magnetic Resonance Spectroscopy 1Sharon Ashbrook, Daniel Dawson and John Griffin1.1 Overview 11.2 Theoretical Background 31.2.1 Fundamentals of NMR 31.2.2 Acquisition of Basic NMR Spectra 41.2.3 Relaxation 71.2.4 Interactions in NMR Spectroscopy 71.3 Basic Experimental Methods 151.3.1 Spin I = 1/2 Nuclei 151.3.2 Spin I > 1/2 Nuclei 241.3.3 Wideline NMR Spectroscopy 301.4 Calculation of NMR Parameters 311.4.1 Introduction to Density Functional Theory 311.4.2 Basis Sets and Periodicity 321.4.3 Reducing the Computational Cost of Calculations 331.4.4 Application of First-principles Calculations 341.5 Applications of Solid-state NMR Spectroscopy 361.5.1 Local and Long-range Structure 361.5.2 Measuring Internuclear Interactions 431.5.3 Disordered Materials 461.5.4 Studying Dynamics 501.5.5 Challenging Nuclei and Systems 541.5.6 Paramagnetic Materials and Metals 561.6 Commonly Studied Nuclei 591.6.1 Hydrogen 591.6.2 Lithium 611.6.3 Boron 621.6.4 Carbon 621.6.5 Oxygen 621.6.6 Fluorine 631.6.7 Sodium 631.6.8 Aluminium 641.6.9 Silicon 641.6.10 Phosphorus 641.6.11 Xenon 651.7 NMR of Materials 651.7.1 Simple Ionic Compounds and Ceramics 651.7.2 Microporous Materials 671.7.3 Minerals and Clays 741.7.4 Energy Materials 761.7.5 Glasses 781.7.6 Polymers 811.8 Conclusion 83References 842 X-ray Absorption and Emission Spectroscopy 89Pieter Glatzel and Amelie Juhin2.1 Introduction: What is Photon Spectroscopy? 892.2 Electronic Structure and Spectroscopy 932.2.1 Total Energy Diagram 932.2.2 Interaction of X-rays with Matter 962.3 Calculation of Inner-shell Spectra 1062.3.1 The Single-particle Extended Picture of Electronic States 1072.3.2 The Many-body Atomic Picture of Electronic States 1092.3.3 Comparison of Theoretical Approaches 1122.3.4 The Many-body Extended Picture of Electronic States 1132.3.5 Single-particle Calculation of the Absorption Cross-section 1142.3.6 Many-body Atomic Calculation of the Cross-section 1182.3.7 Which Approach Works Best for Inner-shell Spectroscopy? 1182.3.8 Beyond Standard DFT Methods 1192.4 Experimental Techniques 1202.4.1 X-ray Absorption Spectroscopy 1212.4.2 X-ray Raman Spectroscopy 1302.4.3 Nonresonant X-ray Emission (X-ray Fluorescence) 1312.4.4 Resonant Inelastic X-ray Scattering 1372.5 Experimental Considerations 1552.5.1 Modern Sources of X-rays 1552.5.2 Ultrafast X-ray Spectroscopy 1572.5.3 Measuring XAS/XES 1582.6 Conclusion 163Acknowledgement 164References 1643 Neutrons and Neutron Spectroscopy 173A. J. Ramirez-Cuesta and Philip C. H. Mitchell3.1 The Neutron and How it is Scattered 1743.1.1 The Scattering Law 1753.2 Why Neurons? 1793.2.1 The S(Q,w) Map 1803.2.2 Modelling of INS Spectra 1813.2.3 Example of the Effects of Sampling of the Brillouin Zone 1833.2.4 INS Spectrometers 1843.2.5 Measurement Temperature 1893.2.6 Amount of Sample Required 1893.3 Molecular Hydrogen (Dihydrogen) in Porous Materials 1903.3.1 The Rotational Spectrum of Dihydrogen 1903.3.2 The Polarising Power of Cations and H2 Binding 1913.3.3 Hydrogen in Metal Organic Frameworks 1953.3.4 Hydrogen Trapped in Clathrates 1983.4 Ins and Catalysis 2013.4.1 Hydroxyl Groups on Surfaces 2063.5 CO2 and SO2 Capture 2073.6 What Could be Next? 2113.6.1 How Could we Improve INS? 2113.6.2 A Hypothetical INS Instrument for Catalysis 2163.7 Conclusion 219References 2204 Electron Paramagnetic Resonance Spectroscopy of Inorganic Materials 225Piotr Pietrzyk, Tomasz Mazur and Zbigniew Sojka4.1 Introduction 2254.2 Electron Spin in a Magnetic Field 2264.2.1 Electron Zeeman Effect and the Resonance Phenomenon 2284.2.2 Spin Relaxation 2304.2.3 Electron–Nucleus Hyperfine Interaction 2334.2.4 EPR Spectrometers 2384.2.5 Samples, Sample Holders and Registration of EPR Spectra 2424.3 Spin Hamiltonian and Symmetry 2444.3.1 The g Tensor 2444.3.2 The Hyperfine A Tensor 2504.3.3 The Fine Structure D Tensor 2564.3.4 The Quadrupole Q Tensor 2604.3.5 Electron–Electron Exchange Interactions J 2614.3.6 The Spin Hamiltonian 2644.4 Principal Types of EPR Spectrum and Their Characteristic Features 2674.4.1 Single-crystal Spectra 2674.4.2 Static and Dynamic Disorder 2694.4.3 EPR Spectra of Powder and Nanopowder Materials 2744.4.4 Unusual Spectral Features 2784.4.5 Computer Simulation of Powder Spectra 2804.5 Advanced EMR Techniques 2824.5.1 High-field and Multifrequency EPR 2824.5.2 Pulsed EPR Methods 285References 2965 Analysis of Functional Materials by X-ray Photoelectron Spectroscopy 301Karen Wilson and Adam F. Lee5.1 Introduction 3015.1.1 The Basic Principles of XPS 3025.1.2 Quantification of X-ray Photoelectron Spectra 3055.1.3 The Origin of Surface Sensitivity 3085.1.4 Angular Resolved XPS 3095.1.5 Chemical Shift Information from XPS 3115.2 Imaging XPS 3155.3 Time-resolved High-resolution XPS 3185.3.1 Selective Catalytic Alcohol Oxidation 3195.3.2 Selective Oxidation of Allylic Alcohols 3225.3.3 C–X Activation 3245.4 High- or Ambient-pressure XPS 3265.4.1 AP-XPS Studies of the Surface Chemistry of Oxidised Metal Surfaces 3295.4.2 Selective Hydrogenation 3335.4.3 HP-XPS Studies of Core–Shell Nanoparticulate Materials 3355.5 Applications to Inorganic Materials 3355.5.1 Bimetallic Nanoparticles 3355.5.2 XPS Studies of Heteropolytungstate Clusters 3385.5.3 XPS Studies of Acid–Base Sites in Oxide Catalysts 3425.6 Conclusion 345References 345Index 351

Series EditorsDuncan W. Bruce, Department of Chemistry, University of York, UKDermot O’Hare, Chemistry Research Laboratory, University of Oxford, UKRichard I. Walton, Department of Chemistry, University of Warwick, UK

• Inorganic Materials Series Preface xi Preface xiiiList of Contributors xv1 Solid-state Nuclear Magnetic Resonance Spectroscopy 1Sharon Ashbrook, Daniel Dawson and John Griffin1.1 Overview 11.2 Theoretical Background 31.2.1 Fundamentals of NMR 31.2.2 Acquisition of Basic NMR Spectra 41.2.3 Relaxation 71.2.4 Interactions in NMR Spectroscopy 71.3 Basic Experimental Methods 151.3.1 Spin I = 1/2 Nuclei 151.3.2 Spin I > 1/2 Nuclei 241.3.3 Wideline NMR Spectroscopy 301.4 Calculation of NMR Parameters 311.4.1 Introduction to Density Functional Theory 311.4.2 Basis Sets and Periodicity 321.4.3 Reducing the Computational Cost of Calculations 331.4.4 Application of First-principles Calculations 341.5 Applications of Solid-state NMR Spectroscopy 361.5.1 Local and Long-range Structure 361.5.2 Measuring Internuclear Interactions 431.5.3 Disordered Materials 461.5.4 Studying Dynamics 501.5.5 Challenging Nuclei and Systems 541.5.6 Paramagnetic Materials and Metals 561.6 Commonly Studied Nuclei 591.6.1 Hydrogen 591.6.2 Lithium 611.6.3 Boron 621.6.4 Carbon 621.6.5 Oxygen 621.6.6 Fluorine 631.6.7 Sodium 631.6.8 Aluminium 641.6.9 Silicon 641.6.10 Phosphorus 641.6.11 Xenon 651.7 NMR of Materials 651.7.1 Simple Ionic Compounds and Ceramics 651.7.2 Microporous Materials 671.7.3 Minerals and Clays 741.7.4 Energy Materials 761.7.5 Glasses 781.7.6 Polymers 811.8 Conclusion 83References 842 X-ray Absorption and Emission Spectroscopy 89Pieter Glatzel and Amelie Juhin2.1 Introduction: What is Photon Spectroscopy? 892.2 Electronic Structure and Spectroscopy 932.2.1 Total Energy Diagram 932.2.2 Interaction of X-rays with Matter 962.3 Calculation of Inner-shell Spectra 1062.3.1 The Single-particle Extended Picture of Electronic States 1072.3.2 The Many-body Atomic Picture of Electronic States 1092.3.3 Comparison of Theoretical Approaches 1122.3.4 The Many-body Extended Picture of Electronic States 1132.3.5 Single-particle Calculation of the Absorption Cross-section 1142.3.6 Many-body Atomic Calculation of the Cross-section 1182.3.7 Which Approach Works Best for Inner-shell Spectroscopy? 1182.3.8 Beyond Standard DFT Methods 1192.4 Experimental Techniques 1202.4.1 X-ray Absorption Spectroscopy 1212.4.2 X-ray Raman Spectroscopy 1302.4.3 Nonresonant X-ray Emission (X-ray Fluorescence) 1312.4.4 Resonant Inelastic X-ray Scattering 1372.5 Experimental Considerations 1552.5.1 Modern Sources of X-rays 1552.5.2 Ultrafast X-ray Spectroscopy 1572.5.3 Measuring XAS/XES 1582.6 Conclusion 163Acknowledgement 164References 1643 Neutrons and Neutron Spectroscopy 173A. J. Ramirez-Cuesta and Philip C. H. Mitchell3.1 The Neutron and How it is Scattered 1743.1.1 The Scattering Law 1753.2 Why Neurons? 1793.2.1 The S(Q,w) Map 1803.2.2 Modelling of INS Spectra 1813.2.3 Example of the Effects of Sampling of the Brillouin Zone 1833.2.4 INS Spectrometers 1843.2.5 Measurement Temperature 1893.2.6 Amount of Sample Required 1893.3 Molecular Hydrogen (Dihydrogen) in Porous Materials 1903.3.1 The Rotational Spectrum of Dihydrogen 1903.3.2 The Polarising Power of Cations and H2 Binding 1913.3.3 Hydrogen in Metal Organic Frameworks 1953.3.4 Hydrogen Trapped in Clathrates 1983.4 Ins and Catalysis 2013.4.1 Hydroxyl Groups on Surfaces 2063.5 CO2 and SO2 Capture 2073.6 What Could be Next? 2113.6.1 How Could we Improve INS? 2113.6.2 A Hypothetical INS Instrument for Catalysis 2163.7 Conclusion 219References 2204 Electron Paramagnetic Resonance Spectroscopy of Inorganic Materials 225Piotr Pietrzyk, Tomasz Mazur and Zbigniew Sojka4.1 Introduction 2254.2 Electron Spin in a Magnetic Field 2264.2.1 Electron Zeeman Effect and the Resonance Phenomenon 2284.2.2 Spin Relaxation 2304.2.3 Electron–Nucleus Hyperfine Interaction 2334.2.4 EPR Spectrometers 2384.2.5 Samples, Sample Holders and Registration of EPR Spectra 2424.3 Spin Hamiltonian and Symmetry 2444.3.1 The g Tensor 2444.3.2 The Hyperfine A Tensor 2504.3.3 The Fine Structure D Tensor 2564.3.4 The Quadrupole Q Tensor 2604.3.5 Electron–Electron Exchange Interactions J 2614.3.6 The Spin Hamiltonian 2644.4 Principal Types of EPR Spectrum and Their Characteristic Features 2674.4.1 Single-crystal Spectra 2674.4.2 Static and Dynamic Disorder 2694.4.3 EPR Spectra of Powder and Nanopowder Materials 2744.4.4 Unusual Spectral Features 2784.4.5 Computer Simulation of Powder Spectra 2804.5 Advanced EMR Techniques 2824.5.1 High-field and Multifrequency EPR 2824.5.2 Pulsed EPR Methods 285References 2965 Analysis of Functional Materials by X-ray Photoelectron Spectroscopy 301Karen Wilson and Adam F. Lee5.1 Introduction 3015.1.1 The Basic Principles of XPS 3025.1.2 Quantification of X-ray Photoelectron Spectra 3055.1.3 The Origin of Surface Sensitivity 3085.1.4 Angular Resolved XPS 3095.1.5 Chemical Shift Information from XPS 3115.2 Imaging XPS 3155.3 Time-resolved High-resolution XPS 3185.3.1 Selective Catalytic Alcohol Oxidation 3195.3.2 Selective Oxidation of Allylic Alcohols 3225.3.3 C–X Activation 3245.4 High- or Ambient-pressure XPS 3265.4.1 AP-XPS Studies of the Surface Chemistry of Oxidised Metal Surfaces 3295.4.2 Selective Hydrogenation 3335.4.3 HP-XPS Studies of Core–Shell Nanoparticulate Materials 3355.5 Applications to Inorganic Materials 3355.5.1 Bimetallic Nanoparticles 3355.5.2 XPS Studies of Heteropolytungstate Clusters 3385.5.3 XPS Studies of Acid–Base Sites in Oxide Catalysts 3425.6 Conclusion 345References 345Index 351

Series EditorsDuncan W. Bruce, Department of Chemistry, University of York, UKDermot O’Hare, Chemistry Research Laboratory, University of Oxford, UKRichard I. Walton, Department of Chemistry, University of Warwick, UK

• Inorganic Materials Series Preface xi Preface xiiiList of Contributors xv1 Solid-state Nuclear Magnetic Resonance Spectroscopy 1Sharon Ashbrook, Daniel Dawson and John Griffin1.1 Overview 11.2 Theoretical Background 31.2.1 Fundamentals of NMR 31.2.2 Acquisition of Basic NMR Spectra 41.2.3 Relaxation 71.2.4 Interactions in NMR Spectroscopy 71.3 Basic Experimental Methods 151.3.1 Spin I = 1/2 Nuclei 151.3.2 Spin I > 1/2 Nuclei 241.3.3 Wideline NMR Spectroscopy 301.4 Calculation of NMR Parameters 311.4.1 Introduction to Density Functional Theory 311.4.2 Basis Sets and Periodicity 321.4.3 Reducing the Computational Cost of Calculations 331.4.4 Application of First-principles Calculations 341.5 Applications of Solid-state NMR Spectroscopy 361.5.1 Local and Long-range Structure 361.5.2 Measuring Internuclear Interactions 431.5.3 Disordered Materials 461.5.4 Studying Dynamics 501.5.5 Challenging Nuclei and Systems 541.5.6 Paramagnetic Materials and Metals 561.6 Commonly Studied Nuclei 591.6.1 Hydrogen 591.6.2 Lithium 611.6.3 Boron 621.6.4 Carbon 621.6.5 Oxygen 621.6.6 Fluorine 631.6.7 Sodium 631.6.8 Aluminium 641.6.9 Silicon 641.6.10 Phosphorus 641.6.11 Xenon 651.7 NMR of Materials 651.7.1 Simple Ionic Compounds and Ceramics 651.7.2 Microporous Materials 671.7.3 Minerals and Clays 741.7.4 Energy Materials 761.7.5 Glasses 781.7.6 Polymers 811.8 Conclusion 83References 842 X-ray Absorption and Emission Spectroscopy 89Pieter Glatzel and Amelie Juhin2.1 Introduction: What is Photon Spectroscopy? 892.2 Electronic Structure and Spectroscopy 932.2.1 Total Energy Diagram 932.2.2 Interaction of X-rays with Matter 962.3 Calculation of Inner-shell Spectra 1062.3.1 The Single-particle Extended Picture of Electronic States 1072.3.2 The Many-body Atomic Picture of Electronic States 1092.3.3 Comparison of Theoretical Approaches 1122.3.4 The Many-body Extended Picture of Electronic States 1132.3.5 Single-particle Calculation of the Absorption Cross-section 1142.3.6 Many-body Atomic Calculation of the Cross-section 1182.3.7 Which Approach Works Best for Inner-shell Spectroscopy? 1182.3.8 Beyond Standard DFT Methods 1192.4 Experimental Techniques 1202.4.1 X-ray Absorption Spectroscopy 1212.4.2 X-ray Raman Spectroscopy 1302.4.3 Nonresonant X-ray Emission (X-ray Fluorescence) 1312.4.4 Resonant Inelastic X-ray Scattering 1372.5 Experimental Considerations 1552.5.1 Modern Sources of X-rays 1552.5.2 Ultrafast X-ray Spectroscopy 1572.5.3 Measuring XAS/XES 1582.6 Conclusion 163Acknowledgement 164References 1643 Neutrons and Neutron Spectroscopy 173A. J. Ramirez-Cuesta and Philip C. H. Mitchell3.1 The Neutron and How it is Scattered 1743.1.1 The Scattering Law 1753.2 Why Neurons? 1793.2.1 The S(Q,w) Map 1803.2.2 Modelling of INS Spectra 1813.2.3 Example of the Effects of Sampling of the Brillouin Zone 1833.2.4 INS Spectrometers 1843.2.5 Measurement Temperature 1893.2.6 Amount of Sample Required 1893.3 Molecular Hydrogen (Dihydrogen) in Porous Materials 1903.3.1 The Rotational Spectrum of Dihydrogen 1903.3.2 The Polarising Power of Cations and H2 Binding 1913.3.3 Hydrogen in Metal Organic Frameworks 1953.3.4 Hydrogen Trapped in Clathrates 1983.4 Ins and Catalysis 2013.4.1 Hydroxyl Groups on Surfaces 2063.5 CO2 and SO2 Capture 2073.6 What Could be Next? 2113.6.1 How Could we Improve INS? 2113.6.2 A Hypothetical INS Instrument for Catalysis 2163.7 Conclusion 219References 2204 Electron Paramagnetic Resonance Spectroscopy of Inorganic Materials 225Piotr Pietrzyk, Tomasz Mazur and Zbigniew Sojka4.1 Introduction 2254.2 Electron Spin in a Magnetic Field 2264.2.1 Electron Zeeman Effect and the Resonance Phenomenon 2284.2.2 Spin Relaxation 2304.2.3 Electron–Nucleus Hyperfine Interaction 2334.2.4 EPR Spectrometers 2384.2.5 Samples, Sample Holders and Registration of EPR Spectra 2424.3 Spin Hamiltonian and Symmetry 2444.3.1 The g Tensor 2444.3.2 The Hyperfine A Tensor 2504.3.3 The Fine Structure D Tensor 2564.3.4 The Quadrupole Q Tensor 2604.3.5 Electron–Electron Exchange Interactions J 2614.3.6 The Spin Hamiltonian 2644.4 Principal Types of EPR Spectrum and Their Characteristic Features 2674.4.1 Single-crystal Spectra 2674.4.2 Static and Dynamic Disorder 2694.4.3 EPR Spectra of Powder and Nanopowder Materials 2744.4.4 Unusual Spectral Features 2784.4.5 Computer Simulation of Powder Spectra 2804.5 Advanced EMR Techniques 2824.5.1 High-field and Multifrequency EPR 2824.5.2 Pulsed EPR Methods 285References 2965 Analysis of Functional Materials by X-ray Photoelectron Spectroscopy 301Karen Wilson and Adam F. Lee5.1 Introduction 3015.1.1 The Basic Principles of XPS 3025.1.2 Quantification of X-ray Photoelectron Spectra 3055.1.3 The Origin of Surface Sensitivity 3085.1.4 Angular Resolved XPS 3095.1.5 Chemical Shift Information from XPS 3115.2 Imaging XPS 3155.3 Time-resolved High-resolution XPS 3185.3.1 Selective Catalytic Alcohol Oxidation 3195.3.2 Selective Oxidation of Allylic Alcohols 3225.3.3 C–X Activation 3245.4 High- or Ambient-pressure XPS 3265.4.1 AP-XPS Studies of the Surface Chemistry of Oxidised Metal Surfaces 3295.4.2 Selective Hydrogenation 3335.4.3 HP-XPS Studies of Core–Shell Nanoparticulate Materials 3355.5 Applications to Inorganic Materials 3355.5.1 Bimetallic Nanoparticles 3355.5.2 XPS Studies of Heteropolytungstate Clusters 3385.5.3 XPS Studies of Acid–Base Sites in Oxide Catalysts 3425.6 Conclusion 345References 345Index 351