X-Ray Absorption and X-Ray Emission Spectroscopy, 2 Volume Set

Jeroen van Bokhoven has been an Associate Professor of Heterogeneous Catalysis in the Department of Chemistry and Applied Biology at ETH since 2010. He completed a degree in chemistry at Utrecht University in 1995 and went on to obtain a PhD in inorganic chemistry and catalysis in 2000. From 1999 until 2002 he was head of the XAS (X-ray absorption spectroscopy) users - support group at Utrecht University. In 2006 he obtained an SNF assistant professorship in the Department of Chemistry and Applied Biology. He was the 2008 recipient of the Swiss Chemical Society Werner Prize. Van Bokhoven works in the field of heterogeneous catalysis and (X-ray) spectroscopy. His main interests are heterogeneous catalysts and developing advanced tools in X-ray spectroscopy to study the catalyst structure under catalytic relevant conditions. Carlo Lamberti achieved his degree in Physics in 1988 with a thesis in the field of many body Physics. From 1988 to 1993 he worked in the CSELT laboratories Torino, on the characterization of the interfaces of semiconductor heterostructures with high resolution XRD and X-ray absorption spectroscopies. He presented his PhD defense in solid state physics on this topic in Rome in 1993. He was appointed to the position of researcher in October 1998 at the Department of Inorganic, Physical and Materials Chemistry of the Torino University, and as Associate Professor in December 2006. In recent years he has become an expert in the techniques based on Synchrotron Radiation and Neutrons beams in the characterization of materials, performing more than 90 experiments approved by international committees on the following large scale facilities.He has authored and co-authored more than 200 research articles and five book chapters and two books. He is member of the PhD School in Material Science of the Torino University, and is the Italian coordinator of the MaMaSELF European Master in Materials Science.

• VOLUME IList of ContributorsForewordI INTRODUCTION: HISTORY, XAS, XES, AND THEIR IMPACT ON SCIENCE1 Introduction: Historical Perspective on XASJeroen A. van Bokhoven and Carlo Lamberti1.1 Historical Overview of 100 Years of X-Ray Absorption: A Focus on the Pioneering 1913−1971 Period1.2 About the Book: A Few Curiosities, Some Statistics, and a Brief OverviewII EXPERIMENTAL AND THEORY2 From Synchrotrons to FELs: How Photons Are Produced; Beamline Optics and Beam CharacteristicsGiorgio Margaritondo2.1 Photon Emission by Accelerated Charges: from the Classical Case to the Relativistic Limit2.2 Undulators, Wigglers, and Bending Magnets2.2.1 Undulators2.2.2 Wigglers2.2.3 Bending magnets2.2.4 High flux, high brightness2.3 The Time Structure of Synchrotron Radiation2.4 Elements of Beamline Optics2.4.1 Focusing devices2.4.2 Monochromators2.4.3 Detectors2.5 Free Electron Lasers2.5.1 FEL optical amplification2.5.2 Optical amplification in an X-FEL: details2.5.3 Saturation2.5.4 X-FEL time structure: new opportunities for spectroscopy2.5.5 Time coherence and seeding3 Real-Space Multiple-Scattering Theory of X-ray SpectraJoshua J. Kas, Kevin Jorisson and John J. Rehr3.1 Introduction3.2 Theory3.2.1 Independent-particle approximation3.2.2 Real-space multiple-scattering theory3.2.3 Many body effects in x-ray spectra3.3 Applications3.3.1 XAS, EXAFS, XANES3.3.2 EELS3.3.3 XES3.3.4 XMCD3.3.5 NRIXS3.3.6 RIXS3.3.7 Compton scattering3.3.8 Optical constants3.4 Conclusion4 Theory of X-ray Absorption Near Edge StructureYves Joly and Stephane Grenier4.1 Introduction4.2 The x-ray Absorption Phenomena4.2.1 Probing material4.2.2 The different spectroscopies4.3 X-ray Matter Interaction4.3.1 Interaction Hamiltonian4.3.2 Absorption cross-section for the transition between two states4.3.3 State description4.3.4 The transition matrix4.4 XANES General Formulation4.4.1 Interaction times and the multi-electronic problem4.4.2 Absorption cross-section main equation4.5 XANES Simulations in the Mono-Electronic Scheme4.5.1 From multi- to mono-electronic4.5.2 The different methods4.5.3 The multiple scattering theory4.6 Multiplet Ligand Field Theory4.6.1 Atomic multiplets4.6.2 The crystal field4.7 Current Theoretical Developments4.8 Tensorial Approaches4.9 Conclusion5 How to Start an XAS ExperimentDiego Gianolio5.1 Introduction5.2.1 Identify the scientific question5.2.2 Can XAS solve the problem?5.2.3 Select the best beamline and measurement mode5.2.4 Write the proposal5.3 Prepare the Experiment5.3.1 Experimental design5.3.2 Best sample conditions for data acquisition5.3.3 Sample preparation5.4 Perform the Experiment5.4.1 Initial set-up and optimization of signal5.4.2 Data acquisition6 Hard X-ray Photon-in/Photon-out Spectroscopy: Instrumentation, Theory and ApplicationsPieter Glatzel, Roberto Alonso-Mori, and Dimosthenis Sokaras6.1 Introduction6.2 History6.3 Basic Theory of XES6.3.1 One- and multi-electron description6.3.2 X-ray Raman scattering spectroscopy6.4 Chemical Sensitivity of x-ray Emission6.4.1 Core-to-core transitions6.4.2 Valence-to-core transitions6.5 HERFD and RIXS6.6 Experimental x-ray Emission Spectroscopy6.6.1 Sources for x-ray emission spectroscopy6.6.2 X-ray emission spectrometers6.6.3 Detectors6.7 Conclusion7 QEXAFS: Techniques and Scientific Applications for Time-Resolved XASMaarten Nachtegaal, Oliver Muller, Christian Konig and Ronald Frahm7.1 Introduction7.2 History and Basics of QEXAFS7.3 Monochromators and Beamlines for QEXAFS7.3.1 QEXAFS with conventional monochromators7.3.2 Piezo-QEXAFS for the millisecond time range7.3.3 Dedicated oscillating monochromators for QEXAFS7.4 Detectors and Readout Systems7.4.1 Requirements for detectors7.4.2 Gridded ionization chambers7.4.3 Data acquisition7.4.4 Angular encoder7.5 Applications of QEXAFS in Chemistry7.5.1 Following the fate of metal contaminants at the mineral–water interface7.5.2 Identifying the catalytic active sites in gas phase reactions7.5.4 Synthesis of nanoparticles7.5.5 Identification of reaction intermediates: modulation excitation XAS7.6 Conclusion8 Time-Resolved XAS Using an Energy Dispersive Spectrometer: Techniques and ApplicationsOlivier Mathon, Innokenty Kantor and Sakura Pascarelli8.1 Introduction8.2 Energy Dispersive X-Ray Absorption Spectroscopy8.2.1 Historical development of EDXAS and overview of existing facilities8.2.2 Principles: source, optics, detection8.2.3 Dispersive versus scanning spectrometer for time-resolved experiments8.2.4 Description of the EDXAS beamline at ESRF8.3 From the Minute Down to the Ms: Filming a Chemical Reaction in Situ 8.3.1 Technical aspects8.3.2 First stages of nanoparticle formation8.3.3 Working for cleaner cars: automotive exhaust catalyst8.3.4 Reaction mechanisms and intermediates8.3.5 High temperature oxidation of metallic iron8.4 Down to the μs Regime: Matter under Extreme Conditions8.4.1 Technical aspects8.4.2 Melts at extreme pressure and temperature8.4.3 Spin transitions at high magnetic field8.4.4 Fast ohmic ramp excitation towards the warm dense matter regime8.5 Playing with a 100 ps Single Bunch8.5.1 Technical aspects8.5.2 Detection and characterization of photo-excited states in Cu+ complexes8.5.3 Opportunities for investigating laser-shocked matter8.5.4 Non-synchrotron EDXAS8.6 Conclusion9 X-Ray Transient Absorption SpectroscopyLin X. Chen9.1 Introduction9.2 Pump-Probe Spectroscopy9.2.1 Background9.2.2 The basic set-up9.3 Experimental Considerations9.3.1 XTA at a synchrotron source9.3.2 XTA at X-ray free electron laser sources9.4 Transient Structural Information Investigated by XTA9.4.1 Metal center oxidation state9.4.2 Electron configuration and orbital energies of X-ray absorbing atoms9.4.3 Transient coordination geometry of the metal center9.5 X-Ray Pump-Probe Absorption Spectroscopy: Examples9.5.1 Excited state dynamics of transition metal complexes (TMCs)9.5.2 Interfacial charge transfer in hybrid systems9.5.3 XTA studies of metal center active site structures in metalloproteins9.5.4 XTA using the X-ray free electron lasers9.5.5 Other XTA application examples9.6 Perspective of Pump-Probe X-Ray Spectroscopy10 Space-Resolved XAFS, Instrumentations and ApplicationsYoshio Suzuki and Yasuko Terada10.1 Space-Resolving Techniques for XAFS10.2 Beam-Focusing Instrumentation for Microbeam Production10.2.1 Total reflection mirror systems10.2.2 Fresnel zone plate optics for x-ray microbeam10.2.3 General issues of beam-focusing optics10.2.4 Requirements on beam stability in microbeam XAFS experiments10.3 Examples of Beam-Focusing Instrumentation10.3.1 The total-reflection mirror system10.3.2 Fresnel zone plate system10.4 Examples of Applications of Microbeam-XAFS Technique to Biology and nenvironmental Science10.4.1 Speciation of heavy metals in willow10.4.2 Characterization of arsenic-accumulating mineral in a sedimentary iron deposit10.4.3 Feasibility study for microbeam XAFS analysis using FZP optics10.4.4 Micro-XAFS studies of plutonium sorbed on tuff10.4.5 Micro-XANES analysis of vanadium accumulation in ascidian blood cell10.5 Conclusion and Outlook11 Quantitative EXAFS AnalysisBruce Ravel11.1 A Brief History of EXAFS Theory11.1.1 The n-body decomposition in GNXAS11.1.2 The exact curved wave theory in EXCURVE11.1.3 The path expansion in FEFF11.2 Theoretical Calculation of EXAFS Scattering Factors11.2.1 The pathfinder11.2.2 The fitting metric11.2.3 Constraints on parameters of the fit11.2.4 Fitting statistics11.2.5 Extending the evaluation of χ211.2.6 Other analytic methods11.3 Practical Examples of EXAFS Analysis11.3.1 Geometric constraints on bond lengths11.3.2 Constraints on the coordination environment11.3.3 Constraints and multiple data set analysis11.4 Conclusion12 XAS Spectroscopy: Related Techniques and Combination with Other Spectroscopic and Scattering MethodsCarlo Lamberti, Elisa Borfecchia, Jeroen A. van Bokhoven and Marcos Fernández-Garcia12.1 Introduction12.2 Atomic Pair Distribution Analysis of Total Scattering Data12.2.1 Theoretical description12.2.2 Examples of PDF analysis12.3 Diffraction Anomalous Fine Structure (DAFS)12.3.1 Theoretical description12.3.2 Examples of DAFS12.4 Inelastic Scattering Techniques12.4.1 Extended energy-loss fine structure (EXELFS)12.4.2 X-ray Raman scattering (XRS)12.5 β-Environmental Fine Structure (BEFS)12.6 Combined Techniques12.6.1 General considerations12.6.2 Selected examples12.7 ConclusionVOLUME IIList of ContributorsForewordIII APPLICATIONS: FROM SEMICONDUCTORS TO MEDICINE TO NUCLEAR MATERIALS13 X-Ray Absorption and Emission Spectroscopy for CatalysisJeroen A. van Bokhoven and Carlo Lamberti13.1 Introduction13.2 The Catalytic Process13.2.1 From vacuum and single crystals to realistic pressure and relevant samples13.2.2 From chemisorption to conversion and reaction kinetics13.2.3 Structural differences within a single catalytic reactor13.2.4 Determining the structure of the active site13.3 Reaction Kinetics from Time-Resolved XAS13.3.1 Oxygen storage materials13.3.2 Selective propene oxidation over α-MoO313.3.3 Active sites of the dream reaction, the direct conversion of benzene to phenol13.4 Sub-Micrometer Space Resolved Measurements13.5 Emerging Methods13.5.1 X-ray emission spectroscopy13.5.2 Pump probe methods13.6 Conclusion and outlook14 High Pressure XAS, XMCD and IXS 383Jean-Paul Itie, Francois Baudelet and Jean-Pascal Rueff14.1 Introduction14.1.1 Why pressure matters14.1.2 High-pressure generation and measurements14.1.3 Specific drawbacks of a high-pressure set-up14.2 High Pressure EXAFS and XANES14.2.1 Introduction14.2.2 Local equation of state14.2.3 Pressure-induced phase transitions14.2.4 Glasses, amorphous materials, amorphization14.2.5 Extension to low and high energy edges14.3 High-Pressure Magnetism and XMCD14.3.1 Introduction14.3.2 Transition metal14.3.3 Magnetic insulator14.3.4 The rare earth system14.4 High Pressure Inelastic X-Ray Scattering14.4.1 Electronic structure14.4.2 Magnetic transitions in 3d and 4f electron systems14.4.3 Metal insulator transitions in correlated systems14.4.4 Valence transition in mixed valent rare-earth compounds14.4.5 Low-energy absorption edges: chemical bonding and orbital configuration14.5 Conclusion15 X-Ray Absorption and RIXS on Coordination ComplexesThomas Kroll, Marcus Lundberg and Edward I. Solomon15.1 Introduction15.1.1 Geometric and electronic structure of coordination complexes15.1.2 X-ray probes of coordination complexes15.1.3 Extracting electronic structure from X-ray spectra15.2 Metal K-Edges15.2.1 The case of a single 3d hole: Cu(II)15.2.2 Multiple 3d holes: Fe(III) and Fe(II)15.3 Metal L-Edges15.3.1 The case of a single 3d hole: Cu(II)15.3.2 Multiple 3d holes: Fe(III) and Fe(II)15.4 Resonant Inelastic X-Ray Scattering15.4.1 Ferrous systems15.4.2 Ferric systems15.5 Conclusion16 SemiconductorsFederico Boscherini16.1 Introduction16.2 XAS Instrumental Aspects16.3 Applications16.3.1 Dopants and defects16.3.2 Thin films and heterostructures16.3.3 Nanostructures16.3.4 Dilute magnetic semiconductors16.4 Conclusion17 XAS Studies on Mixed Valence OxidesJoaquýn Garcýa, Gloria Subýas and Javier Blasco17.1 Introduction17.1.1 X-ray absorption spectroscopy (XAS)17.1.2 XES and XAS17.1.3 Resonant x-ray scattering17.2 Solid State Applications (Mixed Valence Oxides)17.2.1 High tc superconductors17.2.2 Manganites17.2.3 Perovskite cobaltites17.3 Conclusion18 Novel XAS Techniques for Probing Fuel Cells and BatteriesDavid E. Ramaker18.1 Introduction18.2 XANES Techniques18.2.1 Data analysis18.2.2 Data collection18.2.3 Comparison of techniques by examination of O(H)/Pt and CO/Pt18.3 In Operando Measurements18.3.1 Fuel cells18.3.2 Batteries18.4 Future Trends18.5 Appendix18.5.1 Details of the ΔμXANES analysis technique18.5.2 FEFF8 theoretical calculations19 X-ray Spectroscopy in Studies of the Nuclear Fuel CycleMelissa A. Denecke19.1 Background19.1.1 Introduction19.1.2 Radioactive materials at synchrotron sources19.2 Application Examples19.2.1 Studies related to uranium mining19.2.2 Studies related to fuel19.2.3 Investigations of reactor components19.2.4 Studies related to recycle and lanthanide/actinide separations19.2.5 Studies concerning legacy remediation and waste disposal (waste forms, near-field and far-field)19.3 Conclusion and Outlook20 Planetary, Geological and Environmental SciencesFrancois Farges and Max Wilke20.1 Introduction20.2 Planetary and Endogenous Earth Sciences20.2.1 Planetary materials and meteorites20.2.2 Crystalline deep earth materials20.2.3 Magmatic and volcanic processes20.2.4 Element complexation in aqueous fluids at P and T20.3 Environmental Geosciences20.3.1 General trends20.3.2 Environmentally relevant minerals and phases20.3.3 Mechanisms and reactivity at the mineral-water interfaces20.3.4 Some environmental applications of x-ray absorption spectroscopy20.4 Conclusion21 X-Ray Absorption Spectroscopy and Cultural Heritage: Highlights and PerspectivesFrançois Farges and Marine Cotte21.1 Introduction21.2 Instrumentation: Standard and Recently Developed Approaches21.2.1 From centimetric objects to micrometric cross-sections21.2.2 Improving the spectral resolution of XRF detectors21.2.3 From hard X-rays to soft X-rays21.2.4 Spectro-imaging in the hard X-ray domain21.3 Some Applications21.3.1 Glasses21.3.2 Ceramics21.3.3 Pigments and Paintings21.3.4 Inks21.3.5 Woods: from historical to fossils21.3.6 Bones and ivory21.3.7 Metals21.3.8 Rock-formed monuments21.4 Conclusion22 X-ray Spectroscopy at Free Electron LasersWojciech Gawelda, Jakub Szlachetko and Christopher J. Milne22.1 Introduction to X-ray Free Electron Lasers in Comparison to Synchrotrons22.1.1 Overview of facilities22.1.2 X-ray properties from an XFEL22.1.3 Scanning the X-ray energy22.1.4 Comparison with existing time-resolved techniques at synchrotrons22.2 Current Implementations of X-Ray Spectroscopy Techniques at XFELs22.2.1 X-ray absorption spectroscopy22.2.2 X-ray emission spectroscopy22.3 Examples of Time-Resolved X-Ray Spectroscopy at XFELs22.3.1 Ultrafast spin-crossover excitation probed with X-ray absorption spectroscopy22.3.2 Ultrafast spin cross-over excitation probed with X-ray emission spectroscopy22.3.3 Simultaneous measurement of the structural and electronic changes in Photosystem II after photoexcitation22.3.4 Investigating surface photochemistry22.3.5 Soft X-ray emission spectroscopy measurements of dilute systems22.4 Examples of Nonlinear X-Ray Spectroscopy at XFELs22.4.1 X-ray-induced transparency22.4.2 Sequential ionization and core-to-core resonances22.4.3 Hollow atoms22.4.4 Solid-density plasma22.4.5 Two-photon absorption22.5 Conclusion and Outlook23 X-ray Magnetic Circular DichroismAndrei Rogalev, Katharina Ollefs and Fabrice Wilhelm23.1 Historical Introduction23.2 Physical Content of XMCD and the Sum Rules23.3 Experimental Aspects and Data Analysis23.3.1 Sources of circularly polarized x-rays23.3.2 Sample environment23.3.3 Detection modes23.3.4 Standard analysis23.4 Examples of Recent Research23.4.1 Paramagnetism of pure metallic clusters23.4.2 Magnetism in diluted magnetic semiconductors23.4.3 Photomagnetic molecular magnets23.5 Conclusion and Outlook24 Industrial ApplicationsSimon R. Bare and Jeffrey Cutler24.1 Introduction24.2 The Patent Literature24.2.1 Catalysts24.2.2 Batteries24.2.3 Other applications24.3 The Open Literature24.3.1 Semiconductors, thin films, and electronic materials24.3.2 Fuel cells, batteries, and electrocatalysts24.3.3 Metallurgy and tribology24.3.4 Homogeneous and heterogeneous catalysts24.3.5 Miscellaneous applications: from sludge to thermographic films24.4 Examples of Applications from Light Sources24.4.1 Introduction24.4.2 Industrial science at the Canadian Light Source24.4.3 Use of SOLEIL beamlines by industry24.4.4 Industrial research enhancement program at NSLS24.4.5 The Swiss Light Source: cutting-edge research facilities for industry24.5 Examples of Applications from Companies24.5.1 Introduction24.5.2 Haldor Topsøe A/S24.5.3 UOP LLC, a Honeywell Company24.5.4 General Electric Company24.5.5 IBM Research Center24.6 Conducting Industrial Research at Light Sources24.7 Conclusion and Outlook25 XAS in Liquid SystemsAdriano Filipponi and Paola D'Angelo25.1 The Liquid State of Matter25.1.1 Thermodynamic considerations25.1.2 Pair and higher order distribution functions25.2 Computer Modelling of Liquid Structures25.2.1 Molecular Dynamics simulations25.2.2 Classical Molecular Dynamics25.2.3 Born-Oppenheimer Molecular Dynamics25.2.4 Car-Parrinello Molecular Dynamics25.2.5 Monte Carlo simulation approaches25.3 XAFS Calculations in Liquids/Disordered Systems25.3.1 XAFS sensitivity and its specific role25.3.2 XAFS signal decomposition25.3.3 XAFS signal from the pair distribution25.3.4 The triplet distribution case in elemental systems25.4 Experimental and Data-Analysis Approaches25.4.1 Sample confinement strategies and detection techniques25.4.2 High pressure, temperature control, and XAS sensitivity to phase transitions25.4.3 Traditional versus atomistic data-analysis approaches25.5 Examples of Data Analysis Applications25.5.1 Elemental systems: icosahedral order in metals25.5.3 Transition metal aqua ions25.5.4 Lanthanide aqua ions25.5.5 Halide aqua ions: the bromide case26 Surface Metal Complexes and Their ApplicationsJoseph D. Kistler, Pedro Serna, Kiyotaka Asakura and Bruce C. Gates26.1 Introduction26.1.1 Ligands other than supports26.1.2 Supports26.1.3 Techniques complementing x-ray absorption spectroscopy26.1.4 Data-fitting techniques26.2 Aim of the Chapter26.3 Mononuclear Iridium Complexes Supported on Zeolite HSSZ-53: Illustration of EXAFS Data Fitting and Model Discrimination26.4 Iridium Complexes Supported on MgO and on Zeolites: Precisely Synthesized Isostructural Metal Complexes on Supports with Contrasting Properties as Ligands26.5 Supported Chromium Complex Catalysts for Ethylene Polymerization Characterization of Samples Resembling Industrial Catalysts26.6 Copper Complexes on Titania: Insights Gained from Samples Incorporating Single-Crystal Supports26.7 Gold Complexes Supported on Zeolite NaY: Determining Crystallographic Locations of Metal Complexes on a Support by Combining EXAFS Spectroscopy and TEM26.8 Gold Supported on CeO2: Conversion of Gold Complexes into Clusters in a CO Oxidation Catalyst Characterized by Transient XAFS Spectroscopy26.9 Mononuclear Rhodium Complexes and Dimers on MgO: Discovery of a Catalyst for Selective Hydrogenation of 1,3-Butadiene26.10 Osmium Complexes Supported on MgO: Determining Structure of the Metal-Support Interface and the Importance of Support Surface Defect Sites26.11 Conclusion27 Nanostructured MaterialsAlexander V. Soldatov and Kirill A. Lomachenko27.1 Introduction27.2 Small Nanoclusters27.3 XAS and XES for the Study of Nanoparticles27.4 Nanostructures and Defects in Solids27.5 Conclusion and OutlookIndex