Chemical Applications of Synchrotron Radiation

The following sections are included:

• INTRODUCTION

• PREFACE

• CONTENTS

The following sections are included:

• Introduction

• Experimental

• Photochemistry
  • Dimethyl Sulfoxide
  • Substituted Ethylenes
    • Acrylonitrile
    • Vinyl Chloride
  • Oxalyl Chloride
  • Propyne and Allene

• Reactive Scattering
  • Crossed-Beam Reaction Dynamics: Cl + Propane
  • CI + n-Pentane

• Conclusion

• Acknowledgments

• References

The following sections are included:

• Introduction

• Overview of Photon-Impact Studies of Molecular Superexcited States

• Dissociation of Superexcited Molecular Hydrogen

• Dissociation of Superexcited States of Diatomic and Triatomic Molecules

• VUV-Optical Oscillator-Strength Distributions of Polyatomic Molecules

• Photoionization Quantum Yields

• Dissociation of Superexcited States of Polyatomic Molecules
  • Acetylene
  • Silane
  • Dimethyl Ether
  • Other Related Studies

• Superexcited States as Reaction Intermediates in Some Collision Processes

• Superexcited States in Reaction Kinetics

• Superexcited States in the Condensed Phase

• Summary

• Acknowledgments

• References

The following sections are included:

• Introduction
  • General
  • Background and Motivations

• Delving Deeper into the Continuum (the Case for Global Surveys)

• Experimental
  • Using Dispersed Fluorescence to Decouple the Excitation and Detection Bandwidth
  • Experimental Details

• Vibrationally Resolved Studies
  • Cooper Minima
  • Shape Resonances in Linear Triatomic Systems: Mode-Specificity
  • Studies of Dipole Forbidden Vibrations: Bending in Linear Systems
  • Nonlinear Polyatomics

• Rotationally Resolved Studies
  • Background
  • Cooper Minima
  • Shape Resonances
  • Improvements and Long Range Behavior

• Fluorescence Polarization and Alignment

• Conclusions

• Acknowledgments

• References

The following sections are included:

• Introduction
  • Scope of this Review
  • Related Techniques
  • Inner Shell Molecular Photofragmentation

• Experimental Methods

• Modes of Operation of a Photoionization Coincidence Spectrometer
  • Total Yield Spectroscopy
  • Symmetry Resolved Ion Yield Spectroscopy
  • Mass Spectroscopy
    • Pulse Extraction TOF
    • High Field PEPICO
    • Low Field PEPICO
  • Correlated Ion Signals — PIPICO, PEPIPICO and PE3PICO

• Deducing Fragmentation Kinematics from Ion Flight Time Peak Shapes
  • Theory
    • Two-Body Dissociation
    • Three-Body Dissociation
    • Four-Body Dissociation
  • An Example — Ion Pair Peak Shapes of P 2p Ionized PF₃

• Highlights of Recent Studies
  • Mass Spectra and Partial Ion Yield Spectroscopy
  • Photoabsorption and Partial Photoionization Yield Spectroscopy
  • Other Examples of Inner Shell Photoionization-Dynamics Studies
    • Position Sensitive Ion Detection
    • State-Selective Fragmentation
    • Fixed-in-Space Molecules
    • Vibrationally Resolved Photofragmentation
    • Complete Determination of Dissociation Channels for Polyatomic Molecules

• Summary

• Acknowledgments

• References

The following sections are included:

• Introduction

• Diatomic Molecules
  • Symmetry-Resolved Inner-Shell Excitation Spectroscopy
  • Rydberg Series in Inner-Shell Excitations of N₂ and CO
  • 3pσ_u-Rydberg and -Valence Mixing in the O 1s Excitation of O₂

• Linear Molecules
  • Angle-Resolved Ion-Yield Measurement for Polyatomic Molecules
  • Rydberg States in CO₂ and C₂H₂ and Core-Hole Localization Effects
  • Renner-Teller Effects in the C 1s → π* Excited States of CS₂, OCS, and CO₂
  • Vibronically Induced C 1sσ_g → nsσ_g Rydberg States in CO₂

• Nonlinear Molecules
  • Low-lying S 1s Excited States in SO₂ and Thiophene (C₄H₄S)
  • Jahn-Teller Effects in the C 1s → 3pt₂ Rydberg State of CH₄

• Linear and Planar Cu Complexes
  • Shakedown-Like Final State Effects in the Cu 1s Excitation
  • Crystal Field Effects in the Cu 1s Excitation

• Planar Ni Complexes
  • Ni 1s Excitations to Ni 4pπ* and Ligand π* Orbitals
  • Ni 2p Excitations to Ni 3dσ* and Ligand π* and σ* Orbitals
  • Symmetry of the Ni 3d Holes in [Ni^II(mnt)₂]²⁻ and [Ni^II(mnt)²]⁻
  • Resonant Behaviors of the Ni 3p and 3d Photoelectrons at the Ni 2p Edge
  • Comparison with Metallic and Correlated Systems

• Conclusions

• Acknowledgements

• References

The following sections are included:

• Introduction

• NEXAFS Spectroscopy
  • Instrument Aspects of NEXAFS and Electron Energy Loss Spectroscopy
  • NEXAFS Spectroscopy of Polymers: Chemical Sensitivity
    • Chemical Sensitivity: Examples
  • NEXAFS Spectroscopy of Polymers: Orientational Sensitivity
  • NEXAFS Spectroscopy of Polymers: Quantitative Analysis
    • Blends of Polycarbonate and Poly(butylene terephthalate)
    • Quantitative Analysis of the Chemical Composition of Polyurethanes

• NEXAFS Microscopy: Instrumentation and Analysis Tools
  • Quantitative Image Analysis

• NEXAFS Microscopy: Applications
  • Surfaces and Thin Films
    • Polyimide Films and Surface
    • Overcoats and Lubricating Layers on Hard Disks
    • Confined, Free Standing Homopolymer Thin Films
    • Thin Film Blends
    • Thin Film Polymer Bilayers
    • Block Copolymer Thin Films
  • Bulk Morphology and Composition of Multicomponent, Multiphasic Polymers
    • NEXAFS Microscopy of Poly(ethylene terephthalate)/Vectra™ Blends
    • Engineered Polyurethane Polymers
    • Multilayers
    • Elastomer Composites
  • Fibers
  • Organic Geochemistry
  • Meteoritics and Interplanetary Dust Particles
  • Soils and Environmental Studies
  • Other Applications

• Summary and Future Outlook

• Acknowledgments

• References

The following sections are included:

• Introduction

• Experimental Details
  • General
  • Synchrotron Source
  • Surface Science
  • Microspectroscopy

• Experimental Results and Discussion
  • Surface Science

• Other Surface Science Experiments
  • Surface Reactions
  • Adsorbate-Adsorbate Coupling

• Infrared Microspectroscopy

• Acknowledgments

• References

The following sections are included:

• Introduction

• UV Photoelectron Spectroscopy (UPS)
  • Methodology
    • General and Experimental Aspects
    • Theoretical Analysis of UPS Spectra
    • Energy Band Mapping for One-Dimensional Systems
  • Electronic Structure of Molecular Solids
    • Density of States, Solid State Effect, and Angular Dependence
    • The Use of the Tunability of Synchrotron Radiation
    • Intermolecular Energy Band Mapping
  • Polymers and Oligomers
    • Density of States
    • Band Evolution in Oligomers
    • Intramolecular Energy Band Mapping
  • Electronic Structure of Binary Systems
    • Complexes
    • Interfaces
  • ARUPS as a Novel Probe of Molecular Orientation

• NEXAFS Spectroscopy
  • General and Experimental Aspects
  • Characteristics of Core Excitations
    • Selection Rules
    • Core Excitonic Effect
    • Spectral Assignments
    • Theoretical Simulation and Analysis
  • Molecular Orientation and Chemical States of π-Conjugated Systems
    • Molecules on Well Defined Surfaces
    • Other Studies of Molecules and Polymers in Various States
  • Electronic Structures of the Unoccupied States of π-Conjugated Systems
    • Aromatic Molecules
    • Fullerenes and Nanotube
    • Metal Complexes
    • π-Conjugated Polymers
    • Doping and Reactions
  • Alkanes and Compounds with Long Alkyl Chains
    • C K edge Absorption of Alkyl Chain
    • Compounds with Long Alkyl Chains
  • Other Polymers and Their Surfaces
    • Polymers with Fluorinated Chains
    • Silicon-Backboned Polymers
    • Polyimides and Their Rubbed States
    • Other Polymers
  • Other Applications

• Acknowledgments

• References

The following sections are included:

• Introduction
  • History and Overview
  • Attributes of SR for Engineered Surface Chemistry
  • Current Status of Research in SR-Initiated Surface Chemistry
  • Work in Related Areas
  • Scope and Chapter Synopsis

• Relevant Surface Physics and Chemistry
  • Electronic Structure and Bonding
  • Factors that Influence Ion Desorption Yields

• Mechanisms
  • Basic Processes
  • Direct vs. Indirect Mechanisms

• Cross Sections and Quantum Yields
  • Definition of Cross Section and Quantum Yield
  • Photon Flux Density and Exposure Determinations
  • Mechanistic Aspects

• Methodology
  • Approaches
  • Analytical Techniques
  • Sample Preparation

• Examples of SR-Initiated Surface Photochemistry
  • Methylhalide Photolysis
  • Halosilane Photolysis
  • Energy Dependent Adamantane Reactions
  • Applications of SR-Induced Photochemistry
    • Localized Changes in Electronic Structure: SR-Induced Delta Doping of Si
    • Hard X-Ray-Induced Reactions at the Solid/Liquid Interface

• Future Directions
  • Modeling
  • Systematic Studies

• Acknowledgments

• References

The following sections are included:

• Introduction

• General

• Experimental
  • Grating Spectrometers for Soft X-Ray Emission
  • Sample Arrangements
  • Angular Dependent Detection

• Surfaces and Interfaces
  • Surface Adsorbates
  • Buried Layers
  • Hydrogen Modification

• Resonant Soft X-Ray Emission

• Carbon Systems and Polymers
  • Fullerene Systems
  • Polymers
  • Low-k Carbon Fims

• Correlated Materials
  • High Temperature Superconductors

• Dichroic Soft X-Ray Emission
  • Magnetic Materials

• References

The following sections are included:

• Introduction

• Background

• Layer Resolved Spectroscopy

• CO Adsorption

• Oxidation

• Sulfidation

• SO₂ Reaction

• Etching and Passivation

• Outlook

• Acknowledgments

• References

The following sections are included:

• Introduction

• Semiconductor Technology
  • Surface Chemistry During Growth, Etching, and Passivation
  • Interfaces

• Magnetic Materials
  • Electronic States in Magnetoelectronics
  • Magnetic Multilayers

• Nanostructures, Tailored Materials
  • Quantum Wells
  • One- and Zero-Dimensional Structures

• Acknowledgments

• References

The following sections are included:

• Introduction

• Experimental

• Theoretical Background
  • The Multiple Scattering Approach
  • The Multiplet Theory
  • Electronic Structure Calculations

• Applications
  • Solid State Chemistry and Materials Science
    • The Silicon Compounds
    • The High T_c Superconductors
    • Intercalated Systems
    • Other Systems
  • Earth’s Science and Environmental Studies
    • The Basic Elements (Sodium, Magnesium, Aluminum, Silicon)
    • Minority Elements
  • Coordination Chemistry, Magnetism, Catalysis
    • The Ligand Study of Metallic Complexes
    • Polymers
    • Catalysis
    • Magnetic Studies
  • Molecular Studies

• Conclusions

• References

The following sections are included:

• Introduction

• Principle of Surface XAFS
  • NEXAFS Spectroscopy
  • SEXAFS Spectroscopy

• Experimental

• Application to Atomic Adsorbates
  • Surface Anisotropic Vibration and Anharmonicity
  • Coverage Dependence of Surface Chemical Bonding

• Application to Molecular Adsorbates
  • Thiophene on Ni(100), Cu(100) and Pd(100)
  • The Structures of SO₂ Adsorbed on Metals
  • Surface Chemical Reaction of SO₂ on Cu(100)
  • Alkanethiols Adsorbed on Cu(111) and Cu(100)

• Future Prospects

• Acknowledgments

• Appendix

• References

The following sections are included:

• XEOL Emission Spectra and Applications
  • Introduction
  • Applications Ranging from Analytical Chemistry to X-ray Detection
    • Rare Earths in Inorganic Host Matrices
    • Low Temperature Organic Shpol’skii Matrices and Glassy Systems
    • X-ray Detection Using Spontaneous or Stimulated Luminescence
  • Advances Stimulated by Synchrotron Radiation Sources
    • Optical Activity in Emission Spectra
    • Time Resolved XEOL Decays
    • Imaging and Spectromicroscopy

• Near Edge and Extended Structures in XEOL Excitation Spectra
  • Review of Published Literature
    • Positive and/or Negative Edge Jumps
    • Site-Selectivity and Implicit Restrictions
    • Luminescence of Porous Silicon
  • Theoretical Bases for the Analysis of Excitation Spectra
    • Energy Conversion and Thermalization
    • Energy Transfer Mechanisms
      • Photoconductivity
      • Radiative Transfer and Self-Absorption
      • Forster-Dexter Mechanisms, and Exciton Diffusion
      • Luminescence Time Decays and Diffusion Lengths
      • Surface Recombination Allowed by Diffusion
    • Luminescence Yield and Nonlinear Luminescence

• Conclusion and New Perspectives

• Acknowledgments

• References

The following sections are included:

• Introduction

• X-ray Reflectivity
  • Index on Refraction
  • Reflection from Interfaces
  • The Penetration Depth

• XAFS
  • Basic Principles of EXAFS
  • Detection of XAFS for Thin Films
    • Glancing Angle Techniques
    • Fluorescence Detection
    • Electron Yield Detection

• Experimental Examples
  • Transition Metal/Aluminum Bilayers
  • Total Reflection X-ray Flourescence Spectroscopy
  • Reflectivity Study on Liquid-vapor Interfaces
  • Polarization Dependent XAFS Studies on Thin Hetero-epitaxial Metallic Films
  • In situ MOCVD Growth Studies

• Acknowledgments

• References

The following sections are included:

• Introduction

• Experimental Designs
  • Kratky Block Collimation System
  • Pinhole Collimation System
  • Advanced Polymers Beamline
  • ChemMat CARS Undulator Beamline at the APS
    • Undulator X-Ray Source
    • ChemMat CARS Beamline
    • X-Ray Beam Delivery
    • Beamline Layout

• Theoretical Background
  • Particulate Scattering
  • Nonparticulate Scattering
  • Scattering from Semicrystalline Polymers
  • Analysis from Time Resolved Measurements

• Scientific Examples for Synchrotron Research
  • Supramolecular Structures in Complex Fluids
    • Structures of Polyelectrolyte Surfactant Complexes
    • Block Copolymer in Solution
  • Kinetics of Phase Transition
    • Semistiff Chain Polymers
    • Flexible Chain Polymers and Blends
  • Experiments under Supercritical Conditions
  • Polymers under Deformation
  • In situ Study of Fiber Spinning

• Acknowledgments

• References

The following sections are included:

• Introduction

• Theoretical Background

• Experimental Configurations

• Applications
  • X-Ray Raman Scattering
    • General Description
    • Excitations of Inner Shell Electrons: XANES, EXAFS, Polarization Dependence
    • Excitations of Valence Electrons: Bethe Surfaces and Complete Optical Spectra of Water
    • S(q) and Electron Correlation Effects
  • Resonant Raman and Resonant Inelastic Scattering
    • X-Ray Resonant Raman Scattering
    • Many Electron Effects in XRRS
    • Magnetic Sensitivity in XRRS
    • X-Ray Resonant Inelastic Scattering
    • Example: RIXS in NiO
  • Compton Scattering
    • Theory and Approximations
      • A phenomenological description
      • Impulse approximation and Compton profile
    • Sharp Feature for Valence Electrons: Relevance to Chemical Bonding
    • Kinetic Energy
    • Technical Issues in the Interpretation of Compton Profiles
      • Subtraction of core electrons contribution and multiple scattering correction
      • Momentum density reconstruction
    • Examples and Applications
      • Qualitative interpretations of Compton profiles
      • Limitation of the rigid band model in Lithium-Graphite intercalation compounds
      • Refinement of a local wavefunction model from a set of DCPs

• Conclusions

• Acknowledgments

• References

The following sections are included:

• Introduction

• Background
  • Principle of Powder Diffraction
  • The Intensity of Diffraction

• Experimental Techniques
  • Energy Dispersive Diffraction
  • Forward Reflection Method
  • Para-Focussing Techniques
  • Rietveld Refinement
  • Measurement of High Quality Powder Diffraction Pattern

• Structural Analysis Using Powder Diffraction Pattern
  • Unit Cell Determination
  • Extraction of Integrated Intensities
  • Solving the Structural Phase Problem
  • The Patterson Method
  • The Direct Method

• Direct Determination of Charge Density Distribution

• Selected Examples
  • Powder Diffraction at High Pressure
  • Solution of the Crystal Structure of Complex Low Symmetry Organic Compounds
  • Structural Refinement of a Protein Crystal
  • A New Strategy for Improving Data Collection
  • Direct Evaluation of Charge Density

• Concluding Remarks

• References

The following sections are included:

• Introduction

• Experimental Methods
  • Time Resolved Diffraction Measurements
  • Preparation of Combustion Synthesis Specimens
  • Temperature Profile Measurements
  • Spatially Resolved X-ray Diffraction (SRXRD) Measurements
  • Titanium Samples for Welding
  • Welding Setup and Procedure

• Results
  • Time Resolved Diffraction Data
    • The Synthesis of TaC
    • The Synthesis of Ta₂C
    • Temperature Profiles of the Combustion Front
  • Spatially Resolved X-ray Diffraction Data
    • Phase Mapping in the HAZ of Ti Fusion Welds
    • The α Pattern
    • The α_AR Pattern
    • The α_RG Pattern
    • The α_BT Pattern
    • The β Pattern

• Discussion
  • Combustion Reaction Temperature
  • Chemical Dynamics of the Ta-C Combustion Synthesis
  • Thermal Distribution in a Ti Fusion Weld
  • The α_AR Pattern: Location and Associated Microstructure
  • The α_RG Pattern: Location and Associated Microstructure
  • The β and β_L Pattern: Location and Associated Microstructure
  • The α_BT Pattern: Location and Associated Microstructure

• Concluding Remarks

• Acknowledgments

• References

The following sections are included:

• Introduction

• Basic Processes

• Free-ion Yields in Hydrocarbons vs. X-ray Energy
  • Theoretical Yields
  • Experimental Yields
  • Ion Yields at K Edges

• Excited State Yields in Hydrocarbons vs. X-ray Energy
  • Theoretical Predictions
  • Experimental Results
  • Edge Effects

• Decomposition of Water and Aqueous Solutions
  • Radical and Molecular Yields — Theory
  • Radical and Molecular Yields — Experimental
  • Effects at K Edges

• Concluding Remarks

• Acknowledgments

• References

The following sections are included:

• Introduction

• Basic Approaches
  • Synchrotron X-ray Production
  • X-ray Cross Sections
  • Synchrotron Radiation Induced X-ray Emission (SRIXE)
  • Extended X-ray Absorption Fine Structure (EXAFS) and Extended X-ray Absorption Near Edge Structure (XANES)
  • Computed Microtomography (CMT)
  • Sample Radiation Damage Effects

• Applications
  • Biological Applications
    • Reversible Effect of Low Lead Levels on Neuronal Growth
    • Analysis of Zinc Binding Capabilities of a Protein Domain
    • Stroke and Calcium Concentrations in the Brain
    • Studies of Bone and Cartilage
  • Geological and Extraterrestrial Materials
    • Microstructure of Shock-recovered Berea Sandstone
    • Internal Structure of Two Type-I Deep Sea Spheres by X-ray Computed Microtomography
    • Hydrothermal Vents
    • Investigation of New York/New Jersey Harbor Dredged Material
  • Environmental Chemistry
    • Secondary Ion Mass Spectroscopy and Synchrotron X-ray Fluorescence in the Study of the Qualitative Variation in Metal Content with Time in Tree Rings
  • Materials Analysis
    • Thermal Spray
    • Study of Supported Catalysts
    • Investigation of Integrated Circuit Structures Using CMT and Microdiffraction

• Summary

• Acknowledgments

• References

The following sections are included:

• Introduction

• Etching and CVD Experiments
  • Experimental Systems
    • Beamline and Multilayered Mirror Monochromator
    • Reaction Chamber
  • Etching and Unique Material-Selectivity
  • CVD and Unique Material-Selectivity
  • SR Assisted Epitaxial Growth
  • SR Irradiation Effects on the Low Temperature Condensed Layer of Dimethyl Aluminum Hydride (DMAH)

• In Situ Monitoring Techniques and Reaction Mechanism Study
  • BML-IRAS
    • Principle of BML-IRAS
    • Application of BML-IRAS to Reaction Mechanism Study of SR Assisted GS-MBE
    • IRAS with SR Irradiation Effects on Chemisorbed Hydrogen/Si(100)
  • Scanning Tunnelling Microscopy (STM)

• Core Electron Excitation in SR Process

• Future Prospects: Nanostructure Fabrication by SR Processes

• Acknowledgment

• References

The following sections are included:

• Introduction
  • X-ray Absorption Spectroscopy Using Synchrotron Radiation
  • Detection Methods
  • Comparison of Laboratory XPS and XANES

• Antiwear Films Generated from Zinc Dialkyldithiophosphates (ZDDPs)

• XANES Characterization of Model Compounds
  • Polyphosphate Chain Length Effect on P K and L Edge XANES
  • Cation Effect P K and L Edge XANES
  • O K Edge XANES Spectra of Model Compounds
  • S K Edge XANES of Model Compounds

• Characterization of Tribochemical Films Using XAS
  • EXAFS Characterization of Antiwear Films and Wear Particles Generated from ZDDPs
  • XANES Characterization of Antiwear Films Generated from ZDDPs

• ZDDP in Combination with Other Additives
  • ZDDP + Detergents and Dispersants
  • ZDDP + Molybdenum Dithiocarbamate (MoDTC)

• Polyphosphate Film Thickness Using P K Edge XANES Spectroscopy

• XANES Studies of Phosphate Coatings Generated from ZDDPs

• X-ray Spectromicroscopy
  • X-ray Spectromicroscopy of Alkyl and Aryl ZDDP Derived Antiwear Films
  • Neutral and Overbased Ca Sulphonate in Combination with and without ZDDP

• Conclusions and Future Work

• Acknowledgments

• References

The following sections are included:

• Introduction

• General Considerations
  • Absorption Coefficient and Photon Penetration Depth
  • Escape Depths of Various Yields
  • Instrumentation

• Applications
  • Ni/Si(100): Evolution of Nickel Silicide Thin Films
    • General Considerations
    • Ni and Si K edge XANES for the Blanket Films
    • Ni and Si L edge XANES for the Blanket Films and Submicron Lines
  • Al Diffusion Through a TiN_x Diffusion Barrier on Si(100)
    • General Considerations
    • Al K edge: TEY
    • Al K edge: FLY
    • Al L edge TEY and FLY
  • Porous Silicon
    • General Considerations
    • Synchrotron Radiation Induced Luminescence
    • XEOL and Optical XAFS at the Si K edge and the Origin of Luminescence from PS
    • XEOL and Optical XAFS at the Si L_3,2 edge
    • A MCMD Study of the Distribution of Luminescence Sites

• Summary

• Acknowledgments

• References

• Appendix: Recent Publications Using Multidetection X-ray Absorption Spectroscopy (MD-XAS) Techniques

The following sections are included:

• Introduction

• Unified MS XAFS and NEXAFS Calculations
  • Curved Wave Scattering Theory
  • Path Filters
  • Scattering Potentials
  • Self-energy and Mean Free Path
  • Thermal and Configurational Disorder

• Applications to XAFS and XANES
  • Information Content in XAFS
  • Example of MS XAFS Calculation
  • NEXAFS and Shape Resonances
  • Application to XANES

• Conclusions

• Acknowledgments

• References

The following sections are included:

• INDEX