Photoelectron and Auger Spectroscopy

1 Introduction.- 1. History.- 2. Scope of Present Book and Review of Past Books.- 3. Name-Calling.- 4. Areas Related to Electron Spectroscopy Not to be Discussed in Detail.- 4.1. Electron-Impact Spectroscopy.- 4.2. Photoemission.- 4.3. Penning Ionization Spectroscopy.- 4.4. Ion Neutralization Spectroscopy.- 5. Fields Related to Electron Spectroscopy.- 2 Instrumentation and Experimental Procedures.- 1. Source Volume.- 1.1. Excitation Devices.- 1.1.1. Electron Gun.- 1.1.2. X-Ray Tube.- 1.1.3. Synchrotron Radiation.- 1.1.4. Vacuum-UV Sources.- 1.2. Target Sample.- 1.2.1. Gases.- 1.2.2. Solids.- 1.2.3. Condensed Vapors, Liquids, and Targets at Other Than Room Temperature.- 1.3. Chamber for Angular Distribution Studies.- 1.4. Preacceleration and Deceleration.- 2. Analyzer.- 2.1. Cancellation of Magnetic Fields.- 2.1.1. Helmholtz Coils.- 2.1.2. Magnetic Shielding.- 2.2. Types of Analyzers.- 2.2.1. Retarding Grid.- 2.2.2. Dispersion.- 3. Detector Systems and Data Analysis.- 3.1. Single-Channel Detector.- 3.2. Position-Sensitive Detector.- 3.3. Scanning the Spectrum.- 3.4. Data Analysis.- 4. New Developments.- 5. Review of Commercial Instruments.- 5.1. AEI.- 5.2. Du Pont.- 5.3. Hewlett-Packard.- 5.4. McPherson.- 5.5. Perkin-Elmer.- 5.6. Physical Electronics.- 5.7. McCrone-RCI.- 5.8. Vacuum Generators, Inc..- 5.9. Varian.- 5.10. Others.- 3 Fundamental Concepts.- 1. Photoelectric Effect.- 2. Binding Energy.- 3. Final States and the Sudden Approximation.- 3.1. Spin-Orbit Splitting.- 3.2. Multiplet Splitting.- 3.3. Jahn-Teller Splitting.- 3.4. Electron Shakeoff and Shakeup.- 3.5. Configuration Interaction.- 3.6. Koopmans' Theorem and the Sudden Approximation.- 3.7. Vibrational and Rotational Final States.- 4. Atomic Wave Functions.- 5. Molecular Orbital Theory.- 5.1. Theoretical Models.- 5.1.1. Ab Initio Calculations.- 5.1.2. Semiempirical Calculations.- 5.2. Basis Set Extension and MO Mixing.- 5.3. Atomic and Molecular Orbital Nomenclature.- 5.3.1. Atoms.- 5.3.2. Molecules.- 4 Photoelectron Spectroscopy of the Outer Shells.- 1. Introduction.- 2. Energy Level Scheme.- 2.1. Binding Energy.- 2.2. Final States.- 2.2.1. Spin-Orbit Splitting.- 2.2.2. Multiplet Splitting due to Spin Coupling.- 2.2.3. Jahn-Teller Effect.- 2.2.4. Electron Shakeoff and Shakeup.- 2.2.5. Configuration Interaction.- 2.2.6. Resonance Absorption.- 2.2.7. Collision Peaks.- 3. Identification of the Orbital.- 3.1. Ionization Potentials.- 3.1.1. Characteristic Ionization Bands.- 3.1.2. Effects of Substituents.- 3.1.3. Sum Rule.- 3.1.4. The Perfluoro Effect.- 3.1.5. Dependence on Steric Effects.- 3.2. Identification of Orbitals by Vibrational Structure.- 3.3. Identification of Molecular Orbitals from Intensities of Ionization Bands.- 3.4. Identification of Molecular Orbitals by Angular Distribution.- 4. Comparison of PESOS with Other Experimental Data.- 4.1. Optical Spectroscopy.- 4.2. Mass Spectroscopy.- 5. Survey of the Literature on PESOS.- 5.1. Atoms.- 5.2. Diatomic Molecules.- 5.2.1. H2.- 5.2.2. N2 and CO.- 5.2.3. O2 and NO.- 5.2.4. Diatomic Molecules Containing Halogen.- 5.3. Triatomic Molecules.- 5.3.1. Linear Triatomic Molecules.- 5.3.2. Bent Triatomic Molecules.- 5.4. Organic Molecules.- 5.4.1. Methane, Alkanes, and Tetrahedral Symmetry.- 5.4.2. Unsaturated Aliphatics.- 5.4.3. Ring Compounds.- 5.4.4. Multiring Compounds.- 5.4.5. Organic Halides.- 5.4.6. Miscellaneous Organic Compounds Containing Oxygen, Nitrogen, Sulfur, and Phosphorus.- 5.5. Organometallics and Miscellaneous Inorganic Polyatomic Molecules.- 5.6. Ions, Transient Species, and Other Special Studies in PESOS.- 6. Studies on Solids.- 7. Analytical Applications of PESOS.- 5 Photoelectron Spectroscopy of the Inner Shells.- 1. Atomic Structure.- 2. Theoretical Basis of Chemical Shifts of Core Electrons.- 2.1. Valence Shell Potential Model.- 2.2. Effect of Neighboring Atoms.- 2.3. Calculation of Net Charge from Electronegativity.- 2.4. Calculation of Net Charge from Semiempirical MO.- 2.5. Use of Ab Initio Calculations for Chemical Shifts.- 2.6. Correlation of Chemical Shift with Thermochemical Data.- 3. Summary of Data on Chemical Shifts as a Function of the Periodic Table.- 3.1. Carbon.- 3.2. Nitrogen and Phosphorus.- 3.3. Sulfur and Oxygen.- 3.4. Group IIIA, IVA, VA, and VIA Elements.- 3.4.1. Group IIIA: B, Al, Ga, In, and Tl.- 3.4.2. Group IVA: C, Si, Ge, Sn, and Pb.- 3.4.3. Group VA: N, P, As, Sb, and Bi.- 3.4.4. Group VIA: O, S, Se, and Te.- 3.5. Halides and Rare Gases.- 3.6. Alkali Metals and Alkaline Earths.- 3.7. Transition Metals.- 3.7.1. First Transition Metal Series: Sc, Ti, V, Cr, Mn, Fe, Co, Ni.- 3.7.2. Second Transition Metal Series: Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd.- 3.7.3. Third Transition Metal Series: Hf, Ta, W, Re, Os, Ir, Pt.- 3.8. Groups IB and IIB: Cu, Ag, Au, Zn, Cd, Hg.- 3.9. Rare Earths and Actinides.- 4. Special Topics on Shifts in Core Binding Energies.- 4.1. Experimental and Interpretive Problems in PESIS.- 4.1.1. Comparative Problems in the Gas and Solid Phases.- 4.1.2. Charging.- 4.1.3. Definition of Binding Energy for Insulators.- 4.1.4. Binding Energy of Surface Atoms.- 4.1.5. Radiation Effects.- 4.1.6. Linewidths.- 4.2. Inorganic Compounds.- 4.2.1. Multiple Chemical Environment.- 4.2.2. Coordination Complexes.- 4.3. Organic Compounds.- 4.3.1. Resonance.- 4.3.2. Substituent Effects.- 4.3.3. Group Analysis.- 4.3.4. Specific Studies on Organic Molecules.- 4.4. Comparison of Core Electron Binding Energy Shifts with Other Physical Quantities.- 4.4.1. Mossbauer Isomer Shift.- 4.4.2. NMR.- 4.4.3. Other Physical Data.- 5. Other Applications of PESIS.- 5.1. Multicomponent Structure.- 5.1.1. Multiplet or Exchange Splitting.- 5.1.2. Electron Shakeoff and Shakeup.- 5.1.3. Configuration Interaction.- 5.1.4. Characteristic Energy Losses.- 5.1.5. Determining the Nature of Multicomponent Structure.- 5.2. PESIS for Surface Studies.- 5.3. Angular Studies with PESIS.- 6. Use of PESIS for Applied Research.- 6.1. PESIS as an Analytical Tool.- 6.2. Biological Systems.- 6.3. Geology.- 6.4. Environmental Studies.- 6.5. Surface Studies.- 6.6. Polymers and Alloys.- 6.7. Radiation Studies.- 6.8. Industrial Uses.- 6 Auger Electron Spectroscopy.- 1. Theory of the Auger Process.- 2. Comparison of the Auger Phenomenon with the Photoelectric Effect and X-Ray Emission.- 3. Use of Auger Spectroscopy for Gases.- 3.1. Atoms.- 3.2. Molecules.- 3.3. Study of Ionization Phenomena by Auger Spectroscopy.- 3.4. Autoionization.- 3.5. Auger Spectroscopy for Use in Gas Analysis.- 4. Use of Auger Spectroscopy in the Study of Solids.- 4.1. Special Problems Encountered on Using AES with Solids.- 4.1.1. Variables Concerned with Production of Auger Electrons.- 4.1.2. High-Energy Satellite Lines.- 4.1.3. Characteristic Energy Losses.- 4.1.4. Charging in Nonconducting Samples.- 4.2. High-Resolution Auger Spectroscopy with Solids.- 4.3. General Analytical Use of Auger Spectroscopy.- 4.4. Use of Auger Spectroscopy in the Study of Surfaces.- 4.4.1. General Considerations.- 4.4.2. Literature Survey of Surface Applications.- 4.5. Other Methods for Surface Analysis.- 4.5.1. Comparison of PESIS and Auger Spectroscopy for Surface Studies.- 4.5.2. Methods of Surface Analysis Other than AES and PESIS.- Appendixes.- 1. Atomic Binding Energies for Each Subshell for Elements Z = 1-106.- 3. Compilation of Data on Shifts in Core Binding Energies.- 4. Acronyms and Definitions of Special Interest in Electron Spectroscopy.- References.