Photoelectron Spectroscopy

ContentsPreface to the Second Edition Preface to the First Edition 1 Principles of Photoelectron Spectroscopy 1.1 Introduction 1.2 Main Features of Photoelectron Spectra 1.2.1 Atoms 1.2.2 Diatomic Molecules 1.2.3 Triatomic and Larger Molecules 1.3 Intensities of Photoelectron Bands 1.3.1 Limiting Rules For Relative Intensities 1.3.2 Band Intensity and Orbital Character 1.4 The Analysis of Photoelectron Spectra 1.4.1 Examples 1.4.2 External Evidence For Band Assignments 1.5 The Literature of Photoelectron Spectroscopy 1.5.1 General Bibliography 2 Experimental Methods 2.1 Introduction 2.2 Light Sources 2.2.1 Discharges in Helium and Other Gases 2.2.2 Continuum Sources: Synchrotron Radiation 2.2.3 Lasers 2.3 Electron Energy Analysers 2.3.1 Retarding-Field Analysers 2.3.2 Deflection Analysers 2.3.3 Hybrid Analysers 2.4 Electron Detectors and Recording Systems 2.4.1 Electron Time-Of-Flight Analysis 2.4.2 Position-Sensitive Detectors 2.5 The Operation of Photoelectron Spectrometers 2.5.1 High Resolution 2.5.2 Calibration and Energy Measurements 2.5.3 Intensity Measurements 2.6 Sample Preparation 2.7 Vacuum Requirements 3 Ionization 3.1 Introduction 3.2 Photoionization 3.2.1 Multi-Photon Ionization 3.3 Ionization at Different Wavelengths 3.3.1 Direct Photoionization 3.3.2 Fine Structure in Photoionization Cross-Sections 3.4 Angular Distributions of Photoelectrons 3.4.1 Form of The Angular Distribution 3.4.2 Experimental Methods and Examples 3.4.3 Molecular Rotation 3.4.4 Orientated Molecules 3.4.5 Photoelectron Spin Polarization 3.5 Related Techniques 3.5.1 Ion Emission Spectra 3.5.2 Ion Absorption Spectra 3.5.3 Photoionization Techniques 3.5.4 Penning Ionization 3.5.5 Electron Energy-Loss Spectra 3.5.6 Electron Impact Ionization 4 Electronic Energies of Ionic States 4.1 Introduction 1 4.2 Energies From Photoelectron Spectra 4.3 Molecular Orbitals, Orbital Energies and Koopmans' Theorem 4.4 Molecular Orbital Calculations 4.5 Orbital Energies and Ionization Potentials 4.5.1 Hartree-Fock Calculations 4.5.2 Ab Initio SCF Calculations 4.5.3 Semi-Empirical Calculations 4.5.4 Empirical Calculations 4.6 Beyond Orbitals and Koopmans' Approximation 4.7 Ionization Potentials and Molecular Charge Distributions 5 Photoelectron Band Structure—I 5.1 Introduction 5.2 Analysis of Vibrational Structure 5.2.1 Vibrational Selection Rules 5.3 Interpretation of Vibrational Structure 5.3.1 Frequencies and Anharmonicities 5.3.2 Identity of the Vibrations Excited 5.3.3 Changes in Molecular Geometry On Ionization 5.3.4 Rotational Structure of Photoelectron Peaks 5.4 Unresolved Bands 5.4.1 The Existence of Continuous Bands 5.4.2 The Shapes of Unresolved Bands 5.5 Orbital Bonding Character 6 Photoelectron Band Structure—II: Degenerate Ionic States 6.1 Introduction 6.2 Spin-Orbit Coupling 6.2.1 Linear Molecules 6.2.2 Non-Linear Molecules 6.2.3 Spin-Orbit Coupling Without Degeneracy 6.3 The Jahn-Teller Effect 6.3.1 Jahn-Teller Effects in Photoelectron Spectra 6.3.2 Vibronic Splittings 6.3.3 Triply Degenerate States 6.3.4 The Magnitude of Jahn-Teller Distortions 6.4 Jahn-Teller Versus Spin-Orbit Effects 6.5 Renner-Teller Effects and Multiple Potential Energy Minima 7 Reactions of Positive Ions 7.1 Introduction 7.2 Ions and Molecules 7.3 State Selection by Coincidence Methods 7.4 Internal State Changes 7.4.1 Vibrational Energy Flow 7.4.2 Electronic Energy Flow 7.5 Models of Ion Dissociation 7.5.1 Direct Dissociation 7.5.2 Pre-Dissociation 7.5.3 Internal Conversion Plus Vibrational Pre-Dissociation 7.5.4 Correlation Rules 7.6 Experimental Results On Ion Dissociation 7.6.1 Chemical Nature of Products-Branching 7.6.2 Product Angular Distributions 7.6.3 Ion Dissociation Rates 7.6.4 Slow Ion Dissociations 7.6.5 Energy Disposal 7.7 Ion Fluorescence 7.7.1 Diatomic Ions 7.7.2 Triatomic Ions 7.7.3 Polyatomic Ions 7.8 Bimolecular Ion Reactions 7.8.1 The Role of Internal Energy8 Applications in Chemistry 8.1 Introduction 8.2 D Orbitals in Bonding 8.2.1 Transition Metal Complexes 8.2.2 Dπ-Pπ Bonding 8.3 Non-Bonded Interactions 8.3.1 Heteroatom Lone Pairs 8.3.2 Isolated Double Bonds 8.4 Spectra of Ions in Liquids and Solids 8.5 Photoelectron Spectra of Transients 8.6 Analytical Applications 8.7 Photoelectron Spectroscopy of Surfaces and Adsorbates 8.7.1 Pure Solids 8.7.2 Adsorbed Species 8.8 Photoelectron Spectra of Liquids Appendix I—The Names of Electronic States in Atoms, Molecules and Ions Appendix II—Important Constants and Conversion FactorsIndex