Photoelectron Spectroscopy (eBook)

Front Cover 1
Photoelectron Spectroscopy: An Introduction to Ultraviolet Photoelectron Spectroscopy in the Gas Phase 4
Copyright Page 5
Table of Contents 10
Preface to the second edition 6
Preface to the first edition 8
Chapter 1. Principles of photoelectron spectroscopy 16
1.1 Introduction 16
1.2 Main features of photoelectron spectra 17
1.3 Intensities of photoelectron bands 28
1.4 The analysis of photoelectron spectra 33
1.5 The literature of photoelectron spectroscopy 42
Chapter 2. Experimental methods 45
2.1 Introduction 45
2.2 Light sources 46
2.3 Electron energy analysers 54
2.4 Electron detectors and recording systems 67
2.5 The operation of photoelectron spectrometers 70
2.6 Sample preparation 78
2.7 Vacuum requirements 79
Chapter 3. Ionization 82
3.1 Introduction 82
3.2 Photoionization 82
3.3 Ionization at different wavelengths 87
3.4 Angular distributions of photoelectrons 97
3.5 Related techniques 109
Chapter 4. Electronic energies of ionic states 120
4.1 Introduction 120
4.2 Energies from photoelectron spectra 120
4.3 Molecular orbitals, orbital energies and Koopmans' theorem 122
4.4 Molecular orbital calculations 125
4.5 Orbital energies and ionization potentials 126
4.6 Beyond orbitals and Koopmans' approximation 141
4.7 Ionization potentials and molecular charge distributions 143
Chapter 5. Photoelectron band structure—I 149
5.1 Introduction 149
5.2 Analysis of vibrational structure 150
5.3 Interpretation of vibrational structure 156
5.4 Unresolved bands 164
5.5 Orbital bonding character 168
Chapter 6. Photoelectron band structure—II: Degenerate ionic states 173
6.1 Introduction 173
6.2 Spin–orbit coupling 173
6.3 The Jahn–Teller effect 188
6.4 Jahn–Teller versus spin–orbit effects 197
6.5 Renner–Teller effects and multiple potential energy minima 198
Chapter 7. Reactions of positive ions 203
7.1 Introduction 203
7.2 Ions and molecules 204
7.3 State selection by coincidence methods 206
7.4 Internal state changes 207
7.5 Models of ion dissociation 211
7.6 Experimental results on ion dissociation 218
7.7 Ion fluorescence 231
7.8 Bimolecular ion reactions 236
Chapter 8. Applications in chemistry 241
8.1 Introduction 241
8.2 d Orbitals in bonding 242
8.3 Non-bonded interactions 248
8.4 Spectra of ions in liquids and solids 257
8.5 Photoelectron spectra of transients 260
8.6 Analytical applications 261
8.7 Photoelectron spectroscopy of surfaces and adsorbates 264
8.8 Photoelectron spectra of liquids 270
Appendix I: —The names of electronic states in atoms, molecules and ions 274
Appendix II: —Important constants and conversion factors 279
Index 282