Field Ionization Mass Spectrometry

PrefaceIntroduction1. Theory of Field Ionization (FI) and Field Emission (FE) 1.1. FI Probability 1.2. Particle Supply 1.3. Minimum Distance for FI 1.4. Field Electron Emission2. Field Ionization Sources 2.1. General Design of FI Sources 2.1.1. Non-Focusing FI Sources 2.1.2. Focusing FI Sources 2.1.3. Lens Systems 2.1.4. Fluctuations of the FI Currents 2.2. Tips as FI Emitters 2.2.1. Methods for Production of FI Tips 2.2.2. Measurement of Tip Radius and Shape Factor 2.2.3. Angular Distribution of FI Currents Emitted from Tips 2.2.4. FI Current-Voltage Curves for Tips as Emitters 2.2.5. Threshold Field Strength 2.2.6. Heating of Emission Tips 2.3. Thin Wires as FI Emitters 2.3.1. Production of Thin Wires for FI 2.3.2. Strength of Wires and Forces Acting on Them 2.3.3. Current-Voltage Curves for FI Wires 2.3.4. Activation of Thin Wires for FI 2.3.5. FI Mass Spectra Taken with Heated Wires 2.4. Sharp Metal Edges as FI Emitters 2.5. Comparison of Tips, Thin Wires and Sharp Metal Edges for FI 2.6. Means for Stabilizing Thin Wires during FI 2.7. Actual Design of Some FI Sources 2.8. Pulsed FI Sources 2.9. FI Microscopes as Sources for Mass Spectrometers 2.9.1. FI Microscopes 2.9.2. Mass Analyses in Modified FI Microscopes 2.9.3. The Atom-Probe FI Microscope 2.10. Resolving Power of FI Mass Spectrometers3. Application of the FI Mass Spectrometer to Physicochemical Problems 3.1. Charge Distribution of Organic Ions in High Electric Fields 3.1.1. Quantum Mechanical Treatment 3.1.2. Semi-Classical Approximation 3.2. Field Dissociation of Molecular Ions 3.3. Bond Energies of Molecular Ions 3.4. Kinetics of Unimolecular Decomposition of Ions in High Electric Fields 3.4.1. Life Time of Molecular Ions and Peak Shape of Fragment Ions 3.4.2. Mechanisms for Ion Decomposition in High Electric Fields 3.5. Temperature Dependence of FI Mass Spectra 3.6. Processes in Adsorbed Layers on FI Emitters 3.6.1. Formation of Protonated Molecules 3.6.2. Field Condensation and Ion Cluster Formation 3.6.3. Shift of Chemical Equilibria by Electric Fields 3.6.4. Field Desorption and Field Evaporation 3.6.5. Change of FI Current with Work Function 3.6.6. Dependence of FI Currents on Surface Diffusion 3.7. Field-Induced Resonance States at a Surface 3.8. Isotopic Effects in FI Mass Spectra 3.9. Negative Ion Emission from Field Emitting Metal Surfaces4. Qualitative Analyses with the FI Mass Spectrometer 4.1. FI Mass Spectra of Homologous Series of Organic Substances 4.1.1. Alkanes 4.1.2. Alkenes 4.1.3. Alkynes 4.1.4. Amines 4.1.5. Alcohols 4.1.6. Cyclic Compounds 4.1.7. Other Compounds 4.1.8. Sensitivity Factors for FI and EI Mass Spectra 4.2. Detection of Free Radicals by FI Mass Spectrometry 4.2.1. Photochemically Produced Free Radicals 4.2.2. Thermally Produced Free Radicals 4.3. Elucidation of Structure, Mechanism and Kinetics of Decomposition of Organic Ions by FI Mass Spectrometry 4.3.1. Determination of Molecular Weights by FI Mass Spectrometry 4.3.2. Discussion of Combined FI and EI Fragment Mass Spectra 4.3.3. Kinetics of Rearrangement Reactions 4.3.4. The FI Emitter Dipping Technique 4.4. Quantitative Analyses of Mixtures 4.4.1. Analyses of Mixtures with Tip Emitters 4.4.2. Analyses of Mixtures with Wire Emitters 4.4.3. Foundations of Gasoline Sample Analysis 4.4.4. Analyses of Heavy Petroleum Fractions (Paraffin Waxes) 4.4.5. Analyses of the Products of Pyrolysis of Polymers 4.4.6. FI Metastable Fragment Maps5.