Table of Contents
1 Introduction
Learning Objectives
1.1 Aims and Scope
1.1.1 Filling the Black Box
1.2 What Is Mass Spectrometry?
1.2.1 Mass Spectrometry
1.2.2 Mass Spectrometer
1.2.3 Mass Scale
1.2.4 Mass Spectrum
1.3 Ion Chromatograms
1.4 Performance of Mass Spectrometers
1.4.1 Sensitivity
1.4.2 Detection Limit
1.4.3 Signal-to-Noise Ratio
1.5 Terminology - General Aspects
1.5.1 Basic Terminology in Describing Mass Spectra
1.6 Units, Physical Quantities, and Physical Constants
References
2 Principles of Ionization and Ion Dissociation
Learning Objectives
2.1 Gas Phase Ionization by Energetic Electrons
2.1.1 Formation of Ions
2.1.2 Processes Accompanying Electron Ionization
2.1.3 Ions Generated by Penning Ionization
2.1.4 Ionization Energy
2.1.5 Ionization Energy and Charge-Localization
2.2 Vertical Transitions
2.3 Ionization Efficiency and Ionization Cross Section
2.4 Internal Energy and the Further Fate of Ions
2.4.1 Degrees of Freedom
2.4.2 Appearance Energy
2.4.3 Bond Dissociation Energies and Heats of Formation
2.4.4 Randomization of Energy
2.5 Quasi-Equilibrium Theory
2.5.1 QET's Basic Premises
2.5.2 Basic QET
2.5.3 Rate Constants and Their Meaning
2.5.4 k(E) Functions - Typical Examples
2.5.5 Reacting Ions Described by k(E)Functions
2.5.6 Direct Cleavages and Rearrangement Fragmentations
2.6 Time Scale of Events
2.6.1 Stable, Metastable, and Unstable Ions
2.6.2 Time Scale of Ion Storage Devices
2.7 Internal Energy - Practical Implications
2.8 Reverse Reactions and Kinetic Energy Release
2.8.1 Activation Energy of the Reverse Reaction
2.8.2 Kinetic Energy Release
2.8.3 Energy Partitioning
2.9 Isotope Effects
2.9.1 Primary Kinetic Isotope Effects
2.9.2 Measurement of Isotope Effects
2.9.3 Secondary Kinetic Isotope Effects
2.10 Determination of Ionization Energies
2.10.1 Conventional Determination of Ionization Energies
2.10.2 Improved IE Accuracy from Data Post-Processing
2.10.3 IE Accuracy - Experimental Improvements
2.10.4 Photoionization Processes
2.11 Determining the Appearance Energies
2.11.1 Kinetic Shift
2.11.2 Breakdown Graphs
2.12 Gas Phase Basicity and Proton Affinity
References
3 Isotopic Composition and Accurate Mass
Learning Objectives
3.1 Isotopic Classification of the Elements
3.1.1 Monoisotopic Elements
3.1.2 Di-isotopic Elements .
3.1.3 Polyisotopic Elements
3.1.4 Representation of Isotopic Abundances
3.1.5 Calculation of Atomic, Molecular, and Ionic Mass
3.1.6 Natural Variations in Relative Atomic Mass
3.2 Calculation of Isotopic Distributions
3.2.1 Carbon: An X+I Element
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4 Instrumentation
5 Practical Aspects of Electron Ionization...
6 Fragmentation of Organic Ions and Interpretation of E1 MassSpectra
7 Chemical Ionization
8 Field Ionization and Field Desorption
9 Tandem Mass Spectrometry
10 Fast Atom Bombardment
11 Matrix-Assisted Laser Desorption/Ionization
12 Electrospray Ionization
13 Ambient Mass Spectrometry
14 Hyphenated Methods
15 Inorganic Mass Spectrometry
Appendix
Subject Index