Ralf Zimmermann, PhD, is full professor for Analytical Chemistry at University of Rostock (Germany) and director of the joint mass spectrometry center of University of Rostock and the Helmholtz Zentrum München. His research interests include mass spectrometry instrumentation, the analysis of complex molecular system and biomedical analysis.Luke Hanley, PhD, is a LAS Distinguished Professor in the Department of Chemistry at the University of Illinois at Chicago. His research interests include the development of laser ablation and photoionization for mass spectrometry imaging in microbiology, materials science, and geology.

• Preface xi1 Fundamentals and Mechanisms of Vacuum Photoionization 1Johannes Passig, Ralf Zimmermann, and Thomas Fennel1.1 Preface 11.2 Light 21.3 Photoabsorption 51.3.1 Transitions in First Order Perturbation Theory 51.3.2 Perturbation Theory 61.3.3 Absorption 71.3.4 Dipole Approximation 91.3.5 Selection Rules 111.3.6 Electronic Line Width and Lifetime 111.3.7 Electronic Transitions of Molecules 131.3.8 Single-photon Ionization (SPI) 15References 202 Fundamentals and Mechanisms of Resonance-Enhanced Multiphoton Ionization (REMPI) in Vacuum and its Application in Molecular Spectroscopy 23Ulrich Boesl and Ralf Zimmermann2.1 Introductory Remarks 232.2 Beginnings of REMPI 252.3 Principle of REMPI: Rate Equations and Quantification of Detection Efficiency 292.3.1 Rate Equations 292.3.2 Quantification of the REMPI Detection Efficiency 312.3.3 Special Situations and Problems in REMPI Processes and Countermeasures 332.3.3.1 Situation (A): Too energetic ionization threshold 342.3.3.2 Situation (B): Too energetic intermediate state 352.3.3.3 Situation (C): Too small FC-factors 362.3.3.4 Situation (D): Too fast relaxation of intermediate state 372.4 REMPI and Dissociation 402.5 Application of REMPI for Optical Spectroscopy 452.5.1 Effusive Gas Beam Molecules at Room or Elevated Temperature: REMPI Spectra with Medium Optical Selectivity 452.5.2 Supersonic Gas Beams for Cold Molecules: REMPI Spectra with High Optical Selectivity for Discrimination of Structural Isomers and Spectroscopic Studies on the Transition State 482.5.2.1 REMPI Spectroscopy of Jet-Cooled Biphenylene 502.5.2.2 REMPI Spectroscopy of Jet-Cooled Dibenzo-p-dioxin and Its Derivatives as well as of [2,2]-Paracyclophane 612.5.3 Supersonic Gas Beams for Cold Molecules: REMPI Spectra with High Optical Selectivity for Discrimination of Isotopomers 672.5.4 Chiral Molecules: Discrimination of Enantiomers by Enantioselective REMPI Spectroscopy 692.5.5 Advanced Photoelectron Spectroscopy Based on REMPI: The PES, TPES, ZEKE, MATI, Anion-PES, and Anion-ZEKE Approaches 72References 793 Analytical Application of Single-Photon Ionization Mass Spectrometry (SPI-MS) 89Thorsten Streibel, Hendryk Czech, and Ralf Zimmermann3.1 VUV Light Sources 893.2 Lamp-Based VUV Light Sources 903.3 Laser-Based VUV Light Sources 923.4 Mass Spectrometry with Lamp or Laser-Based VUV Light Sources 943.5 On-line Analysis of Complex Mixtures by Single-Photon Ionization (SPI) Mass Spectrometry 953.6 SPI-MS in Hyphenated Applications 1073.7 Ambient Monitoring 1173.8 Commercial Solutions 118References 1194 Analytical Application of Resonance-Enhanced Multiphoton Ionization Mass Spectrometry (REMPI-MS) 125Thorsten Streibel, Ulrich Boesl, and Ralf Zimmermann4.1 Investigation of Model Flames 1294.2 Applications to Internal Combustion Engines 1304.3 Monitoring Combustion Process Emissions in an Industrial Environment 1354.4 Further Applications of REMPI Mass Spectrometry 1384.5 REMPI-MS in Hyphenated Analytical Systems 1424.6 Commercial REMPI-MS Solutions and Applications 150References 1525 Probing Chemistry at Vacuum Ultraviolet Synchrotron Light Sources 159Kevin R. Wilson and Fei Qi5.1 Introduction 1595.2 Combustion Chemistry 1625.2.1 Pyrolysis in Flow Reactor 1635.2.2 Jet-Stirred Reactor Oxidation 1665.2.3 Premixed Flames 1675.2.3.1 Low-Pressure Laminar Premixed Flame 1675.2.3.2 Atmospheric Pressure Laminar Premixed Flame 1715.2.4 Coflow Diffusion Flame 1735.2.5 Biomass/Coal Pyrolysis 1745.3 Isomer-Resolved Studies of Elementary Chemical Reactions 1765.3.1 Multiplexed Chemical Kinetics Photoionization Mass Spectrometer 1775.3.2 Shock Tube Kinetics 1795.3.3 Pyrolysis Reactors 1805.3.3.1 Bimolecular Kinetics 1815.3.3.2 Unimolecular Kinetics 1815.3.4 Low-Temperature Elementary Reactions in a Pulsed Laval Nozzle 1825.4 Summary 1865.4.1 Atmospheric Aerosol Chemistry 1885.4.1.1 Aerosol Mass Spectrometry 1895.4.1.2 Gas Chromatography and SVUV Photoionization Mass Spectrometry 1955.4.2 Future Outlook 202Acknowledgments 203References 2036 Resonance Ionization Mass Spectrometry (RIMS): Fundamentals and Applications Including Secondary Neutral Mass Spectrometry 215Michael Savina and Reto Trappitsch6.1 Introduction 2156.2 Resonance Ionization Fundamentals 2176.2.1 Laser Spectroscopy 2176.2.2 Selection Rules 2206.2.3 Odd–Even Effect 2226.3 Reduction to Practice 2246.3.1 Laser Selection 2246.3.2 Mass Spectrometer Selection 2256.3.3 Laser Overlap 2296.4 Applications 2306.4.1 Useful Yield and Abundance Sensitivity 2316.4.2 Stardust Grains 2346.4.3 Multielement Analysis 2366.4.4 Electronic Processes During Vaporization 2386.5 Resources 240References 2417 Ultrashort Pulse Photoionization for Femtosecond Laser Mass Spectrometry 245Cornelius L. Pieterse, Jason M. Gross, and Luke Hanley7.1 Introduction 2457.2 Mechanisms of Ultrashort Pulse Photoionization 2467.3 Studies of Amino Acids, Dipeptides, and C60 Leading to Advanced SFI Models 2497.4 Volumetric Intensity Dependence and Multiply Charged Ions 2517.5 Direct and Gas Chromatography-Coupled Analysis of Explosives 2537.6 Gas Chromatography-Coupled Analysis of Polyaromatic Hydrocarbons, Pesticides, and Fragrances 2557.7 Laser Secondary Neutral Mass Spectrometry 2567.8 Conclusions 259Acknowledgments 260Disclosure Statement 260References 2618 Photoionization at Elevated or Atmospheric Pressure: Applications of APPI and LPPI 267Tiina J. Kauppila and Jack Syage8.1 Introduction 2678.2 Atmospheric Pressure Photoionization 2678.2.1 Atmospheric Pressure Photoionization Ion Source 2678.2.2 General Principles of Atmospheric Pressure Photoionization 2688.2.2.1 Ionization Mechanism in Positive Ion APPI 2688.2.2.2 Effect of the Dopant 2708.2.2.3 Ionization Mechanism in Negative Ion APPI 2718.2.3 APPI in Liquid Chromatography Mass Spectrometry 2728.2.4 APPI in Gas Chromatography Mass Spectrometry 2748.2.5 APPI As an Interface for Capillary Electrophoresis Mass Spectrometry 2778.2.6 APPI in Multimode Ion Sources 2788.2.7 Ambient Mass Spectrometry Utilizing Photoionization 2788.3 Low-Pressure Photoionization (LPPI) 2798.4 Applications of APPI and LPPI 2818.4.1 Drugs, Pharmaceuticals, and Metabolites 2818.4.2 Steroids 2888.4.3 Other Endogenic Compounds 2888.4.4 Plant Research 2898.4.5 Environmental Monitoring 2898.4.6 Oil Analysis 2918.4.7 Food Analysis 2918.5 Conclusions 292Acknowledgments 292References 2929 Fundamentals of Laser Desorption Ionization 305Fabrizio Donnarumma, Kermit K. Murray, and Luke Hanley9.1 Introduction 3059.2 Experimental and Computational Parameters and Observables 3069.3 General Mechanistic Considerations 3079.4 Laser-Induced Thermal or Acoustic Desorption of Neutrals from Metal Surfaces 3079.5 Molecular Resonantly Enhanced Desorption: UV-MALDI and IR-LA 3099.5.1 MALDI with UV Lasers 3109.5.2 Nanosecond to Picosecond IR Laser Ablation 3139.6 Nanophotonic Desorption 3149.7 Femtosecond Laser Ablation 3159.8 Internal Energy Transferred by LDI and Supersonic Cooling 3179.9 Conclusions 318Acknowledgments 319Disclosure Statement 319References 31910 Applications of Laser Desorption Ionization and Laser Desorption/Ablation with Postionization 327Yeni P. Yung, Fabrizio Donnarumma, Kermit K. Murray, and Luke Hanley10.1 Nature of Samples and Information to be Gained from Laser Desorption and Laser Ablation Mass Spectrometry 32710.2 Laser Ablation and Laser Desorption Ionization MS for Elemental Analysis 32810.3 Nonimaging MALDI-MS for Molecular Analysis 32910.3.1 Qualitative and Quantitative Performance for Different Types of Analytes 32910.3.2 Peptides, Proteins, Lipids, and Sugars 33010.3.3 DNA and RNA 33010.3.4 Polymers 33110.4 MALDI-MS Imaging for Molecular Analyses 33210.5 Example of Standard MALDI-MS vs. Imaging Mode: Pseudomonas aeruginosa 33310.6 MALDI Alternatives: Matrix Free, Ambient, Nanostructure Induced, and High Energy 33510.7 Molecular LD/LA-MS Beyond Nanosecond UV Lasers 33610.8 Laser, Electrospray, and Other Postionization of Plumes Formed by LD/LA 33710.8.1 LDPI-MS: Laser Desorption Postionization of Neutrals in Vacuum 33710.8.2 Postionization Coupled to LD/LA at Elevated Pressures 34010.9 Laser Ablation Sampling for Solid or Liquid Collection 34110.9.1 Laser Ablation Sampling with Online MS Analysis 34210.9.2 Laser Ablation Sampling with Off-line Analysis 34310.10 Conclusions 344Acknowledgments 345Disclosure Statement 345References 34511 Laser Ionization in Single-Particle Mass Spectrometry 359Johannes Passig and Ralf Zimmermann11.1 Relevance of Atmospheric Aerosols for Climate and Health –The Single-particle Perspective 35911.2 Analysis of Individual Particles by Laser Ionization MS – Historical Development and Basic Principle 36211.3 Ionization in Single-Particle Mass Spectrometry: Laser Desorption/Ionization (LDI) 36511.3.1 Single-Particle LDI – The Physical Framework 36611.3.2 Laser Light Sources for LDI 37111.3.3 Chemical Quantification Approaches for LDI 37211.4 Ionization in SPMS: Laser Photoionization of Previously Desorbed Species 37311.5 Instrumental Realizations 38111.5.1 Mass Analyzers 38111.5.2 Aerosol Inlet 38311.5.3 Particle Sizing 38411.6 Data Evaluation 38611.7 Applications 38711.7.1 Ambient Aerosols in Urban and Densely Populated Areas 38711.7.2 Ambient Aerosols in Rural and Marine Environments 38811.7.3 Aircraft-Based Studies 38911.7.4 In Situ Characterization of Cloud and Ice Condensation Nuclei 38911.7.5 Focus on Organic Compounds 39011.7.6 Bioaerosols 39211.7.7 Combustion Aerosols 39211.8 Commercial Laser Ionization Single-Particle Mass Spectrometry Systems 393References 394Index 413

"...a well balanced book presenting an up-to-date monograph covering the entire range of topics related to this field. As promised in the subtitle, it combines explanatory sections on the underlying principles of photoionization processes and application orientated chapters. Overall, it presents a highly recommended resource of the wide field of photoionization in mass spectrometry. "—Jürgen H. Gross, Analytical and Bioanalytical Chemistry, May 2021