Photoionization And Photo Induced Processes In Mass Spectrometry Fundamentals And Applications Ralf Zimmermann full chapter pdf docx

Photoionization and Photo-Induced
Processes in Mass Spectrometry:

Fundamentals and Applications Ralf
Zimmermann
Visit to download the full and correct content document:
https://ebookmass.com/product/photoionization-and-photo-induced-processes-in-mas
s-spectrometry-fundamentals-and-applications-ralf-zimmermann/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...
Fundamentals and Applications of Fourier Transform Mass

Spectrometry 1st Edition Philippe Schmitt-Kopplin
https://ebookmass.com/product/fundamentals-and-applications-of-
fourier-transform-mass-spectrometry-1st-edition-philippe-schmitt-
kopplin/
Ambient Ionization Mass Spectrometry in Life Sciences:

Principles and Applications Kei Zaitsu (Editor)
https://ebookmass.com/product/ambient-ionization-mass-
spectrometry-in-life-sciences-principles-and-applications-kei-
zaitsu-editor/
Heat and mass transfer : fundamentals and applications

6th Edition Yunus A Çengel
https://ebookmass.com/product/heat-and-mass-transfer-
fundamentals-and-applications-6th-edition-yunus-a-cengel/
Applications in High Resolution Mass Spectrometry: Food

Safety and Pesticide Residue Analysis 1st Edition
Romero-Gonz Lez
https://ebookmass.com/product/applications-in-high-resolution-
mass-spectrometry-food-safety-and-pesticide-residue-analysis-1st-
edition-romero-gonz-lez/
Heat And Mass Transfer: Fundamentals And Applications
5th Edition – Ebook PDF Version
https://ebookmass.com/product/heat-and-mass-transfer-
fundamentals-and-applications-5th-edition-ebook-pdf-version/
Nanofluids for Heat and Mass Transfer Fundamentals,

Sustainable Manufacturing and Applications Bharat
Bhanvase
https://ebookmass.com/product/nanofluids-for-heat-and-mass-
transfer-fundamentals-sustainable-manufacturing-and-applications-
bharat-bhanvase/
High-Throughput Mass Spectrometry in Drug Discovery 1.

Edition Chang Liu
https://ebookmass.com/product/high-throughput-mass-spectrometry-
in-drug-discovery-1-edition-chang-liu/
Energy Sources. Fundamentals of Chemical Conversion

Processes and Applications 1st Edition Balasubramanian
Viswanathan
https://ebookmass.com/product/energy-sources-fundamentals-of-
chemical-conversion-processes-and-applications-1st-edition-
balasubramanian-viswanathan/
Introduction to Spatial Mapping of Biomolecules by

Imaging Mass Spectrometry Bindesh Shrestha
https://ebookmass.com/product/introduction-to-spatial-mapping-of-
biomolecules-by-imaging-mass-spectrometry-bindesh-shrestha/
Photoionization and Photo-Induced Processes in Mass Spectrometry
Photoionization and Photo-Induced
Processes in Mass Spectrometry
Fundamentals and Applications
Edited by
Ralf Zimmermann
Luke Hanley
Editors All books published by Wiley-VCH
are carefully produced. Nevertheless,
Ralf Zimmermann authors, editors, and publisher do not
Helmholtz Zentrum München warrant the information contained in
Institut für Ökologische Chemie these books, including this book, to
Ingolstädter Landstr. 1 be free of errors. Readers are advised
85764 Oberschleißheim to keep in mind that statements, data,
Germany illustrations, procedural details or other
items may inadvertently be inaccurate.
Luke Hanley
University of Illinois Library of Congress Card No.:
Department of Chemistry applied for
United States
British Library Cataloguing-in-Publication
Cover Images: Courtesy of Jonathan Data
Aldrich, The University of Illinois at A catalogue record for this book is
Chicago available from the British Library.
Bibliographic information published by

the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists
this publication in the Deutsche
Nationalbibliografie; detailed
bibliographic data are available on the
Internet at <http://dnb.d-nb.de>.
© 2021 WILEY-VCH GmbH,

Boschstr. 12, 69469 Weinheim,
Germany
All rights reserved (including those of

translation into other languages). No
part of this book may be reproduced in
any form – by photoprinting,
microfilm, or any other means – nor
transmitted or translated into a
machine language without written
permission from the publishers.
Registered names, trademarks, etc. used
in this book, even when not specifically
marked as such, are not to be
considered unprotected by law.
Print ISBN: 978-3-527-33510-7

ePDF ISBN: 978-3-527-68223-2
ePub ISBN: 978-3-527-68222-5
oBook ISBN: 978-3-527-68220-1
Cover Design: Wiley

Typesetting SPi Global, Chennai, India
Printing and Binding
Printed on acid-free paper
10 9 8 7 6 5 4 3 2 1
v
Contents
Preface xi
1 Fundamentals and Mechanisms of Vacuum Photoionization 1

Johannes Passig, Ralf Zimmermann, and Thomas Fennel
1.1 Preface 1
1.2 Light 2
1.3 Photoabsorption 5
1.3.1 Transitions in First Order Perturbation Theory 5
1.3.2 Perturbation Theory 6
1.3.3 Absorption 7
1.3.4 Dipole Approximation 9
1.3.5 Selection Rules 11
1.3.6 Electronic Line Width and Lifetime 11
1.3.7 Electronic Transitions of Molecules 13
1.3.8 Single-photon Ionization (SPI) 15
References 20
2 Fundamentals and Mechanisms of Resonance-Enhanced

Multiphoton Ionization (REMPI) in Vacuum and its Application
in Molecular Spectroscopy 23
Ulrich Boesl and Ralf Zimmermann
2.1 Introductory Remarks 23
2.2 Beginnings of REMPI 25
2.3 Principle of REMPI: Rate Equations and Quantification of Detection
Efficiency 29
2.3.1 Rate Equations 29
2.3.2 Quantification of the REMPI Detection Efficiency 31
2.3.3 Special Situations and Problems in REMPI Processes and
Countermeasures 33
2.3.3.1 Situation (A): Too energetic ionization threshold 34
2.3.3.2 Situation (B): Too energetic intermediate state 35
2.3.3.3 Situation (C): Too small FC-factors 36
2.3.3.4 Situation (D): Too fast relaxation of intermediate state 37
2.4 REMPI and Dissociation 40
vi Contents
2.5 Application of REMPI for Optical Spectroscopy 45

2.5.1 Effusive Gas Beam Molecules at Room or Elevated Temperature:
REMPI Spectra with Medium Optical Selectivity 45
2.5.2 Supersonic Gas Beams for Cold Molecules: REMPI Spectra with High
Optical Selectivity for Discrimination of Structural Isomers and
Spectroscopic Studies on the Transition State 48
2.5.2.1 REMPI Spectroscopy of Jet-Cooled Biphenylene 50
2.5.2.2 REMPI Spectroscopy of Jet-Cooled Dibenzo-p-dioxin and Its
Derivatives as well as of [2,2]-Paracyclophane 61
2.5.3 Supersonic Gas Beams for Cold Molecules: REMPI Spectra with High
Optical Selectivity for Discrimination of Isotopomers 67
2.5.4 Chiral Molecules: Discrimination of Enantiomers by Enantioselective
REMPI Spectroscopy 69
2.5.5 Advanced Photoelectron Spectroscopy Based on REMPI: The PES,
TPES, ZEKE, MATI, Anion-PES, and Anion-ZEKE Approaches 72
References 79
3 Analytical Application of Single-Photon Ionization Mass

Spectrometry (SPI-MS) 89
Thorsten Streibel, Hendryk Czech, and Ralf Zimmermann
3.1 VUV Light Sources 89
3.2 Lamp-Based VUV Light Sources 90
3.3 Laser-Based VUV Light Sources 92
3.4 Mass Spectrometry with Lamp or Laser-Based VUV Light
Sources 94
3.5 On-line Analysis of Complex Mixtures by Single-Photon Ionization
(SPI) Mass Spectrometry 95
3.6 SPI-MS in Hyphenated Applications 107
3.7 Ambient Monitoring 117
3.8 Commercial Solutions 118
References 119
4 Analytical Application of Resonance-Enhanced Multiphoton

Ionization Mass Spectrometry (REMPI-MS) 125
Thorsten Streibel, Ulrich Boesl, and Ralf Zimmermann
4.1 Investigation of Model Flames 129
4.2 Applications to Internal Combustion Engines 130
4.3 Monitoring Combustion Process Emissions in an Industrial
Environment 135
4.4 Further Applications of REMPI Mass Spectrometry 138
4.5 REMPI-MS in Hyphenated Analytical Systems 142
4.6 Commercial REMPI-MS Solutions and Applications 150
References 152
Contents vii
5 Probing Chemistry at Vacuum Ultraviolet Synchrotron Light

Sources 159
Kevin R. Wilson and Fei Qi
5.1 Introduction 159
5.2 Combustion Chemistry 162
5.2.1 Pyrolysis in Flow Reactor 163
5.2.2 Jet-Stirred Reactor Oxidation 166
5.2.3 Premixed Flames 167
5.2.3.1 Low-Pressure Laminar Premixed Flame 167
5.2.3.2 Atmospheric Pressure Laminar Premixed Flame 171
5.2.4 Coflow Diffusion Flame 173
5.2.5 Biomass/Coal Pyrolysis 174
5.3 Isomer-Resolved Studies of Elementary Chemical Reactions 176
5.3.1 Multiplexed Chemical Kinetics Photoionization Mass
Spectrometer 177
5.3.2 Shock Tube Kinetics 179
5.3.3 Pyrolysis Reactors 180
5.3.3.1 Bimolecular Kinetics 181
5.3.3.2 Unimolecular Kinetics 181
5.3.4 Low-Temperature Elementary Reactions in a Pulsed Laval
Nozzle 182
5.4 Summary 186
5.4.1 Atmospheric Aerosol Chemistry 188
5.4.1.1 Aerosol Mass Spectrometry 189
5.4.1.2 Gas Chromatography and SVUV Photoionization Mass
Spectrometry 195
5.4.2 Future Outlook 202
Acknowledgments 203
References 203
6 Resonance Ionization Mass Spectrometry (RIMS):

Fundamentals and Applications Including Secondary Neutral
Mass Spectrometry 215
Michael Savina and Reto Trappitsch
6.2 Resonance Ionization Fundamentals 217
6.2.1 Laser Spectroscopy 217
6.2.2 Selection Rules 220
6.2.3 Odd–Even Effect 222
6.3 Reduction to Practice 224
6.3.1 Laser Selection 224
6.3.2 Mass Spectrometer Selection 225
6.3.3 Laser Overlap 229
6.4 Applications 230
6.4.1 Useful Yield and Abundance Sensitivity 231
viii Contents
6.4.2 Stardust Grains 234

6.4.3 Multielement Analysis 236
6.4.4 Electronic Processes During Vaporization 238
6.5 Resources 240
References 241
7 Ultrashort Pulse Photoionization for Femtosecond Laser Mass

Spectrometry 245
Cornelius L. Pieterse, Jason M. Gross, and Luke Hanley
7.2 Mechanisms of Ultrashort Pulse Photoionization 246
7.3 Studies of Amino Acids, Dipeptides, and C60 Leading to Advanced SFI
Models 249
7.4 Volumetric Intensity Dependence and Multiply Charged Ions 251
7.5 Direct and Gas Chromatography-Coupled Analysis of Explosives 253
7.6 Gas Chromatography-Coupled Analysis of Polyaromatic
Hydrocarbons, Pesticides, and Fragrances 255
7.7 Laser Secondary Neutral Mass Spectrometry 256
7.8 Conclusions 259
Acknowledgments 260
Disclosure Statement 260
References 261
8 Photoionization at Elevated or Atmospheric Pressure:

Applications of APPI and LPPI 267
Tiina J. Kauppila and Jack Syage
8.2 Atmospheric Pressure Photoionization 267
8.2.1 Atmospheric Pressure Photoionization Ion Source 267
8.2.2 General Principles of Atmospheric Pressure Photoionization 268
8.2.2.1 Ionization Mechanism in Positive Ion APPI 268
8.2.2.2 Effect of the Dopant 270
8.2.2.3 Ionization Mechanism in Negative Ion APPI 271
8.2.3 APPI in Liquid Chromatography Mass Spectrometry 272
8.2.4 APPI in Gas Chromatography Mass Spectrometry 274
8.2.5 APPI As an Interface for Capillary Electrophoresis Mass
Spectrometry 277
8.2.6 APPI in Multimode Ion Sources 278
8.2.7 Ambient Mass Spectrometry Utilizing Photoionization 278
8.3 Low-Pressure Photoionization (LPPI) 279
8.4 Applications of APPI and LPPI 281
8.4.1 Drugs, Pharmaceuticals, and Metabolites 281
8.4.2 Steroids 288
8.4.3 Other Endogenic Compounds 288
8.4.4 Plant Research 289
8.4.5 Environmental Monitoring 289
Contents ix
8.4.6 Oil Analysis 291

8.4.7 Food Analysis 291
8.5 Conclusions 292
Acknowledgments 292
References 292
9 Fundamentals of Laser Desorption Ionization 305

Fabrizio Donnarumma, Kermit K. Murray, and Luke Hanley
9.2 Experimental and Computational Parameters and Observables 306
9.3 General Mechanistic Considerations 307
9.4 Laser-Induced Thermal or Acoustic Desorption of Neutrals from
Metal Surfaces 307
9.5 Molecular Resonantly Enhanced Desorption: UV-MALDI and
IR-LA 309
9.5.1 MALDI with UV Lasers 310
9.5.2 Nanosecond to Picosecond IR Laser Ablation 313
9.6 Nanophotonic Desorption 314
9.7 Femtosecond Laser Ablation 315
9.8 Internal Energy Transferred by LDI and Supersonic Cooling 317
9.9 Conclusions 318
Acknowledgments 319
References 319
10 Applications of Laser Desorption Ionization and Laser

Desorption/Ablation with Postionization 327
Yeni P. Yung, Fabrizio Donnarumma, Kermit K. Murray, and Luke Hanley
10.1 Nature of Samples and Information to be Gained from Laser
Desorption and Laser Ablation Mass Spectrometry 327
10.2 Laser Ablation and Laser Desorption Ionization MS for Elemental
Analysis 328
10.3 Nonimaging MALDI-MS for Molecular Analysis 329
10.3.1 Qualitative and Quantitative Performance for Different Types of
Analytes 329
10.3.2 Peptides, Proteins, Lipids, and Sugars 330
10.3.3 DNA and RNA 330
10.3.4 Polymers 331
10.4 MALDI-MS Imaging for Molecular Analyses 332
10.5 Example of Standard MALDI-MS vs. Imaging Mode: Pseudomonas
aeruginosa 333
10.6 MALDI Alternatives: Matrix Free, Ambient, Nanostructure Induced,
and High Energy 335
10.7 Molecular LD/LA-MS Beyond Nanosecond UV Lasers 336
10.8 Laser, Electrospray, and Other Postionization of Plumes Formed by
LD/LA 337
x Contents
10.8.1 LDPI-MS: Laser Desorption Postionization of Neutrals in

Vacuum 337
10.8.2 Postionization Coupled to LD/LA at Elevated Pressures 340
10.9 Laser Ablation Sampling for Solid or Liquid Collection 341
10.9.1 Laser Ablation Sampling with Online MS Analysis 342
10.9.2 Laser Ablation Sampling with Off-line Analysis 343
10.10 Conclusions 344
Acknowledgments 345
References 345
11 Laser Ionization in Single-Particle Mass Spectrometry 359

Johannes Passig and Ralf Zimmermann
11.1 Relevance of Atmospheric Aerosols for Climate and Health – The
Single-particle Perspective 359
11.2 Analysis of Individual Particles by Laser Ionization MS – Historical
Development and Basic Principle 362
11.3 Ionization in Single-Particle Mass Spectrometry: Laser
Desorption/Ionization (LDI) 365
11.3.1 Single-Particle LDI – The Physical Framework 366
11.3.2 Laser Light Sources for LDI 371
11.3.3 Chemical Quantification Approaches for LDI 372
11.4 Ionization in SPMS: Laser Photoionization of Previously Desorbed
Species 373
11.5 Instrumental Realizations 381
11.5.1 Mass Analyzers 381
11.5.2 Aerosol Inlet 383
11.5.3 Particle Sizing 384
11.6 Data Evaluation 386
11.7 Applications 387
11.7.1 Ambient Aerosols in Urban and Densely Populated Areas 387
11.7.2 Ambient Aerosols in Rural and Marine Environments 388
11.7.3 Aircraft-Based Studies 389
11.7.4 In Situ Characterization of Cloud and Ice Condensation Nuclei 389
11.7.5 Focus on Organic Compounds 390
11.7.6 Bioaerosols 392
11.7.7 Combustion Aerosols 392
11.8 Commercial Laser Ionization Single-Particle Mass Spectrometry
Systems 393
References 394
Index 413
xi
Preface
The goal of this book is to explain the fundamentals of photoionization (PI) and
the associated applications of PI that are playing an increasingly important role
in mass spectrometry (MS). The target audience of this book includes practic-
ing scientists, including PhD and MSc students, whose primary interest is in the
application of PI to elemental or molecular analysis by mass spectrometry. An
overly simplistic analysis provides several motivations for the use of PI in mass
spectrometry:
1. Enhance ion yields for specific important compounds of substance classes
where other ionization strategies have proven insufficient,
2. Selectively ionize individual molecular structures or classes of molecules from
mixtures,
3. Form ions from neutrals with reduced or controlled degree of fragmentation,
and
4. Induce desorption or ablation of solids for sampling.
Photoionization comes in different versions and technological realizations,
making it somewhat more complicated and thus less popular than standard
ionization methods in mass spectrometry such as electrospray ionization and
electron ionization. Nevertheless, one goal of this book is to demonstrate how
these and other motivations drive the use of PI in MS-based analyses. The editors
and authors hope that the readers will use this work as a series of building blocks
for future advances in this promising area.
Actually, PI was central to the early development of mass spectrometry and
single photon ionization (SPI) remains perhaps the best method for introducing
a well-defined amount of internal energy into a molecular ion. Early work in
SPI used vacuum ultraviolet (VUV) gas discharge lamps. However, the advent
of lasers and the associated nonlinear optical methods made multiphoton
ionization (MPI) possible, dramatically expanding PI as a fundamental strategy
to probe molecular structure. The continuing improvement of laser technology
has also created ongoing opportunities for MS-based applications of PI. For
example, MPI via the excimer laser-pumped dye laser was deployed in many
early fundamental studies, but was costly, difficult to use, and relatively unre-
liable. However, the development of smaller and rugged, field-deployable laser
sources, such as compact excimer lasers, solid-state lasers as Nd:YAG lasers with
integrated harmonic generation, and tunable solid-state lasers such as sealed,
xii Preface
Nd:YAG-pumped optical parametric oscillators (OPOs) or Ti:sapphire cavities

rendered MPI sufficiently robust for more widespread MS applications.
This interplay between fundamental methods and instrumental considerations
has driven the development of analytical applications of PI, so attention is paid
here to both considerations. Photodissociation is only discussed here when it
occurs in conjunction with PI, such as via the formation of fragment ions from
neutral precursors during MPI or SPI. Thus, the burgeoning use of photodisso-
ciation of the precursor or molecular ions to form fragment ions for structural
elucidation of the former is not discussed here. The fundamentals and mecha-
nisms of low pressure, gas-phase molecular PI for mass spectrometry is covered
in Chapters 1, 2, 5, and 7, while molecular atmospheric pressure PI is a topic in
Chapter 8. Applications and experimental methods of low-pressure, gas-phase
photoionization mass spectrometry (PIMS) are presented in Chapters 3, 4, and 7.
Elemental analysis by PI is covered exclusively in Chapter 5. Processes and appli-
cations that include a laser desorption (LD) or direct laser desorption/ionization
(LDI) of analytes from the condensed phase are covered in Chapters 9 and 10,
while Chapter 11 focuses on the direct analysis of individual aerosol particles
using LDI, LD, and PI.
In the following, the content of the book is briefly highlighted chapterwise.
The first chapter entitled FUNDAMENTALS and MECHANISMS of VACUUM
PHOTOIONIZATION, is serving as an introduction to mechanistic issues com-
mon to PI of molecules, atoms, and clusters under vacuum. It provides a funda-
mental description of light and the interaction of light and matter in the form of
photoabsorption on a quantum mechanical level. This includes an excursion in
perturbation theory and the dipole approximation and leads to an elucidation of
the photon absorption selection rules. Finally, the SPI process, as an absorption
in a continuum, nonbound state, is discussed and the most important parameters
for SPI, the SPI cross sections and ionization energies, are deducted.
Fundamental aspects of MPI of molecules in the absence of gas-phase col-
lisions are covered in the following chapter, entitled FUNDAMENTALS and
MECHANISMS of RESONANCE-ENHANCED MULTIPHOTON IONIZA-
TION ( REMPI) in VACUUM and APPLICATION of REMPI for MOLECULAR
SPECTROSCOPY (Chapter 2). Here, the theoretical consideration of pho-
toionization processes is extended to MPI processes of molecular species and
MPI-based spectroscopy, while multiphoton ionization of atoms is covered
in Chapter 6. Different MPI and REMPI processes are presented and a rate
equation approach is used to deduct the influence of molecular physical proper-
ties on ionization efficiency. Special REMPI schemes are discussed, which can
bypass unfavorable photophysical properties. In the following, MPI-induced
fragmentation and dissociation processes are discussed. The application of
REMPI for molecular spectroscopy with and without supersonic jet cooling is
demonstrated in an exemplary manner via a detailed discussion of the REMPI
wavelength spectrum of supersonic jet-cooled biphenylene and some other
interesting aromatic molecules. REMPI wavelength spectroscopy, in particular
with supersonic jet cooling, reveals the selectivity of the REMPI process that
connects high-resolution ultraviolet (UV) spectroscopy to mass spectrometry.
The selective ionization of isomeric and isobaric compounds, however, can be
Preface xiii
extended to the differentiation of isotopomers and – by using a special REMPI

technique with circular polarized laser light – even of enantiomers. Finally, in
this chapter, REMPI-based photoelectron spectroscopic (PS) techniques such as
zero kinetic energy photoelectron spectroscopic (ZEKE-PS) are introduced. The
explanation of the fundamental aspects of SPI and REMPI leads to the analytical
application of these two PI approaches.
In the beginning of Chapter 3, which is entitled “ANALYTICAL APPLICA-
TIONS of SINGLE-PHOTON IONIZATION MASS SPECTROMETRY ,” a brief
introduction into common VUV–light sources, is given. These can be distin-
guished as incoherent light sources (“lamp”-based technologies) or coherent
light sources (lasers). Also, a brief introduction to the generation of synchrotron
light in the VUV range is elaborated (for applications of synchrotron-based
SPI, see Chapter 5). The general setup of SPI mass spectrometry systems with
laser- and lamp-based sources is introduced. Depending on the used VUV
wavelengths, SPI can be a very soft ionization method, enabling the detection
of the molecular mass fingerprint of complex mixtures. This renders SPI-MS
to an ideal approach for direct real time monitoring of complex gas and vapor
mixtures. Different applications for online monitoring of combustion and pyrol-
ysis processes are introduced, including online monitoring of gas phases from
industrial processes, such as the coffee-roasting and/or the biomass pyrolysis
process. Hyphenated instrumental analytical concepts, e.g. gas chromatography
(GC) or thermal analysis (TA) coupled to SPI mass spectrometry, are presented
and typical results are shown.
Chapter 4, “ANALYTICAL APPLICATION of RESONANCE-ENHANCED
MULTIPHOTON IONIZATION MASS SPECTROMETRY ( REMPI-MS),” gives,
in a similar way as Chapter 3 for SPI, an overview of analytical applications of
REMPI mass spectrometry. The preferential detection of aromatic analytes by
the REMPI process with common laser is emphasized in Chapter 3. An overview
on typical fixed-frequency laser lines (excimer lasers or frequency-multiplied,
solid-state lasers) is provided along with typical wavelength ranges of tunable
laser systems. In the following, several exemplary analytical concepts and
applications using tunable and fixed-frequency lasers are presented. The tunable
laser sources can be used to focus on specific analytes, which work particularly
well with supersonic jet expansion inlet systems. For many applications, how-
ever, fixed-frequency wavelength laser and effusive, heated gas inlets can be
applied for a useful and often very sensitive “overview” MS-profiling of many
aromatic compounds. Exemplary process monitoring applications comprise
detection of combustion by-products in flue gases of incineration plants or
flavor and roast degree, indicating compounds in coffee-roasting off-gas.
Hyphenated instruments connecting gas chromatography or a thermo-optical
carbon analyzer (for aerosol loaded filters) to REMPI-MS devices are discussed.
A direct inlet of liquid samples into REMPI mass spectrometry is possible via
a membrane inlet or a direct liquid introduction into the ion source. Note that
SPI and REMPI processes can be performed in the same MS system. Finally,
REMPI under atmospheric conditions is discussed (atmospheric pressure laser
ionization – APLI; see also Chapter 8 for SPI-based atmospheric pressure-based
ionization).
xiv Preface
The application of synchrotron VUV light for SPI-MS-based investigation of

combustion and pyrolysis processes is laid out in Chapter 5, “PROBING CHEM-
ISTRY AT VACUUM ULTRAVIOLET SYNCHROTRON LIGHT SOURCES.”
By direct molecular beam sampling from flames as well as from oxidation or
pyrolysis reactors, molecules from the reaction zone can be directly introduced
in the mass spectrometer without wall contact. This enables the analysis of stable
molecules and intermediates from the reaction zones. The flow reactors and
model flame apparatus is often compact enough to be brought to synchrotron
light source facilities and can be used for kinetic investigations. Unlike classical
VUV sources, the synchrotron light from appropriate beamlines (i.e. equipped
with VUV monochromators) exhibit a wide tunability, high energy resolution,
and a relatively high photon flux. The identification of individual compounds
from isobaric mixture components is possible by photoionization efficiency
(PIE) spectroscopy, i.e. the recording of the ion yield as a function of the VUV
wavelength. Chapter 5 also presents, an overview on different synchrotron-based
PIMS apparatus and analytical results for several reactors and applications.
REMPI of atoms is commonly referred to as “resonance ionization mass
spectrometry (RIMS). The RIMS technology and applications are described
in the Chapter 6, RESONANCE IONIZATION MASS SPECTROMETRY
(RIMS): FUNDAMENTALS AND APPLICATIONS INCLUDING SECONDARY
NEUTRAL MASS SPECTROMETRY . Unlike in molecules, atomic transitions
are very narrow and thus very high ionization efficiencies can be achieved. Laser
spectroscopic principles, atomic selection rules, and the principle setup of RIMS
instruments are discussed. In many cases, two or more tunable lasers are required
for high-resolution RIMS. This high effort, however, in many cases allows even
an isotope-selective ionization and the suppression of nearly all interferences.
Applications are focusing on the analyses of ultratraces of radioactive elements
in the environment (e.g. plutonium fall out) or the characterization of very
precious samples such as stardust grains.
MPI is often performed with nanosecond laser pulses, but shortening the
pulses into the subpicosecond regime can fundamentally change the ionization
process, as discussed in Chapter 7, “ULTRASHORT PULSE PHOTOIONIZA-
TION for FEMTOSECOND LASER MASS SPECTROMETRY ”. The mechanisms
of ultrashort pulse ionization, in particular nonresonant multiphoton ionization
(NRMPI) and strong field ionization (SFI), are elucidated. One advantage of
ultrashort pulse ionization is to overcome problems in REMPI ionization caused
by the short lifetime of intermediated states (see also Chapter 2). Thus, for
example, molecular ions of explosives, such as trinitrotoluene (TNT), which
exhibit an unstable S1 state due to fast predissociation (NO-cleavage from nitro
groups), can be obtained by a fs-laser ionization process. In addition to gas-phase
ionization, ultrashort pulse ionization is also beneficial for postionization of
neutrals to enhance ion signal in secondary ion mass spectrometry (SIMS) or
laser desorption (LD)-based mass spectrometry.
Mass spectrometry of samples at ambient pressure has become a major applica-
tion, which is served by atmospheric pressure photoionization (APPI) using VUV
for induction of the ionization process. Chapter 8, “PHOTOIONIZATION at
ELEVATED or ATMOSPHERIC PRESSURE: APPLICATION of APPI and LPPI,”
Preface xv
is devoted to such ionization mechanisms at elevated pressures and their

experimental implementation. Furthermore, some characteristic applications of
APPI are shown. The higher pressures during APPI allow abundant gas-phase
ion-molecule and molecule-molecule collisions that finally lead to energy and/or
charge transfer in the APPI process. Therefore, very high sensitivities can be
observed in APPI. However, although such secondary chemical ionization
processes often are dominating the ionization process, APPI is commonly seen
as a photoionization technology, although the term “photoinduced chemical
ionization” may better describe the APPI process in many cases. In addition to
SPI, the REMPI process can also be used to initiate ionization under atmospheric
conditions (atmospheric pressure laser ionization, APLI, see Chapter 4).
Laser irradiation of condensed phase matter can also lead to PI as well as
other energy transfer events that in turn lead to desorption and/or ablation
that is widely used for sampling. Although this book is focusing on pho-
toionization processes in vacuum or in the gas phase, laser desorption-based
processes and applications in mass spectrometry are not be excluded. Chapter 9,
“FUNDAMENTALS of LASER DESORPTION/IONIZATION,” introduces the
mechanisms of laser desorption/ionization (LDI) and matrix-assisted laser
desorption/ionization (MALDI), while Chapter 10, “APPLICATIONS OF LASER
DESORPTION IONIZATION AND LASER DESORPTION/ABLATION WITH
POSTIONIZATION,” introduces the corresponding applications. The MALDI
approach for ionization of biopolymers (e.g. proteins or lipids), polymers, and
other larger molecules is broadly applied, and numerous reviews and book
chapters and whole books have already covered this topic. However, for com-
pleteness, the knowledge on the MALDI process is summarized in Chapter 9,
although more focus is put on less common strategies such as fs-laser ablation.
In the laser desorption applications discussed in Chapter 10, in addition to the
molecular detection also, MALDI imaging applications are considered and a
focus is put on the approaches using postionization of laser desorbed neutrals.
Finally, Chapter 11, “LASER IONIZATION in SINGLE-PARTICLE MASS
SPECTROMETRY ,” elaborates on an online laser mass spectrometric single
(aerosol)-particle measurement technique, which is based either on the LDI or on
a laser desorption – laser postionization approach. After an introduction to the
historical development of single-particle laser ionization MS systems, the LDI
process is discussed in context of the particle analysis background. This includes
the ionization mechanism, laser sources, and quantification aspects. After the
discussion of approaches based on the laser postionization of molecules des-
orbed from individual particles, instrumental realizations and applications are
presented and discussed.
Finally, we hope that the readers will enjoy and learn from our exposition of
photoionization fundamentals as well as the versatility of the photoionization
mass spectrometry methodology for cutting edge applications.
Ralf Zimmermann Luke Hanley

University of Rostock, Germany University of Illinois, Chicago, USA
1
Fundamentals and Mechanisms of Vacuum Photoionization

Johannes Passig 1,2 , Ralf Zimmermann 1,2 , and Thomas Fennel 3
1 Universität Rostock, Institut für Chemie, Analytical Chemistry and Joint Mass Spectrometry Centre (JMSC),
Dr.-Lorenz-Weg 2, D-18059 Rostock, Germany

2
Helmholtz Zentrum München, German Research Center for Environmental Health GmbH, Research Unit
Comprehensive Molecular Analytics (CMA) and Joint Mass Spectrometry Centre, Gmunder Str. 37, D-81379
München, Germany
3
Institute of Physics, University of Rostock, Albert-Einstein-Straße 23, D-18059 Rostock, Germany
1.1 Preface
Within the past decades, the progress of laser-based light sources have opened
various new research directions in the area of light-matter interactions. The
ionization of free molecules with the purpose of their detection and mass-based
identification may appear as an easy task in this context. However, experience
has shown that already the simplest approach, the fragment-free ionization with
single photons of sufficient energy, remains technically challenging. Beyond
practical issues and applications, advanced photoionization techniques are
an important field of study in spectroscopy and fundamental research. As an
example, resonance-enhanced multiphoton ionization (REMPI, see chapters
2 and 4 of this book) bridges the gap between mass spectrometry (MS) and
molecular spectroscopy, offering two-dimensional selectivity both in mass and
in structure. In general, the absorption of a single photon by a molecule can
lead to its ionization if the photon energy E = h𝜈 = ℏ𝜔 is equal to or larger than
the ionization potential IP , where h = 2𝜋ℏ is the Planck constant, 𝜈 = c∕𝜆 is the
photon frequency; 𝜆 is its wavelength, and c is the speed of light. It is worth to
have a look on the typical energy- and timescales that constitute the framework
of photoionization processes as illustrated in Figure 1.1. Electron motion and
electronic transitions are much faster than atomic motion on molecular scales.
This is the basis for important approximations in atom and molecular physics
and spectroscopy. Current tabletop laser systems are available from infrared
(IR) to ultraviolet (UV), with ultrashort pulses that allow to analyze molecular
processes on their physical or natural timescale. Laser intensities for (multi-)
photoionization MS span the range from the onset of REMPI (≈ 106 W∕cm2 ) to
the strong field regime (> 1014 W∕cm2 ) and beyond for complex laser sources.
Tuning the photon energy remains rather complicated both for lamp- and
laser-based sources. However, the latter implicates further parameters as phase
Photoionization and Photo-Induced Processes in Mass Spectrometry: Fundamentals and Applications,

First Edition. Edited by Ralf Zimmermann and Luke Hanley.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
2 1 Fundamentals and Mechanisms of Vacuum Photoionization
Energy XUV VUV VIS IR Microwave

spacing of
microscopic
103 100 10–3 10–6
Energy (eV)
processes
Microscopic Outer shell/
Molecular Molecular el. state ro.-vib.
processes valence band
vibration rotation lifetimes lifetimes
electrons
Technical VUV attosecond Ti:Sapphire Nd:YAG/Excimer Pulsed TOF-MS

processes laser pulse fs laser pulse ns laser pulse lamps cycle
Timescale
10–18 10–15 10–12 10–9 10–6 Time (s) 10–3
Figure 1.1 Typical energy- and timescales of processes related to photoionization.
or chirp, which are linked to the coherence of laser pulses and are likely to
increase the selectivity in future applications.
When dealing with photoionization MS, natural questions about the under-
lying mechanisms of photoabsorption and photoionization arise at some point.
A brief standard answer might be as follows: Assume two eigenstates of a molec-
ular system with different electronic charge distributions. Upon excitation from
the lower to the upper state and assuming a single active electron, the system
corresponds to a quantum superposition of those two states and the electronic
charge oscillates with an amplitude that reflects the transition dipole moment.
Now, assume a light field acting on it. Thus, the electron “feels” an oscillating
electric field from the light. If the frequencies, direction (polarization), and shape
of charge distribution associated with a transition, match the light field and the
molecule couple and the electron will be resonantly driven into the excited state
while the light wave is damped. If the excited state is a continuum state, the elec-
tron is ejected.
This description provides a basic, phenomenological understanding, and
some readers consider now to skip the following pages with complicated
formulas. However, it is a problematic simplification, mixing different concepts
and principles. The following section will provide an introductory survey on
photoabsorption, being the physical basics of photoionization. The scope is not
to treat the full complexity of optics and spectroscopy but to give an outline of
some fundamental principles being useful for its conceptual understanding.
1.2 Light
The physics of classical light propagation, optics, and electromagnetism is based
on the Maxwell equations, a set of partial differential equations that describe the
behavior of the electric field E(r, t) and the magnetic field B(r, t) with respect to
charges 𝜌 and currents j:
𝛁 ⋅ E(r, t) = 𝜌(r, t)∕𝜖0 (1.1)
𝛁 ⋅ B(r, t) = 0 (1.2)
𝜕
𝛁 × E(r, t) = − B(r, t) (1.3)
𝜕t
𝜕
𝛁 × B(r, t) = 𝜇0 j + 𝜇0 𝜖0 E(r, t) (1.4)
𝜕t
1.2 Light 3
𝜕F 𝜕F 𝜕F
The divergence 𝛁 ⋅ F = 𝜕xx + 𝜕yy + 𝜕zz of a vector field F produces a scalar field,
giving the quantity of F’s source (outward flux) at each point. An expanding vec-
tor field (e.g. heated air) yields positive divergence values, whereas a contracting
one (e.g. cooled air) yields negative values. The curl 𝛁 × F yields a vector field that
describes the infinitesimal rotation of F at each point, e.g. the circulation density
of a flow.
Fundamental properties of light can be derived from this set of equations. Later,
we will have to construct a Hamiltonian to describe photoabsorption. Because
it represents the system total energy in quantum mechanics, it will be natural
to use potentials rather than fields. In electrostatics, the field is related to the
electrostatic potential through
E(r) = −𝛁Φ(r) (1.5)
However, for a field that varies in time and in space, the electrodynamic potential
must be expressed in terms of both the time-dependent scalar potential 𝜙(r, t)
and the vector potential A(r, t). According to Eq. (1.5), the fields E(r, t) and
B(r, t) can be expressed as
𝜕
E(r, t) = −𝛁𝜙(r, t) − A(r, t) (1.6)
𝜕t
B(r, t) = 𝛁 × A(r, t) (1.7)
This definition automatically fulfills Eqs. (1.2) and (1.3). Furthermore, it
allows a transformation of the potentials into Coulomb gauge, where A is
divergence-free (𝛁 ⋅ A = 0), whereas the physical observables E(r, t) and B(r, t)
remain unchanged (not shown here). In Coulomb gauge, the scalar potential is
identical with the Coulomb potential, yielding 𝜙 = −𝜌∕𝜀0 for Eq. (1.1). Further-
more, if charges and currents are absent, only Eq. (1.4) determines A (and thus
E and B) in the following form of a wave equation:
1 𝜕2 1
𝛁2 A(r, t) − A(r, t) = 0 with c2 = √ (1.8)
c 𝜕t
2 2
𝜇 0 𝜖0
Solutions are linearly polarized plane waves
1
A(r, t) = Ã𝜀ei(k⋅r−𝜔t)+𝛿 + c.c. = Ã𝜀 cos(k ⋅ r − 𝜔t + 𝛿) (1.9)
2
with amplitude Ã, polarization vector 𝜀, imaginary unit i, wave vector k, angu-
lar frequency 𝜔, and phase offset 𝛿. Several primary properties of light can now
be derived, such as the dispersion relation 𝜔 = ck when inserting the solution
into Eq. (1.8) or the orthogonality of wave and polarization vectors k ⋅ 𝜀 = 0 that
directly results from the gauge condition 𝛁 ⋅ A = 0. The electric and magnetic
fields follow as plane waves, mutually orthogonal also with the propagation direc-
tion due to the vector product k × 𝜀
̃ sin(k ⋅ r − 𝜔t + 𝛿)
E(r, t) = E𝜀 (1.10)
Ẽ
B(r, t) = (k × 𝜀) sin(k ⋅ r − 𝜔t + 𝛿) (1.11)
𝜔
E Figure 1.2 Illustration of a linearly

polarized light wave as a solution of
Eq. (1.8) with mutually orthogonal electric
ε
field E, magnetic field B, and propagation
B S as well as energy transport in direction of
the Poynting vector S. Polarization vector 𝜀.
Eq. (1.16).
with Ẽ = −𝜔Ã. A key parameter for many applications is the light intensity,
respectively the photon density. They follow from the (instantaneous) energy
density of the electromagnetic field
[ ]
1 1
u= 𝜖 |E | + |B | = 𝜖0 Ẽ 2 sin2 (k ⋅ r − 𝜔t + 𝛿)
2 2
(1.12)
2 0 𝜇0
The rapid oscillations can be averaged as ⟨sin2 ⟩ = 1∕2, yielding the mean energy
that can alternatively be expressed in terms of the photon density nph = dNph ∕dV
1 ̃2
⟨u⟩ = 𝜖 E = nph ℏ𝜔 (1.13)
2 0
Energy transport by light propagation is characterized using the Poynting vector
1 k
S= E × B = 𝜖0 c Ẽ 2 sin2 (k ⋅ r − 𝜔t + 𝛿) (1.14)
𝜇0 k
The absolute value of its time-average |⟨S⟩| is the commonly used light intensity
(unit W∕m2 )
1 ̃2
I= 𝜖 cE = cnph ℏ𝜔 (1.15)
2 0
Note that the intensity I is proportional to the square of the field (amplitude)
Ẽ 2 . The photon flux 𝜑 (unit photons∕(m2 s)) can be expressed in terms of the
intensity and photon energy or via the photon density nph and the speed of
light c.
I
𝜑= = nph c (1.16)
ℏ𝜔
Next, the general cross section 𝜎 is a coefficient of proportionality between the
rate W of an induced transition and the photon flux
W = 𝜑𝜎(𝜔) (1.17)
with unit megabarn (1 Mb = 10−18 cm2 ).
1.3 Photoabsorption
In classical physics, light absorption is interpreted as damping of a periodic
electric field by dipoles oscillating with opposite phase at the same frequency.
This basic picture provides a descriptive explanation of optical properties and
some fundamental interactions. However, a description of the photoionization
of atoms and molecules is only possible in a quantum mechanical context.
Upon light absorption, a system undergoes a transition from an initial state to
a final state of higher energy with energy difference ℏ𝜔. Because the charge
distributions of the states differ, their coherent superposition results in an
oscillating dipole that can couple to the light field under appropriate conditions.
1.3.1 Transitions in First Order Perturbation Theory

Some essential principles needed for the quantum mechanical description are the
representation of (electronic) states by wavefunctions Ψ(r, t) and physical observ-
ables by their corresponding operators.
In quantum mechanics, the state |𝜓⟩ of a system can be described by a complex

wavefunction 𝜓(r, t) in coordinate space representation. A physical observable is
represented by a linear operator Ô acting on the state producing a new vector
Ô|𝜓⟩ = |𝜓 ∗ ⟩. If |𝜓⟩ is an eigenstate of an observable, the equation Ô|𝜓⟩ = a ⋅ |𝜓⟩
yields the associated eigenvalues a, corresponding to the value of the observable
in that eigenstate. Eigenvalues a can be continuous (e.g. for the position operator
r̂ ) or discrete as for the angular momentum operator and thus be expressed by
quantum numbers.
The time evolution of a physical system is described by solutions of the

time-dependent Schrödinger equation (TDSE) in its general form
𝜕 ̂
iℏ Ψ(r, t) = HΨ(r, t) (1.18)
𝜕t
where i is the imaginary unit, ℏ is the Planck constant, and Ĥ is the Hamiltonian
operator representing the system’s total energy.
An analytical solution is only possible for very simple systems, such as the hydro-
gen atom. Already the presence of an external field or a second electron renders
closed and analytical solutions impossible. Typically, several approximations allow
for the treatment of a molecular system with minimum deficiency, depending on
the framework of the scientific problem. Common approaches for atom-light inter-
actions apply the single active electron approximation (SAE) that treats a single
interacting electron in an effective potential (e.g. Hartree-Fock) resembling both
the atomic core and the (mean) electron-electron interactions.
In general, photoionization can be understood as one of several possible

secondary processes upon photoabsorption. For the weak field regime1 , which
applies even beyond typical REMPI intensities of about 107 W∕cm2 , the
description of photoabsorption is convenient via perturbation theory. Its basic
concept is the partition of the Hamiltonian Ĥ into the calculable Hamiltonian
Ĥ 0 of a simplified and known system (which may be artificial) and an addi-
tional Hamiltonian Ĥ ′ representing the weak disturbance to the system that is
quantified using approximate methods.
1.3.2 Perturbation Theory

For our basic considerations of photoabsorption via electronic states, we describe
an atom by a single electron of charge q = e and mass me = m in a Coulomb
potential VC = −Ze2 ∕4𝜋𝜖0 r, which represents a stationary nucleus. The vector
potential remains classical. Considering that in Coulomb gauge, the scalar poten-
tial equals VC (see Section 1.2), the Hamiltonian of the electron splits into a
stationary part of the undisturbed atom Ĥ0 and a time-dependent part Ĥ int (t)
for the interaction with the light field. Ĥ int (t) can be derived from the classical
Hamiltonian for a charged particle in a radiation field (not shown here)
ℏ2 2 e q2 2
Ĥ = − 𝛁 + Vc − iℏ A ⋅ 𝛁 + A (1.19)
2m m 2m
⏟⏞⏞⏞⏞⏞⏟⏞⏞⏞⏞⏞⏟ ⏟⏞⏞⏞⏞⏞⏞⏞⏞⏞⏞⏞⏟⏞⏞⏞⏞⏞⏞⏞⏞⏞⏞⏞⏟
Ĥ 0 Ĥ int (t)
For the first term Ĥ 0 , the analogy to the corresponding classical total energy Ekin +
p2 𝜕
V = 2m + V is clearly visible, if the notation of the momentum operator p̂ = −iℏ 𝜕x
is considered.
For moderate field strengths (I ≪ 1015 W∕cm2 ), the last term is small com-
pared to the cross term, which simplifies the interaction Hamiltonian Hint to
e
Hint ≈ −iℏ A ⋅ 𝛁 (1.20)
m
According to perturbation theory, the wavefunction Ψ(r, t) can be expressed
as a linear combination of unperturbated eigenstates Ψ(r) of the stationary
Schrödinger equation (time-independent Hamiltonian) H0 Ψj (r) = Ej Ψj (r) with
the time-dependent coefficients cj (t)
∑
Ψ(r, t) = cj (t)Ψj (r)e−iEj t∕ℏ (1.21)
j
1 The term “weak disturbance” indicates an important limitation for laser-based photoionization:
The external laser field, treated as perturbation, has to be small against the inner atomic forces.
Thus, laser intensities exceeding 1012 W∕cm2 and molecular interactions induced thereby are often
referred to as “nonperturbative” (Baumert and Gerber 1997), while typical intensities for
single-photon ionization (SPI) and REMPI applications are below 108 W∕cm2 .
Inserting in the TDSE (Eq. (1.18)) yields

∑ d ∑
(iℏ cj (t) + Ej )e−iEj t∕ℏ |Ψj ⟩ = (Ek + Hint (t))ck (t)e−iEk t∕ℏ |Ψk ⟩ (1.22)
j
dt k
The “ket” vector |Ψ⟩ represents the state that is associated with the wavefunction
Ψ(r, t). With the corresponding “bra” vector ⟨Ψ|, that corresponds to the complex
conjugated wavefunction Ψ∗ (r, t) in coordinate space, and with the inner product
⟨Ψ|Ψ⟩ = ∫ Ψ∗ Ψdr and the operator H acting on |Ψ⟩, we can express the expecta-
tion value of the observable (here energy) represented by operator H in the state
|Ψ⟩ by ⟨Ψ|H|Ψ⟩.
Considering the orthogonality of the eigenstates, the result is a set of coupled

equations for the time evolution of coefficients cj (t) with the transition frequency
𝜔jk = (Ej − Ek )∕ℏ:
d 1 ∑
cj (t) = ⟨Ψj |Hint (t)|Ψk ⟩ck (t)ei𝜔jk t (1.23)
dt iℏ k ⏟⏞⏞⏞⏞⏞⏞⏞⏟⏞⏞⏞⏞⏞⏞⏞⏟
jk
Hint (t)
Assuming a two-level system with initial state |Ψa ⟩ and the interaction
Hamiltonian (1.20), the coefficient cb (t) for the state |Ψb ⟩ can be expressed in
the following form.
t t
1 e
⟨Ψb |A ⋅ 𝛁|Ψa ⟩ei𝜔ba t dt ′
′ ′
cb (t) = H ba (t ′ )ei𝜔ba t dt ′ = − (1.24)
iℏ ∫0 int m ∫0
Applying the vector potential A for the electromagnetic field representing the
classic description of light (Section 1.2)
1
A(r, t) = Ã𝜀 cos(kr − 𝜔t + 𝛿) = Ã𝜀[ei(kr−𝜔t+𝛿) + e−i(kr−𝜔t+𝛿) ] (1.25)
2
yields the time-dependent amplitude of state |Ψb ⟩ in first-order perturbation
theory
e t
Ã[ei𝛿 ⟨Ψb |eikr 𝜀 ⋅ 𝛁|Ψa ⟩ ∫0 ei(𝜔ba −𝜔)t dt ′
′
cb (t) = − 2m
⏟⏞⏞⏞⏞⏞⏞⏞⏞⏞⏟⏞⏞⏞⏞⏞⏞⏞⏞⏞⏟
Mba (𝜔)
t
⟨Ψb |e 𝜀 ⋅ 𝛁|Ψa ⟩ ∫0 ei(𝜔ba +𝜔)t dt ′ ]
′
−i𝛿 −ikr
+e (1.26)
The first integral describes the absorption of a photon. Because the complex
e-function is periodic with mean value zero for 𝜔ba ≠ 𝜔, it contributes only for
𝜔ba = 𝜔 ⇒ Eb = Ea + ℏ𝜔 while the second integral corresponds to the photon
emission if 𝜔ba = −𝜔 ⇒ Eb = Ea − ℏ𝜔.
1.3.3 Absorption
The matrix element associated with the perturbation Mba (𝜔) = ⟨Ψb |eikr 𝜀 ⋅ 𝛁|Ψa ⟩
in Eq. (1.26) connects the initial state with the final state and thus determines
the system interaction strength with the light. Before its further evaluation, we
F(ω,t) (a.u.)
e
m
Ti
ωba
Frequency ω
Figure 1.3 Behavior of the function F(𝜔, t) (Eq. (1.28)) that determines the time evolution of
the transition when the field and the system are in resonance. If the light frequency 𝜔 equals
the transition frequency 𝜔ba of the states |Ψa ⟩ and |Ψb ⟩, the function peaks increasingly and
transforms into the 𝛿-function in the long-time limit.
derive corresponding transition rates and cross sections. During absorption, the
occupation probability cb (t) of the state |Ψb ⟩ increases with time, which can be
expressed through integration of the first term in Eq. (1.26)
| e ei(𝜔ba −𝜔)t − 1 ||
2
1 e2 2
|cb (t)|2 = ||− Ãei𝛿 Mba (𝜔) = Ã |Mab (𝜔)|2 F(t, 𝜔)
̃
| 2mi 𝜔ba − 𝜔 || 2 m2
(1.27)
with
1 − cos(𝜔t)
̃
F(t, 𝜔)
̃ = (1.28)
𝜔̃ 2
and the frequency offset 𝜔̃ = 𝜔 − 𝜔ba . As illustrated in Figure 1.3, the transition
probability increases sharply with time according to function (1.28) when the
external field and the system are in resonance, hence 𝜔 = 𝜔ba .
Equations (1.27) and (1.28) describe the evolution of the occupation probability of
state |Ψb ⟩ with time and thus characterize the rate with which transitions appears.
During excitation, the states |Ψa ⟩ and |Ψb ⟩ form a coherent superposition and the
associated dipole oscillates with the transition frequency.
For timescales longer than a cycle (t ≫ 2𝜋∕|𝜔ba |), Eq. (1.28) changes to a delta
̃ ⇒ 𝜋t𝛿(𝜔 − 𝜔ba ) (note: 𝛿(𝜔)
function F(t, 𝜔) ̃ → ∞ for 𝜔̃ → 0). Furthermore, we
express the amplitude Ã of the vector potential by the light intensity I (compare
Eq. (1.15)).
2 2I
Ã = (1.29)
𝜖0 c𝜔2
and find the frequency-dependent absorption rate

𝜋e2 I
Wba (𝜔) = |M (𝜔)|2 𝛿(𝜔 − 𝜔ba ) (1.30)
𝜖0 cm2 𝜔2 ba
So far, we assumed perfectly monochromatic light corresponding to an infinite
plane wave. However, the intensity of realistic light has components covering at
least a narrow band over a frequency range I(𝜔) = dI∕d𝜔; thus, the total absorp-
tion rate has to be integrated over the entire spectrum
Wba = Wba (𝜔)I(𝜔)d𝜔 (1.31)

∫
In the long-time limit, only the value at 𝜔ba contributes to Wba by nature of the
delta function
𝜋e2 I(𝜔ba )
Wba = |Mba (𝜔ba )|2 (1.32)
𝜖0 cm2 𝜔2ba
To express the associated cross section, we use Eq. (1.17)
ℏ𝜔ba Wba = I(𝜔ba )𝜎ba (1.33)
which yields the absorption cross section for the spectral intensity associated
with the considered transition. Note that the unit of the cross section is therefore
area times frequency.
𝜋ℏ e2 1
𝜎ba = |M (𝜔 )|2 (1.34)
𝜖0 c m2 𝜔ba ba ba
Of note, the integration (1.31) assumes a sum of incoherent spectral components.
The treatment of absorption from coherent and ultrashort laser pulses has to con-
sider the explicit pulse waveform.
Molecules typically have numerous states in a small energy interval that con-
tributes to the absorption. Hence, the transition probability into this band is the
sum of all transition probabilities matching the frequency of the incident light.
The number of states in an energy range between Eb and Eb + dE can be expressed
as 𝜌(Eb )dE, where 𝜌(Eb ) is called the density of states. Assuming that the matrix
elements for transitions into such a band of states are comparable, Fermi’s golden
rule can be derived via spectral integration of the transition rates (not shown).
2𝜋
Wba = 𝜌(Eb )|Mba |2 (1.35)
ℏ
Thus, to calculate the transition rate into a band, multiply the square of the matrix
element by the density of states of the involved bands.
1.3.4 Dipole Approximation

So far, the matrix elements are dependent on the wavelength and direction of the
light wave (photon) via the eikr term. For interactions with visible, (V)UV, and IR
(but not X-ray) radiation, the wavelength is much larger than the atomic length
scale; hence, the system “feels” an oscillating dipole field. As a consequence, the
wave vector dependence of the vector potential can be neglected, according to
eikr ≈ 1 for 𝜆 → ∞; k → 0. In this so-called dipole approximation, the vector

potential A(r, t) → A(t) describing the light field becomes spatially homogenous
and, as a consequence, the magnetic field B = 𝛁 × A vanishes. Descriptively, the
electron velocity ve is low enough to neglect both the magnetic Lorentz force
e(ve × B) and the relativistic effects that arise if the electron is driven at very high
intensities (> 1016 W∕cm2 ), predominantly for long wavelengths. The matrix
D
elements Mba can now expressed by the dipole matrix element in the so-called
length form via the transition dipole moment Dba = −erba containing spatial
coordinates (̂x, ŷ , ẑ ) of the position operator r
m𝜔ba m𝜔ba
MbaD
= 𝜀 ⋅ (−e⟨Ψb |r|Ψa ⟩) = 𝜀 ⋅ Dba (1.36)
ℏe ℏe
Thus, the matrix element of the interaction Hamiltonian, representing the
expectation value of its energy spectrum, is now related to the much more
descriptive dipole matrix element Dba , which represents the charge distribution
within the wavefunction.
The dipole matrix element Dba (and also Mba ) determines the interaction strength
between light and the atom or molecule. Its scalar part describes the change of
charge distribution during transition from |Ψa ⟩ to |Ψb ⟩ that determines the tran-
sition probability. The vector part demands projection of the light field onto the
dipole moment, i.e. it defines the required light polarization.
The corresponding absorption rate can be derived to

𝜋 𝜋e2
D
Wba = I(𝜔 ba )|D ba |2
= I(𝜔ba )|rba |2 (1.37)
3𝜖0 cℏ2 3𝜖0 cℏ2
If the dipole matrix element is zero, the transition is so-called dipole-forbidden.
However, such transitions are often observed because they may be allowed as
(weaker) magnetic dipole or electric quadrupole transitions. Commonly used in
spectroscopy to describe the absorption strength is the dimensionless oscillator
strength fij of a transition between states i and j
2me 𝜔ij
fij = |rij |2 (1.38)
3ℏ
Oscillator strength values are between 0 and 1. Typical values are shown in
Table 1.2.
An interesting application of transition rates is related to the famous Einstein

coefficients. Therefore, the Boltzmann distribution is applied to the level popula-
tion of an ensemble of atoms in equilibrium and the Planck distribution to the
photon field. An interesting finding in the context of VUV sources is that spon-
taneous emission increases relative to stimulated emission as the cube of light
frequency. Hence, population inversion, which is a basis of laser sources, is difficult
to generate and maintain in highly excited systems. Instead of cooperating in a
stimulated emission process, the excited populations randomly loose energy via
spontaneous emission.
1.3.5 Selection Rules

To calculate absorption rates, the corresponding matrix elements have to
be evaluated by spatial integration over the corresponding wave functions
⟨Ψb |r|Ψa ⟩ = ∫ Ψb r Ψa dr in Eq. (1.36). If the integral vanishes, a transition
does not occur (with the exception of higher order transitions), which is called
dipole-forbidden. In particular, this is the case if the function Ψb r Ψa is antisym-
metric, and thus, its integral over space yields zero. This can often be determined
by analysis of the wavefunction symmetry without explicit calculation of the
integral. For example, dipole transitions (e.g. |s⟩ → |s⟩) are not allowed for the
hydrogen atom. The symmetry behavior is reflected by the parity selection rule
(ref. third column in Table 1.1). Using quantum numbers to term the states,
further selection rules for dipole transitions can be derived by evaluation of
zero and nonzero matrix elements, as Δl = ±1 and Δm = 0, ±1, where l is the
angular momentum quantum number and m is the magnetic quantum number
in a one-electron system. Descriptively, these rules reflect conservation of
angular momentum because the spin of the absorbed photon contributes to the
system’s angular momentum L. The z-component of L is associated with the
electrons’ magnetic moment, which couples to the photon spin, thus yielding
Δm = 0 in the case of linear polarization and Δm = ±1 for circularly polarized
light. For multielectron systems, the total angular and orbital momentum as
well as the total spin is evaluated, and coupling schemes of angular momen-
tum sources are considered. In realistic systems, especially molecules, several
dipole-forbidden transitions can nevertheless be observed. For example, the
dipole-forbidden transitions may be allowed as multipole transitions. Typically,
the rate drops down by three orders of magnitude from one multipole to the next,
see Table 1.2.
1.3.6 Electronic Line Width and Lifetime

So far, we assumed that the states have sharp eigen energies and can be described
via time-dependent wavefunctions of the form 𝜓e−iEt∕ℏ (ref. Figure 1.4a,d).
Suppose a state that is exponentially decaying in amplitude as the system
changes to another state (Figure 1.4b). The decaying function corresponds
Table 1.1 Dipole selection rules for electronic transitions in a Hydrogen-like atom. J = L + S is
the total angular momentum, L is the total orbital momentum quantum number, S is the total
spin quantum number, MJ is the total magnetic quantum number, and 𝜋 is the parity.
Intermediate
Rigorous LS coupling coupling
ΔJ = 0, ±1 ΔMJ = 0, ±1 𝜋b = −𝜋a a)
Δl = ±1 b)
if ΔS = 0: c)
if ΔS = ±1:
(J = 0 ⇎ 0) ΔL = 0, ±1, (L = 0 ⇎ 0) ΔL = 0, ±1, ±2
a) Rigorous for one-electron systems.

b) Small atoms with low LS-coupling.
c) Heavier atoms with transitions between several multiplet states.
re[e–iEt/ħ] re[e–iEt/ħ–t/2τ]
Collision
Amplitude
(a) Time (b) (c)

Amplitude
ħ/τ
(d) Frequency (energy) (e) (f)
Figure 1.4 Schematic wavefunctions (top) and their spectra (bottom). (a, d) Stationary state.
(b, e) Decaying state and resulting Lorentzian line profile. (c, f ) Collision-induced phase
distortion and its resulting spectrum (fast Fourier transformed).
to a superposition of oscillations whose frequencies can be Fourier analyzed

according to
′ 1 (ℏ∕𝜏)
e−iEt∕ℏ−t∕𝜏 = g(E′ )e−iE t∕ℏ dE′ with g(E′ ) = (1.39)
∫ 𝜋 (E − E′ )2 + (ℏ∕𝜏)2
where 𝜏 is the time constant of the decay. Therefore, the decaying dipole oscil-
lation is associated with a finite energy range. The width at half height of the
Lorentzian function g(E′ ) is ℏ∕𝜏 and called natural line width (Figure 1.4e). Con-
sidering that the state to which the transition appears may also have a finite life-
time 𝜏b , the line width is given by
( )
1 1
𝛿E = ℏ + (1.40)
𝜏b 𝜏a
Hence, the shorter the state lifetime, the less precise its energy and vice
versa. This concept is particularly important for REMPI (see Chapter 2), where
ionization rates depend on the energy match between the photon and possible
intermediate states as well as the photon density. It further gives rise to the
concept of virtual states of uncertain energy, which may be employed at high
photon densities.
Measured line widths are typically much larger, which can be attributed to
the other origins of broadening. First, collisions with other atoms may lead
to (radiative or nonradiative) transitions and randomize the phase of emitted
radiation (ref. Fig. 1.4c,f ). Both reduces the effective lifetime of the state and
leads to the (pressure-dependent) collision broadening of the Lorentzian line
profile. Secondary, the relative motion of atoms results in frequency shift. Thus,
the so-called Doppler broadening increases with temperature and decreases
with atomic mass and produces a Gaussian profile, which convolves with the
Lorentzian profile.
1.3.7 Electronic Transitions of Molecules

So far, we treated light absorption using a simple model system undergoing
electronic transitions. However, real electronic spectra of molecules are highly
complex. This cannot be comprehended by single-electron transitions in a static
potential model as the nucleic motion is completely neglected. Indeed, any elec-
tronic transition changes a real system’s charge distribution inducing vibration
of the nuclei, which, in turn, changes the rotational state. Moreover, full under-
standing of the molecule response implies consideration of all possible sources
of angular momentum and their coupling scheme. Note that for photoionization,
REMPI cross sections are a consequence of the actual electronic structure. In
direct SPI, the outgoing states are continuum states, being less restricted.
Corresponding to atoms, selection rules arise from the conservation of
total angular momentum and the total parity changes in dipole transitions,
refer Table 1.2. Initial estimates on cross sections can be derived from typical
oscillator strength values and respective transition probabilities, as summarized
in Table 1.2 and indicated by exemplary absorption spectrum of benzene
(Figure 1.5).
Several schemes allow for (at least qualitative) indications on the molecules’
electronic spectra and transition probabilities. Hund’s rules describe how the four
sources of angular momentum (electron orbital angular momenta L, rotation of
nuclear framework O, and spin of electrons S and nucleus I), are coupled (in a
diatomic molecule). Any electronic transition changes the charge distribution.
The nuclei readjust to these forces causing vibration. Consequently, electronic
transitions in molecules are accompanied with vibrational transitions, giving rise
to the term vibronic transitions that have many lines in the absorption spectra.
Of note, nuclear rearrangement is much slower than electronic transitions, see
also Figure 1.1. This is the basis for the Franck–Condon principle that makes
statements on the most probable vibronic (electronic + induced vibrational) tran-
sitions, see Figure 1.6. Electronic excitation is virtually instantaneous before the
nuclei can readjust to the distance rB and must therefore be drawn as a “vertical”
transition (blue arrow). From the numerous vibrational states of the upper elec-
tronic level, the one with the greatest overlap with the original state vibrational
wavefunction is occupied.
Table 1.2 Typical oscillator strengths for transitions according to the selection rules
Oscillator strength f
Electric dipole allowed ≲1

Parity forbidden 10−1
Magnetic dipole allowed 10−5
Electric quadrupole allowed 10−5
Spin forbidden 10−5
Electric dipole
- allowed
5
4 Symmetry-/ electric
dipole-forbidden
3 + Photo– singlet π* ←π
dissociation
2
1 Rydberg-
series
log ε
–1 Spin-forbidden
triplet π* ←π
–2
–3
1.500 2.000 2.500 3.000 3.500
Wavelength (Å)
Figure 1.5 Absorption spectrum of benzene, illustrating the dipole transition probabilities
according to selection rules. Source: Modified from Barrow (1962).
Energy Electronic state B Figure 1.6 Electronic transitions are

faster than nuclear motion. The
nuclei rearrange after electronic
3 excitation (vertical blue arrow) to
the new distance rB . Transition
2 probability is highest between the
vibration states of the greatest
1 waveform overlap, determining the
possible final states (Franck-Condon
principle). For examples on
0 Franck-Condon controlled vibronic
spectrum, see the analysis of the
Electronic state A biphenylene REMPI spectrum and
other molecules in chapter 2.
1
Vibration states
0
rA rB Internuclear distance
Vibronic transitions in turn induce rotational transitions contributing many

more absorption lines, according to the selection rules. Comparable to ice skaters,
who extend their arms during a pirouette to slow down their spin, the vibration
affects molecular rotation.
Complexity further increases for polyatomic molecules. For small molecules,
application of the selection rules must consider their whole symmetry,
as the electronic excitation affects the complete structure. Detailed electronic

structures are calculated with methods of computational chemistry that are based
on several approximations, e.g. Hartree-Fock (ab initio), Post-Hartree-Fock
(considers electron correlations), or density functional theory. In many appli-
cations, a particular group of atoms in the molecule is considered because they
show a characteristic absorption feature. These subgroups, called chromophores,
may occur in different molecules contributing absorption bands of the same
wavelength. Basic considerations on a molecule’s absorption behavior can often
be reduced to the presence of such chromophores and perturbations from other
groups in the molecule. A prominent example is the B-band of benzene and
derivatives originating from 𝜋 → 𝜋 ∗ transitions. Although this benzenoid band
is forbidden by symmetry for pure electronic states, it is allowed with respect to
the overall symmetry of vibronic states. In context of analytical applications, it
contributes the intermediate REMPI states giving the aromatic ring structures
high REMPI cross sections for e.g., the fourth harmonic of the Nd:YAG laser
(266 nm). Comprehensive collections of photoabsorption spectral information
can be found in the literature, e.g. Berkowitz (2002). Having regard to the
scope on photoionization for analytical mass spectrometry, many structural and
spectroscopic details can be omitted here, and in the following, we can focus
on specific aspects that have practical implications to mass spectrometry. In
chapter 2 the application of REMPI in molecular spectroscopy using tunable
lasers is discussed with the help of photoabsorption and ionization spectra of
suited interesting molecular systems.
1.3.8 Single-photon Ionization (SPI)

So far, electronic transitions between bound states were treated. Their probabil-
ities at given photon energies and radiation intensities are formally determined
by (dipole-) transition matrix elements or more practically by absorption cross
sections (ref. Eqs. (1.33, 1.34)) (Berkowitz 2002). Corresponding absorption spec-
tra are often characterized using oscillator strength values (Eq. (1.38)). If an elec-
tron is released by the absorption process, the final state has a free electron,
allowing continuous values for its energy Ekin and momentum pe (continuum
state). Consequently, SPI is less constrained to structural and electronic proper-
ties, and its cross sections show a rather narrow distribution, enabling to use SPI
for a universal ionization of molecules (threshold selectivity Eh𝜈 ≥ IE), see also
Chapter 3 for SPI-MS applications. SPI and possible subsequent fragmentation
of a molecule AB in the ground vibronic state can be formally written as
AB + h𝜈 → [AB+ ]′ + e− (1.41)
[AB ] → AB and∕or A + B
+ ′ + +
(1.42)
with the quotation mark indicating the excited state. Again, the timescale of the
electron ejection process (Eq. (1.41)) is much shorter compared to the relaxation
described by Eq. (1.42). Consequently, the electron energy Ekin can be measured
to probe the energy EB of the excited state of the molecular ion [AB+ ]′ via pho-
toelectron spectroscopy (PES) according to Ekin = h𝜈 − EB . Detailed ionization
and fragmentation studies are facilitated by combining MS with PES, ideally in
a single-event coincidence setup, called photoelectron photoion coincidence

(PEPICO) spectroscopy (Baer 2000). The special case of Ekin ≃ 0 eV (“threshold
PEPICO”) allows the precise determination of the energy EB of the molecular
ion and has been used to work out the thermochemistry of many gas-phase
species (Sztáray et al. 2010).
Allowing multiple charging (n > 1) and with the focus on mass spectrometry,
Eqs. (1.41) and (1.42) may also be summarized as
AB + h𝜈 → [ABn+ ]′ + ne− (1.43)
↳ AB n+
(1.44)
↳A p+
+B q+
(1.45)
↳ A+ + B− (n = 0) (1.46)
For chemical analyses using single-photon ionization mass spectrometry
(SPI-MS), the case of Eq. (1.44) with n = 1 is typically desired, while Eq. (1.45)
refers to production of fragment ions of charge p+ and q+ and Eq. (1.46) refers to
ion-pair production. Ionization energies (IEs) of organic molecules reside in the
range of 8–12 eV. Because the values of atmosphere gases as N2 , O2 , H2 O, etc. ,
are higher, they typically do not interfere in SPI-MS analyses. Fragmentation
increases with photon energy; thus, the desired photon energy is about 10–15 eV,
a region where the ionization efficiency varies strongly and where compact,
robust, and intense light sources are rare. Dependent on the analyte molecules,
the gap between IE and the appearance energies of one or more fragmentation
pathways differs widely and molecules may not only be ionized but also undergo
direct or metastable fragmentation, see Figure 1.7 for an example.
7.5 8 8.5 9 9.5 10 10.5 11 11.5 eV

(a) Electron impact ionization(EI) (c)
VUV spectrum
1.0 mass spectrum 182 1.0
m/z =182 (fragment signal)
m/z = 211 (molecule signal)
EI@70 eV (a.u.)
211
0.5 167 H3C
O
Ion signal from SPI (a.u.)
O
H3C
0.0 H3C
80 120 160 200 240
(b) 211 O NH2
1.0 Single photon ionization (SPI)
SPI@140.9 nm (a.u.)
mass spectrum
IE = 8.0 eV
0.5
0.0 0.0
80 120 160 200 240 170 160 150 140 130 120 110
m/z Wavelength (nm)
Figure 1.7 Ionization and fragmentation behavior of mescaline. (a) Electron impact ionization
with 70 eV electron energy leads to substantial fragmentation, in contrast to (b) single-photon
ionization (SPI) with 8.8 eV synchrotron radiation. (c) Fragment-free SPI is possible for a photon
energy around 8–9 eV, limiting the choice of VUV light sources for SPI. Source: Kleeblatt et al.
(2013). Modified with permission of SAGE.
This behavior is typical for several relevant compounds classes, e.g. for many
explosives, drugs of abuse and pharmaceutical active compounds, as well as for
the majority of metabolites. For many other compounds, such as alkanes or alky-
lated aromatic compounds, however, a totally soft ionization by SPI is achieved.
Particular high stability is observed for aromatic compounds because the charge
is delocalized throughout the whole ring (resonance stabilization) (Edirisinghe
et al. 2006; Gunzer et al. 2019). The ionization energy can be obtained with
relatively good accuracy by quantum chemical calculations: According to Koop-
mans’ theorem, the vertical IE equals the negative energy of the highest occupied
molecular orbital (HOMO). The underlying approximation neglects changes of
the energy levels through rearrangements upon removal of the electron from the
HOMO. Adiabatic values for IE can be obtained from the difference of the total
energies of the geometry-optimized molecular ground state and the respective
ionic state (Gross 2011). In general, smaller homologues of a molecular sub-
stance class exhibit higher ionization energies than its larger homologues. For
organic compounds, IE can also be influenced by substituents, which can either
withdraw electron density from the HOMO or push electron density into the
HOMO via mesomeric or inductive effects. The highest molecular IE values
are observed for small inorganic compounds such as HF (16.03 eV, highest
molecular IE), F2 (15.70 eV), N2 (15.58 eV), H2 (15.43 eV), CO2 (13.78 eV), H2 O
(12.62 eV), or O2 (12.07 eV). Methane has the highest IE for a hydrocarbon
(12.61 eV). Ionization energies as a function of molecular weight (m∕z) for
different organic compound classes are shown in Figure 1.8. Generally, the
values of IE decrease with increasing molecular size within a homologous series.
For very large molecules, they hyperbolically approach a value close to the work
function of the respective bulk material, see the intersections with the y-axis
in Figure 1.8(b). Obviously, there is no apparent size limit in photoionization
as demonstrated in studies on large molecules (Akhmetov et al. 2010; Schätti
et al. 2017). The IE of condensed aromatic compounds are generally lower than
the values of aliphatic compounds, as the ionization occurs from the HOMO of
the aromatic 𝜋-electron system (delocalized). Substitution can induce different
effects on IE, as illustrated in Figure 1.8: substituents that withdraw electron
density from the 𝜋-electron system, such as the halogens, fluorine, and chlorine,
tend to increase IE upon successive substitution of H-atoms at the aromatic
moieties. On the other hand, substitution by electron-donating groups, such as
methyl groups, causes a decrease of IE with an increasing degree of substitution.
The second fundamental parameter for SPI is the single-photon ionization
cross section 𝜎SPI . From the photon flux 𝜑 through the sample volume V (cm3 ),
the concentration C of molecules (n cm−3 ) and the absolute 𝜎SPI value, the
ionization rate RSPI (n∕s) can be calculated according to
RSPI = 𝜎SPI 𝜑VC (1.47)
Experimental values of 𝜎SPI for several homologous or substituted compounds
as a function of molecular weight are depicted in Figure 1.9. The measurements
have been performed using a gas chromatograph coupled to a mass spectrometer
equipped with an electron beam excimer lamp for SPI (Eschner and Zimmer-
mann 2011). For all compounds, a slight increase of the 𝜎SPI values with rising
molecular weight is observed. The similarities of SPI cross sections for members
13
Linear alkanes
1-alkenes
12 2-alkanones
Aldehydes
lonization energy (eV)
Linearly condensated PAHs

11 Alternately condensated PAHs
Annuarly condensated PAHs
10 Methylated benzenes
Fluorinated benzenes
Chlorinated benzenes
9 Chlorinated dibenzo-p-dioxins
6
0 50 100 150 200 250 300 350 400 450 500
(a) m/z
12
11
10
lonization energy (eV)
8
Linear alkanes
7 1-alkenes
2-alkanones
Aldehydes
6
Linearly condensated PAHs
5 Alternately condensated PAHs
Annuarly condensated PAHs
4
0 0.05 0.1 0.15 0.2 0.25
(b) 1/# atoms
Figure 1.8 Ionization energies plotted against (a) the molecular weight for different
homologous organic compounds and (substituted) aromatic hydrocarbons (homologous
series for alkanes, 1-alkenes, aldehydes and alkanones; increasing substitution degree from
1-6 for benzene derivatives (for alkylated benzenes: 1-5, from toluene to pentamethyl-
benzene) and 1-8 for chlrorinated dibenzo-p-dioxins; differently condensed rings for polycyclic
aromatic hydrocarbons (PAH)). (b) The molecular IE values plotted against the inverse number
of atoms illustrate their approach toward material’s work function (conducting material) or
ionization energy (insulators) for large atom numbers. Source: Data from NIST Chemistry
Webbook and National Institute of Standard and MD Technology.
within a particular compound class can be used for approximate (semi-) quan-
tification. Note that 𝜎SPI also depends on the spectral shape of the respective light
source. For compounds with an IE within the emission band, only the fraction of
photons exceeding IE can contribute to ionization. This results in a relative sup-
pression of the observed 𝜎SPI compared to the compounds with lower IE. The
effect can be noticed for the n-alkanes as depicted in Figure 1.9(b). Here, the
slope of 𝜎SPI of n-alkanes (red) is lower for the smaller homologues (1∕n ⪆ 0.02),
exhibiting IE values within the lamp’s emission band.
70
Linear alkanes
Photoionization cross section (Mb)
60 2-alkanones
Methylated benzenes
Chlorinated benzenes
50 PAHs
40
30
20
10
0
50 100 150 200 250 300
(a) m/z
70
Linear alkanes
Photoionization cross section (Mb)
60 2-alkanones
Methylated benzenes
PAHs
50
40
30
20
10
0
0 0.05 0.1 0.15
(b) 1/# atoms
Figure 1.9 Single-photon ionization cross sections 𝜎SPI at 9.8 eV (0.4 eV FWHM) plotted
against (a) the molecular weight and (b) the inverse atom number of different compound
classes (homologous series for alkanes and alkanones; increasing substitution degree from 1-6
for benzene derivatives, linearly condensed rings for polycyclic aromatic hydrocarbons (PAH):
naphthalene, anthracane, tetracene). The flatten of the curve toward smaller linear alkanes is
due to their relatively high IEs, in particular for the lower molecular weight species (see Figure
1.8). Therefore, only a fraction of the VUV-emission spectrum of the used lamp can be used for
the ionization. Source: Data from Eschner and Zimmermann (2011).
If the IE is plotted against the inverse number of atoms (Figure 1.8b) the IE
limit for very large molecules can be estimated. For infinitely large molecules
this IE converges to the respective solid state material property. In the case of
the PAH this correspond to graphite, which is a conducting solid with a work
function of 4.7 eV (Rut’kov 2020), or an individual graphene layer with a work
function of 4.3 eV (Rut’kov 2020). Polypropylene (PP) in contrary is a model
for a fully saturated, insulating solid state polymer, which exhibit a solid state
ionisation energy of 8.65 eV (Rajopadhye, 1986). The extended lines for the
linearly condensed PAH and the fully saturated linear alkanes in Figure 1.8b hit
the x axis (i.e. infinitely large molecule) at the values of 4.4 eV (PAH) and 8.8 eV
(alkanes), showing a very good agreement of estimation and experimental

data. With respect to the photoionization of very large molecules it is notable
that there was an intense discussion about the question, if larger molecules
indeed can be efficiently photoionized (Schlag 1992). It was suggested, that SPI
efficiency of larger molecules is decreasing with molecular size due the incensing
density of states, which supports the rapid dissipation of energy supplied by
photon absorption into internal charge transfer states.
The dissipated energy then cannot be recombined quickly enough for a timely
(auto-)ionization. However, already in 1995 single photon ionization of fullerenes
and carbon clusters up to 2000 m/z was reported (Becker 1995). Recently, a fs
laser desorption SPI-post ionization experiment demonstrated that efficient SPI
of complex polypeptides with more 20.000 m/z is possible (Schätti 2018).
Generally, cross sections for SPI are lower than the values of the standard
ionization via electron impact (EI). In contrast to the rather weak dipole interac-
tion with the light field in SPI, the electron’s de Broglie wavelength in EI (70 eV,
≈ 1.5 pm) matches the typical bond lengths in organic molecules. Thus, the
energy transfer to the analyte and ionization efficiency is maximized. Also, the
cross-sectional variance of about 10 for different compound classes is rather low
for the universal ionization method EI (Adam and Zimmermann 2007). However,
despite lower cross sections, respective sensitivity, SPI features ionization with
very low fragmentation and produces no interfering signals from the carrier
gas (higher IE), rendering it an ideal method for complex organic mixtures.
Such practical considerations and the unique features of (resonance-enhanced)
multiphoton ionization will be discussed in Chapters 2, 4 and 11 of this book.
References
Adam, T. and Zimmermann, R. (2007). Determination of single photon ionization
cross sections for quantitative analysis of complex organic mixtures. Anal.
Bioanal. Chem. 389 (6): 1941–1951.
Akhmetov, A., Moore, J.F., Gasper, G.L. et al. (2010). Laser desorption
postionization for imaging MS of biological material. J. Mass Spectrom. 45 (2):
137–145.
Baer, T. (2000). Ion dissociation dynamics and thermochemistry by photoelectron
photoion coincidence (PEPICO) spectroscopy. Int. J. Mass Spectrom. 200 (100):
443–457.
Barrow, G.M. (1962). Introduction to Molecular Spectroscopy. McGraw Hill.
Baumert, T. and Gerber, G. (1997). Molecules in intense femtosecond laser fields.
Phys. Scr. T72: 53–68.
Becker, C.H. and Wu, K.J. (1995) On the photoionization of large molecules. J. Am.
Soc. Mass. Spectrom. 6: 883–888.
Berkowitz, J. (2002). Atomic and Molecular Photoabsorption. Absolute Total Cross
Sections. London: Academic Press.
Edirisinghe, P.D., Moore, J.F., Calaway, W.F. et al. (2006). Vacuum ultraviolet
postionization of aromatic groups covalently bound to peptides. Anal. Chem. 78
(16): 5876–5883.
References 21
Eschner, M. and Zimmermann, R. (2011). Determination of photoionization

cross-sections of different organic molecules using gas chromatography coupled
to single-photon ionization (SPI) time-of-flight mass spectrometry (TOF-MS)
with an electron beam pumped rare gas excimer light source (EBEL): influence of
molecular structure and analytical implications. Appl. Spectrosc. 65: 806–816.
Gross, J.H. (2011). Mass Spectrometry. Springer.
Gunzer, F., Krüger, S., and Grotemeyer, J.H.C. (2019). Photoionization and
photofragmentation in mass spectrometry with visible and UV lasers. Mass
Spectrom. Rev. 38 (2): 202–217.
Kleeblatt, J., Ehlert, S., Hölzer, J. et al. (2013). Investigation of the photoionization
properties of pharmaceutically relevant substances by resonance-enhanced
multiphoton ionization spectroscopy and single-photon ionization spectroscopy
using synchrotron radiation. Appl. Spectrosc. 67 (8): 860–872.
National Institute of Standard and MD Technology NIST Chemistry WebBook.
Standard reference database. Gaithersburg. http://webbook.nist.gov/chemistry.
Rajopadhye, N.R. and Bhorarkar, S.V. (1986). Ionization potential and work function
measurements of PP, PET and FEP using low-energy electron beam. J. Mat. Sci.
Lett. 5: 603–605.
Rut’kov, E.V., Afanas’eva, E.Y., and Gall, N.R., (2020). Graphene and graphite work
function depending on layer number on Re. Diamond Rel. Mat. 101: 107576.
Schätti, J., Rieser, P., Sezer, U., et al. (2018). Pushing the mass limit for intact launch
and photoionization of large neutral biopolymers. Commun. Chem. 1: 93.
https://doi.org/10.1038/s42004-018-0095-y.
Schätti, J., Sezer, U., Pedalino, S. et al. (2017). Tailoring the volatility and stability of
oligopeptides. J. Mass Spectrom. 52 (8): 550–556.
Schlag, E.W., Grotemeyer, J., and Levine, R.D. (1992). Do large molecules ionize?
Chem. Phys. Lett. 190: 521–527.
Sztáray, B., Bodi, A., and Baer, T. (2010). Modeling unimolecular reactions in
photoelectron photoion coincidence experiments. J. Mass Spectrom. 45 (11):
1233–1245.
23
Fundamentals and Mechanisms of Resonance-Enhanced

Multiphoton Ionization (REMPI) in Vacuum and its
Application in Molecular Spectroscopy
Ulrich Boesl 1 and Ralf Zimmermann 2,3
1 Technical University of Munich, Department of Chemistry, Chair of Physical Chemistry, Lichtenbergstraße 4,
85748 Garching, Germany

2
University of Rostock, Institute of Chemistry, Chair of Analytical Chemistry and Joint Mass Spectrometry
Centre (JMSC), Dr.-Lorenz-Weg 2, D-18051 Rostock, Germany
3
Helmholtz Zentrum München – German Research Center for Environmental Health GmbH, Research Unit
Comprehensive Molecular Analytics (CMA) and Joint Mass Spectrometry Centre, Gmunder Str. 37, D-81379
München, Germany
2.1 Introductory Remarks

The fundamentals of resonance-enhanced multiphoton ionization (REMPI) are
the main topic of this chapter (Sections 2.3 and 2.4). REMPI is an outstanding
ionization method in mass spectrometry with respect to selectivity as molecu-
lar spectroscopy is directly involved in the ionization process (Boesl et al. 2000;
Johnson 1980; Letochov 1987; Lubman 1990; Vertes 1993). In consequence, the
application of REMPI for molecular spectroscopy is the second theme of this
chapter (Section 2.5). In REMPI, a first photon is absorbed into a bound interme-
diate state of the molecule, if the photon energy is in resonance with the transition
“ground state ⇒ excited state” (Figure 2.1: M ⇒ M* ). These resonances reflect the
spectroscopy of the molecule and cause the high selectivity of REMPI. In a second
absorption process, one or more further photons are absorbed into the ionization
continuum (M* ⇒ M+ ). Figure 2.1 illustrates this combination of spectroscopic
and ionizing steps. Chapter 1 of this book is dedicated to the quantum chem-
ical basics of the photo absorption (absorption in bound electronic state) and
photoionization (absorption in free electron continuum state) processes.
The efficiency of two-photon REMPI (the most common and efficient mul-
tiphoton ionization (MPI) process, see Figure 2.1a,b) ideally depends on the
square of the light intensity and is unmeasurably small for conventional light
sources. However, modern pulsed lasers supply a high density of photons such
that ionization efficiencies of 10% and more are achievable in best cases in the
region where laser and molecular gas beam are overlapping (Boesl et al. 2000).
In combination with mass spectrometry, REMPI enables detection sensitivities
in the ppb- down to ppt range with reasonable effort for laser and vacuum
system (Gittins et al. 1997; Hafner et al. 2001; Heger et al 1999; Oser et al. 2001;
Tanada et al. 1993; Velazquez et al. 1998). Albeit some examples in this chapter
Photoionization and Photo-Induced Processes in Mass Spectrometry: Fundamentals and Applications,

First Edition. Edited by Ralf Zimmermann and Luke Hanley.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
24 2 Fundamentals and Mechanisms of Resonance-Enhanced Multiphoton Ionization (REMPI)
Resonance-enhanced multiphoton-ionization (REMPI)

Spectroscopy Species selective ion source
MA+
Mass
photon energy
M+
Ion current
M* Ion current
Absorption MA MB MA MA
M
(a) (b) (c) (d)
Figure 2.1 Schematic representation of the different possibilities of REMPI: (a) tuning the
wavelength of the ionizing laser: the ion current (REMPI signal) reflects the gas-phase UV
spectrum; (b) resonance-enhanced, two-photon ionization with photons of same energy
(one-color REMPI) and illustration of selective ionization; (c) resonance-enhanced, two-photon
ionization with photons of different energies (two-color REMPI); and (d) resonance-enhanced,
three-photon ionization of higher order, here the example of (2 + 1)-REMPI.
are already referring to analytical employments of REMPI-MS, Chapter 4 of this

book is giving a self-contained and comprehensive representation of analytical
REMPI-MS applications.
Selectivity of REMPI is intrinsically influenced by the resolution of the
involved optical spectroscopy (Section 2.5). High-resolution spectroscopy is
possible by cooling the molecular species in a supersonic molecular beam
(jet), which often allow to discriminate isobaric or isomeric species (and which
can not be separated by mass spectrometry alone) (Velazquez et al. 1998;
Weickhardt et al. 1993). However, for many practical analytical applications, it
may be advisable to avoid the extra effort required for the supersonic jet inlet
system (sophisticated additional vacuum system, electronics, and mechanics).
Medium- and low-resolution ultraviolet (UV) spectroscopy (typical for larger
molecules such as polycyclic aromatic hydrocarbons (PAHs) at room temper-
ature) primarily enables one to selectively analyze and investigate classes of
molecules such as aromatics, aldehydes, or alcohols. This is a useful feature in
itself, for instance, for fast screening applications. In some cases, REMPI allows
distinction of isomers even without supersonic jet inlet (e.g. see Figure 2.17: the
carcinogenic benzo[a]pyrene can be separated from the less harmful isomers
benzo[b]fluoranthene and benzo[k]fluoranthene, all of mass 252).
However, not only the spectroscopic feature of REMPI may be exploited but
the fact that light is characterized by its state of polarization can also be used, e.g.
for analyzing the enantiomeric excess of chiral molecules. A special feature of
REMPI, which enhances its usefulness for mass spectrometric ion sources con-
siderably, is the possibility of ion formation with very low or even no fragment
formation at all. On the other hand, controlled fragmentation is possible and
delivers useful information about the structure of the investigated molecule. This
information is primarily interesting for basic research but may also be useful for
the analytical characterization of chemical trace compounds (another possibility
to discriminate isomeric or isobaric species).
In Figure 2.2, the basic feature of REMPI combined with mass spectrometry
(MS), namely, the two-dimensional selectivity due to the two variables
(a) (b)
REMPI at
M+ M+
ν = 38 620.5 (cm–1) Mass Mass
78 m/z M* M*
hν hν
M M
12C
6H6
78 m/z
REMPI at
ν = 38 622.4 (cm–1)
12
C513CH6 Δν
79 m/z 79 m/z 78 m/z
79 m/z
80 78 76 80 78 76 38 600 38 610 38 620 38 630

Mass Excitation energy (cm–1)
Figure 2.2 A historically early demonstration of the two dimensionality of REMPI-MS at the
example of benzene and 13 C1 -benzene isotopologue (isotopic homologue). (a)
wavelength-selected mass spectra showing the region of the all 12 C-benzene at 78 m/z and
the 13 C1 -benzene isotopologue at 79 m/z (molecular peak region). According to the natural
isotope distribution of carbon, the latter one should have a contribution of about 6.5% in the
mass spectrum. By ionizing with REMPI at 38620.5 cm−1 (left mass spectrum), the ratio
between 78 and 79 m/z roughly resembles the natural isotope distribution. In contrast,
ionizing with REMPI at 38622.4 cm−1 (right mass spectrum) results in an about equal (albeit
lower) intensity of 78 and 79 m/z, i.e. in a strong relative enrichment of the 13 C1 -benzene
isotopologue. (b) The mass-selected REMPI wavelengths (excitation) spectra recorded at 78
m/z (upper trace) and 79 m/z (lower trace) depict the spectral differences in the vibrionic band
of the S1 -system of the two isotopologues. These are due to the mass dependence of the
zero-point energy in the vibrionic potential.
wavelength and mass, is illustrated at the example of a very early REMPI mass
spectrum and mass-selected optical REMPI spectrum of benzene.
Already in the first 4–5 years since its introduction, most features of REMPI
and resonant laser MS of molecules have been discovered. The basics of most
of the later steps of its development have been laid at this early stage, providing
insight in the typical features and possibilities of REMPI. The early history of the
REMPI method development is summarized in the following Section 2.2.
2.2 Beginnings of REMPI

Successful laser-induced (although not resonance-enhanced) ionization of
molecules in the gas phase followed by mass selection was reported as early
as 1970 (see Table 2.1) (Berezhetskaya et al. 1970; Chin 1971). REMPI was
applied to molecules five years later (Johnson 1980). The method was originally
introduced as a new means for UV and visible molecular spectroscopy rather
than mass spectrometry. Even its combination with mass selection (Feldman
et al. 1977; Herrmann et al. 1977, 1978; Rothe et al. 1978; Zandee et al. 1978) was
originally rather a further step toward a new form of molecular spectroscopy
than toward chemical analysis. In this context, it is interesting that another new
technique, namely the cooling of molecular rotational and vibrational internal
motions in a supersonic gas beam (Hayes 1987; Levy 1981; Smalley et al. 1975,
1977), revolutionized molecular spectroscopy. It did not take long for resonant
laser ionization and supersonic molecular beams to be combined, thus starting
a fruitful period of molecular spectroscopy on larger molecules.
Although the first application of laser ionization (both resonant Feldman
et al. 1977; Herrmann et al. 1977, 1978; Rothe et al. 1978; Zandee et al. 1978
and nonresonant Berezhetskaya et al. 1970; Chin 1971) was on small, mostly
two-atomic molecules, first mass-selective laser ionization experiments on
polyatomic molecules were reported in 1977 and 1978. The first polyatomics
were benzaldehyde, benzophenone, and nitrotoluene, which were still ionized
using a fixed-frequency laser (Antonov et al. 1978), and benzene, which was
ionized by tuning the wavelength of a dye laser to its S1 –S0 transition (Boesl
et al. 1978, 1979). These experiments were followed by many publications on all
kinds of molecules, their mass-selected laser spectroscopy, or spectroscopically
selected mass spectra (see Table 2.1) (Boesl et al. 1980, 1981; Brophy and Rettner
1979a,b; Cooper et al. 1980; Dietz et al. 1980a,b; Duncan et al. 1979; Fisanick
et al. 1980; Lubman et al. 1980; Newton et al. 1981; Zandee and Bernstein
1979a,b). Already in the early years of REMPI (1982–85), several groups tried
to characterize molecules according to their behavior under resonant laser
ionization conditions summarized in Bernstein (1982), Gedanken et al. (1982),
and Gobeli and El-Sayed (1985).
One should mention that when early REMPI of molecules came up, a similar
process has been applied to atoms at the same time, which was called resonance
ionization spectroscopy (RIS) or, in combination with MS detection, resonance
ionization mass spectrometry (RIMS). Successful single-atom detection and exci-
tation schemes for all atoms in the period table were published in Hurst et al.
(1979, 1980) and the RIMS approach is discussed in detail within Chapter 6 of
this book.
Two outstanding features of resonant laser ionization – very soft ionization
and variability from metastable decay to extreme fragmentation – were already
detected in some of the first experiments. Several research groups investigated
the mechanisms of fragment ion formation during resonant laser ionization
(Boesl et al. 1980; Carney and Baer 1981; Meek et al. 1980; Newton et al. 1981;
Pandolfi et al. 1981; Parker et al. 1981; Proch et al. 1981; Zandee and Bernstein
1979b). Different methods have been used for this purpose, such as secondary
fragment ion excitation using a time-delayed second laser (representing the first
steps toward tandem laser MS), a new kind of photoelectron spectroscopy (PES)
revealing fast intramolecular processes in the neutral intermediate state, and
picosecond laser excitation. In fact, in addition to molecular spectroscopy, the
new tool of resonant laser ionization has been applied in these days mainly to
the study of internal molecular dynamic processes.
Table 2.1 The early beginnings of REMPI and REMPI-MS.
Type of spectroscopy Investigated substances Year Ref.
Ionization of molecules by lasers: fixed-frequency lasers, mass selection

H2 , I2 , D2 O, CCl4 1970/71 Berezhetskaya et al.
(1970) and Chin (1971)
Resonance ionization spectroscopy in the gas cell
C6 H6 1976 Johnson (1980)
Resonance ionization spectroscopy: diatomic molecules, wavelength tunable lasers,
mass selection
Na2 , K2 , I2 , Li2 , BaCl, NO 1977/78 Feldman et al. (1977),
Herrmann et al. (1977,
1978), Rothe et al.
(1978), and Zandee
et al. (1978)
Ionization of molecules by lasers: polyatomic molecules, fixed-frequency lasers,
mass selection
Benzaldehyde, benzophenone, 1977/78 Antonov et al. 1978
nitrotoluene
Resonance ionization spectroscopy: polyatomic molecules, wavelength tunable lasers,
mass selection
Benzene 1978 Boesl et al. (1978, 1979)
Aniline 1979/80 Brophy and Rettner
(1979a,b)
Triethylenediamine, benzene, Zandee and Bernstein
butadiene (1979a,b) and Newton
et al. (1981)
Metal carbonyls, aniline, Dietz et al. (1980a,b)
bromobenzene, iodobenzene and Duncan et al.
(1979)
Azulene, naphthalene 1980 Lubman et al. (1980)
Acetaldehyde Fisanick et al. (1980)
Pyrrole, N-methylpyrrole, Cooper et al. (1980)
furan
Cross sections Boesl et al. (1981)
Resonance ionization and fragmentation of polyatomic molecules
Extreme fragmentation 1979 Zandee and Bernstein
(1979b) and Newton
et al. (1981)
Extreme fragmentation 1980 Boesl et al. (1980,
(model) 1982b) and Dietz et al.
(1982)
Photoelectron analysis Meek et al. (1980)
The role of the neutrals 1981 Pandolfi et al. (1981)
2,4-Hexadiyne Carney and Baer (1981)
Tertiary amines Parker et al. (1981)
Aniline Proch et al. (1981)
Table 2.2 The beginning of REMPI: early combinations with other techniques.
Method Year Ref.
Supersonic beams Since 1979 Dietz et al. (1980a,b), Duncan et al.

(1979), and Smalley et al. (1975, 1977)
Gas chromatography Since 1980 Klimcak and Wessel (1980); Rhodes
et al. (1983), and Rothe et al. (1978)
Trace analysis Since 1979 Antonov et al. (1981), Brophy and
Rettner (1979b), and Zacharias et al.
(1981)
Laser desorption of Since 1982/87 Antonov et al. (1982), Boesl et al. (1987),
neutral molecules Engelke et al. (1987); Grotemeyer et al.
(1986b), Tembreull and Lubman (1986),
Vastola and Pirone (1968), and
Weyssenhoff et al. (1985, 1986)
Picosecond laser Since 1984 Gobeli et al. (1984, 1985) and Knee et al.
excitation (1985)
The combination of resonant laser MS with other techniques proved to be an

important factor in its development since the very beginning. Some relevant
early experiments are listed in Table 2.2. The combination with supersonic
molecular beams has already been mentioned above (Dietz et al. 1980a,b; Dun-
can et al. 1979; Smalley et al. 1975, 1977). It provided means of isomer- and even
isotopomer-selective molecular ionization as well as important spectroscopic
information about larger molecules (Dietz et al. 1980a,b; Duncan et al. 1979,
1981; Herrmann et al. 1979; Leutwyler and Even 1981; Murakami et al. 1981).
Another intriguing early combination was the hyphenation of REMPI-MS
with gas chromatography (Klimcak and Wessel 1980; Rhodes et al. 1983). On
the one hand, this allows the gas chromatography (GC) of very complex gas
mixtures without the need for laborious chemical separation of interfering
species in advance (because of the high level of selective detection achieved by
resonant laser MS). On the other hand, this combination permits to quantify
or calibrate resonant laser mass spectra or to test its sensitivity. Also very early,
the advantages and new possibilities of resonant laser ionization for ultratrace
analysis were recognized. Limits of detection for aniline (Brophy and Rettner
1979a) and NO (Zacharias et al. 1981) and detection of single naphthalene
molecules in the laser focus volume (Antonov et al. 1981) were reported between
1979 and 1981. Another important technique used in conjunction with resonant
laser MS is reflectron time-of-flight mass spectrometry. In addition to high mass
resolution, this provides new means of performing tandem mass spectrometry
and of studying and practically applying the process of metastable decay of
molecular ions (Boesl et al. 1992; Kaufmann et al. 1994).
A third combined technique is neutral laser desorption in a REMPI-MS spec-
trometer. For details on laser desorption and laser desorption-postionization
processes see also Chapters 9, 10 and 11 of this book. The different facets of laser
desorption-REMPI postionization, such such as picosecond laser desorption
2.3 Principle of REMPI: Rate Equations and Quantification of Detection Efficiency 29
(Antonov et al. 1982), supersonic beam cooling of desorbed neutral molecules

(Boesl et al. 1987; Tembreull and Lubman 1986; Weyssenhoff et al. 1985, 1986),
and application to large biomolecules (Antonov et al. 1982; Boesl et al. 1987;
Engelke et al. 1987; Grotemeyer et al. 1986b) were already exploited in the first
years of REMPI. Another early combination (Gobeli et al. 1984, 1985; Knee et al.
1985), namely, that of REMPI with picosecond lasers, represents a precursor of
later REMPI with ultrashort lasers (Pedersen et al. 1994; Zewail 1994). This is
applied to study fast intramolecular processes in the neutral intermediate states,
which may reduce ionization efficiency or the appearance of the molecular
ions. Short laser pulses may, however, also represent a means to surpass these
unwanted intramolecular processes.
2.3 Principle of REMPI: Rate Equations

and Quantification of Detection Efficiency
2.3.1 Rate Equations
In most cases of molecular photoexcitation, laser intensities (photons per second
per square centimeter) are not large enough, or concurring processes such as
nonradiative relaxation k nr (see Figure 2.2) or the ejection of an electron are much
faster than the absorption processes 𝛼 and 𝛽. Then, the so-called coherent photo
effects do not play a role and need not be considered. In this case, rate equations
can be used to calculate the yield of a multiphoton process and determine the
threshold of detection for a REMPI process (Zakheim and Johnson 1980).
In Figure 2.3, a typical excitation scheme is displayed with molecules M in the
ground state, molecules M* in the excited state, and molecular ions M+ . The rate
of the first absorption step is 𝛼, that of the second ionizing step is 𝛽, and the nonra-
diative decay rate of the excited state is k nr . In addition, the excited state is depop-
ulated by the stimulated emission rate 𝛼 and the spontaneous emission rate k r
(fluorescence). As 𝛼, 𝛽, k nr , and k r all are unimolecular processes, their dimension
is 1 s−1 . On the other hand, M, M* , and M+ are concentrations (particles/cm3 ).
Please note that the photoprocesses 𝛼 and 𝛽 must not be single-photon processes
but can be multiple photon processes by themselves. For a general n-photon
process, the corresponding absorption (or emission) rates depend on the cross
section 𝜎 n and the nth power of the laser intensity P (photons/(s cm2 )).
𝛼 = 𝜎n Pn (2.1a)
𝛽 = 𝜎m Pm (2.1b)
The dimension of the n-photon cross section is (cm2n /sn−1 ). In the case of a
(1 + 1)-REMPI process (see Figure 2.1a–c), the rates of the photoprocesses are
given by Eq. (2.2a). The case of a (2 + 1)-REMPI process (see Figure 2.1d) is
described by Eq. (2.2b). The numbers (1) and (2) denote the first and the second
absorption step, respectively.
(1 + 1) − REMPI 𝛼 = 𝜎(1)P and 𝛽 = 𝜎(2)P (2.2a)
(2 + 1) − REMPI 𝛼 = 𝜎2 (1)P2 and 𝛽 = 𝜎(2)P (2.2b)
M+ IE
knr
Energy
M*
α α kr
M
Figure 2.3 Typical energy level scheme of general REMPI process with first absorption step 𝛼,
second (ionizing) absorption step 𝛽, nonradiative relaxation process knr , spontaneous
radiation emission kr , and stimulated radiation emission 𝛼. Rates 𝛼 and 𝛽 can be due to 1, 2 or
more photon absorption.
Another important parameter is the laser pulse duration t L because that is the
time during which the photoprocesses are active. For a single-photon process
such as in conventional UV absorption spectroscopy or VUV single-photon ion-
ization process, it does not matter if P is large and t L is short or vice versa as long
as the total number of photons per square centimeter P ⋅ t L is constant. This is not
the case for multiphoton processes in general. Considering all this, one obtains
the following coupled rate equations:
dM∕dt = −𝛼M + (𝛼 + kr )M∗ (2.3a)
dM∗ ∕dt = 𝛼M − (𝛼 + kr + knr )M∗ (2.3b)
dM+ ∕dt = 𝛽M∗ (2.3c)
The general solution is quite complicate and given in Eq. (2.4):
𝛽M ( L −KtL K −LtL
)
M+ = 1+ e − e (2.4a)
𝛽 + knr K −L K −L
with
A+𝛼 1√
K, L = (±) (A + 𝛼)2 − 4𝛼(𝛽 + knr ) (2.4b)
2 2
(for K the (+), for L the (−) sign is valid) and
A = 𝛼 + 𝛽 + knr + kr (2.4c)
However, there exist several limiting cases, which describe sufficiently most
experimental cases of molecular REMPI. The first case concerns the situation
where all neutral molecules are excited because the rates 𝛼 and 𝛽 are larger than
the reciprocal laser pulse length 1/t L . The second case describes the situation
where the absorption rate of the first step is small but that of the ionizing step is
2.3 Principle of REMPI: Rate Equations and Quantification of Detection Efficiency 31
large. The third case is similar to the second case; however, now the nonradiative
relaxation rate k nr is very large, too. Finally, the fourth case describes the most
frequent case in molecular REMPI, where all four rates 𝛼, 𝛽, k nr , and k r are
smaller than the reciprocal laser pulse length 1/t L .
( )
1 𝛽
Case 1 𝛼, 𝛽 ≫ M+ = M (2.5a)
tL 𝛽 + knr
( )
1
Case 2 𝛽 ≫ , knr ≪ 𝛽 M + = 𝛼 M tL (2.5b)
tL
( )
1 𝛽
Case 3 𝛽, knr ≫ M+ = 𝛼 M t (2.5c)
tL 𝛽 + knr L
( )
1 1
Case 4 𝛼, 𝛽, knr ≪ M+ = 𝛼 𝛽M tL 2 (2.5d)
tL 2
All cases, where 𝛼 ≪ t1 , may be denoted as a situation of small laser intensity,
L
where the first resonant absorption step is not saturated (𝜎(1)Pt L ≪ 1). This
is important for selectivity because saturation will reduce spectral resolution.
For the most common REMPI process, the (1 + 1)-REMPI, case 4 can be
formulated as
1 1
M+ = 𝛼 𝛽M tL 2 = M𝜎(1)𝜎(2)P2 tL 2 (2.6)
2 2
2.3.2 Quantification of the REMPI Detection Efficiency

Equation (2.6) will now be used to give an estimation of the limit of detection of
a concentration M of sample molecules in a gas mixture.
In Figure 2.4, the situation of a (1 + 1)-REMPI process is illustrated. The
situation of “small” laser intensities as defined above and used in Eq. (2.6) is
assumed. In typical cases (e.g. aromatic molecules), the cross section of the
first absorption step is 𝜎(1) = 10−18 cm2 . A cross section of 𝜎(2) = 10−17 cm2 is
typical for absorption into the ionization continuum well above the molecular
ionization threshold (e.g. by 1 eV). To use Eq. (2.6), the photon flux per square
centimeter is needed. A laser pulse energy at 250 nm of 0.1 mJ, a diameter of the
laser focus d = 0.03 cm, and a pulse length of 10 ns are assumed. These are quite
reasonable numbers for conventional pulsed tunable lasers (dye lasers) equipped
with a frequency doubling crystal to reach the UV range. The transformation
of energy per laser pulse into photon numbers gives nphoton = 1.25 × 1014
photons for a laser pulse energy of 0.1 mJ and a wavelength of 250 nm (due
to Elaserpulse = n h 𝜈 = n h c/𝜆, 𝜆 = 250 nm). The photon flux density is then
nphoton /(t laser ⋅ 𝜋/4 ⋅ d2 ) = 1.25 × 1014 /(10−8 s ⋅ 𝜋/4 ⋅ 0.9 × 10−3 cm2 ) = 1.8 × 1025
photons/(cm2 s). Inserting these numbers in Eq. (2.6) gives a relative ion yield of
[M+ ]/[M] = 1/10.
With this ion yield, the sensitivity for a selected target molecule can be esti-
mated. For that, we need the size of the ionization volume (see Figure 2.4). The
pressure in the gas beam can then be transformed into a total number of gaseous
atoms or molecules in this volume. The minimum number of detectable target
Another random document with
no related content on Scribd:
dormir en buen lecho, leer algun libro, hacer resonar bajo sus dedos
la lira de Thracia.
Pero si el viento de las tempestades se lleva mis vanas palabras,
¡que al menos favorezca Galatea á la nave que te conduce! Si llega
á perecer tal belleza, vuestro seria el crímen y de vuestro padre,
Diosas y Nereidas. Parte pensando en mí para volver al primer
viento propicio, y que su soplo más fuerte hinche entonces tus velas.
Que el poderoso Nereo vuelva la mar inclinada sobre esta ribera;
que el viento empuje las naves hácia aquí: y por aquí el flujo
precipite las aguas. Tú misma ruega á los céfiros soplen de lleno en
tus velas, que tus propias manos ayudarán á hacer mover.
Yo seré el primero en descubrir desde la ribera tu nave querida; y
diré: «esa nave trae otra vez mis dioses.» Te recibiré en mis brazos,
tomaré rápidamente desordenados besos; la víctima ofrecida para tu
regreso caerá al pié de los altares. Extenderé en forma de lecho la
lijera arena de la playa, y el primer otero nos servirá de mesa. Allí
con el vaso en la mano me contarás todas tus aventuras; me
describirás tu navío medio engullido por las oleadas; me dirás que
viniendo hácia mí no temias ni al frio ni á la noche, ni á los austros
impetuosos. Todo esto, aunque fuese fingido, será verdad para mí;
lo creeré todo. ¿Y por qué no he de creer yo con complacencia lo
que más deseo? ¡Ojalá pudiese la estrella de la mañana, brillando
en un cielo sin nubes, traerme desde luego este dichoso dia!
ELEGIA DUODÉCIMA.
ARGUMENTO.
Se goza de haber por fin obtenido los favores de Corina.

Ceñid mi frente, laureles de la victoria. Soy vencedor: Corina está
en mis brazos; aquella que un marido, que un guardian, que una
puerta de encina, ¡que tanto antemural ponian al abrigo de una
sorpresa! La victoria que, ante todas las otras, merece los honores
del triunfo, es seguramente aquella que no está manchada por la
sangre del vencido. No son humildes murallas, no son plazas
cercadas por estrechos fosos, una bella es la que he sabido tomar
por asalto.
Cuando Pérgamo cayó, despues de diez años de guerra, ¿qué
parte de honor, entre tantos sitiadores, alcanza el hijo de Atreo? Mi
gloria, es mia, me es toda personal: ningun soldado puede reclamar
su parte, ninguno tiene título para pretenderla. Como jefe y soldado
á la vez he logrado mis fines: yo mismo fuí á la vez caballero,
infante, abanderado, y en mis hechos no tuvo lugar la casualidad.
¡Para mí, pues, mi triunfo que es premio de mis esfuerzos!
No seré tampoco la causa de una nueva guerra. Sin el rapto de la
hija de Píndaro, la paz de Europa y del Asia no se hubiese alterado.
Una mujer es quien, con el vino, arma vergonzosamente, unos
contra otros, á los salvajes Lapithas y la raza monstruosa de los
Centauros. Una mujer es quien en tu reino, justo latino, obligó á los
Troyanos á empezar de nuevo desastrosas guerras. Una mujer es
quien, desde los primeros tiempos de Roma, fué causa del
sangriento combate en que los Romanos tuvieron que defenderse
contra sus suegros. He visto pelearse los toros por una blanca
vaquilla, que, espectadora de la lucha, animaba su valor. Yo tambien
soy uno de los numerosos soldados del Amor; pero es sin efusion
de sangre como me hace seguir sus estandartes.
ELEGÍA DÉCIMOTERCIA.
ARGUMENTO.
A Isis: le pide proteja la preñez de Corina.

La imprudente Corina tratando de desembarazarse de la carga
que lleva en su seno, se expone ella misma á perder la vida.
Ciertamente por haber afrontado, sin saberlo, tan gran peligro,
merecia toda mi cólera; pero la cólera cede ante el temor. Pues ó
habia concebido por mi causa ó al menos yo así lo creo: porque
frecuentemente tomo por un hecho cierto, lo que no es más que
posible.
Isis, tú que habitas el Paretonio, y los campos deliciosos de
Canope, y Mémfis, y Pharos fértil en palmeras, y aquellas llanuras
en donde el Nilo, abandonando su vasto cauce, va, por siete bocas,
á llevar sus aguas al mar; yo te conjuro por tu sistro[8], por la cabeza
misteriosa de Anubis, (y que á este precio el pio Osiris acepte
siempre tus sacrificios, la serpiente amodorrada se arrastre
lentamente en torno de las ofrendas, y en medio del cortejo se
adelante Apis con su media luna sobre la frente); fija tus miradas en
Corina: ahorra en ella sola dos víctimas, porque ambas recibiremos
la vida, ella de tí, yo de ella. Muy frecuentemente tú la has visto, en
los dias que te son consagrados, celebrar tus misterios, á la hora en
que tus sacerdotes coronen sus frentes con laureles.
Y tú, que tienes piedad de las jóvenes esposas en los dolores del
parto, cuando el fruto que llevan escondido busca salir de su prisión,
Ilithyia, séasme propicia, y dígnate atender mis súplicas: ella merece
que tú la cuentes en el número de tus protegidas. Y yo, revestido de
una ropa blanca, iré á hacer ahumar el incienso en tus altares: iré á
cumplir mis votos, depositar mis ofrendas á tus piés, con esta
inscripcion: «Ovidio, por la salud de Corina.» Dígnate solamente dar
lugar á mis ofrendas y á esta inscripcion.
Y tú, Corina, si en mi espanto, me es permitido darte un aviso,
despues de una tal lucha, no aventuro una segunda.
NOTAS AL PIE:
[8] Instrumento músico.

ELEGIA DÉCIMOCUARTA.
ARGUMENTO.
A Corina: aprovecha su restablecimiento para exponerle más

libremente la gravedad de su falta.
¿De qué sirve á las bellas el estar fuera de combates, de no tener
que seguir, escudo en mano, nuestras formidables legiones, si, lejos
de los peligros de la guerra, ellas se lastiman con sus propias
armas, si con sus ciegas manos atentan á sus dias? La que primero
ensayó hacer abortar en sus entrañas el tierno fruto que llevaba,
merecia perecer en esta lucha empeñada por ella. ¡Qué! ¡para
ahorrar á tu vientre algunas arrugas, convendrá asolar el triste
campo en que se libró el combate!
Si, en las primeras edades del mundo, las madres hubieran tenido
esta viciosa costumbre, el género humano hubiera desaparecido de
la tierra; y para repoblar el universo y sembrar las piedras de que
nacieron nuestros abuelos, seria menester otra Deucalion. ¿Quién
hubiera destruido el imperio de Príamo, si la diosa de los mares,
Thétis, no hubiera querido llevar su fruto hasta el término fijado por
la naturaleza? Si Ilia hubiese ahogado los mellizos de quienes
estaba embarazada, no hubiese existido el fundador de la villa
señora del mundo. Si Vénus hubiese hecho morir á Eneas en su
seno, la tierra hubiese sido privada de los Césares. Tú misma, que
debias nacer tan bella, hubieras perecido, si tu madre hubiese
hecho lo que tú acabas de osar. Y yo, más bien nacido para morir de
amor, no hubiese jamás existido, si mi madre me hubiese muerto de
antemano.
¿Por qué despojar á la viña fecunda del racimo que crece? ¿Por
qué, con mano cruel, arrancar el fruto antes de su madurez? muerto
caerá por sí mismo; una vez nacido, déjale crecer; la vida es
bastante buen premio para algunos meses de paciencia.
Mujeres, ¿por qué manchais vuestras entrañas con un hierro
homicida? ¿Por qué presentais el cruel veneno al niño que aun no
existe? Se maldice á la madrastra de Colquida, que se manchó con
la sangre de sus hijos y se compadece á Itis degollado por su
madre. Sí, estas dos mujeres fueron bárbaras; pero su barbarie
tenia un motivo: se vengaban de sus esposos en los hijos que tenian
de ellos. ¿Os escita, decidme, algun Tereo, algun Jason á
despedazar vuestras entrañas con sacrílega mano?
Jamás se ha visto tanta crueldad en los tigres de las cuevas de la
Armenia; jamás la leona se atrevió á procurar el aborto. Á las tiernas
bellezas estaba reservado el intentarlo, pero no impunemente.
Ahogando á su hijo en su seno, perece muchas veces la madre.
Perece, y se lo lleva toda desmelenada en su lecho de dolor; y todos
exclaman al verla: «¡Lo tiene bien merecido!»
Pero que mis vanas palabras se pierdan en el aire; ¡que mis
presajios queden sin efecto! Dioses clementes, sufrid que Corina
haya cometido impunemente una primera falla, es todo lo que pido.
Que el castigo sea reservado para la segunda.
ELEGÍA DÉCIMAQUINTA.
ARGUMENTO.
Al anillo que él habia enviado como presente á su señora.

Anillo, que vas á ceñir el dedo de mi bella señora, tú que no tienes
otro precio que el amor de aquel que te dá, sé para ella un presente
agradable: ojalá te reciba con placer, ¡y te coloque desde luego en
su dedo! Sé hecho para ella, como ella para mí; que tu círculo
abrace cómodamente su dedo, sin lastimarlo.
Dichoso anillo, tú vas á ser tocado por mi señora. ¡Ay! yo envidio
ya la suerte de mi presente. ¡Oh! que no pueda yo de un golpe
transformarme en tí, por el arte del májico de Ea ó del viejo de
Carpthos. Entonces yo querría que tú tocaras su cuello, ó te
introdujeses con su mano izquierda bajo su túnica. Yo me escaparia
de su dedo, por muy apretado y ajustado que estuviese, y me
libertaria por encantamiento para ir á caer sobre su seno. Yo
tambien, cuando ella querria sellar sus tabletas misteriosas, é
impedir á la cera adherirse á la piedra muy seca, yo tocaria ante
todo los húmedos lábios de mi bella señora, con tal solamente de no
sellar jamás un escrito doloroso para mí. Si ella quiere hacerme
colocar en su joyero, rehusaré dejar su dedo; me encojeré para
sujetarle más fuertemente.
Que jamás, oh tú que eres mi vida, sea yo para tí un motivo de
vergüenza, una carga muy pesada para tu delicado dedo. Llévame,
ya te zambullas en un baño tibio, ya te bañes en el agua corriente.
Pero quizá entonces viéndote desnuda, el amor despertará mis
sentidos, y ese mismo anillo tomará de nuevo su papel de amante.
¡Ay! ¿qué significan estos avisos inútiles? Parte, débil presente, y
que mi señora no vea en tí más que la prenda de mi fidelidad.
ELEGIA DÉCIMASEXTA.
ARGUMENTO.
Á Corina, induciéndola á que vaya á verle en su casa de campo

de Sulmona.
Estoy en Sulmona, tercer canton del territorio de los Sabinos[9].
Este canton es pequeño, pero el aire es saludable, gracias á frescas
fuentes de agua viva. Aunque los rayos más cercanos del sol
hienden aquí la tierra, aunque se sienten los ardores funestos de la
canícula, límpidos arroyos serpentean á través de los campos
Pelignos, y una vejetacion vigorosa cubre el suelo de fresco césped.
El pais es fértil en trigo, más fértil aun en uva: produce alguna vez
ademas la almendra que viene del árbol de Palas. Las aguas que
corren por las praderas las tienen al instante cubiertas de una yerba
nueva, y el suelo, siempre refrescado, presenta un espeso tapiz de
verdura.
Pero allí no se encuentra mi amor; me engaño de una palabra: allí
no se encuentra el objeto de mi amor, mi amor se encuentra solo.
Aunque se me colocase entre Castor y Pollux, sin tí yo no querria
habitar el cielo.
¡Que la muerte sea cruel y la tierra pesada á aquellos que han
trazado los primeros, en sus carreras, lejanos surcos en el globo! Al
menos debian mandar á las jóvenes bellezas á acompañar á sus
amantes, si fuera menester surcar la tierra por caminos
interminables. Por lo que á mí toca, si habia de trepar, helado de
frio, los Alpes expuestos á todos los vientos, este viaje, penoso
como es, me pareceria dulce con mi señora; con mi señora, no
dudaria en atravesar los Sirtes de la Libia, en presentar mi vela al
pérfido Noto; con ella no temería ni á los mónstruos marinos que
ladran á los lados de Scila, ni tus estrechas gargantas, tortuosa
Malea, ni las aguas que el infatigable Caribdis, hartada sin cesar de
navíos sumergidos, vomita y engulle de nuevo.
Que si los vientos son más fuertes que Neptuno, si las olas se
llevan los dioses que nos protejen, enlaza á mis hombros tus brazos
tan blancos como la nieve, yo llevaré fácilmente tan dulce peso.
Frecuentemente, para ir á ver á Hero, su jóven amante habia
atravesado los mares á nado; no hubiese perecido, sin la oscuridad
que ocultó el camino á sus ojos.
Yo, aquí solo sin mi señora, tengo agradable vista de ricos
viñedos, de campos en todas partes bañados por límpidos rios; veo
al agua, obedeciendo al cultivador, dividirse en numerosos arroyos,
y las hojas de los árboles suavemente agitadas por el fresco aliento
de los vientos; mas no creo habitar el bello pais de los Pelignos; no
encuentro la heredad de mis antepasados, el lugar que me ha visto
nacer; me creo en medio de la Scythia, de los bravos cilicianos, de
los Bretones con el rostro pintado de verde y entre peñascos teñidos
con la sangre de Prometheo.
El olmo ama la viña, la viña se une al olmo; ¿por qué estoy tan á
menudo lejos de mi señora? Sin embargo, tú debias no separarte
nunca: tú me lo habias jurado, y por mí y por tus ojos que son mis
astros tutelares. Más lijeras que las hojas de otoño, las vanas
promesas de la belleza huyen siempre á merced de los céfiros y de
las aguas.
Si por tanto eres aun sensible á mi desamparo, comienza en fin á
cumplir tus promesas; sube sin más tardar en un carro lijero tirado
por dos veloces caballos, y sacude tú misma las riendas sobre su
clin flotante. Y vosotros, montes orgullosos, humillaos á su paso; y
vosotros, tortuosos valles, abridle fácil camino.
NOTAS AL PIE:
[9] Abruzo.
ELEGIA DÉCIMASÉPTIMA.
ARGUMENTO.
Se compadece de Corina, demasiado engreida de su belleza.

Si hay alguno que piense que es vergonzoso el ser el esclavo de
una bella, acepto su condenacion. Que me declare pues infame, con
tal que la diosa que reina á Paphos y á Cytheres me trate con un
poco más miramiento. ¿Por qué no he sido el esclavo de una
amante sensible y dulce, puesto que yo habia nacido para ser el
esclavo de una bella? La belleza dá orgullo: la belleza de Corina la
vuelve intratable. ¡Ay! ¡por qué se conoce tan bien! De su espejo
saca su arrogancia; aunque no se mira en él mas que despues de
componerse.
Si tu belleza, nacida para hechizar mis ojos, te asegura el imperio
de todos los corazones, no debes, comparándome á tí,
despreciarme; la inferioridad puede asociarse con la grandeza. Se
sabe que la ninfa Calipso, ardiendo en amor por un simple mortal, le
retiene contra su voluntad para hacerle su esposo. Se sabe que una
de las Nereidas no se abochornaba por tener comercio con el rey de
Phthia, Egeria con el justo Numa, Vénus con Vulcano, cojo, y todo
sucio como está al dejar su yunque. Estos versos no son de un
metro igual, y por tanto el verso heróico se combina muy bien con
un verso de más pequeño corte.
Tú tambien, oh alma mia, acójeme á cualquier título que sea. Que
de lo alto de tu lecho te plazca dictarme leyes. No verás nunca en
mí un acusador pronto á vengarse de su desgracia: no tendrás que
negar nuestro amor.
Que cerca de tí mis versos suplan en mí la riqueza. Más de una
bella quiere deberme su celebridad. Sé de una que en todas partes
va haciéndose pasar por Corina: ¿por serlo efectivamente qué no
daria ella? Pero como no se vé correr por un mismo cauce al fresco
Eurotas y al Pó guarnecido de chopos, del mismo modo ninguna
otra que tú será el objeto de mis cantos: solo á tí está reservado
inspirar mi genio.
ELEGIA DÉCIMAOCTAVA.
ARGUMENTO.
A Macer: se justifica de entregarse enteramente á cantos

eróticos.
Mientras que juntas en tus versos la cólera de Aquiles, y revistes
de sus primeras armas á los héroes encadenados por sus
juramentos, yo, Macer, gozo del reposo á la sombra de la indolente
Vénus, y el tierno Amor viene á parar el vuelo audaz de mi genio.
Más de una vez he dicho á mi señora: «Basta ya, retírate,» y al
punto ella se sienta sobre mis rodillas. Frecuentemente le he dicho:
«En verdad estoy avergonzado;» y ella, reteniendo con pena sus
lágrimas, exclamaba: «¡Qué desgraciada soy! ¡ya te avergüenzas de
amarme!» Entónces estrechándome entre sus brazos, me prodigaba
mil besos de aquellos que hacen mi perdicion. Estoy vencido; mi
espíritu no sueña en los combates: lo que yo canto son mis hazañas
domésticas y mis guerras privadas. No obstante he manejado el
cetro; mi pluma ha osado abordar la trajedia, y la empresa no era
superior á mis fuerzas. El Amor se echó á reir al ver mi noble manto,
mi coturno pintado y mi cetro tan bien llevado por manos para las
cuales está hecho. Las exigencias de una señora imperiosa me han
arrancado de este trabajo, y el poeta de coturno es batido por el
Amor.
Puesto que esta es mi suerte, me limito á profesar el arte de
amar; y soy el primero ¡ay! abrumado bajo el peso de mis preceptos.
O escribo una carta de Penélope á Ulyses, ó pinto tus lágrimas,
Phyllis, cuando te ves abandonada. Escribo á Páris y á Macarea, y
al ingrato Jason, y al padre de Hippólyto, y al mismo Hippólyto.
Repito los lamentos de la infortunada Didon, armada de su
amenazante espada, y los suspiros de la heroina de Lesbos, amiga
de la lira Eolia.
¡Con qué velocidad mi amigo Sabino ha recorrido el mundo, y
traido de mil diversos lugares la respuesta á estas letras! La casta
Penélope ha reconocido el sello de Ulyses, y la suegra de Hippólyto
ha leido los reproches que él le dirije. Ya el piadoso Eneas ha
respondido á la muy desgraciada Elisa; y Phyllis, si con todo eso ella
respirara, tambien tiene su respuesta. Las tristes despedidas de
Jason han llegado á Hypsipyle; y Safo, querida de Apolo, no tiene
mas que depositar á los piés del Dios la Lyra que le tiene
consagrada.
Pero tú tambien, Macer, cantando los combates y los trabajos de
Marte, tú tambien has hablado, tanto como has podido, del amor y
de sus tesoros. En tu poema figuran Páris, y aquel adúltero cuyo
crímen ha hecho tanto ruido, y Laodamia acompañando á su esposo
que ya no existe. Sí, te conozco bien, tratas estos asuntos tan de
buena gana como los combates, y pasas frecuentemente de tu
campo al mio.
ELEGIA DÉCIMANOVENA.
ARGUMENTO.
A un hombre cuya mujer amaba.

Insensato, si para tí tú no tienes necesidad de vigilar tu mujer,
vigílala al menos para mí á fin de hacérmela desear más. Lo que
nos está permitido nos es insípido; lo que nos está prohibido excita
más fuertemente nuestra pasion.
Aquel que ama lo que otro le permite amar, tiene un corazon de
hierro. En cuanto á nosotros, los que sabemos amar, nos falta
esperar y temer á la vez, y, para desear más vivamente, tener que
sufrir algunas repulsas.
Que no se me hable de una fortuna que me pondria al abrigo de
toda decepcion. No sabria amar lo que no pueda inquietarme en
ningun tiempo. Este es mi flaco; bien lo habia visto la astuta Corina:
demasiado sabia ella por dónde podíaseme cojer. ¡Cuántas veces,
ay le tengo visto ¡la mentirosa! fingir un violento mal de cabeza, á fin
de despedirme! ¡Cuántas veces he debido, aunque me costase,
alejarme á paso lento! ¡Cuántas veces me ha supuesto culpas, y,
culpable ella misma, se ha supuesto la inocente! Despues de
haberme atormentado, despues de haber así reanimado mis fuegos
medio apagados, volvía á estar dulce y sensible á mis deseos. ¡Qué
de caricias, qué de ternuras entonces me prodigaba! ¡Cuántos
besos y ¡grandes dioses! qué besos!
Tú tambien, que recientemente has embelesado mis ojos, recurre
frecuentemente á la astucia, seas á menudo sorda á mis súplicas;
déjame tendido en el umbral de tu puerta, sufrir el penetrante frio de
una larga noche de invierno. Mi amor no tiene fuerza, únicamente á
este precio tiene duracion. Vé ahí lo que le falta, vé ahí lo que
alimenta mi pasion. Un amor llano y sin dificultad me llega á ser
insípido: es como un manjar muy dulce, que no puede excitarme el
corazon. Si nunca Danae hubiese estado encerrada en una torre de
metal, jamás Júpiter la hubiese hecho madre. Juno, haciendo vigilar
á Io, con la frente cargada de cuernos, la volvió á los ojos de Júpiter
más graciosa que antes.
Aquel que limita sus deseos á lo que es fácil y permitido, vaya á
cojer la hoja sobre los árboles, y beba en plena ribera. Bellas, si
quereis aseguraros un largo imperio, sabed abusar de vuestros
amantes. ¡Ay! ¿Para qué es menester que yo dé lecciones contra mí
mismo? No importa; ame quien quiera una complacencia sin límites:
á mí me sirve de molestia. Yo huyo de quien se detiene á mi paso, y
me detengo al paso de quien de mí huye.
Pero tú, que estás tan seguro á la vista de tu bella compañera,
comienza desde hoy á cerrar tu puerta desde la caida del dia;
comienza á preguntar á quien viene tan frecuentemente á golpearla
furtivamente; lo que hace ladrar á tus perros en el silencio de la
noche; entérate de los billetes que lleva y vuelve á llevar una
diligente sirvienta; y por qué tu bella, tan á menudo, quiere dormir
sola en su cama. Deja en fin estos cuidados roedores penetrar
alguna vez hasta la médula de tus huesos, y dame lugar para
recurrir á la astucia.
Ha nacido para hurtar la arena de las riberas desiertas, quien
puede ser amante de la mujer de un tonto. Te prevengo, que si no
vigilas más á tu mujer, no tardará en cesar de ser mi señora. Yo
esperaba que llegaria dia en que tu atenta vigilancia me obligase á
más astucia. Tú no te mueves, tú sufres lo que no sufriria ningun
marido. ¡Ah, bien! soy yo quien pondrá fin á un amor que tú
permites.
¡Qué desgraciado soy! ¿No es esto lo mismo que decir que jamás
me impedirás la entrada en tu casa? ¿Que no estaré durante la
noche expuesto á tu venganza? ¿Que jamás tendré nada que temer
de tí? ¿Que jamás encontrará mi sueño un suspiro tímido? ¡Qué!
¿no harás nada que me dé el derecho de desear tu muerte? ¿Es á
mí á quien conviene un marido fácil, un marido que prostituye á su
mujer? Tú acabas de emponzoñar mis placeres con tu
complacencia. ¿Por qué no buscas á otro, que se avenga á una tan
prolongada paciencia? Si te conviene que yo sea tu rival, prohíbeme
serlo.
LIBRO TERCERO.
ELEGÍA PRIMERA.
ARGUMENTO.
La Tragedia y la Elegía se disputan la posesion de Ovidio.

Existe una antigua selva, que durante largos años ha
permanecido virgen, y se la cree el santuario de una divinidad. En
medio hay una fuente sagrada, que domina una gruta cortada en la
roca: el aire resuena al alrededor, con el dulce murmullo de las aves.
Paseándome un dia en los espesos sotos de este bosque, pensaba
sobre qué género de obra ocuparia mi musa.
Ví venir hácia mí la Elegía con los cabellos olorosos y atados con
arte; y, si no me engaño, uno de sus piés era más largo que el otro.
Su aire era decente: su ropa, del tisú más lijero; su aspecto, el de
una amante. El defecto mismo de sus piés aumentaba su gracia. Ví
venir tambien á la Tragedia avanzándose á grandes pasos, la
mirada feroz, los cabellos dispersos, la ropa talar. En su mano
izquierda llevaba con arrogancia el cetro de los reyes; sus piés
calzaban noblemente el coturno Lydio.
La primera, dirigiéndose á mi, me dijo: «¿Cuál será, cuál será el
término de tus amores, poeta infiel á mi culto? En los festines
licenciosos cuéntanse tus locuras, cuéntanse en las encrucijadas.
Casi siempre que pasas te señalan con el dedo, y dicen: «Ved ahí
ese poeta á quien consume el cruel Amor.» Tú eres, sin duda, la
fábula de la capital cuando cuentas sin pudor tus espansiones
amorosas. Tiempo es ya de que, cediendo á los impulsos del thyrso,
trates asuntos más elevados. Por largo tiempo has estado reposado;
emprende una nueva obra. El asunto de tus cantos apoca tu génio:
celebra los grandes hechos de los guerreros. ¿Soy yo, dirás tú, para
servir en esa carrera? ¿Pero tu Musa no ha prodigado bastantes
canciones á las bellas? Tu primera juventud está enteramente
entregada á esas bagatelas. Sé conmigo ahora; que yo te debo el
nombre de Tragedia romana. Tu génio puede bastar para esta noble
tasca.» Dijo ella, y, apoyándose con altanería en sus coturnos
bordados, sacudió tres ó cuatro veces su cabeza sombreada por
una espesa cabellera.
La Elegía, si no recuerdo mal, sonrió mirándome de soslayo.
Tenia, si no me engaño, un ramo de mirto en la mano. «¿Por qué,
dijo, orgullosa Tragedia, me tratas con tan pocos miramientos? ¿no
puedes jamás dejar de ser severa? Esta vez no obstante has tenido
á bien combatirme en versos desiguales con mi propia rima. No
comparo mis cantos á tus sublimes acentos: tu soberbio palacio
aplasta mi humilde morada. Lijera como soy, me deleito con Cupido,
no menos lijero que yo. No tengo la vanidad de creerme superior á
mi papel. Sin mí, la madre del voluptuoso Amor no tendria tantos
encantos: soy la auxiliar y la compañera de esta diosa. La puerta
que no sabria forzar tu duro coturno, se abre á los dulces acentos de
mi voz; y sin embargo, si mi poder es superior al tuyo, lo debo á la
paciencia con la cual sufro bien las cosas que sublevarian tu orgullo.
De mí aprende Corina á engañar á su guardian, á forzar la cerradura
de una puerta rigurosamente cerrada, á salir furtivamente de su
lecho, vestida de una túnica arremangada, y á avanzar con paso
sordo, en las tinieblas de la noche.
«¡Cuántas veces me he visto suspendida en una puerta rebelde,
importándome poco ser vista por los paseantes! Hay más: recuerdo
que la sirvienta de Corina me recibió y tuvo escondida en su seno,
hasta que vió alejarse al severo guardian de su señora. ¿Te
recordaré que para celebrar el aniversario del nacimiento de tu bella,
me enviabas á ella en presente, y que me rasgó y me arrojó
despiadada en el agua? Soy yo la primera que ha hecho germinar
en tí las semillas fecundas de la poesía: á mí debes el privilegiado
talento que reclama para sí mi rival.»
Las dos Musas habian acabado, y, dirigiéndome á ellas, les dije:
«Por vosotras mismas os conjuro; acojed sin prevencion mis tímidas
palabras. Vosotras me ofreceis el cetro y el noble coturno y ya los
acentos sublimes salen de mi boca apenas entreabierta; y vosotras
haceis inmortales mis amores. Sé, pues, propicia á mis votos y
déjame mezclar entre sí el grande y el pequeño verso: otórgame
una poca dilacion, majestuosa Tragedia: tus obras exigen años, y
las de tu rival solamente algunas horas.»
No fué sorda á mi ruego: los tiernos amores esméranse en
aprovechar la próroga otorgada: he de ultimar una obra mucho más
grande que me apremia.
ELEGIA SEGUNDA.
ARGUMENTO.
Los juegos del Circo.

«Si me siento aquí, no es por el interés que tomo en los famosos
corceles; y sin embargo, mis votos no son menos para aquel que tú
favoreces. Vengo para charlar contigo, para estar á tu lado, para no
dejarte ignorar todo el amor que tú me inspiras. Tú miras la corrida y
yo te miro á tí. Gocemos los dos del espectáculo que nos agrada,
ambos repasemos nuestras miradas holgadamente. ¡Oh, dichoso,
sea quien quiera, el competidor que tú favorezcas! tiene la dicha de
interesarte. Que semejante dicha me alcance; al instante me
lanzaria de la barrera, abandonándome á mis impetuosos corceles.
Sabria, aquí, soltarles las riendas; allá, marcar sus flancos con
golpes de látigo; más lejos, estrechar el círculo dando vuelta. Pero
si, en mi carrera rápida, llegara á divisarte, ¡oh! me detendria, y las
riendas se me escaparian de las manos. ¡Ah! faltó poco para que
Pelops no cayera en medio de la carrera de Pisa, ocupado como
estaba en contemplarte, ¡bella Hippodamia! Y no obstante él debió
su victoria á los votos de su señora. ¡Así pudiesen todos los
amantes deber su triunfo á los votos de sus bellas!
¿Por qué tratas vanamente de alejarte de mí? la misma grada nos
retiene al uno junto al otro: es una ventaja que debo á los
reglamentos del Circo. Pero tú, que estás á la derecha de mi bella,
sostente bien; la molestas, apoyándote sobre ella. Y vosotros que
estais colocados detrás, no extendais tanto vuestras piernas; tened
bastante circunspeccion para no ajar sus espaldas con vuestra ruda
rodilla. Cuidado, amiga mia, tu ropa demasiado baja arrastra por
tierra; levántala como voy á hacerlo yo mismo. Oh ropa, estabas
celosa por cubrir tan bellas piernas; tú querias ser sola en verlas; si,
tú estabas celosa. Tales eran las piernas de la lijera Atalante, que
Milanion hubiera querido tocar con sus manos: tales tambien las de
Diana, cuando, levantada la ropa, perseguia en las selvas los
venados, menos intrépidos que ella misma. Estoy encendido por

Photoionization And Photo Induced Processes In Mass Spectrometry Fundamentals And Applications Ralf Zimmermann full chapter pdf docx

Uploaded by

Copyright:

Available Formats

You might also like

Photoionization And Photo Induced Processes In Mass Spectrometry Fundamentals And Applications Ralf Zimmermann full chapter pdf docx

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Photoionization And Photo Induced Processes In Mass Spectrometry Fundamentals And Applications Ralf Zimmermann full chapter pdf docx

Uploaded by

Copyright:

Available Formats

Photoionization and Photo-Induced

Processes in Mass Spectrometry:

Fundamentals and Applications of Fourier Transform Mass

Ambient Ionization Mass Spectrometry in Life Sciences:

Heat and mass transfer : fundamentals and applications

Applications in High Resolution Mass Spectrometry: Food

Nanofluids for Heat and Mass Transfer Fundamentals,

High-Throughput Mass Spectrometry in Drug Discovery 1.

Energy Sources. Fundamentals of Chemical Conversion

Introduction to Spatial Mapping of Biomolecules by

Fundamentals and Applications

Bibliographic information published by

© 2021 WILEY-VCH GmbH,

All rights reserved (including those of

Print ISBN: 978-3-527-33510-7

Cover Design: Wiley

Printed on acid-free paper

1 Fundamentals and Mechanisms of Vacuum Photoionization 1

2 Fundamentals and Mechanisms of Resonance-Enhanced

2.5 Application of REMPI for Optical Spectroscopy 45

3 Analytical Application of Single-Photon Ionization Mass

4 Analytical Application of Resonance-Enhanced Multiphoton

5 Probing Chemistry at Vacuum Ultraviolet Synchrotron Light

6 Resonance Ionization Mass Spectrometry (RIMS):

6.4.2 Stardust Grains 234

7 Ultrashort Pulse Photoionization for Femtosecond Laser Mass

8 Photoionization at Elevated or Atmospheric Pressure:

8.4.6 Oil Analysis 291

9 Fundamentals of Laser Desorption Ionization 305

10 Applications of Laser Desorption Ionization and Laser

10.8.1 LDPI-MS: Laser Desorption Postionization of Neutrals in

11 Laser Ionization in Single-Particle Mass Spectrometry 359

Nd:YAG-pumped optical parametric oscillators (OPOs) or Ti:sapphire cavities

extended to the diﬀerentiation of isotopomers and – by using a special REMPI

The application of synchrotron VUV light for SPI-MS-based investigation of

is devoted to such ionization mechanisms at elevated pressures and their

Ralf Zimmermann Luke Hanley

Fundamentals and Mechanisms of Vacuum Photoionization

Dr.-Lorenz-Weg 2, D-18059 Rostock, Germany

Photoionization and Photo-Induced Processes in Mass Spectrometry: Fundamentals and Applications,

Energy XUV VUV VIS IR Microwave

Technical VUV attosecond Ti:Sapphire Nd:YAG/Excimer Pulsed TOF-MS

Figure 1.1 Typical energy- and timescales of processes related to photoionization.

E Figure 1.2 Illustration of a linearly

1.3.1 Transitions in First Order Perturbation Theory

In quantum mechanics, the state |𝜓⟩ of a system can be described by a complex

The time evolution of a physical system is described by solutions of the

In general, photoionization can be understood as one of several possible

1.3.2 Perturbation Theory

Inserting in the TDSE (Eq. (1.18)) yields

Considering the orthogonality of the eigenstates, the result is a set of coupled

and ﬁnd the frequency-dependent absorption rate

Wba = Wba (𝜔)I(𝜔)d𝜔 (1.31)

1.3.4 Dipole Approximation

eikr ≈ 1 for 𝜆 → ∞; k → 0. In this so-called dipole approximation, the vector

The corresponding absorption rate can be derived to

An interesting application of transition rates is related to the famous Einstein

1.3.5 Selection Rules

1.3.6 Electronic Line Width and Lifetime