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Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:

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Page 1: Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:
Page 2: Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:
Page 3: Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:

Edited by

Gunter Gauglitz and David S. Moore

Handbook of Spectroscopy

Page 4: Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:

Related Titles

Gunther, H.

NMR SpectroscopyBasic Principles, Concepts andApplications in ChemistryThird, Completely Revised and UpdatedEdition

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Zerbe, O., Jurt, S.

Applied NMR Spectroscopy forChemists and Life Scientists

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ISBN: 978-3-527-32774-4

Friebolin, H.

Basic One- andTwo-Dimensional NMRSpectroscopyFifth, Completely Revised and EnlargedEdition

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Page 5: Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:

Edited byGunter Gauglitz and David S. Moore

Handbook of Spectroscopy

Second, Enlarged Edition

Volume 1

Page 6: Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:

Edited byGunter Gauglitz and David S. Moore

Handbook of Spectroscopy

Second, Enlarged Edition

Volume 2

Page 7: Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:

Edited byGunter Gauglitz and David S. Moore

Handbook of Spectroscopy

Second, Enlarged Edition

Volume 3

Page 8: Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:

Edited byGunter Gauglitz and David S. Moore

Handbook of Spectroscopy

Second, Enlarged Edition

Volume 4

Page 9: Edited by€¦ · Third, Completely Revised and Updated Edition 2013 ISBN: 978-3-527-33004-1 Zerbe, O., Jurt, S. Applied NMR Spectroscopy for Chemists and Life Scientists 2013 ISBN:

The Editors

Prof. Dr. Gunter GauglitzUniversity of TubingenInstitute for Physical and TheoreticalChemistryAuf der Morgenstelle 1872076 TubingenGermany

Dr. David S. MooreShock and Detonation PhysicsLos Alamos National LaboratoryMS-P952, Los Alamos, NM 87545USA

All books published by Wiley-VCH arecarefully produced. Nevertheless, authors,editors, and publisher do not warrant theinformation contained in these books,including this book, to be free of errors.Readers are advised to keep in mind thatstatements, data, illustrations, proceduraldetails or other items may inadvertently beinaccurate.

Library of Congress Card No.: applied for

British Library Cataloguing-in-PublicationDataA catalogue record for this book is availablefrom the British Library.

Bibliographic information published by theDeutsche NationalbibliothekThe Deutsche Nationalbibliotheklists this publication in the DeutscheNationalbibliografie; detailed bibliographicdata are available on the Internet at<http://dnb.d-nb.de>.

© 2014 Wiley-VCH Verlag & Co. KGaA,Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those oftranslation into other languages). No partof this book may be reproduced in anyform – by photoprinting, microfilm, or anyother means – nor transmitted or translatedinto a machine language without writtenpermission from the publishers. Registerednames, trademarks, etc. used in this book,even when not specifically marked as such,are not to be considered unprotected by law.

Print ISBN: 978-3-527-32150-6ePDF ISBN: 978-3-527-65473-4ePub ISBN: 978-3-527-65472-7mobi ISBN: 978-3-527-65471-0oBook ISBN: 978-3-527-65470-3

Cover-Design Bernd Adam Design,Weinheim, GermanyTypesetting Laserwords Private Limited,Chennai, IndiaPrinting and Binding Markono Print MediaPte Ltd, Singapore

Printed on acid-free paper

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V

Contents

List of Contributors XVIIPreface XXIX

Volume 1

Section I Sample Preparation and Sample Pretreatment 1

1 Preparation of Liquid and Solid Samples 3Brian M. Cullum and Tuan Vo-Dinh

1.1 Introduction 31.2 Preparation of Samples for Analysis 31.2.1 Measurement Process 31.2.2 Preparation of Samples for Analysis 41.2.3 Solid Samples 51.2.4 Liquid Samples 10

References 13

2 Liquid and Solid Sample Collection 15Paolo de Zorzi

2.1 Introduction 152.2 Sampling Process 162.3 Sampling Strategy and Collection 182.3.1 Liquid Sampling 202.3.2 Solid Sampling 222.4 QA/QC in Sampling 23

References 26

Section II Methods 1: Optical Spectroscopy 27

Introduction 29References 30

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VI Contents

3 Basics of Optical Spectroscopy 31Martin Hof and Radek Machan

3.1 Absorption of Light 313.2 Infrared Spectroscopy 333.3 Raman Spectroscopy 353.4 UV–vis Absorption and Luminescence 36

References 38

4 Instrumentation 39Valdas Sablinskas

4.1 MIR Spectrometers 404.1.1 Dispersive Spectrometers 404.1.2 Fourier-Transform Spectrometers 414.2 NIR Spectrometers 454.2.1 FT-NIR Spectrometers 464.2.2 Scanning-Grating Spectrometers 464.2.3 Diode Array Spectrometers 474.2.4 Filter Spectrometers 474.2.5 LED Spectrometers 474.2.6 AOTF Spectrometers 474.3 Terahertz Spectrometers 484.4 Raman Spectrometers 494.4.1 Raman Grating Spectrometer with Single Channel

Detector 494.4.2 FT-Raman Spectrometers with Near-Infrared

Excitation 524.4.3 Raman Grating Polychromator with Multichannel

Detector 534.4.4 Handheld Raman Spectrometers 554.5 UV/vis Spectrometers 564.5.1 Sources 574.5.2 Monochromators 574.5.3 Detectors 584.6 Fluorescence Spectrometers 594.7 Spectral Imaging Devices 614.8 Instrumentation for Nonlinear Vibrational Spectroscopy 644.8.1 Stimulated Raman Scattering (SRS) Spectrometers 644.8.2 Sum Frequency Generation (SFG) Spectrometers 654.8.3 Coherent Anti-Stokes Raman Scattering (CARS)

Systems 66Further Reading 69

5 Measurement Techniques 71Gerald Steiner

5.1 Transmission Measurements 71

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Contents VII

5.2 Reflection Measurements 745.2.1 External Reflection 745.2.2 Reflection Absorption 765.2.3 Attenuated Total Reflection (ATR) 765.2.4 Reflection at Thin Films 785.2.5 Diffuse Reflection 795.3 Spectroscopy with Polarized Light 815.3.1 Optical Rotatory Dispersion (ORD) 815.3.2 Circular Dichroism (CD) 825.4 Photoacoustic Measurements 835.5 Microscopic Measurements 855.5.1 Infrared Microscopes 855.5.2 Confocal Microscopes 865.5.3 Near-Field Microscopes 875.6 Infrared Spectroscopic Imaging 885.6.1 Analysis of Spectroscopic Images 89

Further Reading 94

6 Applications 95Valdas Sablinskas, Gerald Steiner, Martin Hof,and Radek Machan

6.1 Mid-Infrared (MIR) Spectroscopy 956.1.1 Sample Preparation and Measurement 956.1.2 Structural Analysis 1046.1.3 Special Applications 1096.1.4 Infrared and Raman Spectroscopic Imaging 1126.2 Near Infrared Spectroscopy 1146.2.1 Sample Preparation and Measurement 1146.2.2 Application of NIR Spectroscopy 1156.3 Raman Spectroscopy 1206.3.1 Sample Preparation and Measurements 1216.3.2 Special Applications 1296.4 UV/vis Spectroscopy 1356.4.1 Sample Preparation 1366.4.2 Structural Analysis 1366.4.3 Metal Complexes and Semiconductors 1406.4.4 UV/vis Spectroscopic Imaging 1456.4.5 Metal Nanoparticles 1466.5 Fluorescence Spectroscopy 1476.5.1 Sample Preparation and Measurements 1486.5.2 Special Applications 166

Acknowledgments 174References 174

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VIII Contents

Section III Methods 2: NMR 183

Introduction 185

7 An Introduction to Solution, Solid-State, and Imaging NMRSpectroscopy 193Leslie G. Butler

7.1 Introduction 1937.2 Solution-State 1H NMR 1957.3 Solid-State NMR 2037.3.1 Dipolar Interaction 2047.3.2 Chemical Shift Anisotropy 2067.3.3 Quadrupolar Interaction 2077.3.4 Magic Angle Spinning (MAS) NMR 2097.3.5 T1 and T1ρ Relaxation 2107.3.6 Dynamics 2147.4 Imaging 2157.5 3D NMR: The HNCA Pulse Sequence 2197.6 Conclusion 221

References 223

8 Solution NMR Spectroscopy 225Gary E. Martin, Chad E. Hadden, and David J. Russell

8.1 Introduction 2258.2 1D (One-Dimensional) NMR Methods 2268.2.1 Proton Spin Decoupling Experiments 2278.2.2 Proton Decoupled Difference Spectroscopy 2278.2.3 Nuclear Overhauser Effect (NOE) Difference Spectroscopy 2288.2.4 Selective Population Transfer (SPT) 2288.2.5 J-Modulated Spin Echo Experiments 2298.2.6 Off-Resonance Decoupling 2318.2.7 Relaxation Measurements 2328.3 Two-Dimensional NMR Experiments 2348.3.1 2D J-Resolved NMR Experiments 2358.3.2 Homonuclear 2D NMR Spectroscopy 2388.3.3 Gradient Homonuclear 2D NMR Experiments 2488.3.4 Heteronuclear Shift Correlation 2498.3.5 Direct Heteronuclear Chemical Shift Correlation Methods 2508.3.6 HSQC, Heteronuclear Single Quantum Coherence Chemical Shift

Correlation Techniques 2528.3.7 Long-Range Heteronuclear Chemical Shift Correlation 2558.3.8 Hyphenated-2D NMR Experiments 2688.3.9 One-Dimensional Analogs of 2D NMR Experiments 2718.4 Conclusions 283

References 285

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Contents IX

9 Suspended-State NMR Spectroscopy (High-Resolution Magic AngleSpinning (HR-MAS) NMR Spectroscopy) 293Markus Kramer and Klaus AlbertReferences 294

10 Solid-State NMR 297Steven P. Brown and Lyndon Emsley

10.1 Introduction 29710.2 Solid-State NMR Lineshapes 30010.2.1 The Orientational Dependence of the NMR Resonance

Frequency 30010.2.2 Single-Crystal NMR 30110.2.3 Powder Spectra 30310.2.4 One-Dimensional 2H NMR 30510.3 Magic-Angle Spinning 30710.3.1 Cross Polarization Magic-Angle Spinning Nuclear Magnetic

Resonance CP MAS NMR 30910.3.2 1H Solid-State NMR 31310.4 Recoupling Methods 31510.4.1 Heteronuclear Dipolar-Coupled Spins: REDOR 31510.4.2 Homonuclear Dipolar-Coupled Spins 31710.4.3 The CSA: CODEX 31910.5 Homonuclear Two-Dimensional Experiments 31910.5.1 Establishing the Backbone Connectivity in an Organic

Molecule 32010.5.2 Dipolar-Mediated Double-Quantum Spectroscopy 32410.5.3 High-Resolution 1H Solid-State NMR 32710.5.4 Anisotropic–Isotropic Correlation: the Measurement

of CSAs 32710.5.5 The Investigation of Slow Dynamics: 2D Exchange 32910.5.6 1H–1H DQ MAS Spinning-Sideband Patterns 33310.6 Heteronuclear Two-Dimensional Experiments 33510.6.1 Heteronuclear Correlation 33510.6.2 The Quantitative Determination of Heteronuclear Dipolar

Couplings 33710.6.3 Torsional Angles 34010.6.4 Oriented Samples 34110.7 Half-Integer Quadrupole Nuclei 34210.8 Summary 347

Acknowledgments 348Appendix 349Anisotropic Interactions: The Orientation Dependence of theResonance Frequency 349References 350

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X Contents

Section IV Methods 3: Mass Spectrometry 355

11 Mass Spectrometry 357Michael Przybylski

11.1 Introduction: Principles of Mass Spectrometry 35711.1.1 Application Areas of Mass Spectrometry to Biopolymer Analysis 35811.2 Techniques and Instrumentation of Mass Spectrometry 35911.2.1 Sample Introduction and Ionization Methods 35911.2.2 Mass Spectrometric Analyzers 36311.2.3 High-Resolution Mass Spectrometers 36811.2.4 Ion Detection and Spectra Acquisition 37211.2.5 Sample Preparation and Handling in Bioanalytical Applications 37311.2.6 Combination of Mass Spectrometry with Microseparation Methods

and New Mass Spectrometric Hybrid Systems 37611.3 Applications of Mass Spectrometry to Biopolymer Analysis 38311.3.1 Introduction 38311.3.2 Analysis of Peptide and Protein Primary Structures and

Posttranslational Structure Modifications 38411.3.3 Tertiary Structure Characterization by Chemical Modification and

Mass Spectrometry 38711.3.4 Characterization of Noncovalent Supramolecular

Complexes 38911.3.5 Mass Spectrometric Proteome Analysis 39111.3.6 Application of Affinity-Mass Spectrometry to the Analysis of

Biomolecular Recognition Structures 39311.3.7 Identification of Oligomerization – Aggregation Structures and

Pathways of Neurodegenerative Proteins by Ion Mobility MassSpectrometry 397Acknowledgments 398References 399

12 Multiparametric Analysis of Mass Spectrometry-Based ProteomeProfiling in Gestation-Related Diseases 407Michael O. Glocker, Claudia Rower, Manja Wolter, Cornelia Koy,Toralf Reimer, and Ulrich Pecks

12.1 Introduction on Gestational Diseases 40712.1.1 Preeclampsia 40712.1.2 HELLP Syndrome 40912.1.3 Intrauterine Growth Restriction (IUGR) 41012.2 Mass Spectrometric Data Acquisition from Plasma Samples 41112.2.1 Mass Spectrometric Data Collection Without Sample

Fractionation 41212.2.2 Mass Spectrometric Data Collection upon Sample Fractionation 41412.3 Multiparametric Analysis of Mass Spectrometry Data 41512.3.1 Recalibration and Standardization Strategies 415

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Contents XI

12.3.2 Statistical Procedures for Baseline Subtraction and Correction forIntercenter Offsets 417

12.3.3 Determination of Cut-Off Values for Ion Signal Areas 41812.3.4 Biostatistical Assay Evaluation and Data Visualization 41912.4 Conclusion and Clinical Relevance 422

References 423

13 Laser-Assisted Mass Spectrometry 429David Touboul and Renato Zenobi

13.1 Introduction 42913.2 Laser Desorption/Ionization 43013.2.1 Laser Microprobe Mass Spectrometry 43013.2.2 Matrix-Assisted Laser Desorption/Ionization (MALDI) 43213.2.3 Small-Molecule Desorption/Ionization 43713.3 Laser Ablation 43813.4 Laser Postionization 44013.5 Laser Ion Excitation 44113.6 Typical Applications of Laser Mass Spectrometry 44113.6.1 MALDI-MS in Proteomics 44213.6.2 Imaging Mass Spectrometry 442

References 446

Volume 2

Section V Methods 4: Elemental Analysis 449

14 X-ray Fluorescence Analysis 451Koen Janssens

15 Atomic Absorption Spectrometry (AAS) and Atomic EmissionSpectrometry (AES) 507Erwin Rosenberg and Ulrich Panne

16 Inductively Coupled Plasma Spectrometry 583Jose Alfons Clement Broekaert

17 Laser Ablation Inductively Coupled Plasma Mass Spectrometry(LA-ICPMS) 647Bodo Hattendorf and Detlef Gunther

Section VI Methods 5: Surface Analysis 699

Introduction 701

18 Electron Probe Techniques 709Christopher George Havelock Walker

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XII Contents

19 Ion/Neutral Probe Techniques 741Anna Mackova and Andrew Pratt

20 Photon Probe Techniques 779Simon Morton

Section VII Methods 6: Spectroscopy in Nano Dimensions 821

21 Single-Molecule Spectroscopy 823Frank Schleifenbaum, Christian Blum, Marc Brecht, and Alfred J. Meixner

22 Single-Molecule Interfacial Electron-Transfer Dynamics 877Hong Peter Lu

23 Scanning Near-Field Gap-Mode Microscopy 911Dai Zhang and Alfred J. Meixner

Volume 3

Section VIII Applications 1: Bioanalysis 941

24 Trends in Bioanalytical Spectroscopy 943Willem M. Albers

25 Quality Assessment of Spectroscopic Methods in ClinicalLaboratories 977Heike Schneider, Georg Kurz, and Peter B. Luppa

26 UV–Vis and NIR Fluorescence Spectroscopy 999Gabor Patonay, Garfield Beckford, and Pekka Hanninen

27 Principles of Vibrational Spectroscopic Methods and their Applicationto Bioanalysis 1037David S. Moore, Peter Uhd Jepsen, and Karel Volka

28 Bioanalytical NMR Spectroscopy 1079Perttu Permi

29 Direct Optical Detection in Bioanalytics 1115Gunter Gauglitz and Nicholas J. Goddard

Section IX Applications 2: Polymer Analysis 1159

30 Surface Plasmon Spectroscopy Methods and ElectrochemicalAnalysis 1161Akira Baba and Rigoberto Advincula

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Contents XIII

31 Applications of Fourier Transform Infrared (FTIR) Imaging 1179Al de Leon, Brylee Tiu, Joey Mangadlao, Katrina Pangilinan, Pengfei Cao,and Rigoberto Advincula

32 Photon Correlation Spectroscopy Coupled with Field-Flow Fractionationfor Polymer Analysis 1201J. Ray Runyon and S. Kim Ratanathanawongs Williams

33 Surface Plasmon Resonance Spectroscopy and Molecularly ImprintedPolymer (MIP) Sensors 1229Allan Cyago and Rigoberto Advincula

Section X Applications 3: Environmental Analysis 1259

34 LC-MS in Environmental Analysis 1261Sophie Bourcier and Michel Sablier

35 Ion Attachment Mass Spectrometry for Environmental Analysis 1287Yuki Kitahara, Seiji Takahashi, Masamichi Tsukagosi, Juhasz Marta,and Toshihiro Fujii

36 Immunoassays 1313Gunther Proll and Markus Ehni

Section XI Applications 4: Process Control 1335

Introduction 1337

37 Process Control in Chemical Manufacturing 1343Dieter Fischer, Stefan Stieler, and Stephan Kuppers

38 Process Control Using Spectroscopic Tools in Pharmaceutical Industryand Biotechnology 1363Michael Brudel, Uwe Schmidt, Holger Mueller, and Stephan Kuppers

39 Applications of Optical Spectroscopy to Process Environments 1397Stephan Kuppers

40 Spectral Imaging in Quality and Process Control 1409Rudolf W. Kessler and Waltraud Kessler

41 Trends in Spectroscopic Techniques for Process Control 1419Michael Maiwald, Igor Gornushkin, and Markus Ostermann

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XIV Contents

Volume 4

Section XII Applications 6: Spectroscopy at Surfaces 1439

42 Optical Spectroscopy at Surfaces 1441Georgeta Salvan and Dietrich R. T. Zahn

43 NEXAFS Studies at Surfaces 1485Maria Benedetta Casu and Thomas Chasse

44 The X-Ray Standing Wave Technique 1507Alexander Gerlach and Frank Schreiber

45 Photoelectron Spectroscopy Applications to Materials Science 1523Maria Benedetta Casu and Thomas Chasse

Section XIII Applications 7: Nano-Optics 1557

46 Miniaturized Optical Sensors for Medical Diagnostics 1559Seong-Soo Kim and Boris Mizaikoff

47 Tip-Enhanced Near-Field Optical Microscopy 1585Achim Hartschuh

48 Optical Waveguide Spectroscopy 1611James S. Wilkinson

Section XIV Hyphenated Techniques 1643

49 Mass Spectral Detection 1645John C. Fetzer

50 Optical Detection 1657John C. Fetzer

51 Atomic Spectral Detection 1667John C. Fetzer

52 NMR as a Chromatography Detector 1679Klaus Albert

Section XV General Data Treatment: Databases/SpectralLibraries 1717

53 Optical Spectroscopy 1719Steffen Thiele and Reiner Salzer

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Contents XV

54 Nuclear Magnetic Resonance Spectroscopy 1749Wolfgang Robien

55 Mass Spectrometry 1769Wolfgang Werther

56 Raman Spectroscopy Fundamentals 1813David Moore

Index 1831

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V

Contents

List of Contributors XXIIIPreface XXXV

Volume 1

Section I Sample Preparation and Sample Pretreatment 1

1 Preparation of Liquid and Solid Samples 3Brian M. Cullum and Tuan Vo-Dinh

2 Liquid and Solid Sample Collection 15Paolo de Zorzi

Section II Methods 1: Optical Spectroscopy 27

Introduction 29

3 Basics of Optical Spectroscopy 31Martin Hof and Radek Machan

4 Instrumentation 39Valdas Sablinskas

5 Measurement Techniques 71Gerald Steiner

6 Applications 95Valdas Sablinskas, Gerald Steiner, Martin Hof, and Radek Machan

Section III Methods 2: NMR 183

Introduction 185

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VI Contents

7 An Introduction to Solution, Solid-State, and Imaging NMRSpectroscopy 193Leslie G. Butler

8 Solution NMR Spectroscopy 225Gary E. Martin, Chad E. Hadden, and David J. Russell

9 Suspended-State NMR Spectroscopy (High-Resolution Magic AngleSpinning (HR-MAS) NMR Spectroscopy) 293Markus Kramer and Klaus Albert

10 Solid-State NMR 297Steven P. Brown and Lyndon Emsley

Section IV Methods 3: Mass Spectrometry 355

11 Mass Spectrometry 357Michael Przybylski

12 Multiparametric Analysis of Mass Spectrometry-Based ProteomeProfiling in Gestation-Related Diseases 407Michael O. Glocker, Claudia Rower, Manja Wolter, Cornelia Koy,Toralf Reimer, and Ulrich Pecks

13 Laser-Assisted Mass Spectrometry 429David Touboul and Renato Zenobi

Volume 2

Section V Methods 4: Elemental Analysis 449

14 X-ray Fluorescence Analysis 451Koen Janssens

14.1 X-ray Fluorescence Analysis – Outline 45114.2 Basic Principles 45314.2.1 X-ray Wavelength and Energy Scales 45314.2.2 Interaction of X-rays with Matter 45314.2.3 Photoelectric Effect 45514.2.4 Scattering 45714.2.5 Bremsstrahlung 45714.2.6 Selection Rules, Characteristic Lines, and X-ray Spectra 45814.2.7 Figures-of-Merit for XRF Spectrometers 46214.3 Instrumentation 46514.3.1 X-ray Sources 46614.3.2 X-ray Detectors 469

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Contents VII

14.3.3 Wavelength-Dispersive XRF 47514.3.4 Energy-Dispersive XRF 47914.3.5 Portable and Radioisotope XRF 48314.3.6 Total Reflection XRF 48414.3.7 Microscopic XRF 48514.4 Matrix Effects 48714.4.1 Thin and Thick Samples 48714.4.2 Primary and Secondary Absorption, Direct and Third-Element

Enhancement 48914.5 Data Treatment 49014.5.1 Counting Statistics 49114.5.2 Spectrum Evaluation Techniques 49114.5.3 Quantitative Calibration Procedures 49514.5.4 Error Sources in X-ray Fluorescence Analysis 50114.5.5 Specimen Preparation for X-ray Fluorescence 50214.6 Advantages and Limitations 50314.6.1 Qualitative Analysis 50314.6.2 Detection Limits 50414.6.3 Quantitative Reliability 50414.7 Summary 504

References 505Further Reading 506

15 Atomic Absorption Spectrometry (AAS) and Atomic EmissionSpectrometry (AES) 507Erwin Rosenberg and Ulrich Panne

15.1 Introduction 50715.2 Theory of Atomic Spectroscopy 50715.2.1 Basic Principles 50715.2.2 Fundamentals of Absorption and Emission 51215.3 Atomic Absorption Spectrometry (AAS) 52015.3.1 Introduction 52015.3.2 Instrumentation 52115.3.3 Spectral Interferences 54015.3.4 Chemical Interferences 54915.3.5 Data Treatment 55115.3.6 Hyphenated Techniques 55215.4 Atomic Emission Spectrometry (AES) 55715.4.1 Introduction 55715.4.2 Instrumentation 55815.4.3 Matrix Effects and Interferences 57115.4.4 Quantitative and Qualitative Analysis 57415.4.5 Advantages and Limitations 57615.5 Summary 578

References 580

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VIII Contents

16 Inductively Coupled Plasma Spectrometry 583Jose Alfons Clement Broekaert

16.1 The Inductively Coupled Plasma (ICP) 58316.1.1 Historical Development 58316.1.2 Excitation and Ionization Processes 58516.1.3 Diagnostics of the ICP 58716.2 Inductively Coupled Plasma Optical Emission

Spectrometry 59616.2.1 Instrumentation 59616.2.2 Figures of Merit 60916.2.3 Application Fields 61316.3 ICP Mass Spectrometry 61516.3.1 Instrumentation 61516.3.2 Figures of Merit 62116.3.3 Alternative Methods for Sample Introduction 62916.3.4 Time-of-Flight ICP-MS 63116.3.5 Fields of Application 63216.4 Outlooks and Comparative Aspects 635

References 636

17 Laser Ablation Inductively Coupled Plasma Mass Spectrometry(LA-ICPMS) 647Bodo Hattendorf and Detlef Gunther

17.1 Introduction 64717.2 Fundamental Aspects of Laser Ablation 65117.2.1 Aerosol Generation and Transport 65217.2.2 Requirements for Quantification 65717.3 ICPMS Detection 65817.3.1 Instrumentation 65817.3.2 Spectral Interferences 66417.3.3 Non-Spectral Interferences 66917.3.4 Instrument Drift 67117.4 Sampling Strategies 67217.4.1 Bulk Analysis 67217.4.2 Depth Profiling 67317.4.3 Lateral Profiling 67417.4.4 Inclusion Analysis 67717.5 Data Treatment 67817.5.1 Qualitative Analysis 68117.5.2 Quantitative Analysis 68117.5.3 Isotope Ratio Determination 68417.6 Summary and Outlook 68517.6.1 Characteristics, Figures of Merit, Applications 686

References 688

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Contents IX

Section VI Methods 5: Surface Analysis 699

Introduction 701Definition of the Surface 703Selection of Method 704Acknowledgments 708References 708

18 Electron Probe Techniques 709Christopher George Havelock Walker

18.1 Appearance Energy Spectroscopy 70918.1.1 Introduction 70918.1.2 Instrumentation 71018.1.3 Sample 71018.1.4 Analytical Information 71018.1.5 Performance Criteria 71118.1.6 Applications 71118.1.7 Other Techniques 71118.2 Auger Electron Spectroscopy 71118.2.1 Introduction 71118.2.2 Instrumentation 71118.2.3 Sample 71218.2.4 Analytical Information 71218.2.5 Performance Criteria 71218.2.6 Applications 71318.2.7 Other Techniques 71318.3 Cathodoluminescence Spectroscopy 71418.3.1 Introduction 71418.3.2 Instrumentation 71418.3.3 Sample 71418.3.4 Analytical Information 71518.3.5 Performance Criteria 71518.3.6 Applications 71518.4 Electron Momentum Spectroscopy 71518.4.1 Introduction 71518.4.2 Instrumentation 71518.4.3 Sample 71618.4.4 Analytical Information 71618.4.5 Performance Criteria 71618.4.6 Applications 71618.5 Electron Probe Microanalysis 71618.5.1 Introduction 71618.5.2 Instrumentation 71718.5.3 Sample 71718.5.4 Analytical Information 717

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X Contents

18.5.5 Performance Criteria 71818.5.6 Applications 71818.6 Electron-Stimulated Desorption 71818.6.1 Introduction 71818.6.2 Instrumentation 71918.6.3 Sample 71918.6.4 Analytical Information 71918.6.5 Performance Criteria 71918.6.6 Applications 72018.7 Electron-Stimulated Desorption Ion Angular

Distributions 72018.7.1 Introduction 72018.7.2 Instrumentation 72018.7.3 Sample 72018.7.4 Analytical Information 72118.7.5 Performance Criteria 72118.7.6 Applications 72118.8 Extended Energy Loss Fine Structure 72118.8.1 Introduction 72118.8.2 Instrumentation 72218.8.3 Analytical Information 72218.8.4 Performance Criteria 72218.8.5 Applications 72218.8.6 Other Techniques 72318.9 High-Resolution Electron Energy Loss

Spectroscopy 72318.9.1 Introduction 72318.9.2 Instrumentation 72318.9.3 Sample 72318.9.4 Analytical Information 72318.9.5 Performance Criteria 72418.9.6 Applications 72418.9.7 Other Techniques 72518.10 Inelastic Electron Tunneling Spectroscopy 72518.10.1 Introduction 72518.10.2 Instrumentation 72518.10.3 Sample 72618.10.4 Analytical Information 72618.10.5 Performance Criteria 72618.10.6 Applications 72618.10.7 Other Techniques 72618.11 Inverse Photoelectron Spectroscopy 72618.11.1 Introduction 72618.11.2 Instrumentation 72718.11.3 Sample 727

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Contents XI

18.11.4 Analytical Information 72818.11.5 Performance Criteria 72818.11.6 Applications 72818.12 Reflection Electron Energy Loss Spectroscopy 72818.12.1 Introduction 72818.12.2 Instrumentation 72918.12.3 Sample 72918.12.4 Analytical Information 72918.12.5 Performance Criteria 72918.12.6 Applications 73018.12.7 Other Techniques 73018.13 Scanning Electron Microscopy 73018.13.1 Introduction 73018.13.2 Instrumentation 73018.13.3 Sample 73118.13.4 Analytical Information 73218.13.5 Performance Criteria 73218.13.6 Applications 73318.14 Scanning Tunneling Spectroscopy 73318.14.1 Introduction 73318.14.2 Instrumentation 73318.14.3 Sample 73318.14.4 Analytical Information 73418.14.5 Performance Criteria 73418.14.6 Applications 73418.14.7 Other Techniques 73418.15 Scanning Tunneling Microscopy – Inelastic Electron Tunneling

Spectroscopy 73518.15.1 Introduction 73518.15.2 Instrumentation 73518.15.3 Sample 73618.15.4 Analytical Information 73618.15.5 Performance Criteria 73618.15.6 Applications 73618.15.7 Other Techniques 73618.16 Secondary Electron Emission Spectroscopy 73618.16.1 Introduction 73618.16.2 Instrumentation 73718.16.3 Sample 73718.16.4 Analytical Information 73718.16.5 Performance Criteria 73818.16.6 Applications 73818.16.7 Other Techniques 738

References 738

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XII Contents

19 Ion/Neutral Probe Techniques 741Anna Mackova and Andrew Pratt

19.1 Atom Probe Field Ion Microscopy 74119.1.1 Introduction 74119.1.2 Instrumentation 74219.1.3 Analytical Information 74219.1.4 Performance Criteria 74219.1.5 Applications 74219.2 Charged Particle Activation Analysis 74219.2.1 Introduction 74219.2.2 Instrumentation 74319.2.3 Sample 74319.2.4 Analytical Information 74319.2.5 Performance Criteria 74319.2.6 Application 74419.2.7 Other Technique 74419.2.8 Related Techniques 74519.3 Elastic Recoil Detection Analysis 74519.3.1 Introduction 74519.3.2 Instrumentation 74519.3.3 Sample 74619.3.4 Analytical Information 74719.3.5 Performance Criteria 74719.3.6 Applications 74719.3.7 Other Techniques 74819.4 Glow Discharge Optical Emission Spectrometry 74919.4.1 Introduction 74919.4.2 Instrumentation 74919.4.3 Sample 74919.4.4 Analytical Information 74919.4.5 Performance Criteria 75019.4.6 Application 75019.4.7 Other Techniques 75019.5 Ion Microprobe Analysis 75119.5.1 Introduction 75119.5.2 Instrumentation 75119.5.3 Sample 75119.5.4 Analytical Information 75219.5.5 Performance Criteria 75219.5.6 Application 75219.5.7 Other Techniques 75319.6 Low-Energy Ion Scattering Spectrometry 75319.6.1 Introduction 75319.6.2 Instrumentation 75319.6.3 Sample 754

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Contents XIII

19.6.4 Analytical Information 75419.6.5 Performance Criteria 75419.6.6 Application 75519.6.7 Other Techniques 75519.7 Metastable Deexcitation Spectroscopy 75519.7.1 Introduction 75519.7.2 Instrumentation 75519.7.3 Sample 75619.7.4 Analytical Information 75619.7.5 Performance Criteria 75719.7.6 Applications 75719.7.7 Other Techniques 75819.8 Neutron Depth Profiling 75819.8.1 Introduction 75819.8.2 Instrumentation 75819.8.3 Sample 75819.8.4 Analytical Information 75819.8.5 Performance Criteria 75919.8.6 Application 75919.9 Nuclear Reaction Analysis 76019.9.1 Introduction 76019.9.2 Instrumentation 76019.9.3 Sample 76119.9.4 Analytical Information 76119.9.5 Performance Criteria 76119.9.6 Application 76219.9.7 Other Technique 76219.10 Particle-Induced Gamma Emission 76219.10.1 Introduction 76219.10.2 Instrumentation 76219.10.3 Sample 76319.10.4 Analytical Information 76319.10.5 Performance Criteria 76319.10.6 Application 76319.11 Particle-Induced X-Ray Emission 76419.11.1 Introduction 76419.11.2 Instrumentation 76419.11.3 Sample 76419.11.4 Spectrum 76419.11.5 Analytical Information 76519.11.6 Performance Criteria 76519.11.7 Application 76619.11.8 Other Techniques 76619.12 Positron Annihilation Auger Electron Spectroscopy 76619.12.1 Introduction 766

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XIV Contents

19.12.2 Instrumentation 76719.12.3 Sample 76719.12.4 Analytical Information 76719.12.5 Performance Criteria 76819.12.6 Applications 76819.12.7 Other Techniques 76819.13 Rutherford Backscattering Spectrometry 76819.13.1 Introduction 76819.13.2 Instrumentation 76919.13.3 Sample 76919.13.4 Analytical Information 76919.13.5 Spectrum 76919.13.6 Performance Criteria 77019.13.7 Applications 77119.13.8 Other Techniques 77119.14 RBS-Channeling Spectrometry 77119.14.1 Introduction 77119.14.2 Instrumentation 77219.14.3 Sample 77219.14.4 Analytical Information 77219.14.5 Performance Criteria 77219.14.6 Application 77319.14.7 Other Techniques 77419.15 Secondary Ion Mass Spectrometry 77419.15.1 Introduction 77419.15.2 Instrumentation 77419.15.3 Sample 77519.15.4 Analytical Information 77519.15.5 Performance Criteria 77519.15.6 Application 77619.15.7 Other Techniques 776

Further Information 776References 776

20 Photon Probe Techniques 779Simon Morton

20.1 Angle-Resolved Ultraviolet Photoelectron Spectroscopy 77920.1.1 Introduction 77920.1.2 Instrumentation 77920.1.3 Sample 78020.1.4 Analytical Information 78020.1.5 Performance Criteria 78020.1.6 Applications 78120.1.7 Other Techniques 78120.2 Attenuated Total Reflection Spectroscopy 781