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Handbook of SpectroscopyEdited by G.Gauglitz and T.Vo-DinhHandbook of Spectroscopy.Edited by Gnter Gauglitz and Tuan Vo-DinhCopyright?2003 WILEY-VCH Verlag GmbH&Co.KGaA,WeinheimISBN 3-527-29782-0Related Titles from WILEY-VCHH.Gnzler and H.-U.Gremlich(eds)IR Spectroscopy2002.ca.361 pages.Hardcover.ISBN 3-527-28896-1H.W.Siesler,Y.Ozaki,S.Kawata and H.M.Heise(eds)Near-Infrared SpectroscopyPrinciples,Instruments,Applications2001.ca.348 pages.Hardcover.ISBN 3-527-30149-6H.Gnzler and A.Williams(eds)Handbook of Analytical Techniques2001.2 Volumes,1182 pages.Hardcover.ISBN 3-527-30165-8J.F.Haw(ed)In-situ Spectroscopy in Heterogeneous Catalysis2002.ca.276 pages.Hardcover.ISBN 3-527-30248-4Handbook of Spectroscopy.Edited by Gnter Gauglitz and Tuan Vo-DinhCopyright?2003 WILEY-VCH Verlag GmbH&Co.KGaA,WeinheimISBN 3-527-29782-0Handbook of SpectroscopyEdited by G.Gauglitz and T.Vo-DinhHandbook of Spectroscopy.Edited by Gnter Gauglitz and Tuan Vo-DinhCopyright?2003 WILEY-VCH Verlag GmbH&Co.KGaA,WeinheimISBN 3-527-29782-0Prof.Dr.Guenter GauglitzInstitute for Physical and TheoreticalChemistryUniversity of TbingenAuf der Morgenstelle 872976 TbingenGermanyProf.Dr.Tuan Vo-DinhAdvanced Biomedical Scienceand Technology GroupOak Ridge National LaboratoryP.O.Box 2008Oak Ridge,Tennessee 37831-6101USAThis book was carefully produced.Never-theless,editors,authors and publisher donot warrant the information containedtherein to be free of errors.Readers areadvised to keep in mind that statements,data,illustrations,procedural details orother items may inadvertently be inaccurate.Library of Congress Card No.:applied forA catalogue record for this book is availablefrom the British Library.Bibliographic information published byDie Deutsche BibliothekDie Deutsche Bibliothek lists this publicationin the Deutsche Nationalbibliografie;detailed bibliographic data is available in theInternet at http:/dnb.ddb.de.?2003 WILEY-VCH Verlag GmbH&Co.KGaA,WeinheimAll rights reserved(including those oftranslation in other languages).No part ofthis book may be reproduced in any form by photoprinting,microfilm,or any othermeans nor transmitted or translated intomachine language without written permis-sion from the publishers.Registered names,trademarks,etc.used in this book,evenwhen not specifically marked as such,arenot to be considered unprotected by law.Printed in the Federal Republic of Germany.Printed on acid-free paper.TypesettingHagedorn Kommunikation,ViernheimPrintingStrauss Offsetdruck GmbH,MrlenbachBookbindingJ.Schffer GmbH&Co.KG,GrnstadtISBN3-527-29782-0ContentsVolume 1PrefaceXXVIIIList of ContributorsSection ISample Preparation and Sample Pretreatment1Introduction31Collection and Preparation of Gaseous Samples41.1Introduction41.2Sampling considerations51.3Active vs.Passive Sampling81.3.1Active Air Collection Methods81.3.1.1Sorbents91.3.1.2Bags111.3.1.3Canisters111.3.1.4Bubblers121.3.1.5Mist Chambers131.3.1.6Cryogenic Trapping131.3.2Passive Sampling131.4Extraction and Preparation of Samples141.5Summary152Sample Collection and Preparation of Liquid and Solids172.1Introduction172.2Collection of a Representative Sample172.2.1Statistics of Sampling182.2.2How Many Samples Should be Obtained?212.2.3Sampling222.2.3.1Liquids222.2.3.2Solids232.3Preparation of Samples for Analysis24VContentsHandbook of Spectroscopy.Edited by Gnter Gauglitz and Tuan Vo-DinhCopyright?2003 WILEY-VCH Verlag GmbH&Co.KGaA,WeinheimISBN 3-527-29782-02.3.1Solid Samples242.3.1.1Sample Preparation for Inorganic Analysis252.3.1.2Decomposition of Organics282.3.2Liquid Samples292.3.2.1Extraction/Separation and Preconcentration292.3.2.2Chromatographic Separation31Section IIMethods 1:Optical Spectroscopy373Basics of Optical Spectroscopy393.1Absorption of Light393.2Infrared Spectroscopy413.3Raman Spectroscopy433.4UV/VIS Absorption and Luminescence444Instrumentation484.1MIR Spectrometers484.1.1Dispersive Spectrometers494.1.2Fourier-Transform Spectrometers504.1.2.1Detectors534.1.2.2Step-scan Operation534.1.2.3Combined Techniques544.2NIR Spectrometers544.2.1FT-NIR Spectrometers554.2.2Scanning-Grating Spectrometers554.2.3Diode Array Spectrometers564.2.4Filter Spectrometers564.2.5LED Spectrometers564.2.6AOTF Spectrometers564.3Raman Spectrometers574.3.1Raman Grating Spectrometer with Single Channel Detector574.3.1.1Detectors594.3.1.2Calibration604.3.2FT-Raman Spectrometers with Near-Infrared Excitation614.3.3Raman Grating Polychromator with Multichannel Detector614.4UV/VIS Spectrometers634.4.1Sources644.4.2Monochromators644.4.3Detectors644.5Fluorescence Spectrometers665Measurement Techniques705.1Transmission Measurements715.2Reflection Measurements735.2.1External Reflection73VIContents5.2.2Reflection Absorption755.2.3Attenuated Total Reflection(ATR)755.2.4Reflection at Thin Films775.2.5Diffuse Reflection785.3Spectroscopy with Polarized Light815.3.1Optical Rotatory Dispersion815.3.2Circular Dichroism(CD)825.4Photoacoustic Measurements835.5Microscopic Measurements845.5.1Infrared Microscopes855.5.2Confocal Microscopes855.5.3Near-field Microscopes866Applications896.1Mid-Infrared(MIR)Spectroscopy896.1.1Sample Preparation and Measurement896.1.1.1Gases906.1.1.2Solutions and Neat Liquids916.1.1.3Pellets and Mulls926.1.1.4Neat Solid Samples946.1.1.5Reflection?Absorption Sampling Technique946.1.1.6Sampling with the ATR Technique956.1.1.7Thin Samples966.1.1.8Diffuse Reflection Sampling Technique976.1.1.9Sampling by Photoacoustic Detection976.1.1.10Microsampling986.1.2Structural Analysis986.1.2.1The Region from 4000 to 1400 cm?11026.1.2.2The Region 1400?900 cm?11026.1.2.3The Region from 900 to 400 cm?11026.1.3Special Applications1036.2Near-Infrared Spectroscopy1046.2.1Sample Preparation and Measurement1056.2.2Applications of NIR Spectroscopy1106.3Raman Spectroscopy1126.3.1Sample Preparation and Measurements1126.3.1.1Sample Illumination and Light Collection1136.3.1.2Polarization Measurements1186.3.1.3Enhanced Raman Scattering1196.3.2Special Applications1206.4UV/VIS Spectroscopy1256.4.1Sample Preparation1256.4.2Structural Analysis1296.4.3Special Applications1326.5Fluorescence Spectroscopy135VIIContents6.5.1Sample Preparation and Measurements1386.5.1.1Fluorescence Quantum Yield and Lifetime1386.5.1.2Fluorescence Quencher1396.5.1.3Solvent Relaxation1446.5.1.4Polarized Fluorescence1486.5.2Special Applications152Section IIIMethods 2:Nuclear Magnetic Resonance Spectroscopy169Introduction1717An Introduction to Solution,Solid-State,and ImagingNMR Spectroscopy1777.1Introduction1777.2Solution-state1H NMR1797.3Solid-state NMR1877.3.1Dipolar Interaction1887.3.2Chemical Shift Anisotropy1907.3.3Quadrupolar Interaction1917.3.4Magic Angle Spinning(MAS)NMR1947.3.5T1and T1?Relaxation1957.3.6Dynamics1987.4Imaging1997.53D NMR:The HNCA Pulse Sequence2047.6Conclusion2078Solution NMR Spectroscopy2098.1Introduction2098.21D(One-dimensional)NMR Methods2108.2.1Proton Spin Decoupling Experiments2118.2.2Proton Decoupled Difference Spectroscopy2128.2.3Nuclear Overhauser Effect(NOE)Difference Spectroscopy2128.2.4Selective Population Transfer(SPT)2138.2.5J-Modulated Spin Echo Experiments2138.2.5.1INEPT(Insensitive Nucleus Enhancement by PolarizationTransfer)2148.2.5.2DEPT(Distortionless Enhancement Polarization Transfer)2158.2.6Off-Resonance Decoupling2168.2.7Relaxation Measurements2178.3Two-dimensional NMR Experiments2188.3.12DJ-Resolved NMR Experiments2198.3.2Homonuclear 2D NMR Spectroscopy2238.3.2.1COSY,Homonuclear Correlated Spectroscopy2238.3.2.2Homonuclear TOCSY,Total Correlated Spectroscopy2268.3.2.3NOESY,Nuclear Overhauser Enhancement Spectroscopy228VIIIContents8.3.2.4ROESY,Rotating Frame Overhauser Enhanced Spectroscopy2308.3.2.5NOESY vs.ROESY2318.3.2.6Other Homonuclear Autocorrelation Experiments2318.3.3Gradient Homonuclear 2D NMR Experiments2328.3.4Heteronuclear Shift Correlation2348.3.5Direct Heteronuclear Chemical Shift Correlation Methods2348.3.5.1HMQC,Heteronuclear Multiple Quantum Coherence2348.3.6HSQC,Heteronuclear Single Quantum Coherence Chemical ShiftCorrelation Techniques2368.3.6.1Multiplicity-edited Heteronuclear Shift Correlation Experiments2378.3.6.2Accordion-optimized Direct Heteronuclear Shift CorrelationExperiments2398.3.7Long-range Heteronuclear Chemical Shift Correlation2408.3.7.1HMBC,Heteronuclear Multiple Bond Correlation2428.3.7.2Variants of the Basic HMBC Experiment2438.3.7.3Accordion-optimized Long-range Heteronuclear Shift CorrelationMethods.2448.3.7.42J3J-HMBC2488.3.7.5Relative Sensitivity of Long-range Heteronuclear Shift CorrelationExperiments2518.3.7.6Applications of Accordion-optimized Long-range HeteronuclearShift Correlation Experiments2528.3.8Hyphenated-2D NMR Experiments2528.3.9One-dimensional Analogues of 2D NMR Experiments2558.3.10Gradient 1D NOESY2558.3.11Selective 1D Long-range Heteronuclear Shift CorrelationExperiments2578.3.12Small Sample NMR Studies2578.4Conclusions2629Solid-State NMR2699.1Introduction2699.2Solid-state NMR Lineshapes2729.2.1The Orientational Dependence of the NMR Resonance Frequency2729.2.2Single-crystal NMR2739.2.3Powder Spectra2759.2.4One-dimensional2H NMR2789.3Magic-angle Spinning2809.3.1CP MAS NMR2819.3.21H Solid-State NMR2859.4Recoupling Methods2879.4.1Heteronuclear Dipolar-coupled Spins:REDOR2879.4.2Homonuclear Dipolar-coupled Spins2909.4.3The CSA:CODEX2919.5Homonuclear Two-dimensional Experiments292IXContents9.5.1Establishing the Backbone Connectivity in an Organic Molecule2939.5.2Dipolar-mediated Double-quantum Spectroscopy2959.5.3High-resolution1H Solid-state NMR2989.5.4Anisotropic Isotropic Correlation:The Measurement of CSAs3009.5.5The Investigation of Slow Dynamics:2D Exchange3039.5.61H?1H DQ MAS Spinning-sideband Patterns3059.6Heteronuclear Two-dimensional Experiments3079.6.1Heteronuclear Correlation3079.6.2The Quantitative Determination of Heteronuclear DipolarCouplings3109.6.3Torsional Angles3129.6.4Oriented Samples3139.7Half-integer Quadrupole Nuclei3159.8Summary319Section IVMethods 3:Mass Spectrometry32710Mass Spectrometry32910.1Introduction:Principles of Mass Spectrometry32910.1.1Application of Mass Spectrometry to Biopolymer Analysis33010.2Techniques and Instrumentation of Mass Spectrometry33110.2.1Sample Introduction and Ionisation Methods33110.2.1.1Pre-conditions33110.2.1.2Gas Phase(“Hard”)Ionisation Methods33110.2.1.3“Soft”Ionisation Techniques33210.2.2Mass Spectrometric Analysers33510.2.2.1Magnetic Sector Mass Analysers33510.2.2.2Quadrupole Mass Analysers33710.2.2.3Time-of-Flight Mass Analysers33810.2.2.4Trapped-Ion Mass Analysers33910.2.2.5Hybrid Instruments34010.2.3Ion Detection and Spectra Acquisition34010.2.4High Resolution Fourier Transform Ion Cyclotron Resonance(ICR)Mass Spectrometry34110.2.5Sample Preparation and Handling in Bioanalytical Applications34410.2.5.1Liquid?Liquid Extraction(LLE)34410.2.5.2Solid Phase Extraction(SPE)34510.2.5.3Immunoaffinity Extraction(IAE)34510.2.5.4Solid-phase Microextraction34510.2.5.5Supercritical-Fluid Extraction(SFE)34610.2.6Coupling of Mass Spectrometry with Microseparation Methods34610.2.6.1Liquid Chromatography-Mass Spectrometry Coupling(LC-MS)34710.2.6.2Capillary Electrophoresis(CE)-Mass Spectrometry34810.3Applications of Mass Spectrometry to Biopolymer Analysis349XContents10.3.1Introduction34910.3.2Analysis of Peptide and Protein Primary Structuresand Post-Translational Structure Modifications34910.3.3Tertiary Structure Characterisation by Chemical Modificationand Mass Spectrometry35310.3.4Characterisation of Non-Covalent Supramolecular Complexes35410.3.5Mass Spectrometric Proteome Analysis356Section VMethods 4:Elemental Analysis36311X-ray Fluorescence Analysis36511.1Introduction36511.2Basic Principles36711.2.1X-ray Wavelength and Energy Scales36711.2.2Interaction of X-rays with Matter36711.2.3Photoelectric Effect36911.2.4Scattering37111.2.5Bremsstrahlung37211.2.6Selection Rules,Characteristic Lines and X-ray Spectra37311.2.7Figures-of-merit for XRF Spectrometers37611.2.7.1Analytical Sensitivity37611.2.7.2Detection and Determination Limits37711.3Instrumentation38011.3.1X-ray Sources38011.3.2X-ray Detectors38411.3.3Wavelength-dispersive XRF39011.3.4Energy-dispersive XRF39311.3.5Radioisotope XRF39711.3.6Total Reflection XRF39811.3.7Microscopic XRF39911.4Matrix Effects40111.4.1Thin and Thick Samples40111.4.2Primary and Secondary Absorption,Direct and Third ElementEnhancement40311.5Data Treatment40411.5.1Counting Statistics40411.5.2Spectrum Evaluation Techniques40511.5.2.1Data Extraction in WDXRF40611.5.2.2Data Extraction in EDXRF:Simple Case,No Peak Overlap40711.5.2.3Data Extraction in EDXRF,Multiple Peak Overlap40811.5.3Quantitative Calibration Procedures40911.5.3.1Single-element Techniques41211.5.3.2Multiple-element Techniques41311.5.4Error Sources in X-ray Fluorescence Analysis415XIContents11.5.5Specimen Preparation for X-ray Fluorescence41611.6Advantages and Limitations41711.6.1Qualitative Analysis41711.6.2Detection Limits41811.6.3Quantitative Reliability41811.7Summary41912Atomic Absorption Spectrometry(AAS)and Atomic EmissionSpectrometry(AES)42112.1Introduction42112.2Theory of Atomic Spectroscopy42112.2.1Basic Principles42112.2.2Fundamentals of Absorption and Emission42612.2.2.1Absorption42912.2.2.2Line Broadening43012.2.2.3Self-absorption43112.2.2.4Ionisation43212.2.2.5Dissociation43412.2.2.6Radiation Sources and Atom Reservoirs43412.3Atomic Absorption Spectrometry(AAS)43612.3.1Introduction43612.3.2Instrumentation43612.3.2.1Radiation Sources43712.3.2.2Atomisers44012.3.2.3Optical Set-up and Components of Atomic AbsorptionInstruments45312.3.3Spectral Interference45412.3.3.1Origin of Spectral Interference45412.3.3.2Methods for Correcting for Spectral Interference45512.3.4Chemical Interferences46212.3.4.1The Formation of Compounds of Low Volatility46312.3.4.2Influence on Dissociation Equilibria46312.3.4.3Ionisation in Flames46412.3.5Data Treatment46512.3.5.1Quantitative Analysis46512.3.6Hyphenated Techniques46612.3.6.1Gas Chromatography-Atomic Absorption Spectrometry46712.3.6.2Liquid Chromatography-Atomic Absorption Spectrometry46912.3.7Conclusion and Future Directions47012.4Atomic Emission Spectrometry(AES)47112.4.1Introduction47112.4.2Instrumentation47112.4.2.1Atomisation Devices47112.4.2.2Optical Set-up and Detection48012.4.2.3Instrumentation for Solid Sample Introduction483XIIContents12.4.3Matrix Effects and Interference48612.4.3.1Spectral Interferences48612.4.3.2Matrix Effects and Chemical Interferences48712.4.4Quantitative and Qualitative Analysis48812.4.5Advantages and Limitations49112.4.5.1Absolute and Relative Sensitivity49112.4.5.2Hyphenated Techniques49112.5Summary493Section VIMethods 5:Surface Analysis Techniques49713Surface Analysis Techniques49913.1Introduction49913.2Definition of the Surface50113.3Selection of Method50113.4Individual Techniques50613.4.1Angle Resolved Ultraviolet Photoelectron Spectroscopy50613.4.1.1Introduction50713.4.1.2Instrumentation50713.4.1.3Sample50713.4.1.4Analytical Information50713.4.1.5Performance Criteria50713.4.1.6Applications50813.4.1.7Other Techniques50813.4.2Appe