David L. Andrews (Ed.) Perspectives in Modem Chemical Spectroscopy With Contributions by D. L. Andrews, P. S. Belton, C. S. Creaser, M. E. A. Cudby, S. F. A. Kettle, M. R. S. McCoustra, F. A. Mellon, D. B. Powell, N. Sheppard, J. R. Sodeau, A. J. Thomson, D. J. Williamson H. A. Willis and R. H. Wilson Springer-Verlag Berlin Heidelberg New York London Paris Tokyo Hong Kong David L. Andrews, B. Sc., Ph. D., C. Chern., F. R. S. C. School of Chemical Sciences University of East Anglia Norwich NR4 7TJ, Great Britain Library of Congress Cataloging·in-Publication Data Perspectives in modern chemical spectroscopy 1 David L. Andrews. (ed.); with contributions by D.L. Andrews ... ret al.l. Includes bibliographical references. ISBN-13: 978-3-540-52218-8 e-ISBN-13: 978-3-642-75456-2 DOl: 10.1007/978-3-642-75456-2 L ~pectrum analysIs. 1. Andrews. David L. QD95.P28 1990 543' .0858-dc20 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, re-use of illustrations, recitation, broadcasting, reproduction on microfilms or in other ways, and storage in data banks. Duplication of this publication or parts thereof is only permitted under the provisions of the German Copyright Law of September 9, 1965, in its current version, and a copyright fee must always be paid. Violations fall under the prosecution act of the German Copyright Law. © Springer-Verlag Berlin Heidelberg 1990 The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Thomson Press Ltd., India Offsetprinting: Color-Druck Dorfi GmbH, Berlin; Bookbinding: Ltideritz & Bauer, Berlin 2152/3020-543210 Printed on acid-free paper List of Contributors Andrews D. L. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England Belton, P. S. AFRC Institute of Food Research, Norwich Laboratory, Colney Lane, Norwich NR4 7UA, England Creaser, C. S. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England Cudby, M.E.A. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England Kettle, S. F. A. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England McCoustra, M. R. S. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England Mellon, F. A. AFRC Institute of Food Research, Norwich Laboratory, Colney Lane, Norwich NR4 7UA, England Powell,D.B. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England Sheppard, N. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England VI List of Contributors Sodeau, J. R. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England Thomson, A.J. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England Williamson, D. J. School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England Willis, H. A. 4 Sherrards Park Avenue, Welwyn Garden City, Herts AL8 7JP, England Wilson, R. H. AFRC Institute of Food Research, Norwich Laboratory, Colney Lane, Norwich NR4 7UA, England Foreword A course entitled Perspectives in Modern Chemical Spectroscopy has been annually held at the University of East Anglia (UEA) since 1979. It is a course designed principally for chemists in industry, offering broad coverage of all the major spectroscopic methods, together with an introduction to some of the most recently available techniques. The week-long course is now one of the longest running of its kind, and reflects a commitment to the development of spectroscopic technique which has from the earliest days characterised much of the research at UEA's School of Chemical Sciences. As research links with the nearby Institute of Food Research Norwich (IFRN) have strengthened over the years, several members of the Institute have also become involved in the teaching. With the tenth anniversary of the course, the notion of publishing a book essentially based on the lectures was conceived, and the end result is the present volume. It has been a great pleasure to undertake the editing of a book involving so many of my friends and colleagues at UEA and IFRN, and I am indebted to them for all the new spectroscopy I have learnt in the process. I must also record my thanks to the staff of Springer-Verlag, and particularly to Rainer Stumpe for his unswerving enthusiasm for this project. It is our hope that the book will prove both useful and interesting to its readers, and encourage further developments and still wider applications of modern chemical spectroscopy. Norwich, April 1990 David L. Andrews Contents Chapter 1 Chemical Applications of Molecular Spectroscopy - A Developing Perspective (N. Sheppard) ............................... 1 1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2 A Historical Perspective. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 3 An Introduction to the Use of Fourier-Transform Methods in Chemical Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 4 The Electromagnetic Spectrum (The Photon Spectroscopies) . . . . . . . . . . 7 5 Mass Spectrometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 28 6 Some More Specialised Spectroscopies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 31 7 Sampling Considerations and Conclusions Across the Spectroscopies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 37 8 References .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 40 Chapter 2 Recent Advances in Vibrational Spectroscopy (H. A. Willis and D. B. Powell)......................................... 43 1 Introduction........................................................... 43 2 Data Handling and Library Search. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 45 3 Reflectance Methods ............................................. , , .. ' 51 4 Quantitative Analysis ......................... ,....................... 51 5 Fast Spectroscopy ..... , .... , .. , ... , ...... , , .................... , .. . ... 56 6 Microsampling , ......... ,............................................. 57 7 Inorganic Applications .................... , ........ , ................ ,. 64 8 Future Developments , ........... , ..... , .... , . . . . .. . .. . . . . . .. . .. .. . . .. 66 9 References ................................... , ......... , ............... 66 Chapter 3 Infrared Sampling Methods (P. S. Belton and R. H. Wilson)............ 67 1 Introduction ... , .......... , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 67 2 Transmission Methods ...... , , ......... , , ....... , , . , , ... , . , .... , .... , ,. 67 X Contents 3 Diffuse Reflectance.. .. . .. . . . . .. . . .. .. . . ... . .. . . .. . . .. .. . . . ... .. . .. .... 70 4 Attenuated Total Reflectance... . .. .. ... . . . .. . . ... .. . . .. .... . .. . .. . .. .. 77 5 Photo acoustic Spectroscopy ........................................... 80 6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 85 7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 86 8 Bibliography .......................................................... 86 Chapter 4 Electronic Absorption Spectroscopy: Theory and Practice (M. R. S. McCoustra)................................................... 87 1 Introduction... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 87 2 Electronic Energy Levels and Transitions. . . . .. . .. . . .. .. . . . .. . .. . .. . ... 87 3 Instrumentation in Electronic Absorption Spectroscopy. . . . . . . . . . . . . .. 96 4 Applications of Electronic Absorption Spectroscopy. . . . . . . . . . . . . . . . . .. 99 5 References ............................................................ 101 Chapter 5 Luminescence Spectroscopy (c. S. Creaser and l. R. Sodeau) .......... 103 1 Introduction ........................................................... 103 2 Fundamentals of Photo physics ......................................... 103 3 Luminescence Instrumentation ........................................ 117 4 Luminescence Measurement and Analytical Applications ............. 120 5 References ............................................................ 135 Chapter 6 An Introduction to Nuclear Magnetic Resonance in Fluids (P. S. Belton) ........................................................... 137 1 Basic Principles ........................................................ 137 2 Spectral Acquisition ................................................... 139 3 Transverse Relaxation ................................................. 142 4 Spin Lattice Relaxation ................................................ 145 5 Spin Labelling Methods ............................................... 146 6 Two-Dimensional NMR ............................................... 149 7 Summary .............................................................. 153 8 Bibliography .......................................................... 154 Chapter 7 Multinuclear High-Resolution NMR in Solids (M.E.A. Cudby and D.l. Williamson) ................................. 155 1 Introduction ........................................................... 155 2 Techniques Based on Carbon-13 ....................................... 156 3 Techniques Based on other Nuclei ..................................... 177 4 References ............................................................ 183 Contents XI Chapter 8 Principles and Techniques of Laser Spectroscopy (D. L. Andrews and M. R. S. McCoustra) .............................. 185 1 General Principles of Laser Operation ................................ 185 2 Properties of Laser Light, and their Applications ...................... 187 3 Laser Sources of Spectroscopic Importance ............................ 191 4 Absorption Spectroscopy .............................................. 199 5 Fluorescence Spectroscopy ............................................ 208 6 Raman Spectroscopy .................................................. 211 7 Free Jet Expansions and Laser Spectroscopy .......................... 218 8 Laser Ionisation Mass Spectrometry ................................... 220 9 References ............................................................ 223 Chapter 9 Raman Spectroscopy (S. F. A. Kettle) .................................. 225 1 What Is Raman Spectroscopy? ........................................ 225 2 How Does the Raman Effect Occur? .................................. 225 3 How Is a Raman Spectrum Measured? ................................ 227 4 What Can Be Learned from Raman Spectroscopy? ................... 233 5 Other Raman Spectroscopies .......................................... 237 6 The Future ............................................................ 239 7 References ............................................................ 241 8 Bibliography .......................................................... 241 Chapter 10 Natural and Magnetic Circular Dichroism Spectroscopies (A. J. Thomson) .................... , ................. " .. " ............ 243 1 Introduction ........................................................... 243 2 Natural Circular Dichroism ............................................ 244 3 Magnetic Circular Dichroism .......................................... 255 4 References ............................................................ 259 Chapter 11 Mass Spectrometry (C. S. Creaser and F. A. Mellon) ................... 261 1 History and Introduction .............................................. 261 2 Ionisation Methods .................................................... 262 3 Mass Analysis ......................................................... 271 4 Ion Detection ......................................................... 279 5 Data Systems .......................................................... 280 6 Combined ChromatographylMass Spectrometry ....................... 283 7 Tandem Mass Spectrometry ........................................... 290 8 References ............................................................ 293 XII Contents Chapter 12 Electron Paramagnetic Resonance and Electron Nuclear Double Resonance Spectroscopy (A. J. Thomson) ...................... 295 1 Introduction......................................................... 295 2 EPR Spectrometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 296 3 Spectral Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 299 4 Radicals in Polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 302 5 Molecular Motion and Spin Labels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 305 6 Spin Traps ........................................................... 311 7 Transition-Metal Ions in Proteins .................................... 312 8 Electron Nuclear Double Resonance ................................ 314 9 Pulsed EPR and Electron Spin Echo Envelope Modulation. . . . . . . .. 319 10 References .......................................................... 319 11 Bibliography ........................................................ 320 Index ................................................................... 321