Handbook of Raman Spectroscopy1. 12. 13. 14. 15. 16. 17. 18. 19. 20. 24 22. 23, 24, 25. 27. 28. A SERIES Infrared and Raman Spectroscopy (in three parts), edited by Edward G. Brame, Jr, and Jeanette G. Grasselli X-Ray Spectrometry, edited by H. K. Herglotz and L. S. Birks Mass Spectrometry (in two parts), edited by Charles Merritt, Jr, and Charles N. McEwen Infrared and Raman Spectroscopy of Polymers, H. W. Siesler and K. Holland-Moritz NMR Spectroscopy Techniques, edited by Ceci! Dybowski and Robert L. Lichter Infrared Microspectroscopy: Theory and Applications, edifed by Robert G. Messer- schmidt and Matthew A. Harthcock Flow Injection Atomic Spectroscopy, edited by Jose Luis Burguera Mass Spectrometry of Biological Materials, edited by Charles N. McEwen and Barbara S. Larsen Field Desorption Mass Spectrometry, Laszi6 Prokai . Chromatography/Fourier Transform Infrared Spectroscopy and Its Applications, Robert White Modern NMR Techniques and Their Application in Chemistry, edited by Alexander |. Popov and Klaas Hallenga Luminescence Techniques in Chemical and Biochemical Anal G. Baeyens, Denis De Keukeleire, and Katherine Korkiais Handbook of Near-Infrared Analysis, edited by Donald A. Burns and Emil W. Ciurczak Handbook of X-Ray Spectrometry: Methods and Techniques, edited by René E. Van Grieken and Andrzej A. Markowicz Internal Reflection Spectroscopy: Theory and Applications, edited by Francis M. Mirabella, Jr. roscopic and Spectroscopic Imaging of the Chemical State, edited by Michael D. Morris Mathematical Analysis of Spectral Orthogonality, John H. Kalivas and Patrick M, Lang Laser Spectroscopy: Techniques and Applications, E. Roland Menzel Practical Guide to Infrared Microspectroscopy, edited by Howard J. Humecki Quantitative X-ray Spectrometry: Second Edition, Ron Jenkins, R. W. Gould, and Dale Gedcke NMR Spectroscopy Techniques: Second Edition, Revised and Expanded, edited by Martha D. Bruch Spectrophotometric Reactions, Irena Nemcova, Ludmila Cermakova, and Jiri Gasparic Inorganic Mass Spectrometry: Fundamentals and Applications, edited by Christopher M. Barshick, Douglas C. Duckworth, and David H. Smith Infrared and Raman Spectroscopy of Biological Materials, edited by Hans-Ulrich Gremilich and Bing Yan Near-Infrared Applications In Biotechnology, edited by Ramesh Raghavachari edited by Willy R. . Ultrafast Infrared and Ramen Spectroscopy, edited by M. D. Fayer Handbook of Near-Infrared Analysis: Second Edition, Revised and Expanded, edited by Donald A. Bums and Emil W. Ciurczak Handbook of Raman Spectroscopy: From the Research Laboratory to the Process Line, edited by lan R. Lewis and Howell G. M. Edwards Copyright © 2001 by Taylor & Francis Group, LLCApplied Electrospray Mass Spectrometery, edited by Ashit K. Ganguly, Birendra Pra- ‘manik, and Michael L. Gross Ultraviolet Spectroscopy and UV Lasers, edited by Prabhakar Misra and Mark A Dubinskii Near-Infrared Spectroscopy in Pharmaceutical Applications, Emil W. Ciurezak and James Drennen Copyright © 2001 by Taylor & Franeis Group, LLCHandbook of Raman Spectroscopy From the Research Laboratory to the Process Line edited by lan R. Lewis Kaiser Optical Systems, Inc. Ann Arbor, Michigan Howell G. M. Edwards University of Bradford Bradford, West Yorkshire, England Manrcet Dekker, INc. New York + Base. Copyright © 2001 by Taylor & Franeis Group, LLCISBN: 0-8247-0557-2 This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-261-8482; fax: 41-61-261-8896 World Wide Web http:/www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above. Copyright © 2001 by Marcel Dekker, Inc. All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit) 09876543 PRINTED IN THE UNITED STATES OF AMERICA 2001 by Taylor & Francis Group, LLCIan Lewis would like to thank his mother, Valerie, his wife, Mary, and his children, Valerie, Henry, Maria, and Edward, for their unceasing support during this project. In addition he would like to thank Mary for proofreading much of this work and for her help in compiling the index. Howell Edwards dedicates his contributions to this volume to his wife, Gill, and daughter, Kate, for their continued support and encouragement over many years, and to the memory of Dr. Leonard Woodward, who first introduced him to Raman Spectroscopy as a research student, which developed into a lifelong study. Finally, both editors express their gratitude to all the chapter authors who spent many hours on their respective contributions and met many deadlines despite their very busy schedules. Copyright © 2001 by Taylor & Franeis Group, LLCPreface Since 1928, when Raman and Krishnan published their manuscript in Nature that heralded the experimental discovery of a “new type of secondary radiation,” —later to be termed Raman scattering—the field has undergone several distinct phases. From its discovery until World War II, when a commercial infrared spectrometer was produced, Raman spec- troscopy retained its position as the predominant vibrational spectroscopic technique. Since the widespread adoption of infrared spectroscopy, Raman has existed as a poor cousin but has had two notable periods of user expansion. The first, in the 1960s, coincided with the development of the double monochromator, the laser, and electronic methods of signal detection. The second and current period started approximately 15 years ago and is still progressing. During this time, three major developments have driven the field of Raman spectroscopy forward: the advent of laser-line blocking filters, the successful demonstration and quick acceptance of FT-Raman spectroscopy, and the adoption of scientific-grade charge coupled device (array) detectors as the preferred detector for the majority of dis- persive Raman spectroscopic experiments. The developments noted above have indeed changed the perception of Raman spec- troscopy completely. However, it should be noted that there are still several applications in which using a triple monochromator equipped with either a PMT or an array detector may be the only appropriate technology. This is especially true for applications in which low-frequency vibrations need to be observed. ‘These instrumental developments have had a dramatic effect on the applications of Raman spectroscopy. In the early to mid-1980s, Raman spectroscopy was considered to be a purely academic research tool with some industrial applications acknowledged by the academic community. Now, observing the composition of practitioners in the field of Raman spectroscopy it can be clearly seen that there are two groups. The first is composed almost exclusively of academics and scientists working in government laboratories, while the second comprises academics, industrial problem solvers, process and control engineers, and quality control technicians who started to use or reuse Raman spectroscopy as a tool from the late 1980s. Copyright © 2001 by Taylor & Franeis Group, LLCSeveral texts have appeared over the last few years, that have concentrated on either theory or instrumentation, FT-Raman, and dispersive spectrometers. When we first con- ceived this book, there was not a single reference source whose basis was (a) Can Raman spectroscopy be of use? and if it can, (b) what type of instrumentation will allow the user to obtain the most useful data? We have tried to identify as many areas of topical interest as possible, that will be appropriate to the second group of Raman practitioners described above. We have drawn together and blended industrial and academic spectroscopists to produce a comprehensive text for modern Raman spectroscopists. In the early chapters, the principles of Raman theory, instrumentation, selection of appropriate instrumentation, important instrumental measurement parameters, the use of data for the practitioner's benefit, and extracting the important analytical information from recorded data are introduced and discussed. These early chapters, where appropriate, use specific examples to illustrate the necessary concepts. ‘The later chapters provide extensive coverage of applications (semiconductors, carbon, hard-disk analysis, catalysts, glasses, pigments, gemmology, environmental science, in vivo biomedical studies, pharmaceutical studies, biodynamics, process control, archaeology, fo- rensics, polymer films and fibers) where Raman spectroscopy has proven to be an appro- priate tool is provided. In addition, fundamental reviews of gaseous, liquid, and solid phase Raman analysis are separate topics of discussion. Again, these chapters incorporate specific case-studies which should provide useful guidelines for the scientist planning to embark on the use of Raman spectroscopy as well as for the more experienced spectroscopist who plans to expand the use of Raman spectrometry into newer applications. The miniaturization of Raman spectrometers is now being addressed, and research- grade miniature Raman units will soon be available commercially, The drive to put a Raman spectrometer on Mars by 2005, providing arguably the most remote sensing Raman experiment ever undertaken, is an illustration of how the versatility of Raman spectroscopy is now being expanded. There are reports of suitable field instruments being developed of only several kilograms in mass, and the Raman spectrometers proposed for extraterrestrial planetary explorations are the smallest yet constructed (~1 kg or less). Despite the re- quirements for small size and rugged construction one thing is clear—there can be little or no sacrifice in spectral-quality information (resolution and sensitivity) provided by these miniaturized spectrometers. The already much expanded application portfolio of Raman spectroscopy is clearly ever-increasing. Jan R. Lewis Howell G. M. Edwards 2001 by Taylor & Francis Group, LLCContents Preface Contributors 10 ‘Theory of Raman Scattering Laurence A. Nafie Evolution and Revolution of Raman Instrumentation— Application of Available Technologies to Spectroscopy and Microscopy Fran Adar Raman Spectrometry and Its Adaptation to the Industrial Environment Joseph B. Slater, James M. Tedesco, Ronald C. Fairchild, and lan R. Lewis Raman Microscopy: Confocal and Scanning Near-Field Kurt J. Baldwin, David N. Batchelder, and Simon Webster Raman Imaging Patrick J. Treado and Matthew P. Nelson The Quest for Accuracy in Raman Spectra Charles K. Mann and Thomas J. Vickers Chemometrics for Raman Spectroscopy Jeremy M. Shaver Raman Spectra of Gases Heinz W. Schrétter Raman Spectroscopy Applied to Crystals: Phenomena and Principles, Concepts and Conventions David C. Smith and Constantin Carabatos-Nédelec Raman Scattering of Glass Constantin Carabatos-Nédelec Copyright © 2001 by Taylor & Franeis Group, LLCul 12 13 14 15 16 17 18 19 20 2 2 24 Raman Spectroscopic Applications to Gemmology Lore Kiefert, Henry A. Héinni, and Thomas Ostertag Raman Spectroscopy on II-VI-Semiconductor Nanostructures Bianca Schreder and Wolfgang Kiefer In Vivo Raman Spectroscopy Gerwin J. Puppels, Tom C. Bakker Schut, Peter J. Caspers, Rolf Wolthuis, M. van Aken, A. van der Laarse, Hajo A. Bruining, H. P. J. Buschman, Martin G. Shim, and Brian C. Wilson Some Pharmaceutical Applications of Raman Spectroscopy Adrian C. Williams Low-Frequency Raman Spectroscopy and Biomolecular Dynamics: A Comparison Between Different Low-Frequency Experimental Techniques. Collectivity of Vibrational Modes Ole Faurskov Nielsen Raman Spectroscopic Studies of Ion—Ion Interactions in Aqueous and Nonaqueous Electrolyte Solutions Jose M. Alfa Environmental Applications of Raman Spectroscopy to Aqueous Systems Ted L. Williams and Timothy W. Collette Raman and Surface Enhanced Resonance Raman Scattering: Applications in Forensic Science W. Ewen Smith, C. Rodger, Geoffrey Dent, and Peter C. White Application of Raman Spectroscopy to Organic Fibers and Films Stephen Michielsen Raman Spectroscopy of Catalysts Israel E. Wachs Applications of IR and Raman Spectroscopy to the Study of Medieval Pigments Fernando Rull Perez Raman Spectra of Quasi-Elemental Carbon James L. Lauer Process Raman Spectroscopy lan R. Lewis The Use of Raman Spectroscopy to Monitor the Quality of Carbon Overcoats in the Disk Drive Industry Andrew Whitley © 2001 by Taylor & Francis Group, LLC25 Raman Spectroscopy in the Undergraduate Teaching Laboratory Michael D. Morris 26 Raman Spectroscopy in the Characterization of Archaeological Materials Howell G. M. Edwards Copyright © 2001 by Taylor & Franeis Group, LLCContributors Fran Adar, Ph.D. Worldwide Raman Applications Manager, Raman Division, Horiba Group, Jobin Yvon Inc., Edison, New Jersey Jose M. Alfa, Ph.D., C. Chem., F.R.S.C. Professor, Department of Physical Chemistry, Universidad de Castilla-La Mancha, Ciudad Real, Spain Kurt J. Baldwin, Ph.D. Raman Consultant, Department of Physics and Astronomy, University of Leeds, Leeds, England David N. Batchelder, Ph.D. Professor of Physics, Department of Physics and Astronomy, University of Leeds, Leeds, England Hajo A. Bruining, M.D., Ph.D. Professor, Department of General Surgery, Erasmus University and University Hospital Rotterdam “Dijkzigt,” The Netherlands H. P. J. Buschman Laboratory for Intensive Care Research and Optical Spectroscopy, Department of General Surgery, Erasmus University and University Hospital Rotterdam “Dijkzigt,” Rotterdam, and Leiden University Medical Center, Leiden, The Netherlands Constantin Carabatos-Nédelec, Ph.D. Professor, Centre Lorrain d’optique et Eléctronique des Solides, University of Metz, Metz, France Peter J. Caspers, M.Sc. Department of General Surgery, Erasmus University and University Hospital Rotterdam “Dijkzigt,” Rotterdam, The Netherlands Timothy W. Collette, Ph.D. Research Chemist, National Exposure Research Laboratory, U.S. Environmental Protection Agency, Athens, Geo: G. Dent, Ph.D., C.Phys., Minst.P. Avecia Lid., Hexagon House, Manchester, England Howell G. M. Edwards, M.A., B.Se., D.Phil. C.Chem., FR.S.C. Professor of Molecular Spectroscopy, Department of Chemical and Forensic Sciences, University of Bradford, Bradford, West Yorkshire, England Copyright © 2001 by Taylor & Franeis Group, LLCRonald C. Fairchild, M.S.E. (CICE) Director, Software Development, Kaiser Optical Systems, Inc., Ann Arbor, Michigan Henry A. Hanni, Pr. Dr. Director, SSEF Swiss Gemmological Institute, Basel, Switzerland Wolfgang Kiefer, Prof. Dr. Professor, Department of Physical Chemistry, University of Wiirzburg, Wiirzburg, Germany Lore Kiefert, Ph.D. Assistant Director, SSEF Swiss Gemmological Institute, Basel, Switzerland James L. Lauer, Ph.D. Emeritus Professor and Visiting Scholar, University of California, San Diego, San Diego, California Ian R. Lewis, Ph.D. Research Products Manager, Spectroscopy Products Group, Kaiser Optical Systems, Inc., Ann Arbor, Michigan Charles K. Mann, M.S., Ph.D. Professor, Department of Chemistry, Florida State University, Tallahassee, Florida Stephen Michielsen, Ph.D. Associate Professor, School of Textile and Fiber Engineering, Georgia Institute of Technology, Alanta, Georgia Michael D. Morris, Ph.D. Professor, Department of Chemistry, University of Michigan, Ann Arbor, Michigan Laurence A. Nafie, Ph.D. Distinguished Professor, Department of Chemistry, University, Syracuse, New York Syracuse Matthew P. Nelson, Ph.D. Principal Scientist, ChemIcon Inc., Pittsburgh, Pennsylvania Ole Faurskov Nielsen, M.Sc., D.Se. Professor, Department of Chemistry, University of Copenhagen, Copenhagen, Denmark ‘Thomas Ostertag, Dipl.-Min. Freelance Petrologist, Freiburg, Germany Fernando Rull Perez, Ph.D. Professor, Department of Crystallography and Minerology, University of Valladolid, Valladolid, Spain Gerwin J. Puppels, Ph.D. Associate Professor, Department of General Surgery, Erasmus University and University Hospital Rotterdam “Dijkzigt,” Rotterdam, ‘The Netherlands C. Rodger, Ph.D. Avecia Ltd., Hexagon House, Blackley, Manchester, England Bianca Schreder, Ph.D. Professor, Department of Physical Chemistry, University of Wirzburg, Wurzburg, Germany Heinz W. Schritter, Drrer.nat. Professor, Department of Physics, Ludwig- Maximilians-Universitat Miinchen, Munich, Germany Tom C. Bakker Schut, M.Se., Ph.D. Research Fellow, Department of General Surgery, Erasmus University and University Hospital Rotterdam “Dijkzigt,” Rotterdam, ‘The Netherlands Copyright © 2001 by Taylor & Francis Group, LLCJeremy M. Shaver, Ph.D. Senior Scientist, Eigenvector Research, Inc., Manson, Washington Martin G. Shim, Ph.D. Research & Technology, Digital Security and Controls, Ltd., Concord, Canada Joseph B. Slater, B.S.E.E. Manager, New Product Development, Kaiser Optical Systems, Inc., Ann Arbor, Michigan David C. Smith, M.A., M.Se., Ph.D. Professor, Laboratory of Minerology, National Museum of Natural History, Paris, France W. Ewen Smith, D.Se., FRSE Professor of Inorganic Chemistry, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland James M, Tedesco, M.S.E.E. Senior Staff Scientist, Kaiser Optical Systems, Inc., Ann Arbor, Michigan Patrick J. Treado, Ph.D. President, Chemicon Inc., Pittsburgh, Pennsylvania M. van Aken Laboratory for Intensive Care Research and Optical Spectroscopy, Department of General Surgery, Erasmus University and University Hospital Rotterdam “Dijkzigt,” Rotterdam, The Netherlands A. van der Laarse Laboratory for Intensive Care Research and Optical Spectroscopy, Department of General Surgery, Erasmus University and University Hospital Rotterdam “Dijkzigt,” Rotterdam, The Netherlands ‘Thomas J. Vickers, Ph.D. Professor, Department of Chemistry, Florida State University, Tallahassee, Florida Israel E, Wachs, Ph.D. Professor, Department of Chemical Engineering, Lehigh University, Bethlchem, Pennsylvania Simon Webster, Ph.D, Raman Consultant, Department of Physics and Astronomy, University of Leeds, Leeds, England Peter C. White, Ph.D., C.Chem., FR.S.C. Senior Lecturer, Forensic Science Unit, University of Strathclyde, Glasgow, Scotland Andrew Whitley, Ph.D. Director, Raman Spectroscopy Group, Jobin Yvon Inc., Edison, New Jersey Adrian C. Williams, B.Se., Ph.D., C.Chem, M.R.S.C. Reader in Pharmaceutical Technology, Drug Delivery Group, School of Pharmacy, University of Bradford, Bradford, West Yorkshire, England ‘Ted L. Williams, Ph.D. NRC Postdoctoral Fellow, National Exposure Research Laboratory, U.S. Environmental Protection Agency, Athens, Georgia Brian C. Wilson, Ph.D. Professor, Department of Medical Biophysics, Ontario Cancer Institute/Photonics Research Ontario, University of Toronto, Toronto, Ontario, Canada Rolf Wolthius, M.Sc. Department of General Surgery, Erasmus University and University Hospital Rotterdam “Dijkzigt,” Rotterdam, The Netherlands Copyright © 2001 by Taylor & Franeis Group, LLC1 Theory of Raman Scattering Laurence A. Nafie Syracuse University, Syracuse, New York 1. INTRODUCTION Raman scattering is a fundamental form of molecular spectroscopy [1,2]. Together with infrared (IR) absorption, Raman scattering is used to obtain information about the structure and properties of molecules from their vibrational transitions [3-5]. The theory of Raman scattering is more complex that the theory of IR absorption, but there are a number of close parallels between the two theories [6-10]. As is well known, IR absorption arises from a direct resonance between the frequency of the IR radiation and the vibrational frequency of a particular normal mode of vibration. The property of the molecule involved in the resonant interaction is the change in the dipole moment of the molecule with respect to its vibrational motion. IR absorption is a one-photon event. The IR photon encounters the molecule, the photon disappears, and the molecule is elevated in vibrational energy by the energy of the photon at the frequency of vibrational resonance. By contrast, Raman scattering is a two-photon event. In this case, the property in- volved is the change in the polarizability of the molecule with respect to its vibrational motion. The interaction of the polarizability with the incoming radiation creates an induced dipole moment in the molecule, and the radiation emitted by this induced dipole moment contains the observed Raman scattering. The light scattered by the induced dipole of the molecule consists of both Rayleigh scattering and Raman scattering. Rayleigh scattering corresponds to the light scattered at the frequency of the incident radiation, whereas the Raman radiation is shifted in frequency, and hence energy, from the frequency of the incident radiation by the vibrational energy that is gained or lost in the molecule. The polarizability is a tensor with two Cartesian components; one is associated with the inci- dent photon and the other with the scattered photon. The two photons are connected by a single quantum mechanical process, a coherent event, that makes Rayleigh and Raman scattering different from the two one-photon events of absorption followed by emission. An energy-level diagram is given in Fig. 1, which illustrates IR absorption and Raman scattering. In both cases the initial state is the zeroth vibrational level of the ground Copyright © 2001 by Taylor & Franeis Group, LLCho, go — 0 INFRARED RAMAN ABSORPTION SCATTERING Figure 1 Energy-level diagram for infrared absorption and stokes Raman Scattering for a vibra- tional transition from g0 to gl. The scattering photon energy, fie, is shifted from the incident laser radiation energy by the infrared vibrational energy, fiex,, gained by the molecule. electronic state (g0) and the final state is the first vibrational level of the ground electronic state (g1). IR absorption achieves this state change in one step, whereas Raman scattering requires two steps involving photon energies that are well above that of the IR photon or energy of the vibrational transition. Also indicated in Fig. 1 are the excited vibronic states for the molecule labeled ev for the vth vibrational level of the eth electronic state. If the molecule gains vibrational energy as shown, the scattering is called Stokes Raman, whereas if the molecule loses vibrational energy (by starting from an elevated vibrational level), the process is known as anti-Stokes Raman scattering. To varying degrees, Raman scattering is sensitive to all the excited electronic states of the moiecule. If the incident photon energy approaches the transition energy of an excited electronic state, typically the lowest allowed of such states, the Raman scattering, changes from normal Raman scattering to resonance Raman scattering. The general theory of Raman scattering takes into account this complexity, but there are two important limits that reduce the complexity. One is the far-from-resonance (FER) limit. This is a common situation for colorless samples that have no electronic states in close proximity to the incident photon energy. The other is the single-electronic-state (SES) limit of strong res- onance with a single electronic state. In this limit, the incident photon energy is very close to, or falls within, the absorption band of an excited electronic state of the molecule, and the resulting resonance Raman (RR) scattering is dominated by the properties of thi resonant electronic state. In the past 25 years, a new area of Raman spectroscopy has evolved that is also a new form of molecular optical activity [9,11—13]. Called Raman optical activity (ROA), this form of Raman scattering applies only to chiral molecules, molecules whose mirror- image pairs are nonsuperposable. ROA is broadly defined as the difference in Raman scattering for right versus left circularly polarized (CP) radiation, where the change in the CP state of the light is effected for either the incident radiation, the scattered radiation, or both, either in phase or out of phase. The theory of ROA is more complex than the theory Copyri 2001 by Taylor & Francis Group, LLCof ordinary Raman scattering because it involves additional terms in the expansion of the polarizability beyond the dipole approximation. The new optical activity tensors involve either the magnetic dipole moment or the electric quadrupole moment, In this chapter, we will provide a very basic, unified treatment of the theory of Raman scattering and ROA. More extensive descriptions of theory of Raman and ROA scattering can be found elsewhere [6-10,12,14,15] il. THE RAMAN TENSOR One of the essential properties associated with the Raman scattering of light by molecules is the polarization state of the light [9]. Changes in the polarization state affect the nature and information content of the scattered light. The intensity of light scattering for any experiment can be expressed in terms of the polarizability, &,,, and the polarization vectors for the incident and scattered radiation, é!, and é4, respectively, and is given by We", 90K 22 a.p2l") wo In this equation, the angular brackets designate an average over all angles of orientation of the molecule to the laboratory frame of reference. This is needed for liquid, solution, or gaseous samples where there is no unique orientation of molecular axes relative to the laboratory axes. The polarization vectors have one Greek subscript and the scattering tensor has two. For repeated Greek subscripts, summation over the Cartesian directions x, y, and z is implied. Hence, Eq. (1) has, in general, nine terms (one for each component Pair xx, xy. 42, JM, Ys Yes Lk ZY, and zz) within the vertical brackets, and these brackets with superscript 2 designate the absolute square of the complex quantities within the brackets, The tilde above a quantity, such as a polarization vector or a scattering tensor, indicates that this quantity can be complex. The asterisk superscript for the polarization vector of the scattered light designates complex conjugation. The constant K is given by L fwtwk 90. ( 4aR ) 2 where w is the angular frequency of the scattered light, to is the magnetic permeability, E° jg the electric field strength of the incident laser radiation, and R is the distance from the scattering origin to the detector. The Raman polarizability tensor is given by [12,14] By (qeeualale ' (nb lf) @ OF Wp, ~ @y + it, m+ Oy + iD, where fi is Planck’s constant divided by 277, and the summation is over all excited elec- tronic states, j, of the molecule. The states n and m differ by a vibrational quantum of energy. The denominators contain frequency terms, and @, is the angular frequency dif- ference between the states j and n. The terms iT’, are imaginary terms proportional to the width of the vibronic state j and, hence, inversely proportional to its lifetime. The first of the two terms in Eq. (3) is called the resonance term because the frequency difference between the jn transition frequency and the laser frequency vanishes at the resonance condition. The quantities in angular brackets are quantum mechanical matrix elements with electric dipole moment operators fi,, given by Copyright © 2001 by Taylor & Franeis Group, LLC