Handbook of Raman Spectros

Handbook of
Raman
Spectroscopy
Copyright © 2001 by Taylor & Francis Group, LLC

PRACTICAL SPECTROSCOPY
A SERIES
1. lnfrared and Raman Spectroscopy (in three parts), edited by Edward G. Brame, Jr.,
and Jeanette G. Grasselli
2. X-Ray Spectrometry, edited by H. K. Herglotz and L. S. Birks
3. Mass Spectrometry (in two parts), edited by Charles Merritt, Jr., and Charles N.
McEwen
4. lnfrared and Raman Spectroscopy of Polymers, H. W. Siesler and K. Holland-Moritz
5. NMR Spectroscopy Techniques, edited by Cecil Dybowski and Robert L. Lichter
6. lnfrared Microspectroscopy: Theory and Applications, edited by Robert G. Messer-
schmidt and Matthew A. Harthcock
7. Flow Injection Atomic Spectroscopy, edited by Jose Luis Burguera
8. Mass Spectrometry of Biological Materials, edited by Charles N. McEwen and Barbara
S. Larsen
9. Field Desorption Mass Spectrometry, Laszlt, Prbkai
10. ChromatographyIFourier Transform lnfrared Spectroscopy and Its Applications,
Robert White
11. Modern NMR Techniques and Their Application in Chemistry, edited by Alexander I.
Popov and Klaas Hallenga
12. Luminescence Techniques in Chemical and Biochemical Analysis, edited by Willy R.
G. Baeyens, Denis De Keukeleire, and Katherine Korkidis
13. Handbook of Near-Infrared Analysis, edited by Donald A. Bums and Emil W. Ciurczak
14. Handbook of X-Ray Spectrometry: Methods and Techniques, edited by Rene E. Van
Grieken and Andrzej A. Markowicz
15. Internal Reflection Spectroscopy: Theory and Applications, edited by Francis M.
Mirabella, Jr.
16. Microscopic and Spectroscopic Imaging of the Chemical State, edited by Michael D.
Morris
17. Mathematical Analysis of Spectral Orthogonality, John H. Kalivas and Patrick M. Lang
18. Laser Spectroscopy: Techniques and Applications, E. Roland Menzel
19. Practical Guide to lnfrared Microspectroscopy,edited by Howard J. Humecki
20. Quantitative X-ray Spectrometry: Second Edition, Ron Jenkins, R. W. Gould, and Dale
Gedcke
21. NMR Spectroscopy Techniques: Second Edition, Revised and Expanded, edited by
Martha D. Bruch
22. Spectrophotometric Reactions, lrena Nemcova, Ludmila Cermakova, and Jiri
Gasparic
23. Inorganic Mass Spectrometry: Fundamentals and Applications, edited by Christopher
M. Barshick, Douglas C. Duckworth, and David H. Smith
24. lnfrared and Raman Spectroscopy of Biological Materials, edited by Hans-Ulrich
Gremlich and Bing Yan
25. Near-Infrared Applications In Biotechnology, edited by Ramesh Raghavachari
26. Ultrafast lnfrared and Ramen Spectroscopy, edited by M. D. Fayer
27. Handbook of Near-Infrared Analysis: Second Edition, Revised and Expanded, edited
by Donald A. Bums and Emil W. Ciurczak
28. Handbook of Raman Spectroscopy: From the Research Laboratory to the Process
Line, edited by Ian R. Lewis and Howell G. M. Edwards

ADDITIONAL VOLUMES IN PREPARATION
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. Ciurczak and

James Drennen

Handbook of
Raman
From the Research Laboratory
to the Process Line
edited by
Ian R. Lewis
Kaiser Optical Systems, Inc.
Ann Arbor, Michigan
Howell G. M. Edwards
University of Bradford
Bradford, West Yorkshire, England
MARCEL
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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.

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 11, 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, Rarnan 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.

PREFACE
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.
Ian R. Lewis

Contents
Preface 1 v
Contributors 1 xi
Theory of Raman Scattering / 1

Laurence A. Nafie
Evolution and Revolution of Raman Instrumentation-Application of
Available Technologies to Spectroscopy and Microscopy / 11
Fran Adar
Raman Spectrometry and Its Adaptation to the Industrial Environment / 41
Joseph B. Slatel; James M. Tedesco, Ronald C. Fairchild, and Ian R. Lewis
Raman Microscopy: Confocal and Scanning Near-Field / 145
Kurt J. Baldwin, David N. Batcheldel; and Simon Webster
Raman Imaging 1 191
Patrick J. Treado and Matthew P. Nelson
The Quest for Accuracy in Raman Spectra / 251
Charles K. Mann and Thomas J. Vickers
Chemometrics for Raman Spectroscopy / 275
Jeremy M. Shaver
Raman Spectra of Gases / 307
Heinz W Schrotter
Raman Spectroscopy Applied to Crystals: Phenomena and Principles, Concepts
and Conventions / 349
David C. Smith and Constantin Carabatos-Nkdelec
Raman Scattering of Glass /
Constantin Carabatos-Nkdelec
vii
viii CONTENTS
Raman Spectroscopic Applications to Gemmology / 469

Lore Kiefert, Henry A. Hanni, and Thomas Ostertag
Raman Spectroscopy on 11-VI-Semiconductor Nanostructures / 491

Bianca Schreder and Wolfgang Kiefer
In Vivo Raman Spectroscopy / 549

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 1 575

Adrian C. Williams
Low-Frequency Raman Spectroscopy and Biomolecular Dynamics: A

Comparison Between Different Low-Frequency Experimental Techniques.
Collectivity of Vibrational Modes / 593
Ole Faurskov Nielsen
Raman Spectroscopic Studies of Ion-Ion Interactions in Aqueous and

Nonaqueous Electrolyte Solutions 1 617
Jose M. Alia
Environmental Applications of Raman Spectroscopy to Aqueous Systems 1 683

Ted L. Williams and Timothy W Collette
Raman and Surface Enhanced Resonance Raman Scattering: Applications in

Forensic Science / 733
W Ewen Smith, C. Rodger; Geoffrey Dent, and Peter C. White
Application of Raman Spectroscopy to Organic Fibers and Films / 749

Stephen Michielsen
Raman Spectroscopy of Catalysts 1 799

Israel E. Wachs
Applications of IR and Raman Spectroscopy to the Study of

Medieval Pigments / 835
Fernando Rull Perez
Raman Spectra of Quasi-Elemental Carbon 1 863

James L. Lauer
Process Raman Spectroscopy 1 919

Ian R. Lewis
The Use of Raman Spectroscopy to Monitor the Quality of Carbon Overcoats

in the Disk Drive Industry / 975
Andrew Whitley

CONTENTS
25 Raman Spectroscopy in the Undergraduate Teaching Laboratory I 999

Michael D. Morris
26 Raman Spectroscopy in the Characterization of Archaeological
Materials I 1011
Index 1 104.5

Contributors
Fran Adar, Ph.D. Worldwide Raman Applications Manager, Raman Division, Horiba
Group, Jobin Yvon Inc., Edison, New Jersey
Jose M. Alia, 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-Nbdelec, Ph.D. Professor, Centre Lorrain d'optique et
ElCctronique 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, Georgia
G. Dent, Ph.D., C.Phys., Minst.P. Avecia Ltd., Hexagon House, Manchester, England
Howell G. M. Edwards, M.A., B.Sc., D.Phil., C.Chem., F.R.S.C. Professor of
Molecular Spectroscopy, Department of Chemical and Forensic Sciences, University of
Bradford, Bradford, West Yorkshire, England

xii CONTRIBUTORS
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 Wurzburg, Wurzburg, 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, Atlanta, 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, Syracuse
University, Syracuse, New York
Matthew P. Nelson, Ph.D. Principal Scientist, ChemIcon Inc., Pittsburgh,
Pennsylvania
Ole Faurskov Nielsen, M-Sc., D.Sc. 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
Wurzburg, Wurzburg, Germany
Heinz W. Schrotter, Dr.rer.nat. Professor, Department of Physics, Ludwig-
Maximilians-Universitat Munchen, Munich, Germany
Tom C. Bakker Schut, M.Sc., Ph.D. Research Fellow, Department of General
Surgery, Erasmus University and University Hospital Rotterdam "Dijkzigt," Rotterdam,
The Netherlands

CONTRIBUTORS xiii
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.Sc., Ph.D. Professor, Laboratory of Minerology, National
Museum of Natural History, Paris, France
W. Ewen Smith, D.Sc., 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,
"Dijkzigt," Rotterdam, The Netherlands
A. van der Laarse Laboratory for Intensive Care Research and Optical Spectroscopy,
"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, Bethlehem, Pennsylvania
Simon Webster, Ph.D. Raman Consultant, Department of Physics and Astronomy,
University of Leeds, Leeds, England
Peter C. White, Ph.D., C.Chem., F.R.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.Sc., 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

Theory of Raman Scattering
Laurence A. Nafie
Syracuse University, Syracuse, New York
I. 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 [3-51. 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 [6-101.
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

INFRARED RAMAN
ABSORPTION SCATTERING
Figure 1 Energy-level diagram for infrared absorption and stokes Raman Scattering for a vibra-
tional transition from go to g l . The scattering photon energy, hw, is shifted from the incident laser
radiation energy by the infrared vibrational energy, hw,, gained by the molecule.
electronic state (go) and the final state is the first vibrational level of the ground electronic
state (gl). 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 molecule. 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 (FFR) 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 this
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 [9,11-131. 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

THEORY OF RAMAN SCATTERING 3
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].
II. 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, Gap, and the polarization vectors
for the incident and scattered radiation, e"; and ~ d , ,respectively, and is given by
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, xz, yx, yy, yz, zx, 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
where o is the angular frequency of the scattered light, p,, is the magnetic permeability,
E'O'is 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]
where fi is Planck's constant divided by 27~,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 oj,is the angular frequency dif-
ference between the states j and n. The terms ir, 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 j n 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 fia given by

which is simply the summation over the charge and position in the cvth direction of all
particles, k, in the molecule, electrons, and nuclei. For Raman scattering, only the electrons
of the molecule need to be included in the sum because the nuclei make no contribution
to the polarizability.
The matrix element in Eq. (3) involving the operator fiP describes the interaction of
the molecule with the incident radiation, and the matrix elements with the operator fi,
describes the interaction of the molecule with the scattered radiation. The matrix element
products in each term can be read from right to left in a time-ordered sense; hence, the
resonance term describes the molecule interacting first with a laser photon and subse-
quently creating a scattered photon, whereas the nonresonance terms reverses the natural
order of those two events.
Ill. RAMAN INTENSITY INVARIANTS

The general theory of Raman scattering embraces all possible polarization experiments,
scattering geometries, and degrees of resonance Raman-intensity enhancement. Raman
intensity is proportional to the square of a tensor quantity, as expressed in Eq. (1). For
solid samples whose crystal axes are aligned with laboratory axes, this equation is suffi-
cient for practical use. However, for most applications by chemists, the sample is in a
state where the molecules are oriented randomly with respect to the laboratory axes, such
as a gas, a liquid, a solution or a powder. In these cases, an orientational averaging must
be carried out for the sample molecules. The details of this averaging are complex and
can be found elsewhere [9,16]. After the averaging has been carried out, there are special
linear combinations of polarizability tensors whose values are independent of the orien-
tation of the molecule relative to laboratory frame. Such combinations are called invariants.
These are important quantities in Raman theory because polarizability tensor expressions
can be written down, or calculated, for the molecule independent of its orientation. Other
factors then take care of changes in the laboratory conditions, such as scattering geometry
and polarization states for the incident or scattered light. It turns out that all Raman
intensities from samples of randomly oriented molecules can be expressed in terms of
only three invariants, called the isotropic invariant, the symmetric anisotropy, and the
antisymmetric anisotropy, and these are given by [15,16]
where the symmetric and antisymmetric forms of the polarizability tensors are given by
As before, a repeated Greek subscript in a tensor or tensor product indicates summation

over the Cartesian directions x, y, and z. Thus, in Eqs. (5)-(7), there are nine terms to
consider to write out the full expression. Using these invariants, a general theory of Raman
scattering can be constructed that describes all Raman experiments and depolarization
ratios.
IV. GENERAL THEORY OF RAMAN OBSERVABLES

Any Raman scattering experiment, for samples of randomly oriented molecules, can be
expressed in terms of the three invariants given in Eqs. (5)-(7). We provide here expres-
sions for a few of the more common cases involving right-angle scattering and backscat-
tering. For laser radiation incident along the laboratory positive Z axis, three basic scat-
tering geometries can be defined: forward scattering (0") along the positive Z axis,
right-angle scattering (90") along the Y axis, and backscattering (180") along the negative
Z axis. In the case of right-angle scattering, there are two important scattering experiments.
They are the depolarized case where the incident light is X-polarized while the scattered
light is 2-polarized and polarized scattering where both the incident and scattered beams
are linearly polarized in the X direction. These are given by Eqs. (10) and (11); the
superscript and subscript on the intensity symbol, I, indicate the direction of the polari-
zation of the incident and scattered light, respectively, and the scattering angle is indicated
in parentheses:
The ratio of these two intensities is the depolarization ratio, namely
The depolarization ratio varies from zero for Raman scattering from totally symmetric
modes where only the isotropic invariant is nonzero, through 314 for nontotally symmetric
modes in the case where only the symmetric anisotropic invariant is nonzero, and on to
co for modes where only the antisymmetric anisotropic invariant is nonzero. It can be
shown that the antisymmetric anisotropic invariant can be nonzero only for resonance
Raman scattering.
In general, it is not possible to isolate all three Raman tensor invariants from the two
right-angle scattering measurements, and a third linearly independent measurement is
needed. This can only be achieved using a different scattering geometry and circularly
polarized radiation. Two convenient options are backscattering using purely circularly po-
larized radiation (right or left) where either the sense of the circularly polarized radiation
of the incident and scattered beams is the same (RR or LL) or the opposite (RL or LR).
For the case of incident right circularly polarized radiation, we have
The ratio of these two intensities is called the reversal ratio and is given by
The Raman intensity in Eq. (13) corresponds to corotating circularly polarized backscat-

tering and is a purely depolarized experiment that includes no contribution from either the
isotropic invariant or the antisymmetric anisotropic invariant. The scattering in Eq. (14)
corresponds to contrarotating circularly polarized radiation for the incident and scattered
beams and is a form of polarized Raman scattering.
V. FAR-FROM-RESONANCE LIMIT
The theory of Raman scattering simplifies dramatically in the far-from-resonance (FFR)
limit, where the exciting laser radiation is far from the lowest allowed excited electronic
state of the molecule [15]. In this limit, the interaction of the light with the molecule is
approximately the same for both the incident and the scattered radiation. There, the Raman
tensor becomes symmetric and this symmetry reduces the number of Raman invariants
from three to two, the isotropic and (symmetric) anisotropic invariants. The antisymmetric
anisotropic invariant vanishes, by its antisymmetric definition in Eqs. (7) and (9), and we
have
The equations for the two nonzero Raman invariants are
where the FFR polarizability is given simply by
Here, only the real part (Re) of the matrix element product is needed. This expression can
be compared to the corresponding general expression for the polarizability given in Eq.
(3). Using these invariants, we can write intensity expressions for Raman scattering that
cover all possible polarizations and scattering geometries in the FFR approximation. The
Raman-intensity expressions for right-angle scattering and the depolarization ratio in the
FFR limit are given by
The depolarization ratio given in Eq. (23) is the more familiar form where the allowed
values range from zero for a spherically polarized band to 314 for any non-totally sym-
metric vibration, where the isotropic invariant is zero for the latter. The corresponding
expression for corotating and contrarotating backscattering in the FFR limit are given by

Here, the reversal ratio varies from 0 to 6 for the same limits as the depolarization ratio
in Eq. (23). The above intensity expressions may be combined for other experimental
setups in right-angle scattering and backscattering. For example, for incident linearly po-
larized radiation in right-angle scattering and unpolarized scattering radiation (all scattered
radiation measured, both X- and 2-polarized), one has
Similarly, for backscattering, the same intensity if obtained by summing Eqs. (24) and
(25). Here, for unpolarized light collection, the scattered intensity is independent of the
polarization state incident radiation:
Note that in the FFR limit, the value of both Raman intensity invariants may be obtained
by using only two different polarization measurements and there is no need to change the
scattering geometry, as there is the general case in order to isolate three Raman invariants.
We also note that the distribution of the anisotropic invariant is different between the
polarized and depolarized forms of scattering in right-angle scattering and backscattering
geometries even though the total scattered intensity is the same. The pure backscattered
anisotropic scattering is twice the value for the corotating backscattering compared to the
perpendicular right-angle scattering [compare Eqs. (21) and (24)l. For this reason, there
may be advantages to setting up backscattering compared to right-angle scattering when
one wants to emphasize the difference between the scattering from the isotropic invariant
and that of the anisotropic invariant.
VI. SINGLE-ELECTRONIC-STATE RESONANCE LIMIT

When the frequency of the incident laser radiation in a Raman scattering experiment is in
resonance with a single electronic state (SES), it is well known that strong enhancement
of the Raman scattering occurs [14]. This is because the denominator of the resonant term
in the polarizability expression, Eq. (3), approaches zero and the value of the polarizability
can increase by several orders of magnitude. The resonance condition brings simplifying
conditions to the theory of Raman scattering, and the phenomenon itself becomes known
as resonance Raman (RR) scattering. Under conditions of strong resonance, the nonreso-
nant term [second term in Eq. (3)] can be dropped and the contributions of all other
electronic states can be omitted as too small to consider. The Raman polarizability in Eq.
(3) for a fundamental vibrational transition in the ground electronic state, gO to g l ,
becomes
If the transition moment of the resonant electronic state is taken to lie in the z direction,
the general set of three Raman invariants reduces effectively to only one Raman invariant
as

In addition, it can be shown that this Raman invariant is proportional to the square of the
electronic absorption strength for the resonant electronic state through the relationship
where (P):~is the electric dipole transition moment between the ground and the resonant
electronic state, respectively. From this relationship, it is clear that there is an underlying
connection between RR scattering in the SES limit and the electronic absorption spectrum
of the resonant electronic state. If one varies the excitation frequency of the incident laser
beam and measures the relative intensity of the RR scattering for any particular band, one
obtains a spectrum called the excitation profile of the band, which carries the resonance
dependence of that band. The form of the frequency dependence of the excitation profile
can be seen by taking the absolute square of the denominator of Eq. (29). Usually, the
resonant vibronic states that are most important for a given vibration are the eO and e l
vibronic bands. This assumes that the excited-state potential surface is nearly the same as
that of the ground state except for a shift in the equilibrium nuclear position. If more than
one electronic state participates in the resonance enhancement of bands, either by direct
resonance or indirectly through vibronic coupling, excitation profiles can reveal informa-
tion about the origin and symmetry of individual RR bands.
VII. RAMAN OPTICAL ACTIVITY

A relatively new form of Raman scattering combines ordinary Raman scattering with
natural optical activity. Called Raman optical activity (ROA), this form of Raman scat-
tering arises as the difference of the Raman scattered intensity for left versus right cir-
cularly polarized radiation, either in the incident light, the Raman scattered light, or both
[9,11,12]. In order to describe ROA theoretically, one needs to consider the next higher
interactions of light with matter. One is the magnetic dipole moment whose operator is
closely related to the electric dipole moment operator in Eq. (4) and is given by
This expression contains the vector cross-product, written in Cartesian notation, of the
position of the electron r and its momentum p. Here empYis the antisymmetric tensor which
equals - 1 for an odd permutations of the Cartesian axes x, y, and z, and + 1 for an even
permutation. Similarly, one must consider the electric quadrupole moment operator given
in Cartesian tensor notation by
where Sap is the Kronecker delta function which is equal to + 1 if the Cartesian subscripts
are equal and zero if they differ. These operators can be substituted into the general
expression for the polarizability given in Eq. (3) to yield the magnetic dipole and the
electric quadrupole optical activity tensors. In the FFR limit, simpler expressions for these

tensors are obtained that are analogous to the FFR polarizability tensor given in Eq. (20)
and are given by
where Im and Re represent the imaginary and real parts, respectively, of the expressions
in brackets that follow. From these tensors arise three ROA invariants that are analogous
to the two FFR Raman invariants given in Eqs. (18) and (19). The three ROA invariants
are the magnetic dipole isotropic invariant and the magnetic dipole and electric quadrupole
anisotropic invariants, given respectively by
The two most important experimental setups for the measurement of ROA are backscat-
tering (180") incident circular polarization (ICP) ROA and backscattering in-phase dual
circular polarization (DCP,) ROA. The ROA and parent Raman intensities written in terms
of ROA and Raman invariants in the FFR limit are given by
respectively, for backscattering ICP ROA where the subscript u represents unpolarized
scattered light and the superscript represents the polarization state of the incident laser
radiation. For backscattering DCP, Raman and ROA intensity, the expressions are
The ROA intensities are the same for these two forms of ROA, but the corresponding
Raman intensities differ. This is because ICP ROA does not discriminate the polarization
state of the scattered light and additional Raman scattering is measured that carries no
ROA in the FFR limit, namely the out-of-phase DCP,, Raman and ROA intensities. Back-
scattering ICP, and DCP, ROA are the most efficient ways to measure ROA spectra that
can be devised, and in the last decade, nearly all new measurements of ROA have been
carried out using one or the other of these two setups.
VIII. AB INlTlO CALCULATIONS OF RAMAN INTENSITIES

Raman intensities can now be calculated for any molecule for which the equilibrium
structure and vibrational force field can be determined. This has been achieved [17] by

starting with expressions for the polarizability in the zero-frequency limit of the FFR
approximation as
where the distinction between the initial and final states is not needed, neither is the
frequency of the incident laser radiation in the frequency denominator. The Raman inten-
sities can be obtained from these tensors by calculating their variation with the normal
coordinates of vibrational motion. The method by which these tensors have been calculated
is the electric field perturbation approach. The summation over all the excited states j can
be avoided by substituting field perturbed wavefunctions in first-order perturbation theory
for their nonperturbed counterparts as
where Emis the ath Cartesian component of the electric field, and the prime on the wave
function indicates the first derivative with respect to the field. Using ab initio quantum
mechanical methods, excellent agreement between theory and experiment has been
achieved. A particularly successful approach is the use of density functional theory (DFT)
with the hybrid density functionals B3LYP and BPW94 and basis functions at the level
of 6-3lG* or higher. Once the Raman tensors are calculated, invariants can be constructed
using Eqs. (18) and (19), and then assembled into the combinations appropriate for the
experimental setup desired. Extensions of these calculations have also been carried out for
ROA, where good agreement with experiment has been achieved.
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18 Chapter 18 Raman and Surface Enhanced
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19 Chapter 19 Application of Raman
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and Properties of Bombyx mori silk fibers grafted with
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the study of polymers and polymerization processes. J
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IAM Royaud, HA Willis, V Zichy. The application of Fourier
transform Raman spectroscopy to the identification and
characterization of polyamides-I. Single number nylons.
Spectrochim Acta 46A:747-756, 1990. WF Maddams, IAM
Royaud. The application of Fourier transform Raman
spectroscopy to the identification and characterization of
polyamides-11. Double-number nylons. Spectrochim Acta
47A:1327-1333, 1991. BH Stuart. A Fourier transform Raman
study of water sorption by Nylon 6. Polym Bull 33:681-
686, 1994. SP Bouffard, AJ Sommer, JE Katon, S Godber.
Use of molecular microspectroscopy to characterize
pigment-loaded polypropylene single fibers. Appl Spectrosc
48:1387-1393, 1994. AS Davie, PE Kavanagh, W-H Leong.
Fourier transform Raman spectroscopy for the analysis of
pigmented acrylic latex films. J Coatings Tech
67(847):63-68, 1995. M Olivares, H L6pez-Valivia, G
VBzquez-Polo, MA Mondragbn, R Lima, E Martinez, VM Cataiio.
FT-Raman analysis of the effects of y-radiation on nylon
6-12 filaments. Polym Bull 37:221-228, 1996. JD Louden.
Crystallinity in poly(ary1 ether ketone) films studied by
Raman spectroscopy. Polym Commun 27:82-84, 1986. NJ
Everall, J Lumsdon, JM Chalmers, N. Mason. The use of
polarized Fourier transform Raman spectroscopy in
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structure by laser Raman spectroscopy. In: CD Craver, ed.
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H Noether. Raman microprobe spectra of spin-oriented and
drawn filaments of poly(ethy1ene terephthalate). Polymer
26:1935-1942, 1985. BJ Bulkin, M Lewin, FJ DeBlase.
Conformational change, chain crientation, and crystallinity
in poly(ethy1ene terephthalate) yams: Raman spectroscopic
study. Macromolecules 18:2587-2594, 1985. N Everall, P
Tayler, JM Chalmers, D MacKerron, R Fenverda, JH van der
Maas. Study of density and orientation in poly(ethy1ene
terephthalate) using Fourier transform Raman spectroscopy
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1994. N Everall, K Davis, H Owen, MJ Pelletier, J Slater.
Density mapping in poly(ethy1ene terephthalate) using a
fiber-coupled Raman microprobe and partial least-squares
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Natarajan, S Michielsen. Determination of density and
birefringence of poly(ethy1ene terephthalate) fibers
using Raman microscopy. J Appl Polym Sci 73:943-952, 1999.
PJ Treado, MD Morris. Infrared and Raman spectroscopic
imaging. Appl Spectrosc 29:l-38, 1994. P Schmidt, PJ
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spectroscopy to the determination of conformation in
poly(ocapro1actam) chains. Spectrochim Acta 50A:1999-2004,
1994. SPS Porto. Angular dependence and depolarization
ratio of the Raman effect. J Opt Soc Am 56: 1585-1589,
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distributions by polarized Raman scattering and polarized
fluorescence. J Polym Sci: Polym Phys Ed 10:2135-2153,
1972. DA Jarvis, IJ Hutchinson, DI Bower, IM Ward.
Characterization of biaxial orientation in poly(ethy1ene
terephthalate) by means of refractive index measurements
and Raman and infra-red spectroscopies. Polymer 21:41-54,
1980. LJ Fina, DI Bower, IM Ward. Raman spectroscopy of
stressed samples of oriented poly(ethy1ene terephthalate).
Polymer 29:2146-215 1, 1988. MJ Citra, DB Chase, RM
Ikeda, KH Gardner. Molecular orientation of high-density
polyethylene fibers characterized by polarized Raman
spectroscopy. Macromolecules 28:4007-4012, 1995. PJ
Hendra, HA Willis. Dichroism in the laser excited Raman
spectrum of stretched fibres of polypropylene. Chem Ind
(London) 51:2146-2147, 1967. PD Vasko, JL Koenig. Raman
scattering and polarization measurements of isotactic
polypropylene. Macromolecule 3:597-601, 1970. SK Satija,
CH Wang. Polarized Raman scattering studies of chain
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Effects of chain orientation of Raman and Brillouin
scattering spectra of hydrostatically extruded
polypropylene. J Appl Phys 52:6003-6007, 1981. J Purvis,
DI Bower, IM Ward. Molecular orientation in PET studied by
polarized Raman scattering. Polymer 14:398-400, 1973. J
Purvis, DI Bower. Molecular orientation in poly(ethy1ene
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Hutchinson, DI Bower, IM Ward. Characterization of biaxial
orientation in poly(ethy1ene terephthalate) by means of
refractive index measurements and Raman and infra-red
spectroscopies. Polymer 21:41-54, 1980. NI Everall.
Measurement of orientation and crystallinity in uniaxially
drawn poly(ethy1ene terephthalate) using polarized
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1998. RA Huijts, SM Peters. The relation between molecular
orientation and birefringence in PET and PEN fibres.
Polymer 35:3119-3121, 1994. S Natarajan, S Michielsen. The
use of confocal Raman microscopy for determining the
structure and orientation of the PET interior of PET/PP
corelshell fibers. Textile Res J 69:903-907, 1999. C
Galiotis, IM Robinson, RT Young, BJE Smith, DN Batchelder.
Strain dependence of the Raman frequencies of a Kevlar 49
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Chain stretching in aramid fibres. Polym Commun
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Young, D Lu, RJ Day. Raman spectroscopy of Kevlar fibres
during deformation-Caveat emptor. Polym Int 24:71-76,
1991. RJ Young, D Lu, RJ Day, WF Knoff, HA Davis.
Relationship between structure and mechanical properties
for aramid fibres. J Mat Sci 27:5431-5440, 1992. RJ Day,
IM Robinson, M Zakikhani, RJ Young. Raman spectroscopy of
stressed high modulus poly@-phenylene benzobisthiazole)
fibres. Polymer 28:1833-1840, 1987. RJ Young, RJ Day, M
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Direct observation of taut tie molecules in high-strength
polyethylene fibers by Raman spectroscopy. J Polym Sci B:
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Meier. Molecular deformation of high-modulus polyethylene
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Meier, BJ Kip. Crystal and molecular deformation in
strained high-performance polyethylene fibers studied by
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Young. Analysis of the deformation of gel-spun polyethylene
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on the Raman frequency shift induced by tensile stress
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23 Chapter 23 Process Raman Spectroscopy
1. F Adar, R Geiger, J Noonan. Raman spectroscopy for

processlquality control. Appl Spectrosc Rev 32:45-101,
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2. ED Lipp, MA Leugers. Applications of Rarnan

spectroscopy in the chemical industry. In: MJ Pelletier,
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Blackwell Science, 1999.
3. IR Lewis, PR Griffiths. Raman spectrometry with

fiber-optic sampling. Appl Spectrosc 50:12A, 1996.

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Applied Electrospray Mass Spectrometery, edited by Ashit K. Ganguly, Birendra Pra-

Ultraviolet Spectroscopy and UV Lasers, edited by Prabhakar Misra and Mark A.

Near-Infrared Spectroscopy in Pharmaceutical Applications, Emil W. Ciurczak and

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Theory of Raman Scattering / 1

Raman Spectroscopic Applications to Gemmology / 469

Raman Spectroscopy on 11-VI-Semiconductor Nanostructures / 491

In Vivo Raman Spectroscopy / 549

Some Pharmaceutical Applications of Raman Spectroscopy 1 575

Low-Frequency Raman Spectroscopy and Biomolecular Dynamics: A

Raman Spectroscopic Studies of Ion-Ion Interactions in Aqueous and

Environmental Applications of Raman Spectroscopy to Aqueous Systems 1 683

Raman and Surface Enhanced Resonance Raman Scattering: Applications in

Application of Raman Spectroscopy to Organic Fibers and Films / 749

Raman Spectroscopy of Catalysts 1 799

Applications of IR and Raman Spectroscopy to the Study of

Raman Spectra of Quasi-Elemental Carbon 1 863

Process Raman Spectroscopy 1 919

The Use of Raman Spectroscopy to Monitor the Quality of Carbon Overcoats

Copyright © 2001 by Taylor & Francis Group, LLC

25 Raman Spectroscopy in the Undergraduate Teaching Laboratory I 999

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Copyright © 2001 by Taylor & Francis Group, LLC

Ronald C. Fairchild, M.S.E. (CICE) Director, Software Development, Kaiser Optical

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Jeremy M. Shaver, Ph.D. Senior Scientist, Eigenvector Research, Inc., Manson,

Copyright © 2001 by Taylor & Francis Group, LLC

Copyright © 2001 by Taylor & Francis Group, LLC

Copyright © 2001 by Taylor & Francis Group, LLC

II. THE RAMAN TENSOR

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Ill. RAMAN INTENSITY INVARIANTS

As before, a repeated Greek subscript in a tensor or tensor product indicates summation

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IV. GENERAL THEORY OF RAMAN OBSERVABLES

The ratio of these two intensities is the depolarization ratio, namely

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The equations for the two nonzero Raman invariants are

where the FFR polarizability is given simply by

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VI. SINGLE-ELECTRONIC-STATE RESONANCE LIMIT

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VII. RAMAN OPTICAL ACTIVITY

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VIII. AB INlTlO CALCULATIONS OF RAMAN INTENSITIES

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Copyright © 2001 by Taylor & Francis Group, LLC

2 Chapter 2 Evolution and Revolution of

84. H Owen, JM Tedesco, JB Slater. Remote optical