Cover
Preface
Acknowledgements
Chapter 1: Introduction, Basic Theory and Principles
1. 1.1 INTRODUCTION
2. 1.2 HISTORY
3. 1.3 BASIC THEORY
4. 1.4 MOLECULAR VIBRATIONS
5. 1.5 GROUP VIBRATIONS
6. 1.6 BASIC INTERPRETATION OF A SPECTRUM
7. 1.7 SUMMARY
8. REFERENCES
9. FURTHER READING
Chapter 2: The Raman Experiment – Raman Instrumentation, Sample Presentation, Data Handling and Practical Aspects of Interpretation
1. 2.1 INTRODUCTION
2. 2.2 CHOICE OF INSTRUMENT
3. 2.3 TRANSMISSION RAMAN SCATTERING AND SPATIALLY OFFSET RAMAN SCATTERING
4. 2.4 RAMAN SAMPLE PREPARATION AND HANDLING
5. 2.5 SAMPLE MOUNTING ACCESSORIES
6. 2.6 FIBRE‐OPTIC COUPLING AND WAVE GUIDES
7. 2.7 MICROSCOPY
8. 2.8 CALIBRATION
9. 2.9 DATA MANIPULATION, PRESENTATION AND QUANTITATION
10. 2.10 AN APPROACH TO QUALITATIVE INTERPRETATION
11. 2.11 SUMMARY
12. REFERENCES
Chapter 3: The Theory of Raman Spectroscopy
1. 3.1 INTRODUCTION
2. 3.2 ABSORPTION AND SCATTERING
3. 3.3 STATES OF A SYSTEM AND HOOKE’S LAW
4. 3.4 THE BASIC SELECTION RULE
5. 3.5 NUMBER AND SYMMETRY OF VIBRATIONS
6. 3.6 THE MUTUAL EXCLUSION RULE
7. 3.7 UNDERSTANDING POLARIZABILITY
8. 3.8 POLARIZABILITY AND THE MEASUREMENT OF POLARIZATION
9. 3.9 SYMMETRY ELEMENTS AND POINT GROUPS
10. 3.10 LATTICE MODES
11. 3.11 SUMMARY
12. REFERENCES
Chapter 4: Resonance Raman Scattering
1. 4.1 INTRODUCTION
2. 4.2 THE BASIC PROCESS
3. 4.3 KEY DIFFERENCES BETWEEN RESONANCE AND NORMAL RAMAN SCATTERING
4. 4.4 Practical Aspects
5. 4.5 SUMMARY
6. REFERENCES
Chapter 5: Surface Enhanced Raman Scattering and Surface Enhanced Resonance Raman Scattering
1. 5.1 INTRODUCTION
2. 5.2 ELECTROMAGNETIC AND CHARGE TRANSFER ENHANCEMENT
3. 5.3 SURFACE ENHANCED RESONANCE RAMAN SCATTERING (SERRS)
4. 5.4 SELECTION RULES
5. 5.5 SURFACE CHEMISTRY
6. 5.6 SUBSTRATES
7. 5.7 QUANTITATION AND MULTIPLEX DETECTION
8. 5.8 SUMMARY
9. REFERENCES
Chapter 6: Applications
1. 6.1 INTRODUCTION
2. 6.2 INORGANICS AND MINERALS AND ENVIRONMENTAL ANALYSIS
3. 6.3 ART AND ARCHAEOLOGY
4. 6.4 POLYMERS AND EMULSIONS
5. 6.5 DYES AND PIGMENTS
6. 6.6 ELECTRONICS APPLICATIONS
7. 6.7 BIOLOGICAL AND CLINICAL APPLICATIONS
8. 6.8 PHARMACEUTICALS
9. 6.9 FORENSIC APPLICATIONS
10. 6.10 PROCESS ANALYSIS AND REACTION FOLLOWING
11. 6.11 SUMMARY
12. REFERENCES
Chapter 7: More Advanced Raman Scattering Techniques
1. 7.1 INTRODUCTION
2. 7.2 FLEXIBLE OPTICS
3. 7.3 SPATIAL RESOLUTION
4. 7.4 PULSED AND TUNABLE LASERS
5. 7.5 TIP‐ENHANCED RAMAN SCATTERING AND SNOM
6. 7.6 SINGLE‐MOLECULE DETECTION
7. 7.7 TIME‐RESOLVED SCATTERING
8. 7.8 FLUORESCENCE REJECTION
9. 7.9 RAMAN OPTICAL ACTIVITY
10. 7.10 UV EXCITATION
11. 7.11 SUMMARY
12. REFERENCES
Appendix A: Table of Inorganic Band Positions
Index
End User License Agreement

List of Illustrations

Chapter 1
1. Figure 1.1. The electromagnetic spectrum on the wavelength scale.
2. Figure 1.2. Diagram of the Rayleigh and Raman scattering processes. The lowest ...
3. Figure 1.3. Stokes and anti‐Stokes scattering for cyclohexane. To show the weak...
4. Figure 1.4. Infrared and Raman spectra of benzoic acid. The top trace is infrar...
5. Figure 1.5. Spring and ball models for three modes of vibration for H₂O and CO₂
6. Figure 1.6. Electron cloud model of water and carbon dioxide.
7. Figure 1.7. Dipole and polarisation changes in carbon disulphide, with resultan...
8. Figure 1.8. A displacement diagram for a vibration at about 1200 cm⁻¹ in ...
9. Figure 1.9. Selected displacement diagrams for benzene and for CH₃ in CH₃Br. (a...
10. Figure 1.10. Comparison of aspirin spectra with impurity bands arrowed.
11. Figure 1.11. Paracetamol spectrum with significant chemical groups.
Chapter 2
1. Figure 2.1. A simple diagram outlining the basic components of a dispersive Ram...
2. Figure 2.2. Raman spectra taken across the exciting line. In A the intensity of...
3. Figure 2.3. A small monochromator used in a handheld Raman system. This set up ...
4. Figure 2.4. Wavelength response of a CCD (blue) suitable for Raman scattering a...
5. Figure 2.5. An interferometer‐based Raman spectrometer. Two geometries are usua...
6. Figure 2.6. Schematic diagram of spatially offset Raman spectroscopy (SORS) sho...
7. Figure 2.7. Sampling volume for a simple case. One solution gave – D = 4λf
8. Figure 2.8. Neat sample burning vs. mull spectrum.
9. Figure 2.9. Raman spectrum of copper phthalocyanine: (a) With 632 nm excitation...
10. Figure 2.10. NIR FT Raman spectra of phthalocyanines with various metals.
11. Figure 2.11. Raman spectra of dye in fibre. The top spectrum is from the dyed f...
12. Figure 2.12. Variable pressure and temperature cells.
13. Figure 2.13. Arrangements for measuring thin films.
14. Figure 2.14. Raman scattering collected using evanescent field excitation.
15. Figure 2.15. Raman spectra taken from an OTTLE cell containing a solution of a ...
16. Figure 2.16. Electrochemical cell.
17. Figure 2.17. (a) Pharmaceutical tablet autochanger.
18. Figure 2.18. Fibre optic probe head design. The exciting radiation passes down ...
19. Figure 2.19. (a, b) Fibre optic probe end.
20. Figure 2.20. Schematic illustrating principles of confocal Raman microscopy. (a...
21. Figure 2.21. Confocal depth profile of 78 μm acrylic latex coated on 200 μm PET...
22. Figure 2.22. (a) Lateral scan over a thin cross‐section of PET/PE laminate; the...
23. Figure 2.23. Raman imaging. Photomicrograph and corresponding Raman image of th...
24. Figure 2.24. Raman maps – pixel map (top); 3D map (bottom). Source: Reproduced ...
25. Figure 2.25. Spectrum of indene at 1064 nm–10 mw (top); 350 mw (bottom).
26. Figure 2.26. Cyclohexane uncorrected for instrument response.
27. Figure 2.27. Derivative Raman spectra.
28. Figure 2.28. Deconvolution of Raman bands from a broad spectrum.
29. Figure 2.29. Smoothed Raman spectra with the foot spectrum showing the danger o...
30. Figure 2.30. Diagram of the ‘azo’ stretch in an azo dye clearly showing that ma...
Chapter 3
1. Figure 3.1. A typical Morse curve for an electronic state showing the fundament...
2. Figure 3.2. Illustration of two vibrations in the centrosymmetric ion . The ar...
3. Figure 3.3. A very simple example to explain the process indicated by the integ...
4. Figure 3.4. Parallel arrangement to monitor polarization. The double arrows ind...
5. Figure 3.5. C₃ and C₂ axes in the nitrate ion.
6. Figure 3.6. Two vibrations of water.
7. Figure 3.7. Lattice modes for a single line of sodium chloride atoms showing th...
Chapter 4
1. Figure 4.1. The spectrum of Ellman’s reagent at 10⁻² M (foot) and of the ...
2. Figure 4.2. Spectra and displacements for the heme chromophore in a protein. (a...
3. Figure 4.3. Spectrum of iodine in the solid state obtained using a Raman micros...
4. Figure 4.4. Spectrum with overtones of copper phthalocyanine taken with an exci...
5. Figure 4.5. The spectrum of copper phthalocyanine taken with four different exc...
6. Figure 4.6. Resonant excitation profiles for two copper phthalocyanine vibratio...
7. Figure 4.7. Morse curves for the ground and excited state and an illustration o...
Chapter 5
1. Figure 5.1. The spectra of pyridine at various potentials given as relative to ...
2. Figure 5.2. An early experiment carried out under clean conditions in which ben...
3. Figure 5.3. TEM of a typical colloid used in SERS. It was prepared by citrate r...
4. Figure 5.4. Plot of the intensity dependence of one peak for both a non‐aggrega...
5. Figure 5.5. (a) The intensity of the 1200 cm⁻¹ band of BPE plotted agains...
6. Figure 5.6. The basic concept of charge transfer showing energy levels for a me...
7. Figure 5.7. Resonances for pyridine including the charge transfer term (CT) as ...
8. Figure 5.8. Diagram of pyridine adsorbed on a gold 20 cluster together with the...
9. Figure 5.9. An illustration of the different dimensions involved in the product...
10. Figure 5.10. SERS/SERRS at four different wavelengths for two dyes adsorbed at ...
11. Figure 5.11. Representation of the coupling of the wave functions for the surfa...
12. Figure 5.12. Three general ways an analyte can interact with a silver citrate c...
13. Figure 5.13. One of the pyramidal pits in Klarite which form a regular surface ...
14. Figure 5.14. SERS spectrum of polyethylene terephthalate (PET) taken from a sam...
15. Figure 5.15. (a) Diagram of two Shiners on a smooth gold surface coated with py...
16. Figure 5.16. Distance dependence of the SERRS spectrum of a dye adsorbed onto s...
17. Figure 5.17. Intensity dependence of one peak from the SERRS spectrum of mitoxa...
18. Figure 5.18. SERS of three oligonucleotides labelled with different dyes, FAM, ...
Chapter 6
1. Figure 6.1. NIR FT Raman spectrum of diamond.
2. Figure 6.2. NIR FT Raman spectrum of sulphur showing both Stokes and anti‐Stoke...
3. Figure 6.3. NIR FT Raman spectra of TiO₂ – rutile (top); anatase (bottom).
4. Figure 6.4. Infrared and NIR FT Raman spectra of NaCO₃.
5. Figure 6.5. Raman spectra of three different calcium sulphates from a sample ta...
6. Figure 6.6. Detection and discrimination of four metal ions in water samples by...
7. Figure 6.7. Spectra from a sixteenth‐century German choir book: historiated let...
8. Figure 6.8. NIR FT Raman spectra of polypropylene (top); polyethylene (bottom).
9. Figure 6.9. NIR FT Raman spectra of two polycarbonates with different aliphatic...
10. Figure 6.10. NIR FT Raman spectrum of PET.
11. Figure 6.11. Spectra of polystyrene – infrared transmission spectrum (top); FT ...
12. Figure 6.12. NIR FT Raman spectra of oils – emulsion (top); pure oil (bottom).
13. Figure 6.13. Graphical representation of intensity vs. concentration for four p...
14. Figure 6.14. NIR FT Raman spectra of (a) azo dye, forms I (top) and II (foot); ...
15. Figure 6.15. SERRS spectra of reactive dye attached to a cellulose fibre and in...
16. Figure 6.16. Infrared and NIR FT Raman spectrum of an azo dye.
17. Figure 6.17. (a) NIR FT Raman spectra of various metal phthalocyanines. (b) ...
18. Figure 6.18. NIR FT Raman spectra of photocopier drum showing the spectrum from...
19. Figure 6.19. Spectra of different forms of carbon. a‐C is amorphous carbon.
20. Figure 6.20. LO mode of zinc selenide with different selenium isotope ratios su...
21. Figure 6.21. SESORRS from labelled nanoparticles incorporated into multicellula...
22. Figure 6.22. Noninvasive Raman microscopy analysis of a crystal in an intact vi...
23. Figure 6.23. Crystallinity in pharmaceutical intermediate: crystalline form (to...
24. Figure 6.24. SERRS of smears of lipstick on glass and cotton give sharp spectra...
25. Figure 6.25. Reaction of TNT to form an azo dye to give an intense spectrum. Sp...
26. Figure 6.26. Spectrum of acrylate bead (bottom) and with peptide (top).
27. Figure 6.27. (a) SERS nanozyme concept showing CRP captured by an immobilised a...
Chapter 7
1. Figure 7.1. A handheld SORS spectrometer designed to detect hazardous materials...
2. Figure 7.2. SERRS from a single silver‐coated silica particle detected with a s...
3. Figure 7.3. A few ways lab‐on‐a‐chip technology can be used to aid on chip SERS...
4. Figure 7.4. (a) A simple chip design for the detection of Chlamydia. Amplified ...
5. Figure 7.5. An illustration of 3D imaging. (a) Parts of three CHO cells showing...
6. Figure 7.6. The basic processes of Raman scattering, HRS and CARS. In CARS both...
7. Figure 7.7. SERS (a) and SEHRS (b) of pyrazine on a silver electrode.
8. Figure 7.8. SEHRS of a functionalised carotene with 1064 nm excitation (a) comp...
9. Figure 7.9. CARS of rhodopsin.
10. Figure 7.10. A section of prostate cancer tissue imaged by CARS. The tight focu...
11. Figure 7.11. A simple diagram of a TERS setup. The cantilever carries the SERS‐...
12. Figure 7.12. Images of a tip coated with silver showing tips with one or two si...
13. Figure 7.13. TERS mapping of a single meso‐tetrakis(3,5‐di‐tertiarybutylphenyl)...
14. Figure 7.14. The photo‐dissociation of CO from the heme centre in myoglobin. Th...
15. Figure 7.15. (a) Time‐resolved Raman scattering obtained with a femtosecond pul...
16. Figure 7.16. Spectrum from a mineral taken with a fast detector and with fluore...
17. Figure 7.17. Kerr gated (light line) and normal Raman scattering (heavy line) f...
18. Figure 7.18. Schematic diagram of the basic concept of ICP ROA. What is measure...
19. Figure 7.19. Shows the Raman and ROA spectra from polypeptides in α helix confi...
20. Figure 7.20. UV‐resonance Raman scattering for tyrosines. (a) Actual spectra wi...
21. Figure 7.21. Resonance Raman spectra from myoglobin at three different frequenc...

This edition first published 2019
© 2019 John Wiley & Sons Ltd

Edition History
Modern Raman Spectroscopy – a practical approach, 1st edition, Wiley 2005

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Names: Smith, Ewen, author. | Dent, Geoffrey, 1948– author.
Title: Modern Raman spectroscopy : a practical approach / Ewen Smith, Geoffrey Dent.
Description: Second edition. | Hoboken, NJ : Wiley, [2019] | Includes bibliographical references and index. |
Identifiers: LCCN 2018042658 (print) | LCCN 2018051812 (ebook) | ISBN 9781119440581 (Adobe PDF) | ISBN 9781119440543 (ePub) | ISBN 9781119440550 (hardcover)
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Classification: LCC QD96.R34 (ebook) | LCC QD96.R34 S58 2019 (print) | DDC 535.8/46–dc23
LC record available at https://lccn.loc.gov/2018042658

Preface

Since the first edition of our book, there has been a huge expansion in the use of Raman spectroscopy. Advances in optics, electronics and data handling combined with improvements made by manufacturers and spectroscopists have made Raman scattering easier to record and more informative. Small, portable spectrometers are rugged, reliable and are becoming less expensive. Some can work powered by low‐voltage (1.5 V) batteries and give good performance in hostile environments. At the other end of the scale, advanced equipment is simpler, more sensitive, more flexible and more reliable. New methods with improved performance have been developed. As a result, a technique which was once labelled by some as lacking sensitivity can now, in the correct form, probe the electronic structure of a single molecule or be used to help in the diagnosis of cancer. This has attracted many more users into the field with a wide range of backgrounds.

Our aim in writing this book is to provide the understanding necessary to enable new users to apply the technique effectively. In the early chapters we provide basic theory and practical advice to enable the measurement and interpretation of Raman spectra with the minimum barrier to getting started. However, for those with a deeper understanding of the effect, Raman scattering is a very rich technique capable of providing unique information and a unique insight into specific problems. In writing this book some difficult choices have had to be made around the presentation of the theory, particularly with the wide variety of backgrounds we expect readers to possess. We have used as few equations as possible to show how the theory is developed and those are deliberately placed after the chapters on basic understanding. We concentrate on molecular polarizability, the molecular property which controls intensity. The equations are explained, not derived, so that those with little knowledge of mathematics can understand the conclusions reached and those of a more mathematical bent can use the framework for further investigation. This enables selection rules, resonance Raman scattering and some of the language in modern literature to be understood. This is not the traditional approach but, although deriving scattering theory from first principles is good for understanding, it adds little to Raman interpretation. Classical theory which does not use quantum mechanics cannot deliver the information required by most Raman spectroscopists. For these reasons, references to these areas are given but the theory is not explained.

Surface‐enhanced Raman scattering accounts for a significant fraction of the papers on Raman scattering and is employed in quite a few modern developments, so is given a full chapter. We finish with two chapters designed to enable the reader to come up to speed on the way Raman scattering is now applied in some of the main fields and to introduce the new techniques that are providing key insights and greater performance. Some of the new techniques are still expensive and therefore not so widely available but if the improvements continue, as is likely, they will become much more accessible. In any case the reader should be aware of their advantages.

One of the practical difficulties faced is in compliance with the IUPAC convention in the description of spectrum scales. The direction of the wavenumber shift should be consistent but this is not always the case in the literature. Further, Raman scattering is a shift from an exciting frequency and should be labelled Δcm⁻¹ but it is common practice to use cm⁻¹ with the delta implied. As far as possible we have used the format in which the user is most likely to record a spectrum or to see it in the literature. However, where we have used literature examples in this book, it is not possible to change these. We apologize to the purists who would prefer complete compliance with the IUPAC convention, but we have found that this is not practicable.

The authors hope that those who are just developing or reviving an interest in Raman spectroscopy will very quickly gain a practical understanding from the first two chapters. Furthermore, it is hoped that they will be inspired by the elegance and information content of the technique to delve further into the rest of the book, and explore the vast potential of the more sophisticated applications of Raman spectroscopy.

Modern Raman Spectroscopy:

A Practical Approach

Preface

Acknowledgements