Infrared Spectroscopy j FT-Raman NIRq

DD Le Pevelen, Chiralabs Ltd, Oxford, United Kingdom

© 2017 Elsevier Ltd. All rights reserved.

Introduction

Raman spectroscopy is an important tool in the field of vibrational spectroscopyand is complementary to infrared absorption spec-
troscopy, the latter being the more common vibrational spectroscopy. It is worth emphasizing that these two spectroscopies do not
probe the same vibrational information of a molecule. Raman spectroscopy is based on an inelastic scattering process, whereas
infrared spectroscopy is based on an absorption process. Raman spectroscopy detects vibrations involving a change in polarizability,
whereas infrared spectroscopy detects vibrations involving a change in dipole moment. As a result, the two spectroscopies have
different selection rules and it is possible that a strong vibration mode in Raman spectroscopy could be a weak one in infrared spec-
troscopy and vice versa. In connection with this, Raman spectroscopy is often feasible with aqueous solutions, whereas infrared
spectroscopy is severely limited due to the excessive absorbance of water.
In Raman spectroscopy, the samples are often used neat, in many circumstances making this spectroscopy easier than infrared
spectroscopy for sample preparation. The reader is encouraged to read the other articles of this encyclopedia covering the theory and
methodology of these two complementary techniques to broaden the background provided here.
Like for infrared spectrometers, Raman spectrometers are divided into two categories: the dispersive instruments and the Fourier
transform (FT) instruments.
Historically, the latter provided a big improvement in making Raman spectroscopy a practical technique, but then, the dispersive
instruments took a big market share in the field of Raman spectrometers. However, recently, there has been a new interest in FT
instruments. This article describes the main advantages and the main differences of FT spectrometers over dispersive instruments,
especially when using near-infrared (NIR) lasers as the source for Raman scattering. Some examples of NIR FT-Raman covering
various fields are shown.

FT and Dispersive Spectrometers

General Characteristics
Thorough descriptions of Raman spectrometers are covered in other articles of the encyclopedia and the reader is encouraged to
review these to expand on the brief insight into general Raman instrumentation discussed here. All Raman spectrometers consist

Figure 1 Schematic representation of the main components of FT-Raman spectrometers (top) and dispersive Raman spectrometers (bottom). The angle
of incidence of the exciting laser (q) is chosen as 0 degrees for transmission Raman and 180 degrees for backscattering Raman. © Chiralabs Ltd., 2015.

q
This is a reprint of D.D. Le Pevelen, NIR FT-Raman, Editor(s): John C. Lindon, George E. Tranter, David W. Koppenaal, Encyclopedia of Spectroscopy and
Spectrometry (Third Edition), Academic Press, 2017, pp. 98–109.

112 Encyclopedia of Analytical Science, 3rd edition, Volume 5 https://doi.org/10.1016/B978-0-08-101983-2.12150-4

 Infrared Spectroscopy j FT-Raman NIR 113

Table 1 Comparison between common FT- and dispersive NIR Raman spectrometers

Raman lasers
1064 nm 785 nm

Instrument Fourier transform Dispersive

Category NIR NIR
Detector InGaAs or Ge Si CCD
Working range (cm1) 3600–100 3600–100
Typical power output used (mW)a 800 <100
Advantages Much less prone to problem of sample fluorescence Stronger spectrum intensity
High wavenumber accuracy Good spatial resolution
Disadvantages Intensity in spectrum weaker than other lasers May be prone to problem of sample
fluorescence

a
Vary depending on sample of interest.

of some common elements such as a laser light source, some optics to pass the laser light to the sample and then collect the scattered
light (focusing and collecting), filters (to reject the Rayleigh scattered laser light), and a detector, as shown in Fig. 1.
The main difference between the two types of instruments is that FT-Ramanspectrometers use interferometers (typically
Michelson), whereas dispersive Raman spectrometers use a monochromator (typically a grating) in their design to enable spectral
delineation. In FT-Raman, after the light has interacted with the sample, it goes through the interferometer that generates an
interferogram before going onto the detector; this step can be thought of as a coding of the signal. The Raman spectrum is
obtained from the FT signal of this interferogram. In dispersive instruments, the grating monochromator separates spatially
the different wavelengths, which are then directed towards the detector. It is worth remembering that the response of gratings
is wavelength-dependent, so as a result, the spectral resolution will vary across the Raman spectrum when using dispersive
instruments.
Different detectors are also used in FT-Raman and dispersive instruments; indium gallium arsenide (InGaAs) or germanium
(Ge) detector is usually used for FT-Raman instruments, whereas photon collecting photomultiplier tube or CCD detector is
used in dispersive instruments.
Different choices of Raman lasers are available. They are broadly classified into three different categories depending on their
wavelength: UV lasers (wavelength <360 nm), visible lasers (wavelength of 450 nm up to 660 nm), and NIR lasers (wavelength
in the range 785–1064 nm). For FT instrument, the typical NIR laser used up to now has been a 1064 nm laser mainly because of the
type of detector used in such instrument. For dispersive instrument, the choice of lasers is less restrictive and NIR lasers such as 785
and 830 nm are often used. The characteristics of some of the typical NIR Raman lasers are reported in Table 1.
It is worth pointing out that Raman scattering intensity varies as the fourth power of the inverse of the wavelength (l4) of the
incident light. Thus, all other things being equal, the shorter the wavelength of the Raman laser, the stronger the intensity of a Raman
spectrum will be. This implies that visible lasers give stronger intensity spectra than NIR lasers. However, with the use of shorter
wavelength lasers comes the substantial problem of a high fluorescencebackground from many samples, especially those that
are colored. This high background can easily overcome the relatively weak Raman signals of the sample of interest, leading to spectra
of no use. Against this problem, FT-Raman instruments (1064 nm laser wavelength) are superior to any other Raman spectrometers
as the spectra obtained are much less prone to fluorescence problems.
FT-Raman spectrometers possess a number of advantages over dispersive instruments. The first one is that FT-Raman spectrom-
eters measure all wavelengths at the same time. In other words, every data point on an interferogram contains information about
every frequency of the Raman scattering coming from the sample. It results in a better signal-to-noise ratio for a given scan time. This
is known as “Fellgett’s advantage” or the multiplex advantage.
Another positive aspect of FT-Raman is their superiority in wavelength accuracy. This is due to the fact that with the presence of
an interferometer, there is an internal wavelength calibration using another laser (usually He–Ne laser). This is often referred to as
“Conne’s advantage.” Dispersive instruments typically require regular wavelength calibration (daily is not unusual for accurate
work).
The third main advantage of FT-Raman spectrometers is that, unlike dispersive instruments, they do not require slits that restrict
the amount of light passing through. They use instead an aperture (often referred as a Jacquinot’s stop) that allows more light, thus
resulting in a higher signal-to-noise ratio. This is known as “Jacquinot’s advantage” or throughput advantage.
Another useful aspect of FT-Raman spectrometers is that the resolution can be easily modified unlike in dispersive instruments
where only predefined resolution values are available and this is at the cost of grating change. Moreover, FT-Raman spectrometers
are often an add-on to an FT-IR spectrometer, making them more versatile instruments compared to a dedicated Raman instrument.

Typical Configurations
For both FT- and dispersive Raman spectrometers, it is possible to arrange different configurations regarding the orientation of the
Raman detection relative to the incoming laser illuminating the sample. The most common methods are backscattering
(180 degrees geometry), right-angle scattering (90 degrees geometry), and forwardscattering (transmission; 0 degrees geometry);
114 Infrared Spectroscopy j FT-Raman NIR

Table 2 Available configurations for FT- and dispersive NIR Raman spectrometers

Fourier transform Dispersive

Typical NIR laser 1064 nm 785 nm

Backscattering (180 degrees) U U

90 degrees U U
Transmission (0 degrees) U U
Microspectroscopy U (Less common nowadays) U

Figure 2 Schematic representation of the main configurations used in Raman spectroscopy. © Chiralabs Ltd., 2015.

in addition, these may be combined with optical microscope or optical fibre to provide microspectroscopic methods. The available
configurations using NIR lasers are listed in Table 2 and schematically depicted in Fig. 2.
Each of these techniques/methods has some advantages and disadvantages that are discussed briefly later in the text. Other
approaches are also available such as spatially offset Raman and many variants of the so-called non-linear Raman spectroscopy
(SRS, CARS, etc.). These topics are covered in other articles of the encyclopedia and as a result will not be discussed here.

Backscattering
Backscattering Raman has been the main configuration for Raman studies for many years. A laser irradiates the sample and the scat-
tered radiation is focused back onto the detector (180 degrees geometry). This configuration is available for both FT and dispersive
instruments.
When performing FT-Raman spectroscopy, the most important point to bear in mind is the effect of the size of the laser spot.
Because the probed volume of the sample can be quite small, the spectrum acquired is not necessarily a representative of the bulk
solid. To remedy this, it is important to make sure that the sample is as homogeneous as possible. If not possible or feasible, some
sampling devices exist to limit the effect of non-homogeneity such as rotating devices to acquire spectra averaged over a broader
area. In any case, the best practice is to acquire many spectra for the sample of interest and if the sample is static to acquire spectra
on different locations of the sample.
Another point to be aware of is that a sample can undergo localized heating and even burning if the laser power is too great; the
maximum power allowed will depend on the sensitivity sample to, say, thermal decomposition. Again, rotating devices to average
over larger areas of the sample can ameliorate heating effects to some degree. In addition, in some cases, a thermally conductive
material acting as a heat exchanger can be introduced, or the sample thermostated in some manner.

Transmission
Transmission Raman (otherwise known as forwardscattering) is a relatively recent and growing technique compared to backscat-
tering Raman. The technique has been notably applied in pharmaceutical analysis and has also been employed in the study of
 Infrared Spectroscopy j FT-Raman NIR 115

polymers and food analysis. In transmission Raman, the scattered radiation is detected in the forward direction of the incident laser
beam. The NIR lasers used up to now are 785 and 830 nm for dispersive instruments and 1064 nm for FT instruments.
This approach is known to deal better with the problem of heterogeneous samples compared to backscattering Raman as the
spectra acquired represent generally more of the bulk sample as the beam passes through the full pathlength of the sample. The
main disadvantage of Raman transmission is that it suffers from self-absorption effects, that is, the photons can be absorbed by
sample, diminishing the radiation.
When using dispersive instruments, the technique is also prone to suffer on occasions from fluorescence background because of
the type of lasers used. Against this problem, FT-Raman instruments (1064 nm laser wavelength) are superior to any other Raman
spectrometers as the spectra obtained are much less prone to fluorescence problems. For more details on transmission Raman spec-
troscopy, the reader is referred to the specific article on this method in this encyclopedia.

Right-Angle Scattering
With right-angle scattering Raman (also known as 90 degrees geometry) configuration, a laser irradiates the sample and the scattered
radiation is focused onto the detector at an angle of 90 degrees compared to the incident beam. This configuration was initially
popular because the Rayleigh scatteringof the incoming laser light was minimized in the detection direction. It is mainly viable for
transparent samples. This configuration is available for both FT and dispersive instruments.

Microspectroscopy
The spectroscopic imaging is simply the hyphenation of an optical microscope or fiber probe with a Raman spectrometer. The user is
able to first focus on an area of interest on a particular sample and to acquire subsequently spectroscopic information on the same
area. The analysis area for Raman microspectroscopy is defined by the laser spot size. The main advantage of microscopy is the
minute quantity of sample needed together with the non-destructive sampling. Microscopes can be hyphenated to both FT- and
dispersive Raman spectrometers. However, the former is becoming less common nowadays as dispersive Raman instruments
tend to have a better spatial resolution than FT instruments and allow having true confocal capability.
When using Raman instruments and particularly Raman microscopes and optical fibers, the user should take all precautions to
never look at the laser beam or its reflections. It is worth remembering that lasers produce an intense highly directional beam of light.
This light will be absorbed by materials it is pointed at and will raise its temperature. This applies also for the human body. The skin
and more seriously the eyes are vulnerable to this energy. The extent of the damage of the eye is determined by the laser irradiance
(watts per centimeter squared), the duration of exposure, and the beam size. Table 3 presents the classification and some hazards
of NIR lasers as a general overview but the user should take all precautions necessary as advised for their particular instrument.
Visible and NIR lasers fall in the so-called “retinal hazard region”, that is, the region covering the wavelength range 400–
1400 nm. These lasers can cause catastrophic retinal burns. Due to the fact that NIR lasers are invisible and that the retina lacks
pain sensory nerves, the user may not realize immediately the seriousness of the laser burn happening. The first indication of laser
burn that may be encountered, alas at a too late stage, is the hearing of an audible “pop,” which is often associated with the retina
being damaged. That is why specific protective eyewear (goggles, glasses, shields, etc.) must be worn at all times when using or in
sight of an operating Raman optical device that has the possibility of an exposed beam. Fortunately, many instruments are designed
with cabinets and interlocks that should prohibit exposure to the laser under correct usage.

Table 3 International classification and hazards of common NIR lasers

NIR laser 1064 nm 785 nm

Safety laser class 4 3B

International standards IEC 60825-1:2014 IEC 60825-1:2014
IEC 60601-2-22:2007 IEC 60601-2-22:2007
Maximum power output (mW) >500 <500
Description • High hazard • Medium–high hazard
• Capable of causing severe eye damage with short- • Capable of causing eye damage through direct beam or
duration exposures (0.25 s) through direct beam or specularly reflected beam; diffuse reflections are usually
reflected beam (either specularly or diffusely) non-hazardous, as long as exposure time is <10 s and
• Fire hazard as it can ignite flammable/combustible the eye is no closer than 13 cm from the diffusing
materials surface
• Can pose a risk of igniting flammable material when
diameter beam is small or the beam is focused and the
power of the laser approaches the AELa of class 3B
Effect on the eyes Retinal burns (potentially severe), cataract Retinal burns, cataract
Effect on the skin Skin burns (potentially severe) Skin burns

a
AEL: accessible emission limit (for a CW laser, in the visible or IR range, the class 3B AEL is 500 mW).
116 Infrared Spectroscopy j FT-Raman NIR

Practical Examples

The aim of this section is to show the capability of NIR FT-Ramanspectrometers in recording good quality Raman spectra for mate-
rials ranging from small organic compounds, to inorganic materials, to polymers and proteins. The samples analyzed can be solid or
liquid, colorless or colorful (to a certain extent but generally not black).

Organic Solvents
NIR FT-Raman spectra of organic solvents are readily acquired and give generally strong Raman bands. Figs. 3 and 4 show typical
Raman spectrum obtained for the solvents tert-butyl alcohol (2-methylpropan-2-ol) and cyclohexane in glass cuvettes, respectively.

752.0
16
H 3C
OH
14 H 3C
CH 3

12
relative Raman intensity

10
2920.0
2977.0

1455.0
6

916.0
4

348.0
1210.0
1241.0
2714.0

1027.0

479.0
2

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 3 FT-Raman spectrum of tert-butyl alcohol (800 mW, 4 cm1 resolution, 128 scans). © Chiralabs Ltd., 2015.
2854.0

24
803.0

22
2939.5

20

18
relative Raman intensity

16

14

12

10
2889.0

8
1445.5

1268.0

6
1029.5
2665.5

1159.5
2699.0

2634.5

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 4 FT-Raman spectrum of cyclohexane (800 mW, 2 cm1 resolution, 128 scans). © Chiralabs Ltd., 2015.
 Infrared Spectroscopy j FT-Raman NIR 117

For tert-butyl alcohol, the Raman band associated with the hydroxyl group is observed above 3200 cm1 and the characteristic CH3
modes in the region 2900–3000 cm1 are clearly visible. The strongest band at 752 cm1 is associated with C–C–O stretching mode.
For cyclohexane, the characteristic CH2 modes in the region 2850–2950 cm1give a very strong Raman signal. Another strong
Raman band, the one observed at 803 cm1, is associated with cyclohexane ring breathing mode.

Natural Oils
NIR FT-Raman can be a powerful tool in the analysis and characterization of natural and synthetic oils. For example, it can help in
distinguishing between different types of oils, their quality, the presence of adulterants, etc. Figs. 5 and 6 show typical Raman spec-
trum obtained for commercial essential eucalyptus oil and Australian tea tree oil in glass cuvettes, respectively. Both spectra are
information-rich and can be used as a fingerprint for these specific commercial products.

2931.0
2922.0

5.5

5.0

4.5

653.0
4.0
2972.5
relative Raman intensity

3.5
2883.0

3.0

2.5

2.0
1447.5
1434.0
1.5

547.5
667.5
1274.0

932.0

815.0
1166.5
1082.0
1017.5
1486.0

306.0
1660.5

1.0

444.0
844.0

508.0

388.5
2725.0

264.0
0.5

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 5 FT-Raman spectrum of a commercial essential eucalyptus oil (800 mW, 2 cm1resolution, 64 scans). © Chiralabs Ltd., 2015.
2913.0
2877.0

2.5
2964.0

2.0
relative Raman intensity

1.5
1428.0
1448.0
1612.0

1.0
730.0
2821.0

757.0
1679.0
1702.0

1377.0
1308.0
2726.0

431.0
1162.0

0.5
1209.0

875.0

323.0
888.0

650.0

199.0
952.0

804.0

579.0
491.0

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 6 FT-Raman spectrum of a commercial Australian tea tree oil (800 mW, 4 cm1resolution, 128 scans). © Chiralabs Ltd., 2015.
118 Infrared Spectroscopy j FT-Raman NIR

Pharmaceuticals
NIR FT-Raman plays an important part in the analysis of pharmaceuticals. Together with FT-IR spectroscopy, it gives a valuable
insight on the physical state of the drug of interest. One of the main applications for Raman and IR spectroscopy is the screening
of solid-state forms to detect polymorphism, solvate formation, etc.
Figs. 7 and 8 show the Raman spectrum obtained, respectively, for pyrazinamide (a treatment for tuberculosis) and amoxicillin (an
antibiotic). Both spectra are information-rich, illustrating the ability of Raman to distinguish different molecular species. The use of
statistical analysis such as principal component analysis or pattern recognition may further enhance the information from the spectra.

1024.0
NH 2

4.0
N O
N
3.5
3066.0
relative Raman intensity

3.0

1053.0
2.5

808.0
1580.0
1528.0
3055.0

2.0

1.5

414.0
1184.0
1387.0 1454.0

1083.0

250.0
1.0
1674.0
3091.0

869.0

656.0
1318.0

189.0
1299.0

780.0

612.0
2951.0

499.0
387.0
0.5

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 7 FT-Raman spectrum of pyrazinamide (800 mW, 4 cm1 resolution, 128 scans). © Chiralabs Ltd., 2015.

Figure 8 FT-Raman spectrum of amoxicillin (800 mW, 4 cm1 resolution, 64 scans); nb: the rise in spectra baseline below 600 cm1 is due to the
type of cell used. © Chiralabs Ltd., 2015.
 Infrared Spectroscopy j FT-Raman NIR 119

Natural Resins
NIR FT-Raman can be a valuable tool in the analysis of natural resins (e.g., from an archaeological point of view). It can help in
discriminating between the different types of resins and their origins and help notably in distinguishing the real versus the fake
resins.
Figs. 9 and 10 show Raman spectrum obtained for purported Baltic amber and copal, respectively. It is interesting to note that
despite the samples being colored, good FT-Raman spectra have been obtained; no fluorescence has perturbed the acquisition of the
spectra and the sample has not been damaged.

2927.0
2932.0

6.0

5.5
2870.0

5.0
2851.0

4.5
relative Raman intensity

4.0

3.5

3.0

1443.0
2.5
1648.0
2.0

1205.0
1298.0
1.5
1357.0

1063.0

718.0
1138.0

312.0
453.0
503.0

367.0

237.0
556.0
2724.0

882.0
2661.0

834.0

652.0
1739.0

1.0

0.5

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 9 FT-Raman spectrum of purported Baltic amber (800 mW, 4 cm1 resolution, 128 scans). © Chiralabs Ltd., 2015.
2932.0

4.5
2895.0

4.0
2869.0

3.5
2851.0
relative Raman intensity

3.0
2988.0

2.5
1645.0

1442.0

2.0

1.5
1201.0

747.0
1410.0

1246.0

948.0
1362.0

698.0
3081.0

981.0
1133.0

375.0

1.0
337.0
555.0

197.0
887.0
2662.0
2718.0
2768.0

1727.0

0.5

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 10 FT-Raman spectrum of purported copal (800 mW, 4 cm1 resolution, 128 scans). © Chiralabs Ltd., 2015.
120 Infrared Spectroscopy j FT-Raman NIR

Plastics
NIR FT-Raman can be generally used to identify and characterize plastics. However, it is worth pointing out that if the plas-
tics are dark-colored, the power of the laser has to be drastically lowered to avoid any thermal burning (down to 100 mW or
even less). In extreme cases such as black-colored plastics (e.g., those with carbon additive), it may even not be practical to
perform the analysis without pretreating the sample. Figs. 11 and 12 show Raman spectrum obtained for clear polypro-
pylene and polyethylene terephthalate (PET), respectively. For PET, the characteristic carbonyl C¼O band can be seen
1728 cm 1.

4.0 2885.0
2869.5

3.5
2906.0

3.0
relative Raman intensity

2954.5
2963.0

2842.0

2.5

2.0

811.0
1461.0
1.5

1221.0 1331.0

942.0 843.5
1169.0
1153.5
1437.5
1.0

400.0
975.0
2723.5

1000.0

457.0
530.0
0.5

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 11 FT-Raman spectrum of polypropylene (800 mW, 2 cm1 resolution, 64 scans). © Chiralabs Ltd., 2015.
1615.5

4.0

3.5

3.0
relative Raman intensity

1728.5

2.5
3082.5

2.0
1291.5

860.0

1.5
633.5
1096.0
2968.0

1.0
1119.5

1003.5
3000.5

1414.5

704.0
1180.0
1465.0
2908.0

796.0

0.5

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 12 FT-Raman spectrum of polyethylene terephthalate (800 mW, 2 cm1 resolution, 64 scans). © Chiralabs Ltd., 2015.
 Infrared Spectroscopy j FT-Raman NIR 121

Amino Acids and Proteins

Amino acids and proteins can be also characterized by NIR FT-Raman. For example, it is common to use Raman spectroscopy to
monitor the secondary structure of proteins as the amide bands appear at specific positions according to the type of secondary structure
(a-helix, b-sheet, etc.). Raman spectroscopy can also be used to study other aspects of proteins such as the presence of disulfide bridges.
Other articles in the encyclopedia are covering this topic and the reader is advised to read these articles for more details on this.
Figs. 13 and 14 show typical Raman spectrum obtained for L-proline and lysozyme, respectively. In particular, the lysozyme
Raman spectra shows clearly the amide I band (1660 cm1) and amide II band (1553 cm1).

3006.0
7
H O
N
6
OH
2985.0
relative Raman intensity

900.0
5
2950.0

921.0
843.0
1034.0
1058.0
1375.0

450.0
1452.0

1239.0
1176.0
2879.0

1287.0
2

376.0
298.0
1550.0

643.0
793.0
1627.0

576.0
1

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 13 FT-Raman spectrum of L-proline (800 mW, 4 cm1 resolution, 128 scans); nb: the rise in spectra baseline below 600 cm1 is due to the
type of cell used. © Chiralabs Ltd., 2015.
2937.0

0.9

0.8

0.7
relative Raman intensity

0.6

0.5
1448.0

233.0
1337.0

319.0
1012.0
934.0 1005.0

491.0
1660.0

505.0

0.4
1260.0
1305.0

760.0
3062.0

1361.0
1553.0

878.0
900.0
3315.0

0.3
1179.0
1621.0

0.2

0.1

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 14 FT-Raman spectrum of lysozyme (800 mW, 4 cm1 resolution, 128 scans); nb: the rise in spectra baseline below 600 cm1 is due to
the type of cell used. © Chiralabs Ltd., 2015.
122 Infrared Spectroscopy j FT-Raman NIR

Inorganics
NIR FT-Raman can be used to study inorganic materials and minerals. The FT-Raman spectra of such compounds present usually
very sharp and strong Raman bands, making their identification relatively easy.
As an example, Figs. 15 and 16 show typical Raman spectrum obtained for sodium bicarbonate and sodium nitrate, respectively.

1047.0
5.0

4.5
NaHCO3
4.0
relative Raman intensity

3.5

3.0

2.5

2.0

1269.0
1.5

687.0

227.0
1.0

1436.0

699.0
1459.0

660.0
0.5

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
−1
Wavenumber (cm )

Figure 15 FT-Raman spectrum of sodium bicarbonate (800 mW, 4 cm1 resolution, 64 scans); nb: the rise in spectra baseline below 600 cm1 is
due to the type of cell used. © Chiralabs Ltd., 2015.
1069.0

13

12 NaNO3
11

10
relative Raman intensity

4
193.0
1387.0

726.0

3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Wavenumber (cm−1)

Figure 16 FT-Raman spectrum of sodium nitrate (800 mW, 4 cm1 resolution, 64 scans); nb: the rise in spectra baseline below 600 cm1 is due
to the type of cell used. © Chiralabs Ltd., 2015.
 Infrared Spectroscopy j FT-Raman NIR 123

Future Avenues

It is fair to say that both FT- and dispersive Raman instruments are going to play an important role in the spectroscopic analysis of
materials for many years to come. Progress is continuously made to alleviate some of the pitfalls observed with each type of instru-
ments. For example, a few years ago, it would have been difficult to think that FT-Raman spectrometers could be used with a laser
different of the 1064 nm NIR one. Very recently, an FT-Raman spectrometer working with visible laser (532 nm) has been devel-
oped. The synergy between FT spectrometer and visible laser could lead only to be exciting news for spectroscopists. Likewise,
a new trend of dispersive instruments is being promoted, that is, dispersive instruments using the 1064 nm laser. This is another
promising development. The reader is encouraged to read the “Further Reading” section to get more details on these new aspects
of Raman spectrometers.

Further Reading

Barbillat, J.; da Silva, E. Spectrochim. Acta A 1997, 53, 2411–2422.

Brouillette, C.; Huang, H.; Smith, W.; Farquharson, S. Appl. Spectrosc. 2011, 65, 561–563.
Castro, K.; Pérez-Alonso, M.; Rodriguez-Laso, M. D.; Fernández, L. A.; Madariaga, J. M. Anal. Bioanal. Chem. 2005, 382, 248–258.
Dzsaber, S.; Negyedi, M.; Bernáth, B.; Gyüre, B.; Fehér, T.; Kramberger, C.; Pichler, T.; Simon, F. J. Raman Spectrosc. 2015, 46, 327–332.
Hédoux, A. Adv. Drug Deliv. Rev. 2015. https://doi.org/10.1016/j.addr.2015.11.021.
Johnson, T. J.; Su, Y. F.; Jarman, K. H.; Kunkel, B. M.; Birnbaum, J. C.; Joly, A. G.; Stephan, E. G.; Tonkyn, R. G.; Ewing, R. G.; Dunham, G. C. Int. J. Spectrosc. 2012 (2012),
Article Article ID 297056. 11 pp. https://doi.org/10.1155/2012/297056.
Lewis, M. L.; Lewis, I. R.; Griffiths, P. R. Vib. Spectrosc. 2005, 38, 11–16.
McGoverin, C. M.; Hargreaves, M. D.; Matousek, P.; Gordon, K. C. J. Raman Spectrosc. 2012, 43, 280–285.
Meyer, M. W.; Lupoi, J. S.; Smith, E. A. Anal. Chim. Acta 2011, 706, 164–170.
Parker, S. F. Spectrochim. Acta 1994, 50A, 1841–1856.
Pelletier, M.; Larkin, P.; Santangelo, M. Appl. Spectrosc. 2012, 66, 451–457.
Synytsya, A.; Judexova, M.; Hoskovec, D.; Miskovicova, M.; Petruzelka, L. J. Raman Spectrosc. 2014, 45, 903–911.
Vitek, P.; A Ali, E. M.; M Edwards, H. G.; Jehlicka, J.; Cox, R.; Page, K. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2012, 86, 320–327.
Zhao, J.; McCreery, R. L. Appl. Spectrosc. 1997, 51, 1687–1697.