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Fourier-Transform
Infrared Spectrometer
Task Manual, Part 1, Theory
Table of Content
Table of Content ................................................................................................................................... 2
0. Introduction....................................................................................................................................... 3
0.1 Electromagnetic radiation and units of measurements ............................................................... 3
0.2 Spectrum Representation ............................................................................................................ 5
1. FT-IR Spectrometer Basics............................................................................................................... 7
1.1 Sources of Infrared Radiation ..................................................................................................... 9
Thermal, unpolarized IR sources .................................................................................................. 9
Bright, pulsed, polarized, micro-IR sources ............................................................................... 11
1.2 The Michelson Interferometer .................................................................................................. 13
Obtaining the interferogram........................................................................................................ 14
Real Interferometers.................................................................................................................... 16
What are OPD and ZPD?............................................................................................................ 18
1.3 Infrared Transmitting Materials................................................................................................ 19
1.4 Detectors ................................................................................................................................... 21
1.4 Advantages of FT-IR Instruments over Dispersive Instruments .............................................. 23
Multiplex (Fellgett) Advantage................................................................................................... 24
The Throughput (Jacquinot) Advantage ..................................................................................... 24
High Resolution and Linearity (Connes) Advantage.................................................................. 24
1.5 Older Technology ..................................................................................................................... 25
2. Interferograms and Data Processing ............................................................................................... 26
2.1 Interferograms........................................................................................................................... 26
2.2 Finite Mirror Displacement. Resolution. .................................................................................. 31
2.3 Apodization function. ............................................................................................................... 32
2.3.1 Instrument line shape and Apodization function. .............................................................. 33
2.4 The IR Spectrum ....................................................................................................................... 36
2.4.1 Single Sided and Double Sided Interferograms................................................................. 38
2.4.2 Instrument Resolution and Spectral Noise......................................................................... 39
2.5 Phase Correction ....................................................................................................................... 40
2.5.1 Double-sided Phase Correction.......................................................................................... 41
2.5.2 Single-sided Phase Correction ........................................................................................... 42
Literature............................................................................................................................................. 45
0. Introduction
FT-IR stands for Fourier Transform Infra Red, the preferred method of infrared spectroscopy.
In infrared spectroscopy, IR radiation is passed through a sample. Some of the infrared radiation is
absorbed by the sample and some of it is passed through (transmitted). The resulting spectrum
represents the molecular absorption and transmission, creating a molecular fingerprint of the sample.
Like a fingerprint no two unique molecular structures produce the same infrared spectrum. This
makes infrared spectroscopy useful for several types of analysis.
Infrared spectroscopy is a widely used technique for both qualitative and quantitative analysis.
IR spectra are routinely used in identification of synthesis products for organic chemistry, as well as
for qualitative analysis work in environmental, forensic, and industrial applications. IR spectroscopy
can be used quantitatively for determination of the concentrations of both liquid and gas phase
solutions. In addition, reflective IR techniques can be employed for surface analysis.
The electromagnetic spectrum is divided into different spectral regions depending on the
frequency: radio waves have wavelengths greater than 0.1 m and microwaves between 500 µm and
30 cm; the infrared region is divided into far-, mid- and near infrared. The visible (VIS) region
includes wavelengths from 400 to 800 nm and near ultraviolet (UV) and vacuum UV region extends
from 400 to 200 or 100 nm. Molecular spectroscopic analysis methods are based on interactions
between molecules and light quanta with different energy levels. They are named after spectral
region and imply different effects on the molecules (Table 0.1), depending on the energy, effects
such as electron excitation, molecular vibration and molecular rotation.
Molecular
Type of transfer Molecular rotation Electron excitation
vibration
Spectroscopic Microwave UV-VIS
Infrared spectroscopy
methods Absorption spectroscopy
infrared (IR) X-
Spectral region radio waves microwaves VIS UV
far mid near rays
Wavelength [m]
c 10 1 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9
λ=
v
Frequency [Hz]
c 107 109 1011 1013 1015 1017
v=
λ
Wave number [cm-1]
1 10-3 10-1 103 105 107
v~ = 10
λ
Table 0.1. Electromagnetic radiation.
The nature of various radiation frequencies shown in Table 0.1 have been interpreted by
Maxwell’s classical theory of electro- and magneto- dynamics. According to this theory, radiation is
described as two mutually perpendicular electric and magnetic fields, oscillating in single planes at
right angles to each other. These fields are in phase and are being propagated as a sine wave
(Fig. 0.2).
Fig.0.2. An electromagnetic wave. The electric and magnetic vectors are presented by E and H.
A significant discovery made about electromagnetic radiation was that the velocity of
propagation in a vacuum was constant for all frequencies of spectrum. This is known as the velocity
of light c and it has the following value c = 2.997925 × 108 m/sec.
c
c = λv ⇒ λ = , (0.1)
v
where
c – velocity of light
λ – wavelength
ν – frequency (number of vibrations, [sec-1 or Hz])
Another unit, which is commonly used in infrared spectroscopy, is the wavenumber, which is
expressed as cm-1. This is the number of electromagnetic waves in a length of one centimeter and is
given by the following relationship:
1 v
v~ = = (0.2)
λ c
This unit has the advantage of being linear with photon energy.
In addition to transmittance T, the absorption of the infrared radiation can be presented using
the absorbance scale. Absorbance A is given by the logarithm of the reciprocal transmittance
⎛1⎞
A = Log 10 ⎜ ⎟ = − Log 10T (0.4)
⎝T ⎠
where
A – absorbance
T – transmittance
The Fig. 0.3 (a, b) illustrates the difference in appearance between absorbance and
transmittance spectra. The advantage of using the absorbance scale is that the value of absorbance is
directly proportional to the thickness of the sample (absorption path length), and the concentration of
the sample.
1.0 1.0
0.8 0.8
Absorption, OD
Transmittance
0.6 0.6
0.4 0.4
0.2
0.2
0.0
0.0
1000 1500 2000 2500 3000 3500 4000
1000 1500 2000 2500 3000 3500 4000
-1
Wavenumber, cm -1
Wavenumber, cm
Fig. 0.3 a). Transmittance spectrum of a polymer sample Fig. 0.3 b). Absorbance spectrum of a polymer sample
(pristine MEH-PPV film on BaF2 substrate). (pristine MEH-PPV film on BaF2 substrate).
The development of interferometry was initiated in 1880 when Dr. Albert A. Michelson
invented his interferometer to study the speed of light and to fix the standard meter with the
wavelength of a known spectral line. FT-IR method is based on the old idea of the interference of
two radiation beams to yield an interferogram. An interferogram is a signal produced by two
radiation beams. Interferogram is the interference intensity as a function of the change of optical
path difference. The two domains of distance and frequency are interconvertible by the mathematical
Fourier transformation.
Although the basic optical component of FT-IR spectrometers, the Michelson interferometer
has been known for almost a century, it was not until advantages in data acquisition and computing
in early 80´s and late 70´s that the technique could be successfully and widely applied. Only in
recent years Fourier-transform infrared (FT-IR) spectroscopy has found increasing use in industrial
applications. The number of applications of FT-IR spectrometers is increasing continuously.
Nowadays, there are different kinds of FT-IR spectrometers, especially interferometers that
are used. A typical FT-IR spectrometer consists of a radiation source, a modulator
(interferometer), a sample compartment, a detection unit and an electronic and computing unit
(Fig.1.1).
Each building block varies from manufacturer to manufacturer but basically they all obey the
same laws of physics.
The normal instrumental process is as follows:
1. The Source: Infrared energy is emitted from a glowing black-body source. This beam
passes through an aperture that controls the amount of energy presented to the sample
(and, ultimately, to the detector).
2. The Interferometer: The beam enters the interferometer where the “spectral encoding”
takes place. The resulting interferogram signal then exits the interferometer.
3. The Sample: The beam enters the sample compartment where it is transmitted through or
reflected off of the surface of the sample, depending on the type of analysis being
Because there needs to be a relative scale for the absorption intensity, a background
spectrum must also be measured. This is normally a measurement with no sample in the beam. This
can be compared to the measurement with the sample in the beam to determine the “percent
transmittance”. This technique results in a spectrum, which has all of the instrumental characteristics
removed. Thus, all spectral features, which are present, are strictly due to the sample. A single
background measurement can be used for many sample measurements because this spectrum is
characteristic of the instrument itself (see Fig. 1.2).
All IR spectrometers have a source of infrared radiation which is usually some solid material
heated to incandescence by an electric current. The Nernst Glower is a source composed mainly of
oxides of rare earths such as zirconium, yttrium and thorium, and the Globar is a silicon carbide rod.
Other materials have been used as well. All these sources are fairly efficient emitters of infrared
radiation and approach the energy distribution of a theoretical black body.
Using the quantum hypothesis, Planck derived a distribution law for blackbody radiation,
which holds over all wavelengths. Planck's distribution law giving the radiant energy between the
wavelengths λ to λ + dλ may be expressed in the form
c1λ−5
E λ dλ = dλ (1.1)
e ( c2 / λT ) − 1
where c is the speed of light, 2.998 x 1010 cm/sec, h is Planck's constant, 6.625 x 10–34W
sec2, and k is the Boltzmann constant, 1.380 x 10–23 W sec/oK. Eλ dλ is the radiant energy emitted
per unit area per unit increment of wavelength. With the units shown and dλ in µm, the units of Eλ dλ are
W/cm2/µm.
The wavelength λm at which the energy is at a maximum at any temperature is found by
differentiating Eλ with respect to λ and setting the derivative dEλ/dλ equal to zero. The solution, of
the resulting equation yields Wien's displacement law
b
λm = (1.4)
T
where b is Wien's displacement constant, 2897 µm °K, and T is absolute temperature, °K.
The actual energy distribution of a blackbody radiator at three different temperatures is
shown in Fig. 7. The energy at any wavelength is given by the area of the vertical strip under the
curve at that wavelength. If the height of the strip is Eλ and the width is dλ, then the area is Eλ dλ
as indicated on the 1000 ºC curve in Fig. 7.
Fig. 1.3 also shows how the peak of the energy curve is temperature dependent. For
example, at a temperature of 1000ºC the wavelength at which the energy is at a maximum, Eλm, is
given by Eq. (1.4) and would be (2.897 x 103)/(1000 + 273) = 2.276 µm (see Fig. 1.3). At a lower
temperature of 600°C the energy peak shifts to a longer wavelength, namely, 3.318 µm.
5
1000ºC
4
3
Eλ, W/cm /µm
2
2 800ºC
AREA = Eλ dλ
1
600ºC Eλ
λm = 2.276 dλ
0
0 1 2 3 4 5 6 7 8
Wavelength, µm
Fig.1.3. Energy distribution of a black body radiation at 600, 800, and 1000ºC.
The Stefan-Boltzman law states that the total radiation from a black body (fhe total area
under a curve in Fig.1.3) is proportional to the fourth power of its absolute temperature. It is also
important to note in Fig.1.3 that the energy output falls off very rapidly at long wavelengths. If one
tries to increase the long wavelength energy by increasing the temperature of the source, a small
increase in long wavelength energy will be accompanied by a huge energy increase in the
unwanted short wavelengths as seen in Fig.1.3. Most IR sources are operated at a temperature
where the energy maximum is near the short wavelength limit of the spectrum. Another graphical
representation of Planck's Law is showing the spectral radiance of a black body radiator versus
wavenumber (see Fig.1.4).
There is another problem with using IR sources at high temperature: heating air to high
temperatures can be problematic – generation of the well known (NO)x! The equilibrium N2 + O2 ↔
NO2 ↔N2O4 lies towards the reactants and moves towards NO2 and hence N2O4 at elevated
temperatures. Unfortunately, good modern sources can be hot enough to generate measurable
amounts of NO2 (and other nitrogen oxides like (NO)x ). In the atmosphere, this would be only a
trivial nuisance, one swamped by other sources of pollution but inside the sealed housing of an
FTIR, the (NO)x can well cause unwanted absorption and even corrosion of the metal and plastic
components. So, sources should be hot but not too hot. Temperatures vary but a little above 1000ºC
are typical. Use of 2000ºK is not realistic.
T = 1600 K
T = 1800 K
T = 2000 K
Power, A.U.
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
-1
Absolute Wavenumbers, cm
Fig.1.4. Blackbody curves for a variety of temperatures on an absolute wavenumber abscissa scale in
power units. As the temperature is increased the overall intensity increases and the maximum of the
curve shifts to higher frequencies.
Accelerator-based and laser sources emit IR beams with high spectral radiance and high
spatial resolution (<1 µm to 10's µm) with coherent or polarized radiation. Such sources may be used
for a variety of applications (e.g., commercial and military purposes).
Bright, pulsed, polarized, micro-IR sources are ideal for small samples (e.g., samples relevant
to geomicrobiology, meteoritics, materials synthesized at high pressure), surface species (e.g.,
weathering rinds), and samples with low energy, weak absorption signatures (such as films). Another
advantage is that these high spectral radiance sources may be pulsed to study in situ chemical
reactions on mineral surfaces on rapid time-scales.
Accelerator-based sources have high spectral radiance IR radiation that is produced by
accelerating charged particles (e.g., electrons) in a magnetic field. In synchrotron-based IR, the
electrons are accelerated around a storage ring and may be pulsed at tens of picoseconds to
nanoseconds.
In free electron laser (FEL) sources, the micro-beams are added to create the radiation used
for analysis. These sources may be pulsed at 10-15 to 10-9 seconds. FELs provide high intensity
beams, however intensities fluctuate therefore they are inherently not as stable as synchrotron
sources.
Fig.1.5 b) Irradiation intensity versus wavelengths for different light sources (by Bruker Optics).
Fig.1.6. The interferometer is shown in (a). In (b) the beam splitter transmits half the source
radiation and reflects the other half. In (c), where only one or the other mirror is in place, the
radiation from the mirror is split by the beam splitter. When both minors are in place, interference
will occur where the beams from the two mirrors combine. In (d)-(g), monochromatic radiation is
used. In (d), the minors are equidistant. In (e), the moveable mirror is moved by λ/4. In (f), the
moveable mirror is moved by λ /2. In (g), an interferogram is shown for monochromatic radiation.
The monochromatic radiation intensity going to the detector varies as a cosine function of the
retardation, or twice the mirror displacement, and reaches a maximum every time the retardation
equals a whole number of wavelengths of radiation.
If only one or the other mirror is in place, as seen in Fig.1.6 (c), the beam reflected from the
mirror returns to the beam splitter, which then sends half the radiation to the detector and half back
to the source. If both mirrors are in place, interference occurs at the beam splitter where the radiation
from the two mirrors combine.
The detailed action at the beam splitter is complex, but as shown in Fig.1.6 (d), when the two
mirrors are equidistant from the beam splitter, constructive interference occurs for the beam going to
the detector, and destructive interference occurs for the beam going back to the source, for all
wavelengths of radiation. The path length of the two beams in the interferometer are equal in this
case, and the path length difference, called the retardation, is zero.
Let the source of radiation be a laser that emits only monochromatic radiation of wavelength,
and let the moveable mirror be moved from the equidistant point by λ/4 as seen in Fig.1.6 (e). The
retardation is λ/2. This means that for the beam going to the detector, the radiation wave components
from the two mirrors combine at the beam splitter one-half a wavelength out-of-phase and
destructive interference occurs. Then, when the mirror is moved from the equidistant point by λ/2 as
seen in Fig.1.6 (f), the retardation is A and the wave components from the two mirrors combine in-
phase again for the beam going to the detector. The plot of detector response as a function of
retardation is an interferogram. As seen in Fig.1.6 (g), the interferogram of a monochromatic laser
source described above, is a cosine function (see also Fig.1.7 (a)). The Fourier transform of a single
cosine wave interferogram is a single wavelength of radiation emitted from the laser source.
The total radiation entering the beam splitter from the two mirrors is constant regardless of
the retardation, which means that the total radiation leaving the beam splitter to the detector and
back to the source must also be a constant. That part of the radiation leaving the beam splitter which
does not go to the detector, goes back to the source, as seen in Fig.1.6 (e).
If the laser source described previously is changed so that it emits monochromatic radiation
of a different wavelength with a different intensity, the interferogram will be a cosine wave with a
different maximum amplitude and a different retardation length for one detector signal cycle. If the
radiation from both laser sources described above enters the interferometer, the interferogram will be
the sum of the two individual cosine wave interferograms, see Fig.1.7 (b).
The sample is normally placed between the interferometer and the detector. The spectrum
generated is a single-beam spectrum where the vertical coordinate is the radiation intensity from the
source after sample absorption, measured as a function of radiation wavelength or wavenumber. In
order to generate a percent transmission spectrum, the sample single beam spectrum is stored in the
computer and is later normalized by a reference single-beam spectrum generated without the sample
present.
A central part of a real interferogram is shown in Fig.1.8.
A single scan of the moveable mirror produces a complete single-beam spectrum. However,
usually a number of scans are taken and signal-averaged by the computer, which reduces the noise
by the square root of the number of scans. The resolution is constant over the whole spectrum and is
increased by increasing the length of travel of the moveable mirror. A truly monochromatic emission
line has an interferogram which is in infinitely long cosine function. Of necessity, the measured
retardation is less than infinite and this truncation has the effect of broadening the width of a spectral
line generated from a monochromatic source.
Real Interferometers
Early interferometers (and some persist to this day) use a system identical to that in
Fig.1.6 (a). To make the light parallel, mirror collimators are used and so the instrument looks like
Fig.1.9.
All components are firmly fixed to a base but mirror MM moves backward and forwards on
an axis normal to its surface. The movement must be smooth, reproducible and involve no wobble or
shake. These requirements are hard to achieve and lend to the use of high precision engineering.
Let we have our interferometer and hence, as we shall see our interferogram. The next
problem is to measure the path difference. A ruler is no good, the path difference has to be measured
to an accuracy limited only by the precision of the engineering in the interferometer itself. The way
this is done is to use the interferometer itself to do the job and to feed it with a source of precisely
known wavelength. The He-Ne laser has a wavelength near 632.8 nm and is known to very high
precision. If a He-Ne laser beam passes through the interferometer, its intensity at the output will
generate a superb simple cosine with a peak in intensity every 632.8 nm of change in the path
difference. How this can be done is shown below in Fig. 1.10.
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Fig.1.10. In this scheme of FT-IR spectrometer the He-Ne laser is used for measuring the
optical path difference.
The He-Ne laser generates a parallel beam reflected along the axis of the interferometer by
tiny mirror. The beam leaving the interferometer is picked up by another tiny mirror and passed to a
detector. The output of the detector is a cosine. As the signal switches from positive to negative
about the mean, a trigger circuit is operated providing a pulse twice every 632.8 nm of charge in path
difference. This pulse train is used to measure the path difference as shown in Fig.1.11.
ZPD
IR Interferogram
He-Ne laser
Interferogram
Primary IR
Interferogram that
was sampled
Optical Path Difference (OPD) is the optical path difference between the beams traveling
through the two arms of an interferometer. OPD is equal to the product of the physical distance
traveled by the moving mirror (multiplied by 2, 4, or other multiplier which is a function of the
number of reflecting elements used) and n, the index of refraction of the medium filling the
interferometer arms (air, Nitrogen for purged systems, etc.). The raw FT-IR data consists of a
number of (signal, OPD) pairs of values.
FT-IR has a natural reference point when the moving and fixed mirrors are the same distance
from the beam splitter. This condition is called Zero Path Difference or ZPD (see Fig.1.11). The
moving mirror displacement, ∆, is measured from the ZPD. In Fig.1.6 (a) the beam reflected from
the moving mirror travels 2∆ further than the beam reflected from the fixed mirror. The relationship
between optical path difference, and mirror displacement, ∆, is: OPD = 2∆n.
Cells for holding samples, or windows within the spectrometer must be made of infrared
transmitting material. Table 1.1 lists approximate low wavenuniber transmission limits for some
optical materials used in infrared spectroscopy. All the materials listed transmit in the mid-IR above
the transmission limit except for polyethylene, which is used below 600 cm-1 only, as it has
absorption bands at higher frequencies. The transmission limits are not sharply defined and depend
somewhat on the thickness of the material used. For example, a typical cell for liquid samples which
is made of NaCl has a transmission that starts to drop at about 700 cm-1, is roughly 50% at 600 cm-1,
and is nearly opaque at 500 cm-1. As seen in Table 1.1 glass and quartz can be used in the near-IR
region but not for most of the mid-IR region.
Some of the most useful window materials for the IR are quite soluble in water, which
include NaCl, KC1, KBr, CsBr and CsI. KRS-5 is a synthetic optical crystal, slightly soluble in
water, consisting of about 42% thallium bromide and 58% thallium iodide. The others listed in
Table 1.1 are mostly water insoluble.
glass 3000
quartz 2500
LiF 1500
CaF2 1200
BaF2 850
ZnS 750
Ge 600
NaCl 600
KC1 500
ZnSe 450
KBr 350
AgCl 350
KRS-5 250
CsBr 250
CsI 200
polyethylene (high density) 30
Table 1.1. Approximate transmission limits for optical materials (in cm-1)
The more detailed information (by Bruker optics) about IR transmitting materials is shown in
Table 1.2.
1.4 Detectors
The infrared detector is a device which measures the infrared energy of the source which has
passed through the spectrometer. One way or another these devices change radiation energy into electrical
energy which can be processed to generate a spectrum. There are two basic types, thermal detectors which
measure the heating effects of radiation and respond equally well to all wavelengths, and selective detectors
whose response is markedly dependent on the wavelength.
Examples of thermal detectors include thermocouples, bolometers and pyroelectric detectors. A
thermocouple has a junction of two dissimilar metals . When incident radiation is absorbed at the junction,
the temperature rise causes an increase in the electromotive potential developed across the junction leads. A
bolometer is a detecting device which depends on a change of resistance with temperature.
The pyroelectric detector consists of a thin pyroelectric crystal such as deuterated triglycine
sulfate (DTGS). If such a material is electrically polarized in an electric field, it retains a residual electric
polarization after the field is removed. The residual polarization is sensitive to changes in the temperature.
Electrodes on the crystal faces collect the charges so the device acts as a capacitor across which a voltage
appears, the amount of which is sensitive to the temperature of the device. The pyroelectric detector
operates at room temperature. Being a thermal device, it possesses essentially flat wavelength response
ranging from the near infrared through the far infrared. It can handle signal frequencies of up to several
thousand Hertz and hence is well suited for Fourier transform infrared spectrometers.
The most important type of selective detector is the photoconductive cell which has a very rapid
response and a high sensitivity. An example is the mercury cadmium teiluride detector (MCT) which is
cooled with liquid nitrogen. These cells show an increase in electrical conductivity when illuminated by
infrared light. These detectors utilize photon energy to promote bound electrons in the detector material to
free states, which results in in-creased electrical conduction. There is a long wavelength limit to the
response however, because photons with wavelengths longer than a certain limit will have insufficient
energy to excite the electrons.
The normalized detectivity versus wavelength for different photodetectors is shown in
Fig.1.12.
The output from the detector goes to a preamplifier where it is converted into a voltage signal
varying with time. This signal has to be digitised and the job is usually done with a dedicated
'analogue to digital' converter chip. These devices will measure the input voltage in binary numbers
with 8, 16, 20 or 32 or more digits. Clearly, the number of useful digits is governed by the quality
(S:N ratio) of the signal. 16 and 20 bit devices are frequently used.
Fig. 1.12. Normalized detectivity, D*, for different detectors as a function of optical radiation
wavelength. The NEP (noise equivalent power) is the incident radiant power resulting in a
signal-to-noise ratio of 1 within a given bandwidth of 1 Hz and at a given wavelength. The
numbers given in italics are the equivalent number of light quanta (hν).
An A/D converter will carry out the conversion only when it is told to do so – it needs a
pulse (or ‘handshake’) to tell it to do the job. The pulse is provided by the He-Ne fringe detector and
trigger circuit. So, the A/D converter makes its measurement every 316.4 nm of path difference.
Thus, the He-Ne makes it possible to measure the interferogram at ultra precise path difference
intervals. If the temperature changes, or you lean on the FTIR, the interferometer will very slightly
distort and hence the interferogram will shift. However, the He-Ne beam will also shift helping to
correct for the distortion.
The digitized interferogram is now fed to the F-T processor. This can be a dedicated chip or a
PC. Obviously, a dedicated chip has its advantages (simplicity, lower cost etc) but the PC increases
the versatility enormously.
Some of the major advantages of FT-IR over the dispersive technique include:
• Speed: Because all of the frequencies are measured simultaneously, most
measurements by FT-IR are made in a matter of seconds rather than several minutes.
This is sometimes referred to as the Felgett Advantage.
• Sensitivity: Sensitivity is dramatically improved with FT-IR for many reasons. The
detectors employed are much more sensitive, the optical throughput is much higher
(referred to as the Jacquinot Advantage) which results in much lower noise levels,
and the fast scans enable the coaddition of several scans in order to reduce the
random measurement noise to any desired level (referred to as signal averaging).
• Mechanical Simplicity: The moving mirror in the interferometer is the only
continuously moving part in the instrument. Thus, there is very little possibility of
mechanical breakdown.
• Internally Calibrated: These instruments employ a HeNe laser as an internal
wavelength calibration standard (referred to as the Connes Advantage). These
instruments are self-calibrating and never need to be calibrated by the user.
These advantages, along with several others, make measurements made by FT-IR extremely
accurate and reproducible. Thus, it a very reliable technique for positive identification of virtually
any sample. The sensitivity benefits enable identification of even the smallest of contaminants. This
makes FT-IR an invaluable tool for quality control or quality assurance applications whether it be
batch-to-batch comparisons to quality standards or analysis of an unknown contaminant. In addition,
the sensitivity and accuracy of FT-IR detectors, along with a wide variety of software algorithms,
have dramatically increased the practical use of infrared for quantitative analysis. Quantitative
methods can be easily developed and calibrated and can be incorporated into simple procedures for
routine analysis.
Thus, the Fourier Transform Infrared (FT-IR) technique has brought significant practical
advantages to infrared spectroscopy. It has made possible the development of many new sampling
techniques which were designed to tackle challenging problems which were impossible by older
technology. It has made the use of infrared analysis virtually limitless.
The main advantages are the Fellgett, Jacquinot, and Connes advantage.
The original infrared instruments were of the dispersive type. These instruments separated
the individual frequencies of energy emitted from the infrared source. This was accomplished by the
use of a prism or grating. An infrared prism works exactly the same as a visible prism, which
separates visible light into its colors (frequencies). A grating is a more modern dispersive element
that better separates the frequencies of infrared energy. The detector measures the amount of energy
at each frequency, which has passed through the sample. This results in a spectrum, which is a plot
of intensity versus frequency.
Fourier transform infrared spectroscopy is preferred over dispersive or filter methods of
infrared spectral analysis for several reasons:
• It is a non-destructive technique
• It provides a precise measurement method which requires no external calibration
• It can increase speed, collecting a scan every second
• It can increase sensitivity – one second scans can be co-added together to ratio out
random noise
• It has greater optical throughput
• It is mechanically simple with only one moving part
***
Infrared spectroscopy has been a workhorse technique for materials analysis in the laboratory
for over seventy years. An infrared spectrum represents a fingerprint of a sample with absorption
peaks, which correspond to the frequencies of vibrations between the bonds of the atoms making up
the material. Because each different material is a unique combination of atoms, no two compounds
produce the exact same infrared spectrum. Therefore, infrared spectroscopy can result in a positive
identification (qualitative analysis) of every different kind of material. In addition, the size of the
peaks in the spectrum is a direct indication of the amount of material present. With modern software
algorithms, infrared is an excellent tool for quantitative analysis.
2.1 Interferograms
During an infrared scan (see Fig.2.1), the interferometer sequentially (I) divides light emitted
from the IR source in two beams using a beam splitter, (II) changes the optical path of one beam
using a movable mirror, (III) recombines the two beams to create optical interference, and (IV)
passes the IR light through the sample for measurement of a single-beam spectrum. The ratio of the
single-beam spectra with and without the sample in the light path yields a sample spectrum in
percentage transmittance. As shown, the moving mirror cycles back and forth during an FTIR scan.
The optical path difference for any mirror displacement x is calculated by the equation |2(OM - OF)|
and is denoted optical retardation δ.
equivalently, I(δ) versus optical retardation δ] is shown in Fig.2.2 A. We note that the output of an
interferometer actually contains both an AC and a DC component. The DC component is omitted for
clarity because the spectral information is encoded in the AC component.
Fig. 2.2 A shows that the interferogram of a laser-light source is a pure cosine wave with
constant amplitude. This can be explained by considering the detector signal at discrete mirror
positions. The optical path difference between the light beams which recombine at the beam splitter
is calculated by the equation |2(OM - OF)| and is referred to as optical retardation δ. Starting from
the point where the fixed and moving mirrors have a zero path difference ZPD (i.e., OM = OF as
shown in Fig. 2.1), the two beams interfere constructively and the detector observes a maximum
signal intensity. As shown in Fig. 2.2, this mirror position is at the center of the interferogram. If the
movable mirror is displaced a distance 1/4 λ away from this ZPD, the optical retardation is now
1/2 λ. The laser beams in each arm of the interferometer are exactly 180° out of phase, and upon
recombination at the beam splitter, destructive interference causes a minimum detector response. A
further displacement of 1/4 λ makes the total optical retardation λ, and the two beams are once more
in phase and the condition of constructive interference exists. Therefore for a monochromatic IR
beam, there is no way to determine whether the signal maximum corresponds to ZPD or some
integral number of λ.
Actually modern FTIR spectrometers do not stop the mirror at individual positions of mirror
displacement as described above; rather the mirror moves at a constant velocity during a scan.
Consequently the signal intensity I(δ) oscillates during each 1/2 λ of optical retardation δ. In theory,
the interferogram of a monochromatic source is a simple cosine function described by (2.1)
⎛ δ⎞
I (δ ) = 0.5 I (ν ) cos⎜ 2π ⎟ = 0.5 I (ν ) cos(2πν δ ) , (2.1)
⎝ λ⎠
where I (ν ) is the IR source intensity, δ is the optical path difference |2(OM - OF)|, λ is the
wavelength of light, and 1/ λ = v. The factor 0.5 in Eq. (2.1) results from a physical limitation of the
interferometer; due to the position of the optical components in the interferometer, only 50% of the
reflected light that recombines at the beam splitter travels toward the detector, whereas 50% returns
toward the source. Even for this trivial case using a monochromatic IR source, the experimentally
recorded interferogram is actually a function of several instrument variables, which include the
intensity of the light source, beam-splitter efficiency, detector response, and amplifier
characteristics. Because each of these instrument variables affects the optical throughput of I (δ )
measured at the detector, Eq. (2.1) must be rewritten as
where B(v) is the intensity from the IR light source emitted at a specific wavenumber v as
modified by the instrument. The optical retardation t seconds after ZPD is given by
δ = 2Vt (2.3)
where V is the velocity of the movable mirror in centimeters per second. During a scan, the
product Vt [in Eq. (2.3)] is the distance of mirror movement x (i.e., x = Vt), and since the reflected
light from the moving mirror travels twice the distance that the mirror has moved, the factor 2 in Eq.
(2.3) is needed. In other words, optical retardation δ is always twice the distance of mirror movement
(i.e., δ = 2x). Substituting Eq. (2.3) into the argument of the cosine function in Eq. (2.2) gives
A(t ) = I (t ) (2.6 a)
A0 = B(ν ) (2.6 b)
f = 2Vν (2.6 c)
Thus the interferogram intensity I(x) [or I(t)] resulting from laser light entering an
interferometer, as shown in Fig. 2.2 A, is a pure cosine wave with a frequency f and maximum
amplitude B(ν ) . A real infrared source emits broadband IR radiation, thus each v emitted
contributes a pure cosine wave to the final interferogram and the amplitude of each cosine wave in
the experimentally measured interferogram depends in part on the intensity of the particular ν
emitted from the IR source. In fact, based on Eq. (2.6 c), each unique ν emitted from any IR source
is transformed by the interferometer into a unique cosine-wave interferogram whose modulation
frequency f is dependent on the mirror velocity V.
Equation (2.6 c) is a mathematical description of the critical purpose of all interferometers.
The critical function of the interferometer is to convert high-frequency radiation into low-frequency
signals that can be measured. High-frequency IR light (~1014 Hz) entering the interferometer is
modulated into a strobe-like fringe frequency f. From Eq. (2.6 c) this fringe frequency f is unique for
each ν emitted. The mirror velocity (typically near 0.16 cm/sec for the mid-IR range) of rapid-
scanning interferometers produce modulated frequencies f in the audio frequency range. Detector
response is dependent on f, and therefore the mirror velocity is a user-controlled parameter. In
general, the TGS detector response decreases with increasing mirror velocity (i.e., increasing f);
however, the MCT detector response increases with increasing mirror velocity (i.e., increasing f).
Therefore mirror velocity is set higher for the MCT detector when compared to the TGS detector.
In practice, typical interferograms rapidly decay as the mirror moves away from either side
of the ZPD as shown in Fig. 2.2 B. When the fixed and moving mirrors depicted in Fig. 2.1 are of
equal path length (i.e., zero optical retardation), all wavelengths of infrared light from the source are
in phase and the interferogram elicits a maximum amplitude and maximum constructive interference
occurs. Thus at ZPD the maximum optical throughput occurs for both polychromatic and
monochromatic IR sources and maximum amplitude is expected. However as the mirror travels
away from ZPD, individual ν cosine waves are increasingly out of phase with one another. This
results in greater destructive interference between the ν cosine waves and this causes the
interferogram to decay rapidly. Experimentally, there is usually a small optical phase shift near ZPD,
and consequently most measured interferograms are asymmetric in this region.
Equation (2.2) [or Eq. (2.4)] is a general function that describes interferograms for specific
wavelengths of light, and consequently when multiple v enter an interferometer, the measured
interferogram is described by the use of Eq. (2.2) [or Eq. (2.4)] for each ν emitted. In other words,
Eq. (2.2) applied to each ν emitted is summed to give the interferogram of a broadband IR source
(i.e., the superposition principle applies to the optical waves contributing to the interferogram).
Consider mathematically describing one data point in the actual interferogram produced by a
broadband IR source (e.g., Fig. 2.2 B) at a fixed mirror position x = L (the maximum optical
retardation). In order to describe numerically the intensity of light reaching the detector at the mirror
displacement equal to L cm [i.e., I(L)], Eq. (2.3) must be summed over all ν emitted by the source
and averaged over all wavelengths of light sampled,
k
I ( L) = ∑ Bi (ν ) cos(2πν i L) (2.7)
i =0
We emphasize that the movable mirror is fixed in this hypothetical example, and only one
data point is being mathematically described in the total interferogram. In Eq. (2.7), L is constant and
ν i , and Bi (ν ) are the i-th wavelength and intensity of this wavelength being measured at the
detector. To describe completely the interferogram produced by a typical IR source during a
complete scan, one merely uses Eq. (2.7) for each mirror position associated with data acquisition. In
other words, instead of calculating I(L) at the maximum mirror displacement L (which is a constant),
experimental interferograms require I(x) for all possible mirror positions x (which is a variable).
Data acquisition occurs at multiple discrete mirror positions, and for each mirror position, Eq. (2.7)
can be used to calculate I(x). Thus the general form of Eq. (2.7), for any particular mirror position
associated with data acquisition, is
k
I ( x) = ∑ Bi (ν ) cos(2πν i x) (2.8)
i =0
measured, the desired spectral information B (ν ) is mathematically obtained from this measured
interferogram using the cosine Fourier transform of Eq. (2.9), which is
x =∞
B(ν ) = ∫ I ( x) cos(2πν x)dx,
x = −∞
(2.10)
x =∞
B(ν ) = ∫ I ( x) D
x = −∞
g ( x) cos(2πν x)dx, (2.11)
where Dg(x) has the value of 1 during the scan, |x| ≤ |L|, and the value of zero after the scan,
|x| > |L|, where L defines the maximum mirror displacement. In other words, before integration, the
function “ I ( x ) cos( 2πν x ) ” in the above integral is multiplied by 0 at distances corresponding to
|x| > |L|. This allows the integral to maintain the limits that approach infinity to satisfy the Fourier
transform requirement, and the Dg(x) function accounts for the physical limitation of finite mirror
movement. Since the interferogram I(x) is measured with finite mirror movement x = ± L cm, the
resulting IR spectrum will have a finite resolution of 1/2L cm-1.
The key concept in Eq. (2.11) is that multiplication of each measured interferogram data
point I(x) by Dg(x) occurs before integration, i.e., before calculating B (ν ) intensities. Dg(x) is
denoted as an apodization function. We emphasize that Dg(x) is a function that can depend on the
value of x and that Dg(x) need not have the value either 1 or 0 as described above, and in fact, Dg(x)
is usually a continuous function of x. Any one of approximately eight apodization functions are
routinely used in infrared spectroscopy during data acquisition. For condensed phase spectra the
choice of apodization function usually does not significantly influence the final band shape because
the natural IR bandwidth is much greater than the bandwidth associated with the apodization
function.
The distortion of IR spectral lineshapes caused by apodization functions is best illustrated
using the interferogram produced by a monochromatic light source, i.e., the cosine interferogram in
Fig. 2.3 A. The triangular apodization function described by the equation Dg(x) = 1 – x/L is shown in
Fig. 2.3 B. The triangular apodization function is a triangle with its apex located at x = 0 and the
base ranging from – L cm to L cm. The multiplication of Dg(x) with I(x) results in a triangular-
shaped interferogram I(x)Dg(x) shown in Fig. 2.3 C.
Fig. 2.3. An apodization function Dg(x) changes the interferogram profile and the
lineshape of the corresponding spectrum. The interferogram I(x) of a
monochromatic light source (A) and the triangular apodization function Dg(x)
shape (B) are multiplied together, resulting in an interferogram (C) described by
I(x)Dg(x). The Fourier transformation of this interferogram results in a spectral
lineshape (D) described by the apodization function lineshape F[Dg(x)].
interferogram (Fig. 2.3 C) using Eq. (2.11) results in an IR lineshape described by the equation
F[Dg(x)] = L sinc2(πν L) shown in Fig. 2.3 D. In other words, for this very narrow input frequency,
a monochromatic light source, the IR spectrum has bands with the line-shape dominated by the
Fourier transformation of the apodization function Dg(x). When the instrumental resolution is 2 cm-1
(i.e., 2L = 0.5 cm), the IR linewidth in Fig. 3D (calculated as ∆ν = 1.772/L for this apodization
function) is approximately 3.5 cm-1. Thus a monochromatic IR light source is always measured with
a bandwidth approximately equal to the instrumental resolution regardless of the apodization
function. Apodization functions differ significantly regarding side-lobe intensity and Fig. 3D shows
that the triangular apodization function has only positive side lobes. Other apodization functions,
e.g., boxcar and trapezoidal, have large negative side lobes.
Thus, an apodization function is a function (also called a tapering function) used to bring an
interferogram smoothly down to zero at the edges of the sampled region. This suppresses sidelobes
which would otherwise be produced, but at the expense of widening the lines and therefore
decreasing the resolution.
Instrument function (or Instrument line shape, or Apparatus function) is the finite
Fourier cosine transform of an apodization function, also known as an apparatus function. The
instrument function I (k ) corresponding to a given apodization function A(x ) is
∫e
2 π ikx
I (k ) = A ( x ) dx
−a (2.12)
which, upon expanding the complex exponential,
a
∫e
2πikx
I (k ) = A( x)dx =
−a
a a
= ∫ cos(2πkx) A( x)dx + i ∫ sin(2πkx) A( x)dx
−a −a (2.13)
For A(x ) an even function, the left integrand is even (and hence is equal to twice its value
over half its interval) and the right integrand is odd (and hence equal to 0), so
a
I (k ) = ∫ cos(2πkx) A( x)dx
0 (2.14)
The following are apodization functions for symmetrical (2-sided) interferograms, together
with the instrument functions (or apparatus functions) they produce and a blowup of the instrument
function sidelobes. The instrument function I (k ) corresponding to a given apodization function
A(x ) can be computed by taking the finite Fourier cosine transform.
Instrument
Apodization
Type Instrument function function
function
FWHM
2
Bartlett 1−
|x| ⎛ sin(πka) ⎞
a⎜ ⎟ 1.77179
(Triangle) a ⎝ πka ⎠
2
Connes ⎛ x2 ⎞ J 5 / 2 (2πka)
⎜⎜1 − 2 ⎟⎟ 8a 2π 1.90416
(Biparabolic) ⎝ a ⎠ (2πka) 5 / 2
⎛ πx ⎞ 4a cos(2πak )
Cosine cos⎜ ⎟ 1.63941
⎝ 2a ⎠ π (1 − 16a 2 k 2 )
Uniform
sin( 2πka )
(Rectangle 1 a 1.20671
πka
or Boxcar)
x2
Welch 1− WI (k ) 1.59044
a2
where
⎛ πx ⎞ ⎛ 2πx ⎞
B A (x) = 0.42 + 0.5 cos⎜ ⎟ + 0.08 cos⎜ ⎟
⎝ a⎠ ⎝ a ⎠
a(0.84 − 0.36a 2 k 2 ) sin c(2πak )
B I (k ) =
(1 − a 2 k 2 )(1 − 4a 2 k 2 )
⎛ πx ⎞
Hm A (x) = 0.54 + 0.46 cos⎜ ⎟
⎝a⎠
a(1.08 − 0.64a 2 k 2 ) sin c(2πak )
Hm I (k ) =
1 − 4a 2 k 2
⎛ πx ⎞
Hn A (x) = cos 2 ⎜ ⎟
⎝ 2a ⎠
a sin c(2πak )
Hn I (k ) =
1 − 4a 2 k 2
J 3 / 2 (2πka)
WI (k ) = a 2 2π =
(2πka) 3 / 2
sin(2πka) − 2πka cos(2πka)
= a
2π 3 k 3 a 3
B(ν ) sample
T (ν )[%] = × 100% (2.14)
B(ν ) background
or absorption spectrum
A few final comments on producing a single-beam spectrum by calculating each B(v) using
the numerical form of equation (2.11) are needed. Interferograms, in theory, are symmetrical on both
sides of ZPD and therefore it is convenient to expand Eq. (2.11),
0 ∞
B (ν ) = ∫ I ( x) Dg ( x) cos[2πν x]dx + ∫ I ( x) Dg ( x) cos[2πν x]dx
−∞ 0
(2.16)
Based on the integral limits, these integrals merely calculate the area on each side of ZPD.
This is graphically shown in Fig. 2.2 for both interferograms. The area on each side of ZPD (i.e., x =
0) are equal because the cosine functions in the above integrals are even functions, that is, I(-x) =
I(x). Because the integrals are equal, Eq. (2.16) can be rewritten as
∞
B(ν ) = 2 ∫ I ( x) D g ( x) cos[2πν x]dx (2.17)
0
where the integral limits are now the mirror displacement x for a single-sided scan.
Based on Eq. (2.17), a single-sided scan (mirror movement from 0 to L cm) generates a
single-sided interferogram, whereas a double-sided scan (mirror movement from —L to +L cm)
generates a double-sided interferogram, but both interferograms provide the same spectral
information. Data collection for both double-sided interferograms and single-sided interferograms
occurs as the mirror moves away from the beam splitter. Thus as the movable mirror travels in the
forward direction, data collection occurs (see Fig. 2.1). For a fixed number of scans, double-sided
interferograms provide better signal-to-noise ratios than single-sided scans because the spectral
information is sampled twice (once on each side of ZPD). However, obtaining spectra from single-
sided interferograms allows a greater number of scans per second, which is useful for gas phase
experiments that require rapid data acquisition. Also, obtaining spectra from single-sided
interferogram allows increasing spectral resolution in the FTIR spectrometers with short optical path
difference. Single-sided interferograms begin data collection just to the left of ZPD to allow for
phase correction.
The Fig. 2.6 represents the real double sided and single sided interferograms.
a) b)
Fig. 2.6 Typical interferograms for Double Sided processing (a) and for Single Sided processing (b).
The instrumental resolution, δ0, of IR bands depends solely on the maximum distance of
mirror movement L,
1
δ0 = (2.18)
2L
-1
where δ0 is the instrumental resolution in cm . As L increases the optical retardation
increases [Eq. (2.3)] and the resolution at which the IR data are obtained increases [Eq. (2.18)].
Unfortunately, as L increases, the amount of spectral noise increases. Spectral noise increases
because during a complete scan, electronic and instrument noise remains constant, whereas the
signal decays or decreases (Fig. 2.4 A); therefore the S/N of the interferogram decreases as the
mirror is displaced further from the ZPD. Equation (10) demonstrated that every I(x) value in the
interferogram is used to calculate each B(v) in the single beam spectrum. Thus as L increases, i.e.,
S/N decreases, more interferogram noise causes all IR frequencies to have increased spectral noise.
Measured interferograms decay rapidly with increasing mirror movement beyond ZPD, but at some
finite mirror position, little (or no) IR signal exists and the detector is recording only noise. If the
detector is recording mostly noise because the optical retardation is too high, the instrument
resolution should be decreased to acquire the data. In other words, the S/N depends on the
instrument resolution, and when the maximum mirror displacement causes the spectral signal
intensity to be equal to or less than the instrumental-noise intensity, IR data should not be measured.
It is important to avoid high-resolution IR scans when the actual condensed phase spectra
exhibit naturally wide IR bands. High resolution requires the movable mirror to travel excessive
distances to obtain sufficient optical retardations for the high resolution. For condensed phase
spectra, it is rarely necessary to measure spectra at resolution greater than 2 cm-1, and typically
4 cm-1 resolution is acceptable. To determine the optimum resolution for a particular condensed
phase sample, one merely obtains IR spectra at low, intermediate, and high resolution to determine
when the spectral noise is apparent in the broad IR bands. Alternatively, obtaining one high-
resolution interferogram can yield all the information needed to identify the desired resolution. Prior
to Fourier transformation to obtain the single-beam spectrum, the high-resolution interferogram is
merely truncated at mirror positions corresponding to lower instrument resolution. In other words,
the interferogram is measured with a constant amount (in fact an excessive number of) data points,
but the number of transform points, used to obtain the single-beam spectrum, is reduced to obtain a
low-resolution spectrum. Thus one high-resolution interferogram can be Fourier transformed several
times at sequentially lower resolutions by truncating the measured interferogram prior to Fourier
transformation. Obviously the high-resolution interferogram would have to be stored as a separate
computer file for this experiment.
Laser Teaching Lab., International Laser Center of Moscow State University 39
FTIR Spectrometer Manual. University of Oulu, Finland Phase Correction
Fig. 2.7: Fourier Transform of an uneven double-sided interferogram. The red curve is the real
portion of the spectrum; the blue curve is the imaginary portion of the spectrum.
The process of phase correction moves the components of the spectrum that are located in the
imaginary domain to the real domain.
Much like the Fourier Transform function, the Phase Correction function can be used to
correct either single-sided or double-sided interferograms.
Laser Teaching Lab., International Laser Center of Moscow State University 40
FTIR Spectrometer Manual. University of Oulu, Finland Phase Correction
If the interferograms are double-sided, that is symmetric about the ZPD position, then their
resultant spectra will contain phase information for each spectral element. As such, the phase
correction can take place in the spectral domain. Referring to the eq. (2.20) above, the calculated
spectrum, B(ν )e iϕ (ν ) , can be corrected by way of multiplication with a phase correction function
= B(ν )e iϕ (ν ) × e − iϕ (ν ) = (2.21)
= B (ν )
Note that the PCF is not simply equal to the negative of the measured phase. Rather, a fit is
made to the in-band phase of the calculated spectrum and it is the negative of this fit that is used as
the PCF (see Fig. 2.8). The basis for this is that by only correcting for the fitted phase rather than the
calculated phase, some of the noise associated with the measurement is left in the imaginary domain.
For random sources of measurement noise, this can lead to an increase in the signal-to-noise ratio by
a factor of √2.
Figure 2.8: Fitting a function to the measured phase. The blue curve is the spectral
phase derived from the double-sided interferogram; the red curve is a fitted function to
the in-band portion of the measured phase.
Phase correction for single-sided interferograms, interferograms that are not symmetric about
the ZPD position (see Fig. 2.9), while mathematically equivalent to phase correction of double-sided
interferograms, differs slightly from a procedural point of view. A different procedure must be
employed because, for single-sided interferograms, the uncorrected spectrum (magnitude and phase)
can only be calculated for the symmetric portion of the interferogram.
Fig. 2.9: Single-sided interferogram. Note the short symmetric portion about ZPD (x=0).
− iϕ (ν )
Fig. 2.10: Phase correction function, e . The red curve is the real portion of the
PCF; the blue curve is the imaginary portion of the PCF.
Fig. 2.11. Inverse transform of the phase correction function. Phase correction of
the single-sided interferogram is achieved by convolution with this function.
The result of the convolution given in eq. (2.23) is the single-sided interferogram is rendered
symmetric about its position of zero path difference. Put another way, the single-sided interferogram
is converted to an even function (see Fig. 2.12). As such, only the portion of the single-sided
interferogram where the optical path difference is greater or equal to zero needs to be used to
compute the resultant spectrum (see Fig. 2.13).
Literature
• P.L. King, M.S. Ramsey, P.F. McMillan, and G. Swayze, Chapter 3. Laboratory
fourier transform infrared spectroscopy methods for geologic samples, in Infrared
Spectroscopy in Geochemistry, Exploration, and Remote Sensing, P. King, M.
Ramsey, G. Swayze (eds.), Mineral. Assoc. of Canada, London, ON, vol. 33, 57-91,
2004, http://ivis.eps.pitt.edu/ramsey/papers/GAC2.pdf