Fourier transform infrared spectroscopy

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"FTIR" redirects here. FTIR may also refer to Frustrated total internal reflection.

Fourier transform infrared spectroscopy (FTIR)[1] is a technique which is used to obtain an

infrared spectrum of absorption, emission, photoconductivity or Raman scattering of a solid,
liquid or gas. An FTIR spectrometer simultaneously collects spectral data in a wide spectral
range. This confers a significant advantage over a dispersive spectrometer which measures
intensity over a narrow range of wavelengths at a time. FTIR technique has made dispersive
infrared spectrometers all but obsolete (except sometimes in the near infrared) and opened up
new applications of infrared spectroscopy.

The term Fourier transform infrared spectroscopy originates from the fact that a Fourier
transform (a mathematical algorithm) is required to convert the raw data into the actual
spectrum. For other uses of this kind of technique, see Fourier transform spectroscopy.

Contents
[hide]

 1 Conceptual introduction
 2 Michelson interferometer
o 2.1 Resolution
o 2.2 Beam splitter
o 2.3 Fourier transform
 3 Far-infrared FTIR
 4 Mid-infrared FTIR
 5 Near-infrared FTIR
 6 Applications
 7 References
 8 External links

[edit] Conceptual introduction

An interferogram from an FTIR spectrometer. The horizontal axis is the position of the mirror,
and the vertical axis is the amount of light detected. This is the "raw data" which can be
transformed into an actual spectrum.

The goal of any absorption spectroscopy (FTIR, ultraviolet-visible ("UV-Vis") spectroscopy,

etc.) is to measure how well a sample absorbs light at each wavelength. The most straightforward
way to do this, the "dispersive spectroscopy" technique, is to shine a monochromatic light beam
at a sample, measure how much of the light is absorbed, and repeat for each different
wavelength. (This is how UV-Vis spectrometers work, for example.)

Fourier transform spectroscopy is a less intuitive way to obtain the same information. Rather
than shining a monochromatic beam of light at the sample, this technique shines a beam
containing many different frequencies of light at once, and measures how much of that beam is
absorbed by the sample. Next, the beam is modified to contain a different combination of
frequencies, giving a second data point. This process is repeated many times. Afterwards, a
computer takes all these data and works backwards to infer what the absorption is at each
wavelength.

The beam described above is generated by starting with a broadband light source—one
containing the full spectrum of wavelengths to be measured. The light shines into a certain
configuration of mirrors, called a Michelson interferometer, that allows some wavelengths to
pass through but blocks others (due to wave interference). The beam is modified for each new
data point by moving one of the mirrors; this changes the set of wavelengths that pass through.

As mentioned, computer processing is required to turn the raw data (light absorption for each
mirror position) into the desired result (light absorption for each wavelength). The processing
required turns out to be a common algorithm called the Fourier transform (hence the name,
"Fourier transform spectroscopy"). The raw data is sometimes called an "interferogram".

[edit] Michelson interferometer

Main article: Michelson interferometer
Schematic diagram of a Michelson interferometer, configured for FTIR

In a Michelson interferometer adapted for FTIR, light from the polychromatic infrared source,
approximately a black-body radiator, is collimated and directed to a beam splitter. Ideally 50% of
the light is reflected towards the fixed mirror and 50% is transmitted towards the moving mirror.
Light is reflected from the two mirrors back to the beam splitter and (ideally) 50% of the original
light passes into the sample compartment. There, the light is focussed on the sample. On leaving
the sample compartment the light is refocused on to the detector. The difference in optical path
length between the two arms to the interferometer is known as the retardation. An interferogram
is obtained by varying the retardation and recording the signal from the detector for various
values of the retardation. The form of the interferogram when no sample is present depends on
factors such as the variation of source intensity and splitter efficiency with wavelength. This
results in a maximum at zero retardation, when there is constructive interference at all
wavelengths, followed by series of "wiggles". The position of zero retardation is determined
accurately by finding the point of maximum intensity in the interferogram. When a sample is
present the background interferogram is modulated by the presence of absorption bands in the
sample.

There are two principle advantages for a FT spectrometer compared to a scanning (dispersive)
spectrometer.[2][3]

1. The multiplex or Fellgett's advantage. This arises from the fact that information from all
wavelengths is collected simultaneously. It results in a higher Signal-to-noise ratio for a
given scan-time or a shorter scan-time for a given resolution.
2. The throughput or Jacquinot's advantage. This results from the fact that, in a dispersive
instrument, the monochromator has entrance and exit slits which restrict the amount of
light that passes through it. The interferometer throughput is determined only by the
diameter of the collimated beam coming from the source.

Other minor advantages include less sensitivity to stray light,[3] and "Connes' advantage" (better
wavelength accuracy),[3] while a disadvantage is that FTIR cannot use the advanced electronic
filtering techniques that often makes its signal-to-noise ratio inferior to that of dispersive
measurements.[3]
[edit] Resolution

The interferogram belongs in the length domain. Fourier transform (FT) inverts the dimension,
so the FT of the interferogram belongs in the reciprocal length domain, that is the wavenumber
domain. The spectral resolution in wavenumbers per cm is equal to the reciprocal of the
maximum retardation in cm. Thus a 4 cm−1 resolution will be obtained if the maximum
retardation is 0.25 cm; this is typical of the cheaper FTIR instruments. Much higher resolution
can be obtained by increasing the maximum retardation. This is not easy as the moving mirror
must travel in a near-perfect straight line. The use of corner-cube mirrors in place of the flat
mirrors is helpful as an outgoing ray from a corner-cube mirror is parallel to the incoming ray,
regardless of the orientation of the mirror about axes perpendicular to the axis of the light beam.
Connes measured in 1966 the temperature of the atmosphere of Venus by recording the
vibration-rotation spectrum of Venusian CO2 at 0.1 cm−1 resolution.[4] Michelson himself
attempted to resolve the hydrogen Hα emission band in the spectrum of a hydrogen atom into its
two components by using his interferometer.[1] p25 A spectrometer with 0.001 cm−1 resolution is
now available commercially from Bruker. The throughput advantage is important for high-
resolution FTIR as the monochromator in a dispersive instrument with the same resolution would
have very narrow entrance and exit slits.

[edit] Beam splitter

The beam-splitter can not be made of a common glass, as it is opaque to infrared radiation of
wavelengths longer than about 2.5 μm. A thin film, usually of a plastic material, is used instead.
However, as any material has a limited range of optical transmittance, several beam-splitters are
used interchangeably to cover a wide spectral range.

[edit] Fourier transform

The interferogram in practice consists of a set of intensities measured for discrete values of
retardation. The difference between successive retardation values is constant. Thus, a discrete
Fourier transform is needed. The fast Fourier transform (FFT) algorithm is used.

[edit] Far-infrared FTIR

The first FTIR spectrometers were developed for far-infrared range. The reason for this has to do
with the mechanical tolerance needed for good optical performance, which is related to the
wavelength of the light being used. For the relatively long wavelengths of the far infrared (~10
μm), tolerances are adequate, whereas for the rock-salt region tolerances have to be better than 1
μm. A typical instrument was the cube interferometer developed at the NPL[5] and marketed by
Grubb Parsons. It used a stepper motor to drive the moving mirror, recording the detector
response after each step was completed.

[edit] Mid-infrared FTIR

With the advent of cheap microcomputers it became possible to have a computer dedicated to
controlling the spectrometer, collecting the data, doing the Fourier transform and presenting the
spectrum. This provided the impetus for the development of FTIR spectrometers for the rock-salt
region. The problems of manufacturing ultra-high precision optical and mechanical components
had to be solved. A wide range of instruments is now available commercially. Although
instrument design has become more sophisticated, the basic principles remain the same.
Nowadays, the moving mirror of the interferometer moves at a constant velocity, and sampling
of the interferogram is triggered by finding zero-crossings in the fringes of a secondary
interferometer lit by a helium-neon laser. This confers high wavenumber accuracy on the
resulting infrared spectrum and avoids wavenumber calibration errors.

[edit] Near-infrared FTIR

Main article: Near-infrared spectroscopy

The near-infrared region spans the wavelength range between the rock-salt region and the start of
the visible region at about 750 nm. Overtones of fundamental vibrations can be observed in this
region. It is used mainly in industrial applications such as process control.

[edit] Applications
FTIR can be used in all applications where a dispersive spectrometer was used in the past (see
external links). In addition, the multiplex and throughput advantages have opened up new areas
of application. These include:

 GC-IR (gas chromatography-infrared spectrometry). A gas chromatograph can be used to

separate the components of a mixture. The fractions containing single components are
directed into an FTIR spectrometer, to provide the infrared spectrum of the sample. This
technique is complementary to GC-MS (gas chromatography-mass spectrometry). The
GC-IR method is particularly useful for identifying isomers, which by their nature have
identical masses. The key to the successful use of GC-IR is that the interferogram can be
captured in a very short time, typically less than 1 second. FTIR has also been applied to
the analysis of liquid chromatography fractions.[3]
 TG-IR (thermogravimetry-infrared spectrometry) IR spectra of the gases evolved during
thermal decompostion are obtained as a function of temperature.[6]
 Micro-samples. Tiny samples, such as in forensic analysis, can be examined with the aid
of an infrared microscope in the sample chamber. An image of the surface can be
obtained by scanning.[7] Another example is the use of FTIR to characterize artistic
materials in old-master paintings.[8]
 Emission spectra. Instead of recording the spectrum of light transmitted through the
sample, FTIR spectrometer can be used to acquire spectrum of light emitted by the
sample. Such emission could be induced by various processes, and the most common
ones are luminescence and Raman scattering. Little modification is required to an
absorption FTIR spectrometer to record emission spectra and therefore many commercial
FTIR spectrometers combine both absorption and emission/Raman modes.[9]
 Photocurrent spectra. This mode uses a standard, absorption FTIR spectrometer. The
studied sample is placed instead of the FTIR detector, and its photocurrent, induced by
the spectrometer's broadband source, is used to record the interferrogram, which is then
converted into the photoconductivity spectrum of the sample.[10]
[edit] References
1. ^ a b Griffiths, P.; de Hasseth, J.A. (18 May 2007). Fourier Transform Infrared Spectrometry (2nd
ed.). Wiley-Blackwell. ISBN 0471194042. http://books.google.com/?
id=C_c0GVe8MX0C&printsec=frontcover.
2. ^ Banwell, C.N.; McCash, E.M. (1994). Fundamentals of Molecular Spectroscopy (4th ed.).
McGraw-Hill. ISBN 0-07-707976-0.
3. ^ a b c d e Robert White (1990). Chromatography/Fourier transform infrared spectroscopy and its
applications. Marcel Dekker. ISBN 0824781910. http://books.google.com/?
id=t2VSNnFoO3wC&pg=PA7.
4. ^ Connes, J.; Connes, P. (1966). "Near-Infrared Planetary Spectra by Fourier Spectroscopy. I.
Instruments and Results". Journal of the Optical Society of America 56 (7): 896–910.
doi:10.1364/JOSA.56.000896.
5. ^ Chamberain, J.; Gibbs,J.E.; Gebbie, H.E. (1969). "The determination of refractive index spectra
by fourier spectrometry". Infrared Physics 9: 189–209. doi:10.1016/0020-0891(69)90023-2.
6. ^ Nishikida, K.; Nishio, E.; Hannah, R.W. (1995). Selected applications of FT-IR techniques.
Gordon and Breach. p. 240. ISBN 2884490736. http://books.google.com/?
id=Bjj7wSEP2lsC&pg=PA240.
7. ^ Beauchaine, J.P.; Peterman, J.W.; Rosenthal,R.J. (1988). "Applications of FT-IR/microscopy in
forensic analysis". Microchimica Acta 94: 133–138. doi:10.1007/BF01205855.
8. ^ Prati, S.; Joseph, E.; Sciutto, G.; Mazzeo, R. (2010). "New Advances in the Application of
FTIR Microscopy and Spectroscopy for the Characterization of Artistic Materials". Acc. Chem.
Res. 43 (6): 792–801. doi:10.1021/ar900274f. PMID 20476733.
9. ^ Michael Gaft, Renata Reisfeld, Gérard Panczer (2005). Luminescence spectroscopy of minerals
and materials. Springer. p. 263. ISBN 3540219188. http://books.google.com/?
id=QBoTvW_h1FQC&pg=PA263.
10. ^ Jef Poortmans, Vladimir Arkhipov (2006). Thin film solar cells: fabrication, characterization
and applications. John Wiley and Sons. p. 189. ISBN 0470091266. http://books.google.com/?
id=SvVYBK6YAxAC&pg=PA189.

[edit] External links

 Infracord spectrometer photograph
 The Grubb-Parsons-NPL cube interferometer Spectroscopy, part 2 by Dudley Williams,
page 81
 FTIR application notes from Perkin Elmer
 FTIR application notes from Varian
 Infrared / FTIR Application Notes Recent publications.
 Semiconductor applications FTIR Sampling Techniques Overview.
 infrared materials Properties of many salt crystals and useful links.

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Categories: Infrared spectroscopy