Fourier transform infrared spectroscopy
Encyclopedia
Fourier transform infrared spectroscopy (FTIR) is a technique which is used to obtain an infrared
Infrared
Infrared light is electromagnetic radiation with a wavelength longer than that of visible light, measured from the nominal edge of visible red light at 0.74 micrometres , and extending conventionally to 300 µm...

 spectrum of absorption
Absorption (electromagnetic radiation)
In physics, absorption of electromagnetic radiation is the way by which the energy of a photon is taken up by matter, typically the electrons of an atom. Thus, the electromagnetic energy is transformed to other forms of energy for example, to heat. The absorption of light during wave propagation is...

, emission, photoconductivity
Photoconductivity
Photoconductivity is an optical and electrical phenomenon in which a material becomes more electrically conductive due to the absorption of electromagnetic radiation such as visible light, ultraviolet light, infrared light, or gamma radiation....

 or Raman scattering
Raman scattering
Raman scattering or the Raman effect is the inelastic scattering of a photon. It was discovered by Sir Chandrasekhara Venkata Raman and Kariamanickam Srinivasa Krishnan in liquids, and by Grigory Landsberg and Leonid Mandelstam in crystals....

 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
Dispersion (optics)
In optics, dispersion is the phenomenon in which the phase velocity of a wave depends on its frequency, or alternatively when the group velocity depends on the frequency.Media having such a property are termed dispersive media...

 spectrometer which measures intensity over a narrow range of wavelengths at a time. FTIR has made dispersive infrared spectrometers all but obsolete (except sometimes in the near infrared), opening up new applications of infrared spectroscopy
Infrared spectroscopy
Infrared spectroscopy is the spectroscopy that deals with the infrared region of the electromagnetic spectrum, that is light with a longer wavelength and lower frequency than visible light. It covers a range of techniques, mostly based on absorption spectroscopy. As with all spectroscopic...

.

The term Fourier transform infrared spectroscopy originates from the fact that a Fourier transform
Fourier transform
In mathematics, Fourier analysis is a subject area which grew from the study of Fourier series. The subject began with the study of the way general functions may be represented by sums of simpler trigonometric functions...

 (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
Fourier transform spectroscopy
Fourier transform spectroscopy is a measurement technique whereby spectra are collected based on measurements of the coherence of a radiative source, using time-domain or space-domain measurements of the electromagnetic radiation or other type of radiation....

.

Conceptual introduction

The goal of any absorption spectroscopy
Absorption spectroscopy
Absorption spectroscopy refers to spectroscopic techniques that measure the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a...

 (FTIR, ultraviolet-visible ("UV-Vis") spectroscopy
Ultraviolet-visible spectroscopy
Ultraviolet-visible spectroscopy or ultraviolet-visible spectrophotometry refers to absorption spectroscopy or reflectance spectroscopy in the ultraviolet-visible spectral region. This means it uses light in the visible and adjacent ranges...

, 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
Ultraviolet-visible spectroscopy
Ultraviolet-visible spectroscopy or ultraviolet-visible spectrophotometry refers to absorption spectroscopy or reflectance spectroscopy in the ultraviolet-visible spectral region. This means it uses light in the visible and adjacent ranges...

 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
Broadband
The term broadband refers to a telecommunications signal or device of greater bandwidth, in some sense, than another standard or usual signal or device . Different criteria for "broad" have been applied in different contexts and at different times...

 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
Michelson interferometer
The Michelson interferometer is the most common configuration for optical interferometry and was invented by Albert Abraham Michelson. An interference pattern is produced by splitting a beam of light into two paths, bouncing the beams back and recombining them...

, 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
Fourier transform
In mathematics, Fourier analysis is a subject area which grew from the study of Fourier series. The subject began with the study of the way general functions may be represented by sums of simpler trigonometric functions...

 (hence the name, "Fourier transform spectroscopy"). The raw data is sometimes called an "interferogram".

Developmental background

The first low-cost spectrophotometer capable of recording an infrared spectrum
Infrared spectroscopy
Infrared spectroscopy is the spectroscopy that deals with the infrared region of the electromagnetic spectrum, that is light with a longer wavelength and lower frequency than visible light. It covers a range of techniques, mostly based on absorption spectroscopy. As with all spectroscopic...

 was the Perkin-Elmer Infracord produced in 1957. This instrument covered the wavelength range from 2.5 μm to 15 μm (wavenumber
Wavenumber
In the physical sciences, the wavenumber is a property of a wave, its spatial frequency, that is proportional to the reciprocal of the wavelength. It is also the magnitude of the wave vector...

 range 4000 cm−1 to 660 cm−1). The lower wavelength limit was chosen to encompass the highest known vibration frequency due to a fundamental molecular vibration
Molecular vibration
A molecular vibration occurs when atoms in a molecule are in periodic motion while the molecule as a whole has constant translational and rotational motion...

. The upper limit was imposed by the fact that the dispersing element
Dispersion (optics)
In optics, dispersion is the phenomenon in which the phase velocity of a wave depends on its frequency, or alternatively when the group velocity depends on the frequency.Media having such a property are termed dispersive media...

 was a prism
Dispersive prism
In optics, a dispersive prism is a type of optical prism, normally having the shape of a geometrical triangular prism. It is the most widely-known type of optical prism, although perhaps not the most common in actual use. Triangular prisms are used to disperse light, that is, to break light up into...

 made from a single crystal of rock-salt (sodium chloride
Sodium chloride
Sodium chloride, also known as salt, common salt, table salt or halite, is an inorganic compound with the formula NaCl. Sodium chloride is the salt most responsible for the salinity of the ocean and of the extracellular fluid of many multicellular organisms...

) which becomes opaque at wavelengths longer than about 15 μm; this spectral region became known as the rock-salt region. Later instruments used potassium bromide
Potassium bromide
Potassium bromide is a salt, widely used as an anticonvulsant and a sedative in the late 19th and early 20th centuries, with over-the-counter use extending to 1975 in the United States. Its action is due to the bromide ion...

 prisms to extend the range to 25 μm (400 cm−1) and caesium iodide
Caesium iodide
Caesium iodide is an ionic compound often used as the input phosphor of an x-ray image intensifier tube found in fluoroscopy equipment....

 50 μm (200 cm−1). The region beyond 50 μm (200 cm−1) became known as the far-infrared region; at very long wavelengths it merges into the microwave
Microwave
Microwaves, a subset of radio waves, have wavelengths ranging from as long as one meter to as short as one millimeter, or equivalently, with frequencies between 300 MHz and 300 GHz. This broad definition includes both UHF and EHF , and various sources use different boundaries...

 region. Measurements in the far infrared needed the development of accurately ruled diffraction grating
Diffraction grating
In optics, a diffraction grating is an optical component with a periodic structure, which splits and diffracts light into several beams travelling in different directions. The directions of these beams depend on the spacing of the grating and the wavelength of the light so that the grating acts as...

s to replace the prisms as dispersing elements since salt crystals are opaque in this region. More sensitive detectors than the bolometer
Bolometer
A bolometer is a device for measuring the power of incident electromagnetic radiation via the heating of a material with a temperature-dependent electrical resistance. It was invented in 1878 by the American astronomer Samuel Pierpont Langley...

 were required because of the low energy of the radiation. One such was the Golay detector. An additional issue is the need to exclude atmospheric water vapour because water vapour has in intense pure rotational spectrum in this region. Far-infrared spectrophotometers were cumbersome, slow and expensive. The advantages of the Michelson interferometer
Michelson interferometer
The Michelson interferometer is the most common configuration for optical interferometry and was invented by Albert Abraham Michelson. An interference pattern is produced by splitting a beam of light into two paths, bouncing the beams back and recombining them...

 were well-known, but considerable technical difficulties had to be overcome before a commercial instrument could be built. Also an electronic computer was needed to perform the required Fourier transform and this only became practicable with the advent of mini-computers, such as the PDP-8
PDP-8
The 12-bit PDP-8 was the first successful commercial minicomputer, produced by Digital Equipment Corporation in the 1960s. DEC introduced it on 22 March 1965, and sold more than 50,000 systems, the most of any computer up to that date. It was the first widely sold computer in the DEC PDP series of...

 which became available in 1965.

Michelson interferometer

In a Michelson interferometer adapted for FTIR, light from the polychromatic
Polychromatic
The term polychromatic means having several colours.It is used to describe light that exhibits more than one color. In a technical respect, this can also mean that it contains radiation of more than one wavelength. The study of polychromatics is particularly useful in the production of diffraction...

 infrared source, approximately a black-body radiator, is collimated and directed to a beam splitter
Beam splitter
A beam splitter is an optical device that splits a beam of light in two. It is the crucial part of most interferometers.In its most common form, a rectangle, it is made from two triangular glass prisms which are glued together at their base using Canada balsam...

. 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 focused 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 principal advantages for a FT spectrometer compared to a scanning (dispersive) spectrometer.
  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
    Signal-to-noise ratio
    Signal-to-noise ratio is a measure used in science and engineering that compares the level of a desired signal to the level of background noise. It is defined as the ratio of signal power to the noise power. A ratio higher than 1:1 indicates more signal than noise...

     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
    Monochromator
    A monochromator is an optical device that transmits a mechanically selectable narrow band of wavelengths of light or other radiation chosen from a wider range of wavelengths available at the input...

     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, and "Connes' advantage" (better wavelength accuracy), 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.

Resolution

The interferogram belongs in the length domain. Fourier transform
Fourier transform
In mathematics, Fourier analysis is a subject area which grew from the study of Fourier series. The subject began with the study of the way general functions may be represented by sums of simpler trigonometric functions...

 (FT) inverts the dimension, so the FT of the interferogram belongs in the reciprocal length domain, that is the wavenumber
Wavenumber
In the physical sciences, the wavenumber is a property of a wave, its spatial frequency, that is proportional to the reciprocal of the wavelength. It is also the magnitude of the wave vector...

 domain. The spectral resolution
Spectral resolution
The spectral resolution of a spectrograph, or, more generally, of a frequency spectrum, is a measure of its ability to resolve features in the electromagnetic spectrum...

  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
Corner reflector
A corner reflector is a retroreflector consisting of three mutually perpendicular, intersecting flat surfaces, which reflects waves back directly towards the source, but shifted . Unlike a simple mirror, they work for a relatively wide-angle field of view. The three intersecting surfaces often have...

 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
Venus
Venus is the second planet from the Sun, orbiting it every 224.7 Earth days. The planet is named after Venus, the Roman goddess of love and beauty. After the Moon, it is the brightest natural object in the night sky, reaching an apparent magnitude of −4.6, bright enough to cast shadows...

 by recording the vibration-rotation spectrum
Rovibrational coupling
Rovibrational coupling is a coupled rotational and vibrational excitation of a molecule. It is different from rovibronic coupling, which involves a change in all of electronic, vibrational, and rotational states simultaneously....

 of Venusian CO2 at 0.1 cm−1 resolution. Michelson
Albert Abraham Michelson
Albert Abraham Michelson was an American physicist known for his work on the measurement of the speed of light and especially for the Michelson-Morley experiment. In 1907 he received the Nobel Prize in Physics...

 himself attempted to resolve the hydrogen Hα emission band
H-alpha
H-alpha is a specific red visible spectral line created by hydrogen with a wavelength of 656.28 nm, which occurs when a hydrogen electron falls from its third to second lowest energy level...

 in the spectrum of a hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...

 atom into its two components by using his interferometer. p25 A spectrometer with 0.001 cm−1 resolution is now available commercially from Bruker
Bruker
Bruker is a leading provider of high-performance scientific instruments and solutions for molecular and materials research, as well as for industrial and applied analysis...

. 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.

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.

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
Discrete Fourier transform
In mathematics, the discrete Fourier transform is a specific kind of discrete transform, used in Fourier analysis. It transforms one function into another, which is called the frequency domain representation, or simply the DFT, of the original function...

 is needed. The fast Fourier transform
Fast Fourier transform
A fast Fourier transform is an efficient algorithm to compute the discrete Fourier transform and its inverse. "The FFT has been called the most important numerical algorithm of our lifetime ." There are many distinct FFT algorithms involving a wide range of mathematics, from simple...

 (FFT) algorithm is used.

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 and marketed by Grubb Parsons. It used a stepper motor to drive the moving mirror, recording the detector response after each step was completed.

Mid-infrared FTIR

With the advent of cheap microcomputer
Microcomputer
A microcomputer is a computer with a microprocessor as its central processing unit. They are physically small compared to mainframe and minicomputers...

s 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
Helium-neon laser
A helium–neon laser or HeNe laser, is a type of gas laser whose gain medium consists of a mixture of helium and neon inside of a small bore capillary tube, usually excited by a DC electrical discharge.- History of HeNe laser development:...

. This confers high wavenumber accuracy on the resulting infrared spectrum and avoids wavenumber calibration
Calibration
Calibration is a comparison between measurements – one of known magnitude or correctness made or set with one device and another measurement made in as similar a way as possible with a second device....

 errors.

Near-infrared FTIR

The near-infrared region spans the wavelength range between the rock-salt region and the start of the visible
Visible spectrum
The visible spectrum is the portion of the electromagnetic spectrum that is visible to the human eye. Electromagnetic radiation in this range of wavelengths is called visible light or simply light. A typical human eye will respond to wavelengths from about 390 to 750 nm. In terms of...

 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
Process control
Process control is a statistics and engineering discipline that deals with architectures, mechanisms and algorithms for maintaining the output of a specific process within a desired range...

 and chemical imaging
Chemical imaging
Chemical imaging is the analytical capability to create a visual image of components distribution from simultaneous measurement of spectra and spatial, time informations....

.

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
    Gas chromatography-mass spectrometry
    Gas chromatography–mass spectrometry is a method that combines the features of gas-liquid chromatography and mass spectrometry to identify different substances within a test sample. Applications of GC-MS include drug detection, fire investigation, environmental analysis, explosives investigation,...

    ). The GC-IR method is particularly useful for identifying isomer
    Isomer
    In chemistry, isomers are compounds with the same molecular formula but different structural formulas. Isomers do not necessarily share similar properties, unless they also have the same functional groups. There are many different classes of isomers, like stereoisomers, enantiomers, geometrical...

    s, 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.
  • TG-IR (thermogravimetry-infrared spectrometry) IR spectra of the gases evolved during thermal decomposition are obtained as a function of temperature.
  • Micro-samples. Tiny samples, such as in forensic analysis, can be examined with the aid of an infrared microscope
    Microscope
    A microscope is an instrument used to see objects that are too small for the naked eye. The science of investigating small objects using such an instrument is called microscopy...

     in the sample chamber. An image of the surface can be obtained by scanning. Another example is the use of FTIR to characterize artistic materials in old-master paintings.
  • 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
    Luminescence
    Luminescence is emission of light by a substance not resulting from heat; it is thus a form of cold body radiation. It can be caused by chemical reactions, electrical energy, subatomic motions, or stress on a crystal. This distinguishes luminescence from incandescence, which is light emitted by a...

     and Raman scattering
    Raman scattering
    Raman scattering or the Raman effect is the inelastic scattering of a photon. It was discovered by Sir Chandrasekhara Venkata Raman and Kariamanickam Srinivasa Krishnan in liquids, and by Grigory Landsberg and Leonid Mandelstam in crystals....

    . 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.
  • 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.

External links

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