Fourier transform infrared spectroscopy

Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid or gas. An FTIR spectrometer simultaneously collects high-spectral-resolution data over 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. Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid or gas. An FTIR spectrometer simultaneously collects high-spectral-resolution data over 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. The term Fourier-transform infrared spectroscopy originates from the fact that a Fourier transform (a mathematical process) is required to convert the raw data into the actual spectrum. The goal of any absorption spectroscopy (FTIR, ultraviolet-visible ('UV-Vis') spectroscopy, etc.) is to measure how much light a sample absorbs 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 some 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 (a beam composed of only a single wavelength) at the sample, this technique shines a beam containing many 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 rapidly repeated many times over a short timespan. Afterwards, a computer takes all this data and works backward 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 Michelson interferometer—a certain configuration of mirrors, one of which is moved by a motor. As this mirror moves, each wavelength of light in the beam is periodically blocked, transmitted, blocked, transmitted, by the interferometer, due to wave interference. Different wavelengths are modulated at different rates, so that at each moment the beam coming out of the interferometer has a different spectrum. 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. The Fourier transform converts one domain (in this case displacement of the mirror in cm) into its inverse domain (wavenumbers in cm-1). The raw data is called an 'interferogram'. The first low-cost spectrophotometer capable of recording an infrared spectrum was the Perkin-Elmer Infracord produced in 1957. This instrument covered the wavelength range from 2.5 μm to 15 μm (wavenumber 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. The upper limit was imposed by the fact that the dispersing element was a prism made from a single crystal of rock-salt (sodium chloride), 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 prisms to extend the range to 25 μm (400 cm−1) and caesium iodide 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 region. Measurements in the far infrared needed the development of accurately ruled diffraction gratings to replace the prisms as dispersing elements, since salt crystals are opaque in this region. More sensitive detectors than the bolometer 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 an intense pure rotational spectrum in this region. Far-infrared spectrophotometers were cumbersome, slow and expensive. The advantages of the Michelson interferometer 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, which became available in 1965. Digilab pioneered the world's first commercial FTIR spectrometer (Model FTS-14) in 1969 (Digilab FTIRs are now a part of Agilent technologies's molecular product line after it acquired spectroscopy business from Varian). 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 refracted 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 some fraction 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 or optical path difference (OPD). 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.