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| title | chunk | source | category | tags | date_saved | instance |
|---|---|---|---|---|---|---|
| Fourier-transform infrared spectroscopy | 2/5 | https://en.wikipedia.org/wiki/Fourier-transform_infrared_spectroscopy | reference | science, encyclopedia | 2026-05-05T03:41:27.177904+00:00 | kb-cron |
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 OPD and recording the signal from the detector for various values of the OPD. 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 OPD, when there is constructive interference at all wavelengths, followed by series of "wiggles". The position of zero OPD 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. Commercial spectrometers use Michelson interferometers with a variety of scanning mechanisms to generate the path difference. Common to all these arrangements is the need to ensure that the two beams recombine exactly as the system scans. The simplest systems have a plane mirror that moves linearly to vary the path of one beam. In this arrangement the moving mirror must not tilt or wobble as this would affect how the beams overlap as they recombine. Some systems incorporate a compensating mechanism that automatically adjusts the orientation of one mirror to maintain the alignment. Arrangements that avoid this problem include using cube corner reflectors instead of plane mirrors as these have the property of returning any incident beam in a parallel direction regardless of orientation.
Systems where the path difference is generated by a rotary movement have proved very successful. One common system incorporates a pair of parallel mirrors in one beam that can be rotated to vary the path without displacing the returning beam. Another is the double pendulum design where the path in one arm of the interferometer increases as the path in the other decreases. A quite different approach involves moving a wedge of an IR-transparent material such as KBr into one of the beams. Increasing the thickness of KBr in the beam increases the optical path because the refractive index is higher than that of air. One limitation of this approach is that the variation of refractive index over the wavelength range limits the accuracy of the wavelength calibration.
== Measuring and processing the interferogram == The interferogram has to be measured from zero path difference to a maximum length that depends on the resolution required. In practice the scan can be on either side of zero resulting in a double-sided interferogram. Mechanical design limitations may mean that for the highest resolution the scan runs to the maximum OPD on one side of zero only. The interferogram is converted to a spectrum by Fourier transformation. This requires it to be stored in digital form as a series of values at equal intervals of the path difference between the two beams. To measure the path difference a laser beam is sent through the interferometer, generating a sinusoidal signal where the separation between successive maxima is equal to the wavelength of the laser (typically a 633 nm HeNe laser is used). This can trigger an analog-to-digital converter to measure the IR signal each time the laser signal passes through zero. Alternatively, the laser and IR signals can be measured synchronously at smaller intervals with the IR signal at points corresponding to the laser signal zero crossing being determined by interpolation. This approach allows the use of analog-to-digital converters that are more accurate and precise than converters that can be triggered, resulting in lower noise.
The result of Fourier transformation is a spectrum of the signal at a series of discrete wavelengths. The range of wavelengths that can be used in the calculation is limited by the separation of the data points in the interferogram. The shortest wavelength that can be recognized is twice the separation between these data points. For example, with one point per wavelength of a HeNe reference laser at 0.633 μm (15800 cm−1) the shortest wavelength would be 1.266 μm (7900 cm−1). Because of aliasing, any energy at shorter wavelengths would be interpreted as coming from longer wavelengths and so has to be minimized optically or electronically. The spectral resolution, i.e. the separation between wavelengths that can be distinguished, is determined by the maximum OPD. The wavelengths used in calculating the Fourier transform are such that an exact number of wavelengths fit into the length of the interferogram from zero to the maximum OPD as this makes their contributions orthogonal. This results in a spectrum with points separated by equal frequency intervals. For a maximum path difference d adjacent wavelengths λ1 and λ2 will have n and (n+1) cycles, respectively, in the interferogram. The corresponding frequencies are ν1 and ν2: