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. It can be applied to a variety of types of spectroscopy including optical spectroscopy, infrared spectroscopy (FTIR, FT- IR!", nuclear magnetic resonance ( #R" and magnetic resonance spectroscopic imaging (#R!I",mass spectrometry and electron spin resonance spectroscopy. There are several methods for measuring the temporal coherence of the light (see$ field-autocorrelation", including the continuous wave Michelson or Fourier transform spectrometer and the pulsed Fourier transform spectrograph (which is more sensitive and has a much shorter sampling time than conventional spectroscopic techniques, but is only applicable in a laboratory environment". The term Fourier transform spectroscopy reflects the fact that in all these techniques, a Fourier transform is required to turn the raw data into the actual spectrum, and in many of the cases in optics involving interferometers, is based on the WienerKhinchin theorem.

Conceptual introduction
Measuring an emission spectrum

An example of a spectrum: The spectrum of light emitted by the blue flame of a butane torch. The horizontal axis is the wavelengthof light, and the vertical axis represents how much light is emitted by the torch at that wavelength.

ne of the most basic tas!s in spectroscopy is to characteri"e the spectrum of a light source# $ow much light is emitted at each different wavelength. The most straightforward way to measure a spectrum is to pass the light through a monochromator, an instrument that bloc!s all of the light except the light at a certain wavelength %the un&bloc!ed wavelength is set by a !nob on the monochromator'. Then the intensity of this remaining %single&wavelength' light is measured. The measured intensity directly indicates how much light is emitted at that wavelength. (y varying the monochromator)s wavelength setting, the full spectrum can be measured. This simple scheme in fact describes how some spectrometers wor!.

Fourier transform spectroscopy is a less intuitive way to get the same information. *ather than allowing only one wavelength at a time to pass through to the detector, this technique lets through a beam containing many different wavelengths of light at once, and measures the total beam intensity. +e,t, the beam is modified to contain a different combination of wavelengths, giving a second data point. This process is repeated many times. -fterwards, a computer ta!es all this data and wor!s bac!wards to infer how much light there is at each wavelength. To be more specific, between the light source and the detector, there is a certain configuration of mirrors that allows some wavelengths to pass through but bloc!s 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 can pass through.

Measuring an absorption spectrum

An "interferogram" from a ourier transform spectrometer. This is the "raw data" which can be ourier transformed into an actual spectrum. The pea! at the center is the "#$ position %""ero #ath $ifference"&: 'ere, all the light passes through the interferometer because its two arms have e(ual length.

The method of Fourier transform spectroscopy can also be used for absorption spectroscopy. The primary e,ample is /FT0* 1pectroscopy/, a common technique in chemistry. 0n general, the goal of absorption spectroscopy is to measure how well a sample absorbs or transmits light at each different wavelength. -lthough absorption spectroscopy and emission spectroscopy are different in principle, they are closely related in practice. any technique for emission spectroscopy can also be used for absorption spectroscopy. First, the emission spectrum of a broadband lamp is measured %this is called the /bac!ground spectrum/'. 1econd, the emission spectrum of the same lamp shining through the sample is measured %this is called the /sample spectrum/'. The sample will absorb some of the light, causing the spectra to be different. The ratio of the /sample spectrum/ to the /bac!ground spectrum/ is directly related to the sample)s absorption spectrum. -ccordingly, the technique of /Fourier transform spectroscopy/ can be used both for measuring emission spectra %for e,ample, the emission spectrum of a star', and absorption spectra %for e,ample, the absorption spectrum of a liquid'.

Continuous wave Michelson or Fourier transform spectrograph

The ourier transform spectrometer is )ust a Michelson interferometer but one of the two fully reflecting mirrors is movable, allowing a variable delay %in the travel*time of the light& to be included in one of the beams.

The 2ichelson spectrograph is similar to the instrument used in the 2ichelson&2orley e,periment. 3ight from the source is split into two beams by a half&silvered mirror, one is reflected off a fi,ed mirror and one off a moving mirror which introduces a time delay4the Fourier transform spectrometer is 5ust a 2ichelson interferometer with a movable mirror. The beams interfere, allowing the temporal coherence of the light to be measured at each different time delay setting, effectively converting the time domain into a spatial coordinate. (y ma!ing measurements of the signal at many discrete positions of the moving mirror, the spectrum can be reconstructed using a Fourier transform of the temporal coherence of the light. 2ichelson spectrographs are capable of very high spectral resolution observations of very bright sources. The 2ichelson or Fourier transform spectrograph was popular for infra&red applications at a time when infra&red astronomy only had single pi,el detectors. 0maging 2ichelson spectrometers are a possibility, but in general have been supplanted by imaging Fabry67rot instruments which are easier to construct.

+xtracting the spectrum

The intensity as a function of the path length difference %also denoted as retardation' in the interferometer and wavenumber , where is the spectrum to be determined. +ote that it is not necessary for to be modulated by the sample before the interferometer. 0n fact, most FT0* spectrometers place the sample after the interferometer in the optical path. The total intensity at the detector is is

This is 5ust a Fourier cosine transform. The inverse gives us our desired result in terms of the measured quantity #

6ulsed Fourier transform spectrometer

- pulsed Fourier transform spectrometer does not employ transmittance techniques. 0n the most general description of pulsed FT spectrometry, a sample is e,posed to an energi"ing event which causes a periodic response. The frequency of the periodic response, as governed by the field conditions in the spectrometer, is indicative of the measured properties of the analyte.

+xamples of pulsed ourier transform spectrometry

0n magnetic spectroscopy %86*, +2*', an *F pulse in a strong ambient magnetic field is used as the energi"ing event. This turns the magnetic particles at an angle to the ambient field, resulting in gyration. The gyrating spins then induce a periodic current in a detector coil. 8ach spin e,hibits a characteristic frequency of gyration %relative to the field strength' which reveals information about the analyte. 0n Fourier transform mass spectrometry, the energi"ing event is the in5ection of the charged sample into the strong electromagnetic field of a cyclotron. These particles travel in circles, inducing a current in a fi,ed coil on one point in their circle. 8ach traveling particle e,hibits a characteristic cyclotron frequency&field ratio revealing the masses in the sample.

ree induction decay

6ulsed FT spectrometry gives the advantage of requiring a single, time&dependent measurement which can easily deconvolute a set of similar but distinct signals. The resulting composite signal, is called a free induction decay, because typically the signal will decay due to inhomogeneities in sample frequency, or simply unrecoverable loss of signal due to entropic loss of the property being measured.

1tationary forms of Fourier transform spectrometers

0n addition to the scanning forms of Fourier transform spectrometers, there are a number of stationary or self&scanned forms.While the analysis of the interferometric output is similar to that of the typical scanning interferometer, significant differences apply, as shown in the published analyses. 1ome stationary forms retain the Fellgett multiple, advantage, and their use in the spectral region where detector noise limits apply is similar to the scanning forms of the FT1. 0n the photon&noise limited region, the application of stationary interferometers is dictated by specific consideration for the spectral region and the application.

Fellgett advantage
ne of the most important advantages of Fourier transform spectroscopy was shown by 6.(. Fellgett, an early advocate of the method. The Fellgett advantage, also !nown as the multiple, principle, states that when obtaining a spectrum when measurement noise is dominated by detector noise %which is independent of the power of radiation incident on the detector', a multiple, spectrometer such as a Fourier transform spectrometer will produce a relative improvement in signal&to&noise ratio, compared to an equivalent scanning monochromator, of the order of the square root of m, where m is the number of sample points comprising the spectrum. $owever if the detector is shot noise dominated, the noise will be proportional to the square root of the power, thus for a broad bo,car spectrum %continuous broadband source', the noise is proportional to the square root of m, thus precisely offset the Fellgett)s advantage. 1hot noise is the main reason Fourier Transform 1pectrometry was never popular for 9: and visible spectrum.

Converting spectra from time domain to frequency domain

The sum is performed over all contributing frequencies to give a signal 1%t' in the time domain.

gives non&"ero value when 1%t' contains a component that matches the oscillating function. *emember that

-s me