168 FOURIER TRANSFORM SPECTROSCOPY ABorghest Dipartimento di Psica “A Volts dell Univesith ¢ Unita GNSM-CISM, Via Basi 6, 27100 Pavia, Italy. 1. INTRODUCTION Fourier Transform (FT) Infrared Spectroscopy, also_known as interferometric spectroscopy, is based on the principle of the interferometer developed by Michelson in 1880. In this spectroscopy, the electromagnetic radiation emitted from the source ( Fig 1) "A jeu Fig Schematics of a Michelson interferometer used in spectroscopy. {s collected by a collimator mirror, and directed to a device called beam-spliter (©/s) which divides the ight in two beams with the same intensity which are reflected by flat mirrors £ and F. On b/s, the two partial beams recombine and the resulting radiation is focused by R on detector D. In spectrofotometric applications, the saniple i usually placed un position SCD. ‘The intensity of the radiation reaching the detector versus the difference of the ‘optical path (obtained by the movement of one mirror with respect to the other) represents the interferogram of the radiation emitted by the source: Michelson was the first to demonstrate that the inverse Fourier transform CFT) of the interferogram coincides with the spectrum of the radiation emitted from the source. ‘The disadvantage of Fourier spectroscopy lies in the difficulty of expressing the interferogram in an analytical form. In fact the spectrum is ‘obtained by analytically IFT of the interferogram only in the simplest cases Given this dificlty following the pioneering efforts by Rubens and Wood(®), interferometric spectroscopy was not further considered until 1950 sehen Sitong’s group) decided to Study its fundamental aspects ard develop application ‘in 1965, Cooley and Tukey (8 were able to optimize the calculations of the IFT ofthe interferogram using a digital computer. In this case, the interferogram. recorded by the detector is sampled, and the values, converted into digital form and computed, yield the spectrum of the source. 169 eT coer a a ats a tas ea eee ne nee Free cie mire cee orig ae eee teres toe ee re oo ata dca age se aay comer eee aee eee EP eat i ee he hol = SE ean parent tna mn Sie aee es oe ernie nrese es Saewe o,2) = Eafe) ex ilat— 2002) ‘The b/s of the interferometer, which is assumed to be perfect, divides the field in two halves: i) the field E1, which is reflected by b/s toward the fixed mirror E and ii) the transmitted field Ez, which passes through the b/s and reaches the ‘movable mirror F. ‘As can be seen in Fig, the two electric fields, after having traveled optical paths Zy and Za respectively, recombine on b/s. Therefore, the field resulting from the interference of Ey and E2 can be written | exp|lot~ Bron) + explilet—280m))) ‘rand tare the reflection and transmission coefficients, which represent the effect ‘of b/s on the light rays. The detector measures the mean energy of radiation per unit area and per ‘unit time, expressed for each wavelength by suum) = EGER md ERC ae) @ where ¢ represents the velocity of light in a vacuum while‘ is the dielectric constant of a vacuum. Combining (1) and (2), we obtain Balen.) = Pe BSLeH(2 + exe ltmle ne} + exp[-2eilen— 2} or if we indicate the optical path difference between two waves withthe variable bemnn Balos8) = ect? E(t + con(2re] @170 In the case of a on-monochromatc point source, the total power of the radiation incidenton the detector Jg(4) is expressed by the integral Of equation @) 8 [> eal +caltaed)lae @ where 1/3 isa normalization factor. Equation (3) is clearly constituted of two parts, representing a constant and a variable component. Since it is easier for the detector to convert the variable component of the Juminous intensity into an electric signal than the constant component (which is not essential), we will define an interferogram to be the function #(4) expressed by 6) = Sine? [tay condeobto a Given me) = “501 te inteterogram ofthe source becomes ° ‘with the constant x = 28 In passing to complex fornalism and considering that fe} ~ B(-e) equation (5) becomes ney= x [Beene o i.e the interferogram is Fourier transform ofthe spectrum emitted by the source, ‘Analogously we can express the source spectrum as a function of the interferogram, ie. Bie = « [FNC mde = HP) o i.e. the spectrum is the inverse Fourier transform of the interferogram. Equations (6, 7) are fundamental permitting us to determine the spectrum of the source from the interferogram (é) , by calculating the integral (7) for every wavenumber m 2. EXAMPLES It can be useful to consider equations (6,7) in relation toa few simple cases. Example 1. ‘We will first examine the case in which the source is ideally monochromatic, $0 thatthe spectrum is equal to He) = 1 6te—o) +6100) where 1/2 is a normalization factor and. &'() is Dirac delta function, Satisfying the normalization conditions [ 8 (e te0)de = 1 (One should recall that the function B(¢) 1s defined for both positive and negative wavenumbers and is symmetric with respect tothe variable @ ‘Ale/Ne laser is an example of a monochromatic source. Its normally utilized in FT spectrometers to sample the interferogram, emitting a radiation with ‘wavelength ty = 6928 wm and wavenumber ey = 1/e = 15800 emt “The interferogram of this source is obtained by Fourier transforming the spectrum Ble) ref ml [6 e =e) +6'(e +eul]emhde = con(2eo96) 8) ‘The interferogram is represented by a cosine function of | § , with a period 4 and with constant amplitude as shown in Fig.2, “| 2) “ANNAN >) os o 0 g Fig? (a)Spectrum of a monochromatic source and (b) its interferogram. Example 2 Now let's suppose that the source consists of two monochromatic lines, both ‘with unit amplitude and wavenumbers ey and oy respectively (Fig:3a) with aaam ble) = He (exes) +6100] while the interferogram is 1) = Ef Wee) 46 eaenjemtte = realest) nearer +5] @) In this way, the interferogram is a cosine function of & , modulated in amplitude witha frequency v= § (Fig3b), depending on the distance d between the two spectral ines. vid Fig3_(@) Spectrum of two monochromatic lines and (b) thelr respective interferogram. When the source has a broad band spectrum we must Fourier transform all the different monochromatic contributions, each of which is represented by Dirac’s function. We can suppose, in this case, that the interferogram is an overlapping of cosine functions having different wavenumbers, which interfere among themselves, producing a central high peak at_$=0 with exponentially decreasing amplitude oscillations, as shown in Fig. In general itis difficult to obtain F(8 in an analytical form, it is therefore not possible to obtain the spectrum Ble) by analytically transforming the interferogram. It is alveays possible to obtain the spectrum of a source from an experimental interferogram, by a simmetrical inverse Fourier transform with a digital computer, “ » i ee 6 Fig (@) Broad band spectrum and (b) corresponding interlerogram, 18 3. APODIZATION Previously we derived equations (6) and (7), which relate the source spectrum to the interferogram, assuming that the optical path difference between the two beams is known from - c to too . In fact the movable mirror of the interferometer has limited displacement for example from L to L), which limits the acquired values of interferogram to the interval -L, +L, while they are zero ‘outside this interval, as shown in Fig.5. The spectrum 3;(e) obtained by inverse Fourier trasforming this limited interferogram will be: aie) = [/roemetas Cr) F(8) F(9) 6 6 Fig (a) Ideal interferogram and () interferogram limited to interval (1) This instrumental spectrum B,(0) does not coincide with the ideal spectrum B(e) which is obtained by inverse Fourier transforming the unlimited interferogram on the entire Saxis. ‘Now we will examine the differences between the spectra Bye) and B,(e) First, let's consider the case of an interferogram which is presented. as a periodic function of the optical path difference Le. F(0)~se(3rei). I we eumpute the inverse Fourier transform of this interferogram, keeping in mind the limited displacement L of the interferometer, the instrumental spectrum is equal to er = fetuses =} fetes nas} [le Since * afro segnee = iB tODH «santos Bele dei) where = sinelaefo +03)t]