16.

3 Fourier Transform
Infrared (FTIR)
• FTIR uses the Fourier integral to compute
a spectrum from a spatial cosine
• a Michelson interferometer is used to
measure spatial cosines, utilizing distant-
dependent interference at the detector
• the interferometer consists of a beam
splitter, a fixed mirror, and a moving mirror
• spectral resolution depends upon how far
the mirror is moved
• FTIR can be used to obtain spectra quickly
or with a high signal-to-noise ratio
16.3 : 1/11
 Time-to-Frequency Transform

The Fourier transform is an integral that can be used to interconvert

two ________________ that describe a wave. For a wave given by
cos(2πft), the two variables are time and frequency. The goal is to
compute a spectrum, φ(f), by measuring the temporal response,
F(t).

The spectrum is computed using the Fourier integral,

∞
− j 2π f t
φ( f ) = ∫ F (t ) e dt
−∞

where exp(-j2πft) is a complex wave. To obtain the spectrum, the

signal is digitized to obtain F(t). Then the complex integral is
evaluated ______________.

This procedure is used in nuclear magnetic resonance and mass

spectrometry where signals are in the megahertz to kilohertz
domain. Unfortunately, infrared frequencies range from 7.5×1012 to
1.2×1014 Hz, which are too _____ to follow with today's electronics.
16.3 : 2/11
 Distance-to-Wave Number Transform

An infrared wave can be written in an alternative form using the

conjugate variables _______ and ___________, cos ( 2π vx ) .
∞
φ (v ) = ∫ F ( x ) e − j 2π vx dx
−∞

The integral is solved using the same computer program as that

used for f and t. The program has no knowledge of the physical
nature of the variable, it works on vectors of unitless numbers.
To obtain a spectrum, the signal is digitized to obtain F(x).

The infrared spectrum from 4,000 - 250 cm-1 corresponds to

wavelengths from 2.5 - 40 μm. These wavelengths are easy to
measure - the trick is figuring out how to "stop" the wave from
moving!

The wave is stopped using an _______________. By using two

mirrors, one fixed and one moving, the spatially dependent
amplitude is reproduced at the detector due to interference.

16.3 : 3/11
 The Michelson Interferometer
fixed mirror
Light from the source is collimated and movable
directed to a beam splitter. Half the light mirror

is reflected to the fixed mirror and half source

transmitted to the moving mirror. Light
returning from each of the two mirrors is
again split, with half returning to the beam
source and half passing through the splitter
sample
sample to the detector. The extent of
interference between the two beams
depends upon the ___________ in the detector
two interferometer path lengths.
When the two paths differ by an ____________ of wavelengths, the
detector sees a large signal. When the two paths differ by an odd
number of ______ wavelengths, the detector sees no signal. As a
result, every frequency of the source is converted into an offset
cosine at the output of the detector.

The detector output is digitized and transformed numerically.

16.3 : 4/11
 Interference at the Detector (1)

Source output is cos(2πx/λ), where λ = 4 μm. Delay is in μm.

delay = 0 avg = 0.125 delay = 1 avg = 0.0625

0.5 0.5

con ( xi) con ( xi)

var ( xi , f) 0 var ( xi , f) 0
sum ( xi) sum ( xi)

0.5 0.5
0 2 4 6 8 0 2 4 6 8
xi xi

0.2 0.2
avg
sum ( xi) sum ( xi)
2 2
0.1 0.1 avg

0 0
0 2 4 6 8 0 2 4 6 8
xi xi

16.3 : 5/11
 Interference at the Detector (2)

Source output is cos(2πx/λ), where λ = 4 μm. Delay is in μm.

delay = 2 avg = 0 delay = 3 avg = 0.0625

0.5 0.5

con ( xi) con ( xi)

var ( xi , f) 0 var ( xi , f) 0
sum ( xi) sum ( xi)

0.5 0.5
0 2 4 6 8 0 2 4 6 8
xi xi

0.2 0.2

sum ( xi) sum ( xi)

2 2
0.1 0.1 avg

avg
0 0
0 2 4 6 8 0 2 4 6 8
xi xi

16.3 : 6/11
 Interference at the Detector (3)

Source output is cos(2πx/λ), where λ = 4 μm. Delay is in μm.

delay = 4 avg = 0.125

0.5 detector output: average versus delay
0.13
con ( xi)

var ( xi , f) 0 signal0.063
sum ( xi)

0
0.5 0 2 4 6 8
0 2 4 6 8
delay
x
xi

0.2 Every source wavelength

avg produces an offset cosine at
sum ( xi) the detector. The offset
2
0.1
cosine has the same
0
wavelength as the source.
0 2 4 6 8
xi

16.3 : 7/11
 FTIR Spectrophotometer

mirror piston
with air bearing

• without the aperture the _______

_______ would determine spectral
movable
mirror
resolution source

resolution controlling
aperture
beam
splitter
• the optical filters are used to
eliminate ________, since the data optical
filter
are processed by an ADC fixed
mirror
• to calculate T or A, the reference
and sample are alternately
examined by the use of mirrors TGS pyroelectric
mirrors flip 90 deg
between sample
• since infrared radiation cannot be detector and reference

seen with the eye, the reference

spectrometer includes a visible

collimated
white

alignment beam
alignment
light

mirror swings
out of the way
for alignment
sample

16.3 : 8/11
 Mirror Movement and Data Collection

• the mirror is supported by a piston

travel

"frictionless" ________ and driven

back and forth by a solenoid electromagnetic

• the range of motion is

solenoid driver
helium:neon

determined by the two

single-frequency
laser
@ 0.6328 μm white
LED/photodiode pairs 15,802 cm -1 light "frictionless"
air bearing
• zero distance difference is
determined by the ___________ visible beam splitter
made from two prisms fixed
visible
interferogram on the backside of mirror
start of travel
transducer
the moving mirror
• mirror displacement is
position indicating
photodiode detectors paddle

determined by the ________ end of travel

transducer
interferogram
• data are collected every peak of moving
visible
the laser cosine, of which there are mirror mirror
travel

15,802 peaks per cm

• the highest frequency that is not moving to infrared

aliased is 15,802/2 = 7,901 cm-1

infrared infrared beam splitter
mirror beam

16.3 : 9/11
 Effect of Mirror Movement

The mirror velocity (cm/sec) is adjusted so that the He:Ne laser

reference cosine is reproduced at 5 kHz. This makes 3,500 cm-1
occur at 1.11 kHz and 250 cm-1 occur at 79 Hz. Low pass
electronic filters can be used prior to the ADC to increase the
signal-to-noise ratio of the detector output.

Spectral resolution of a Michelson interferometer depends upon

the maximum difference between the two interferometer paths,
ν = 1/Δx. Because light makes a round trip between the beam
splitter and the mirror, Δx is twice the mirror movement.

mirror movement (cm) 0.05 0.5 5.0

spectral resolution (cm-1) ____ ____ ____

Because the measurement abruptly starts and ends, absorption

bands have the intrinsic shape of a sinc function. Most
instruments use a mathematical procedure called apodizing to
convert the oscillatory sinc shape into smoother-looking peak.

16.3 : 10/11
 Why FTIR?

The FTIR obtains spectra, (1) with a higher signal-to-noise ratio

than possible with scanning spectrometers, or, (2) faster than
possible with scanning spectrometers.

High resolution grating monochromators have ________ f-numbers,

whereas Michelson interferometers have ____ f-numbers. This
permits more light to reach the detector.

Because the interferometer observes all of the frequencies all the

time, one spectrum can be obtained much faster than a scanning
instrument.

Rapid data collection can obviously be used for applications like

__________ where the chromatographic peaks are only present for
short periods of time.

Rapid data collection can also be used to average many spectra and
obtain a higher signal-to-noise ratio.

16.3 : 11/11