10.

2 Fourier Transform
Infrared Spectroscopy
overview of the infrared including measurement
difficulties
spectrometer throughput
instead of a t f transform use an x transform
introduction to the Michelson interferometer, and its
behavior as an optical autocorrelator
block diagram of an FTIR spectrometer, including details
of mirror movement and controlling when the ADC takes
data
example far infrared spectrum of K2ReCl6
optical resolution including an example of gas-phase
ammonia
apodization to eliminate sinc function oscillations
overall signal-to-noise enhancement that can be expected
historic types of measurements that drove the
development of FTIR
10.2 : 1/22
 Overview of the Infrared

The highest frequency vibration is the H2 stretching motion which

occurs at 4,400 cm-1. Although this transition is not infrared
active (it is Raman active), ~4,000 cm-1 is usually taken to be the
upper limit of the infrared. The lower limit is determined by
instrumental considerations and is often near 50 cm-1.

The mid infrared extends from 4,000 to 200 cm-1. This region is
usually composed of characteristic bond frequencies or normal
modes of molecules.

The far infrared extends from 200 to 50 cm-1. This region is

usually composed of characteristic metal bond frequencies, or
normal modes of large molecules. The end of the range overlaps
with high energy rotations.

The resolution of spectra depends upon their use. Solution phase

spectra are usually taken with bandwidths of 5-10 cm-1, while gas
phase spectra of small molecules usually require a bandwidth of
0.1 cm-1.

10.2 : 2/22
 Measurement Difficulties

infrared photons are difficult to distinguish from thermal noise,

with the result that the measurement is detector noise limited

PN = 4kT f
for f = 1 Hz and T = 298 K
PN = 828 cm-1

infrared transitions have very low molar absorptivities,

~ 1 L mol-1 cm-1, requiring high concentrations to obtain a
reasonable level of absorption
high resolution spectrometers have a very low optical
throughput, which limits the signal-to-noise ratio of the
absorption measurement
the experiment would benefit enormously from multiplexed
detection

10.2 : 3/22
 Spectrometer Optical Throughput

The standard measure of optical collection efficiency is the f/#

(pronounced f-number). An f/# is the focal length of a lens or
mirror, divided by the diameter of the lens or mirror. Collection
efficiency is inversely proportional to the square of the f/#.

f/# 1 2 5 10 20
percent 6.2 1.5 0.25 0.06 0.02

A grating or prism bends different wavelengths at different angles.

To obtain high resolution the wavelengths are separated by moving
as far as possible away from the focusing lens or mirror. That is,
long focal lengths are required.

It is very difficult to construct a grating or prism monochromator

with a low f/# because the size of the grating or prism would need
to increase in proportion to the focal length. Large gratings and
prisms are either impossible to manufacture or are very expensive.
A typical f/# for a 0.1 cm-1 resolution grating spectrometer is 12,
which is about a 0.05% throughput.

10.2 : 4/22
 Impossibility of a t f Transform

To obtain an infrared spectrum via a Fourier transform, the signal

would be recorded (digitized) as a function of time to obtain F(t).
Then the spectrum would be computed using the following
expression,

( f ) = F (t )e i 2 ft dt

This will not work in the infrared because the frequencies are too
fast. An infrared spectrum has frequencies from 1.21014 Hz
(4,000 cm-1) to 6.01012 Hz (200 cm-1). The fastest electronic
temporal resolution with commercial instrumentation is 710-12 s
or ~840-42 times too slow.

10.2 : 5/22
 Possibility of an x Transform

Fortunately, an infrared wave can be written in an alternative

form using distance and wave number, where = 1/.
x
cos 2 = cos(2x)

The Fourier transform equation takes the same form, simply
exchanging for f and x for t. It is numerically solved using the
same computer program as that used for t to f transforms.

( ) = F ( x)e i 2 x dx

The infrared spectral range from 4,000 cm-1 to 250 cm-1

corresponds to wavelengths of 2.5 m to 40 m. These lengths
are easy to measure, all one has to do if figure out how to "stop"
the wave from moving!

10.2 : 6/22
 The Michelson Interferometer
light from an infrared source is
fixed mirror
collimated and directed to a beam movable
splitter mirror
at the beam splitter, half is reflected
source
toward the fixed mirror and half is
transmitted toward the movable mirror
when light reaches each mirror it is
beam
reflected back to the beam splitter splitter
at the beam splitter, half the light sample
from the fixed mirror is reflected back
to the source and half is transmitted to
the detector detector

at the beam splitter, half the light from the movable mirror is
transmitted back to the source and half is reflected to the detector
half the light reaches the detector, 0.25 from each path
light of every wavelength is always traveling through the sample to
the detector (multiplexed)
an interferogram is obtained by moving the mirror and measuring
the resultant intensity at the detector

10.2 : 7/22
 Optical Autocorrelator (1)

Light traveling toward the detector can be described as the sum of

two cosines,
1 1
cos(2x) + cos(2[ x + ])
2 2

where is the extra distance (nearer or farther) traveled by light

along the path involving the movable mirror.

moving the mirror a distance /2 farther from the beam splitter

delays light by the distance +.
the beam splitter divides intensity, not amplitude. Thus, 1/4 of
the total photons reach the detector from each path. This
corresponds to 1/2 the amplitude from each path.
the detector responds to intensity, which is the square of the
electric field.

10.2 : 8/22
 Optical Autocorrelator (2)

Although the detector output is averaged as a function of time,

determination of a functional form for the signal requires that
integration be over distance. In the FTIR instrument the optical
signal (square of the amplitude) is averaged for 100 s or longer.
This corresponds to averaging the waveform over a distance of
x0 = 3104 meters.
x0
1 2
( 0.5cos(2 vx ) + 0.5cos(2 v ( x + )) ) dx
x0
0

Expansion of the square yields three integrals.

x0 x0 x0
0.25 0.25 0.50
cos ( 2 ( x + ) )
2
cos(2x)cos ( 2 ( x + ) ) dx
2
x0 cos(2 x ) dx +
x0
dx +
x0
0 0 0

By letting x0 , the first two integrals each reduce to 0.125.

x0
0.50
0.125 + 0.125 +
x0 cos(2x) cos ( 2 ( x + ) ) dx
0
10.2 : 9/22
 Optical Autocorrelator (3)

The third integral on the previous slide is the autocorrelation function,

x0
1
C1,1 ( ) = cos(2x) cos(2 ( x + ))dx
x0
0
C1,1 ( ) = 0.5cos(2)

where Fourier transforms were used to evaluate the integral. The

detector output is then given by C1,1() plus the dc offset.

0.25 + 0.25cos(2)

As the mirror is moved, the output of the detector will be an offset

cosine. Each individual wavelength of light will have its own offset
cosine. These offset cosines are added together in the detector
output. As the mirror is moved the output of the detector is
digitized with sufficient resolution to reproduce all optical
wavelengths. After collecting the data a Fourier transform is
computed to extract the spectrum - amplitude versus .
10.2 : 10/22
 Instrument Block Diagram

source/aperture
the aperture controls the maximum mirror piston
with air bearing

possible resolution
optical filters minimize aliasing of movable

non-infrared radiation
mirror
resolution source
controlling
aperture beam
splitter

sample chamber optical

filter
has a sample and reference so that fixed
mirror

transmission can be computed

the collimated white light source is
mirrors flip 90 deg
used to align the sample and reference TGS pyroelectric
detector
between sample
and reference

with the infrared beam reference

collimated
white
alignment
detector light

output is electronically amplified

electronically low pass filtered mirror swings
out of the way
digitized at specified mirror for alignment
sample
displacements from zero

10.2 : 11/22
 Mirror Movement & Data Collection

mirror design piston

travel

supported by a near frictionless air

bearing electromagnetic
solenoid driver

driven back and forth by an helium:neon

single-frequency

electromagnetic solenoid
laser
@ 0.6328 m white
-1
15,802 cm light "frictionless"
the range of motion is determined air bearing

by two light emitting visible beam splitter

fixed
made from two prisms
diode/photodiode pairs visible
mirror
start of travel

when the position paddle transducer

interrupts the travel transducers,

position indicating
photodiode detectors paddle

the polarity of the electromagnet is end of travel

transducer
changed and the mirror travel
direction changes moving
visible
mirror
zero delay is about where the
mirror
travel

"position paddle" is shown

moving to infrared
infrared infrared beam splitter
mirror beam

10.2 : 12/22
 Measuring

zero delay determination

determined by white light and a visible interferometer constructed
on the backside of the moving mirror
the interferogram of white light is a "spike" when the delay is zero
an electronic circuit monitoring the output of the white light
photodiode can easily detect this spike
the fixed visible mirror is factory adjusted so that zero delay with
the white light beam corresponds to zero delay with the infrared
beam in the infrared interferometer

distance determination
distance is measured by single frequency light from a He:Ne laser
the wavelength of the laser is 0.6328 m, meaning that the output
of the photodiode is an offset cosine with a maximum every
0.6328 m
the analog-to-digital converter is set so that it only takes data
whenever the He:Ne cosine is at a maximum

10.2 : 13/22
 Analog-to-Digital Conversion
mirror velocity
since the velocity of the mirror can be experimentally controlled,
the apparent frequency of the cosine can be controlled to match
the speed of the detector electronics
in this instrument the mirror velocity is adjusted to make the
He:Ne laser produce a 5 kHz cosine at the detector
the highest un-aliased frequency that can be measured by
sampling every peak of the cosine is 15,802/2 = 7,901 cm-1
the spectrum then appears at frequencies from 2.5 kHz to dc

undersampling
since the upper end of the infrared spectrum is near 4,000 cm-1,
lower digitizing rates can be used - this is called under sampling
for the far infrared the data will be under sampled by 16 to
produce a highest optical frequency of 493.8 cm-1 corresponding
to a 313 Hz
for a fixed resolution, under sampling decreases the size of the
data set that needs to be numerically processed
under sampling permits the use of low pass filters with lower
f3dB frequencies, thus a better SNR
10.2 : 14/22
 Example Data: Infrared Source

The two figures below show the source (reference) interferogram

(distance vs. amplitude) and the spectrum (frequency vs. amplitude).

10.2 : 15/22
 Example Data: K2ReCl6

The three figures below show the sample interferogram, the sample
intensity, and the sample transmission. The very sharp line at
~375 cm-1 is aliasing of an electric interference. The 330 cm-1 band
is the Re-Cl stretch and the 180 cm-1 band is a Cl-Re-Cl bend. The
peak at 80 cm-1 is an artifact due to low source intensity.

10.2 : 16/22
 Optical Resolution

Consider a cosine signal. The process of digitizing the

interferogram involves starting and stopping, thus the cosine is
multiplied by a rectangle with width 0. The result is convolution
by a sinc function (with 0 = 1/0 ).

0 8 4 2 1 0.1

0 (cm) 0.125 0.25 0.5 1 10

mirror
0.0625 0.125 0.25 0.5 5
(cm)

The spectral resolution (bandpass) depends only upon how far the
mirror is moved!

10.2 : 17/22
 Gas-Phase Ammonia Spectrum (1)

10.2 : 18/22
 Gas-Phase Ammonia Spectrum (2)

10.2 : 19/22
 Apodization

effect of abruptly starting and stopping the mirror movement

the process of starting and stopping the digitization of the cosine
produces a spectrum convolved with a sinc function
a sinc function is said to have "feet," and the feet often make
spectral interpretation difficult
apodization is literally "no feet making," and involves
multiplication of the collected data by some function other than a
rectangle

apodization functions
when computers were slow and had little memory, simple
functions were used for apodization, i.e. trapezoid and triangle
with modern computers any desirable function can be used, e.g.
Gaussian or exponential
note that apodization will decrease resolution via convolution
with the spectral peaks

10.2 : 20/22
 Signal-to-Noise Enhancement

multiplexing (Fellgett advantage)

0.1 cm-1 resolution: 3,500 400
decrease in measurement time: = 31,000
0.1
increase in SNR: 31,000 = ~ 176
5 cm-1 resolution 3,500 400
decrease in measurement time: = 620
5
increase in SNR: 620 = 25
optical throughput (Jacquinot advantage)
0.1 cm-1 resolution
scanning f/# = ~12 for ~0.05% throughput
interferometer f/# = ~1 for ~6.2% throughput
result = 124 more light reaches the detector
5 cm-1 resolution
scanning f/# = ~5 for 0.25% throughput
result = 25 more light reaches the detector

sum of the two advantages

0.1 cm-1 resolution = 21,824
5 cm-1 resolution = 625

10.2 : 21/22
 Original Drivers for FTIR

low concentrations (large amount of light on the detector, allows

precise measurement of transmission)
high resolution spectra (large mirror movement)
unstable or transient species (fast measurement time)
gas chromatography detector (fast measurement time)
mixture spectra using Beer's Law (a precise transmission allows
a precise absorption)
far infrared spectra (interferometer instead of grating - tough to
rule appropriate gratings)
high sample throughput (fast measurement time)

10.2 : 22/22