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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 mid infrared extends from 4,000 to 200 cm-1. This region is
usually composed of characteristic bond frequencies or normal
modes of molecules.
10.2 : 2/22
Measurement Difficulties
PN = 4kT f
for f = 1 Hz and T = 298 K
PN = 828 cm-1
10.2 : 3/22
Spectrometer Optical Throughput
f/# 1 2 5 10 20
percent 6.2 1.5 0.25 0.06 0.02
10.2 : 4/22
Impossibility of a t f Transform
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
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)
10.2 : 8/22
Optical Autocorrelator (2)
0.25 + 0.25cos(2)
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
10.2 : 11/22
Mirror Movement & Data Collection
electromagnetic solenoid
laser
@ 0.6328 m white
-1
15,802 cm light "frictionless"
the range of motion is determined air bearing
10.2 : 12/22
Measuring
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
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
0 8 4 2 1 0.1
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
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
10.2 : 21/22
Original Drivers for FTIR
10.2 : 22/22