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Fourier-Transform Infrared Spectroscopy

(FTIR)
+Principles of the Fourier Transform Spectroscopy
+FTIR Spectrometer
Mostly based on:
Introductory Fourier Transform Spectroscopy
Robert John Bell
&
Michelson Interferometer
( ) r k t E E = e cos
0
c
k
t
e
t
u
2 2
1
~
= = =
( ) x t E E = u t e
~
2 cos
0
( )
1 0 1
~
2 cos x t E tr E = u t e q
X
1
/2
X
1
/2
o
1
2
(r,t)
( ) ( ) o u t e q + =
1 0 2
~
2 cos x t E tr E
( ) ( ) o u t u t e q
~
cos
~
2 cos 2
1 0 2 1
x t E tr E E E
R
= + =
( ) ( ) | | o u t u o
~
2 cos 1
~
) ( + = B i
Polychromatic source
( ) ( ) | | ( ) ( ) ( ) u o u t u u u u o u t u o
u u u
~ ~
2 cos
~ ~ ~ ~ ~
2 cos 1
~
) (
max max max
~
0
~
0
~
0
d B d B d B i
} } }
+ = + =
( )
}
=
max
~
0
~ ~
2 ) 0 (
u
u u d B i ( ) ( ) 0
2
1
~ ~
) (
max
~
0
i d B i = =
}
u
u u
3.0
2.5
2.0
1.5
1.0
0.5
0.0
i
(
o
)
-3 -2 -1 0 1 2 3
o
i()
i(0)
( ) ( ) u o u t u o o
u
~ ~
2 cos
~
) 0 (
2
1
) ( ) ( ) (
max
~
0
d B i i i i
}
= =
Consider a source of monochromatic wave:
2
E i
time
i The detector measures where
0
Fourier-Transform
( ) ( ) u o u t u o o
u
~ ~
2 cos
~
) 0 (
2
1
) ( ) ( ) (
max
~
0
d B i i i i
}
= =
( ) ( ) o o u t o u d i i B
~
2 cos ) 0 (
2
1
) (
~
0
}

=
FT
u
max

Two obvious technical difficulties:
1. The retardation o is always finite, o s o
max
Consequence: Signal (in frequency space) appears convoluted with an Instrumental
Line Shape (ILS) function Limits the measuring resolution
Solution: Apodization
2. The zero retardation o =0 (ZPD) is needed for calculating the spectrum
Consequence: Asymmetry of the interferogram, phase error
Solution: Double-sided interferogram
( ) ( ) ( ) u o
u o
~
) ( ) (
~
2 2 ~
B f B t Volt t i i
scanner v scanner
V f FFT Detector t V

= =
The FTIR spectrometer:
Bruker 113v/IR98
Advantages of the FTIR spectrometer
mmrc.caltech.edu/FTIR/FTIRintro.pdf
http://www.thermo.com/eThermo/CMA/PDFs/Product/productPDF_21615.pdf
Important Properties of Fourier-Transform
( )
}


= dx e x f g
x iu t
u
~
2
) (
~
( )
}



= u u
u t ~ ~
) (
~
2
d e g x f
x i
( ) ( ) ( )
} }


+ = dx x x f i dx x x f g u t u t u
~
2 sin ) (
~
2 cos ) (
~
( ) ( ) ( ) ( )
} }


= u u t u u u t u
~ ~
2 sin
~ ~ ~
2 cos
~
) ( d x g i d x g x f
1. If f(x) is even (f(x)=f(-x) ) FT(f(x)) is real and even
If f(x) is odd (f(x)=-f(-x) ) FT(f(x)) is imaginary and odd
http://dagsaw.sdsu.edu
Convolution: ( ) ( ) ( ) t t t d t g f t g t f = -
}


) (
2. Convolution Theorem: The FT of the product of two function is the convolution of their individual FTs
( )
( )
( ) ( ) ( ) ) ( ) ( ) ( ) (
) ( ) (
) ( ) (
t g FT t f FT t g t f FT
t g FT t g
t f FT t f
- =
)
`

( ) ( ) o u t u o
~
2 cos
~
) ( = B i
FT
o
max
( ) ( ) ( ) o o u t o u d i B
}


=
~
2 cos
~
-o
max
( ) ( ) ( ) ( ) ) ( ) ( ) (
~
2 cos
~
o o o o o u t o u H H =
}


i FT d i B
H(x)=
1 if -o
max
s o s o
max
0 if , o , > o
max
Finite retardation Multiplication of the real
space interferogramwith a boxcar function
4
3
2
1
0
-4 -2 0 2 4
1.0
0.0
-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
4
3
2
1
0
-1
A
m
p
l
i
t
.
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
Freq.
( ) ( ) o u t u o
1 1
~
2 cos
~
) ( = B i
FT
( ) ( ) ( ) )
~
(
~
2 cos
~
1 1 1
u o o u t o u A = =
}


d i B
( ) ( ) ( ) ( ) )
~
(
~
) (
~
2 cos
~
1 1
u u o o o u t o u G B d i B - = H =
}


Finite retardation the real spectrum is the true spectrum B(u
1
) convoluted with the ILS
Monochromatic radiation of frequency u
1
:
H(x)=
1 if -o
max
s o s o
max
0 if , o , > o
max
FT
( )
max max
~
2 sin 2 )
~
( o u t o u c G =
1.0
0.0
-5 -4 -3 -2 -1 0 1 2 3 4 5
4
3
2
1
0
-5 -4 -3 -2 -1 0 1 2 3 4 5
v
1
1/(2o
max
)
v
1
+1/(2o
max
)
v
1
u
1
=3
Instrumental Line Shape (ILS)
1.0
0.5
0.0
-5 -4 -3 -2 -1 0 1 2 3 4 5
2o
max
1/o
max
0.605/o
max
o
max
=0.5
ILS
Broadening of the spectral line
( ) ( ) ( ) | |
max 1 1 max
~ ~
sin
~
2
~
o u u u o u = c B B
Delta Function
4
3
2
1
0
5.0 4.5 4.0 3.5 3.0 2.5 2.0
The resolution of an instrument:
Two adjacent lines of equal intensity, having sinc
2
(x) shape, are resolved
when the center of one line coincides with the first zero of the other
1 Rayleigh criterion :
Intuitively, the resolution Au
min
=1/o
max
2. FWHH criterion: Two triangularly shaped lines of equal intensity are resolved when the
spacing between lines is grater than the FWHH of either line.
6
5
4
3
2
1
0
-1
6 5 4 3 2 1 0
0.5/o
max
1.0
0.0
6 5 4 3 2 1 0
v
6
5
4
3
2
1
0
-1
6 5 4 3 2 1 0
0.73/o
max
1.0
0.0
6 5 4 3 2 1 0
v
Apodization
If we use the triangular function A(x) instead of the boxcar function H(x) ILS sinc
2
(x)
2.0
1.0
0.0
-4 -3 -2 -1 0 1 2 3 4
1.0
0.0
-2 -1 0 1 2
1.0
0.0
-4 -3 -2 -1 0 1 2 3 4
o
max
0.88/o
max
2/o
max
1.0
0.5
0.0
-5 -4 -3 -2 -1 0 1 2 3 4 5
2o
max
1/o
max
0.605/o
max
Other Apodization Functions:
Particularly common in FTIR spectrometers:
Happ-Genzel
Sampling Phase Errors & Two-Side Interferogram
( ) | | ( ) o o u t o u d i i B
~
2 cos ) ( ) (
~
0
}

=
Phase errors may arrive from misalignments of the interferometer (optical effects), from filters
(electronic effects) and/or from sampling errors
Lets assume that the ZPD is not correctly determined:
c o o = = 0 ) ( ) ( c o o i i

( ) | | ( ) o o u t c o u d i i B
meas
~
2 cos ) ( ) (
~
0
}

=
The effect: ( ) ( ) ( ) c u t u u
~
2 exp
~ ~
i B B
meas
=
Consider the complex FT on both sides of o=0, from -o
max
to o
max
:
( ) | | ( ) o o u t c o u d i i i B
meas
~
2 exp ) ( ) (
~
}


=
Compute both real (cos) part, C(u), and imaginary (sine) part, S(u) of the FT:
( ) ( ) ( ) ( ) u u u u
~ ~ ~ ~ 2 2
B S C B
meas
= + =

Mathematical proof for phase correction : TO BE ADDED


Sampling interval
Nyquist Criterion: The sampling frequency (wavenumber) should be equal or larger than
twice the highest measured frequency (wavenumber).
The effect of undersampling is aliasing, or folding:
max
2 f f
samp
>
http://zone.ni.com/devzone/cda/tut/p/id/5509
f
f
f f f f f
f
f
samp
real samp imag samp
samp
real
A = = < A + =
2 2
alias
FTIR Spectrometer:
( ) ( ) o u t u o
~
2 cos
~
) ( = B i
( ) ( ) ( ) u o
u o ~
) (
~
2 2 ~
B f B t i i
scanner v scanner
V f FFT t V

= =
( ) ( ) t V B t i
scanner
= 2
~
2 cos
~
) ( u t u
( ) ( ) t f E t E t E = = t e 2 cos cos ) (
0 0
u
u
~
2 ~ =
scanner
V f
(

=
(


cm s
cm
s
Hz
1 1
It is better to sample equal intervals of retardation (Au) rather than equal intervals of time (At)
If we want to measure up to max
~
u
( )
( )
max
max max max max
~
2 2
1
~
2 2
~
2
~
u
u u u

= A = =
scanner
samp scanner samp
Nyquist
scanner
V
t V f V f
( )
| |
| |
1
max
2
max
~
2
1
~
2 2
1

A = A
= A

= A
cm
cm
V
t
samp
t V
scanner
samp
scanner
u
o
u
o
The Scanning Process & Duty Cycle Efficiency
V
s
c
a
n
n
e
r
time
Duty Cycle Efficiency =
cycle whole a of Time
measured is ram interferog while Time
When the interferograms are sampled
coherently, i.e. between same retardation limits
around ZPD:
) (N Scans of Number Signal
scans

) (N Scans of Number Noise


scans

The noise varies continuously (randomly) with


time, it is not expected to have the scanning cycle
periodicity
scans
N SNR
Different flavors of scanning cycles:
+Rapid-Scan Interferometer
+Step-Scan Interferometer
Requirements:
Data collection needs to start at the same retardation from the ZPD each cycle
Sampling needs to take place at the same retardations each cycle
t V
scanner
= 2 o
http://www.chem.uic.edu/tak/chem524/notes16/figureIR_3.gif
( ) ( ) ( ) u o
u o ~
) (
~
2 2 ~
B f B t i i
scanner v scanner
V f FFT t V

= =
How the interferogramis sampled or why we need He-Ne laser and white light ?
The He-Ne frequency sets the sampling frequency (for one sample/cycle):
1
15800
~ ~

= cm
samp Ne He
u u
1
max max
7900
~
5 . 0
~
= = cm u u
The white light determines when the first data point is taken (t=0), i.e. initiates data collection
V
trig
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-4 -2 0 2 4
Initiate
Data Collection
White Light
He-Ne
IR
time
Sub-sequential data collection is triggered by the zero crossings of the He-Ne laser interferogram
| |
Ne He scanner Ne He
V Hz f

= u
~
2
Example:
1
3 . 0 2

= s cm V
scanner
KHz f
Ne He
74 . 4 15800 3 . 0 = =

(This is how OPUS labels scanner velocity)


V
trig
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-4 -2 0 2 4
Initiate
Data Collection
White Light
He-Ne
IR
time
The sampling electronics (ADC board) starts measuring when a thresold signal V
trig
is detected
It is important that the white light interferogramoccurs before the IR interferogram
DAQ can only take place when scanning mirror moves in one direction
single-sided interferogramand poor duty cycle efficiency
Position of the white light interferogrammust remain constant and cannot be adjusted with
maximum retardation
How is the phase correction achieved? To be discussed