Lecture V

Infrared (IR)
Lecture Outline
Theory
What is a vibration?
Morse potential energy curves!!
Why molecules (bonds) are IR active?
IR Techniques
FT-IR
ATR
PAS
Instrumentation
FT-IR
ATR
FT-IR microscope
Sample Analysis
Applications
Infrared Spectroscopy
IR spectroscopy is the study of the interaction of
infrared light with matter. This interaction can
provide structural information, quantification, and
identification. The fundamental measurement
obtained in IR spectroscopy is an IR spectrum
which is a plot of measured IR intensity
(absorbance or transmittance) versus wavelength
(or wavenumber) of light. The instrument used to
make these measurements is called an infrared
spectrometer. There are several types.
IR spectroscopy is sensitive to the presence of
chemical functional groups (chromophores) in a
sample. A functional group is a structural
fragment within a molecule.
Why molecules absorb IR?
In order to answer this question, need to
know what is the makeup of a chemical
bond.
Also, how can you classify this chemical
bond, i.e. is it a spring?
What is the geometry of the molecule and
how does this affect its interaction with
IR?
Several approaches need to be addressed.
Classical or mechanical description of the bond.
Quantum mechanical description of the bond.
Infrared sub-regions
Region Transition Wavelength
m
Wavenumber
cm
-1
Near IR
(NIR)
overtones 0.75-2.5 13,300-
4,000
Fundamental vibs, rots 2.5-25 4000-400
Far IR skeletal,
rots
25-1000 400-10
Wavenumbers
4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400
T
r
a
n
s
m
i
t
t
a
n
c
e
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
4
0
5
.
0
0
3
5
9
7
.
8
6
2
1
0
1
7
.
0
1
1
1
6
4
.
8
7
1
4
0
9
.
1
5
1
5
9
0
.
4
4
1
7
3
4
.
4
4
2
8
5
4
.
3
1
2
9
2
5
.
0
2
3
3
9
3
.
0
3
9.spc
LCAO
H
2
Molecule
Making Chemical Bonds
Molecular Vibrations
Chemical bonds
Consider the hydrogen chloride (H-Cl)
molecule whose structure is shown to
the right. The H-Cl molecule is shown
as a ball and spring model where the
atoms in the molecule are represented
by balls and the chemical bond by a
spring. Because there is a difference
in electronegativity between the two
atoms, the electrons in the H-Cl bond
have a higher probability of being
found on the Cl atom. As a result,
the chlorine has a partial negative
charge on it as indicated by the o
and the hydrogen atom o+.
Dipole moment
Subsequently the H-Cl molecule contains
two charges separated by a distance, r.
This phenomenon is known as a dipole
moment. The dipole moment is a measure
of the charge asymmetry of a molecule.
The magnitude of the dipole moment is
calculated from the following equation:
=qr where q = charge, r = distance.
Electric field interaction
The alternating electric field interacts with the
changing dipole moment. If the electric vector
polarity is positive, it will repel the partial positive
charge on the hydrogen atom because like charges
repel. Consequently, the hydrogen atom will move
away from the electric vector and the H-Cl bond
will shorten. Once the polarity of the electric
vector changes to being negative, it will attract
the hydrogen atom because opposite charges
attract. Therefore, the H-Cl bond will get
shorter and longer and shorter and longer. During
this process, the molecule vibrates at the same
frequency as the electric vector, and the energy
of the light beam is transferred to the molecule.
Hence an infrared absorbance takes place.
Dipole Moments
Electromagnetic wave
Two fields, electric and
magnetic
Electric field component
IR Absorbance
Before the IR beam and molecule interact, the
H-Cl molecule is at rest, and the IR photon has
energy equal to hv. After the interaction, the
photon has been absorbed, and its energy
deposited into the H-Cl molecule as bond
stretching motion. Energy is conserved in the
reaction since all the photons energy has been
transferred to the molecule as vibrational energy.
We detect the absorbance of the photon by a
decrease in infrared intensity at the wavenumber
of the light absorbed, giving an absorption feature
in the IR spectrum of the molecule. Can say that
the dipole moment is the handle on the molecule
that the IR light grasps so it can interact with the
molecule.
HCl
20
40
60
80
100
5000 4500 4000 3500 3000 2500 2000 1500 1000
Transmi ssi on / Wavenumber (cm-1) Paged X-Zoom CURSOR
Fi le # 1 = HCL 3/4/1992 2:23 PM Res=.001
Hi gh resol uti on IR gas phase spectrum of HCL
High resolution HCl, fine structure
3250 3200 3150 3100 3050 3000 2950 2900 2850 2800 2750 2700 2650 2600 2550 2500
Wav enumber (cm-1)
0
10
20
30
40
50
60
70
80
90
100
%
T
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c
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Requirements for IR Absorption
shows that the transition probability
is related to a change in dipole
moment.
.... )
r
( ) r - r (
2
1
)
r
)( r - r ( =
o
2
2
2
e o e o
+ + +
0
0
0
0

( ) t
0
0
d
j
o
e o
*
i
r
r - r = R
(

|
.
|

\
|
+
}
Classical harmonic oscillator
Consider a mass m attached to a
stationary object through a spring.
As the mass is displaced from
equilibrium position, it will return
with a restoration force that is
proportional to its displacement
from equilibrium. This spring is
said to obey Hookes law.
F = -kx. k is the force constant.
Newtons law: F= m d
2
x/dt
2
.
Combine equations:
-kx = m d
2
x/dt
2
Can integrate and
get the potential energy of this
oscillator.
V=1/2 kx
2
M
Classical harmonic oscillator
This equation is
that of a
parabola or
simple harmonic
oscillator.
V=1/2 kx
2.

Frequency of
vibration is:
v =1/2t(f/m)
1/2
V
x
Classical harmonic oscillator, diatomic
Now consider a
diatomic molecule
of two masses, m
1

and m
2
.
m
1
m
2
Fundamental stretch frequency
v
t

v
t
v

=
=
+
=
+
=
=

1
2
6 02 10
7 76 10
2
4 12
1 2
1 2
1 2
1 2
23
11
1
c
K
m m
m m
M M
M M x
x
c
K
cm
K
or masses of at oms in amu
wher e K = for ce const ant in dynes / cm
( )( . )
,
.
( ) .
m
1
m
2
Quantum mechanical approach to
harmonic oscillator
Solving the
Schrodinger equation
gives:






Shows that the
spacings between levels
is constant.

t
t
k h
E E E
k h
v E
v v
v
2
2
)
2
1
(
1
= = A
+ =
+
Relationship
Equation is similar to the classical case.
This equation shows that the transition is
quantized.
However, in a diatomic or larger
molecule, dont have a simple harmonic
oscillator. Instead, anharmonic oscillator
in which we need to add more terms onto
the simple harmonic oscillator expression.
This contributes to overtones and Near
IR.
...... )
2
1
( )
2
1
(
2
+ + + = v hcx v hc E
e e v
e
Vibrational Energy Diagram
Conditions for IR absorption
Need quantized energy
Mode must have a change in dipole
moment
Fundamental Frequencies for
non-diatomics
For linear
triatomic,
symmetric:


|
|
.
|

\
|
+ =
|
|
.
|

\
|
=

2 1
1
2 1
1303
1
1303
m m
f
m
f
as
v
v
m
1 m
2
Bent tri-atomic
m
1
m
2
Angle o
|
|
.
|

\
|

+ =
|
|
.
|

\
|
+
+ =

2 1
2 1
cos 1 1
1303
cos 1 1
1303
m m
f
m m
f
as
s
o
v
o
v
Predictions of vibrational modes.
3n-5 (linear molecule) vibrational
modes. 3n-6 for non-linear.
Can use group theory to determine
which modes will be IR and Raman
active. Depends on what point group
the molecule belongs to. These point
groups or character tables can assist
in determine the active modes of IR
or Raman.
Water molecule
H
O
H
H
O
H
H
O
H
Water vibrations
H
O
H
H
O
H
H
O
H
Asymmetric stretch
Symmetric stretch
Bending or scissors
stretch
All modes IR active!!!
Modes for CO
2
+
-
+
symmetric
stretch no IR
asymmetric stretch, IR
Bending, 667 cm-1
Bending, out of plane, 667 cm-1
Point groups
Multi-vibrations
FT-IR (Non dispersive)
The ac component of the detector
signal S(x) as a function of mirror
displacement is related to the source
spectrum

|
.
|

\
|
u =
|
.
|

\
|
u =

t
u t

u
x
K
c
x
K x S
4
cos
4
cos ) (
FT-IR
where K is the constant that includes
detector response and geometrical
factors, x is the mirror displacement.
The signal S(x) measured vs.
displacement x is called the
interferogram.
If the mirror is moved at a constant
rate (r= dx/dt), the detector signal
oscillates with a frequency f=2rv/c.
FT-IR
The ac signal is the integral over all
frequencies:

dx x x S
d x x S
) 4 cos( ) (
: by given is transform
Fourier whose integral Fourier a is This
) 4 cos( ) (
}
}
+

+


= u
u =
v t
v t
v
v
v
Interferogram:
Interferogram






where o is the difference between
moveable mirror and stationary mirror
=2(OM-OS) in diagram below.
( )
I( ) B( ) cos
B( ) cos
o u
to

u tou
=
|
\

|
.
|
=
2
2
FT-IR
Fourier Transform:







where the coefficients a
n
and b
n
are
determined to reconstruct the curve.

( ) ( ) | |
1 2
0
2
cos sin a
x x
x n b x n
n
n n

=
+

=
t
e
e e
FT
4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500 250
-0.08
-0.06
-0.04
-0.02
0
0.02
BRITISH MODERN BN.0 (2)
Wavenumbers
4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.1
BRITISH MODERN BN.0 (1)
Advantages of FT-IR
1. Speed of analysis
2. Small samples can be analyzed i.e.
use a microscope
3. Signal to noise is 100,000 : 1.
4. Data manipulation
Quantitative Analysis
I
o
(u)
I

(u)
sample
IR
V
0
V
1
Beers law
I
o
b
I
d
k db
kb
e
c
kb
|
|
|
|
| |
|
|
0
0
} }
=
=

ln
and
=
0
0
Concentration Determination
A
C
o
n
c
e
n
t
r
a
t
i
o
n

0
C = (slope)(A) + intercept
Sample Analysis Procedure
Run blank spectrum
For solids, grind in a wiggle bug with
Nujol and then press a pellet under high
pressure.
Liquids can be analyzed in special quartz
cell.
For solids, can use a diamond anvil,
microscope, or ATR.
Gases can be analyzed in special gas cell.
S/N is very important
Wavenumbers
4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500
T
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0.1
0.2
0.3
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0.5
0.6
0.7
0.8
0.9
1
TUMIX.SPC
Wavenumbers
4000 3950 3900 3850 3800 3750 3700 3650 3600 3550 3500 3450 3400 3350 3300 3250
T
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s
m
i
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0.905
0.91
0.915
0.92
0.925
0.93
0.935
0.94
0.945
0.95
0.955
TUMIX.SPC
Background spectra
Wavenumbers
4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.1
BRITISH MODERN BN.0 (1)
Wavenumbers
4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500
T
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s
m
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a
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0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
1
BRITISH MODERN BN.5 (3)
Instrumentation Dispersive
Source Dispersing
Sample
Detector
Computer
Instrumentation FT-IR (non-dispersive)
Source
Interferometer
Sample
Detector
Computer
Instrumentation
Sources: based on blackbody radiator and using
the Wien displacement law:

max
=3000 /T (K)
W filament lamp for Near-IR
Nernst glower about 1500 C is fused mixture of
Zr, Y, and Th oxides. Good for Mid-IR. See
figure below.
Globar is rod of SiC about 1300 C. Also good for
Mid-IR.
High pressure Hg arc lamp for Far-IR.
Tuneable dye lasers can be used for non-dispersive
work where an intense source is needed to monitor
one wavelength.
Nernst glower
More instrumentation
Dispersing element:
Prism, filter, or monochromator
(dispersive)
Detectors
Photoconductive cells
Thermopile, thermister, pyroelectric,
semiconductor (Ge and InGaAs), Golay,
DTGS
More detectors
Photoconductive detectors have higher
sensitivity and are based on the
photoconductive properties of mercury
cadmium telluride (MCT). Operate at liquid
nitrogen temperatures. Increases the
signal/noise.
Less sensitive by a factor of 10 are the
pyroelectric detectors such as deuteriated
triglycine sulphate (DTGS) or lithium
tantalate (LiTaO3). Rapid response
detectors that are used with FTIR.
Michelson Interferometer
Modern Day FT-IR
Bruker Equinox 55
Demountable cells for liquids or gases
liquids
gases
Different IR modes
Attenuated Total Reflectance (ATR)
ATR is a great method for analyzing
solids non-destructively. Also can
analyze liquids. It is based on having
the sample in close contact with a
highly reflecting surface such as a
diamond. The IR beam will partial
penetrate the sample and totally
reflect giving a good IR spectrum.

ATR Equation
2 / 1 2
sp
2
p
p
) n (sin n 2
d

=
u t

Where n
sp
and n
p
are the ratio of the
refractive indices of the sample vs the
support and the support respectively. Theta
is the angle of incidence and is the
wavelength. For ZnSe and a polymer sample,
depth is 2.0 m at 1,000 cm
-1.
SensIR ATR
Jasco IR Microscope
The optical system is shown below. The
interference light from the FT/IR main
unit is introduced to the main unit by
the plane mirror M1. The changeover
mirror M2 reflects the light upward in
reflection measurement and downwards
in transmission measurement. In
reflection measurement, the light
reflected upward is reflected towards
the sample by the beam splitter BS and
is converged onto the sample surface
by the upper Cassegrain mirror CM1.
The light reflected by the sample is
collected by the same Cassegrain mirror
CM1 and is focused through the
aperture AP to the detector D which is
a high sensitivity infrared detector
(MCT detector). In transmission
measurement, the light reflected
downwards is focussed onto the sample
by the Cassegrain mirror CM2 below.
The light transmitted by the sample is
collected by the Cassegrain mirror CM1
above (as in reflection measurement)
and is again detected by the high
sensitivity infrared detector D.
Advantages of IR
A universal technique i.e. solids, liquids,
gases, semi-solids, powders, and polymers
can be routinely analyzed.
IR spectra are information rich; peak
positions, intensities, widths, and shapes in
a spectrum all give useful information about
the analyte.
IR is relatively fast and easy technique.
Most samples can be prepared and scanned
in less than five minutes.
IR is very sensitive. Micro to nano gram
quantities can routinely be detected.
Disadvantages of IR
Homonuclear compounds dont absorb.
Aqueous solutions difficult to analyze
because the strong absorbance of water.
Some compounds give broad bands that
interfere with other compounds.
Complex mixtures difficult.
Dark (black) compounds often absorb the
IR beam completely, i.e. 0% transmittance.
Software
Robust software is needed to manipulate
the FT-IR spectrum. This includes
smoothing, peak area determination,
subtraction, switching back and forth
between absorbance and transmittance.
Can be used to create spectral libraries for
searching.
Program to identify peaks and use
correlation diagrams to determine
structure. (Go to KnowItAll)
How to purchase?
Depends on needs?
Solid samples only, ATR-FT-IR.
Ease of use, resolution, S/N, vacuum or N
2

purged system.
Range of instrument?
NIR for overtones
Mid IR for fundamentals
Software and data manipulation ease
Ruggedness of instrument for field sampling
Cost: $15,000 - $90,000

PE Spectrum Spotlight 300 FT-IR
Imaging System
IR Imaging
IR image showing the
distribution of a carbonyl
contaminant through the
inclusion. Image contains
more than 5000 spectra at
6.25 pixel size. Total data
collection time was 90
seconds.
Visible image of an inclusion in a
polypropylene film. Sample size
is approximately 450 x 450
Imaging another view
Fingerprint analysis
Closer examination in right figure reveals that
the spectrum at one of the spots has CH3, CH2,
NH and OH absorptions typical of proteins, while
neighbouring spectra just show finger grease.
Instrument Vendors
SensIR (microscope, ATR)
Bruker
Schmazhu
Agilent
Perkin Elmer
Digilab
Nicolet
Buck Scientific (inexpensive)

FT-IR Applications
Forensics
Drugs, fibers, paint
Cell biology
Proteins
Polymers
Structures, film layers
Lubricants
Food analysis (NIR)
Summary
For IR to occur, the vibration must
undergo a change in dipole moment.
Must have the correct energy to couple to
this dipole moment so that the bond can be
promoted to a higher vibrational energy
level. As a result, will get an absorption.
Structure of molecule is important to
determine the absorption characteristics.
FT-IR is very rapid and sensitive. In
addition, spectra can be manipulated easily.
Raman Spectroscopy
Review molecule polarization
Raman instrumentation
What is the difference between
Raman and IR?
What does a Raman spectrum look
like?
Some applications