Infrared Spectroscopy

(Fourier Transform IR)

Part 1
IR Spectroscopy

I. Introduction
A. Spectroscopy is the study of the interaction of matter with the
electromagnetic spectrum

1. Electromagnetic radiation displays the properties of both particles and

waves

2. The particle component is called a photon

3. The energy (E) component of a photon is proportional to the frequency .

Where h is Planck’s constant and n is the frequency in Hertz (cycles per
second)

E = hn

4. The term “photon” is implied to mean a small, massless particle that

contains a small wave-packet of EM radiation/light – we will use this
terminology in the course
IR Spectroscopy

I. Introduction
5. Because the speed of light, c, is constant, the frequency, n, (number of
cycles of the wave per second) can complete in the same time, must be
inversely proportional to how long the oscillation is, or wavelength:
c
___ hc
n= ___
E = hn =
l l
c = 3 x 1010 cm/s

6. Amplitude, A, describes the wave height, or strength of the oscillation

7. Because the atomic particles in matter also exhibit wave and particle
properties (though opposite in how much) EM radiation can interact with
matter in two ways:
• Collision – particle-to-particle – energy is lost as heat and movement

• Coupling – the wave property of the radiation matches the wave

property of the particle and “couple” to the next higher quantum
mechanical energy level
IR Spectroscopy

I. Introduction
8. The entire electromagnetic spectrum is used by chemists:
Frequency, n in Hz
~1019 ~1017 ~1015 ~1013 ~1010 ~105

Wavelength, l
~.0001 nm ~0.01 nm 10 nm 1000 nm 0.01 cm 100 m

Energy (kcal/mol)
> 300 300-30 300-30 ~10-4 ~10-6

g-rays X-rays UV IR Microwave Radio

nuclear core electronic molecular molecular Nuclear Magnetic
excitation electron excitation vibration rotation Resonance NMR
(PET) excitation (p to p*) (MRI)
(X-ray
cryst.)

Visible
IR Spectroscopy

I. Introduction
C. The IR Spectroscopic Process
1. The quantum mechanical energy levels observed in IR spectroscopy are
those of molecular vibration

2. We perceive this vibration as heat

3. When we say a covalent bond between two atoms is of a certain

length, we are citing an average because the bond behaves as if it were
a vibrating spring connecting the two atoms

4. For a simple diatomic molecule, this model is easy to visualize:

IR Spectroscopy

I. Introduction
C. The IR Spectroscopic Process
5. There are two types of bond vibration:
• Stretch – Vibration or oscillation along the line of the bond
H H
C C
H H

symmetric asymmetric

• Bend – Vibration or oscillation not along the line of the bond

H H H H
C C C C
H H H
H
scissor rock twist wag
in plane out of plane
Infrared Spectroscopy

C.The IR Spectroscopic Process

6.As a covalent bond oscillates – due to the oscillation of
the dipole of the molecule – a varying electromagnetic
field is produced

7.The greater the dipole moment change through the

vibration, the more intense the EM field that is generated
Infrared Spectroscopy

C. The IR Spectroscopic Process

8.When a wave of infrared light encounters this oscillating EM field
generated by the oscillating dipole of the same frequency, the two
waves couple, and IR light is absorbed

9.The coupled wave now vibrates with twice the amplitude

IR beam from spectrometer

“coupled” wave

EM oscillating wave
from bond vibration
Infrared Spectroscopy

D. The IR Spectrum
1. Each stretching and bending vibration occurs with a
characteristic frequency as the atoms and charges
involved are different for different bonds
The y-axis on an IR
spectrum is in units of % In regions
transmittance where no osc.
bond is
In regions where the EM interacting with
field of an osc. bond IR light,
interacts with IR light of transmittance
the same n – nears 100%
transmittance is low (light
is absorbed)
IR Spectroscopy

D. The IR Spectrum
2. The x-axis of the IR spectrum is in units of wavenumbers, n, which is
the number of waves per centimeter in units of cm-1 (Remember E = hn
or E = hc/l)
IR Spectroscopy

D. The IR Spectrum
3. This unit is used rather than wavelength (microns) because
wavenumbers are directly proportional to the energy of transition
being observed –chemists like this, physicists hate it

High frequencies and high wavenumbers equate higher energy

is quicker to understand than
Short wavelengths equate higher energy

4. This unit is used rather than frequency as the numbers are more
“real” than the exponential units of frequency

5. IR spectra are observed for what is called the mid-infrared: 400-4000

cm-1

6. The peaks are Gaussian distributions of the average energy of a

transition
IR Spectroscopy

D. The IR Spectrum
7. In general:
Lighter atoms will allow the oscillation to be faster – higher energy
This is especially true of bonds to hydrogen – C-H, N-H and O-H

Stronger bonds will have higher energy oscillations

Triple bonds > double bonds > single bonds in energy

Energy/n of oscillation
Infrared Spectroscopy

E. The IR Spectrum – The detection of different bonds

7. As opposed to chromatography or other spectroscopic methods, the
area of a IR band (or peak) is not directly proportional to concentration
of the functional group producing the peak

8. The intensity of an IR band is affected by two primary factors:

Whether the vibration is one of stretching or bending

Electronegativity difference of the atoms involved in the bond

• For both effects, the greater the change in dipole moment in a

given vibration or bend, the larger the peak.

• The greater the difference in electronegativity between the atoms

involved in bonding, the larger the dipole moment

• Typically, stretching will change dipole moment more than

bending
Infrared Spectroscopy

E. The IR Spectrum – The detection of different bonds

9. It is important to make note of peak intensities to show the effect of
these factors:

• Strong (s) – peak is tall, transmittance is low (0-35 %)

• Medium (m) – peak is mid-height (75-35%)

• Weak (w) – peak is short, transmittance is high (90-75%)

• * Broad (br) – if the Gaussian distribution is abnormally broad

(*this is more for describing a bond that spans many energies)

Exact transmittance values are rarely recorded

Infrared Spectroscopy

II. Infrared Group Analysis

A. General
1. The primary use of the IR spectrometer is to detect functional
groups

2. Because the IR looks at the interaction of the EM spectrum with actual

bonds, it provides a unique qualitative probe into the functionality of a
molecule, as functional groups are merely different configurations of
different types of bonds

3. Since most “types” of bonds in covalent molecules have roughly the

same energy, i.e., C=C and C=O bonds, C-H and N-H bonds they
show up in similar regions of the IR spectrum

4. Remember all organic functional groups are made of multiple bonds

and therefore show up as multiple IR bands (peaks)
Infrared Spectroscopy

II. Infrared Group Analysis

A. General
5. The four primary regions of the IR spectrum

Bonds to H Triple bonds Double bonds Single Bonds

O-H single bond C≡C C=O C-C

N-H single bond C≡N C=N C-N
C-H single bond C=C C-O

Fingerprint
Region

4000 cm-1 2700 cm-1 2000 cm-1 1600 cm-1 400 cm-1
Vibrations
What is a vibration in a molecule?
Any change in shape of the molecule- stretching of
bonds, bending of bonds, or internal rotation
around single bonds

Can a vibration change the dipole moment

of a molecule? (Shockwave animation)
Asymmetrical stretching/bending and internal rotation
change the dipole moment of a molecule. Asymmetrical
stretching/bending are IR active.

Symmetrical stretching/bending does not. Not IR active

What wavelength of electromagnetic radiation is
involved in causing vibrations in molecules?

Infrared (IR) electromagnetic radiation causes

vibrations in molecules (wavelengths of 2500-
15,000 nm or 2.5 – 15 mm)

For a vibration at 4111 cm-1 (the stretch in H2),

how many vibrations occur in a second?
120 trillion vibration per second!!!!
120 x 1012 vibrations/sec or a vibration every
8 x 10-15 seconds!
WOW !!!!!
How does the mass influence the vibration?

H2 I2

MM =2 g/mole
MM =254 g/mole

The greater the mass - the lower the wavenumber

 How much movement occurs in the
vibration of a C-C bond?
stretching vibration
154 pm
For a C-C bond with a bond
length of 154 pm, the
variation is about 10 pm.
10 pm

bending vibration
For C-C-C bond angle a
10 pm
change of 4o is typical.
4o
This moves a carbon atom
about 10 pm.
A little physics of electromagnetic radiation

 Energy (E) E = hn = hc/l = hcn’

◦ where h is Planck’s constant, c is the speed of light,
n is frequency or the number of vibrations per
second and l is the wavelength

 Wavenumber (n’) n’ = 1/ l
◦ given in cm-1

 Period (P) P = 1/n

◦ the time between a vibration

Energy, frequency, and wavenumber are directly proportional to each other.

What type of vibrations would
occur in pentane?
Let’s examine the IR spectrum of pentane.
 IR spectrum
C-H
stretching C-H
bending

Increasing
absorption of IR
radiation
C-C
bending

Increasing wavelength

Increasing wavenumber (energy, frequency)

 IR Spectra of chloroform and deuterochloroform
Increasing absorbance

Shift of peak due to

replacement of H with
D (2x mass)

Mode of vibration CHCl3 CHCl3 CDCl3

Calculated* Measured Measured
C-H stretching 3002 3020 2256
C-H bending 1120 1219 912
C-Cl stretching 701 773 737
C-Cl bending 418 671 652
* Spartan ’02 AM1 minimization
 Calculated values using computational
software give lower wave numbers

 Increasing mass of substituted atoms shifts

wave numbers to lower values
(Excel spreadsheet)

 Stretching energies > bending energies >

internal rotation energies (occur at higher
wavelengths)

Some results
Does the stretching energy have
any relationship to the strength of
the bond?
5000 Wavenumber vs. Bond Energy
Wavenumber (cm )
-1

4000
3000
2000
W = 6.3286BE + 401.38
1000
r2 = 0.7979
0
200 300 400 500 600
Bond energy (kJ/mole)
Let’s examine the carbonyl group on three
compounds
formaldehyde phosgene acetone

How does the C=O stretching energy compare for

these three molecules?
2053 cm-1 1951 cm-1 2063 cm-1
The carbonyl group has a range of 1700-3000 cm-1.
 Unlike atomic spectroscopy where sharp
energy transitions occur due to well quantized
electron transitions, molecular spectroscopy
tends to show bands.

 Molecular vibrations are influenced by the

surrounding groups!

Functional group analysis in organic

compounds
bending Basic Functional Groups
C-H

O-H

C=O C-O

alkenes
stretching

O-H aromatic

C-H ChC C=C C-C

4000 3000 2000 1000 400

WAVENUMBER (cm-1)
 Identification of functional groups on a
molecule – this is a very important tool in
organic chemistry

 Spectral matching can be done by computer

software and library spectra

 Since absorbance follows Beer’s Law, can do

quantitative analysis

Use of IR spectra
FTIR Theory
 The spectrometer described here is a modified
Bomem MB-100 FTIR.
 The heart of the FTIR is a Michelson
interferometer (figure 2).
 The mirror moves at a fixed rate. Its position is
determined accurately by counting the
interference fringes of a collocated Helium-Neon
laser.
 The Michelson interferometer splits a beam of
radiation into two paths having different lengths,
and then recombines them.
 A detector measures the intensity variations of
the exit beam as a function of path difference.
 A monochromatic source would show a simple
sine wave of intensity at the detector due to
constructive and destructive interference as the
 In the general case, a superposition of
wavelengths enter spectrometer, and the detector
indicates the sum of the sine waves added
together.
 Figure 3 shows some idealized light sources, and
the interferograms that they would theoretically
produce.
 The difference in path length for the radiation is
known as the retardation d (OM = OF + d) in
figure 1 and 2.
 When the retardation is zero, the detector sees a
maximum because all wavenumbers of radiation
add constructively.
 When the retardation is l/2, the detector sees a
minimum for the wavelength l. An interferogram
is the sum of all of the wavenumber intensities.
Figure 1.
Figure 2.

Schematic of Michelson Interferometer

Source: MS thesis submitted by Carl George Schmitt, UNR , 1998.
Wave Interference
Figure 3.

Sample interferograms and their theoretical source intensity

Source: MS thesis submitted by Carl George Schmitt, UNR , 1998.

Calibration of the FTIR spectrometer
Source: MS thesis submitted by Carl George Schmitt, UNR , 1998.
 The spectrometer produces a complex voltage at
each wavenumber. A linear model for the
spectrometer response is assumed, where A is an
instrument offset, and C is a scaling factor,
V= A+CI (1)
 If the spectrometer views a perfect blackbody,
Eq. (1) gives
V = A+ CBT (2)
where BT is the Planck emission curve for a
blackbody of temperature T.
 The two unknowns (A and C) can be determined
from blackbody measurements at two different
temperatures,
V1 = A+ CBT1
V2 = A+ CBT2
 Solving for the unknowns yields
C = (V1-V2)/(BT1-BT2)
and A = {V1(BT1-BT2)-BT1 (V1-V2)}/(BT1-BT2)

 Returning to Eq (1), The FTIR voltage of another

target (Vtarget) is related to the target radiance
(Itarget) by
Itarget=[(BT1-BT2)Vtarget–BT1V2+BT2V1]/(V1-V2)

 Thus, with measurements of blackbodies at two

temperatures, the calibrated radiance from a
target (cloud) can be determined.