Infrared absorption spectroscopy and Its Applications

[I] Introduction
Infrared spectral range is in the range of 0.78 ~ 1000 m (or 12800 ~
10 cm-1).
Molecular absorption spectroscopy based on ultraviolet, visible and
infrared radiations is widely used for the identification and quantitative
analysis of inorganic, organic and biological molecules. Molecular
UV-Visible absorption spectroscopy is mainly used for quantitative
analysis. Infrared (IR) absorption spectroscopy is one of the powerful
tools for structural identification of molecules. IR absorption
spectroscopy can be employed in the applications of quantitative and
qualitative analyses. Typically, the IR region in terms of wavelength or
frequency are divided into three regions:

Meanwhile, the majority of analytical applications of IR has been

devoted to the mid-IR region: 4000 ~ 400 cm-1 (namely, 2.5 ~ 25 m). In
comparison, the most important use of IR has been the identification of
organic compounds, because the IR spectra can provide unique fingerprints
for organic molecules.

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[II] Theory of Infrared Absorption
For molecules, the total energy, Emol, can be described as a sum of the
external and internal energies of the molecule, including translational
energy, the energy for the electronic transition, vibrational motions and
rotational motions, i.e.,
Emol = ETrans + EEle + EVib + ERot + the other
Here ETrans: the translational energy of a molecule;
EEle: energy for electronic transition of atoms in a molecule;
EVib: energy for vibration between two atoms in the molecule;
ERot: energy for molecular rotation.
The schematic view of these energies are shown below:
Rotational
states

Electronic
state

Electron
transition

Vibrational
states
v=1
v=0

As the electric field of an incident light can interact with the electric field
of a chemical bond of a molecule during vibration, the molecule can thus
absorb the photon and be brought to a higher vibrational state, i.e., the
vibratioal excited state. Because the energy absorbed often matches
with the energy of photons with a frequency of 4000 ~ 400 cm-1, IR
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absorption spectra can thus be observed.

A. Dipole moment change during vibrational or rotational motions.

In order to absorb IR radiation, a molecule must undergo a net change
in dipole moment in its vibrational or rotational motion. Only under these
circumstances can the alternating electrical field of radiation interact with
the molecule and cause changes in the vibrational state of that molecule.
Here dipole moment () for a chemical bond: A+-B- is defined as:

= |
e| × d (unit: debye);

d is the distance between two atoms.

Taking HCl as an example, the charge distribution over H and Cl atoms is
not symmetric, like H+--Cl-. Because of this, HCl is considered as a
polar molecule and has a significant dipole moment. As HCl vibrates, a
regular fluctuation in dipole moment occurs. An electrical field is thus
induced and can interact with the electrical field of light. If the frequency
of the radiation exactly matches the natural vibratioanl frequency of HCl, a
transfer of energy takes place and results in an increase in the amplitude of
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the molecular vibration. Absorption of that radiation is the consequence.
Similarly, the rotation of asymmetric molecules around their center of mass
results in a periodic dipole moment fluctuation that can also interact with
EM waves with similar frequency. In this case, absorption of radiation
can also occur.
Note 1: No net change in dipole moment occurs during the vibration or
rotation of “
homonuclear species”
, such as O2, N2 or Cl2. Because of
this reason, theses molecules will not absorb IR radiation. They are
IR-inactive.
Note 2: Vibrational energy is quantized, and for most molecules, the
energy difference between vibrational quantum states corresponds to the
energy of the mid-infrared radiation.
Note 3: For gaseous molecules, a series of closely spaced lines
corresponding to rotational states can be seen near each vibrational state.
For liquid or solid, since the more atoms can interact with each other,
the vibrational states become broadened and considered as bands instead
of lines.
B. Types of vibration
Molecular vibrations can be described into two categories:
1. Stretching
2. Bending
They are schematically shown as follows:

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C. Mechanical Model of a stretching vibration in a diatomic molecule.
A chemical bond can be considered as a single mass attached to an
immovable object with a spring of force constant. According Hooke’
s
law, a force F will be induced as the mass is compressed or stretched with a
displacement y:
F = -ky
If the mass is moved from y to y + dy, a net work of dE will be done,
which is proportional to F and the displacement dy,
Thus, dE = -Fdy = kydy
E = 1/2ky2
The potential energy curve against the displacement y can be drawn as
follows:

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In this mode, the potential energy wll reach a maximum value when the
spring is compressed or stretched to its maximum amplitude A.
Since F = ma
a = d2y/dt2
F = -ky = m d2y/dt2
y = Acos(2mt)
m = (1/2)(k/m)1/2
where m is called the natural vibrational frequency.
However, a chemical bond is, in fact, linked by two movable atoms. In
:
this case, the mass should be modified as the reduced mass

= m1m2/(m1 + m2)
Thus, the natural vibrational frequency becomes
m = (1/2)(k/)1/2 = (1/2)[k(m1 + m2)/m1m2]1/2
The energy of light can be absorbed must match
E = hm, = (h/2)(k/)1/2

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D. Quantum treatments of vibration
Using quantum mechanics to treat this problem based on the harmonic
oscillator model, a similar result can be drawn:
E = (v + 1/2)(h/2)(k/)1/2 , where v = 0, 1,2,3 …
This result indicates that only quantized states exist for the molecular
vibration, where
E = (v + 1/2)hm, v is the vibrational quantum number = 0, 1, 2, 3 …
E = hm, = (h/2)(k/)1/2

v =4

v =3

v =2

v =1

v =0

For an allowed energy transfer, the selection rule is v = 1. This result
agrees well with conclusion reached by the classical mechanics.

E. Anharmonic oscillator
However, molecular vibration is not harmonic oscillator, because the
energy-distance is not symmetric. Thus, the actual vibrational states are
thus slightly different from the diagrams shown above. The energy
diagram looks like
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F. Vibrational modes:
For molecular motions, three types exist, they are translation,
rotation and vibration.
According to quantum mechanics, there exist at maximum 3N
degrees of freedom for molecular motions:(a) 3 freedom degrees for
translation motions, (b) 2 or 3 freedom degrees for rotation motions,
(a) the remaining (3N - 6) or (3N - 5) degrees for vibration.
Note: (3N - 6) for non-linear molecule, and (3N - 5) for the linear
molecule.In fact, more or less modes can be found due to the effects of
overtone or molecular symmetry.
Besides, shorter- or longer-wavelength shifts may also be found.
When chemical bonds vibrate, radiation energy of 0.06 ~ 0.6 eV,

equivalent to 500 ~ 5000 cm-1 may thus be absorbed, of which the

frequency falls into the IR region. Because of this reason, IR

radiation can be absorbed by molecules as molecules vibrate. As a
consequence, absorption signals can thus be detected by the IR absorption
spectrometer.
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 The vibrational states are closely packed with each electronic state,
within which rotational states are also overlapped. In general, the
energy for rotation is equivalent to 1/10 of the vibrational energy, and the
latter is about 1/10 of the energy for electron transition. Due to these
effects, a band structure instead of line structure is described for the
molecular orbitals.

G. Prediction of the absorption frequency

In general, we can assume that the force constants k:

k = 5n × 105 dyne/cm

for single bond (n = 1)

double bond (n = 2)

triple bond (n = 3)For CH single bond k = 5×105 dynes/cm,

(C-H) = 2,900 cm-1For CO single bond k = 5×105 dynes/cm, 

(C-O) = 1,100 cm-1For CO double bond k = 10×105 dynes/cm,


(C=O) = 1,730 cm-1

For CN triple bond k = 15×105 dynes/cm, (C=N) = 2,000 cm-1

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H. Vibrational coupling
1. Stretching-stretching coupling
2. Bending-bending coupling
3. Stretching-Bending coupling
4. Interactions between two groups with similar energy
5. No interaction exists between two bonds as separated by two or
more bonds.
6. Coupling between species with same symmetry

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For CO2, four degrees of freedom are available for vibration:

The symmetric stretching is IR inactive;

The asymmetric stretching is IR active: = 2330 cm-1
Two bending modes are degenerate and also IR active: 667 cm-1.

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For SO2, the molecule is nonlinear. There are (3N –6) = 3 degrees of
freedom available for vibration:

3650 cm-1 3760 cm-1 1595 cm-1

Symmetric stretching Asymmetric stretching Scissoring

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[III] Characteristic absorptions for functional groups

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[IV] Isotope effects

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[V] Substituent effects

[VI] Typical IR absorption Spectra

(1) Functional Group region: 4000 ~ 1300 cm-1(2) Fingerprint region:

1300 ~ 600 cm-1. => The absorption peaks observed in the functional

group region are closely related with the functional groups contained by
molecules.
=> The absorption peaks observed in the fingerprint region are closely
related with the real structures of the analytes.

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[VII] Applications of IR absorption techniques
a. Qualitative analysis

b. Quantitative analysis

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[VIII] Instrumentation
a. Non-dispersive Spectrometer
b. Dispersive Spectrometer
c. Fourier Transform (FT) Spectrometer
For typical dispersive spectrometer, four parts of elements are
I) Light sources
a. Glowbar source (1300 ~ 1500 K)
b. Tungsten Halogen lamp
c. Incandescent wire Arc (1100 K)
d. Mercury lamp
e. Lasers

II) Wavelength selectors

a. Prisms
b. Interference filters
c. Gratings

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 d. Monochromators

III) Sample holders

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IV) Infrared transducers

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[IX] Elemental Materials for absorption spectrometers

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[X]. Attenuated total reflectance apparatus (ATR)

[XI] Diffuse Reflectance

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[XII] Experiments: Infrared Spectrometry
________________________________________________
Group 1: Benzophenone Acetone
Methyl ethyl ketone Cyclohexanone
Benzaldehyde Acetaldehyde
iso-Butyraldehyde Acetophenone
Group 2: n-Butyl alcohol Benzyl alcohol
sec-Butyl alcohol tert-Butyl alcohol
Group 3: Benzonitrile p-Nitrotoluene
Nitrobenzene o-Nitrotoluene
Benzene
Group 4: Ethyl benzoate Ethyl acetate
Ethyl malonate Propionic anhydride
Acetic anhydride Phthalic anhydride
Group 5: Acetamide Dimethyl formamide
Acetanilide
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Sample preparations

A. 混合法 (Mull Technique, Nujol)

B. 壓片法 (KBr Pallet)

C. 薄膜法 (Film Technique)

D. 溶液法 (Solution Cell Technique)

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