MOLECULAR SPECTROSCOPY 02

TO VIBRATE THE BONDS

SUMMARY
GENERAL CLASSIFICATION OF ANALYTICAL TECHNIQUES

SPECTROSCOPIC TECHNIQUES

Atomic Spectroscopy

AAS

AES

ICP (AES & MS)

Molecular Spectroscopy

XRF

UV-Vis

Luminescence

FT-IR

FT- Raman

REFERENCES

1. Fundamentals of Molecular Spectroscopy, C N Banwell and E M McCash, 4th Edition,

McGraw Hill, New York, 1994.
2 Principles
2.
P i i l off instrumental
i t
t l analysis,
l i D A Skoog,
Sk
F J Holler
H ll and
d T A Ni
Nieman, 5th Edition,
Editi
Thomson Learning, Crawfordsville, 1998.
3. Spectrometric Identification of Organic Compounds, R M Silverstein and
F X Webster,
W b t 6th Edition,
Editi
JJohn-Wiley
h Wil & S
Sons, N
New Y
York,
k 2001
2001.
4. Infrared and Raman Characteristic Group Frequencies Tables and Charts, 3rd
Edition, G Socrates, John Wiley & Sons, 2000.
5. Infrared Spectroscopy: Fundamentals and Applications, B H Stuart, John Wiley &
Sons, Sydney, 2004.

MOLECULAR SPECTROSCOPY IR SPECTRA

Vibration, Dipole Change and Absorption:
Infrared radiation is less energetic and its absorption leads a molecule only to excite at vibrational
and rotational levels. For a molecule to absorb IR it should have a permanent dipole, i.e. with a
slight positive and negative electrical charges developed on its component atoms.
Examples: O-- H+, C+- ClIf such a bond vibrates
vibrates, a regular fluctuation in dipole moment occurs and a field is established
which can interact with the electrical field of the IR radiation. If the frequency of IR radiation
matches (resonance) with the natural vibrational frequency of a bond a net transfer of energy
occurs resulting in change in amplitude of the vibration (increased vibration) which results in an
absorption (vibrational excitation).
If the charge separation is large the vibration will be rapid; faster vibrations result in
rapid rate of change of dipole leading to intense/stronger absorption of radiation.
Since the vibrational energy levels are quantized the absorption is characteristic of a bond. Thus
the energy of the radiation (photon) absorbed must equal the energy differences between the
vibrational energy states and can be given as: E = Evib 1 Evib 2 = hv = hc/.

IR SPECTRA QUANTUM TREATMENT

Through quantum mechanical treatment the vibration of a bond can be related to the bond
strength and mass of the joining atoms as follow:

1
2c

m1

m2
k

where, v = wavenumber of an absorption in cm-1 (= 1/)

k = force constant (bond strength) in Newton per meter (N/m) (Note: 1 N = kg
kg.m/s
m/s2)
c = velocity of light in cm/s
= reduced mass in kg (m1.m2/ m1 + m2)
From the above equation it is clear that a strong bond (large force constant) and a small
correspond to higher wavenumber and hence absorption should occur at higher wavenumber
in the IR region.
Thus C-H
C H absorbs at higher wavenumber (~ 3000cm-11) than C-D
C D (~ 2100cm-11) and the energy of
absorption frequency of C-C bonds follows the sequence: CC > C=C > C-C and the respective
wavenumbers are: ~ 2200cm-1 ~ 1640cm-1 ~ 1000cm-1.

IR SPECTRA REQUIREMENTS FOR ABSORPTION

1
1.

The change in vibration must stimulate changes in the dipole moment of the bonds
present in a molecule. Thus not all vibrations are IR active.

2.

The frequency of the radiation must satisfy the energy difference between each
vibrational level
level, ii.e.
e the incident energy should be quantized (E = hv) to exert the
transition between two vibrational levels.
v=3
Average b
A
bond
d llength
th
increases

v=2
v=1
hv
v=0

3.

The selection rule is that always v = 1 is allowed and stronger. Other transitions such
as v = 2,
2 3
3, etc., though
h
h not allowed
ll
d (f
(forbidden),
bidd ) may occur as weaker
k transitions.
ii

4.

The excitation from the ground state v0 to the first excited state v1 is the most likely
transition and is called fundamental transition ((v = 1).
) These are veryy strong
g when
compared to other transitions such as v0 = v2 (v = 2), or v0 = v3 (v = 3), which are called
as overtone transitions.

IR SPECTRA TYPES OF VIBRATION

Types of Molecular Vibrations:
The bonds present in a molecule are not rigid, instead they vibrate continuously like a spring.
Thus the atoms are not fixed and the vibrations of bonds largely depend on the type of the
atoms. There are two types of vibrations: stretching and bending. A stretching vibration
i
involves
l
a continuous
ti
change
h
i the
in
th inter-atomic
i t
t i distance
di t
along
l
th axis
the
i off the
th bond
b d between
b t
two atoms. Bending vibrations involve a change in the angle between the two bonds.
Vibrations
Stretching
Symmetric

Asymmetric

Bending
Scissoring Rocking Wagging Twisting
+
+
+

The sign +
+ indicates the movement towards the view point and - indicates away from that
that.
The energy associated with stretching vibrations are higher than the bending vibrations
and normally observed in higher wavenumber region of the IR spectrum.

IR SPECTRA TYPES OF VIBRATION

Notations:
Bending Vibrations:
Stretching
St
etc g Vibrations:
b at o s

Scissoring:
g

Symmetric: s

Rocking:

Asymmetric: as

Wagging:
Twisting:

For a molecule containing more than two atoms all the vibrations shown may be possible.
However for bigger molecules which may contain several types of atoms and bonds, the
multitude of possible vibrations is complex.

REPRESENTATION OF IR SPECTRUM
Units, Range and Representation of IR Spectra:
IR spectra are normally given in wavenumber (v) against percentage transmittance (%T). The
wavenumber expression is taken because of the convenience that it is directly proportional
to energy.
Wavenumber (v) = 1/ (cm)

100%

The energy of the radiation can

be related as:
E = h = hc/ = hcv

%T

1 eV = 1.602 10-19 J
0%
4000cm1

400cm1

IR SPECTRA THE RANGE

There are three important ranges in IR:
IR

Near IR

10,000

4000

Mid IR

Far IR

200

10 cm-1

Mid IR: There are two regions under this range:

Group Frequency region (~ 4000cm-1 1400cm-1): where organic functional groups
show characteristic absorptions
absorptions.
Finger Print Region (~1400cm-1 200cm-1): which is unique for a particular type of molecule
and no two molecules can have the same spectrum at this region.
Near-IR: It is on the higher energy side, overtone transitions and combination bands are
observed. This region is useful for the quantitative analysis since the spectrum is less crowded
.
Far-IR
Far
IR : It is less studied for organic molecules but for smaller molecules and also for
inorganic compounds where the vibrations are very weak due to bonding between heavy atoms,
this region is quite useful.

IR SPECTRAL INTERPRETATION
IR SPECTRAL CHART (stretching)
Type of Compound
Wavenumber Range, cm-1

Bond
CC
C-C

Alkanes

1000 - 1040

C=C

Alkenes

1610 - 1680

C=C

Aromatic rings

1500 - 1600

CC
C
C

Alkynes

2100 - 2260

C-N

Amines, Amides

1180 - 1360

CN

Nitriles

2210 - 2280

C-O

Alcohols, Ethers, Carboxylic acids, Esters

1050 - 1300

C=O

Aldehydes, Ketones, Carboxylic acids, Esters

1690 - 1760

C-H

Aldehydes

2700 - 2900

C-H

Alkanes

2850 - 2970

C-H

Alkenes

3000 - 3095

C-H

Alkynes

3300

C-H

Aromatic rings

3010 - 3100

NH
N-H

A i
Amines,
Amides
A id

3300 - 3500

O-H

Monomeric alcohols, Phenols

3590 - 3650

Hydrogen-bonded alcohols, phenols

3200 - 3600

Monomeric carboxylic acids

3500 - 3650

Hydrogen-bonded carboxylic acids

2500 - 3000

C-F (1000 - 1150cm-1) > C-Cl (700 - 800cm-1 ) > C-Br (600 - 700cm-1) > C-I (500 - 600cm-1)

IR SPECTRAL INTERPRETATION
IR SPECTRAL CHART ((bending/deformation)
g
)
Type of Compound

Wavenumber Range, cm-1

Alkanes:
CH3 (deformation)
CH2 (scissoring)
CH2 (wagging)
CH2 (twisting)
CH2 (rocking)

1470 (as),
) 1380 (s)
1465
1180-1350
1300
720

Alkenes:
=C-H (ip deformation)
=C-H (oop deformation)

1400
600-1000

Alkynes:
C-H (ip deformation)
C-H (oop deformation)

620-730
580-700

Aromatic ring:
=C-H (ip deformation)
=C-H (oop deformation)

1000-1275
690-900

ip in plane
oop- out of plane

IR SPECTRA OBTAINING THE SPECTRUM

Obtaining the Spectrum: Before obtaining an IR spectrum a background measurement
should be done to avoid any atmospheric interferences. Main ingredients of air are: N2,
O2, CO2 and H2O, among these the first two wont interfere in the IR (IR inactive) due to
their symmetric nature. But the latter two interfere very strongly. A spectrum of this type is
called as background spectrum. After this instrument is performed for sample to get
sample spectrum.
B k
Background
d spectrum
t
((mid-IR):
id IR)
5.0

background

4.5
4.0

Res
sponse

3.5
3.0
2.5

??

2.0

??

1.5
1.0
05
0.5
0.0
7500

7000

6500

6000

5500

5000

4500
4000 3500
Wavenumber

3000

2500

2000

1500

1000

500

Background spectrum after dry air purging:

Unprocessed spectrum:

Polymer sample spectrum (processed, mid-IR):

Group Frequency

Finger Print

Note that the Y-axis is given as %Transmittance: the transmittance can be related to
absorbance as follows:

IR SPECTRA INSTRUMENTATION
Instrumentation: The older double beam technique which is known as dispersive IR spectrometer
has been outdated.
outdated Instead the latest equipment is referred as Fourier Transform-Infra
Transform Infra Red (FT(FT
IR) spectrometer which utilises a single beam of un-dispersed IR radiation which is passed through
the sample and the absorptions at all wavelengths are received at the detector simultaneously.
A computerized mathematical manipulation (known as Fourier Transform) is performed to obtain
absorption data for each and every wavelength. To perform this type of calculation periodic
interference of light pattern is required. This is accomplished by splitting the IR beam into two using
a beam splitter and reconstructing the split beam again by a combination of two mirrors, one fixed
and another moveable. The following is the simplified version of the instrument:
Fixed Mirror

Movable Mirror

IR Beam

Sample
Compartment

Detector

FT-IR Spectrometers

IR SPECTRA SAMPLING TECHNIQUES

Sampling technique is very important in obtaining a good IR spectrum. Depending on the
sample and region (near- or mid- or far-IR) the technique varies. As for the concentration is
concerned a 0.5-1% of the sample is enough.
Solid Sampling: The sample is mixed with the solid solvent which depends on the range and
hard pressed to form as a pellet using a hand press and die.
Near-IR: CaF2
Mid-IR: KBr, NaCl
Far-IR: Polyethylene granules
Liquid Sampling: The solute is diluted in a proper liquid solvent and transferred to a liquid
transmission cell. The type of windows for the liquid cell depends on the range.
Near-IR: Quartz, CaF2
Mid-IR: aqueous (ZnSe, KRS-5, CdTe), organic (KBr, NaCl, ZnSe, KRS-5, CdTe)
Far-IR: Polyethylene, Si
For quantitative studies accurate determination of path length is desired
Note: Water is a bad solvent for IR
Thin films are used as such or stretched to obtain the optimum spectrum

IR SPECTRA APPLICATIONS
Applications: It finds extensive use in the identification and structural analysis of organic
compounds, natural products, polymers, etc. The presence of particular functional group in a
given organic compound can be easily identified. With the finger print region a new compound
can be identified, as no two compounds can have the same spectral characteristics at this region.
There are various modes of measurements other than transmission as follow:
Specular reflectance (for thin films, reflective substrates)
Diffuse reflectance (for powders)
Attenuated total reflectance (ATR) (for strong absorbing substances)
Photo-acoustic detector (for strong absorbing substances, depth profiling)
IR-Microscope
IR
Microscope (for direct Identification of impurities and micro
micro-sampled
sampled substances).
Disadvantages:
- Samples containing mixture of substances can not be analysed.
- Solid sample processing and liquid sample handling are time consuming.
- For mid-IR range the beam splitter and window materials for holding organic liquids are made of
KBr or NaCl which are highly
g y hygroscopic.
yg
p
- For every range the source, beam splitter and detector need to be changed.

IR SPECTRA MODES OF MEASUREMENTS

Measurement Modes

Transmission

Absorbance

Specular

Grazing Angle

Reflection

Others

External

Internal

DRIFTS

ATR

PAS

Transmission

Microscopy

Reflection

DRIFTS: Diffuse Reflectance Infrared Fourier Transform Spectroscopy

ATR Attenuated
ATR:
Atten ated Total Reflectance
PAS: Photo Acoustic Spectroscopy

ATR

RetroReflection

Grazing
g
Angle

IR SPECTRA Example

Broad OH stretch at ~ 3000 cm-1

CH stretch at ~ 2800 cm-1
C=O ester at ~ 1757 cm-1
C=O
C
O carboxyl at ~ 1690 cm-1
C=C aromatic at ~ 1608 &1460 cm-1

IR SPECTRAL INTERPRETATION PEAK IDENTIFICATION

Dehydration
D
h d ti off cyclohexanol
l h
l ((a)) tto 1
1-cyclohexene
l h
(b)
(b), note
t th
the di
disappearance off O H
-1
band at ~3500 cm and appearance of C = C band at ~1600 cm-1 for (b)

IR SPECTRAL INTERPRETATION TYPE OF GROUP

Both as and s are visible at

~3400 cm-1

Only s is visible at ~3400 cm-1

No peak at ~3400 cm-1

IR SPECTRAL INTERPRETATION PREDICTION OF BANDS

O

1
1.

CH3

CH3

C = O band appears at ~1700 cm-1

CH3 CH2 O

CH3

C O band appears at ~1100 cm-1

O

O
C

CH3

OH

2
2.
OH

Inter-molecular H-bonding exists and O H band appears

att ~3000
3000 cm-11 and
daC=Ob
band
d appears att ~1700
1700 cm-11

No inter-molecular H-bonding and O H band

appears att ~3500
3500 cm-11 besides
b id C = O b
band
d

3.

OH

OH

OH
OH

Intra-molecular
Intra
molecular H
H-bonding
bonding exists and O H band appears
at ~3000 cm-1

No intra-molecular
intra molecular H
H-bonding
bonding and O H band
appears at ~3500 cm-1

IR SPECTRAL INTERPRETATION PREDICTION OF BANDS

4
4.

CH3

OH

Inter molecular H-bonding

Inter-molecular
H bonding exists and O H band appears
at ~3000 cm-1 and a C = O band appears at ~1710 cm-1

5.

(CH3CH2)2NH
N H band appears at 3300 3500 cm-1

CH3

OC2H5

No O H band and only C = O band appears

(CH3CH2)3N
No N H band

EXERCISE: IR SPECTRAL INTERPRETATION GROUP FREQUENCY REGION

Always to be remembered that most of the stretching vibrations fall in the group frequency region
and follow the series as: O-H > N-H > C-H > C-O > C-C
All bending vibrations fall in finger print region.
Carbonyl and hydroxyl groups are to be identified in first place:
Look for C=O peak (1690 -1760cm-1)
1. If C=O check for OH (2500 - 3000 cm-1) - indicates carboxylic acid

IR SPECTRAL INTERPRETATION - GROUP FREQUENCY REGION

2. If C=O check for NH (3300 - 3500 cm-1) - indicates amide

3. If C=O check for C-O (1050 - 1300 cm-1) - indicates ester

IR SPECTRAL INTERPRETATION - GROUP FREQUENCY REGION

4. If C=O check for aldehydic C-H stretching (2800 - 2900cm-1 and 2680 - 2775cm-1)

5. If no OH, NH, C-O or aldehydic C-H - indicates ketone

IR SPECTRAL INTERPRETATION - GROUP FREQUENCY REGION

6. If no C=O check for OH (3200 - 3600 cm-1) - indicates alcohol

7. If no C=O check for NH (3300 - 3500 cm-1) - indicates amine

IR SPECTRAL INTERPRETATION - GROUP FREQUENCY REGION

8. If no C=O & no OH check C-O (1050 - 1300cm-1) - indicates ether

9 Identification of double bonds (alkene and arene systems)

9.

FTIR-ATR

Attenuated total reflectance (ATR) is a FTIR technique

in which total reflectance of IR beam is used
ATR crystal: Ge or Si (high refractive index)

3364, 3294, primary amine

1650,C=N

N
Si

Cl
Cl Cl

p p
peptide
bond

OTS

Traansmittan
nce (%))

ethylenediamine

IgG

1645,1550
peptide bond

after plasma treatment

OTS
2840,2919,2960, CH2 ,CH3

4000

3500

3000

2500

2000

1732, HC=O

1500

-1

Wavenumbers (cm )
C.-Y. Xue, K.-L Yang, Langmuir, 23 (10), 5831, 2007.

END OF MOLECULAR SPECTROSCOPY