Molecular Spectroscopy: The interaction of light and molecules.

Classifications of electromagnetic radiation: Spectral classification: X-ray, Ultraviolet,

Visible, Infrared, Microwave, Radio.

Infrared Spectroscopy
(IR or FTIR)
Infrared spectroscopy measures the absorption of electromagnetic radiation by
molecules. When molecules absorb infrared radiation of a certain energy, their
bonds vibrate (stretch, contract, bend, wiggle, twist, etc.).

We can measure how much energy is absorbed at each particular wavelength

and make inferences about the types of bonds that are present in the molecule.

1
The Infrared Region

2
3
Bond are acting as a spring which can be described as the balance
Between the force due to acceleration and to the restoring force of the spring

F  ma
Set equal
F  k y
4
Change in dipole moment of molecule
5
 Bond Stretching Bending

scissoring wagging

symmetric asymmetric

rocking twisting

In general, asymmetric stretching vibrations occur at higher frequencies than symmetric

stretching vibrations; also, stretching vibrations occur at higher frequencies than
bending vibrations. The terms scissoring, rocking, wagging, and twisting are
6
commonly used in the literature to describe the origins of infrared bands
In any group of three or more atoms, at least two of which are identical, there are two modes of
stretching: symmetric and asymmetric. Examples of such groupings are -CH 3, -CH2, -NO2, -NH2,
and anhydrides. The methyl group gives rise to a symmetric stretching vibration at about 2872 cm −1
and an asymmetric stretch at about 2962 cm −1. The anhydride functional group gives two
absorptions in the C=O region because of the asymmetric and symmetric stretching modes. A
similar phenomenon occurs in the amino group, where a primary amine (NH 2) usually has two
absorptions in the N-H stretch region, while a secondary amine (R 2NH) has only one absorption
peak. Amides exhibit similar bands. There are two strong N=O stretch peaks for a nitro group,
with the symmetric stretch appearing at about 1350 cm −1 and the asymmetric stretch appearing7 at
about 1550 cm−1.
IR stretching frequencies of two bonded atoms
in a molecule
Frequency, , Depend on what parameter ?

1 k m1 m2
 mr 
m1  m2
2 mr
 = frequency
k = spring strength (bond stiffness
between two atoms)
mr = reduced mass (~ mass of largest atom)
 Vibrations, potential energy and motion
between two atoms
X Y X Y F = dPE/ dr
a b

X Y X Y
PE
c d

r re re

Internuclear Internuclear
separation separation
X Y X Y

Light atoms Heavy atoms

and/ or and/or
strong bonds weak bonds
 IR stretching frequencies for vibrations of bond depends
upon ?

Directly on the strength of the bonding between the two atoms ( ~ k)

Inversely on the reduced mass of the two atoms (v ~ 1/m)

Examples of stretching frequencies and correlations with bond
strengths (bond order)

Bond strength* Bond order 

C-C 350 1 1000 cm-1

C=C 600 2 1600 cm-1

CC 3 2200 cm-1

840

*In k=/mol For same reduced

mass!
 What does the absorption intensity depend on?
The absorption intensity directly depends on the efficiency
of the energy of an electromagnetic wave of frequency  can
be transferred to the atoms involved in the vibration
The greater the change in dipole moment during a vibration, the
higher the intensity of absorption of a photon
Would the O–H stretching mode be expected to vary in intensity when hydrogen
bonded. If so, would it decrease or increase?

The intensity of an infrared absorption depends on the change in dipole moment during the
vibration. When a hydrogen atom is held in a hydrogen bond, it is in a much more polar
environment than when unchelated. The hydrogen atom is moving between two polar centres. It
is therefore reasonable to expect an increase in intensity from dimeric and higher polymeric
species.

What would be the effect of an increase in temperature on the infrared spectrum of a

hydrogen-bonded compound?

Increasing temperature means that each molecule will have more energy on average and weak
associative forces, such as hydrogen bonds, are likely to be broken. This should lead to a lesser
degree of hydrogen bonding, and thus changes in wavenumber to greater values would be
observed for groups forming the hydrogen bond.
 Spectral Analysis

• To recognize the characteristic bands that appear in the mid-infrared, nearinfrared

and far-infrared regions.

• To understand how hydrogen bonding affects an infrared spectrum.

• To develop a strategy for the interpretation of infrared spectra.

• To understand and use a variety of techniques to compensate for background

absorption and overlapping peaks.

• To convert transmittance values to the corresponding absorbance values.

• To use the Beer–Lambert law for the quantitative analysis of samples studied
using infrared spectroscopy.

• To analyse simple mixtures using their infrared spectra.

• To analyse multi-component systems using their infrared spectra.

 12820 ~ 4000 cm-1
Mid-IR 400~4000 cm-1
400 ~ 33 cm-1
Spectrum interpretation is simplified by the fact that the bands that appear can usually
be assigned to particular parts of a molecule, producing what are known as group
frequencies.

Mid-Infrared Region

 The mid-infrared spectrum (4000–400 cm−1) can be approximately divided into four
regions and the nature of a group frequency may generally be determined by the region
in which it is located.

The regions are generalized as follows:

1.X–H stretching region (4000–2500 cm−1),

2.Triple-bond region (2500–2000 cm−1),
3.Double-bond region (2000–1500 cm−1)
4.Fingerprint region (1500–600 cm−1).

The fundamental vibrations in the 4000–2500 cm−1 region are generally due to O–H, C–H
and N–H stretching.

O–H stretching produces a broad band that occurs in the range 3700–3600 cm−1. By
comparison, N–H stretching is usually observed between 3400 and 3300 cm−1. This
absorption is generally much sharper than O–H stretching and may, therefore, be
differentiated.
C–H stretching bands from aliphatic compounds occur in the range 3000–2850 cm−1. If
the C–H bond is adjacent to a double bond or aromatic ring, the C–H stretching
wavenumber increases and absorbs between 3100 and 3000 cm−1

Triple-bond stretching absorptions fall in the 2500–2000 cm−1 region because of the high
force constants of the bonds.

C≡C bonds absorb between 2300 and 2050 cm−1, while the nitrile group (C≡N) occurs
between 2300 and 2200 cm−1.

These groups may be distinguished since C≡C stretching is normally very weak, while
C≡N stretching is of medium intensity.

These are the most common absorptions in this region, but you may come across some
X–H stretching absorptions, where X is a more massive atom such as phosphorus or
silicon. These absorptions usually occur near 2400 and 2200 cm−1, respectively.

The principal bands in the 2000–1500 cm−1 region are due to C=C and C=O stretching.
Carbonyl stretching is one of the easiest absorptions to recognize in an infrared
spectrum. It is usually the most intense band in the spectrum, and depending on the
type of C=O bond, occurs in the 1830–1650 cm−1 region. Note also that metal
carbonyls may absorb above 2000 cm−1. C=C stretching is much weaker and occurs at
around 1650 cm−1, but this band is often absent for symmetry or dipole moment reasons.
C=N stretching also occurs in this region and is usually stronger.
Finger Print region ???

Near-Infrared Region ????

Far-Infrared Region ????

Inductive and Resonance Effects: The replacement of an alkyl group of the saturated
aliphatic ketone by a heteroatom (O, N) shifts the C=O stretching frequencies due to
inductive and resonance effects. In esters, the oxygen due to inductive effect withdraws the
electrons from carbonyl group (figure) and increases the C=O bond strength and thus the
frequency of absorption. In amides, due to the conjugation of lone pair of electrons on
nitrogen atom, the resonance effect increases the C=O bond length and reduces the C=O
absorption frequency. Therefore, C=O absorption frequencies due to resonance effects in
amides are lowered but due to inductive effect in esters are increased than those observed in
ketones.

In acid chlorides, the halogen atom strengthens the C=O bond through inductive effect
and shifts the C=O stretching frequencies even higher than are found in esters. The acid
anhydrides give two bands in C=O stretching frequency region due to symmetric (~1820
cm-1) and asymmetric (~1760 cm-1) stretching vibrations (figure).
Ring Size Effects: Six-membered rings with carbonyl group e.g. cyclohexanone absorb at
normal value i.e. 1715 cm-1. Decrease in ring size increases the C=O stretching
frequency. Smaller rings require the use of more p- character to make C-C bonds for the
requisite small angles. This gives more s character to the C=O sigma bond and thus
results in strengthening of C=O double bond. The comparison of C=O stretching
frequencies of various compounds in figure 28 shows that in ketones and esters, ~ 30
cm-1 increase in frequency occurs on moving to one carbon lower ring
Conjugation Effects: The C=O stretching frequencies for carbon-carbon double bond
conjugated systems are generally lower by 25-45 cm-1 than those of corresponding non-
conjugated compounds. The delocalization of π-electrons in the C=O and C=C bonds
lead to partial double bond character in C=O and C=C bonds and lowers the force
constant (figure). Greater is the ability of delocalization of electrons, the more is
lowering in C=O stretching frequency. In general s-cis conformations absorb at higher
frequency than s-trans conformations. A similar lowering in C=O stretching frequency occurs
when an aryl ring is conjugated with carbonyl compound.
Hydrogen Bonding Effects: Hydrogen bonding to a C=O group withdraws electrons
from oxygen and lowers the C=O double bond character. This results in lowering of
C=O absorption frequency. More effective is the hydrogen bonding, higher will be the
lowering in C=O absorption frequencies.

The monomeric carboxylic acids (in very dilute solutions) absorb at ~1760 cm-1. The
dimerization of carboxylic acids in their concentrated solutions or in solid state lowers
the carboxyl carbonyl frequency to 1710 cm-1. The more effective intramolecular
hydrogen bonding in methyl salicylate lowers the C=O stretching frequency to 1680 cm-
1 than observed at 1700 cm-1 in case of methyl p-hydroxybenzoate
Alkene: Factors influencing vibration frequency
1- Strain move peak to right (decrease) ʋ C
C
C
angle

1566
1611
1646 1656 : exception
1650

2- Substitution increase ʋ 1566 1641 1675

1611 1650 1679

1646 1675 1681

3- conjugation decrease
ʋ
C=C-Ph 1625 cm-1
 IR: Alcohols and Phenols
O-H Free : Sharp 3650-3600

O-H H-Bond : Broad 3400-3300

Intermolecular Hydrogen bonding Increases with concentration

=> Less “Free” OH
 IR: Alcohols and Phenols
C-O : 1260-1000 cm-1 (coupled to C-C => C-C-O)

C-O Vibration is sensitive to substitution:

Phenol 1220
3` Alcohols 1150
2` Alcohols 1100
1` Alcohols 1050
 IR: Ether
C-O-C => 1300-1000 cm-1

Ph-O-C => 1250 and 1040 cm-1

Aliphatic => 1120 cm-1

C=C in vinyl Ether => 1660-1610 cm-1

appear as Doublet => rotational isomers

H2C CH ~1620
H2C CH
O CH3
O CH3

H 2C CH
~1640
O

H3C
 IR: Carbonyl From 1850 – 1650 cm-1

1810 1800 1760 1735 1725 1715 1710 1690

Anhydr Acid Anhydr Ester Aldehyde Ketone Acid Amide
Band Chloride Band 2

Ketone 1715 cm-1 is used as reference point for comparisons

Factor influencing C=O O O-

1) conjugation C C
C=C C —C
+

Conjugation increase single bond character of C=O

 Lower force constant  lower frequency number

H OH
H3C O

CH CH3
O O
H3C 1715 1690 1725  1700 1710 1680
 Ketone and Ring Strain
Factors influencing C=O

H3C
2) Ring size
O
H3C
O
O
O

1715 cm-1 1751 cm-1 1775 cm-1

Angle ~ 120o < 120o << 120o

Ring Strain: Higher

n
 Factors influencing carbonyl: C=O
3) a substitution effect (Chlorine or other halogens)

—C—C— Result in stronger bound  higher frequency n

X
O

Cl 1750 cm-1

4) Hydrogen bonding Decrease C=O strenghtlower frequency

CH3
O

O
1680 cm-1
H
O
 Factors influencing carbonyl: C=O
5) Heteroatom

Inductive effect Y Y Resonance effect

Stronger bond O Weaker bond
O
higher frequency Lower frequence
R R
e.g. ester e.g. amides

Y C=O

Cl 1815-1785
inductive Br 1812
OH (monomer) 1760
OR (Ester) 1705-1735

NH2 1695-1650
resonance
SR 1720-1690
 Ester Carbonyl
Esters C=O ʋ ~ 1750 – 1735 cm -1

Conjugation => lower freq.

O-C : 1300 – 1000 2 or more bands

R OR Inductive effect with O

reinforce carbonyl => higher
ʋ

Conjugation with CO
weaken carbonyl => Lower
ʋ
 Lactone carbonyl: C=O
Lactones  Cyclic Ester

O O O
O O O

1720 1735 1760

O O
O O O
O

1750 1770 1800

 Carbonyl compounds : Acids
Carboxylic acid

Exist as dimer : O HO

H3C C C CH3

OH O

Strong Hydrogen bond

OH : Very broad  3400 – 2400 cm-1

C=O : broad  1730 – 1700 cm-1

C—O : 1320 – 1210 cm-1 Medium intensity

There are a few general rules that can be used when using a mid-infrared spectrum
for the determination of a molecular structure.
The shape and fine structure of a peak often give clues to its identity as well. Thus,
although the N-H and O-H regions overlap,

O-H 3650–3200 cm−1

N-H 3500–3300 cm−1
Inductive and Resonance Effects: The replacement of an alkyl group of the saturated
aliphatic ketone by a heteroatom (O, N) shifts the C=O stretching frequencies due to
inductive and resonance effects. In esters, the oxygen due to inductive effect withdraws the
electrons from carbonyl group (figure) and increases the C=O bond strength and thus the
frequency of absorption. In amides, due to the conjugation of lone pair of electrons on
nitrogen atom, the resonance effect increases the C=O bond length and reduces the C=O
absorption frequency. Therefore, C=O absorption frequencies due to resonance effects in
amides are lowered but due to inductive effect in esters are increased than those observed in
ketones.

In acid chlorides, the halogen atom strengthens the C=O bond through inductive effect
and shifts the C=O stretching frequencies even higher than are found in esters. The acid
anhydrides give two bands in C=O stretching frequency region due to symmetric (~1820
cm-1) and asymmetric (~1760 cm-1) stretching vibrations (figure).
Conjugation Effects: The C=O stretching frequencies for carbon-carbon double bond
conjugated systems are generally lower by 25-45 cm-1 than those of corresponding non-
conjugated compounds. The delocalization of π-electrons in the C=O and C=C bonds
lead to partial double bond character in C=O and C=C bonds and lowers the force
constant (figure). Greater is the ability of delocalization of electrons, the more is
lowering in C=O stretching frequency. In general s-cis conformations absorb at higher
frequency than s-trans conformations. A similar lowering in C=O stretching frequency occurs
when an aryl ring is conjugated with carbonyl compound.
Hydrogen Bonding Effects: Hydrogen bonding to a C=O group withdraws electrons
from oxygen and lowers the C=O double bond character. This results in lowering of
C=O absorption frequency. More effective is the hydrogen bonding, higher will be the
lowering in C=O absorption frequencies.

The monomeric carboxylic acids (in very dilute solutions) absorb at ~1760 cm-1. The
dimerization of carboxylic acids in their concentrated solutions or in solid state lowers
the carboxyl carbonyl frequency to 1710 cm-1. The more effective intramolecular
hydrogen bonding in methyl salicylate lowers the C=O stretching frequency to 1680 cm-
1 than observed at 1700 cm-1 in case of methyl p-hydroxybenzoate
 IR: Alcohols and Phenols
O-H Free : Sharp 3650-3600

O-H H-Bond : Broad 3400-3300

Intermolecular Hydrogen bonding Increases with concentration

=> Less “Free” OH