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Subject Chemistry

Paper No and Title 11. Inorganic Chemistry –III (Metal π-Complexes and Metal
Clusters)
Module No and Title Module 6. Elementary ideas of IR spectroscopy and
evidences in favour of M CO π-bonding

Module Tag CHE_P11_M6

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
____________________________________________________________________________________________________

TABLE OF CONTENTS
1. Introduction
2. Vibration of diatomic molecules
3. Population of vibrational energy levels
4. Number of vibrational degrees of freedom
5. Interaction of radiations with vibrating molecules: Selection rules
6. Number of fundamental absorption bands
7. Hot bands and overtone bands
8. Region of vibrational spectrum
9. Evidences in favour of M CO π-bonding
10. Summary

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
____________________________________________________________________________________________________

1. Learning Outcomes
After studying this module, you will be able to learn about

• Vibration of diatomic molecules

• Population of vibrational energy levels
• Number of vibrational degrees of freedom
• Interaction of radiations with vibrating molecules: Selection rules
• Number of fundamental absorption bands
• Hot bands and overtone bands
• Region of vibrational spectrum
• Evidences in favour of M CO π-bonding

2. Introduction
In the rigid rotor model of the diatomic molecules, it is assumed that the covalent bonds
are rigid and inflexible, i.e., the internuclear distance of atoms connected together by covalent
bonds remains constant during rotation of the molecule. But it is not true.
In fact, the atoms of molecule do not remain at fixed relative positions but they vibrate
about some mean position. It imparts vibrational energy to the molecule. The vibrational motion
of a molecule is confined to very small space and, therefore, the vibrational energy of molecule is
quantized. In other words, a vibrating molecule can acquire only certain discrete values of
vibrational energy.
When electromagnetic radiations are incident on a vibrating molecule, it absorbs
electromagnetic radiation of suitable frequency and it undergoes transition from lower vibrational
energy level to higher vibrational energy level and thus an absorption band is obtained. The
spectrum obtained in this way is called vibrational spectrum. It is obtained in the infrared region
of the electromagnetic spectrum and, therefore, it is also called infrared (IR) spectrum.
By the measurement of IR absorption spectrum, we can derive information about the spacing
of allowed vibrational energy levels. On this basis, we can obtain various informations about the
molecular parameters.
It must be noted that when IR radiations are passed through a gaseous sample, both
vibrational and rotational energy of gaseous phase molecule change as a result of absorption of
radiation quanta. This combination of vibrational and rotational effects results in additional
complexity of the spectrum. The spectrum obtained in this way is called rotational-vibrational
spectrum. It can be avoided by taking the sample in the pure liquid state or in a solution. Each
molecule, in this case, is surrounded closely by neighboring molecules which prevents it from
rotating like gaseous molecules. Thus pure vibrational spectrum is obtained.

Ø The covalent bonds of molecules have spring-like nature and they oscillate about
some mean position. The covalent molecules may be regarded as harmonic
oscillator.
Ø The vibrational motion of molecule imparts vibrational energy to the molecule.
CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
____________________________________________________________________________________________________

Ø The vibrational energy of molecules is quantized.

Ø The energy difference between two consecutive vibrational energy levels is greater
than the thermal energy available at room temperature. Therefore, at room
temperature only ground state vibrational energy level (v=0) is populated and the
excited energy levels are almost unoccupied.
Ø The no. of vibrational degrees of freedom =3N-6 (If molecule is non-linear).
Ø The no. of vibrational degrees of freedom =3N-5 (If molecule is linear).
Ø The mode of vibration which leads to oscillation in the vertical component of the
dipole vector can interact with the electromagnetic radiation and give rise to
vibrational spectrum.
Ø Such molecule absorbs IR radiation and undergoes transition v=0 to v=1 producing
fundamental band which is sharp and generally strong.
Ø The wave number of the fundamental band increases with increase in the force
constant of the bond.
Ø The free CO molecule exhibits fundamental band at 2143 cm-1 due to stretching
mode of vibration.
Ø The position of fundamental band shifts to lower wave number for coordinated CO
molecule due to M CO π- bonding and it further deceases with increase in the
extent of back π-bonding.
Ø The positive charge on metal increases the CO stretching frequency because it
discourages back M CO π- bonding.
Ø The negative charge on metal facilitates the back M CO π- bonding and hence it
decreases the CO stretching frequency.

3. Vibration of diatomic molecules

Two atoms A and B of a diatomic molecule (AB) may be regarded as two balls of masses MA and
MB and the covalent bond connecting these atoms may be regarded as weightless spring holding
such balls together.
A B A B A B
MA MB MA MB MA MB

Compressed position
Mean position Stretched position

Because of the spring-like nature, the covalent bonds vibrate constantly and obey Hooke’s law for
harmonic oscillators-

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
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“The restoring force acting on a system undergoing simple harmonic motion is directly
proportional to its displacement from the mean position.”
Such molecules are called classical harmonic oscillators.
The frequency of vibration of vibrating diatomic molecule (harmonic oscillator) is given by
ν = 1/2π x (κ / µ) ½ (1)
Where, κ=Force constant of the bond. It is the measure of toughness or stiffness or strength of the
bond. Greater the value of κ, stronger will be the bond. It is defined as the force required to
displace the bond from the mean position by unit distance. Its unit is dyne/cm or N/m.

1N/m =103 dyne/cm

µ =Reduced mass of the molecule.

MA X MB
=
MA + MB

The vibrational energy of diatomic vibrating molecule is given by

h κ
Evib = x (v +1/2) (2)
2π µ

Where, v= vibrational quantum number

= 0, 1, 2, 3…
It is obvious that the vibrational energy of molecule is quantized and it can acquire only certain
discrete values as shown in the following figure.

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
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3 7/2 x h/2π x (κ / µ) 1/2

1/2
h/2π x (κ / µ)
2 5/2 x h/2π x (κ / µ) 1/2
1/2
Energy h/2π x (κ / µ)
1 3/2 x h/2π x (κ / µ) 1/2
1/2
h/2π x (κ / µ)
0 1/2 x h/2π x (κ / µ) 1/2
v
Energy

It is obvious from the above that

i) The vibrational energy of molecule increases with increase in the value of v.
ii) The energy difference between two consecutive vibrational energy levels is constant [h/2π x
(κ/ µ) ½]
iii) The molecule has a certain vibrational energy even in the lowest vibrational energy level
(v=0).The vibrational energy of a molecule in the lowest vibrational energy level is called zero-
point energy.
Ezero-point = 1/2 x h/2π x (κ / µ) ½ (3)
iv) The vibrational energy of a molecule increases with increase in the value of force constant
and deceases with increase in reduced mass of the molecule.
Equations 1) and 2) can be combined together as
Evib = hʋ (v+1/2) (4)

4. Population of vibrational energy levels

The energy difference between the ground state vibrational energy level (v=0) and the first
excited vibrational energy level (v=1) is h/2π x (κ / µ) ½ and it is much larger than the thermal
energy available at room temperature. Therefore, most of the molecules are present in the ground
state vibrational energy level (v=0) and the excited vibrational energy levels (v=1, 2, 3….) are
almost unpopulated at room temperature. At higher temperatures, the excited vibrational energy
levels are populated to more or less extent.

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
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5. Number of vibrational degrees of freedom

A linear diatomic molecule has only one vibrational degree of freedom and it is the stretching and
compression of bond and leads to the to and fro motion of the atoms connected by it. For a
polyatomic molecule having N atoms,
No. of vibrational degrees of freedom, i.e., no. of fundamental modes of vibration
=3N-6 (Non- linear molecule)
= 3N-5(Linear molecule)

Polyatomic molecule Shape No.of fundamental modes of

vibration
H 2O Bent(non-linear) 3x3-6=3
CO2 Linear 3x3-5=4

O O O
H
H H H
H H

Symmetric stretching Antisymmetric stretching Bending

O C O O C O C

O O

Symmetric stretching Antisymmetric stretching Bending

The bending mode of vibration of CO2 molecule is doubly degenerate.

The stretching modes of vibration involve rhythmic back and forth movement of atoms linked
together by covalent bond and during this process the distance between the atoms decreases and
increases periodically. The bending vibrations occur in molecules having more than two atoms

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
____________________________________________________________________________________________________

which are not directly connected by a covalent bond and it involves a change in the angles
between bonds with a common atom.

6. Interaction of radiations with vibrating molecules: Selection rules

There are two selection rules for the interaction of vibrating molecules with the electromagnetic
radiations and the transition of molecules from one vibrational energy level to another vibrational
energy level.
a) The fundamental mode of vibration of a molecule which leads to oscillation or
fluctuation in the vertical component of dipole moment of molecule periodically is infrared active
,i.e., can interact with IR radiation and the molecule can undergo transition from one vibrational
energy level to another vibrational energy level.
For example, the symmetric stretching mode of vibration of CO2 molecule is IR inactive
because it does not lead to the fluctuation in vertical component of the dipole moment of the
molecule. On the other hand, the antisymmetric and bending modes of CO2 molecule are IR
active. It has been illustrated in the following figure.

O
O O

C C C

O O
O

Stretched Mean position Comprssed

Dipole moment 0 0 0
(IR inactive symmetric stretching mode of vibration)

O
O
O
O O
O

C C C C C
C

O
O O
O O

0 0 0
Dipole
moment

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
____________________________________________________________________________________________________

Vertical
Component of
Dipole moment

(IR active antisymmetric mode of vibration)

b) Only those transitions between the vibrational energy levels are allowed which lead to the
change in vibrational quantum number by unity, i.e., ∆v= ±1 .
Since most of the molecules are present in the ground state vibrational energy level( v=0 ) ,the
only possible transition between vibrational energy levels is
v=0 v=1

and the absorption band arising in this way is called is called fundamental absorption band. The
energy required for this transition can be given by
Energy of electromagnetic radiation absorbed during the transition v =0 v = 1 = Ev=1 – Ev = 0

or, hν = 3/2 x h/2π x (κ / µ) ½ - 1/2 x h/2π x (κ / µ) ½

or, hc/λ = h/2π x (κ / µ) ½

or, 1/λ = 1/2πc x (κ / µ) ½

_ _
or, νfundamental = 1/2πc x (κ / µ) ½ ; Where, νfundamental is the position of fundamental band in cm-1.

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
____________________________________________________________________________________________________

The positions of fundamental bands of some diatomic molecules and their force constant are
given in the following table.

Molecule Position of fundamental Reduced mass(µ) in Force constant(dyne/cm)

band(cm-1) g
HF 2143 1.59 x10-24 9.7 x105
HCl 2886 1.63 x10-24 4.8 x105
HBr 2650 1.65 x10-24 4.2 x105
HI 2309 1.66 x10-24 3.1 x105
NO 2140 11.4 x10-24 18.5 x105
CO 1876 12.4 x10-24 15.5 x105

7. Number of fundamental absorption bands

The heteronuclear diatomic molecules such as HF, HCl, HBr, HI, CO, NO, etc. are IR active
and they have only one fundamental mode of vibration and it is stretching mode of vibration.
Such molecules exhibit only one fundamental absorption band in the IR spectrum. On the other
hand, the polyatomic molecules have more than one fundamental mode of vibration, i.e., more
than one pattern of vibratinal energy levels. Each fundamental mode of vibration produces one
fundamental absorption band. Therefore, polyatomic molecules exhibit more than one
fundamental band in the IR spectrum. For example, H2O exhibits three fundamental bands in the
IR spectrum at
a) 1595 cm-1 due to symmetric bending mode of vibration
b) 3652 cm-1 due to symmetric stretching mode of vibration
c) 3756 cm-1 due to antisymmetric stretching mode of vibration

8. Hot bands and overtone bands

At the room temperature only ground state vibrational energy level is populated by
molecules and the excited vibrational energy vibrational are almost unoccupied. But at higher
temperatures such as at 2000 C, the first excited vibrational energy level ( v =1) is also populated
appreciably and the transition v
v =1 to v =2 will give rise to a weak band in addition to v = 0 to v =1 transition. The absorption
band arising due to the transition v =1 to v =2 is called hot band. Its intensity increases with
increase in temperature due to the increase in the population of v = 1 vibrational energy level.
The vibrating molecules do not behave perfectly like a harmonic oscillator. It means, the
restoring force is not exactly directly proportional to the displacement from the mean position.
Such molecules are called anharmonic oscillators. As a result of this anharmonic motion, there is
relaxation in the selection ∆ v = ±1 and some weak absorption bands are also observed due to
transitions involving
∆ v = ±2 or ∆ v = ±3 . These are called overtone bands. The origin of various absorption bands
has been represented diagrammatically below:

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
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v=3

Energy v=2
iv) Vibrational
energy levels
v=1

i) ii) iii)
v=0

Transition between vibrational energy levels Name of absorption band arising

v = 0 to v = 1 Fundamental absorption band
v = 0 to v = 2 First overtone band
v = 0 to v = 3 Second overtone band
v = 1 to v = 2 Hot band

The intensity of the absorption bands decreases in the sequence:

𝐹𝑢𝑛𝑑𝑎𝑚𝑒𝑛𝑡𝑎𝑙  𝑎𝑏𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛  𝑏𝑎𝑛𝑑 ≫ 𝐹𝑖𝑟𝑠𝑡  𝑜𝑣𝑒𝑡𝑜𝑛𝑒  𝑏𝑎𝑛𝑑 > 𝑆𝑒𝑐𝑜𝑛𝑑  𝑜𝑣𝑒𝑟𝑡𝑜𝑛𝑒  𝑏𝑎𝑛𝑑

9. Region of vibrational spectrum

The vibrational spectrum is generally scanned in the wave number range 650 cm-1 to 4000 cm-1
which falls in the infrared region of the electromagnetic spectrum and therefore it is called IR
spectrum. The IR spectrum is generally divided into two regions.
a) Fingerprint region: The absorption bands in the range 650 cm-1 to 1250 cm-1 are more
numerous and associated with a number of rotational and vibrational energy changes in the
molecule and, therefore, less valuable for the identification of the functional groups. This region
is called fingerprint region and it is quite useful in determining whether two samples are identical
or not. Two identical samples have identical patterns of absorption bands in this region but
different compounds have different pattern of absorption bands in this region.
b)Group frequency region:
The absorptions in the region 1250 cm-1 to 4000 cm-1 involve the change in the vibrational
states of various bonds and are generally characteristics of the types of bonds/functional group

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
____________________________________________________________________________________________________

present on the molecule. There are relatively a few peaks in this region and their position is only
slightly changed from one molecule to another molecule. This region is called group frequency
region and it is very useful in the identification of the functional groups present in the molecule.

10. Evidences in favour of M CO π-bonding

From the vibrational spectra of metal carbonyls, it is possible to infer directly and semi
quantitatively the existence and extent of M – C multiple bonding, i.e., M CO π-bonding in
metal carbonyls. This is more easily done by studying CO stretching frequencies rather than MC
stretching frequencies. This is due to the fact that the former give rise to strong and sharp bands
which are well separated from the other vibrational modes of the molecules. On the other hand,
MC stretching frequencies are in the similar region with other types of vibration e.g. MCO
bending modes of vibration and therefore the assignments are not easy to make.
The prediction of M – C bond orders from the behavior of C – O vibrations is based on
the assumption that the valence of carbon is constant, so that a given increase in M – C bond
order must cause an equal decrease in the C – O bond order which, in turn, will cause a decrease
in the CO vibrational frequency.

Free CO molecule exhibits an absorption band at 2143 cm-1 due to its stretching mode of
vibration. The M CO π-bonding places the electron density of metal d atomic orbital of the
central metal to the vacant antibonding π* molecular orbital of CO molecule. As a result, the C –
O bond order of coordinated CO molecule decreases. It decreases the force constant of C – O
bond. It leads to leads to the shift in the position of CO absorption band to shorter wave number
region.
Species CO [Ni(CO)4 [Cr(CO)6]
_ 2143 2060 2000
νCO (cm-1)

Greater the extent of M CO π- bonding

i) Greater will be the electron density transferred from metal d atomic orbital of the central
metal to the vacant antibonding π* molecular orbital of CO molecule.
ii) Lower will be the C – O bond order
iii) Lower will be the force constant of C – O bond
iv) Lower will be the CO stretching frequency, and
v)lower will be the wave number of CO absorption band .
This fact has been verified experimentally by IR spectra.
The positive charge on the metal in a metal carbonyl discourages M CO π-bonding
and therefore it increases CO stretching frequency in comparison to the metal carbonyl with
neutral metal. On the other hand, the negative charge on the metal in a metal carbonyl facilitates

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding
____________________________________________________________________________________________________

M CO π-bonding and therefore it deceases CO stretching frequency. These facts are supported
by the following IR spectral data.

Species [Cr(CO)6] [Mn(CO)6]+ [Ni(CO)4] [Co(CO)4]- [Fe(CO)4]2-

_ 2000 2090 2060 1890 1790
νCO (cm-1)

Summary

• The covalent bonds of molecules behave like spring and they vibrate about a mean
position
• The vibrational motion of molecule is confined to a small space and hence the vibrational
energy of vibrating molecule (harmonic oscillator) is quantized
• The energy difference between the ground state vibrational energy level and the first
excited vibrational energy level is much greater than the thermal energy available at
room temperature
• The mode of vibration which leads to fluctuation in vertical component of the dipole
vector of molecule can interact with the electromagnetic radiation. Such vibrating
molecule undergoes transition to higher vibrational energy level involving ∆v = +1 by
absorbing emr of suitable frequency
• The vibrational spectrum is obtained in the IR region of the electromagnetic spectrum
and it is also called IR spectrum
• No. of vibrational degrees of freedom is 3N-6 for non-linear molecule while 3N-5 for
linear molecule
• The absorption band arising due to the transition v = 0 to v = 1 is called fundamental
band
• The absorption band arising due to the transition v = 0 to v = 2 is called first overtone
band
• The absorption band arising due to the transition v = 0 to v = 3 is called second overtone
band
• At higher temperatures, excited vibrational energy level (v =0) is populated appreciably
and the transition v = 1 to v = 2 produces a weak absorption band known as hot band
• The intensity of hot band increases with increase in temperature
• The wave number of the fundamental absorption band increases with increase in the force
constant, i.e., bond order of the bond
• Free CO molecule exhibits vibrational absorption band at 2143 cm-1
• Coordinated CO molecule exhibits vibrational absorption band at lower wave numbers
due to M CO π- bonding which decreases the C – O bond order
• The positive charge on the metal disfavours M CO π- bonding and hence it increases
CO vibrational frequency while the negative charge on metal reverses this effect.

CHEMISTRY Paper no.11: Inorganic Chemistry –III (Metal π- Complexes and Metal Clusters)
Module No.6: Elementary ideas of IR spectroscopy and evidences in favour of M
CO π-bonding