‫‪Dr.Abdulhadi Kadhim.

‬‬ ‫‪Spectroscopy‬‬

‫‪Ch.3‬‬
‫اﻟﺠﺎﻣﻌﺔ اﻟﺘﻜﻨﻮﻟﻮﺟﯿﺔ‬
‫اﺳﺘﺎذ اﻟﻤﺎدة ‪ -:‬اﻟﺪﻛﺘﻮر ﻋﺒﺪ اﻟﮭﺎدي ﻛﺎﻇﻢ‬ ‫ﻗﺴﻢ اﻟﻌﻠﻮم اﻟﺘﻄﺒﯿﻘﯿﺔ‬
‫ﻓﺮع اﻟﻔﯿﺰﯾﺎء اﻟﺘﻄﺒﯿﻘﯿﺔ‬
‫اﻟﻤﺮﺣﻠﺔ اﻟﺮاﺑﻌﺔ‬

‫‪Chapter three:‬‬
‫‪Infrared Spectroscopy‬‬
‫)‪(IR‬‬

‫‪42‬‬
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

Infrared Spectroscopy (IR)

Fundamental region (2.5-15.4µm)
IR Near IR (0.75-2.5µm)
Far IR (15.4-microwave)

Vibrational energy of diatomic molecule:-

We are all familiar with the vertical oscillations of amass (m)
connected to a stretched spring of a force constant k whose ether end
is fixed.
The simple harmonic motion with a fundamental frequency:-

° =

If two masses in a diatomic molecule m1 and m2 we used the reduced

mass

∴ =

in quantum mechanically, the vibrational energy is given by

° = + ° υ = 0,1,2,3 − − − −

Where υ is the vibrational quantum No.

The energy in Cm-1
° \
= =( + ) =( + ) °

Where ° the freq. in cm-1. These energy levels are equally spaced
\
and the energy of lowest state ° = ° ∶

43
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

An harmonic oscillator
In addition to rotational motion , molecule has vibrational motion
which is an harmonic. Hence a further correction to the centrifugal
distortion to be made to account for the vibrational excitation of the
molecule.
The empirical equation of the potential energy of the diatomic
molecule is given by
( )
V =D 1−e This equation called morse equation.

V = morse potential.
This potential represent the actual curve to a very good degree of
approximation except when r=0 → Vm gives a high finite value while
the actual value is infinity.

v At r→ ∞ → Vm→De
De: dissociation energy.

v At r=re → Vm→0

re r

44
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3
Let x=r-re x<< 1 very small

= 1− + − + ⋯ … … … … … … ..
2! 3!
( ) ( )
Or = 1− + − + ⋯ … … … … … … ..
! !

We take the first two term

( )
=1− = 1−
= [1 − ( − )] = [− ( − )] = ( − )

≅1−

( − ) = (2 )( − ) = \(
≅ − )
\
Where : 2a2De=force constant for small displacement.

\
= = in (Hz)

: freq. for small displacement.

Substitution Vm solving this eq. using pert buation theory we

gets G(v) = ω v+ −ω x v+

ω x :an harmonicity correction and constant.

ω >> ω x
The effects of an harmonicity:-
1- The energy levels are not equally spaced.
2- Selection rules for allowed transition
∆v=±1,±2,±3,……
v When ∆v=±1→ G(v1)= G(1)- G(0)

45
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

First fundamental freq.= ω -2ω x

v When ∆v=±2 → G(v2)= G(2)- G(0)
First over ton fundamental freq.=2 ω -6ω x
ω
D =
4ω x

We can derive the equation of D

1 1
( )
G v =ω v+ −ω x − − − −(1)
2 2
The maximum energy at =0
Then G(v) =De

( )
= ω -2ω x v+ = ω − 2vω x − ω x

2vω x =ω − ω x

ω ω
∴ =
ω
Sub in eq. (1)

∴ ( )= + − +

− + − + 2
=
2
− 2

= − ( )

46
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

= − =

D = Dissociation energy

Example(1):-
The fundamental vibration spectrum of Co molecule at
the wave number 2138 Cm-1 and the line which represent by
the transition v=2→ v=3 at wave number 2091 Cm-1 calculate

1. The harmonic constant ( ).

2. The unharmonic constant ( ).
3. The Dissociation energy.

The solution:-
1 1
G(v) = ω v+ −ω x
2 2
G(v1)= G(1)- G(0)

( )= 1+ − 1+ − 0+ − 0+

3 9 1 1
( )= − − +
2 4 2 4
( )= −2
2138 = −2 − − − −(1)
By the same way
G(v2)= G(3)- G(2)

47
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3
7 49 5 25
G(v ) = ω − ω x − ω − ω x
2 4 2 2
= ω − 6ω x
∴ 2091 = −6 − − − −(2)

2091 = −6 − − − −(2) ‫ﺑﺎﻟﻄﺮح‬

2138 = −2 − − − −(1)
-47 cm-1 = -4

∴ω x = cm = 11.75 cm

Sub in eq.(1)
2138 cm-1 = (2 × 11.75 )
∴ = 2161.5
(2161.5) 4.44 × 10
= = =
4 4 × 11.75 9.94 × 10
1 1
= 9.94 × 10 × 3 × 10 = 29.82 × 10

1
D = 29.82 × 10 × 6.63 × 10 J. S
sec
= 147.7 × 10 Joul
147.7 × 10
∴D = = 123.56 × 10 ev = 12.356 ev
1.6 × 10

48
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

H.W.(1):-
The absorption spectrum of HF molecule in the IR region ,
the first line at 3961 cm-1 and the second line at 7751 cm-1
calculate
1. The dissociation constant 2f.
2. The Dissociation energy D .

Population of vibration energy levels

According to Boltzman distribution
∆ / /
= =

∆E For first three transitions

(1) V=0 → V=1 ( Fundamental frequency ) ∆V=+1
∆E = εv=1 - εv=0
∆E = 1 + − 1+ − −
∆E= (1 − 2 )
(2) V=0 → V=2 ∆V=+2
∆E=2 −6
∆E=2 (1 − 3 )
(3) V=0 → V=3 ∆V=+3
∆E=3 − 12
∆E=3 (1 − 3 )

49
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

Example(2):-
HCl molecule is absorb the radiation at 2885.9 cm-1 by
using Boltzman distribution calculate the relative Number
for first vibrational level and the ground level at 25oC
suppose the No. of molecule at ground level is one.

The solution:-
∆ / /
= =

. × . × × × / . × ×
=
= 9.245 × 10

H.W.(2):-
HCl molecule is absorb the IR radiation at fundamental
vibrational frequency =2890 cm-1 calculate the force
constant ?

H.W(3):- Calculate the force constant for OH which can

be the spectrum absorb at IR region .

Infrared selection Rules

The selection Rule of IR if the vibration quantum
Number change
1. ∆V=±1 under harmonic approximation.
2. ∆V=±1, ±2, ±3 for anharmonic oscillator.

50
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

Over tones frequency:-

On other transitions may be take place furthermore
the fundamental frequency, at 2V1, 3V1, 4V1
1. 2V1, 3V1, 4V1 for transition began from v=0.
2. 2V2, 3V2, 4V2 for transition began from v=1.
3. 2V3, 3V3, 4V3 for transition began from v=2.
And the frequency of the 1st overtone = 2 e(1-3xe)
The absorption due to these transition called (( Over tones
frequencies))
The following figure represent the overtones frequencies for
Hcl molecule in IR region.

Zero point energy = − 1−

V =0 →1
Fundamental frequencies

First over ton 2nd over ton 3rd over ton 4th over ton
freq. freq. freq. freq.

V =0 →2 V =0 →3 V =0 →4 V =0 →5

0 5000
V (cm-
10000
1)

51
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

Combination bands and differences bands:-

The selection rules allowed by other transitions to
produce combination bands and difference bands. The
combination bands
is arise by added two or more fundamentals frequencies or
over tons frequencies such as:-
+ ,2 + , + +
These frequencies become allowed but the intensity is very
low.
The difference bands is similar to combination bands but the
transition appear in complex spectra.
− ,2 − , + −
Born-Oppenheimer principle
((The electrons movements is high speed compared with
nuclei movements , then can be considered the nuclei is
constant when studies the electronic properties of molecules
and the energy of electrons is independent on nuclei energy
and the total energy is equal to sum of vibration energy))
Plus Rotational energy plus electronic energy

. = . + . + .

Vibration – Rotation spectroscopy of diatomic

molecules
The vibration and rotation motion happen in any molecule
at the same time, and for any vibration level consist from

52
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3
many Rotational levels. The following figure explain the first
two vibrational level v=0 and v=1 and the rotational levels.
The vibration – rotation spectrum produce by transitions
from rotational levels of vibration level like v=0 to another
rotational levels of vibration level like v=1 and the selection
rule for vibration- Rotation spectra
∆V=±1 , ∆J =±1
The energy of vibration-Rotation for diatomic molecule
E(J,V) = E(J) + E(V)

= BJ(J+1) + + °

=ℎ ( + 1) + + + +

v=0 , v=1 ‫ﻣﺜﻼ ﻟﺪﯾﻨﺎ ﺣﺎﻟﺔ اﻻﻧﺘﻘﺎل ﺑﯿﻦ ﻣﺴﺘﻮﯾﯿﻦ‬

∆ J=-1 ∆ J=+1
J
/

3
v=1
2

1
0

“
J
4

3
v=0

2
1
vo 0
P-branch R-branch 53

2B 4 2B
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

\ \ \\ \\ \ \\
= + − + + + ± +

The vibrational-rotational absorption spectrum

Consists of two groups of equally spaced lines(R+P)branches with

a gap between them, the center of this gap is υo But experimentally it
is found that the spacing is not constant , this is due to the vibration-
rotation coupling.
When take the distortion effect ( centrifugal distortion ) in account the

= , = ( + 1) − ( + 1) + + − +

Consider the vibrational rotational transition υ=0→υ=1

Assuming B and D the same for both υ=0, and υ=1 states and
denoting upper state by single prime and lower state by double prime
\ \ \\ \\ \ \ \\ \\
= +1 − +1 − +1 − +1
3 9 1 1
+ − − −
2 4 2 4
(1 − 2 )+ \ \\ \ \\ \ \ \\ \\
= − + +1 − +1 − +1 -
(1)

Use of the selection rule ∆J=+1 ∴ J\-J\\=1 gives

\\ \\
= +2 +1 −4 +1 , = 0,1,2, − − − − −

∆J=-1 ∴ J\-J\\=-1 gives

\ \
= −2 +1 +4 +1 , = 0,1,2, − − − − −

Where = (1 − 2 ) which is the freq. of the υ=0→υ=1transition

54
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3
Lines corresponding to ∆J=-1 called P branch.

Lines corresponding to ∆J=+1 called R branch.

, = + − (m=J\\+1 and J\+1)

usually D is extremely small and in such cases

, = +

Example(3):-

The normal modes of vibration of Co2 molecule are υ1=1330

cm-1, υ2=667 cm-1, υ3=2349 cm-1 and υ4=2349 cm-1 evaluate the zero
point energy of Co2 molecule.
Solution:-
The Co2 molecule has 4 normal modes of vibration the
symmetric bending mode υ2 is double degenerate.
\
The zero point energy Eo of Co2= ℎ ∑
\
∑ = (1330 + 667 + 667 + 2349) = 5013 × 100

∴ ° = 6.6 × 10 × 3 × 10 × 5013 × 100

= 4.98 × 10 = 0.311

55
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

H.W.(4) :-
The equilibrium vibration frequency of the Iodine molecule is υs
-1
cm and the anharmonicity constant = 0.003

What is the intensity of hot band υ=1→υ=2 relative to that of the

fundamental υ=0→υ=1 , if the temperature is 300 oK ?
Note: - The hot band occurs in the temperature higher than the room
temp.

Example(4):-
The fundamental and first over tone transition of 14N16O are
centered at 1876.06 cm-1 and 3724.20 cm-1 respectively. Evaluate the
equilibrium vibration frequency, the anharmonicity constant, zero
point energy and force constant of molecule?
Solution:-
= (1 − 2 ) = 1876.06 cm

over tone = 2 (1 − 3 ) = 3724.20 cm

\
= 7.332 × 10 = 1903.98
\
Zero point energy ° = 1−

56
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3
= × 1903.98 (1 − 0.003666) = 948.5
14 -27
Mass of N =23.25x10 Kg
16 -27
Mass of O =26.56x10 Kg
. × .
= × 10 = 12.3975 × 10 Kg
. .
\
=4 =4 × 12.3975 × 10 × 9 × 10 × (904 × 100)

= 1597 N/m

H.W.(5):-
Estimate the position of the band center and B value of the
HCl from the few lines of the P and R branches listed below:-

line line
P1 2865.1 Ro 2906.24
P2 2843.62 R1 2925.90
P3 2821.56 R2 2944.90
P4 2798.94 R3 2963.29

57
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

Example(5):-
The fundamental band for HCl is centered at 2886 cm-1 .
Assuming that the inter nuclear distance is 1.276 oA. Calculate the
wave No. of the first two lines of each of the P and R branches of
HCl.
Solution:-
( . )×( . )
The reduced mass of HCl = ( ) ( . )
= 1.627 × 10
.

. ×
= = )
× . × ×( . × ×

= 10.6129

, = +2 = ∓1, ∓2, ∓3 − − − − −

= 2886 − 2 × 10.6129 = 2864.77

= 2886 − 4 × 10.6129 = 2843.55
= 2886 + 2 × 10.6129 = 2907.23
= 2886 + 4 × 10.6129 = 2928.45

58
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

IR Spectrometer:-
Consist from the following parts:-
(1) Source of radiation:-
Rod from silicon carbide heated to 1500 oC.

(2) Two mirrors to produce two beams, the first beam

reference beam and the second beam is sample beam.
(3) Cell of sample: - made from nacl.
(4) Grating or lit row mount prism.
(5)The sample may be solid or liquid ((If the sample is gas
must be used special cells of some millimeters thickness))

IR applications:-
(1) Diagnosis the structure of organic compounds.
(2) Determine the purity of compounds.
(3) Quantitative analysis for different compounds.
(4) A study of chemical interactions.
(5) A study of Hydrogen bonding.
(6) Analysis of orientation and geometric shapes for small
molecules in gas state.
(7) A study of polymers chemical.

59
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

Orational Infrared spectrum for polyatomic

molecules
1- Linear Polyatomic molecules
When molecule contain N of atoms then the axis (x, y, z) this
leads to 3N of axis this molecule need or called 3N freedom degree.
This means
(3N) to characterized the position or motion of center of
molecule mass, and (2N) for rotational motion then:-

3N-5 No. of degree of freedom for vibrational motion

N:-No. of atoms
For Diatomic molecules 3N-5=1 means the No. of vibrational motion
equal to one.
For Linear molecule have three atoms such as Co2 3N-5=3x3-5=4 No.
of vibrational ( Fundamental vibration) two as parallel of axis bond
and two represented the atom motion outside of axis bond .
The first one called ( stretching ) and the second called (bending)

Starching Starching

60
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3

2- Non Linear Polyatomic molecules:-

The No. of vibration equal to 3N-6 Three for transition motion
and Three for rotational motion.
Example:-
Water molecule H2o
The No. of vibration 3N-6=3

O O
O

H H
H H H
H

The energy of stretching is higher than the energy of bending

vibration.
The rotational energy level occurs as a result of rotation of molecules
around axis perpendicular on has symmetry axis and the axis of
symmetry has been neglected due to the mass of atom insure in
nuclear and radius of nuclear is very small compared with atomic
radius this leads to the moment of inertia due to electron rotation
around the axis.

61
 Dr.Abdulhadi Kadhim. Spectroscopy

Ch.3
The Features of Rotational levels:-
(1) The separated energy between the spectrum lines about 10-3ev.
(2) The wave length about ( 0.1mm-several cm).
(3) Lie in micro wave region.

(4) The moment of inertia equal to I=µr2 .

ℏ
(5) The energy = Iω = J(J + 1).

(6) Appear clearly in permanent dipole molecule and does not appear
in symmetrical molecule like H2,N2 .

(7) The selection rules ∆J=±1 and µ≠0 .

(8) The energy in room temp. greater than rotational energy
( KT= 2.6 x 10-2 ev) .
(9) Most rotational spectrum shown in absorption spectrum and
appear in cases and vapor.

62