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This part (Series-4 from Q.no 81 - 100) is updated on 22nd Nov and going to be updated
frequently. For recent updates and other parts, join the following group
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SOLVED
CSIR UGC JRF NET
CHEMICAL SCIENCES
PAPER 1 (PART-B)
SERIES-4
NOTE: Related and additional questions appeared in previous GATE exams are also
solved.
81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100
87) Overtones are observed in the vibrational spectra of diatomic molecules when
1. anharmonicity is large
2. anharmonicity is absent
3. vibration and rotational modes are coupled
4. an alternating electric field is applied
Explanation:
* Overtones are formed due to anharmonicity. More explanation is given in the additional
information.
Additional information:
Basic principles of IR spectroscopy:
* The IR spectrum results from the interaction of radiation with molecular vibrations and, in
gases,with molecular rotations.
* Molecular vibrations require energy in the IR region of electromagnetic spectrum.
* The spectrum is a plot of sample transmission of IR radiation as a function of wavelength or
related units (usually that of wavenumber).
* The vibrational frequency of a bond ( ) can be calculated as follows:
1 2
1 2
1 2
1

2
where
force constant (derived from Hooke's law)
=reduced mass =
where
and are the masses of bonded atoms
k
k
mm
m m
m m

 

=
=
+
* Hence the frequency of vibration decreases with increase in the mass of bonded atoms.
* Above equation can be written in terms of wavenumber (

) as:
1
2
k
c

 
=
* Note: The masses (atoms) move in a manner that keeps the center of mass stationary.Prepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
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Degrees of freedom:
* Molecules with N number of atoms have total 3N degrees of freedom as each atom can
move independently in three directions (along x, y and z axes).
* Among these, 3 are translational degrees of freedom and the remaining are rotational and
vibrational degrees of freedom.
Type of degrees of freedom Linear Non-linear
Translational 3 3
Rotational 2 3
Vibrational 3N-5 3N-6
Total 3N 3N

Modes of vibrations:
* Basically the vibrations are of two types:
1) Stretching: which causes change in bond length.
2) Bending: which causes change in bond angle.
* They are again of two types: in-phase (symmetrical stretching) or out-of-phase (asymmetric
stretching).
Harmonic oscillator approximation:
Classical oscillator:
* In classical approach, the energy of a vibration is given by:
2
max
max
1

2
Where
k =force constant
x =maximum distance from the equilibrium position
E kx =
* In the classical oscillator, the lowest possible energy is zero when there is no vibration
(since ‘x’ is zero).
* The energy of the classical harmonic oscillator is continuously variable and can have any
value.
Quantum mechanical oscillator:
* The energy of a quantum mechanical oscillator is given by:
1
( )
2
Where
n =quantum number (0, 1, 2, 3 _ _ _ _)
frequency
n
E n h

= +
=
* Vibrational energy is quantized i.e. only certain vibrational energies are allowed, which are
entirely decided by quantum number, n.
* In the quantum mechanical oscillator, the zero point vibrational energy is
1
2
h
(i.e., when n
=0). As it is not zero the molecule never stops vibrating entirely.
Selection rules:
* The vibrations are IR active only when the dipole moment of the molecule is changedPrepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
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during the vibration. i.e., parity must change during vibration.
* According to Harmonic oscillator approximation only transitions between adjacent vibra-
tional levels are possible (
1 n A =
).
Anharmonicity:
* According to harmonic oscillator approach, there is equal spacing between successive
vibrational energy levels and bond breaking is not allowed.
But this is not true for real oscillators (bonds) as the they lose their elasticity and tend to
break. Hence the restoring force and dipole moment change is not the linear function of mass
displacement from equilibrium position. This is referred to as anharmonicity.
* The energy of anharmonic oscillator is given by:
2
1 1

2 2
Where
=anharmonicity constant
n e
e
E n h n h x
x
 
| | | |
= + ÷ +
| |
\ . \ .
* As a result of anharmonicity, the spacing between successive vibrational levels decreases
with increasing quantum numbers.
* And the vibrations with
1 n A >
are also possible.
Fundamental bands: Formed due to transition from n =0 to n =1.
Hot bands: Formed due to transition from n=1 to n=2.
Overtones: When
1 n A >
; e.g. n =0 to n =2; Though now possible, they have low intensity. .
Combinations: These bands are formed when two modes of vibrations (like stretching and
bending) are excited by one photon. The frequency of combination bands is the sum of
frequencies of two types of vibrations.
Difference bands: In a difference type transition, the molecule that is already vibrating in an
excited state for one mode of vibration (say, v
1
=1) absorbs a photon of the proper energy and
changes to an excited state of a different mode of vibration (say, v
2
=1).
Like overtones, the combination and difference bands are also weak.
Fermi resonance: In fermi resonance, two closely spaced bands appear, when only one is
expected. This occurs when the overtone of one type of vibration has nearly same energy as
that of fundamental vibration of another type. It is also possible when a combination band of
two vibrations has same energy as that of fundamental vibration of another type (third one).
Comparison with Raman spectrum:
* The vibrational mode is Raman active only when the polarizability of molecule is changed.
* A vibrational mode can be IR active or Raman active or both.
* But for a molecule with centre of inversion, the vibrations are either IR active or Raman
active.
e.g. CO
2
, CS
2
etc.,
In above molecules, particularly, the symmetric stretching is Raman active (polarizability is
changed) but IR inactive (no change in dipole moment).Prepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
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Whereas, the asymmetric stretching is IR active (as the dipole moment is changed) but
Raman inactive (no change in the polarizability).
Broadening of IR peaks: The infrared peaks are not infinetely narrow due to following
reasons:
* Doppler effect (for gases).
* Collisions between molecules.
* finite(short) lifetime of particular state of molecule. (from Heisenberg’s uncertainty
principle, shorter the life time of state, the less well defined is its energy)
* The combination of a vibrational transition with rotatory transitions leads to a number of
closely spaced bands that are only resolved in the gas phase. In solutions, the rotatory levels
are unresolved, the net effect is a broadening of the IR bands.
Additional questions:
87.1) An IR band corresponding to the Co–H stretch is observed at 1840 cm
–1
for
[Co(CN)
5
H]
3–
. The expected wave number of the corresponding band in [Co(CN)
5
D]
3–
is:
a) 1650 cm
–1
b) 1301 cm
–1
c) 1580 cm
–1
d) 1857 cm
–1
Ans:-
1

2
1


x
x x 1840
1 59 2
= x x 1840 (
59 1 2
Co D Co H
Co H Co D
Co D Co H Co D
Co H Co H Co D
Co H Co D
Co D
Co H Co D
k
c
Hence
and
m m m m
m m m m
m m m m
m m m m

 


 
 



÷ ÷
÷ ÷
÷
÷
÷
=
=
=
+
=
+
+
=
+
+
+

H D
-1
m =2m )
1
x 1840 =0.707 x 1840 =1301 cm
2

Practice questions:
1) The zero point energy of a harmonic oscillator is
a) he b) zero c)
1

2
d)
2

3
2) Which of the following molecules has the lowest vibrational stretching frequency?
a)
4
H
35
Cl b)
2
H
35
Cl c)
4
H
36
Cl d)
4
H
37
Cl
95) The following statement is true for any hermitian operator:Prepared by V. Aditya vardhan adichemadi(at)gmail.com WARANGAL
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1. All eigenvalues are real and non-degenerate
2. All eigenfunctions are real
3. All eigenfunctions are complex
4. All eigenvalues are real
Practice questions:
1) Which of the following is NOT a correct aspect of the Born-Oppenheimer approximation
A) The electrons in a molecule move much faster than the nuclei.
B) Excited electronic states have the same equilibrium internuclear distance as the
ground electronic state.
C) The electronic and vibrational motions of a molecule are approximately separable.
D) The typical amplitude of nuclear vibration is much smaller than that characterizing the
motion of electrons.
2) Which of the following statements about the eigenfunctions is NOT true:
A) Eigenfunctions belonging to different eigenvalues are orthogonal.
B) No two eigenfunctions can have the same eigenvalue.
C) An eigenfunction is normalized if
*
1
n n
d    =
}
.
D) A constant multiplied by an eigenfunction is still an eigenfunction.
E) All the eigenfunctions must be single-valued, finite and continuous.
3) To be physically acceptable, a quantum-mechanical wavefunction must be
A) single-valued B) finite everywhere C) continuous D) All
4) The eigenvalue a
n
must be
A) an integer B) a multiple of 
C) a real number D) part of a continuum
5) If ( ) x  is the normalised wavefunction of a particle in a particular quantum state, the
probability of finding that particle at a position between x and x+dx is:
a) ( ) x dx  b) *( ) x dx  (* denotes the complex conjugate)
c) *( ) ( ) x x   d) ψ*(x) ψ(x)dx