VIBRATIONAL SPECTROSCOPY

Spectroscopy
3 Vibrational Spectroscopy
Contents

1 Introduction
2 Vibration of Diatomic Molecules
- Harmonic Oscillator Model
- Anharmonic Oscillator Model
- Dissociation Energy
- Rovibrational Spectroscopy
3 Vibration of Polyatomic Molecules
- Normal Modes of Vibration
- Activity of Normal Modes in Polyatomic Molecules
 Spectroscopy
3.1 Vibrational Spectroscopy
Introduction. Summary.

1. Shows up at the infrared region of the electromagnetic spectrum

(≈100-10000 cm-1).

2. The bands correspond to transitions between vibrational energy

levels.

3. Vibrational energy is quantized.

4. The allowed energy levels of a molecule can be determined through

solution of the Schrödinger equation for the vibrational motion.

5. Vibrational spectra allow the determination of parameters related to

the structure of the molecule.
VIBRATIONAL
SPECTROSCOPY OF
DIATOMIC MOLECULES
III Vibrational Spectroscopy Spectroscopy

Molecular Energy Levels - Born-Oppenheimer approximation

 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Quantum Mechanics of Vibration: Diatomic Molecules

 2 ˆ 2 
 −  + U ( R) ( R) = E( R)
 2 
U(R) might be complex-shaped, but at ordinary temperatures,
when only low energy states are populated, the system will

not venture far from the minimum at Re.

Taylor series expansion of U around Re and truncate the series at some term

dU 1 d 2U 1 d 3U
U ( R)  U ( Re ) + ( R − Re ) + ( R − Re ) +
2
( R − Re ) 3 + 
dR Re 2! dR 2 Re
3! dR 3 Re

Re is a minimum of U
 Spectroscopy
3.2 Vibrational Spectroscopy
The Harmonic Oscillator Model

The Harmonic Oscillator

if the system does not go far from the minimum at Re, then all terms higher than (R-Re)2
are very small and can be neglected. Then:

R − Re = x 1
1 U ( x) = U ( Re ) + ke x 2
U ( R)  U ( Re ) + U ( Re )( R − Re ) 2 U ( Re ) = ke 2
2!

d
f ( x) = − U ( x) = −kx
dx
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
The Harmonic Oscillator Model

 2 ˆ 2 1 
 −  + U ( Re ) + ke x 2 ( x) = E( x)
 2 2 

 2 ˆ 2 1 
 −  + ke x 2  ( x) = Evib ( x)
 2 2 

The Harmonic Oscillator Model

Ev = hn e ( v+ 12 ) v = N v H v ( x)e −ax
2

1
2
1  ke 
ne =  
2p    Hermite Polynomials

v = 0, 1, 2, 3, 4 ··
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
The Harmonic Oscillator Model

The Force Constant, ke

Measures the strength of the bond: how deformable it is:

1 ke
R
ne =
2p 

E(k large ) n e (H 35Cl) (D35Cl)

=
n e (D35Cl) (H 35Cl)
E(k small )
n e (H 35Cl)  n e (D 35Cl)

• The force constant does not depend on mass.

Is the same for all isotopologues of a molecule.
• Frequencies do depend on mass:
III Vibrational Spectroscopy: Part I_Diatomic Molecules Spectroscopy

Harmonic Oscillator Model

Force constants

1 ke
ne =
2p m

Molecule ke (N·m-1) Molecule ke (N·m-1) Molecule Ke (N·m-1)

HCl 515.74 F2 440 CO 1902

HF 965.5 O2 1177 N2 2297

Cl2 328.6 NO 1594

III Vibrational Spectroscopy: Part I_Diatomic Molecules Spectroscopy

Harmonic Oscillator Model

Fundamental frequencies

1 ke
ne =
2p m

Molecule n (cm-1) Molecule n (cm-1) Molecule n (cm-1)

HCl 2885.7 F2 892 CO 2143.4

HF 3958.4 O2 1556.2 N2 2330.7

Cl2 556.9 NO 1876.1

They depend on both, the force constant and the reduced mass.
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
The Harmonic Oscillator Model: Selection Rules

A transition will be allowed in

Selection Rules
non-Raman vibrational
spectroscopy if the following apply
In non-Raman spectroscopy, selection rules simultaneously:
are derived from :
1. Dipole moment varies along
vibration

Ԧመ v′′ 𝑑𝜏 ≠ 0
𝜇Ԧv′ v′′ = නΨv∗ ′ 𝜇Ψ 
d 
0
dR Re

2. Δv= ±1
The dipole moment of a molecule changes
when it vibrates.

• Homonuclear diatomic molecules do not have non-raman vibrational spectrum

• Only transitions between consecutive energy levels will be observed.
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
The Harmonic Oscillator Model: Selection Rules

Energy levels are evenly separated

𝐸v = ℎ𝜈𝑒 (v + 12)
Zero-Point Energy (ZPE)
U(x)

v 1
9 E0 = hn e
4 𝐸4 = ℎ𝜈𝑒
2
2
7
𝐸3 = ℎ𝜈𝑒
Δv= ±1
3
hn e

2
5 𝜈v+1՚v = 𝜈𝑒
hn e

2 𝐸2 = ℎ𝜈𝑒
2
3
hn e

1 𝐸1 = ℎ𝜈𝑒
2
1
The 0→ 1 transition corresponds to
0 𝐸0 = ℎ𝜈𝑒
2
the fundamental band (most intense).

0 x
Transitions from v > 0 lead to hot
bands.

a SINGLE LINE at frequency ne

n
n
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Anharmonic Model

The harmonic oscillator model...

• Describes reasonably well the small-amplitude vibrational motions, but fails to do so

when elongation (or compression) exceeds ≈10% of Re.

• Cannot describe molecular dissociation.

Morse Function

U ( x) = De [1 − e −x ]2

lim U ( x) = De
x →
D0

De

De: Spectroscopic Dissociation Energy

D0: Chemical Dissociation Energy
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Anharmonicity

Energy Levels

𝐸v = ℎ𝜈𝑒 (v + 1ൗ2) − ℎ𝜈𝑒 𝜒𝑒 (v + 1ൗ2)2 v = 0,1,2,3 ⋯

Anharmonicity Constant (dimensionless)

Harmonic Oscillator Anharmonic Oscillator

E3 =
7
hn e v=3 7 49
2 E3 = hn e − hn e  e
v=3 2 4
5
E 2 = hn e v=2 5 25
2 v=2 E2 = hn e − hn e  e
2 4
3
E1 = hn e 3 9
2 v=1 v=1 E1 = hn e − hn e  e
2 4
1
E 0 = hn e 1 1
2 v=0 v=0 E0 = hn e − hn e  e
2 4

n10 = n e n10 = n e − 2n e e
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Anharmonicity: Spectrum.

Selection Rules

The electric dipole-allowed transitions are less restrictive than those for the harmonic oscillator:

Δv = ±1, ±2, ± 3, ··· The most intense, however, keeps being Δv = ±1

The 1 ← 0 transition is the “fundamental band”

Transitions of type v’ ← 0 are called “overtones”, if

v’ > 1:
First Overtone: 2←0
Second Overtone 3 ← 0

Transitions starting at v’’ > 0 give rise to “hot bands”

 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules

Band Intensity:

• Intensity of overtone-like bands is noticeably smaller than that of the fundamental band.
• Selection rules for transitions where the quantum number changes by ±1 apparently
should be of similar intensity – however, the most intense is the fundamental band,
and hot bands with ±1 changes to the quantum number are difficult to see. Why?

Population of Vibrational Energy Levels:

Assume, for instance:
ne  2000 cm −1  e  1

−(ℎ𝜈𝑒 (v+ 1ൗ )−1ℎ𝜈 ))

𝑁v −Δ𝐸ൗ 2 2 𝑒 ൘ −ℎ𝜈𝑒 v N1 N2
=𝑒 𝑘 𝑇
𝐵 = 𝑒 𝑘𝐵 𝑇 =𝑒
ൗ𝑘 𝑇
𝐵  10−5  10−8
𝑁0 N0 N0

At room temperature only the ground vibrational state is appreciably

populated. Hence, the fundamental band is the most intense, as more systems
can undergo this transition.
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Anharmonicity. Spectrum.
1 1 1 1
It suffices to consider only “cold” bands, as 𝜈lj v՚0 = 𝜈lj𝑒 (v + ) − 𝜈lj𝑒 𝜒𝑒 (v + )2 − 𝜈lj𝑒 − 𝜈lj𝑒 𝜒𝑒
2 2 2 4
= 𝜈lj𝑒 v − 𝜈lj𝑒 𝜒𝑒 v(v + 1)
v=0 is the only appreciably populated level
at low T.

Transition Description n harm. n anhar.

0→1 Fundamental ne ne – 2nexe
0→2 First Overtone 2n e 2ne – 6nexe
0→3 Second Overtone 3n e 3ne – 12nexe
0→4 Third Overtone 4ne 4ne – 20nexe

Transition n observed n (harm) n (anhar)

0→1 2888 2886 2886
0→2 5668 5772 5668
0→3 8347 8658 8347
0→4 10923 11544 10923
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Dissociation Energy

Dissociation Energy

Dissociation occurs at a vibrational energy level, vdiss, in

ndiss
which energy is at (or above) the assymptote of the
potential energy curve.

D0
Nuclear motion energy levels are no longer quantized:
(energy is continous) above the dissociation limit. De

Chemical Dissociation Energy (D0)

Well Depth (De)
vdiss −1
𝐷0 = ෍ Δ𝐸v+1՚v 𝐷𝑒 = 𝐷0 + 𝐸v=0
v=0
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Dissociation Energy

Vibrational levels get closer upon increasing the value of the vibrational quantum number in
an anharmonic oscillator. A way to estimate the level of dissociation, vdiss, consists of
determining at what value the levels become so close as to be degenerate: Δ𝐸v+1՚v =0

3 3 1 1
Δ𝐸v+1՚v = ℎ𝜈𝑒 (v + ) − ℎ𝜈𝑒 𝜒𝑒 (v + )2 − ℎ𝜈𝑒 (v + ) − ℎ𝜈𝑒 𝜒𝑒 (v + )2
2 2 2 2
= ℎ𝜈𝑒 − 2ℎ𝜈𝑒 𝜒𝑒 − 2ℎ𝜈𝑒 𝜒𝑒 v

Δ𝐸v+1՚v = ℎ𝜈𝑒 − 2ℎ𝜈𝑒 𝜒𝑒 − 2ℎ𝜈𝑒 𝜒𝑒 vdiss = 0 1 𝐷𝑒 = 𝐸v

vdiss = −1 diss
2𝜒𝑒 𝐷0 = 𝐸v − 𝐸v=0
diss

Substituting vdiss into the expression of the

Anharmonic energy levels:

𝐷𝑒 = ℎ𝜈𝑒 (vdiss + 1ൗ2) − ℎ𝜈𝑒 𝜒𝑒 (vdiss + 1ൗ2)2

De
D0
ROVIBRATIONAL
SPECTROSCOPY
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Rotation-Vibration Interaction

Rotation-Vibration Interaction

Rotation and vibration can (and do) occur simultaneously. In

each vibrational state, the molecule is able to rotate.

Vibrational transitions occur in the infrared (100-10000 cm-1). Purely

rotational transitions, in the microwave region (1-100 cm-1).

A transition in the infrared will

involve changes not only in the

3 vibrational state, but also in

n’ = 1

2 J’ the rotational state.

1
0

Transition v’←v’’ involves

n’’= 0

3
several possible different
2
1
J’’ transitions J’←J’’,
0 with slightly different energies
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Rotation-Vibration Interaction

Uncoupled Model
A first approximation to study the simultaneous rotation & vibration model consists of assuming
that both motion types are uncoupled, that is:
Evib−rot = Evib + Erot

This simple model implies combining the results for rotational energy and vibrational energy
obtained so far.

Rovibrational Energy Levels: Anharmonic Oscillator+Rigid Rotor

𝐸v,𝐽 = ℎ𝜈𝑒 (v + 1ൗ2) − ℎ𝜈𝑒 𝜒𝑒 (v + 1ൗ2)2 + ℎ𝐵𝐽(𝐽 + 1)

Vibrational Rotational
(anharmonic oscillator) (rigid rotor)

Selection Rules Δv = ±1, ±2, ±3,···

Δ𝐽 = ±1
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Rotation-Vibration Interaction. Rovibrational Spectrum.

Rovibrational Spectrum
To see the kind of spectrum and what information it contains, let us focus on the fundamental
band, n = 1 ← 0.
J = +1 R Branch
J’
5 Ev =1, J +1 − E0, J = hn e − 2hn e  e + 2hB( J + 1)
4
= hn10 + 2hB( J + 1)
n’= 1 3
2
1
0
J = 0 Q Branch
J”
5 Forbidden, violates the selectrion rule for J.
4
n”= 0 3
2 J = −1 P Branch
1
0
P Branch R Branch Ev =1, J −1 − E0, J = hn e − 2hn e  e − 2hBJ
= hn10 − 2hBJ
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Rotation-Vibration Interaction. Rovibrational Spectrum.

Line Intensity
The intensity of each R, P branch line depends on the n Branch J -Source
population of the starting rotational level:

P Branch, J = -1 R Branch, J = +1
Ev =1, J −1 − E0, J = hn10 − 2hBJ Ev =1, J +1 − E0, J = hn10 + 2hB( J + 1)

P2 R2
P3 R1
P1 R3
n P1 = n 0 − 2 B 1←2 R0
3←2 n R0 = n 0 + 2 B
P4 0←1 R4
2←3 2←1 4←3
n P2 = n 0 − 4 B P5 R5 n R1 = n 0 + 4 B
3←4 1←0 5←4
n P3 = n 0 − 6 B 4←5 6←5 n R2 = n 0 + 6 B
 
n0 n

Within this model (anharmonic oscillator + rigid rotor), the spectrum is composed
of lines evenly spaced by 2B.
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Rotation-Vibration Interaction. Rovibrational Spectrum.

Vibration-Rotation Coupled Model

In actuality, band separation is not even: R branch

P R
lines get closer, P branch lines farther apart: CO

P R

n0 n
Rotation and vibrational motions are not independent. In fact, in each vibrational state,
the expectation value for the interatomic distance varies, and so does the inertia
moment and rotational constant: B depends on the vibrational state.

𝐸v,𝐽 = ℎ𝜈𝑒 (v + 1ൗ2) − ℎ𝜈𝑒 𝜒𝑒 (v + 1ൗ2)2 + ℎ𝐵v 𝐽(𝐽 + 1)

III Vibrational Spectroscopy: Part I_Diatomic Molecules Spectroscopy

Ro-vibrational Energy Levels Vibration-Rotation Coupling Constant

Rotational
constant in the Bv = Be − a (v + 12 ) Be = rot. constant
at the equilibrium
vibrational level u
bond length value
roto-vibrational constant

h h h
B0 = B1 = Be = Be  B0  B1
8p 2cI 0 8p 2cI1 8p 2cI e

R Branch
𝐸v=1,𝐽+1 − 𝐸0,𝐽 = ℎν1՚0 + ℎ𝐵1 (𝐽 + 1)(𝐽 + 2) − ℎ𝐵0 𝐽(𝐽 + 1)
= ℎν1՚0 + ℎ(𝐵0 + 𝐵1 )(𝐽 + 1) − ℎ(𝐵0 − 𝐵1 )(𝐽 + 1)2

P Branch
𝐸v=1,𝐽−1 − 𝐸0,𝐽 = ℎν1՚0 + ℎ𝐵1 (𝐽 − 1)𝐽 − ℎ𝐵0 𝐽(𝐽 + 1)
= ℎν1՚0 − ℎ(𝐵0 + 𝐵1 )𝐽 − ℎ(𝐵0 − 𝐵1 )𝐽2

On increasing J: P-lines get apart and R-lines get closer

 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Rotation-Vibration Interaction. Rovibrational Spectrum.

R4 R5 R
R3 6
R2
R7
R1
Band Head of the R Branch

R0 R8

n
1 R10 R9
𝜈𝐽𝑅 = 𝐸 − 𝐸0,𝐽
ℎ v=1,𝐽+1
= ν1՚0 + (𝐵0 + 𝐵1 )(𝐽 + 1) − (𝐵0 − 𝐵1 )(𝐽 + 1)2 Band Head

R branch lines get close together as J increases. For high values of J, new lines
might occur at lower frequencies (go back). This creates a frequency over which
no more lines appear: The Band Head.
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Vibrational Raman Spectroscopy

nn0
n=n0

Anti-Stokes
nn0
n=n0 nn0 n=n n=n0 nn0
0
nn0
Stokes
Rayleigh
nn0
n=n0
 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Vibrational Raman Spectroscopy

Selection Rules

The Raman selection rules are derived from the interaction of the induced dipole moment
with the electrical field in the radiation field. Remember that this implies that the transition
probability is proportional to the modulus of the matrix elements of the polarizability tensor:

2
Pv ' J 'v '' J " a  v ' J ' aˆ v '' J " d

This brings about two conditions for the transition to be allowed:

1. Polarizability must change along molecular vibration, and

2. Quantum number changes must abide by the following rules simultaneously:

v = +1 n  n0 Stokes lines INTENSE
v = 1
v = −1 n  n0 Anti − Stokes lines WEAK

J = 0,  2 Only seen in gas phase


 Spectroscopy
3.2 Vibrational Spectroscopy of Diatomic Molecules
Vibrational Raman Spectroscopy

Gas-Phase Spectra: Complete Raman Spectra with Rotational Structure

− 2 “O” Branch

J =  0 “Q” Branch
+ 2 “S” Branch

Δv=0, ΔJ=0
Vibrational
Vibrational Anti-Stokes
Stokes (Should be less intense)

Δv=+1 Δv= -1
Q ΔJ=+2 ΔJ=-2 Q

S O S O
ΔJ=+2 ΔJ=-2 ΔJ=+2 ΔJ=-2

0 → n = n − n0
VIBRATIONAL
SPECTROSCOPY OF
POLYATOMIC MOLECULES
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Introduction

Vibrational Coordinates

Each atom requires 3 coordinates to be specified (x,y,z), hence, a molecule of N

atoms needs 3N. Of these:
• 3 describe the location of the center of mass. Translation.
• 3 (2 for linear molecules) describe the orientation of the molecule. Rotation.

Molècula diatòmica
3 traslation
6 movements 2 rotation
1 vibration
Molècula poliatòmica
Linear Non linear
3 traslation 3 traslation
3N mouvements 2 rotation 3 rotation
3N-5 vibrations 3N-6 vibrations
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
The Normal Mode Approach

Harmonic Oscillator Approximation

The energy depends on 3N-6 (3N-5 for linear) coordinates.

If q1, q2, q3, .... q3N-6 are the coordinates defining the atomic displacements with respect
to equilibrium positions, the Taylor series expansion of U around the potential
energy mínimum is:

3 N −6  U  1 3 N −6 3 N −6   2U 
U (q1 ,···,q3 N −6 ) = U e (q1 ,···,q3 N −6 ) +    qi +  
  qi q j +····
i =1  qi  e 2! i =1 j =1  qi q j 
e

1 3 N −6 3 N −6   2U 
U (q1 ,···,q3 N −6 ) = U e (q1 ,···,q3 N −6 ) +     qi q j
2! i =1 j =1  qi q j 
e

Second order truncation

 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
The Normal Mode Approach

This potential energy term brings up a Shrödinger equation that is difficult to solve, because of
the cross-terms:
2 3 N −6
1  2 1 3 N −6 3 N −6   2U 
Hˆ vib = −
2
 +  
mi qi2 2 i =1 j =1  qi q j
 qi q j
i =1  Re

In the atomic coordinates (or displacements), the corresponding Schrödinger equation cannot
be solved.

The equation can be split into 3N-6 (or 3N-5 for linear molecules) uncoupled equations, by
means of the normal mode transformation.

Change coordinates q→ Q Normal modes coordinates

 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
The Normal Mode Approach

What are Normal Modes?

The normal modes represent a coordinate change, a different

way of representing the geometry of the molecule. In these
coordinates, potential energy is uncoupled → the molecule
behaves as a sum of independent oscillators.

In each normal mode:

• all atoms move in phase...
• ...with the same frequency,
• ...though not to the same extent (amplitude).
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
The Normal Mode Approach. H2O

Normal modes are then a different coordinate set to represent the same
molecule. This means that no information is lost and each and every arrangement
of the molecule can be represented also in normal modes. For instance:

NORMAL MODE COORDINATES

d1
INTERNAL COORDINATES

Q1

d2 H2O
Q2
3N-6=3

Q3

 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
The Normal Mode Approach

3 N −6
−  2
 2
1
Hˆ vib =  Hˆ k ˆ
on H k =
2 Qk2 2
+  Q
k k
2

k =1

3𝑁−6
𝛼𝑘 𝑄𝑘2൘
−
Ψ = ෑ Ψ𝑘 on Ψk (𝑄𝑘 ) = 𝑁v𝑘 𝐻v𝑘 (𝑄𝑘 )𝑒 2
𝑘=1

3𝑁−6
1
𝐸𝑣𝑖𝑏 = ෍ 𝐸𝑘 on Ek = ℎ𝜈𝑒,𝑘 (v𝑘 + )
2
𝑘=1

nk és el vibrational quantum number of the mode k

3𝑁−6
1
𝐸𝑣𝑖𝑏 = ෍ ℎ𝜈𝑒,𝑘 (v𝑘 + )
2
𝑘=1

5
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Quantum Mechanical Solution

Vibrational Energy

The vibrational energy is the sum of energies of each vibrational mode.

3𝑁−6
(𝑘) (𝑘) (𝑘) 1 𝐸vib = 𝐸(v1 , v2 ,·····, v3𝑁−6 )
𝐸vib = ෍ 𝐸vib where 𝐸vib = ℎ𝜈𝑒 (v𝑘 + )
2
𝑘=1

Zero-Point Energy (ZPE)

The lowest possible energy is attained when all vibrational modes are in their

ground states, that is, all vk=0.

1 3 N −6 ( k )
ZPE = E (0,,0) = h  n e
2 k =1
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Quantum Mechanical Solution

Selection Rules

In polyatomic molecules the selection rule is the same as for diatomic

molecules, but on a per mode basis:

Δv𝑖 = ±1

plus the requirement that normal mode i has a dipole moment that changes
along its vibration.

Spectrum: Fundamental Bands

One fundamental band per mode. 1 ՚ 0 = v𝑖 , v𝑗≠𝑖 = 0

(𝑖) 3 (𝑖) 1
Δ𝐸1՚0=v𝑖 ,𝑣𝑖≠𝑘 =0 = ℎ𝜈𝑒 (v𝑖 + ) − ℎ𝜈𝑒 (v𝑖 + )
2 2
(𝑖)
= ℎ𝜈𝑒
n (e1) n (e2 ) n (e3) n
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Quantum Mechanical Solution
Spectrum: Combination Bands

• The harmonic oscillator model forbids changes in the vibrational quantum number
of a specific mode exceeding ±1.

• There is nothing, however, that prevents more than one mode to change in a
given transition, provided that all modes involved abide by the selection rule

Δv=±1.

• Thus, it is possible to have two or three vibrational modes simultaneously excited,

The resulting bands are called combination bands.

Example: combination band of modes i and j:

n (e j ) + n (e j ) n
3𝑁−6
(𝑘) 1 n (ie ) n (e j )
𝐸vib (v1 , ⋯ , v3𝑁−6 ) = ℎ ෍ 𝜈𝑒 v𝑘 +
2
𝑘=1
Δ𝐸(𝑖 + 𝑗) = 𝐸vib (v1 , ⋯ , v𝑖 + 1, ⋯ , v𝑗 + 1, ⋯ , v3𝑁−6 ) − 𝐸vib (v1 , ⋯ , v𝑖 , ⋯ , v𝑗 , ⋯ , v3𝑁−6 )
(𝑖) (𝑗)
= ℎ 𝜈𝑒 + 𝜈𝑒
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Quantum Mechanical Solution. An Example.

Example: H2O

Normal Modes of Vibration: 3N-6 = 3

(1) 1 (2) 1 (3) 1

𝐸(v1 , v2 , v3 ) = ℎ𝜈𝑒 (v1 + ) + ℎ𝜈𝑒 (v2 + ) + ℎ𝜈𝑒 (v3 + )
2 2 2

Zero-point Energy

E (0,0,0) = 12 hn (e1) + 12 hn (e2 ) + 12 hn (e3) = 12 h(n (e1) + n (e2 ) + n (e3) )

Fundamental Bands A maximum of three fundamental bands will be seen

(1)
v1 1 ՚ 0; v2 = v3 = 0 𝐸(1,0,0) − 𝐸(0,0,0) = ℎ𝜈𝑒
(2)
v2 1 ՚ 0; v1 = v3 = 0 𝐸(0,1,0) − 𝐸(0,0,0) = ℎ𝜈𝑒
(3)
v3 1 ՚ 0; v1 = v2 = 0 𝐸(0,0,1) − 𝐸(0,0,0) = ℎ𝜈𝑒
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Quantum Mechanical Solution. An Example.

Example: H2O

First Overtones (“harmonics”)

(1)
v1 2 ՚ 0; v2 = v3 = 0 𝐸(2,0,0) − 𝐸(0,0,0) = 2ℎ𝜈𝑒
(2)
v2 2 ՚ 0; v1 = v3 = 0 𝐸(0,2,0) − 𝐸(0,0,0) = 2ℎ𝜈𝑒
(3)
v3 2 ՚ 0; v1 = v2 = 0 𝐸(0,0,2) − 𝐸(0,0,0) = 2ℎ𝜈𝑒

Remember: in the harmonic oscillator, these transitions are forbidden.

Combination Bands Changes in more than one quantum number

e.g.: v1 1 ՚ 0; v2 1 ՚ 0; v3 = 0 E (1,1,0)-E (0,0,0) = hn (e1) + hn (e2 )

 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Form and Activity of Normal Vibrations.

Normal vibrations in a polyatomic molecule depend on its structure, strength of the

bonds, and the masses of the atoms. A vibrational mode almost never corresponds
to the exclusive vibration of a single bond.

Stretchings bond distances change

Vibration Types
Bendings bond angles change

H2O 3N-6=3

n (e1) = 1595 cm -1 n (e2 ) = 3650 cm-1 n (e3) = 3755 cm-1

Bending Symmetric Stretch Asymmetric Stretch

All modes are IR-active, because in all of them the dipole moment changes.
A total of three bands will be seen.
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Form and Activity of Normal Vibrations.
Bending
Symmetric
Stretch
Asymmetric
Stretch
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Form and Activity of Normal Vibrations.

CO2 3N-5=4, a linear molecule

n (e1a ) = 667 cm-1 n (e1b ) = 667 cm-1

Bending Bending

n (e2) = 1330 cm-1 n (e3) = 2350 cm-1

Symmetric Stretch Asymmetric Stretch

Question: how many bands are to be seen in the IR spectrum?

 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Form and Activity of Normal Vibrations.
Bending (2X)
Symmetric
Stretch
Asymmetric
Stretch
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Form and Activity of Normal Vibrations. General Rules.

• Stretching vibrations have higher frequencies than bending vibrations.

• Stretching vibrations of bonds with light atoms have higher frequencies than those of heavier
atoms.
• Stretching vibrations of bonds of different order follow the order of frequencies as follows: “≡“
> “=“ > “—”
• Strictly speaking, no individual bonds vibrate in a polyatomic molecule. However, some bonds retain
their characteristics in different molecules.

Group vibrations are observed,

which allow to determine
information on the structure of
the molecule.
SYMMETRY OF MOLECULAR
VIBRATIONS
49
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Symmetry of Molecular Vibrations

It is possible (and very helpful!) to classify the normal modes of a molecule according to their
symmetry, by inspecting how the motions transform under all symmetry operations of the point
group.

Example: Water

Here is how:

1. Draw arrows on all atoms that n (e1) n (e2 ) n (e3)

move in each normal mode.
2. Apply the symmetry
C2v E C2 sv(xz) sv(yz)
operations to them. A1
n (1)
e
1 1 1 1
3. Observe how the arrows of
displacement change. n (e2 ) 1 1 1 1 A1
n (e3) 1 -1 -1 1 B2
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Systematic Determination of the Symmetry of Normal Vibrations

• The energy levels, on a per mode basis

3𝑁−6
(𝑘) (𝑘) (𝑘) 1
𝐸vib = ෍ 𝐸vib where 𝐸vib = ℎ𝜈𝑒 (v𝑘 + ) 𝐸vib = 𝐸(v1 , v2 ,·····, v3𝑁−6 )
2
𝑘=1

• Selection rules. Transition will be allowed (i.e. mode will be active) if simultaneously:

• The normal mode changes the dipole moment of the molecule...

• Δv𝑖 = ±1

• How can we know, from the form of the normal mode, whether it is active or not?

The answer is: Symmetry

 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Systematic Determination of the Symmetry of Normal Vibrations

Symmetry of Normal Modes

Find the reducible representation in the basis of individual atomic displacements, of 3N

elements.
Ê
 11 00 00 00 00 00 00 00 00  x1   xx11
     
E.g. H2O  00 11 00 00 00 00 00 00 0  
0 y1   yy11
 00 00 11 00 00 00 00 00 00  z1   zz11
    

?
z 
 00 00 00 11 00 00 00 00 00  x2   xx22 
 00  y2  =  y?y22 

 00 00 00 11 00 00 00 00 
z1
 00 00 00 00 00 11 00 00 00  z 2   zz22 
     
O y1  00 00 00 00 00 00 11 00 0
0   x3   xx33 
y
z3
x1 z2  00 00 00 00 00 00 00 11 00  y3   yy33 
     
 00 00 00 00 00 00 00 00 11  z3   zz33 
H y3 H y2
()
3N
x3 x2 ( Eˆ ) = Tr Eˆ =  Eii = 9
i =1
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Systematic Determination of the Symmetry of Normal Vibrations

z1
Ĉ 2
O y1
x1 z2
y −−11 00 00 00 00 00 00 00 00  x1   −xx1 1
z3      
 00 − 11 00 00 00 00 00 00 0  
0 y1   −yy1 1
H y3 H y2  00 00 11 00 00 00 00 00 00  z1   zz1 1
    

?

x3 x2  00 00 00 01 00 00 − 10 00 00  x2   −xx2 3
 
 00 00 00 00 01 00 00 − 10 00  y2  =  −?yy2 3
z 
 00 00 00 00 00 01 00 00 10  z 2   zz2 3
z1      
 00 00 00 − 10 00 00 01 00 00  x3   −xx3 2
-y1 -x1
O y  00 00 00 00 − 10 00 00 01 00  y3   −yy3 2
     
 00 00 00 00 00 10 00 00 01  z3   z3 2 z
H H

( )
(Cˆ 2 ) = Tr Cˆ 2 = −1
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Systematic Determination of the Symmetry of Normal Vibrations

Suggested Exercise:

z
Find the character of the “atomic displacements
basis” corresponding to the remaining
z1
operations, and verify:

O y1
x1 z2 y
z3

H y3 H y2 (sˆ xz ) = 1
x3 x2
(sˆ yz ) = 3
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Systematic Determination of the Symmetry of Normal Vibrations

Reducible Representation of the Atomic Displacements (H2O)

C2v E C2 s(xz) s(yz)

Γ(3N) 9 -1 1 3
NDA 3 1 1 3
(G(x,y,z) 3 -1 1 1

G(3N) = NDA (R) x (R )

Rule:
For each atom (with three coordinates) that remains in place, the contribution to the trace is:

2p
( Eˆ ) = 3 (Cˆ n ) = 1 + 2 cos
n
(sˆ ) = 1
2p
(iˆ) = −3 ( Sˆn ) = −1 + 2 cos
n
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Systematic Determination of the Symmetry of Normal Vibrations

Decomposing the Representation of Atomic Displacements (H2O)

C2v E C2 s(xz) s(yz)

Character

A1 1 1 1 1
Symmetry composition
Table

A2 1 1 -1 -1 of atomic
B1 1 -1 1 -1 displacements

B2 1 -1 -1 1
? Γ(3N) 9 -1 1 3 = 3 A1 + A2 + 2B1 + 3B2
a A1 =
1
(1 9 1 + 1 (−1) 1 + 111 + 1 3 1) = 3
4
a A2 = (1 9 1 + 1 (−1) 1 + 11 (−1) + 1 3  (−1) ) = 1
1
1
 g C i (C ) G (C )
4
ai =
aB1 = (1 9 1 + 1 (−1)  (−1) + 111 + 1 3  (−1) ) = 2
h C 1
4
aB2 = (1 9 1 + 1 (−1)  (−1) + 11 (−1) + 1 3 1) = 3
1
4
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Systematic Determination of the Symmetry of Normal Vibrations

The decomposed representation of the atomic displacements contains also the

representations of the global traslations (x, y, z) and rotations (Rx, Ry, Rz). These
need to be taken away to leave only those of the vibrational normal modes:

G3 N = 3 A1 + A2 + 2 B1 + 3B2
Rotations &
G3 N −6 = G3 N − G( x, y, z ) − G( Rx , R y , Rz ) Translations
Character
Table

G3 N −6 = 3 A1 + A2 + 2 B1 + 3B2 − ( B1 + B2 + A1 ) − ( B2 + B1 + A2 ) G3 N −6 = 2 A1 + B2
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Systematic Determination of the Symmetry of Normal Vibrations

Decomposing the Representation of Atomic Displacements (H2O)

The symmetry analysis does not provide a description of which of these modes are
stretchings and which bendings.

Stretchings can be analized using the basis of the bonds and decomposing the
representation thus obtained:

Stretchings

z Asymmetric
stretch
C2v E C2 sv(xz) sv(yz)
y
GO-H 2 0 0 2 = A1 + B2
Symmetric stretch
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Activity of Normal Modes. Selection Rules

Selection Rules

Δv = ±1, ±2, ± 3, ···

෠Ԧ
𝜇Ԧv′ v′′ = නΨv∗ ′ 𝜇Ψ Harmonic Oscillator
v′′ 𝑑𝜏 ≠ 0 AND

Dipole moment must change along vibration

Symmetry Conditions that Make the Integral Non-Zero

Ԧመ v′′ 𝑑𝜏 ≠ 0
𝜇Ԧv′ v′′ = නΨv∗ ′ 𝜇Ψ ΓΨv′ ⊗ Γ𝜇 ⊗ ΓΨv′ ′ ⊃ ΓTSR Product must be, or contain, the
totally symmetric representation

x  Γ𝜇𝑥
   ΓΨv′ ⊗ Γ𝜇𝑦 ⊗ ΓΨv′ ′ = ΓTSR
It is enough that one of the three
 = y  products contains the TSR to have
  Γ𝜇𝑧
 z an active mode.
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Activity of Normal Modes. Selection Rules

Fundamental Bands (v’=1 ← v’’=0): Active or Not?

If a mode is active, G1  G  G0  GTSR

the fundamental band is the most intense, because the ground state is the most
populated in each mode at all temperatures.

Symmetry Species of the Three Terms Involved:

v (Qi ) = N v H v (Qi )e − aQi

2

 G x   G x 
0 (Qi ) = N 0e − aQi 2 G0 = GTSR    
G1   G y   G0 = G1   G y 
G1 G  G 
1 (Qi ) = NQi e −aQi
2
Has the same  z
  z 
symmetry species as
the mode
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Activity of Normal Modes. Selection Rules

Example: H2O  G x   G x 
   
Symmetries of Vibrational G1   G y   G0  GTSR G1   G y   A1  GTSR
G  G 
Normal Modes:  z 
 z 
G3 N −6 = 2 A1 + B2
C2v E C2 s(xz) s(yz)

Gmode G TSR A1 1 1 1 1 z
A2 1 1 -1 -1 Rz
B1 1 -1 1 -1 x, Ry
 B1   B1 
    B2 1 -1 -1 1 y, Rx
A1   B2  =  B2 
?
ALLOWED

A  A  B2 x B1 1 1 -1 -1 A2
 1  1
B2 x B2 1 1 1 1 A1
 B1   A2  B2 x A1 1 -1 -1 1 B2
   
B2   B2  =  ?
A1 
 A  B  If the symmetry of the normal mode matches the symmetry of any
 1  2
of the components of the dipole moment, then the mode is active
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Vibrational Raman Spectroscopy

C
IR H3C CH3

Rayleigh

Raman
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Vibrational Raman Spectroscopy

Raman Selection Rules

Raman transitions do not depend directly on the molecular dipole moment. They arise thanks to the induced dipole
moment, caused by the polarizing effect of the electromagnetic radiation on the molecule.

The induced dipole moment is determined by the polarizability tensor and the electrical field:

  
induced = aE = aE0 cos t

a v 'v '' =  v ' aˆ v '' d " " 0

A vibrational transition is going to be allowed in the Raman
spectrum if the two following conditions hold:
• Polarizability must change along the molecular motion (Δα v = 1,  2,  3, ··· Harmonic
≠ 0) Oscillator

• At least a non-zero polarizability tensor matrix element  aˆ xx aˆ xy aˆ xz 

 
exists: aˆ =  aˆ yx aˆ yy aˆ yz 
 aˆ aˆ zy aˆ zz 
 zx
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Vibrational Raman Spectroscopy

Fundamental Bands (v’=1 ← v’’=0): Active or Not in Raman?

a v 'v '' =  v ' aˆ v '' d " " 0

As seen before for “conventional” spectroscopy, determining whether a Raman mode is active
in the IR can be assessed by symmetry. The matrix elements of the polarizability tensor will be
non-zero provided that the integrand contains the totally symmetric representation:

G1  Ga  G0  GTSR

 Ga Ga xy Ga xz  And because  Ga Ga xy Ga xz 
 xx  xx
G1   Ga xy Ga yy Ga yz   G0  GTSR G0 = GTSR G1   Ga xy Ga yy Ga yz   GTSR
   
Ga zz   Ga xz Ga yz Ga zz 
 Ga xz Ga yz
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Vibrational Raman Spectroscopy

Example: H2O
All are Raman-
Symmetries of Vibrational Normal Modes: G3 N −6 = 2 A1 + B2 allowed

The elements of the dipole Analogously, the elements of the

moment have the same polarizability tensor have the
symmetry properties as the same symmetry properties as
coordinates coordinate products

If the symmetry of the normal mode coincides with

that of any component of the polarizability tensor,
the mode is Raman-active
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Vibrational Raman Spectroscopy

Mutual Exclusion Rule

For molecules with inversion center (î) Selection Rules

1  0  0 ( = i , aij i, j = x, y, z)
The existence of this symmetry element has specific
consequences for the dipole moment and polarizability tensor
components: Because Ψ0 is gerade, the product ΩΨ0 has the
• Components of the dipole moment are odd (ungerade), as same parity as Ω.
they depend on single coordinates.
• Components of the polarizability tensor are even (gerade), Because Ψ1 can either be gerade or ungerade, a
as they are quadratic forms. given mode cannot be active in IR and Raman at the
same time

“In molecules with inversion

center, a given normal mode
cannot be IR and Raman active”
 Spectroscopy
3.3 Vibrational Spectroscopy of Polyatomic Molecules
Vibrational Raman Spectroscopy
D. J. Willock, “Molecular Symmetry”, Wiley, 2009, p. 185.