PG510

Symmetry and
Molecular Spectroscopy
Lecture no. 7
Molecular Spectroscopy:
Rotational, vibrational and
Roto-vibrational Spectroscopy of diatomic Molecules
Giuseppe Pileio

Learning Outcomes
By the end of this lecture you will be able to:
!! Understand the fundamentals of pure rotational
spectroscopy
!! Understand the fundamentals of pure vibrational
spectroscopy of diatomic molecules
!! Understand the fundamentals of roto-vibrational
spectroscopy of diatomic molecules
!! Extract molecular information from these molecular
spectra
2

Moment of inertia and rotor classification

The moment of inertia is the inertia of a rigid rotating
body with respect to its rotation
Different axes of rotation will have, in general, different
moment of inertia. Thus, the moment of inertia is better
represented by a tensor:
Ijk ! !
N

mi ""r2i "jk

$ rij "rik #

i!1

Ixx Ixy Ixz

Iyx Iyy Iyz
Izx Izy Izz

! principal frame !

Ixx 0
0
0 Iyy 0
0
0 Izz

Rotor (molecules) classification

O2, CO, CO2

1.! Linear

Izz ! 0 and Ixx ! Iyy

2.! Symmetric

Izz ! Ixx " Iyy or Izz # Ixx " Iyy

3.! Spherical

Izz ! Ixx ! Iyy

CH4, SF6

4.! Asymmetric

Izz ! Ixx ! Iyy

H2O, NO2

NH3, CHCl3

Pure Rotational Spectroscopy

Rotational Spectroscopy is the study of the interaction
between a Micro-Wave (MW, 1-1000 GHz or 0.03-33 cm-1)
radiation and the matter
The interaction is between the radiofrequency and the
molecular electric dipole moment

!
!
" e.r
I~

r"

e
! !i,el " "!j,el "% el "! !i,vib "!j,vib "% vib

then if the molecule does not have a permanent dipole

moment it cannot have rotational spectrum
4

Group Theory:
o! If the molecule has a dipole moment it should lie on its
principal axis
o! Homonuclear diatomic molecules cannot have a
permanent dipole since the two atoms equally attract
electrons
o! Molecules with a centre of inversion cannot have a
permanent dipole
o! Spherical molecules cannot have a permanent dipole
Heteronuclear "+
diatomic

Homonuclear
diatomic

"-

Non-centrosymmetric

"+

Spherical

"-

"+

"-

"+

"+

"+
"+

Rotational Energy: linear molecules

1

Rigid Rotor

E!

Classical theory "

I ! r2
!

J=3
6B
4B
2B

J=2
J=1
J=0

"I 2

m1 "m2
m1 % m2

# QuantumTheory
EJ ! B J"!J # 1"
B!

!2
2"I

J ! 0, 1, 2, ...

Non-rigid rotor

Restoring Force
F=-k(r-re)
re

Classical theory:
r

E!

1
2

"Ie 2 $

1 Ie 4
"

2 k

QuantumTheory

J=3

J=3

6B
J=2

4B

J=2

J=1

2B

J=1
J=0

J=0
rigid

non-rigid

EJ ! B J"!J # 1" $ D J2 "!J # 1"2

B!
D!

!2
2"I
!4
2#I3 #k

Pure Rotational Spectra of linear molecule

To understand how a pure rotational spectrum of a linear
molecule will look like we need:
1) Selection rules, i.e. when

! !i " !j "$ & 0

!J " # 1

2) frequencies, i.e. !E " #J$1 % EJ " h

!E " #J$1 % EJ " h
!E " 2'B !J $ 1"

Rigid rotor

This means that if we take a pure rotational spectrum of a

diatomic heteronuclear molecule it is made by a series of peaks
spaced 2B in the rigid hypothesis of whose space decreases as J
increases for the more realistic case of a non-rigid rotor
8

3) intensities, i.e. population of energy levels

nj
ni

gj
gi

"e#$E!kT

Rotational levels are degenerate since for each J

there are 2J+1 levels with mJ=0, 1, 2, , J
gJ ! 2"J # 1

nJ
n0

! !2"J # 1""e$BJ"!J#1"#kT

Pure Vibrational Spectroscopy

Vibrational Spectroscopy is the study of the interaction
between an infra-red (IR, 400-4000 cm-1) radiation and the
matter
Such a radiofrequency stimulates molecular vibrations, i.e.
nuclei move from their original position with the center of
mass unmoved
Although the interaction is, as in rotational spectroscopy,
between the radiation and the dipole moment, the molecule
does not need to have a permanent dipole moment since
some vibrations can generate instantaneous dipoles
10

In other words, the requirement this time is that the

dipole moment is a function of the vibrational coordinates
i.e. the vibration has to create a dipole
Group theory: a D!h molecule
cannot have a permanent dipole
since has an inversion center

"+

a symmetric stretch of the two

bonds do not generate dipoles

"+

"-

"+

"-

"-

"+

"+

the asymmetric stretch of the two

bonds do generate a net dipole

"+

11

Vibrational Spectroscopy of diatomic molecules

We first consider the simplest case of a diatomic molecule
where the only vibrational motion can be the stretch of the
molecular bond
Harmonic oscillator
Classical Theory "

q ! !r " re "

re

F ! "k q
E!

1
2

#k q2

# QuantumTheory
Ev ! v "

1
2#

#h

v ! 0, 1, 2, ...

12

Actually, the harmonic symmetric potential is a poor

representation for diatomic molecules. In fact, when q
decreases the atoms start to repel and if it increases the
molecule start to dissociate. This suggest an asymmetric
potential need to be used
Anharmonic oscillator
#q 2
Classical Theory " Morse Potential E ! De "!1 # e "

QuantumTheory:
Ev ! v "

e !

1
2

#h e %
De

v"

#h e #xe

h e

xe !

2#

4#De
13

Pure vibrational spectra of diatomic molecules

To understand how a pure vibrational spectrum of a
diatomic molecule will look like we need:
1) Selection rules, i.e. when ! !i " !j "$ & 0

!v " # 1

2) frequencies, i.e. !E " #v $ E0 " h

v " e $v % e $xe $v$!v & 1"

Transition from v=0 to v=1 is the fundamental, v=0 to v=2 is the first
overtone, v=0 to v=3 is the second overtone and so on.
Transition from v>0 are unlikely since those levels are scarcely populated

3) intensities, i.e. population of energy levels

nv
n0

"!v# 1 "$h#kT
2

" 1 $h#kT
e 2

! e"vh#kT

14

Roto-vibrational spectroscopy of diatomic molecules

However, since the IR frequencies are bigger that MW then
rotational transitions are also stimulated during a vibrational
$J=2!
transition
~4B!

This make possible to

observe the rotational
fine structure of a
vibrational transition

$v=1!

~2B!

$J=1!
$J=0!

~h#!
~4B!
~2B!

$v=0!

$J=2!
$J=1!
$J=0!

Red pure rotational; Black pure vibrational; Blue vibro-rotational

Of course this can be done if there is enough resolution to

see the small splitting of rotational lines (~2B i.e. few cm-1)
underneath the bigger split of vibrational lines (~h# i.e.
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102-103 cm-1) " low pressure gas phase

Roto-vibrational energies of diatomic molecules

non-rigid rotor

Ev,J ! Be J"!J # 1" $ D J2 "!J # 1"2

# v#

1
2

$e " v #

with

e "

"h e $
1
2

v#

1
2

anharmonic oscillator

"h e "xe

vibro-rotational coupling

"J"!J # 1"

3# !3 #e
2# r2e #De

1
re

1
2 #r2e

and also:
Ev,J ! Bv J"!J # 1" $ D J2 "!J # 1"2 # v #

Bv ! Be " e $ v %

1
2

1
2

"h e $

v#

1
2

"h e "xe

Rotational constants are different

for different vibrational levels

16

Roto-vibrational spectra of diatomic molecules

To understand how roto-vibrational spectra look like we
also need:
1) Selection rules: in this case both rotational and
vibrational rules need to be satisfied, i.e. !v " # 1, !J " # 1
! Transition are indicated as (v,J) -> (v,J)
! in the fundamental band v = 0->1 all transitions are (0,J)->(1,J1)
o! (0,0)->(1,0) is called Q branch observed only in linear polyatomic
and symmetric molecules (two moment of inertia are equal)
Q "!J" # h e % J !J & 1" !B0 % B1 "

o! (0,J)->(1,J-1) is called P branch (frequency lower than !e)

P "!J" # h e % J !B0 & B1 " & J2 !%B0 & B1 "

o! (0,J)->(1,J+1) is called R branch (frequency higher than !e)

R "!J" # h e % 2 B1 % J2 !&B0 % B1 " % J !&B0 % 3 B1 "

Two close lines due to

the two isotopes of Cl
(m=35,m=37)
Be !

!2

2"

r2e

"

m1 #m2

17

~B0,B1

m1 $ m2

HCl

no Q band
18

2) Intensities: the form of a vibrational band is due to

the two rotational bands (P and R) which, in turn, have
the characteristic shape of a rotational spectrum
Temperature effect: the R branch at low temperatures is higher
then P branch since P transitions originates from levels with higher
J that are less populated at low temperatures

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Vibro-rotational Spectra: Information Content

CO

The difference between a P and a R transition that end at

the same value of J is proportional to B0 only
P " E#!1, J $ 1" $ E#!0, J" " h e $ J !1 & J" B0 & !$1 & J" J B1

R " E#!1, J $ 1" $ E#!0, J $ 2" " h e $ !2 & !$3 & J" J" B0 & !$1 & J" J B1
P $ R " 2 !1 $ 2 J" B0

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The difference between a P and a R transition stating from

the same value of J is proportional to B1 only
P " E#!1, J $ 1" $ E#!0, J" " h e $ J !1 & J" B0 & !$1 & J" J B1

R " E#!1, J & 1" $ E#!0, J" " h e $ J !1 & J" B0 & !1 & J" !2 & J" B1
P $ R " $2 !1 & 2 J" B1

Bvs contain info on inter-nuclear

distance in the equilibrium or in
the vibrational excited state
The center of the spectrum is the
pure vibrational frequency which
gives the potential parameters

Bv ! Be " e $ v %

Be !

e "

!2
2" r2e

De
2%
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What did we learn in this lecture?

! The basics of rotational, vibrational and roto-vibrational

spectroscopy
! The rigid and non-rigid rotor description of molecular
rotations
! The harmonic and anharmonic oscillator description of
molecular vibration in diatomic molecules
! The expected spectral patterns
! The info encoded in these spectra
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