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PG510

Symmetry and
Molecular Spectroscopy
Lecture no. 8
Molecular Spectroscopy:
Vibrational Spectroscopy of Polyatomic Molecules
Giuseppe Pileio

Learning Outcomes
By the end of this lecture you will be able to:
!! Understand the concept of vibrational modes
!! Calculate the number, the symmetry and the form of
normal modes of vibrations
!! Use group theory to predict how many of these modes
will contribute to the spectrum and their polarization
!! Extract molecular information from vibrational
spectra
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Normal modes of vibration


A molecular vibration is a movement that involves the nuclei
without changing the position of the center of mass
Although the vibration of a molecule appears a very
complex motion it can be decomposed into a finite set of
normal modes of vibrations

A normal mode is a collective motion of all the atoms. Each


atom moves in phase with each other at a characteristic
frequency.
The blue vector are called displacement vectors

Three are the most important features of normal modes of


vibrations:
1.! Their number is finite and depends on the
number of atoms
2.! Each normal mode oscillates at a frequency
which is characteristic
3.! Each normal mode transforms as one of the
irreducible representations of the group the
molecule belongs to
Group theory: given a molecule the group theory is able to
predict how many normal modes there are, their symmetry
and how many of them are IR active (will contribute to the
vibrational spectrum)
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The number of normal modes


To count the number of normal modes few facts should be
noted:
1.! In a molecule of N atoms each
atom can move in the three
direction of the Cartesian
space, so there are 3N
degrees of freedom
2.! However, if all the N atoms
move along the x (y or z)
direction then the center of
mass translates. Then three of
these 3N modes are in fact
molecular translations

z
z

z
y

x
x

3.! Moreover, the movement in which all the atoms moves


in circular paths about one of the three axes
corresponds to molecular rotations, i.e. another 3* of
the 3N total modes are not vibrations
* linear molecules have only 2 rotational
modes (the rotation along the principal
axis does not, in fact, rotate any atom)

Then, a molecule of N atoms has:


! 3 translational modes
! 3 or 2 rotational modes (non-linear/linear)
! 3N-6 or 3N-5 normal vibrational modes (non-linear/linear)
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The symmetry of normal modes


Each normal mode transforms as one of the irreducible
representations of the group the molecule belongs to.
Also, translations and rotations transform as one of the
IRREP of the group.
Thus, the entire set of 3N Cartesian displacement
vectors can be used as a base for a reducible
representation of the group
z
z
y

x
y

Group theory: Since we have


3N vectors the dimension of
the reducible representation
will be 3N

In order to find out the symmetry of the normal modes


using group theory only we need:
1.! Assign the molecular point group
Group Theory: for H2O, the principal axis is a C2, there are no
other perpendicular C2 but there are planes of symmetry along
the C2 i.e. the point group is C2v

2.! Find out the table of characters and assign the axis
frame correctly according to the table
C2v

C2

!v (xz)

!v (yz)

"1#

x2, y2, z2

"2#

-1

-1

Rz

xy

$1#

-1

-1

x, Ry

xz

$2#

-1

-1

y, Rx

yz

%xyz

-1

3.! Write the 3N-order reducible representation of the


Cartesian displacements, %tot
Group Theory: This step is immediate, just multiply the
representation of the Cartesian axes (!xyz bottom line of
character table or sum of the representation which x, y and z
belong to) by the number of unmoved atoms
E ! leaves all unmoved
C2 ! leaves only O unmoved
"(xz) ! leaves all unmoved
"(yz) ! leaves anly O unmoved
C2v

C2

!v (xz)

!v (yz)

%xyz

-1

unmoved
atoms

%tot

-1

1
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4.! Decompose the reducible representation %tot in the


sum of irreps
Group Theory:

aj = 1/h (!R #(R) #j(R) )

!tot = 3A1 + A2 + 3B1 + 2B2


5.! Remove from the decomposition the 3 IRREP which
translations and the 3 (or 2 if linear molecules) which
rotations belongs to
Group Theory: rotations (Rx, Ry, Rz) and translations (x, y, z)
transformations are reported in the table of characters

!rot = A2 + B1 + B2

!tran = A1 + B1 + B2

!vib = !tot !rot !tran = 2A1 + B1

$
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Separation of modes
Polyatomic molecules have a bunch of different way to
vibrate: stretching of bond, in-plane bending of bonds,
out-of-plane bending, twisting, rocking, torsions etc

It is actually possible to isolate them and look for their


symmetries and properties
This is done using the same technique but substituting
the reducible representation of the Cartesian
displacement with the reducible representation of all the
stretching or bending etc
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Stretching analysis:
1.! Write the reducible representation of
stretching modes
Group Theory: it is possible to calculate the
character of a representative of a symmetry
operation simply using the following rules:
1.! each object moved to another place
contribute as 0
2.! each object inverted contributes as -1
3.! each object unmoved contributes as 1
C2v

C2

!v (xz)

!v (yz)

%str

2.! Decompose the reducible representation %str in the


sum of irreps

!str = A1 + B1

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Bending analysis:
1.! Write the reducible representation of
bending modes
Note that this

is one object only

C2v

C2

!v (xz)

!v (yz)

%str

2.! Decompose the reducible representation %str in the


sum of irreps
Note that in this case the representation of the bending
is already an irrep

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Symmetry Coordinates
Symmetry coordinates are pictures of normal modes, i.e.
it is possible to write down the picture of the normal
mode of a given symmetry

$
S!j ! ! j #"R##R#s
R

Notes:
! The symmetry coordinates are approximations of the normal modes
! In molecules where the principal axis is a Cn the sum can be
restricted to the Cn pure rotational group
! In the case in which the energies of two modes are close (and the
two modes have the same symmetry) then the symmetry coordinates
are no more a good approximation to the real normal modes
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choosing the vector s to be the stretching of OH bonds:


for the mode with A1 symmetry:
1

C2

symmetric
stretch

And the mode with B1 symmetry


1

-1

C2

asymmetric
stretch

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Selection rules
Vibrational selection rules for polyatomic molecules can
be rationalized recalling the form of the transition
moment operator:
"

e
" $i,rot %z $j,rot %' rot ) #" $i,el % %$j,el %' el %" $i,vib %$j,vib %' vib * ! " $i,el %

"x,y,z

Pure vibrational transition

3%N+6
i"1

%$j,el %' el %" $i,vib %Qi %$j,vib %' vib $

Qi

! !i,vib " "!j,vib "% vib

Group Theory: The integral is different from zero only if


%(&i,vib)x%(')x%(&j,vib) does contain the total symmetric of
the group the molecule belongs to
The problem is now to find the symmetry of the three
objects involved

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The dipole moment transforms as x,y and z being


expressed as:
!
!
" e.r

Group Theory: the symmetry of x,y and z is reported in


the table of characters
At room temperature most of the vibrations occur with
their zero point (v=0) energy and since a molecule has
3N-6 (3N-5 if linear) it is possible to write:
!i,vib " !1 #!v1 "#!2 #!v2 " ...#!3#N$6 #!v3#N$6 "

So that the excitation of its normal mode no. 1 from v=0


to v=1 ((v=1) can be written as:
!1 "!0""!2 "!0" ..."!3"N#6 "!0" $ !1 "!1""!2 "!0" ..."!3"N#6 "!0"

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Now it is possible to demonstrate that:


!i "!0" # total symmetric

Moreover, it is also possible to demonstrate that:


!i "!1" # ith normal mode

And, by the way, that for v=even &i(v) is total symmetric


while transforms as the i-th normal mode for v=odd (only
if the mode is not degenerate otherwise more complicate
equations occur)
Thus, basically, the only thing to calculate is !&f(v) and:

Group Theory: the representation of the direct product


AxB (!AB) will contain the totally symmetric only if the
IRREP !A is equal to the IRREP !B
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Overtones, Combination bands and Hot bands


An IR spectrum of a polyatomic molecule shows more
peaks than expected this is because there are:
1.! Overtones: they appear nearly to a multiple of a
fundamental transition and occur when a mode is excited
beyond v=1
!1 "!0""!2 "!0" ..."!3"N#6 "!0" $ !1 "!2""!2 "!0" ..."!3"N#6 "!0"

2.! Combination bands: they occur when more than one mode
is excited and appear at the sum of the frequency of all
the modes involved
!1 "!0""!2 "!0" ..."!3"N#6 "!0" $ !1 "!1""!2 "!1" ..."!3"N#6 "!0"

3.! Hot bands: they occur when an already excited vibration


is further excited and appear at a slightly less frequency
of the fundamental of that mode
!1 "!1""!2 "!0" ..."!3"N#6 "!0" $ !1 "!2""!2 "!0" ..."!3"N#6 "!0"

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Vibrational Spectra of polyatomic molecules


Functional Group

Fingerprint

Ethyl ethanoate

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Information Content
An IR spectrum contains a lot of information that with
the help of group theory give important hints on the
molecule:
The spectrum contains the frequency of normal modes
whose number, symmetry and form can be derived by
group theory
The 400-1200 cm-1 region (called
fingerprint region) is unique for
each molecule
The 1200-4000 cm-1 region
contains the fundamental
transition characteristic of
different functional group

identification of
unknown samples

identification of
functional groups
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Another very interesting information provided by the


combination of IR spectroscopy and group theory is the
assignment of structure. Suppose we have:
L
O=C

C=O
L

C=O

C=O

mer

C=O

C=O

fac

C2v

C2

!v (xz)

!v (yz)

C3v

2C3

3!v

mer %str

fac %str

!str = 2A1 + B2 all IR active

!str = A1 + E all IR active

3 bands expected in the


C=O region

2 bands expected in the


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C=O region

What did we learn in this lecture?

! What is a normal mode


! Number and symmetry of normal modes through group
theory
! How to draw a picture as a good approximation of the
normal mode
! How to calculate how many modes will appear in the
vibrational spectrum and their polarization
! The info encoded in vibrational spectra
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