Symmetry Applications

Chem. 285 Lecture Notes

Advanced Inorganic Chemistry
Symmetry and Dipole Moments
Chirality
Optical Activity or Chirality
Vibrational Spectroscopy
Spectroscopy is the study of the interaction of matter with energy
(radiation in the electromagnetic spectrum). A molecular vibration is a
periodic distortion of a molecule from its equilibrium geometry. The
energy required for a molecule to vibrate is quantized (not
continuous) and is generally in the infrared region of the
electromagnetic spectrum.
r
e
= equilibrium distance between A and B
r
e

For a diatomic molecule (A-B), the bond between the two
atoms can be approximated by a spring that restores the
distance between A and B to its equilibrium value. The
bond can be assigned a force constant, k (in Nm
-1
; the
stronger the bond, the larger k) and the relationship
between the frequency of the vibration, e, is given by the
relationship:
D
AB

r
AB
0
D
AB
= energy required to dissociate into A and B atoms
e

=
k 2t v

c
k
=
or, more typically
Vibrational Spectroscopy
Molecule

v (cm
-1
) k (N/m)

(amu)

HF

3962 878 19/20
HCl 2886 477 35/36 or 37/38
HBr 2558 390 79/80 or 81/82
HI 2230 290 127/128
Cl
2
557 320 17.5
Br
2
321 246 39.5
CO 2143 1855 6.9
NO 1876 1548 7.5
N
2
2331 2240 7
2t v

c
k
=
can be rearranged to solve for k (in N/m): k =

589 10
5 2
. v
For a vibration to be active (observable) in an infrared (IR) spectrum, the
vibration must change the dipole moment of the molecule. (the vibrations for
Cl
2
, Br
2
, and N
2
will not be observed in an IR experiment)
For a vibration to be active in a Raman spectrum, the vibration must change
the polarizability of the molecule.
Vibrational Spectroscopy
For polyatomic molecules, the situation is more complicated because there are
more possible types of motion. Each set of possible atomic motions is known as a
mode. There are a total of 3N possible motions for a molecule containing N
atoms because each atom can move in one of the three orthogonal directions (i.e. in
the x, y, or z direction).
Translational
modes
Rotational
modes
A mode in which all the atoms are moving in the
same direction is called a translational mode because
it is equivalent to moving the molecule - there are three
translational modes for any molecule.

A mode in which the atoms move to rotate (change
the orientation) the molecule called a rotational mode
- there are three rotational modes for any non-linear
molecule and only two for linear molecules.

The other 3N-6 modes (or 3N-5 modes for a linear molecule) for a molecule
correspond to vibrations that we might be able to observe experimentally. We
must use symmetry to figure out what how many signals we expect to see and what
atomic motions contribute to the particular vibrational modes.
Vibrational Spectroscopy and Symmetry

1. Determine the point group of the molecule.

2. Determine the Reducible Representation, I
tot
, for all possible motions of
the atoms in the molecule.

3. Identify the Irreducible Representation that provides the Reducible
Representation.

4. Identify the representations corresponding to translation (3) and rotation
(2 if linear, 3 otherwise) of the molecule. Those that are left correspond
to the vibrational modes of the molecule.

5. Determine which of the vibrational modes will be visible in an IR or
Raman experiment.
We must use character tables to determine how many signals we will see
in a vibrational spectrum (IR or Raman) of a molecule.
Example, the vibrational modes in water.
The point group is C
2v
so we must use the appropriate character
table for the reducible representation of all possible atomic motions,
I
tot
. To determine I
tot
we have to determine how each symmetry
operation affects the displacement of each atom the molecule
this is done by placing vectors parallel to the x, y and z axes on
each atom and applying the symmetry operations.
The sum for the vectors on all atoms is placed into the reducible
representation.
Vibrational Spectroscopy and Symmetry
Make a drawing of the molecule and add in vectors
on each of the atoms. Make the vectors point in
the same direction as the x (shown in blue), the y
(shown in black) and the z (shown in red) axes.
We will treat all vectors at the same time when
we are analyzing for molecular motions.
H
O
H
H O H
top view
The E operation leaves everything where it is so all nine
vectors stay in the same place and the character is 9.
The C
2
operation moves both H atoms so we can ignore the
vectors on those atoms, but we have to look at the vectors on
the oxygen atom, because it is still in the same place. The
vector in the z direction does not change (+1) but the vectors
in the x, and y directions are reversed (-1 and -1) so the
character for C
2
is -1.
The o
v
(xz) operation leaves each atom where it was so we
have to look at the vectors on each atom. The vectors in the
z and x directions do not move (+3 and +3) but the vectors in
the y direction are reversed (-3) so the character is 3.
The o
v
(yz) operation moves both H atoms so we can ignore
the vectors on those atoms, but we have to look at the vectors
on the oxygen atom, because it is still in the same place. The
vectors in the z and y directions do not move (+1 and +1) but
the vectors in the x direction is reversed (-1) so the character
is 1.
C
2V
E C
2
o
v
(xz) o
v
(yz)
I
tot
9 -1 3 1
Example, the vibrational modes in water.
Vibrational Spectroscopy and Symmetry
H O H
C
2
H
O
H
H O H
H O H
H O H
o
v
(xz)

H O H
H O H
o
v
(yz)

z
y
x
C
2V
E C
2
o
v
(xz) o
v
(yz)
A
1
1 1 1 1 z x
2
,y
2
,z
2
A
2
1 1 -1 -1 R
z
xy
B
1
1 -1 1 -1 x, R
y
xz
B
2
1 -1 -1 1 y, R
x
yz
From the I
tot
and the character table, we can figure out the number and types of modes
using the same equation that we used for bonding:
( ) ( )
| |
n
1
order
# of operations in class (character of RR) character of X
X
=

( )( )( ) ( )( )( ) ( )( )( ) ( )( )( )
| |
n
1
4
A
1
= + + + 1 9 1 1 1 1 1 3 1 1 1 1
This gives:
( )( )( ) ( )( )( ) ( )( )( ) ( )( )( )
| |
n
1
4
B
1
= + + + 1 9 1 1 1 1 1 3 1 1 1 1
( )( )( ) ( )( )( ) ( )( )( ) ( )( )( )
| |
n
1
4
B
2
= + + + 1 9 1 1 1 1 1 3 1 1 1 1
( )( )( ) ( )( )( ) ( )( )( ) ( )( )( )
| |
n
1
4
A
2
= + + + 1 9 1 1 1 1 1 3 1 1 1 1
Which gives: 3 A
1
s, 1 A
2
, 3 B
1
s and 2 B
2
s or a total of 9 modes, which is what we
needed to find because water has three atoms so 3N = 3(3) =9.
Vibrational Spectroscopy and Symmetry
C
2V
E C
2
o
v
(xz) o
v
(yz)
I
tot
9 -1 3 1
Vibrational Spectroscopy and Symmetry
Now that we have found that the irreducible representation for I
tot
is (3A
1
+A
2
+
3B
1
+2B
2
), the next step is to identify the translational and rotational modes -
this can be done by reading them off the character table! The three translational
modes have the symmetry of the functions x, y, and z (B
1
, B
2
, A
1
) and the
three rotational modes have the symmetry of the functions R
x
, R
y
and R
z
(B
2
,
B
1
, A
2
).
Translational
modes
Rotational
modes
The other three modes (3(3)-6 = 3) that are left over for
water (2A
1
+B
1
) are the vibrational modes that we might
be able to observe experimentally. Next we have to figure
out if we should expect to see these modes in an IR or
Raman vibrational spectrum.
C
2V
E C
2
o
v
(xz) o
v
(yz)
A
1
1 1 1 1 z x
2
,y
2
,z
2
A
2
1 1 -1 -1 R
z
xy
B
1
1 -1 1 -1 x, R
y
xz
B
2
1 -1 -1 1 y, R
x
yz
Remember that for a vibration to be observable in an IR
spectrum, the vibration must change the dipole moment of
the molecule.
In the character table, representations that change the
dipole of the molecule are those that have the same
symmetry as translations. Since the irreducible
representation of the vibrational modes is (2A
1
+B
1
) all
three vibrations for water will be IR active and we expect to
see three signals in the spectrum.
For a vibration to be active in a Raman spectrum, the
vibration must change the polarizability of the molecule. In
the character table, representations that change the
polarizability of the molecule are those that have the same
symmetry as rotations and products of x,yand z ( x
2
,xy etc). All
three vibrations for water will be Raman active and we
expect to see three signals in the spectrum.
Vibrational Spectroscopy and Symmetry
C
2V
E C
2
o
v
(xz) o
v
(yz)
A
1
1 1 1 1 z x
2
,y
2
,z
2
A
2
1 1 -1 -1 R
z
xy
B
1
1 -1 1 -1 x, R
y
xz
B
2
1 -1 -1 1 y, R
x
yz
The three vibrational
modes for water. Each
mode is listed with a v
(Greek letter nu) and a
subscript and the energy
of the vibration is given
in parentheses. v
1
is
called the symmetric
stretch, v
3
is called the
anti-symmetric stretch
and v
2
is called the
symmetric bend.
How many vibrational modes belong to
each of irreducible representation ?
Vibrational spectrum of H
2
O
Vibrational Spectrum of H
2
O
Sample Problem
MO of Polyatomic Molecules
MO of H
2
O
MO of H
2
O
MO of H
2
O
MO of H
2
O
MO of H
2
O
MO of H
2
O
MO of H
2
O
MO of H
2
O
MO of H
2
O
Now for the Million Question


Why is water Bent ????
MO Theory - Walsh Diagram
Linear XH
2
molecules
MO of BeH
2

Walsh Diagram of XH
2

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of BH
3

MO of NH
3

MO of NH
3

MO of NH
3

MO of NH
3

MO of NH
3

MO of NH
3

MO of NH
3

MO of NH
3

MO of CH
4

MO of CH
4

MO of CH
4

MO of CH
4

MO of CH
4

MO of CH
4

MO of CH
4

MO of CH
4

MO of CH
4

MO of CH
4
C 4 H CH
4
2s
A
1

2p
T
2
1a
1
2a
1
*

1t
2
2t
2
*

C 2 H, 2 Cl CH
2
Cl
2
2s
A
1
,B
1
2p
A
1
,B
2
Molecular Orbital Theory
Polyatomic molecules

1a
1
4a
1
*

1b
1
1b
2
3a
1
*
2b
2
*
2a
1
2b
1
*
Consider what happens to the o-bonding MOs if the symmetry is reduced from T
d
to C
2v
: there
will no longer be triply-degenerate MOs. The four bonding orbitals are split into two sets - those
with more H character (higher in energy) and those with more Cl character (lower in energy).
Since these diagrams are only concerned with the o-bonding,
the AOs and MOs from the 3p orbitals on Cl have been omitted.
The correlation lines from the 2p orbitals are not drawn for
clarity.
2 H
2 Cl
MO of AsF
5

MO of ClF
5
(C
4V
)
MO of SF
6

MO of SF
6

Matrix Representations

in Group Theory
Character Tables
Group theory makes use of the properties of matrices

Each symmetry operation may be expressed as a transformation matrix:
[New coordinates] = [transformation matrix][old coordinates]

Example: in Cartesian coordinate system, reflection in x = 0 plane
Changes the value of x to x, multiplies it by -1
Leaves y unchanged
Leaves z unchanged
|
|
|
.
|

\
|

1 0 0
0 1 0
0 0 1
|
|
|
.
|

\
|
'
'
'
z
y
x
|
|
|
.
|

\
|
z
y
x
Original
coordinates
Transformation
matrix
Results of
transformation.
=
Character Tables - 2
The matrix representation of the symmetry operations of a point group is
the set of matrices corresponding to all the symmetry operations in that group. The
matrices record how the x,y,z coordinates are modified as a result of an operation.
For example, the C
2v
point group consists of the following operations
E: do nothing. Unchanged.
C
2
: rotate 180 degrees about the z axis: x becomes x; y becomes y
and z unchanged.
o
v

(xz): y becomes y
o
v
(yz): x becomes -x
|
|
|
.
|

\
|

1 0 0
0 1 0
0 0 1
|
|
|
.
|

\
|
1 0 0
0 1 0
0 0 1
E
|
|
|
.
|

\
|

1 0 0
0 1 0
0 0 1
C
2

|
|
|
.
|

\
|

1 0 0
0 1 0
0 0 1
o
v
(xz):
o
v
(yz):
Matrix 3 - dimensional of an
n fold rotation
Matrix 3 - dimensional of a
vertical mirror plane
The Group Multiplication Table of the
C
2v
point group
E

E C
2
o
v
(xz) o
v
(yz)
E E C
2
o
v
(xz) o
v

(xz)
C
2
C
2
E o
v
(yz) o
v
(yz)
o
v
(xz o
v
(xz) o
v
(yz) E C
2

o
v

(xz)

o
v

(xz) o
v
(yz) C
2
E
Exercise
1.) Multiply the transformation matrix for C
2

by the transformation matrix for
v

C
2

v
=
v


2.) Show that
v

v

= C
2

3.) Using matrix expression for C
2
and E,
show that C
2
x C
2
= E
Substituting n =2 and m =1 to C
2


Representations
A representation (V) for a point group
any set of square matrices that multiply as the symmetry
operations of the group

A reducible representation
contains matrices that can all be partitioned into the same
block diagonal form consisting of a series of submatrices
that lie along the main diagonal

The submatrices are the matrices for the irreducible
representation


Block - diagonalization
If a reducible representation (V) consists
of the matrices [A], [B] and [C], each of
which can be partitioned into the block
diagonal form,

[X
1
] = [ X
11
X
12
] , [X
2
] = X
33
[X
3
] = X
44

[ X
21
X
22
]

V (direct sum) = V
1
+ V
2
+ V
3



Exercise
Find the irreducible representation for this group ?








V
(direct sum)
= V
3
+ V
4
+ V
1

C
2V
E C
2
o
v

(xz)
o
v

(yz)
A
1
1 1 1 1 V
1
z x
2
,y
2
,z
2
A
2
1 1 -1 -1 V
2
R
z
xy
B
1
1 -1 1 -1 V
3
x, R
y
xz
B
2
1 -1 -1 1 V
4
y, R
x
yz
Character Table for C
3v

Theorems:

The number of irreducible
representations is equal to the number
of classes