Group Theory Explains Molecular Symmetry

SYMMETRY AND
GROUP THEORY
Facial symmetry
Invariance to transformation as an
indicator of facial symmetry:
Mirror image
Symmetry And
Group Theory
The symmetry properties of molecules they can
be used to : predict vibrational spectra,
hybridization, optical activity, NMR, UV-
Visible (electronic spectra), XRD, etc.
Symmetry Elements and
Opertaions

A molecule has a given symmetry element if the
operation leaves the molecule appearing as if
nothing has changed (even though atoms and
bonds may have been moved.)
Symmetry Elements
Element Symmetry Operation Symbol
Entire object Identity E
n-fold axis Rotation by 2/n C
n

Mirror plane Reflection
Center of in- Inversion i
version
n-fold axis of Rotation by 2/n S
n

improper rotation followed by reflection
perpendicular to the
axis of rotation

Identity, E
All molecules have Identity. This operation
leaves the entire molecule unchanged. A highly
asymmetric molecule such as a tetrahedral
carbon with 4 different groups attached has only
identity, and no other symmetry elements.
n-fold Rotation

Water has a 2-fold axis
of rotation. When
rotated by 180
o
, the
hydrogen atoms trade
places, but the molecule
will look exactly the same.
n-fold Axis of Rotation
Ammonia has a C
3
axis. Note that there are two
operations associated with the C
3
axis. Rotation by
120
o
in a clockwise or a counterclockwise direction
provide two different orientations of the molecule.

Mirror Planes
The reflection of the
water molecule in either of
its two mirror planes results
in a molecule that looks
unchanged.
Mirror Planes
The subscript v in
v
,
indicates a vertical plane of
symmetry. This indicates
that the mirror plane
includes the principal axis of
rotation (C
2
).

Mirror Planes
The vertical planes,
v
,
go through the carbon
atoms, and include the C
6
axis.
The planes that bisect
the bonds are called dihedral
planes,
d
.
C
6
.

Mirror Planes
The benzene ring has a
C
6
axis as its principal axis of
rotation.
The molecular plane is
perpendicular to the C
6
axis,
and is designated as a
horizontal plane,
h
.

C
6
.

Inversion
The inversion operation projects each atom
through the center of inversion, and across to
the other side of the molecule.
Improper Rotation
An improper rotation is rotation, followed
by reflection in the plane perpendicular to the
axis of rotation.
Improper Rotation
The staggered
conformation of
ethane has an S
6
axis
that goes through
both carbon atoms.
Improper Rotation
Likewise, an S
2

axis is a center of
inversion.
Point Groups
Molecules with the same symmetry elements
are placed into point groups.
Identifying point groups
Point Groups
Definitions:
1. Point Group = the set of symmetry operations for a molecule
2. Group Theory = mathematical treatment of the properties of the group which
can be used to find properties of the molecule

Assigning the Point Group of a Molecule
1. Determine if the molecule is of high or low symmetry by inspection
a. Low Symmetry Groups
b. High Symmetry Groups

2. If not, find the principle axis

3. If there are C
2
axes perpendicular
to C
n
the molecule is in D
If not, the molecule will be in C or S

a. If o
h
perpendicular to C
n
then D
nh
or C
nh
If not, go to the next step

b. If o contains C
n
then C
nv
or D
nd
If not, D
n
or C
n
or S
2n

c. If S
2n
along C
n
then S
2n
If not C
n

We can use a flow chart such as this one to
determine the point group of any object.
The steps in this process are:

1. Determine the symmetry is special (e.g.
octahedral).

2. Determine if there is a principal rotation
axis.

3. Determine if there are rotation axes
perpendicular to the principal axis.

4. Determine if there are mirror planes.

5. Assign point group.
Point Groups
Molecules are classified and grouped
based on their symmetry. A point group
contains all objects that have the same
symmetry elements.
Point Groups
Water and
ammonia both belong
to the C
nv
class of
molecules. These
have vertical planes of
reflection, but no
horizontal planes.
Point Groups
The D
nh
groups
have a horizontal
plane in addition to
vertical planes. Many
inorganic complexes
belong to these
symmetry groups.
X
X
X
X
Y
Y
C. Examples: Assign point groups of molecules in Fig 4.8
Rotation axes of normal symmetry molecules
Perpendicular C2 axes

Horizontal Mirror Planes
Vertical or Dihedral Mirror Planes and S
2n
Axes

Examples: XeF
4
, SF
4
, IOF
3
, Table 4-4, Exercise 4-3
D. Properties of Point Groups
1. Symmetry operation of NH
3

a. Ammonia has E, 2C
3

(C
3
and C
2
3
) and 3o
v

b. Point group = C
3v

2. Properties of C
3v
(any group)
a. Must contain E

b. Each operation must
have an inverse; doing both
gives E (right to left)

c. Any product equals
another group member

d. Associative property

REPRESENTATIONS OF
POINT GROUPS

Matrices
Why Matrices? The matrix representations of the point groups operations will
generate a character table. We can use this table to predict properties.
Definitions and Rules
Matrix = ordered array of numbers
Multiplying Matrices
The number of columns of matrix #1 must = number of rows of matrix
#2
Fill in answer matrix from left to right and top to bottom
The first answer number comes from the sum of [(row 1 elements of
matrix #1) X (column 1 elements of matrix #2)]
The answer matrix has same number of rows as matrix #1
The answer matrix has same number of columns as matrix #2
| | 5 2 4 3 or
1 7
2 3
(
=
(
+ +
+ +
=
(
54 38
43 27
48 6 24 14
40 3 20 7
8 4
3 7
6 2
5 1
e) Relevant example:
| | | | 3 2 1
1 0 0
0 1 0
0 0 1
3 2 1 =
(
(
(

II.Representations of Point Groups
Matrix Representations of C
2v

Choose set of x,y,z axes
z is usually the C
n
axis
xz plane is usually the plane of the molecule
Examine what happens after the molecule undergoes each symmetry
operation in the point group (E, C
2
, 2o)
3) Transformation Matrix = matrix expressing the effect of a symmetry
operation on the x,y,z axes

4) E Transformation Matrix
a. x,y,z x,y,z
b. What matrix times x,y,z doesnt change anything?

(
(
(
(
(
(
=
(
(
(
z
y
x
? ? ?
? ? ?
? ? ?
z'
y'
x'
transformation
matrix
(
(
(
=
(
(
(
(
(
(
z
y
x
z
y
x
1 0 0
0 1 0
0 0 1
E Transformation Matrix
5) C
2
Transformation Matrix
a. x,y,z -x, -y, z
b. Correct matrix is:

6) o
v
(xz) Transformation Matrix
a. x,y,z x,-y,z

7) o
v
(yz) Transformation Matrix
a. x,y,z -x,y,z
(
(
(
=
(
(
(
(
(
(
z
y -
x -
z
y
x
1 0 0
0 1 0
0 0 1
(
(
(
=
(
(
(
(
(
(
z
y -
x
z
y
x
1 0 0
0 1 0
0 0 1
(
(
(
=
(
(
(
(
(
(
z
y
x -
z
y
x
1 0 0
0 1 0
0 0 1
8) These 4 matrices are the Matrix Representation of the C
2v
point group
a. All point group properties transfer to the matrices as well
b. Example: Eo
v
(xz) = o
v
(xz)

B. Reducible and Irreducible Representations
Character = sum of diagonal from upper left to lower right (only defined
for square matrices)

The set of characters = a reducible representation (I) or shorthand
version of the matrix representation

For C
2v
Point Group:

(
(
(
=
(
(
(

(
(
(
1 0 0
0 1 0
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 0
0 0 1
E C
2
o
v
(xz) o
v
(yz)
3 -1 1 1
2) Reducible and Irreducible Representations
a. Each matrix in the C
2v
matrix representation can be block diagonalized
b. To block diagonalize, make each nonzero element into a 1x1 matrix

c. When you do this, the x,y, and z axes can be treated independently
Positions 1,1 always describe x-axis
Positions 2,2 always describe y-axis
Positions 3,3 always describe z-axis
d. Generate a partial character table from this treatment
| |
| |
| |
| |
| |
| |
| |
| |
| |
| |
| |
| |(
(
(

(
(
(
(
(
(
(
(
(
1 0 0
0 1 0
0 0 1

1 0 0
0 1 0
0 0 1

1 0 0
0 1 0
0 0 1

1 0 0
0 1 0
0 0 1
E C
2
o
v
(xz)
o
v
(yz)
Axis used E C
2
o
v
(xz) o
v
(yz)
x 1 -1 1 -1
y 1 -1 -1 1
z 1 1 1 1
I 3 -1 1 1
Irreducible
Representations
Reducible Repr.
III.Character Tables
The C
2v
Character Table
We have found three of the irreducible representations of the character table
through matrix math
One more (A
2
) irreducible representation is derived from the first three due to
the properties of character tables (below)

R
x
, R
y
, R
z
stand for rotation about the x, y, z axes respectively
xs are p and d orbitals

4) Other symbols we need to know
R = any symmetry operation
_ = character (#)
i,j = different representations (A
1
, B
2
, etc)
h = order of the group (4 total operations in the C
2v
case)
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
B. Molecular Vibrations
1. To use symmetry, we must assign axes
to each atom of the molecule
a. The z-axis is usually the C
n
axis
b. The x-axis is in the molecular plane
c. The y-axis is perpendicular to the molecular plane

2. Degrees of Freedom = possible atomic movements in the molecule
a. 3N degrees of freedom for a molecule of N atoms
b. Nonlinear molecules
3 translations (along x, y, z)
3 rotations (around x, y, z)
3N 6 vibrations
c. Linear molecules
Only 2 rotations change the molecule
3N 5 vibrations

3. We will use group theory to determine the symmetry of all nine motions and
then assign them to translation, rotation, and vibration
Look at the C
2v
character table

Add up how many vectors stay the same after an operation
If the atom moves, none of its vectors stay the same
If the atom stays and the vector is unchanged = +1
If the atom stays and the vector is reversed = -1

Reduce the reducible representation to its irreducible components

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

9 -1 3 1
(
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
=
(
(
(
tion representa e irreducibl

the of character
tion representa reducible
the of character
class in the
operations of number
1
given type a of
tions representa e irreducibl
of number The
order
n
A1
= [(1x9x1)+(1x-1x1)+(1x3x1)+(1x1x1)] = 3 A
1

n
A2
= [(1x9x1)+(1x-1x1)+(1x3x-1)+(1x1x-1)] = 1 A
2

n
A1
= [(1x9x1)+(1x-1x-1)+(1x3x1)+(1x-1x1)] = 3 B
1

n
A1
= [(1x9x1)+(1x-1x-1)+(1x3x-1)+(1x1x1)] = 2 B
2

d) All motions of water match 3A
1
+ A
2
+ 3B
1
+ 2B
2

e) Use the character table to remove translations
x, y, z = A
1
+ B
1
+ B
2

f) Use the character table to remove rotations
R
x
, R
y
, R
z
= A
2
+ B
1
+ B
2

g) The motions remaining are the vibrations = 2A
1
+ B
1

A
1
= totally symmetric
B
1
= antisymmetric to C
2
and to reflection in yz plane

Character Table (C
2v
)
Character Table (C
2v
)
The functions to the right are called basis functions.
They represent mathematical functions such as orbitals,
rotations, etc.
Character Table Representations
1. Characters of +1 indicate that the basis
function is unchanged by the symmetry
operation.
2. Characters of -1 indicate that the basis function
is reversed by the symmetry operation.
3. Characters of 0 indicate that the basis function
undergoes a more complicated change.
Character Table Representations
1. An A representation indicates that the
functions are symmetric with respect to rotation
about the principal axis of rotation.
2. B representations are asymmetric with respect
to rotation about the principal axis.
3. E representations are doubly degenerate.
4. T representations are triply degenerate.
5. Subscrips u and g indicate asymmetric (ungerade)
or symmetric (gerade) with respect to a center of
inversion.
Applications of Group Theory
1. Predicting polarity of molecules. A molecule
cannot have a permanent dipole moment if it
a) has a center of inversion
b) belongs to any of the D point groups
c) belongs to the cubic groups T or O
2. Predicting chirality of molecules. Chiral
molecules lack an improper axis of rotation (S
n
),
a center of symmetry (i) or a mirror plane ().
3. Predicting the orbitals used in bonds. Group
theory can be used to predict which orbitals on a
central atom can be mixed to create hybrid
orbitals.
4. Predicting the orbitals used in molecular orbitals.
Molecular orbitals result from the combining or
overlap of atomic orbitals, and they encompass
the entire molecule.
5. Determining the symmetry properties of all
molecular motion (rotations, translations and
vibrations). Group theory can be used to
predict which molecular vibrations will be seen
in the infrared or Raman spectra.
Molecular Vibrations
Molecular motion includes translations,
rotations and vibrations. The total number of
degrees of freedom (types of molecular motion)
is equal to 3N, where N is the number of atoms
in the molecule.
Of the 3N types of motion, three represent
molecular translations in the x, y or z directions.
Linear molecules have two rotational degrees of
freedom, and non-linear molecules have three
rotational degrees of freedom.
For linear molecules, the number of
molecular vibrations = 3N-3-2 = 3N-5.

For non-linear molecules, the number of
molecular vibrations = 3N-3-3= 3N-6.
To obtain
red
for all molecular motion, we
must consider the symmetry properties of the
three cartesian coordinates on all atoms of the
molecule.
The molecule lies in the xz plane. The x axis
is drawn in blue, and the y axis is drawn in black.
The red arrows indicate the z axis.
x
y
z
The molecule lies in the xz plane. The x axis
is drawn in blue, and the y axis is drawn in black.
The red arrows indicate the z axis.
y
x
If a symmetry operation changes the
position of an atom, all three cartesian
coordinates contribute a value of 0.
x
y
z
For operations that leave an atom in place,
the character is +1 for an axis that remains in
position, -1 for an axis that is reversed, and 0 for
an axis that has been moved.
x
y
z
Page 75
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
=
(
(
(
(
(
(
(
(
(
(
(
(
3
3
3
2
2
2
1
1
1
3
3
3
2
2
2
1
1
1
.
1 0 0 0 0 0 0 0 0
0 1 0 0 0 0 0 0 0
0 0 1 0 0 0 0 0 0
0 0 0 1 0 0 0 0 0
0 0 0 0 1 0 0 0 0
0 0 0 0 0 1 0 0 0
0 0 0 0 0 0 1 0 0
0 0 0 0 0 0 0 1 0
0 0 0 0 0 0 0 0 1
z
y
x
z
y
x
z
y
x
z
y
x
z
y
x
z
y
x
E
For E _ = + 9

(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
=
(
(
(
(
(
(
(
(
(
(
(
(
3
3
3
2
2
2
1
1
1
3
3
3
2
2
2
1
1
1
) (
.
0 0 0 1 0 0 0 0 0
0 0 0 0 1 0 0 0 0
0 0 0 0 0 1 0 0 0
1 0 0 0 0 0 0 0 0
0 1 0 0 0 0 0 0 0
0 0 1 0 0 0 0 0 0
0 0 0 0 0 0 1 0 0
0 0 0 0 0 0 0 1 0
0 0 0 0 0 0 0 0 1
z
y
x
z
y
x
z
y
x
z
y
x
z
y
x
z
y
x
yz
o
Only require the characters: The sum of diagonal elements
For o
(xz)
_ = + 1
E C
2
v(xz)
v(yz)
Identity leaves all 3
atoms in position, so
the character will be
9.

E C
2
v(xz)
v(yz)
9
Identity leaves all 3
atoms in position, so
the character will be
9.

E C
2
v(xz)
v(yz)
9
The C
2
axis goes
through the oxygen
atom, and exchanges
the hydrogen atoms.

E C
2
v(xz)
v(yz)
9
The z axis (red) on
oxygen stays in
position. This axis
contributes +1
towards the
character for C
2
.

E C
2
v(xz)
v(yz)
9
The y axis (black) on
oxygen is rotated by
180
o
. This reverses
the axis, and
contributes -1 to the
character for C
2
.

E C
2
v(xz)
v(yz)
9
The x axis (blue) on
oxygen is also rotated
by 180
o
. This reverses
the axis, and
contributes -1 to the
character for C
2
.

E C
2
v(xz)
v(yz)
9
The character for the C
2
operation will be
+1 (z axis on oxygen) -1 (y axis on
oxygen) -1 (x axis on oxygen) = -1

E C
2
v(xz)
v(yz)
9 -1
The character for the C
2
operation will be
+1 (z axis on oxygen) -1 (y axis on
oxygen) -1 (x axis on oxygen) = -1

E C
2
v(xz)
v(yz)
9 -1
The xz mirror plane is
the molecular plane,
and all three atoms
remain in position.
x
E C
2
v(xz)
v(yz)
9 -1
The z axis and the x
axis both lie within the
xz plane, and remain
unchanged.
x
E C
2
v(xz)
v(yz)
9 -1
Each unchanged axis
contributes +1 to the
character for the
symmetry operation.
x
E C
2
v(xz)
v(yz)
9 -1
For 3 atoms, the
contribution to the
character will be:
3(1+1) =6
x
E C
2
v(xz)
v(yz)
9 -1
The y axis will be
reversed by the mirror
plane, contributing a
value of -1 for each of
the three atoms on the
plane.
x
y
E C
2
v(xz)
v(yz)
9 -1 3
The character for the
xz mirror plane will be:
6-3 = 3
x
y
E C
2
v(xz)
v(yz)
9 -1 3
The yz mirror plane
bisects the molecule.
Only the oxygen atom
lies in the plane.
x
y
E C
2
v(xz)
v(yz)
9 -1 3
The y and z axis lie
within the yz plane,
and each contributes
+1 to the character.
x
y
E C
2
v(xz)
v(yz)
9 -1 3
The x axis on oxygen is
reversed by the
reflection, and
contributes a -1
towards the character.
x
y
E C
2
v(xz)
v(yz)
9 -1 3 1
The character for
reflection in the yz
plane is:
1+1-1=1
x
y
Character Table (C
2v
)
E C
2
v(xz)
v(yz)
9 -1 3 1
3N

This formula was derived from the Great orthorgonality theorem.
n
A1
= [(1x9x1)+(1x1x1)+(1x3x1)+(1x1x1)] = 3 A
1

n
A2
= [(1x9x1)+(1x-1x1)+(1x3x-1)+(1x1x-1)] = 1 A
2

n
B1
= [(1x9x1)+(1x-1x-1)+(1x3x1)+(1x-1x1)] = 3 B
1

n
B2
= [(1x9x1)+(1x-1x-1)+(1x3x-1)+(1x1x1)] = 2 B
2

All motions of water match
3A
1
+ A
2
+ 3B
1
+ 2B
2

E C
2
v(xz)
v(yz)
9 -1 3 1
The above reducible representation is
sometimes called
3N
, because it reduces to all
(3N) modes of molecular motion.

3N
for water reduces to:
3A
1
+ A
2
+ 3B
1
+ 2B
2


3N
for water = 3A
1
+ A
2
+ 3B
1
+ 2B
2

Note that there are 9 modes of motion.
These include vibrations, rotations and
translations.


3N
for water = 3A
1
+ A
2
+ 3B
1
+ 2B
2

Translations have the same symmetry
properties as x, y and z.


3N
for water = 3A
1
+ A
2
+ 3B
1
+ 2B
2



3N
for water = 3A
1
+ A
2
+ 3B
1
+ 2B
2


2

3N
for water = 3A
1
+ A
2
+ 3B
1
+ 2B
2


2 2

3N
for water = 3A
1
+ A
2
+ 3B
1
+ 2B
2


2 2

3N
for water = 3A
1
+ A
2
+ 3B
1
+ 2B
2


2 2 1

rot & vib
= 2A
1
+ A
2
+ 2B
1
+ 1B
2


rot & vib
= 2A
1
+ A
2
+ 2B
1
+ 1B
2

Rotations have the same symmetry as
R
x
, R
y
and R
z
.


rot & vib
= 2A
1
+ A
2
+ 2B
1
+ 1B
2

R
x
, R
y
and R
z
.


rot & vib
= 2A
1
+ 2B
1
+ 1B
2

R
x
, R
y
and R
z
.

1

rot & vib
= 2A
1
+ 1B
1
+ 1B
2

R
x
, R
y
and R
z
.

Rotations and Translations
R
z

R
x

R
y

Trans
z

Trans
y

Trans
x

vib
= 2A
1
+ B
1

The three vibrational modes remain.
Two have A
1
symmetry, and one has B
1

symmetry.

vib
= 2A
1
+ B
1

Two vibrations are symmetric with
respect to all symmetry operations of the
group.

vib
= 2A
1
+ B
1

One vibration is asymmetric with
respect to rotation and reflection
perpendicular to the molecular plane.

vib
= 2A
1
+ B
1

A
1
symmetric stretch
A
1
bend
B
1
asymmetric stretch
TINJAUAN SIMETRI PADA SiH
2
Cl
2
Example - SiH
2
Cl
2
Point group C
2v

Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
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
Si
Cl
2

H
1

Cl
1

H
2

z
x
y
Draw x, y and z vectors on all atoms
Count +1, -1, 0 if vector transforms to itself, minus itself, or moves
Perform symmetry operations
Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
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
Si
Cl
2

H
1

Cl
1

H
2

z
x
y
Operation E
Si atom x transforms into Si x count +1
y transforms into Si y count +1
z transforms into Si z count +1
total +3
Same for other 4 atoms grand total +15
Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
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
Si
Cl
2

H
1

Cl
1

H
2

z
x
y
Operation C
2
Si atom x transforms into Si -x count -1
y transforms into Si -y count -1
total -1
H
1
and H
2
move - swap places count 0
Cl
1
and Cl
2
swap places count 0
grand total -1
Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
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
Si
Cl
2

H
1

Cl
1

H
2

z
x
y
Operation o
v
(xz) Si atom x transforms into Si x count +1
y transforms into Si -y count -1
total +1
H
1
and H
2
also lie in xz plane, and behave as Si count +1 each
Cl
1
and Cl
2
swap places count 0
grand total +3
Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
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
Si
Cl
2

H
1

Cl
1

H
2

z
x
y
Operation o
v
(yz) Si atom x transforms into Si -x count -1
y transforms into Si y count +1
total +1
H
1
and H
2
swap places count 0
Cl
1
and Cl
2
also lie in yz plane, and behave as Si count +1 each
grand total +3
No. of modes of each symmetry species
Example - SiH
2
Cl
2
Point group C
2v

Overall we have:
E C
2
o
v
(xz) o
v
(yz)
+15 -1 +3 +3
This is the reducible representation of the set
of 3N (=15) atomic displacement vectors
We reduce it to the irreducible representations,
using a formula
Character table
C
2v
1E 1C
2
1o
v
(xz) 1o
v
(yz) h = 4
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
Formula is
) ( . ) ( .
1
R R g
h
a
R
R i i
_ _
=
Reducible representation 15 -1 3 3
No. of A
1
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.1 + 1.3.1] = 5
Reduce the reducible representation
Character table
C
2v
1E 1C
2
1o
v
(xz) 1o
v
(yz) h = 4
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
Formula is
) ( . ) ( .
1
R R g
h
a
R
R i i
_ _
=
No. of A
1
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.1 + 1.3.1] = 5
No. of A
2
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.(-1) + 1.3.(-1)] = 2
Character table
C
2v
1E 1C
2
1o
v
(xz) 1o
v
(yz) h = 4
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
Formula is
) ( . ) ( .
1
R R g
h
a
R
R i i
_ _
=
No. of A
1
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.1 + 1.3.1] = 5
No. of A
2
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.(-1) + 1.3.(-1)] = 2
No. of B
1
motions = 1/4 [1.15.1 + 1.(-1).(-1) + 1.3.1 + 1.3.(-1)] = 4
No. of B
2
motions = 1/4 [1.15.1 + 1.(-1).(-1) + 1.3.(-1) + 1.3.1] = 4
Symmetry species of all motions are:-
5A
1
+ 2A
2
+ 4B
1
+ 4B
2
- the irreducible representation
Translations, rotations, vibrations
3 of these are translations of the whole molecule
3 are rotations
Symmetry species of translations are given by
vectors (x, y, z) in the character table
Symmetry species of rotations are given by R
x
,
R
y
and R
z
in the character table

Symmetry species of all motions are:-
5A
1
+ 2A
2
+ 4B
1
+ 4B
2

Character table
C
2v
1E 1C
2
1o
v
(xz) 1o
v
(yz) h = 4
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
Translations are:- A
1
+ B
1
+ B
2

Rotations are:- A
2
+ B
1
+ B
2

- so vibrations are:- 4A
1
+ A
2
+ 2B
1
+ 2B
2
Translations, rotations, vibrations
Symmetry species of vibrations
are:- 4A
1
+ A
2
+ 2B
1
+ 2B
2

Vibrational modes of SiH
2
Cl
2

What does each of these modes look like?
2 rules
(i) there is 1 stretching vibration per bond
(ii) must treat symmetry-related atoms together
2
Cl
2

2 rules
(i) there is 1 stretching vibration per bond
(ii) we must treat symmetry-related atoms together
We therefore have:-
two stretching modes of the SiCl
2
group
two of the SiH
2
group
The remaining five modes must be deformations
(angle bending vibrations)
2
Cl
2

We therefore have:-
2
group
We can stretch the two Si-Cl bonds
together in phase
or together out of phase
Is vibration symmetrical with respect
to each symmetry operation?
- if yes +1, if no -1
From the character table, this belongs
to the symmetry species A
1

We call the mode of vibration v
sym

SiCl
2

E C
2
o
xz
o
yz

+1 +1 +1 +1
x
z
y
Is vibration symmetrical with
respect to each symmetry
operation?
- if yes +1, if no -1
E C
2
o
xz
o
yz

From the character table, this
belongs to the symmetry species
B
2

asym

SiCl
2

+1 -1 -1 +1
x
z
y
2
Cl
2

We therefore have:-
2
group
We can stretch the two Si-H bonds
together in phase
or together out of phase
and two stretching modes of the SiH
2
group
x
z
y
From the character table, this belongs
to the symmetry species A
1

sym
SiH
2

E C
2
o
xz
o
yz

+1 +1 +1 +1
From the character table, this belongs to
the symmetry species B
1

asym
SiH
2

E C
2
o
xz
o
yz

+1 -1 +1 -1
x
z
y
2
Cl
2

We now have:-
2
group
two of the SiH
2
group
The remaining five modes must be deformations
(angle bending vibrations)
As with stretches, we must treat symmetry-
related atoms together
the symmetry species A
1

We call the mode of vibration o
sym
SiCl
2

(or SiCl
2
scissors)
E C
2
o
xz
o
yz

+1 +1 +1 +1
x
z
y
1

We call the mode of vibration o
sym
SiH
2

(or SiH
2
scissors)
+1 +1 +1 +1
E C
2
o
xz
o
yz

x
z
y
1

We call the mode of vibration e SiH
2
(or
SiH
2
wag)
E C
2
o
xz
o
yz

+1 -1 +1 -1
x
z
y
2

We call the mode of vibration SiH
2
(or
SiH
2
rock)
+1 -1 -1 +1
E C
2
o
xz
o
yz

x
z
y
y
x
2

We call the mode of vibration t SiH
2
(or
SiH
2
twist)
E C
2
o
xz
o
yz

+1 +1 -1 -1
2
Cl
2

Overall, we now have:-
2
group
A
1
+ B
2

two of the SiH
2
group
A
1
+ B
1

five deformation modes
2A
1
+ A
2
+ B
1
+ B
2

Together, these account for all the modes we
expect:
4A
1
+ A
2
+ 2B
1
+ 2B
2

For a molecular vibration to be seen in the
infrared spectrum (IR active), it must change the
dipole moment of the molecule. The dipole
moment vectors have the same symmetry
properties as the cartesian coordinates x, y and z.
Raman spectroscopy measures the
wavelengths of light (in the IR range) scatted by
a molecule. Certain molecular vibrations will
cause the frequency of the scattered radiation to
be less than the frequency of the incident
radiation.
For a molecular vibration to be seen in the
Raman spectrum (Raman active), it must change
the polarizability of the molecule. The
polarizability has the same symmetry properties
as the quadratic functions:
xy, yz, xz, x
2
, y
2
and z
2

Molecular Vibrations of Water
vib
= 2A
1
+ B
1

The two vibrations with A
1
symmetry
have z as a basis function, so they will be
seen in the infrared spectrum of water.
This will result in two peaks (at different
frequencies) in the IR spectrum of water.
vib
= 2A
1
+ B
1

1
symmetry
also have quadratic basis functions, so they
will be seen in the Raman spectrum of
water as well.
vib
= 2A
1
+ B
1

1
symmetry
will appear as two peaks in both the IR and
Raman spectra. The two frequencies
observed in the IR and Raman for these
vibrations will be the same in both spectra.
vib
= 2A
1
+ B
1

The vibration with B
1
symmetry has x
and xz as basis functions. This vibration will
be both IR active and Raman active. This
vibration will appear as a peak (at the same
frequency) in both spectra.
vib
= 2A
1
+ B
1

Both the IR and Raman spectra
should show three different peaks.
Summary
1. Obtain the point group of the molecule.
2. Obtain
3N
by considering the three cartesian
coordinates on all atoms that arent moved by
the symmetry operation.
3. Reduce
3N
.
4. Eliminate translations and rotations.
5. Determine if remaining vibrations are IR
and/or Raman active.
Application: Carbonyl Stretches
Can IR and Raman spectroscopy determine the
difference between two square planar
complexes: cis-ML
2
(CO)
2
and trans-ML
2
(CO)
2
?

cis and trans ML
2
(CO)
2

cis isomer C
2v
trans isomer D
2h

cis - ML
2
(CO)
2

C
2v
: E C
2
xz
yz
CO
: 2 0 2 0
cis - ML
2
(CO)
2

CO
reduces to A
1
+ B
1
.
A
1
is a symmetric
stretch, and B
1
is an
asymmetric stretch.
cis - ML
2
(CO)
2

CO
reduces to A
1
+ B
1
.
The symmetric
stretch (A
1
) is IR and
Raman active.
cis - ML
2
(CO)
2

CO
reduces to A
1
+ B
1
.
The asymmetric
stretch (B
1
) is both IR
and Raman active.
trans ML
2
(CO)
2

trans isomer D
2h

The trans isomer lies in
the xy plane. The point
group D
2h
has the
following symmetry
elements:
D
2h
E C
2
(z) C
2
(y) C
2
(x) i
xy

xz
yz
y
x
trans ML
2
(CO)
2

trans isomer D
2h

The trans isomer lies in
the xy plane.
CO
is
obtained by looking
only at the two C-O
bonds.
D
2h
E C
2
(z) C
2
(y) C
2
(x) i
xy

xz
yz
CO
2 0 0 2 0 2 2 0
y
x
trans ML
2
(CO)
2

trans isomer D
2h

CO
reduces to A
g
(a
symmetric stretch) and
B
3u
(an asymmetric
stretch).
y
x
trans ML
2
(CO)
2

trans isomer D
2h

CO
reduces to A
g
(a
symmetric stretch) and
B
3u
(an asymmetric
stretch).
A
g
has x
2
, y
2
and
z
2
as basis functions, so
this vibration is Raman
active.
y
x
trans ML
2
(CO)
2

trans isomer D
2h

A
g
has x
2
, y
2
and
z
2
this vibration is Raman
active.
B
3u
has x as a
basis function, so this
vibration is IR active.
y
x
trans ML
2
(CO)
2

A
g
has x
2
, y
2
and z
2
this vibration is Raman active.
B
3u
has x as a basis function, so this
vibration is IR active.
The IR and Raman spectra will each show
one absorption at different frequencies.
Exclusion Rule

If a molecule has a center of symmetry, none of its modes
of vibration can be both infrared and Raman active.
Exclusion Rule

If a molecule has a center of symmetry, none of its modes
of vibration can be both infrared and Raman active.
The cis and trans isomers of square planar
ML
2
(CO)
2
, can be easily distinguished using
spectroscopy. The cis isomer has absorptions
that are seen in both the IR and Raman spectra,
whereas the trans isomer does not.

Chemical Applications of Group
Theory

We have learnt the point group theory of molecular
symmetry. We shall learn how to use this theory in
our chemical research.
1. Representation of groups

1.1 Matrix representation and reducible representation
1.2 Reducing of representations
Suppose that we have a set of n-dimensional matrices, A, B,
C, , which form a representation of a group. These n-D
matrices themselves constitute a matrix group.
If we make the same similarity transformation on each matrix,
we obtain a new set of matrices,

This new set of matrices is also a representation of the group.
If A is a blocked-factored matrix, then it is easy to prove that
B,C are also blocked-factored matrices.
... C C ; B B A A
1 1 1
' ' ; '

I I = I I = I I =
| |
| |
| |
| |
| |
| |
| |
| |
,..... ' , '
4
3
2
1
4
3
2
1
(
(
(
(
=
(
(
(
(
=
B
B
B
B
B
A
A
A
A
A
A
1
,A
2
,A
3
are n
1
,n
2
,n
3
-D submatrices with n= n
1
+ n
2
+ n
3
+ .
Furthermore, it is also provable that the various sets of
submatrices
{A
1
,B
1
,C
1
}, {A
2
,B
2
,C
2
}, {A
3
,B
3
,C
3
}, {A
4
,B
4
,C
4
},
are in themselves representations of the group.
We then call the set of matrices A,B,C, a reducible
representation of the group.
If it is not possible to find a similarity transformation to reduce
a representation in the above manner, the representation is
said to be irreducible.
The irreducible representations of a group is of fundamental
importance.

2. Character Tables of Point Groups

These translation vectors constitute a set of bases of C
2v
group.

2.2 symmetry species: Mulliken symbols
All 1-D irreducible reps. are labeled by either A or B, 2-D irreducible rep.
by E, 3-D irreducible rep. by T and so on.
A: symmetric with respect to C
n
rotation, i.e., _(C
n
)=1.
B: asymmetric with respect to C
n
rotation, i.e., _(C
n
)=-1.
Subscriptions 1 or 2 designates those symmetric or asymmetric with
respect to a C
2
or a o
v
.
Subscripts g or u for universal parity or disparity.
Superscripts or designates those symmetric or asymmetric with
respect to o
h
This formula was derived from the Great orthorgonality theorem.

CO
2
has 3 modes of vibration
Vibrational spectroscopy
O=C=O O=C=O O=C=O
Infra-red inactive - no
dipole change
IR active IR active
H
2
O has 3 modes of vibration
IR
active
IR active IR active
H
O
H H
O
H H
O
H
Number of active modes tells us about symmetry
Molecular vibrations - number of modes
4 atoms - can move independently in x, y, z directions
x
y
z
x
y
z
x
y
z
x
y
z
3N degrees of freedom for a N-atom molecule.
If atoms fixed, there are: 3 translational degrees
3 rotational degrees
and the rest (3N-6) are vibrational modes
Good Luck In the Final Exam!

Final Exam
Content: Chapters 5-9
Time: June 13, 8:00-10:00
Venue: -102
Tools:
: June 10-12,
316()
4) Symmetry and IR
a. IR only sees a vibration if the vibration changes the molecules dipole
b. Motion along the x, y, z axes creates a changed dipole
a. Infrared Active vibrations match up with x, y, z on character table
b. Infrared Inactive vibrations dont
c. For water, all three vibrations are infrared active

5) Examples and Exercises pages 113-116

C. Molecular Vibrations of ML
2
(CO)
2
complexes
The symmetry of cis- ML
2
(CO)
2
complexes is C
2v

The C=O stretch has only one possible direction of motion
Instead of using xyz vectors at each atom, we can use a single vector

c) Reducible representation from the 2 vectors

d) 2 possible vibrations from reduction formula: A
1
+ B
1
(see both)
C
2v
E C
2
o
v
(xz) o
v
(yz)
I

2 0 2 0
2) The symmetry of trans- ML
2
(CO)
2
complexes is D
2h

a. Symmetry operations on the vectors generate a reducible representation
b. Reduction formula give 2 irreducible representations

c. Only the B
3u
representation is IR Active

d. We can tell cis from trans by the number of C=O IR bands
B. The C
3v
Character Table for NH
3

1) The threefold symmetry of NH
3
makes for complex transformation matrices
2) Though more complex, the C
3v
Character Table can be generated similarly to that
of the C
2v
group

C. Notes on Character Tables
Multiple operations in the same class are listed together
Different C
2
axes are listed separately with primes ()
Those through outer atoms are
Those not through outer atoms are
Symmetry of orbitals are listed except for s orbitals, which are always in the first
listed A irreducible representation
Irreducible Representation Labels
Degeneracy (dimension) is determined by the character of E operation
A if E = 1 and _ of C
n
= 1
B if E = 1 and _ of C
n
= -1
E if E = 2 (doubly degenerate)
T if E = 3 (triply degenerate)
b) Subscripts
1 if symmetric to perpendicular C
2
axis (or o
v
)
2 if antisymmetric to perpendicular C
2
axis (or o
v
)
g if symmetric to i
u if antisymmetric to i
Primes
if symmetric to o
h

if antisymmetric to o
h

IV.Applications of Symmetry
Chiral Molecules
Molecules not superimposable with their mirror images are called chiral or
dissymetric
They may still have some symmetry operations: E, C
n

Chiral molecules cannot have i, o, or S
n
symmetry operations

IV.Applications of Symmetry
Chiral Molecules
Molecules not superimposable with their mirror images are called chiral or
dissymetric
They may still have some symmetry operations: E, C
n

Chiral molecules cannot have i, o, or S
n
symmetry operations

Group Theory Explains Molecular Symmetry

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