Chem 59-651

Symmetry and Introduction to Group Theory

Symmetry is all around us and is a fundamental property of nature.

 Chem 59-651
Symmetry and Introduction to Group Theory

The term symmetry is derived from the Greek word “symmetria” which
means “measured together”. An object is symmetric if one part (e.g. one
side) of it is the same* as all of the other parts. You know intuitively if
something is symmetric but we require a precise method to describe how
an object or molecule is symmetric.

Group theory is a very powerful mathematical tool that allows us to

rationalize and simplify many problems in Chemistry. A group consists of
a set of symmetry elements (and associated symmetry operations) that
completely describe the symmetry of an object.

We will use some aspects of group theory to help us understand the

bonding and spectroscopic features of molecules.
 Chem 59-651
We need to be able to specify the symmetry of molecules clearly.
F H

No symmetry – CHFClBr
Br
Cl F H

Some symmetry – CHFCl2

H H
Cl
Cl

More symmetry – CH2Cl2

Cl
Cl H Cl

More symmetry ? – CHCl3

Cl

Cl

What about ?

Point groups provide us with a way to indicate the symmetry unambiguously.

 Chem 59-651 Symmetry and Point Groups
Point groups have symmetry about a single point at the center of mass of
the system.
Symmetry elements are geometric entities about which a symmetry
operation can be performed. In a point group, all symmetry elements
must pass through the center of mass (the point). A symmetry operation
is the action that produces an object identical to the initial object.
The symmetry elements and related operations that we will find in
molecules are:
Element Operation
Rotation axis, Cn n-fold rotation
Improper rotation axis, Sn n-fold improper rotation
Plane of symmetry, σ Reflection
Center of symmetry, i Inversion
Identity, E

The Identity operation does nothing to the object – it is necessary for

mathematical completeness, as we will see later.
 Chem 59-651
n-fold rotation - a rotation of 360°/n about the Cn axis (n = 1 to ∞)

O(1) 180° O(1)

H(2) H(3) H(3) H(2)

In water there is a C2 axis so we can perform a 2-fold (180°) rotation to get

the identical arrangement of atoms.
H(3) H(4)
H(2)

120° 120°
N(1) N(1) N(1)

H(2) H(4) H(3) H(2)

H(4) H(3)

In ammonia there is a C3 axis so we can perform 3-fold (120°) rotations to

get identical arrangement of atoms.
 Chem 59-651
Notes about rotation operations:
- Rotations are considered positive in the counter-clockwise direction.
- Each possible rotation operation is assigned using a superscript integer m
of the form Cnm.
- The rotation Cnn is equivalent to the identity operation (nothing is moved).
H(3)
H(2) H(4)

C31 C32
N(1) N(1)
N(1)

H(2) H(4)
H(4) H(3) H(3) H(2)

H(2)

C33 = E

N(1)

H(4) H(3)
 Chem 59-651
Notes about rotation operations, Cnm:
- If n/m is an integer, then that rotation operation is equivalent to an n/m -
fold rotation.
e.g. C42 = C21, C62 = C31, C63 = C21, etc. (identical to simplifying fractions)

Cl(5) Cl(2) Cl(3)

C41 C42 = C21

Cl(2) Ni(1) Cl(3) Cl(4) Ni(1) Cl(5) Cl(5) Ni(1) Cl(4)

Cl(4) Cl(3) Cl(2)

C43
Cl(4)

Cl(3) Ni(1) Cl(2)

Cl(5)
 Chem 59-651
Notes about rotation operations, Cnm:
- Linear molecules have an infinite number of rotation axes C∞ because any
rotation on the molecular axis will give the same arrangement.

C(1) O(2)
O(2)
C(1)

O(3) C(1) O(2)

N(2)
N(1)
N(1) N(2)
 Chem 59-651
The Principal axis in an object is the highest order rotation axis. It
is usually easy to identify the principle axis and this is typically
assigned to the z-axis if we are using Cartesian coordinates.

Ethane, C2H6 Benzene, C6H6

The principal axis is the three-fold The principal axis is the six-fold axis
axis containing the C-C bond. through the center of the ring.

The principal axis in a tetrahedron is

a three-fold axis going through one
vertex and the center of the object.
 Chem 59-651
Reflection across a plane of symmetry, σ (mirror plane)

O(1) σv O(1)

H(2) H(3) H(3) H(2)

These mirror planes are

called “vertical” mirror
planes, σv, because they
contain the principal axis.
O(1) σv O(1) The reflection illustrated
in the top diagram is
through a mirror plane
H(2) H(3) H(2) H(3)
perpendicular to the
plane of the water
molecule. The plane
shown on the bottom is in
the same plane as the
Handedness is changed by reflection! water molecule.
 Chem 59-651
Notes about reflection operations:
- A reflection operation exchanges one half of the object with the reflection of
the other half.
- Reflection planes may be vertical, horizontal or dihedral (more on σd later).
- Two successive reflections are equivalent to the identity operation (nothing is
moved).
σh A “horizontal” mirror plane, σh, is
perpendicular to the principal axis.
This must be the xy-plane if the z-
axis is the principal axis.
σd σd In benzene, the σh is in the plane
of the molecule – it “reflects” each
atom onto itself.

σh

Vertical and dihedral mirror

planes of geometric shapes.
σv σv
 Chem 59-651
Inversion and centers of symmetry, i (inversion centers)
In this operation, every part of the object is reflected through the
inversion center, which must be at the center of mass of the object.
1F Cl 2 2F Cl 1

Br 2
i Br 1
1 2 2 1
1 Br 2 Br

1 Cl F2 2 Cl F1

i
[x, y, z] [-x, -y, -z]

We will not consider the matrix approach to each of the symmetry operations in this
course but it is particularly helpful for understanding what the inversion operation
does. The inversion operation takes a point or object at [x, y, z] to [-x, -y, -z].
 Chem 59-651
n-fold improper rotation, Snm (associated with an improper rotation axis
or a rotation-reflection axis) This operation involves a rotation of 360°/n
followed by a reflection perpendicular to the axis. It is a single operation
and is labeled in the same manner as “proper” rotations.
F1 F2
H1
F4 F1
S41 H4 C H2

H3
F2 F3
F2 S41
F3 F4
F1 H2
90° σh H1 C H3 C21
F3 H4

F4 S42
H3

H2 C H4

H1

Note that: S1 = σ, S2 = i, and sometimes S2n = Cn (e.g. in box) this makes

more sense when you examine the matrices that describe the operations.
 Chem 59-651 Identifying point groups

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.

Chem 59-651 Identifying point groups
 Chem 59-651 Identifying point groups
Special cases:
Perfect tetrahedral (Td) e.g. P4, CH4

Perfect octahedral (Oh) e.g. SF6, [B6H6]-2

Perfect icosahedral (Ih) e.g. [B12H12]-2, C60

 Chem 59-651 Identifying point groups
Low symmetry groups:
Only* an improper axis (Sn)

e.g. 1,3,5,7-tetrafluoroCOT, S4
F1

F4

F2

F3

Only a mirror plane (Cs)

e.g. CHFCl2

F H

Cl
Cl
 Chem 59-651 Identifying point groups
Low symmetry groups:
Only an inversion center (Ci)

e.g. (conformation is important !)

F Cl

Br

Br

Cl F

No symmetry (C1)

e.g. CHFClBr
F H

Br
Cl
 Chem 59-651 Identifying point groups
Cn type groups:
A Cn axis and a σh (Cnh)

e.g. B(OH)3 (C3h, conformation is important !)

H
O

B
H

O O

e.g. H2O2 (C2h, conformation is important !)

H

O O

Note: molecule does not have to be planar e.g. B(NH2)3 (C3h, conformation is important !)
 Chem 59-651 Identifying point groups
Cn type groups:
Only a Cn axis (Cn)

e.g. B(NH2)3 (C3, conformation is important !)

H H
N

B
H

N N
H H

e.g. H2O2 (C2, conformation is important !)

O O

H
 Chem 59-651 Identifying point groups
Cn type groups:
A Cn axis and a σv (Cnv)

e.g. NH3 (C3v)

H

H H

e.g. H2O2 (C2v, conformation is important !)

O O

H H
 Chem 59-651 Identifying point groups
Cn type groups:
A Cn axis and a σv (Cnv)

e.g. NH3 (C3v, conformation is important !)

H
H
e.g. carbon monoxide, CO (C∞v)
H

There are an infinite number of possible

H
N
H
Cn axes and σv mirror planes.
H H

H H C O

e.g. trans-[SbF4ClBr]- (C4v) Cl

F F
Sb O
C
F Sb
Br
Cl F F F

Br
F
 Chem 59-651 Identifying point groups
Dn type groups:
A Cn axis, n perpendicular C2 axes
and a σh (Dnh)

e.g. BH3 (D3h)

H

H B
H H

H H

e.g. NiCl4 (D4h)

Cl(2)
Cl Ni
Cl Cl

Cl(4) Ni(1) Cl(5)

Cl Ni Cl
Cl(3)
 Chem 59-651 Identifying point groups
Dn type groups:
e.g. pentagonal prism (D5h)
A Cn axis, n perpendicular C2 axes
and a σh (Dnh)

e.g. Mg(η5-Cp)2 (D5h in the eclipsed conformation)

Mg

Mg
View down the C5 axis

e.g. square prism (D4h)

e.g. carbon dioxide, CO2 or N2 (D∞h)

There are an infinite number of possible

Cn axes and σv mirror planes in addition
to the σh.

O O O
C
 Chem 59-651 Identifying point groups
Dn type groups:
A Cn axis, n perpendicular C2 axes
and no mirror planes (Dn)
-propellor shapes

e.g. Ni(CH2)4 (D4)

H H H H
H H Ni

H H H H

H H

Ni

H H

H H

H H H H

Ni

H H H H
 Chem 59-651
e.g. (SCH2CH2)3 (D3 conformation is important!) e.g. propellor (D3)

e.g. Ni(en)3 (D3 conformation is important!) en = H2NCH2CH2NH2

 Chem 59-651 Identifying point groups
Dn type groups:
A Cn axis, n perpendicular C2 axes
and a σd (Dnd)

e.g. ethane, H3C-CH3

(D3d in the staggered conformation)

H H

H H

H
H

H
H

dihedral means between sides or planes – this is where you find the C2 axes
 Chem 59-651
e.g. Mg(η5-Cp)2 and other metallocenes in the staggered conformation (D5d)

Fe Mg Al M

View down the C5 axis

These are pentagonal
antiprisms

e.g. triagular e.g. square e.g. allene or a tennis ball (D2d)

antiprism (D3d) antiprism (D4d)
 Chem 59-651 Identifying point groups

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. tetrahedral).

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

and where they are.

5. Assign point group.

 Chem 59-651 Character Tables for Point Groups
Each point group has a complete set of possible symmetry operations
that are conveniently listed as a matrix known as a Character Table. As
an example, we will look at the character table for the C2v point group.

Point Group Label Symmetry Operations – The Order is the total number of operations

In C2v the order is 4:

1 E, 1 C2, 1 σv and 1 σ’v
C2V E C2 σv (xz) σ’v (yz)
A1 1 1 1 1
A2 1 1 -1 -1 Character
B1 1 -1 1 -1
B2 1 -1 -1 1 Representation of B2

Symmetry Representation Labels

Representations are subsets of the complete point group – they indicate the
effect of the symmetry operations on different kinds of mathematical
functions. Representations are orthogonal to one another. The Character is
an integer that indicates the effect of an operation in a given representation.
 Chem 59-651 Character Tables for Point Groups
The effect of symmetry elements on mathematical functions is useful to
us because orbitals are mathematical functions! Analysis of the
symmetry of a molecule will provide us with insight into the orbitals
used in bonding.
Symmetry of Functions

C2V E C2 σv (xz) σ’v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz

Notes about symmetry labels and characters:

“A” means symmetric with regard to rotation about the principle axis.
“B” means anti-symmetric with regard to rotation about the principle axis.
Subscript numbers are used to differentiate symmetry labels, if necessary.
“1” indicates that the operation leaves the function unchanged: it is called “symmetric”.
“-1” indicates that the operation reverses the function: it is called “anti-symmetric”.
 Chem 59-651 Symmetry of orbitals and functions
A pz orbital has the same symmetry as an arrow pointing along the z-axis.

z z

≡ y y
E
x C2 x
σv (xz)
σ’v (yz) No change
∴ symmetric
∴ 1’s in table

C2V E C2 σv (xz) σ’v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
 Chem 59-651 Symmetry of orbitals and functions
A px orbital has the same symmetry as an arrow pointing along the x-axis.
z z

y y
E No change
≡ x σv (xz) x ∴ symmetric
∴ 1’s in table
z z

y y
C2 Opposite
x σ’v (yz) x ∴ anti-symmetric
∴ -1’s in table
C2V E C2 σv (xz) σ’v (yz)
A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
 Chem 59-651 Symmetry of orbitals and functions
A py orbital has the same symmetry as an arrow pointing along the y-axis.
z z

y y
E No change
≡ x σ’v (yz) x ∴ symmetric
∴ 1’s in table
z z

y y
C2 Opposite
x σv (xz) x ∴ anti-symmetric
∴ -1’s in table
C2V E C2 σv (xz) σ’v (yz)
A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
 Chem 59-651 Symmetry of orbitals and functions
Rotation about the n axis, Rn, can be treated in a similar way.
y y
The z axis is pointing
out of the screen!
x x
If the rotation is still in
E No change
the same direction (e.g.
C2 ∴ symmetric
counter clock-wise),
∴ 1’s in table
then the result is y y
considered symmetric.

If the rotation is in the

opposite direction (i.e. x x
clock-wise), then the σv (xz) Opposite
result is considered ∴ anti-symmetric
anti-symmetric. σ’v (yz)
∴ -1’s in table
C2V E C2 σv (xz) σ’v (yz)
A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
 Chem 59-651 Symmetry of orbitals and functions
d orbital functions can also be treated in a similar way
y y
The z axis is pointing
out of the screen!
x x
E No change
C2 ∴ symmetric
∴ 1’s in table
y y

x x
σv (xz) Opposite
σ’v (yz) ∴ anti-symmetric
∴ -1’s in table
C2V E C2 σv (xz) σ’v (yz)
A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
 Chem 59-651 Symmetry of orbitals and functions
d orbital functions can also be treated in a similar way
y y
The z axis is pointing
out of the screen!
So these are
representations of the
view of the dz2 orbital
x x
and dx2-y2 orbital down
the z-axis. No change
y y ∴ symmetric
∴ 1’s in table
E
C2
x σv (xz) x
σ’v (yz)

C2V E C2 σv (xz) σ’v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
 Chem 59-651 Symmetry of orbitals and functions
Note that the representation of orbital functions changes depending on the point
group – thus it is important to be able to identify the point group correctly.

C2V E C2 σv (xz) σ’v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz

D3h E 2 C3 3 C2 σh 2 S3 3 σv
A’1 1 1 1 1 1 1 x2 + y2, z2
A’2 1 1 -1 1 1 -1 Rz
E’ 2 -1 0 2 -1 0 (x,y) (x2 - y2, xy)
A’’1 1 1 1 -1 -1 -1
A’’2 1 1 -1 -1 -1 1 z
E’’ 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
 Chem 59-651 Symmetry of orbitals and functions
D3h E 2 C3 3 C2 σh 2 S3 3 σv
A’1 1 1 1 1 1 1 x2 + y2, z2
A’2 1 1 -1 1 1 -1 Rz
E’ 2 -1 0 2 -1 0 (x,y) (x2 - y2, xy)
A’’1 1 1 1 -1 -1 -1
A’’2 1 1 -1 -1 -1 1 z
E’’ 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)
More notes about symmetry labels and characters:
-“E” indicates that the representation is doubly-degenerate – this means that the
functions grouped in parentheses must be treated as a pair and can not be
considered individually.
-The prime (‘) and (“) double prime in the symmetry representation label indicates
“symmetric” or “anti-symmetric” with respect to the σh. cos(120°) = -0.5
y y y sin(120°) = 0.87
+0.87
C2 (x) C3 -0.5
+1
x x x
-1 -0.87 -0.5
(+1) + (-1) = 0 (+0.87) + (-0.87) + (-0.5) + (-0.5) = -1
 Chem 59-651 Symmetry of orbitals and functions
Oh E 8 C3 6 C2 6 C4 3 C2 i 6 S4 8 S6 3 σh 6 σd
(C42)
A1g 1 1 1 1 1 1 1 1 1 1 x2 + y2 + z2

A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0 (2z2 - x2 - y2,
x2 - y2)
T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry, Rz)

T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)

A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)

T2u 3 0 1 -1 -1 -3 1 0 1 -1

More notes about symmetry labels and characters:

-“T” indicates that the representation is triply-degenerate – this means that the
functions grouped in parentheses must be treated as a threesome and can not be
considered individually.
-The subscripts g (gerade) and u (ungerade) in the symmetry representation label
indicates “symmetric” or “anti-symmetric” with respect to the inversion center, i.
 Chem 59-651 Character Tables and Bonding
We can use character tables to determine the orbitals involved in bonding in
a molecule. This process is done a few easy steps.

1. Determine the point group of the molecule.

2. Determine the Reducible Representation, Γ, for the type of bonding you

wish to describe (e.g. σ, π, π⊥, π//). The Reducible Representation
indicates how the bonds are affected by the symmetry elements present
in the point group.

3. Identify the Irreducible Representation that provides the Reducible

Representation; there is a simple equation to do this. The Irreducible
Representation (e.g. 2A1 + B1 + B2) is the combination of symmetry
representations in the point group that sum to give the Reducible
Representation.

4. Identify which orbitals are involved from the Irreducible Representation

and the character table.
 Chem 59-651 Character Tables and Bonding
H
Example, the σ bonding in dichloromethane, CH2Cl2.
H

The point group is C2v so we must use the appropriate character table
for the reducible representation of the sigma bonding, Γσ. To Cl
Cl

determine Γσ all we have to do is see how each symmetry operation

affects the 4 σ bonds in the molecule – if the bond moves, it is given a
value of 0, if it stays in the same place, the bond is given a value of 1.
Put the sum of the 1’s and 0’s into the box corresponding to the
symmetry operation.

The E operation leaves everything where it is so all four bonds stay in

the same place and the character is 4 (1+1+1+1).

The C2 operation moves all four bonds so the character is 0.

Each σv operation leaves two bonds where they were and moves two
bonds so the character is 2 (1+1).

Overall, the reducible representation is thus:

C2V E C2 σv (xz) σ’v (yz)

Γσ 4 0 2 2
 Chem 59-651 Character Tables and Bonding
We now have to figure out what combination of symmetry representations will add
up to give us this reducible representation. In this case, it can be done by
inspection, but there is a simple equation that is useful for more complicated
situations.

C2V E C2 σv (xz) σ’v (yz)

Γσ 4 0 2 2

C2V E C2 σv (xz) σ’v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz

Because the character under E is 4, there must be a total of 4 symmetry

representations (sometimes called basis functions) that combine to make Γσ. Since
the character under C2 is 0, there must be two of A symmetry and two of B symmetry.
The irreducible representation is (2A1 + B1 + B2), which corresponds to: s, pz, px, and
py orbitals – the same as in VBT. You can often use your understanding of VBT to
help you in finding the correct basis functions for the irreducible representation.
 Chem 59-651 Character Tables and Bonding
C2V E C2 σv (xz) σ’v (yz)
Γσ 4 0 2 2

C2V E C2 σv (xz) σ’v (yz)

A1 1 1 1 1 z x2,y2,z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz

The formula to figure out the number of symmetry representations of a given type is:

nX =
1
order
∑ ( [
# of operations in class) × (character of RR) × (character of X ) ]
Thus, in our example:

nA1 =
1
4
[ ]
(1)(4)(1) + (1)(0)(1) + (1)(2)(1) + (1)(2)(1) nB1 =
1
4
[ ]
(1)(4)(1) + (1)(0)(−1) + (1)(2)(1) + (1)(2)(−1)

nA 2 =
1
4
[
(1)(4)(1) + (1)(0)(1) + (1)(2)( −1) + (1)(2)(−1) ] nB2 =
1
4
[ ]
(1)(4)(1) + (1)(0)(−1) + (1)(2)(−1) + (1)(2)(1)
Which gives: 2 A1’s, 0 A2’s, 1 B1 and 1 B2.
 Chem 59-651 Character Tables and Bonding O

Example, the σ and π bonding in SO3. S O

The point group is D3h so we must use the appropriate character table to
find the reducible representation of the sigma bonding, Γσ first, then we can O
go the representation of the π bonding, Γπ. To determine Γσ all we have to
do is see how each symmetry operation affects the 3 σ bonds in the
molecule.

The E and the σh operations leave everything where it is so all three bonds
stay in the same place and the character is 3 (1+1+1).

The C3 and S3 operations move all three bonds so their characters are 0.

The C2 operation moves two of the bonds and leaves one where it was so
the character is 1.

Each σv operation leaves one bond where it was and moves two bonds so
the character is 1.

Overall, the reducible representation for the sigma bonding is:

D3h E 2 C3 3 C2 σh 2 S3 3 σv
Γσ 3 0 1 3 0 1
 Chem 59-651 D3h E 2 C3 3 C2 σh 2 S3 3 σv
Γσ 3 0 1 3 0 1
D3h E 2 C3 3 C2 σh 2 S3 3 σv
A’1 1 1 1 1 1 1 x2 + y2, z2
A’2 1 1 -1 1 1 -1 Rz
E’ 2 -1 0 2 -1 0 (x,y) (x2 - y2, xy)
A’’1 1 1 1 -1 -1 -1
A’’2 1 1 -1 -1 -1 1 z
E’’ 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)

nA'1 =
1
12
[ ]
(1)(3)(1) + (2)(0)(1) + (3)(1)(1) + (1)(3)(1) + (2)(0)(1) + (3)(1)(1) nA'1 =
12
12
=1

nA'2 =
1
12
[
(1)(3)(1) + (2)(0)(1) + (3)(1)(−1) + (1)(3)(1) + (2)(0)(1) + (3)(1)(−1) ] nA'2 =
0
12
=0

nE' =
1
12
[
( ]
1)(3)(2) + (2)(0)( −1) + (3)(1)(0) + (1)(3)(2) + (2)(0)( −1) + (3)(1)(0) nE' =
12
12
=1

We can stop here because the combination (A’1 + E’) produces the Γσ that we determined. None
of the other representations can contribute to the σ bonding (i.e. nA”1, nA”1 and nE” are all 0). The
irreducible representation (A’1 + E’) shows us that the orbitals involved in bonding are the s and
the px and py pair; this corresponds to the sp2 combination we find in VBT.
 Chem 59-651 Character Tables and Bonding O

Now we have to determine Γ for the π bonding in SO3. S O

To determine Γπ we have to see how each symmetry operation affects
O
the π systems in the molecule. The treatment is similar to what we did
for sigma bonding but there are a few significant differences:

1) Pi bonds change sign across the inter-nuclear axis. We must consider the
effect of the symmetry operation on the signs of the lobes in a π bond.

2) There is the possibility of two different π type bonds for any given σ bond
(oriented 90° from each other). We must examine each of these.

This means that we have to find reducible representations for both the π
system perpendicular to the molecular plane (π⊥, vectors shown in red)
and the pi system in the molecular plane (π// , vectors shown in blue).

Note: These are just vectors that are associated

with each sigma bond (not with any particular
O atom) – they could also be placed in the middle
of each SO bond. The vectors should be placed
S O to conform with the symmetry of the point group
(e.g. the blue vectors conform to the C3 axis).
O
 Chem 59-651 Example, the σ and π bonding in SO3.
First determine the reducible representation for the pi bonding
perpendicular to the molecular plane, Γπ⊥. O
S O
The E operation leaves everything where it is so all three vectors stay
in the same place and the character is 3. O
The C3 and S3 operations move all three vectors so their characters σh ,C2
are 0.

The C2 operation moves two of the vectors and reverses the sign of the O
other one so the character is -1.
S O
The σh operation reverses the sign of all three vectors so the character
is -3.
O

Each σv operation leaves one vector where it was and moves the two
others so the character is 1.

Overall, the reducible representation for the perpendicular π bonding is:

D3h E 2 C3 3 C2 σh 2 S3 3 σv
Γπ⊥ 3 0 -1 -3 0 1
 Chem 59-651 D3h E 2 C3 3 C2 σh 2 S3 3 σv
Γπ⊥ 3 0 -1 -3 0 1
D3h E 2 C3 3 C2 σh 2 S3 3 σv
A’1 1 1 1 1 1 1 x2 + y2, z2
A’2 1 1 -1 1 1 -1 Rz
E’ 2 -1 0 2 -1 0 (x,y) (x2 - y2, xy)
A’’1 1 1 1 -1 -1 -1
A’’2 1 1 -1 -1 -1 1 z
E’’ 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)

nA'1 =
1
12
[ ]
(1)(3)(1) + (2)(0)(1) + (3)(−1)(1) + (1)(−3)(1) + (2)(0)(1) + (3)(1)(1) nA'1 =
0
12
=0

nA''2 =
1
12
[
(1)(3)(1) + (2)(0)(1) + (3)(−1)(−1) + (1)(−3)(−1) + (2)(0)(−1) + (3)(1)(1) ] nA''2 =
12
12
=1

nE'' =
1
12
( [
1)(3)(2) + (2)(0)( −1) + (3)( −1)(0) + (1)( −3)( −2) + (2)(0)(1) + (3)(1)(0) ]
nE'' =
12
12
=1

Going through all the possibly symmetry representations, we find that the combination (A”2 + E”)
produces the Γπ⊥that we determined. The irreducible representation shows us that the possible
orbitals involved in perpendicular π bonding are the pz and the dxz and dyz pair. This is in
agreement with the π bonding we would predict using VBT.
 Chem 59-651 Example, the σ and π bonding in SO3.
First determine the reducible representation for the π bonding in the
molecular plane, Γπ//. O
S O
The E operation leaves everything where it is so all three vectors stay
in the same place and the character is 3. O

The C3 and S3 operations move all three vectors so their characters σv ,C2
are 0.

The C2 operation moves two of the vectors and reverses the sign of the
other one so the character is -1. O
The σh operation leaves all three vectors unchanged so the character
S O
is 3. O
Each σv operation reverses the sign one vector where it was and
moves the two others so the character is -1.

Overall, the reducible representation for the parallel π bonding is:

D3h E 2 C3 3 C2 σh 2 S3 3 σv
Γπ// 3 0 -1 3 0 -1
 Chem 59-651 D3h E 2 C3 3 C2 σh 2 S3 3 σv
Γπ// 3 0 -1 3 0 -1
D3h E 2 C3 3 C2 σh 2 S3 3 σv
A’1 1 1 1 1 1 1 x2 + y2, z2
A’2 1 1 -1 1 1 -1 Rz
E’ 2 -1 0 2 -1 0 (x,y) (x2 - y2, xy)
A’’1 1 1 1 -1 -1 -1
A’’2 1 1 -1 -1 -1 1 z
E’’ 2 -1 0 -2 1 0 (Rx, Ry) (xz, yz)

nA'1 =
1
12
[
(1)(3)(1) + (2)(0)(1) + (3)(−1)(1) + (1)(3)(1) + (2)(0)(1) + (3)(1)(−1) ] nA'1 =
0
12
=0

nA'2 =
1
12
( [
1)(3)(1) + (2)(0)(1) + (3)(−1)( −1) + (1)(3)(1) + (2)(0)(1) + (3)( −1)(−1) ] nA'2 =
12
12
=1

nE' =
1
12
[( ]
1)(3)(2) + (2)(0)( −1) + (3)( −1)(0) + (1)(3)(2) + (2)(0)(−1) + (3)( −1)(0) nE' =
12
12
=1

Going through all the possibly symmetry representations, we find that the combination (A’2 + E’)
produces the Γπ// that we determined. The possible orbitals involved in parallel π bonding are only
the dx2-y2 and dxy pair. The A’2 representation has no orbital equivalent. Note: Such analyses do
NOT mean that there is π bonding using these orbitals – it only means that it is possible
based on the symmetry of the molecule.
 O
Chem 59-651 Character Tables and Bonding
Example, the σ and π bonding in ClO4-. O Cl O
The point group is Td so we must use the appropriate character table to find
the reducible representation of the sigma bonding, Γσ first, then we can go O
the representation of the π bonding, Γπ.

The E operation leaves everything where it is so all four bonds stay in the
same place and the character is 4.

Each C3 operation moves three bonds leaves one where it was so the
character is 1.

The C2 and S4 operations move all four bonds so their characters are 0.

Each σd operation leaves two bonds where they were and moves two
bonds so the character is 2.

Td E 8 C3 3 C2 6 S4 6 σd
Γσ 4 1 0 0 2
 Chem 59-651 Td E 8 C3 3 C2 6 S4 6 σd
Γσ 4 1 0 0 2

Td E 8 C3 3 C2 6 S4 6 σd
A1 1 1 1 1 1 x2 + y2 + z2
A2 1 1 1 -1 -1
E 2 -1 2 0 0 (2z2 - x2 - y2, x2 - y2)
T1 3 0 -1 1 -1 (Rx, Ry, Rz)

T2 3 0 -1 -1 1 (x, y, z) (xy, xz, yz)

The irreducible representation for the σ bonding is (A1 + T2), which corresponds
to the s orbital and the (px, py, pz) set that we would use in VBT to construct a the
sp3 hybrid orbitals suitable for a tetrahedral arrangement of atoms. To get the
representation for the π bonding, we must do the same procedure that we did for
SO3, except that in the point group Td, one can not separate the representations
into parallel and perpendicular components. This is because the three-fold
symmetry of the bond axis requires the orthogonal
vectors to be treated as an inseparable pair.
 Chem 59-651 Example, the σ and π bonding in ClO4-.
The analysis of how the 8 vectors are affected by the symmetry operations gives:

Td E 8 C3 3 C2 6 S4 6 σd
Γπ 8 -1 0 0 0

Td E 8 C3 3 C2 6 S4 6 σd
A1 1 1 1 1 1 x2 + y2 + z2
A2 1 1 1 -1 -1
E 2 -1 2 0 0 (2z2 - x2 - y2, x2 - y2)
T1 3 0 -1 1 -1 (Rx, Ry, Rz)

T2 3 0 -1 -1 1 (x, y, z) (xy, xz, yz)

The irreducible representation for the π bonding is (E + T1 + T2), which

corresponds to the dx2-y2 and dxy pair for E and either the (px, py, pz) set or the
(dxy, dxz, dyz) set for T2, since T1 does not correspond to any of the orbitals that
might be involved in bonding. Because the (px, py, pz) set has already been
used in the σ bonding, only the (dxy, dxz, dyz) set may be used for π bonding.