CHEM 228

Inorganic Chemistry



Symmetry and Group Theory

Inorganic Chemistry, G.L. Miessler and D.A. Tarr, Chapter 4



Instructor: Houssam El-Rassy, PhD, Associate Professor
Chemistry Bldg., Room 520, Phone 4051, E-mail: Houssam.Rassy@aub.edu.lb,
O.H.: Tuesday and Thursday 10:00 am 11:30 am, and by appointment
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Introduction
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Symmetry is all around us and is a fundamental property of nature.
Houssam El-Rassy, PhD, Associate Professor
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Introduction
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Houssam El-Rassy, PhD, Associate Professor
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Introduction
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Symmetry concepts can be extremely useful in chemistry


By analyzing the symmetry of molecules, we can:
predict IR and Raman spectra
describe the types of orbitals used in bonding
predict optical activity
interpret electronic spectra
study a number of additional molecular properties


Well define the symmetry very specifically in terms of five symmetry operations
Well describe how molecules can be classified on the basis of types of symmetry
they possess

Houssam El-Rassy, PhD, Associate Professor
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Symmetry elements and operations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
All molecules can be described in terms of their symmetry, even if it is only to say
they have none

Symmetry elements: mirror planes, axes of rotation, inversion center

Symmetry operation: rotation, reflection or inversion


To contain a given symmetry element, a molecule must have exactly the same
appearance after the operation as before
Element Operation
Rotation axis, C
n
n-fold rotation
Improper rotation axis, S
n
n-fold improper rotation
Plane of symmetry, o Reflection
Center of symmetry, i Inversion
Identity, E
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The Identity Operation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
In the identity operation, no change is made in the molecule


Obviously, the result of this operation is not only to produce an equivalent
orientation but an identical one


All molecules possess this symmetry element


This symmetry is indicated by E
Houssam El-Rassy, PhD, Associate Professor
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The Rotation Operation C
n
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
If an imaginary axis can be constructed in a molecule, around which the molecule
can be rotated to produce an equivalent orientation (indistinguishable from the
original), this molecule is said to possess a rotation axis

It may be possible to carry out several symmetry operations around a single rotation
axis

If the molecule can occupy n different equivalent positions about the axis, the axis is
said to be of order n
The order n of this axis is 3. Three
rotations are needed to return to the
original position

The molecule is said to possess a threefold
rotation axis, indicated by the symbol C
3
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The Rotation Operation C
n
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
n-fold rotation - a rotation of 360/n about the C
n
axis (n = 1 to )
H(2)
O(1)
H(3)
H(3)
O(1)
H(2)
In water there is a C
2
axis so we can perform a 2-fold (180) rotation to get the
identical arrangement of atoms.
H(2)
H(3) H(4)
N(1)
H(2)
H(3)
H(4)
N(1)
In ammonia there is a C
3
axis so we can perform 3-fold (120) rotations to get
identical arrangement of atoms.
H(2)
H(3)
H(4)
N(1)
120 120
180
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The Rotation Operation C
n
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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The Rotation Operation C
n
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
H(2)
H(3) H(4)
N(1)
H(2)
H(3)
H(4)
N(1)
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 C
n
m
.
- The rotation C
n
n
is equivalent to the identity operation (nothing is moved).
H(2)
H(3)
H(4)
N(1)
C
3
1 C
3
2
C
3
3
= E

H(2)
H(3) H(4)
N(1)
Houssam El-Rassy, PhD, Associate Professor
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The Rotation Operation C
n
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Cl(4)
Cl(3)
Ni(1)
Cl(2)
Cl(5)
C
4
2
= C
2
1
C
4
1
C
4
3
Cl(4)
Cl(2) Ni(1) Cl(3)
Cl(5)
Cl(4)
Cl(2)
Ni(1)
Cl(3)
Cl(5)
Cl(4)
Cl(3) Ni(1) Cl(2)
Cl(5)
Notes about rotation operations, C
n
m
:
- If n/m is an integer, then that rotation operation is equivalent to an n/m - fold
rotation.
e.g. C
4
2
= C
2
1
, C
6
2
= C
3
1
, C
6
3
= C
2
1
, etc. (identical to simplifying fractions)
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The Rotation Operation C
n
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Notes about rotation operations, C
n
m
:
- Linear molecules have an infinite number of rotation axes C

because any rotation

on the molecular axis will give the same arrangement.
O(2) C(1)
C(1) O(2)
O(3) C(1) O(2)
N(2) N(1)
N(1) N(2)
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The Rotation Operation C
n
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Rotation of the molecule through 2/n produces equivalent orientations, and n
operations produce the starting configuration referred to as the identity

3
2
3
C C
Further examination of the BCl
3
molecule indicates the lack of a center of symmetry
and the presence of 3 additional twofold rotation axes, C
2
C
2
rotation axis
Houssam El-Rassy, PhD, Associate Professor
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The Rotation Operation C
n
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
A rotation axis of order n generates n operations : C
n
, C
n
2
, C
n
3
, , C
n
n-1
, C
n
n

C
4
2
C
2
C
6
2
C
3
C
n
n
is the identity


The highest-fold rotation axis is referred to as the principal axis in a molecule. If all
the C
n
axes are equivalent, any one can be chosen as the principal axis
Houssam El-Rassy, PhD, Associate Professor
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The Rotation Operation C
n
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Reflection Operation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
If a plane exists in a molecule that separates the molecule into two halves that are
mirror images of each other, the molecule possesses the symmetry element of a
mirror plane

This plane cannot lie outside the molecule but must pass through it
Houssam El-Rassy, PhD, Associate Professor
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Reflection Operation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Often rotation axes lie in a mirror plane, but there are examples in which this is not
the case
In general, the presence of a mirror plane is denoted by the symbol . In those
molecules that contain more than one mirror plane, the horizontal plane
h
is taken
as the one perpendicular to the principal axis (highest-fold rotation axis).

Other planes, which contain the principal axis of rotation, are labeled
v
or
d


For the BCl
3
, there is three vertical planes
v
(each one containing the boron atom
and one chlorine atom), perpendicular to
h

Houssam El-Rassy, PhD, Associate Professor
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Reflection Operation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
A horizontal mirror plane, o
h
, is
perpendicular to the principal axis.
This must be the xy-plane if the z-
axis is the principal axis.
In benzene, the o
h
is in the plane of
the molecule it reflects each
atom onto itself.
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 o
d
later).
- Two successive reflections are equivalent to the identity operation (nothing is
moved).
o
h
o
v
o
v
Vertical and dihedral mirror
planes of geometric shapes.
o
d
o
d
o
h
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Reflection Operation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
XeF
4
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The Center of Symmetry, or Inversion Center
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
A molecule is said to possess a center of symmetry or inversion center when every
atom in the molecule encounters a like atom if moved in a straight line through this
center and an equal distance on the other side of the center
This operation corresponds to placing this center at the center of a coordinate
system, and taking every atom with coordinates (x, y, z) and changing its
coordinates to (-x, -y, -z).

At most one atom can be at the center, and all other atoms in the molecule must
exist in pairs

The symbol used to indicate
an inversion center is i
Houssam El-Rassy, PhD, Associate Professor
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The Rotation-Reflection Operation: Improper Rotation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
This operation involves rotation about an axis followed by reflection through a
mirror plane that is perpendicular to the rotation axis, or vice versa (rotation-
reflection is equivalent to reflection-rotation)







When the result of the two operations produces an equivalent structure, the
molecule is said to possess a rotation-reflection axis (alternating axis)


The symbol S is used to indicate this symmetry element. The subscript n in S
n

indicates rotation through 2/n


Two S
n
operations in succession generate a C
n/2
operation
Houssam El-Rassy, PhD, Associate Professor
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The Rotation-Reflection Operation: Improper Rotation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
F
1
F
2
F
3
F
4
S
4
1
90
F
4
F
1
F
2
F
3
o
h

F
1
F
2
F
3
F
4
C
H
1
H
3
H
2
H
4
C
H
2
H
4
H
3
H
1
C
H
1
H
3
H
2
H
4
S
4
1
S
4
2
C
2
1
Houssam El-Rassy, PhD, Associate Professor
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The Rotation-Reflection Operation: Improper Rotation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Note that an S
2
operation is the same as inversion. An S
1
operation is the same as a
reflection plane.

The i and notations are preferred in these cases
Houssam El-Rassy, PhD, Associate Professor
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The Rotation-Reflection Operation: Improper Rotation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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The Rotation-Reflection Operation: Improper Rotation
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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M.C. Escher Examples
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
M.C. Escher Examples
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
A point group is a collection of all the symmetry operations that can be carried out
on a molecule belonging to this group

It is possible to classify any given molecule into one of the point groups

A molecule in the point group C
n
has only one symmetry element, an n-fold rotation
axis

A molecule that has a horizontal mirror plane perpendicular to its C
n
rotation axis,
belongs to the point group C
nh

The point group C
nv
includes molecules like water and sulfuryl chloride, which have
n vertical mirror planes containing the rotation axis, but no horizontal mirror plane

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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
The symbol D
n
is used for point groups that have, in addition to a C
n
axis, nC
2
axes
perpendicular to it

Therefore, the D
n
point group has greater symmetry (more symmetry operations)
than the C
n
group

A D
n
molecule that also has a horizontal mirror plane perpendicular to the C
n
axis
belongs to the point group D
nh
, and as a consequence will also have n vertical mirror
planes

C
2
rotation axis
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
D
n
molecules may also have
d
planes that contain the principal C
n
axis but none of
the perpendicular C
2
axis (these dihedral planes
d
bisect the angle between two of
the C
2
axes)

The notation of a D
n
molecule containing this symmetry element is D
nd

Such a molecule will contain an n-fold axis, n twofold axes perpendicular to C
n
, and
in addition n (vertical) planes of symmetry bisecting the angles between two
twofold axes and containing the n-fold axis
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Houssam El-Rassy, PhD, Associate Professor
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Houssam El-Rassy, PhD, Associate Professor
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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 if 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.
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Perfect icosahedral (I
h
) e.g. [B
12
H
12
]
-2
, C
60
Special cases:
Perfect tetrahedral (T
d
) e.g. P
4
, CH
4
Perfect octahedral (O
h
) e.g. SF
6
, [B
6
H
6
]
-2
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Houssam El-Rassy, PhD, Associate Professor
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Houssam El-Rassy, PhD, Associate Professor
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Houssam El-Rassy, PhD, Associate Professor
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Houssam El-Rassy, PhD, Associate Professor
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Point Groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Houssam El-Rassy, PhD, Associate Professor
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Properties and representations of groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
All mathematical groups (of which point groups are special types) must have some
properties
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Properties and representations of groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Matrices - Summary
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Important information about the symmetry aspects of point groups is summarized
in character tables



To understand the construction and use of character tables, we first need to
consider the properties of matrices, which are the basis for the tables

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Matrices - Summary
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
A matrix is a rectangular array of numbers or symbols that has the following general
form





The entire matrix can be abbreviated with a script letter or by the symbol [a
ij
].

The symbol a
ij
refers to the matrix element in the ith row and jth column

When the number of rows is equal to the number of columns, the matrix is called a
square matrix

The elements a
ij
of a square matrix are called the diagonal elements and the other
elements are called off-diagonal

When all of the off-diagonal elements of a matrix are zero, the matrix is said to be
diagonalized or to be a diagonal matrix

(
(
(

33 32 31
23 22 21
13 12 11
a a a
a a a
a a a
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Matrices - Summary
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
When each of the diagonal elements of a square matrix equals 1 and all off-
diagonal elements are zero, the matrix is called a unit matrix

The unit matrix is often abbreviated by the Kronecker delta,





The trace or character of a square matrix is simply the sum of the diagonal elements

A one-row matrix can be conveniently written on a single line. In order to write a
one-column matrix on a single line, it is enclosed in braces { }

A vector is conveniently represented by a one-column matrix. In a three-
dimensional orthogonal coordinate system, a vector initiating at the origin of the
coordinate system is completely specified by the x, y, and z coordinates of the other
end.

Thus the matrix {x, y, z} is a one-column matrix that represents the vector
o =
(
(
(
(

1 0 0 0
0 1 0 0
0 0 1 0
0 0 0 1
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Matrices - Summary
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Matrices can be added, subtracted, multiplied, or divided by using the appropriate
rules of matrix algebra

In order to add or subtract two matrices U and B to give a matrix C, the matrices
must all be of the same dimension (rows and columns)
c
ij
= a
ij
b
ij


A matrix can be multiplied by a scalar (a single number). When multiplying by a
scalar, each matrix element is multiplied by this scalar
k[a
ij
] = [ka
ij
]

The ijth matrix element of a product matrix is obtained by multiplying the ith row of
the first matrix by the jth column of the second matrix

In order to multiply a matrix by another one, the two matrices must be conformable
(the number of columns in the first matrix must equal the number of rows in the
second matrix)

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Matrices - Summary
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Representations of point groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Symmetry operations: Matrix representations

Consider the effects of the symmetry operations of the C
2v
point group on the set of
x, y, and z coordinates

The water molecule is an example of a molecule having C
2v
symmetry
1 C
2
axis through the oxygen
No perpendicular C
2
axes
No horizontal mirror plane
2 vertical mirror planes


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Representations of point groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Each symmetry operation may be expressed as transformation matrix

[New coordinates] = [ transformation matrix] [ old coordinates]
Houssam El-Rassy, PhD, Associate Professor
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Representations of point groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Representations of point groups
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
This set of matrices satisfies the properties of a mathematical group

We call this a matrix representation of the C
2v
point group

This representation is a set of matrices, each corresponding to an operation in the
group; these matrices combine in the same way as the operations themselves



Houssam El-Rassy, PhD, Associate Professor
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Character
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
The character, defined only for a square matrix, is the trace of the matrix, or the
sum of the numbers on the diagonal from upper left to lower right

C
2v




This set of characters forms a representation


This representation is called a reducible representation, a combination of more
fundamental irreducible representations

Reducible representations are frequently designated with ()
Houssam El-Rassy, PhD, Associate Professor
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Reducible and irreducible representations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Each transformation matrix in the C
2v
set is block diagonalized





All the nonzero elements become 11 matrices along the principal diagonal


When matrices are block diagonalized in this way, the x, y, and z coordinates are
also block diagonalized. As a result, the x, y, and z coordinates are independent of
each other

1,1 positions describe the results of the symmetry operations on the x coordinate
2,2 --> y coordinate
3,3 --> z coordinate


Houssam El-Rassy, PhD, Associate Professor
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Reducible and irreducible representations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
The 4 matrix elements for x form a representation of the group, those for y form a
second representation, and those for z form a third representation
Houssam El-Rassy, PhD, Associate Professor
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Character tables
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
3 of the representations for C
2v
, labeled A
1
, B
1
, and B
2
have been determined. The
fourth, called A
2
, can be determined

A complete set of irreducible representations for a point group is called the
character table for that group


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Character tables
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
C
2V
E C
2
o
v
(xz) o
v
(yz)
A
1
1 1 1 1
A
2
1 1 -1 -1
B
1
1 -1 1 -1
B
2
1 -1 -1 1
Representation of B
2
Point Group Label Symmetry Operations The Order is the total number of operations
Symmetry Representation Labels
In C
2v
the order is 4:
1 E, 1 C
2
, 1 o
v
and 1 o
v
Character

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Character tables
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Character tables
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Character tables
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
The labels have the following general meaning

1. The symbol A indicates a singly degenerate state (it consists of only one
representation) that is symmetric about the principal axis. The character table
contains values of +1 under the column for the principal axis for all A species

2. The symbol B indicates a singly degenerate state that is antisymmetric about the
principal axis. The value -1 under the column for the principal axis for all B
species

3. The subscripts 1 and 2 indicate symmetry or antisymmetry relative to a rotation
axis other than the principal axis. If there is no second axis, the subscripts refer
to the symmetry about a
v
plane (in the C
2v
group, subscript 1 is symmetric
about the xz-plane and 2 is antisymmetric)

4. Subscript g (gerade) designates symmetric to inversion, and subscript u
(ungerade) designates antisymmetric to inversion
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Character tables
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
C
3v
(NH
3
)
-1 0
-1 0
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Symmetry of orbitals and functions
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
z
y
x
z
y
x
A p
z
orbital has the same
symmetry as an arrow
pointing along the z-axis.
E
C
2
o
v
(xz)
o
v
(yz) No change
symmetric
1s in table

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
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Symmetry of orbitals and functions
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
z
y
x
A p
x
orbital has
the same
symmetry as an
arrow pointing
along the x-axis.
E
o
v
(xz)
No change
symmetric
1s in table
z
y
x

z
y
x
C
2
o
v
(yz)
Opposite
anti-symmetric
-1s in table
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
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Symmetry of orbitals and functions
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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
z
y
x
A p
y
orbital has the
same symmetry as
an arrow pointing
along the y-axis.
E
o
v
(yz)
No change
symmetric
1s in table
z
y
x
z
y
x
C
2
o
v
(xz)
Opposite
anti-symmetric
-1s in table
z
y
x

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Symmetry of orbitals and functions
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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
y
x
Rotation about the n axis, R
n
,
can be treated in a similar way.
E
C
2
No change
symmetric
1s in table
y
x
y
x
o
v
(xz)
o
v
(yz)
Opposite
anti-symmetric
-1s in table
y
x
The z axis is pointing out of
the screen!

If the rotation is still in the
same direction (e.g. counter
clock-wise), then the result is
considered symmetric.

If the rotation is in the
opposite direction (i.e. clock-
wise), then the result is
considered anti-symmetric.
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Symmetry of orbitals and functions
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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
y
x
d orbital functions can
also be treated in a
similar way
E
C
2
No change
symmetric
1s in table
y
x
y
x
o
v
(xz)
o
v
(yz)
Opposite
anti-symmetric
-1s in table
y
x
The z axis is pointing out
of the screen!
Houssam El-Rassy, PhD, Associate Professor
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Symmetry of orbitals and functions
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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
y
x
E
C
2
o
v
(xz)
o
v
(yz)

No change
symmetric
1s in table
y
x
The z axis is pointing
out of the screen!
So these are
representations of the
view of the d
z
2 orbital
and d
x
2
-y
2 orbital down
the z-axis.
y
x
y
x
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Chirality
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Many molecules are not superimposable on their mirror image

These molecules, labeled Chiral or dissymmetric may have important chemical
properties










Dissymmetric # having no symmetry

In general we can say that a molecule is chiral if it has no symmetry operations or if
it has only proper rotation axes
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Chirality
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Plane-polarized light will be rotated on passing through chiral molecules.
Clockwise rotation is designated dextrorotatory
Counterclockwise rotation is levorotatory

The ability of chiral molecules to rotate plane-polarized light is termed optical
activity


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Molecular vibrations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Symmetry can be helpful in determining the modes of vibration of molecules






Each atom can move in all 3 directions. So 9 transformations must be considered

For N atoms in a molecule, there are 3N total motions, known as degrees of
freedom
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Molecular vibrations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Use of transformation matrices to determine the symmetry of nine motions














If the atoms changes position during the symmetry operation --> 0
If the atom remains in its original location and the vector direction in unchanged --> 1
If the atom remains but the vector direction in reversed --> -1
Houssam El-Rassy, PhD, Associate Professor
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Molecular vibrations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Only the oxygen atom contributes to the character for this operation, for a total of -1
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Molecular vibrations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Reducing representations to irreducible representations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
The number of times that any irreducible representation appears in a reducible
representation is equal to the sum of the products of the characters of the reducible
and irreducible representations taken one operation at a time, divided by the order
of the group

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1
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Reducing representations to irreducible representations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Examination of the columns on the far right in the character table:
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Reducing representations to irreducible representations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Reducing representations to irreducible representations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Translational Motion
Rotational Motion
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Reducing representations to irreducible representations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Vibrational Motion
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Reducing representations to irreducible representations
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Selected vibrational modes
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
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Selected vibrational modes
Chem 228 : Inorganic Chemistry
Chapter 4: Symmetry and Group Theory
Houssam El-Rassy, PhD, Associate Professor