ACC 32138

Winter Semester 2013-2314

Dr. Sumanta Kumar Padhi

Assistant Professor
Department of Applied Chemistry
Indian School of Mines Dhanbad, 826 004, INDIA

 Symmetry
Relationship between parts of an object with respect to size,
shape and position.
e.g In nature:

 Symmetry Element:

A symmetry element is a geometric entity e.g. a point, a line or a

plane.
Symmetry element is a point, line or plane about which a
symmetry operation is performed

Symmetry Operator:

A symmetry operator performs and action on a three

dimensional object.
A symmetry operation moves an object into an indistinguishable
orientation .
Symmetry operators are like other mathematical operators (x, ,
+, log, cos, sin, etc..)

 There are five types of symmetry operators:

Operator
Identity
Rotation
Mirror Plane
Inversion
Improper rotation

Symbol
E
C

i
S

 There are five symmetry elements, which will be defined relative

to point with coordinate (x1,y1,z1):

Identity, E

E(x1 ,y1 ,z1) = (x1 ,y1 ,z1)

This operator does nothing and is required for a completeness. It
is equivalent to multiplying 1 or adding 0 in algebra.

 Proper rotation axis, Cn (where = 2/n)

Convention is a clockwise rotation of the point.

The symmetry element is called axis of symmetry and denoted
by Cn.
C2(z) (x1 ,y1 ,z1) = (-x1 ,-y1 ,z1) ; in this case = 180
Many molecules have more than one symmetry axis. The axis
with higher n values is called principal axis.

n = (2/)0; n = ; Cn = C

Water has a 2-fold axis of rotation. When rotated by

180o, the hydrogen atoms trade places, but the
molecule will look exactly the same.

Ammonia has a C3 axis. Note that there are two

operations associated with the C3 axis. Rotation by 120o
in a clockwise or a counterclockwise direction provide
two different orientations of the molecule.

principal axis
(highest value of Cn)

C3

Rotational axes of BF3

C3

C2

C2

three-fold axis
viewed from
above

three-fold axis
two-fold axis
viewed from
viewed from
the side
the side
Note: there are 3 C2 axes

two-fold axis
viewed from
above

Rotational axes of BF3

 Plane of Reflection ()

xz (x1 ,y1 ,z1) = (x1 ,-y1 ,z1)

H1

yz

H2

xz

 Plane of Symmetry is of three types

1. Vertical plane (v)

2. Horizontal plane (h)
3. Dihedral plane (d)
Horizontal plane (h)
If a plane is to the principal axis then it is called h

Vertical plane (v)

If the plane is along the principal axis then it is called vertical plane (v)

Dihedral plane (d)

If the plane bisects the angle subtended between two similar consecutive
C2-axis

Mirror planes () of BF3:

Mirror planes can contain the principal axis (v) or be at
right angles to it (h). BF3 has one h and three v planes:
(v = vertical, h = horizontal)

v
mirror plane

C3
principal axis

v mirror plane
contains the C3 axis

h
mirror plane

C3
principal axis

h mirror plane
is at right angles to the C3 axis

Rotational axes and mirror planes of benzene

C6
principal axis

C6

C2

C2

C2

C2
v

C6
principal axis

C6
principal axis

 Inversion (i)
All the points in the molecule are reflected through a single point.
The point is the symmetry element for inversion. The position of the (x,y,z)
coordinate changes to thecorresponding ve coordinate (-x,-y,-z).

center of symmetry

center of symmetry

 Improper rotation (Sn)

Rotation by 2/n followed by reflection, to the rotation axis.
Since performing two times is the same as doing nothing (E), therefore S
can only be performed odd number of times.

 Improper rotation (Sn)

Sn (Improper Rotation Operation) = rotation about 360/n axis followed by reflection

through a plane perpendicular to axis of rotation
a. Methane has 3 S4 operations (90 degree rotation, then reflection)
b. 2 Sn operations = Cn/2 (S24 = C2)
c. nSn = E, S2 = i, S1 = s
d. Snowflake has S2, S3, S6 axes

Types of matrices:

Rectangular Matrix
Column Matrix
Row matrix
Zero null matrix
Square matrix
Diagonal Matrix
Scalar Matrix
Unit or Identity Matrix

Equal Matrices:

Direct product of two matrices:

Trace or Character of a matrix

Trace or character of matrix is the sum of the diagonal elements.
It is represented by .

E or Identity Matrix:
E(x1 ,y1 ,z1) = (x1 ,y1 ,z1)

 Matrix:

xz (x1 ,y1 ,z1) = (x1 ,-y1 ,z1)

Plane of symmetry () Matrix:

 Matrix:

Inversion (i) Matrix:

Inversion (i) Matrix:

Therefore, the inversion (i) matrix is:

Cn Matrix:

x2 = r [cos cos + sin sin ]

x2 = r [sin cos - cos sin ]

Sn Matrix:

Sn Matrix:

The following matrices form a representation of the C2h point group

C2

xy

The following matrices form a representation of the C3v point group

 The symmetry properties of an object (e.g. atoms of a molecule,

set of orbitals, vibrations). The collection of objects is commonly
referred to as a basis set .

Classify objects of the basis set into symmetry operations .

Symmetry operations form a group.
Group mathematically defined and manipulated by group theory.

Definition of a group

Group Multiplication table for C2h:

 E is always in a class by itself. It can be transformed into itself by

all the elements in the group.

Inversion element , i, is in class by itself.

All Cnm axes are in a class.
Similar C2s are in a class.
Like Cnm all Snm axes are in a class. If there are two or many such
types they are placed in as many classes.

Similar vertical (v) and similar dihedral planes (d) are in a class.
Horizontal plane (h) is a special plane and is always placed in a
different class from other planes.

 In all Abelian point groups each element is in a class by itself i.e.,

the number of symmetry elements or order of the group is equal
to the number of classes.
Number of Classes = Order of the group (h)

In non Abelian groups the number of classes is always less than

the order of the group.

No element in the group occurs in more than one class.

 In symmetry, a point group is the collection of symmetry operations that leaves a

molecule unchanged.
Groups with very high symmetry:
1. Icosahedral, Ih
2. Octahedral, Oh
3. Tetrahedral, Td
Groups with low symmetry:
1. C1 molecules with only the E element
2. Cs molecules with E and a single plane of symmetry ().
3. Ci molecules with only E and a center of inversion, i.
Groups with an n-fold axis of rotation:
1. Cn identity (E) and n-fold rotation (Cn)
2. Cnv identity (E), n-fold rotation (Cn) and n vertical reflections (v).
3. Cnh identity (E), n-fold rotation (Cn) and horizontal reflection plane (h).
Dihedral groups:
1. Dn identity (E), n-fold rotation (Cn) and n two-fold rotations (C2) perpendicular to Cn
axis (principal axis). (with no mirror planes)
2. Dnh - identity (E), n-fold rotation (Cn), n two-fold rotations (C2) perpendicular to Cn
axis and horizontal reflection plane (h). (with a horizontal mirror plane)

B2Br4 has the following staggered structure:

Ga2H6 has the following structure in the gas phase:

[Co(Ox)3]3- : D3

S8: D4d

H2O2: C2

H2: Dh

SF5Cl: C4v

HCN: Cv

C3H4: D2d

C60: Ih

CH2ClF:
Cs Or C1h