Symmetry in crystals

• Symmetry Operations and notations

• Matrix Representation of Symmetry
• Character Table (From Group Theory)
 Symmetry

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 Physics/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.
 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.

 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
The symmetry
identical to elements
the initialand related operations that we will find in
object.
molecules are:
Element Operation
Rotation axis, Cn n-fold rotation
Improper rotation axis, Sn n-fold improper rotation
Plane of symmetry,  Reflection
Center of symmetry, i Inversion
Identity, E
The Identity operation does nothing to the object – it is necessary
for mathematical completeness.
 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(2)
H(3) H(4)

120° 120°
N(1) N(1) N(1)

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

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

get identical arrangement of atoms.
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)
 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)
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)
 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.

H
Ethane, C2H6 C C 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.
 C6H6

6C2
1C6
=360/n
The principal axis is taken as the vertical axis that is in the z-direction.
The subsidiary axis is perpendicular to the principal axis and will, hence, be in
the horizontal direction.
If an object has several axes with different order n, then
the one with the highest order is called the principal axis.

Axes that pass through less many bonds, get less many
primes. An axis which is in the same position as the
principal axis gets the least number of primes.

PtCl42- has a C4 principal axis

There is an additional C2 axis where the C4 axis runs.
There are four additional C2 axes, two of them are
denoted C2’,
and two others are denoted C2’’.
 Proper rotational axes in the PtCl42-

The two axes which only have

one prime pass through two Pt-
Cl bonds,
while the ones that have two
primes, do not pass through any
bonds. The two C2’ axes are
conjugate, meaning that they
transform the object in an
equivalent way. The two C2’’
axes are also conjugate
Plane of Symmetry
Plane of Symmetry
 Reflection across a plane of symmetry,  (mirror plane)

O(1) v O(1)

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

These mirror planes are

called “vertical” mirror
planes, v, because they
contain the principal axis.
O(1) v 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 water
Handedness is changed by reflection! molecule.
Next slides for point group
 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 ( d).
- Two successive reflections are equivalent to the identity operation (nothing
is moved).
h A “horizontal” mirror plane, h, is
perpendicular to the principal axis.
This must be the xy-plane if the
z-axis is the principal axis.
d d In benzene, the h is in the plane
of the molecule – it “reflects” each
atom onto itself.

h

Vertical and dihedral mirror

planes of geometric shapes.
v v
 C2 Rotations in BF3 molecule 3C2
F2 F3

C2
B B

F1 F1
F3 F2

F2 F1
C2

B B

F1 F2
F3 F3

C2
F2 F2

B B

F1 F3
F3 F1
 C3 Rotations in BF3 molecule C3

F2 F1

B B

F1 F3
F3 F2
 Vertical Mirror Planes in BF3 molecule 3σv

F2

F1
F3

Horizontal Mirror Planes in BF3 molecule σh

F2 F2

B B

F1 F1
F3 F3
Think About NH3 Home Work
 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]

Inversion Symmetry in FerroElectrics?

The inversion operation takes a point or object at [x, y, z] to [-x, -y, -z].
 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° h H1 C H3 C 21
F3 H4

F4 S42
H3

H2 C H4

H1

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

more sense when you examine the matrices that describe the operations.
Naming Point Groups
HW: Make these molecular structures