3.

0 CRYSTAL SYMMETRY (SYMMETRY ELEMENTS IN CRYSTALS)

Highlights of the previous lecture: A crystal structure can be thought of as an infinitely

repeating array of 3D 'boxes', known as unit-cells. The unit cell is calculated from the
simplest possible representation of molecules, known as the asymmetric unit. The
asymmetric unit is translated to the unit cell through symmetry operations, and the resultant
crystal lattice is constructed through repetition of the unit cell infinitely in 3-dimensions.
Patterns are located upon the points of a lattice, which is an array of points repeating
periodically in three dimensions. The lengths of the edges of a unit cell and the angles
between them are called the lattice parameters.

3.1 Symmetry

A state in which parts on opposite sides of a plane, line, or point display arrangements that
are related to one another via a symmetry operation such as translation, rotation, reflection or
inversion.

The definite ordered arrangement of the faces and edges of a crystal is known as crystal
symmetry. Crystals posses different symmetries or symmetry elements. They are described
by certain operations. A symmetry operation is a transformation performed on the body
which leaves it unchanged or invariant. That is, after performing an operation on the body, if
the body becomes indistinguishable from its initial configuration, the body is said to posses a
symmetry element corresponding to that particular operation. For instance, a circle rotated
about its center will have the same shape and size as the original circle. A circle is then said
to be symmetric under rotation or to have rotational symmetry. It is possible for a figure to
have more than one line of symmetry. Application of the symmetry operators leaves the
entire crystal unchanged.

Symmetry operations performed about a point or a line are called point group symmetry
operations and symmetry operations performed by translation as well are called space group
symmetry operations. Crystals exhibit both types of symmetries independently and in
compatible combinations.

1
The following are the different point group symmetry elements exhibited by crystals.

 Centre of symmetry or inversion centre

 Reflection symmetry

 Rotation symmetry

3.2 Centre of Symmetry

One of the most noticeable features of many crystals, as we have already seen, is certain
regularity in the arrangement of faces. The next regular feature we must notice is the frequent
occurrence of similar faces (of the same size and shape) in parallel pairs on opposite sides of
the crystal. Centre of symmetry: It is a point such that any line drawn through it will meet the
surface of the crystal at equal distances on either side. Since centre lies at equal distances
from various symmetrical positions it is also known as `centre of inversion’. It is equivalent
to reflection through a point. A Crystal may possess a number of planes or axes of symmetry
but it can have only one centre of symmetry. For a unit cell of the cubic lattice, the point at
the body centre represents’ the `centre of symmetry’ and it is shown in figure 3.1.

Figure 3.1: Centre of Inversion of a Cube

A crystal will possess an inversion centre if for every lattice point given by the position
vector r there will be a corresponding lattice point at the position –r.

2
3.3 Reflection Symmetry

Reflection symmetry, (mirror symmetry, mirror-image symmetry, or bilateral symmetry) is

symmetry with respect to reflection. In one dimension, there is a point of symmetry about
which reflection takes place; in two dimensions there is an axis of symmetry, and in three
dimensions there is a plane of symmetry. The axis of symmetry of a two-dimensional figure
is a line such that, if a perpendicular is constructed, any two points lying on the perpendicular
at equal distances from the axis of symmetry are identical.

Figure 3.2: An isosceles triangle with mirror symmetry. The dashed line is the axis of symmetry.
Folding the triangle across the axis results in two identical halves.

Another way to think about it is that if the shape were to be folded in half over the axis, the
two halves would be identical: the two halves are each other's mirror image. Thus a square
has four axes of symmetry, because there are four different ways to fold it and have the edges
all match. A circle has infinitely many axes of symmetry passing through its center, for the
same reason

A crystal is said to possess an axis of symmetry about a plane if it is left unchanged in every
way after being reflected by the plane. Highly regular crystals may be bilaterally symmetrical
about several planes cutting them in different directions. They may have several planes of
symmetry. There is one important characteristic, however, about a crystallographic plane of
symmetry which differentiates it from our ordinary conception of a plane of geometrical
symmetry; that not only must the plane be such that it divides the crystal into two equal
3
portions, but these two portions must be so situated that they are mirror images of each other
with respect to the plane.

A crystal is said to have a plane of symmetry, when it is divided by an imaginary plane into
two halves, such that one is the mirror image of the other. In the case of a cube, there are
three planes of symmetry parallel to the faces of the cube and six diagonal planes of
symmetry

Figure 3.3: The nine mirror planes of a cube

The two symmetry elements namely, centre of inversion and plane of reflection, may easily
be understood by saying that inversion is a symmetry operation similar to reflection, with the
only difference that reflection occurs in a plane through the lattice point, while inversion is
equivalent to reflection through a point.

3.4 Rotational Symmetry

A body is said to possess rotational symmetry about an axis if after rotation of the body about
this axis by some angle Фn, the body appears as it did prior to rotation; i.e. the body is left
invariant as a result of rotation.

The axis of symmetry may thus be defined as a line such that the crystal assumes a congruent
o
 360
position for every rotation of  . The value of n decides the fold of the axis. If
 n 
equivalent configuration occurs after rotation of 180º, 120º and 90º, the axes of rotation are
known as two-fold, three-fold and four-fold axes of symmetry respectively.

If a cube is rotated through 90º, about an axis normal to one of its faces at its mid point, it
brings the cube into self coincident position. Hence during one complete rotation about this

4
axis, i.e., through 360º, at four positions the cube is coincident with its original position. Such
an axis is called four-fold axes of symmetry or tetrad axis.

Figure 3.4; Rotational symmetry of the cubic system

The total numbers of crystallographic symmetry elements of the cubic system are given
below.

Centre of symmetry 1 1

Straight planes 3

Diagonal planes 6 9 planes

Tetrad axes 3

Triad axes 4 13 axes

Diad axes 6

We have seen earlier that the crystalline solids show only 1,2,3,4 and 6-fold axes of
symmetry and not 5-fold axis of symmetry or symmetry axis higher than 6. The reason is
that, a crystal is one in which the atoms or molecules are internally arranged in a very regular
and periodic fashion in a three dimensional pattern, and identical repetition of a unit cell
can take place only when we consider 1,2,3,4 and 6-fold axes. Crystals cannot contain 5-
fold rotations, or any rotation axis other than those listed above, because they are
incompatible with translational symmetry. Note that it is impossible to tile a floor with
pentagons without leaving gaps.

5
3.5 Combination of Symmetry Elements

The different symmetry elements (centre of inversion, reflection and rotation) can also be
combined if they are compatible. The different combinations give rise to different symmetry
points in a crystal. It must be noted that all the crystals do not possess all the symmetries
enumerated above. The different crystal systems exhibit different symmetries. It is found that
there are 32 compatible combinations of the above three point group-symmetry elements, or
simply point groups. Crystals belonging to different crystal systems can be classified on the
basis of point groups.

3.5.1 Rotation-Inversion Axis

Rotation inversion axis is a symmetry element which has a compound operation of a proper
rotation and an inversion. A crystal structure is said to possess a rotation – inversion axis if it
is brought into self coincidence by rotation followed by an inversion about a lattice point
through which the rotation axis passes.

Figure 3.5: Rotation-Inversion axis

Let us consider an axis xx, normal to the circle passing through the centre. Let it operates on
a point (1) to rotate it through 90o to the position (4) followed by inversion to the position (2),
this compound operation is then repeated until the original position is again reached. Thus,
from position (2), the point is rotated a further 90o and inverted to the position (3); from
position (3), the point is rotated a further 90o and inverted to a position (4); from position
6
(4), the point is rotated a further 90o and inverted to resume position (1). Thus if we do this
compound operation about a point four times, it will get the original position. This is an
example for 4-fold rotation inversion axis. Crystals possess 1,2,3,4 and 6-fold rotation
inversion axes.

3.5.2 Translation Symmetry Elements

The translation symmetry elements exhibited by crystals are glide plane and screw axis.

3.5.2.1 Glide plane

When a mirror plane is combined with a simultaneous translation operation in a crystal, one
gets a glide plane. The glide plane in a crystal is always parallel to the mirror plane.

3.5.2.2 Screw axis

Just as it is possible to combine a proper rotation with an inversion to produce a hybrid roto-
inversion axis, it is possible to combine a proper rotation with a translation parallel to the
rotation axis; i.e., rotation about an axis coupled with a translation parallel to the rotation axis
will give rise to a new symmetry element called the screw axis. This rotation is shown in the
figure below.

Figure 3.6: Screw axis

A screw axis is usually represented by the symbol nm. This is performed by a rotation of
7
 2   m
 n  and a translation of  n  times the translation vector parallel to the rotation axis. For

example, the screw axis 42 is performed as follows:

2 1
Rotate the point through 90o about the symmetry axis and translate the point by  times
4 2
the translation vector parallel to the rotation axis. Apply the operation successively until the
cycle is complete.

Figure 3.7: Screw axis 31 [120 rotation, 1/3 unit cell translation]

There are 11 possible screw axes in a crystal

3.6 SPACE GROUPS

Because crystallographic symmetry must be compatible with translational symmetry (i.e. a

crystal), symmetry elements can only occur in certain combinations. Combinations of
symmetry elements that are compatible with translational symmetry in three dimensions are
called space groups.

Bravais in 1848 had shown that all structures can be generated by using only 14 types of
space lattice (14 types of unit cell). These 14 types of unit cells will give rise to 230 types of
lattice structures (space group) by performing such symmetry operations as (i) translation, (ii)
rotation, (iii) translation + rotation and (iv) reflection. It was shown by Federov and
independently by Barlow that it is not possible to have arrangement of lattice points other
than these 230 types that can repeat itself infinitely in three dimensions.
8
SOME HIGHLIGHTS OF THIS LECTURE

Symmetry elements

 When talking about symmetry operations we must distinguish

o Point symmetry elements

o Translational symmetry

 Point symmetry elements will leave at least one point unchanged

o Rotation axes

o Mirror planes

o Rotation-inversion axes

Combining symmetry operations

 An object can possess several symmetry elements

 Not all symmetry elements can be combined arbitrarily

o For example, two perpendicular two-fold axes imply the existence of a third
perpendicular two-fold

 Translational symmetry in 3D imposes limitations

o Only 2, 3, 4 and 6-fold rotation axes allow for space filling translational
symmetry

 The allowed combinations of symmetry elements are called point groups

o There are 32 point groups that give rise to periodicity in 3D

9
Limitations on combination of symmetry elements

 As for point groups, not all symmetry elements can be combined arbitrarily

 For three dimensional lattices

o 14 Bravais lattices

o 32 point groups

o But only 230 space groups

 For two dimensional lattices

o 5 lattices

o 10 point groups

o But only 17 plane groups

The combination of 32 point groups with 14 Bravais lattices lead to 230 unique arrangements
of points in space. They are called `space groups’.

10