Molecular Symmetry

Molecular symmetry is a fundamental concept in chemistry, as it

can predict or explain many of a molecule's chemical properties,
such as its dipole moment and its allowed spectroscopic
transitions.
Symmetry is when one shape becomes exactly like another if you
flip, slide or turn it.

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Symmetrical implies the species possesses a number of
indistinguishable configurations.

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Symmetry operation – an operation performed on an object which
leaves it in a configuration that is indistinguishable from, and
superimposable on, the original configuration.
Typical symmetry operations include rotations, reflections, and
inversions.
Symmetry elements – the points, lines, or planes to which a
symmetry operation is carried out.
For instance, a rotation is carried out around an axis, a reflection is
carried out in a plane, while an inversion is carried our in a point.
Rotational Symmetry
An n-fold rotational symmetry implies that if a rotation of 360/n
degrees is applied, the transformed object is identical to the
original.
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 4 Fold-2/90

Not 8-fold

3 Fold-2/120 6 Fold-2/60

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 Is it possible to have 5, 7 or 8-fold rotation symmetry?
Objects with 5, 7 and 8 or higher order symmetry do exist in nature,
e.g. star fish (5-fold), flowers with 5 or 8-fold symmetry.

However, these are not possible in crystallography as they cannot fill

the space completely.

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 CRYSTAL SYMMETRY
The seven crystal systems are characterized by three symmetry
elements. They are
➢ Centre of symmetry
➢ Planes of symmetry
➢ Axes of symmetry

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 center lies at equal distances from various symmetrical positions
it is also known as `center of inversions’.
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 center of symmetry.
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Plane of symmetry
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.
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Plane of symmetry

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Axis of symmetry

9
Axis of symmetry

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Four-fold Axis of symmetry

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 Two-fold symmetry

Three-fold symmetry

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 SYMMETRICAL ELEMENTS OF CUBE

(a) Centre of symmetry 1

(b) Planes of symmetry 9
(Straight planes -3, Diagonal planes -6)
(c) Diad axes 6
(d) Triad axes 4
(e) Tetrad axes 3
----
Total number of symmetry elements = 23
----
Thus the total number of symmetry elements of a cubic
structure is 23.

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 ROTO INVERSION AXES

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.
X

X1
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Let us consider an axis xx’, normal to the circle passing through the
center.
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 (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 roto
inversion axis. Crystals possess 1,2,3,4 and 6-fold rotation inversion
axes.
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 TRANSLATIONAL SYMMETRY (SCREW AXES)

This symmetry element

has a compound
operation of a proper
rotation with a
translation parallel to
the rotation axis.
A screw axis describes
the following operation:
first, rotate clockwise
about an axis, then
translate along this axis A screw axis consists of a rotation
(think of a spiral followed by a translation
staircase). 17
 TRANSLATIONAL SYMMETRY (GLIDE PLANE)
In crystallography, a glide plane (or transflection) is a symmetry
operation describing how a reflection in a plane, followed by a
translation parallel with that plane, may leave the crystal unchanged.

A glide plane consists of a reflection followed by a translation 18

 COMBINATION OF SYMMETRY ELEMENTS

Apart from the different symmetry elements different

combinations of the basic symmetry elements are also possible.
They give rise to different symmetry points in the crystal.
The combination of symmetry elements at a point is called a
`point group’.
In crystals, 32 point groups are possible.
The combination of 32 point groups with 14 Bravais lattices lead to
230 unique arrangements of points in space.
They are called as `space groups’.

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