Chapter 4

An introduction to molecular symmetry

Dr. Said M. El-Kurdi 1

4.1 Introduction
Understanding of symmetry is essential in discussions of
molecular spectroscopy and calculations of molecular
properties.

consider the structures of BF3, and BF2H, both of which are

planar

BF bond distances the BH bond is shorter (119 pm)

are all identical (131 pm) than the BF bonds (131 pm).
trigonal planar pseudo-trigonal planar

Dr. Said M. El-Kurdi 2

 the molecular symmetry properties are not the same

Group theory is the mathematical treatment of

symmetry.

In this chapter, we introduce the fundamental language of

group theory (symmetry operator, symmetry element,
point group and character table).

Dr. Said M. El-Kurdi 3

 4.2 Symmetry operations and symmetry elements

A symmetry operation is an operation performed on an

object which leaves it in a configuration that is
indistinguishable from, and superimposable on, the original
configuration.

The rotations are performed about an axis perpendicular to

the plane of the paper and passing through the boron atom;
the axis is an example of a symmetry element.
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A symmetry operation is carried out with respect to points,
lines or planes, the latter being the symmetry elements.

Rotation about an n-fold axis of symmetry

The symmetry operation of rotation about an n-fold axis

(the symmetry element) is denoted by the symbol Cn, in
which the angle of rotation is:

n is an integer, e.g. 2, 3 or 4.

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Applying this notation to the BF3 molecule

BF3 molecule contains a C3 rotation axis

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If a molecule possesses more than one type of n-axis, the axis
of highest value of n is called the principal axis; it is the axis of
highest molecular symmetry. For example, in BF3, the C3 axis is
the principal axis.

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 Reflection through a plane of symmetry
(mirror plane)

If reflection of all parts of a molecule through a plane

produces an indistinguishable configuration, the plane is a
plane of symmetry

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the symmetry operation is one of reflection and
the symmetry element is the mirror plane (denoted by  )

 If the plane lies perpendicular to the vertical principal

axis, it is denoted by the symbol h.

 If the plane contains the principal axis, it is labeled v.

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Consider the H2O molecule

A special type of  plane which contains the principal

rotation axis, but which bisects the angle between two
adjacent 2-fold axes, is labeled d
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A square planar molecule: XeF4

One C2 axis coincides with the principal (C4) axis; the molecule lies in a h plane which
contains two C2’ and two C2’’ axes.

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Each of the two v planes contains the C4 axis and one C2’ axis.

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 Each of the two d planes contains the C4 axis and one C2’’ axis.

In the notation for planes of symmetry, , the subscripts h, v

and d stand for horizontal, vertical and dihedral respectively.

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Reflection through a centre of symmetry
(inversion centre)

If reflection of all parts of a molecule through the centre of

the molecule produces an indistinguishable configuration,
the centre is a centre of symmetry, also called a centre of
inversion; it is designated by the symbol i.

CO2
benzene SF6

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 No i

cis-N2F2 SiH4 H 2S

Rotation about an axis, followed by reflection through a

plane perpendicular to this axis

If rotation through about an axis, followed by reflection through a

plane perpendicular to that axis, yields an indistinguishable configuration,
the axis is an n-fold rotation–reflection axis, also called an n-fold
improper rotation axis. It is denoted by the symbol Sn.

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Identity operator

All objects can be operated upon by the identity operator E.

The operator E leaves the molecule unchanged.

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4.3 Successive operations
For NH3

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For example, in planar BCl3, the S3 improper axis of rotation
corresponds to rotation about the C3 axis followed by
reflection through the h plane.

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Summary Table of Symmetry Elements and Operations

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4.4 Point groups

The number and nature of the symmetry elements of a given

molecule are conveniently denoted by its point group

C1 point group

C1 = E

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 Cv point group
-fold axis of rotation; that possessed by a linear molecule
It must also possess an infinite number of v planes
but no h plane or inversion centre.

These criteria are met by

Asymmetrical diatomics such as HF, CO and [CN], and
linear polyatomics that do not possess a centre of
symmetry, e.g. OCS and HCN.

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Dh point group

 Symmetrical diatomics (e.g. H2, [O2]2) and

 linear polyatomics that contain a centre of symmetry
(e.g. [N3],CO2, HCCH) possess a h plane in addition to a
C axis and an infinite number of v planes

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Td, Oh or Ih point groups

Molecular species that belong to the Td, Oh or Ih point groups

possess many symmetry elements

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Determining the point group of a molecule
or molecular ion

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Determine the point group of trans-N2F2.

Apply the strategy shown in Figure 4.10:

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Determine the point group of PF5.

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