ASSIGNMENT

PHYSICAL CHEMISTRY
NAME:SADAF IQBAL

ROLL NO:57

CLASS:BS-CHEMISTRY

SEMESTER:6TH

SUBMITTED TO:MA'AM MADIHA BATOOL

TOPIC

POINT GROUP AND THEIR APPLICATIONS

ON MOLECULAR STRUCTURES
 Point group
Points group are used to describe molecular symmetries and are a

condensed representation of the symmetry elements a molecule may

posses. This includes both bond and orbital symmetry. Knowing

molecular symmetry allows for a greater understanding of molecular

structure and can help to predict many molecular properties.

It is only possible for certain combinations of symmetry elements to be

present in a molecule (or any other object). As a result, we may group
together molecules that possess the same symmetry elements and classify
molecules according to their symmetry. These groups of symmetry elements
are called point groups (due to the fact that there is at least one point in space
that remains unchanged no matter which symmetry operation from the group
is applied). There are two systems of notation for labelling symmetry groups,
called the Schoenflies and Hermann-Mauguin (or International) systems

For molecules we use “point” symmetry operations, which include

rotations, reflections, inversion, improper rotations, and the
identity. At least one point remains stationary in a point operation.
• some symmetry operations are redundant (e.g., S62 ≡ C3); in these
cases, the convention is to list the simpler operation.

Low-Symmetry Point Groups

These point groups only contain one or two symmetry operations
C1 {E} Cs {E, σh} Ci {E, i}
 High-Symmetry Point Groups
These point groups are high-symmetry groups derived from Platonic solids.

Td Oh Ih
{E, 8C3, 3C2, 6S4, {E, 8C3, 6C2, 6C4, 3C2, {E, 12C5, 12C52, 20C3,
6σd}=24 i, 6S4, 8S6, 3σh, 6σd} = 48 15C2, i,12S10,12S103,
20S6, 15σ} =120

The five regular Platonic solids are the tetrahedron (Td), octahedron (Oh),
cube (Oh), dodecahedron (Ih), and icosahedron (Ih)

In addition to Td, Oh, and Ih, there are corresponding point groups that
lack the mirror planes (T, O, and I).
Adding an inversion center to the T point group gives the Th point group.
 Linear Point Groups
These point groups have a C∞ axis as the principal rotation axis
D∞h C∞v
{E, 2C∞φ, …, ∞σv} {E, 2C∞φ, …,∞C2, i, 2S∞φ, ∞σv}

D Point Groups
These point groups have nC2 axes perpendicular to a principal axis (Cn)
Dn Dnh Dnd
{E, (n-1)Cn, n {depends on n, {depends on n, }

perpendicular C2 with h = 4n} with h = 4n}

C Point Groups
These point groups have a principal axis (Cn) but no perpendicular C2 axes
Cn Cnv Cnh
{E, (n-1)Cn} {E, (n-1)Cn, nσv} {depends on n,
with h = 2n}
 S Point Groups

If an object has a principal axis (Cn) and an S2n axis but no perpendicular C2
axes and no mirror planes, it falls into an S2n group
S2n
{depends on n, with h = 2n}

Once you become more familiar with the symmetry elements and point
groups described above, you will find it quite straightforward to classify a
molecule in terms of its point group. In the meantime, the flowchart shown
below provides a step-by-step approach to the problem.
MOLECULAR POINT GROUP
 Combining symmetry operations: ‘group
multiplication’
Now we will investigate what happens when we apply two symmetry operations in
sequence. As an example, consider the NH3 molecule, which belongs to the C3v
point group. Consider what happens if we apply a C3 rotation followed by a ov
reflection. We write this combined operation ovC3 (when written, symmetry
operations operate on the thing directly to their right, just as operators do in quantum
mechanics – we therefore have to work backwards from right to left from the notation
to get the correct order in which the operators are applied). As we shall soon see, the
order in which the operations are applied is important.

The combined operation ovC3 is equivalent to 0v’’, which is also a symmetry

operation of the C3v point group. Now let’s see what happens if we apply the
operators in the reverse order i.e. C3ov (ov followed by C3).

Again, the combined operation C3v is equivalent to another operation of the point group,
this time ov’.
There are two important points that are illustrated by this example:
1. The order in which two operations are applied is important. For two symmetry
operations A and B, AB is not necessarily the same as BA, i.e. symmetry operations do
not in general commute. In some groups the symmetry elements do commute; such
groups are said to be Abelian.
2. If two operations from the same point group are applied in sequence, the result will be
equivalent to another operation from the point group. Symmetry operations that are
related to each other by other symmetry operations of the group are said to belong to the
same class. In NH3, the three mirror planes ov, ov’ and ov’’ belong to the same class
(related to each other through a C3 rotation), as do the rotations C3+ and C3-
(anticlockwise and clockwise rotations about the principal axis, related to each
other by a vertical mirror plane).
The effects of applying two symmetry operations in sequence within a given point group
are summarised in group multiplication tables. As an example, the complete group
multiplication table for C3v using the symmetry operations as defined in the figures above
is shown below. The operations written along the first row of the table are carried out first,
followed by those written in the first column (note that the table would change if we chose
to name ov, ov’ and ov’’ in some different order).

Constructing higher groups from simpler

groups
A group that contains a large number of symmetry elements may often be
constructed from simpler groups. This is probably best illustrated using an example.
Consider the point groups C2 and CS. C2 contains the elements E and C2, and has
order 2, while CS contains E and o and also has order 2. We can use these two
groups to construct the group C2v by applying the symmetry operations of C2 and CS
in sequence.

C2 operation E E C2 C2
CS operation E o(xz) E o(xz)
Result E ov(xz) C2  ov’(yz)
Notice that C2v has order 4, which is the product of the orders of the two lower-order
groups. C2v may be described as a direct product group of C2 and CS. The origin of
this name should become obvious when we review the properties of matrices later on
in the course.

Mathematical definition of a group

Now that we have explored some of the properties of symmetry operations and
elements and their behaviour within point groups, we are ready to introduce the
formal mathematical definition of a group.
A mathematical group is defined as a set of elements (g1,g2,g3…) together with a rule
for forming combinations gigj. The number of elements h is called the order of the
group. For our purposes, the elements are the symmetry operations of a molecule
and the rule for combining them is the sequential application of symmetry operations
investigated in the previous section. The elements of the group and the rule for
combining them must satisfy the following criteria.
1. The group must include the identity E, for which Egi = giE = gi for all the elements
of the group.
2. The elements must satisfy the group property that the combination of any pair of
elements is also an element of the group.
3. Each element gi must have an inverse gi -1, which is also an element of the group,
such that gigi -1 = gi -1gi = E (e.g. in C3v the inverse of C3+ is C3- , the inverse of ov is
ov; the inverse gi -1 ‘undoes’ the effect of the symmetry operation gi).
4. The rule of combination must be associative i.e. gi(gjgk) = (gigj)gk
The above definition does not require the elements to commute (which would require
gigk=gkgi). As we discovered in the C3v example above, in many groups the outcome
of consecutive application of two symmetry operations depends on the order in which
the operations are applied. Groups for which the elements do not commute are
called non-Abelian groups; those for which they elements do commute are Abelian.
Group theory is an important area in mathematics, and luckily for chemists the
mathematicians have already done most of the work for us. Along with the formal
definition of a group comes a comprehensive mathematical framework that allows us
to carry out a rigorous treatment of symmetry in molecular systems and learn about
its consequences.
Many problems involving operators or operations (such as those found in quantum
mechanics or group theory) may be reformulated in terms of matrices. Any of you
who have come across transformation matrices before will know that symmetry
operations such as rotations and reflections may be represented by matrices. It turns
out that the set of matrices representing the symmetry operations in a group obey all
the conditions laid out above in the mathematical definition of a group, and using
matrix representations of symmetry operations simplifies carrying out calculations in
group theory. Before we learn how to use matrices in group theory, it will probably be
helpful to review some basic definitions and properties of matrices.

Drawing a Point Group

A point group is drawn by first identifying all of the symmetry elements and
operations that a molecule possesses.
Then these operations are applied to the mathematical functions i.e. orbitals and
rotations, which results in either a +1 (symmetric) or a -1 (antisymmetric) value
for each of the symmetry operations.This allows us to write down the all the distinct
irreducible representations, followed by allotting them Mulliken’s symbols:

1-dimensional irreducible representation is denoted by A or B.

2-dimensional irreducible representation is denoted by E.

3-dimensional irreducible representation is represented by T.

“A” refers to symmetric rotation about the principal axis, while “B” refers to
antisymmetric rotation about the principal axis.

Symmetric or antisymmetric with respect to the secondary axis is denoted by

subscripts “1” and “2” respectively. In case of the absence of secondary
axes, σv planes are used instead.

Single and double prime (‘ and “) are used to denote the symmetric and
antisymmetric representations of the horizontal plane, σh.

Finally, in groups with a center of symmetry, symmetric or antisymmetric with respect

to the inversion center is indicated with the subscript “g” or “u”.

After assigning Mulliken’s symbols, reducible representations are determined.

How do you identify point groups?

Point groups are identified using the set of symmetry elements they each possess.

Let us take an example of the point group D4h. The subscript “4” implies that there is
a C4 principal axis of rotation. Moreover, the “D” refers to the presence of a further 4
perpendicular C2 axes of rotation (to the C4 principal axis). Finally, the subscript “h”
indicates a σh plane of reflection.

What are the two uses of point groups?

From the point groups of substances, we can predict some of their physical
properties in polarity and chirality.

What is the point group of S8?

The point group of octasulfur, S8 is D4d. This is because it has the symmetry elements
and operations E, a C4 principal axis (associated with 2 rotations: clockwise and
counter-clockwise), a C2 axis (parallel to principal C4 axis), 4C2‘ axes (perpendicular
to principal C4 axis), 4 σd planes of reflection, and finally one S8 rotary-reflection axis.

What is the point group for CIS PT?

Cisplatin belongs to the point group C2v. It contains the symmetry elements E, C2, σv,
and σv‘.

What is the CN– point group?

Cyanide anion possesses the symmetry elements/operations E, 2 C∞, and ∞ σv, so it

belongs to the point group C∞v.

What is the point group of BF3?

The point group of BF3 is D3h. This is because BF3 possesses a C3 principal axis, 3
C2 axes perpendicular to the principal axis, and a σh plane of reflection, in addition to
identity.

What is the point group of H2O2?

H2O2 belongs to the point group C2, as it possesses only a C2 axis other than identity.

What is the point group of PdCl4-2?

PdCl4-2 has the symmetry elements E, 2C4, C2, 2C2‘, 2C2“, i, 2S4, σh, 2σv, 2σd, so its
point group is D4h.

What point groups are chiral / optically active?

A chiral molecule is one that cannot be superimposed upon its mirror image. As
chiral molecules rotate plane-polarized light, they are said to be optically active.

The theory of optical activity states that a molecule may be chiral if it does not
possess a rotary-reflection axis, Sn. However, it may not be directly identified.

For example, Cnh point groups contain Cn and σh, which are the components of
Sn. Any molecule with a center of inversion also possesses S2 (as i is equivalent to
the combination of C2 and σh). Hence all molecules with centers of inversion are also
achiral.

So the point groups that do not contain the symmetry elements mentioned above are
bound to be chiral.
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CONTENT
Point Group

 Introduction

 Low-Symmetry point group

 High-Symmetry point group

 Linear point group

 D point group

 C point group

 S point group

 Flow-Chart of point group

 Molecular point group

 Combining symmetry operations: ‘group

multiplication’

 Constructing higher groups from simpler groups

 Mathematical definition of point group

 Drawing a Point Group

 QUESTIONS

How do you identify point groups?

What are the two uses of point groups?
What is the point group of S8?
What is the point group for CIS PT?
What is the CN– point group?
What is the point group of BF3?
What is the point group of H2O2?
What is the point group of PdCl4-2?
What point groups are chiral / optically active?

 References