Symmetry and Group Theory

Dr. BASAVARAJAIAH S. M.
Assistant Professor and Coordinator
P. G. Department of Chemistry
Vijaya College.
[email protected]
9620012975
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 than the BF bonds (131 pm).
pm) trigonal planar pseudo-trigonal planar
 The molecular symmetry properties are not the same

Group theory is the mathematical treatment of

symmetry.

In this chapter,

Symmetry Element,

Symmetry Operation,

Point Group
Symmetry Elements and
Symmetry Operations

• Identity (E)

• Proper Axis of Rotation (Cn)

• Mirror Planes (σ)

• Center of Symmetry (i)

• Improper Axis of Rotation (Sn)

Identity, E
All molecules have Identity. This
operation leaves the entire molecule
unchanged. A highly asymmetric
molecule such as a tetrahedral carbon
with 4 different groups attached has
only identity, and no other symmetry
elements.
 Proper Axis of Rotation (Cn)
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:

– where n = 2, 180o
rotation
– n = 3, 120o
rotation
– n = 4, 90o
rotation
– n = 6, 60o rotation
– n = , (1/ )o
 For H2O

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.
For NH3
 Applying this notation to the BF3 molecule

BF3 molecule contains a C3 rotation axis

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.
Ethane, C2H6 Benzene, C6H6

The principal axis is the three-fold axis The principal axis is the six-fold axis
containing the C-C bond. through the center of the ring.
 Mirror planes (σ)
The symmetry operation is one of reflection and the
symmetry element is the mirror plane (denoted by  ). If reflection
of all parts of a molecule through a plane produces an
indistinguishable configuration, the plane is a plane of symmetry.

sh => mirror plane perpendicular to a

principal axis of rotation
sv => mirror plane containing principal
axis of rotation
sd => mirror plane bisects dihedral angle made
by the principal axis of rotation and two
adjacent C2 axes perpendicular to principal
rotation axis
 The reflection of
the water molecule in
either of its two mirror
planes results in a
molecule that looks
unchanged.
The subscript “v” in
σv, indicates a vertical
plane of symmetry. This
indicates that the mirror
plane includes the
principal axis of rotation
(C2).
Benzene Ring
Reflection through a plane of symmetry
(mirror plane)
 Center of Symmetry (i)
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.
i
[x, y, z] [-x, -y, -z]

CO2 Benzene SF6

 Improper Axis of Rotation (Sn)

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.
Improper Rotation in a Tetrahedral
Molecule
S1 and S2 Improper Rotations
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.
Summary Table of Symmetry Elements and Operations
Group theory is the mathematical treatment of
symmetry.
 Group
A group is a set, G, together with an operation • (called the group
law of G) that combines any two elements a and b to form another
element, denoted a • b or ab. To qualify as a group, the set and
operation, (G, •), must satisfy four requirements known as the group
axioms:
Closure
For all a, b in G, the result of the operation, a • b, is also
in G.

Associativity
For all a, b and c in G, (a • b) • c = a • (b • c).

Identity element
There exists an element e in G such that, for every
element a in G, the equation e • a = a • e = a holds. Such
an element is unique , and thus one speaks of the identity
element.
Inverse element

For each a in G, there exists an element b in G, commonly

denoted a−1 (or −a, if the operation is denoted "+"), such
that a • b = b • a = e, where e is the identity element.

The result of an operation may depend on the order of the

operands. In other words, the result of combining
element a with element b need not yield the same result as
combining element b with element a; the equation
a•b=b•a
 Abelian and Non-abelian Group
An abelian group is a set, A, together with an operation • that
combines any two elements a and b to form another element
denoted a • b. The symbol • is a general place holder for a concretely
given operation. To qualify as an abelian group, the set and
operation, (A, •), must satisfy five requirements known as
the abelian group axioms:
Closure
Associativity
Identity element
Inverse
Commutativity

For all a, b in A, a • b = b • a

A group in which the group operation is not commutative is called a

"non-abelian group" or "non-commutative group".
Determining the point group of a molecule or molecular ion
 IDENTIFYING POINT GROUPS

We can use a flow chart such as this one to determine the point
group of any object. The steps in this process are:

1. Determine the symmetry is special (e.g. octahedral).

2. Determine if there is a principal rotation axis.

3. Determine if there are rotation axes perpendicular to the principal

axis.

4. Determine if there are mirror planes.

5. Assign point group.

Decision Tree
 COMMON POINT GROUPS
Symmetry Simple description
Point group Example 1 Example 2
operations of typical geometry

no C2H2F2Cl2
C1 E symmetr
Dichlorodifluoro
y, chiral Bromofluorochloro
ethane
methane

mirror SOCl2

plane, no
Cs E, σh other
symmetr Thionyl Chloroiodometh
dichloride ane
y
 Simple
Symmetry
Point group description of Example 1 Example 2
operations
typical geometry

"open
book
C2 E, C2 Hydrogen
geometry
peroxide
," chiral

PPh3
C3 E, C3
Propeller,
chiral
Triphenylphophi
ne

E, 2C∞,
C∞v Linear
∞σv
 Simple
Point group Symmetry operations description of Example 1 Example 2
typical geometry

Sulfur dioxide
(SO2),
E,
C2v C2, σv(xz), Angular
Dichlorometha
σv'(yz)
ne
H2O
CH2Cl2

Trigonal Phosphane
pyramidal (PH3)
C3v E, 2C3, 3σv or
Tetrahedr Chloroform
al Ammonia (CHCl3)
(NH3)
 Simple
Point group Symmetry operations description of Example 1 Example 2
typical geometry

Planar with
C2h E C 2 i σh inversion
center
trans-1, 2-
Dichloroethylene B(OH)3

E,
Propelle
C3h C3,C ,σh,
3
2
r
S3, S 3
5
Boric acid Phloroglucinol

E, C2(x), twist,
D2
C2(y), C2(z) chiral Cyclohexane
Biphenyl (twist)
Tris
 Simple
Point group Symmetry operations description of Example 1 Example 2
typical geometry

E,
Planar
C2(z) ,C2(y),
with
D2h C2(x), i, σ(xy
inversion
), σ(xz),
center Ethylene (C2H4) Diborane (B2H6)
σ(yz)

Trigonal
planar or
E, 2C3, 3C2,
D3h trigonal
σh, 2S3,3σv
bipyramid Boron trifluoride
al (BF3) (PCl5)

E, 2C4,
C2 ,2C2' Square
D4h
2C2 i 2S4 σh2 planar
 Simple
Point group Symmetry operations description of Example 1 Example 2
typical geometry

E
2C6 2C3 C2 3C2
Hexagona
D6h '
l
3C2‘’ i 2S32S6
Coronene
σh 3σd 3σv Benzene (C6H6)
(C24H12)

E, 2S4,C2, 2C2' ,
D2d 90° twist
2σd

Allene

E, 2C3 , 3C2 ,
D3d 60° twist
i ,2S6 3, σd
Ethane
(Staggered)
 Simple description
Point group Symmetry operations Example 1 Example 2
of typical geometry

S2 E, 2S2 , C2 -
Tetraphenylmetha
ne

E, 8C3 , 3C2 ,
Td Tetrahedral
6S4 , 6σd
Phosphorus
Methane pentoxide
E,
8C3 ,6C2 ,6C4 ,
Octahedral
Oh 3C2 , i , Sulfur hexafluoride
or cubic
6S4 ,8S6
3σh ,6σd