1 Symmetry Elements and Symmetry Operations (Part I) - Group Theory

GROUP THEORY AND CHEMISTRY
SYMMETRY ELEMENTS &

SYMMETRY OPERATIONS
(Part I) C. Chitra Thomas
1200
Identity Element E 900
--
Proper rotation axis Cn

C3
(1 of 50 Videos)
C4
GROUP THEORY AND CHEMISTRY
• Group Theory is a branch of the mathematical field of algebra
• The foundation for Group Theory was laid by the work of the French
mathematician Evariste Galois ( 1811- 1832) in the early 19th century
• Group Theory is one of the most important abstract theories in algebra

*Abstract meaning : Existing in thought or as an idea but not
having a physical or concrete existence
Basic and Advanced Chemistry C Chitra Thomas

chitrathomasc@gmail.com
Some important applications of Group Theory in the field of Chemistry include
(i) Prediction of polarity of molecules
(ii) Prediction of chirality of molecules
(iii) Derivation of symmetry selection rules for electronic, vibrational and

Raman spectra
(i) Prediction of IR and Raman active vibrational modes in molecules

(v) Construction of molecular orbitals in compounds
(vi) Prediction of the atomic orbitals involved in various types of hybrid orbitals –
tetrahedral, trigonal planar, square planar, trigonal bipyramidal, octahedral etc.
(vii) Simplification of quantum mechanical calculations. Eg. Simplification of Huckel’s

Molecular Orbital calculations
(viii) Construction of energy level diagrams of coordination complexes in

Ligand Field Theory

THE CONCEPT FUNDAMENTAL TO THE APPLICATION OF GROUP THEORY TO
PROBLEMS IN CHEMISTRY IS SYMMETRY OF MOLECULES

What is Symmetry ?
• In non geometric sense or in everyday language symmetry is associated with
Regularity in form
Pleasing proportions
Harmonious arrangement
Sense of beauty
Sphere Cube Rectangular Slab Stone

Not symmetrical
Symmetrical Symmetrical Symmetrical
• In the geometric sense, symmetry can be defined more precisely in terms of

Symmetry operations and Symmetry elements

What is an operation ?
An operation is any movement of a molecule/object such as
• Rotation about an Axis
• Reflection in a Plane
• Inversion about a Point
• Translation
Translation is a movement which changes the position of a molecule/object

SYMMETRY OPERATIONS
AND
SYMMETRY ELEMENTS

What is a Symmetry Operation ?
A symmetry operation is a movement of a molecule/object such that
the resulting configuration is indistinguishable from the original.
• During any symmetry operation at least one point in the molecule should
remain unchanged. This point is the center of gravity of the molecule
• During translation (bodily movement from one point to another) the center
of gravity of the molecule is changed
• For this reason, a molecule should never be translated during a symmetry

operation

What is a Symmetry element ?
• A symmetry element is a geometric entity such as a line, a plane or a
point about which one can perform an operation of rotation, reflection or
inversion

• A symmetry operation will transform a molecule into an equivalent or identical
configuration
Illustration
The water molecule is planar molecule with an angular shape.
Suppose, H2O molecule is rotated about an axis passing through the oxygen atom and bisecting the
H-O-H bond angle, through 1800
The configurations I and III
are identical
1800
The configurations I and II
are equivalent
1 2 2 1 1 2
The configurations II and III
are equivalent
I II III
The configurations I, II and III are indistinguishable. Therefore this operation is a symmetry operation
The symmetry element is the imaginary line (axis) and the symmetry operation is the rotation of the molecule
about this axis through 1800
• Only 5 basic operations in nature will leave the center of gravity of a
molecule unchanged and hence be symmetry operations
• The 5 symmetry elements associated with these 5 symmetry operations
are
1. Identity E
2. Proper rotation axis Cn
3. Mirror plane σ
4. Inversion center i
5. Improper rotation axis Sn

The 5 symmetry operations in nature and the
5 symmetry elements associated with them
SYMMETRY ELEMENT SYMMETRY OPERATION
1. Identity E Doing nothing
2. Proper rotation axis Cn Rotation about the axis through some angle
3. Mirror plane or Plane of
Reflection about the plane
symmetry σ
4. Inversion center or Center of Inversion. Inversion is reflection about a point
symmetry i
Rotation about an axis through some angle followed by a
5. Improper rotation axis Sn reflection in a plane perpendicular to the rotation axis

IDENTITY E
• This operation does nothing. It is the simplest of all the symmetry operations
• This is the only element/operation possessed by all molecules
• Both the symmetry element and the symmetry operation are denoted by the
same symbol, E
• If this operation is carried out n times it is denoted as En where n is 1,2 ,3, 4, …..
And En = E whether n is odd or even.
• E2 = EE = E
• The identity element E can generate only one operation

• If the rotation of a molecule about an axis through some angle results in a
configuration which is indistinguishable from the original, then the molecule is
said to possess a proper rotation axis. It is denoted by the symbol Cn.
• C stands for cyclic
3600
• n= where θ is the angle through which the molecule is rotated
θ
• Cn is called a n- fold rotation axis and n is the order of the axis

• H2O molecule has to be rotated through 1800 about the axis
passing through the O atom and bisecting the H-O-H bond
angle to get an indistinguishable orientation. So the
symmetry axis is a 3600/1800 = 2 fold rotation axis and is
denoted as C2

Θ in degree 0 3600 Symbol of the proper
n= rotation axis
θ
180 2 C2
120 3 C3
90 4 C4
72 5 C5
60 6 C6

Identifying the proper rotation axis
in some
common molecules

Water H2O Angular Shape
1800 There is only one C2 axis
The C2 axis is in the plane of the molecule
C2

Boron tri fluoride BF3 ( Shape : Planar triangular –The B and the
three F atoms are in the same plane – the molecular plane )
Z One C3 axis and
Three C2 axes
1200 C2 C2
The higher order C3 axis is called
the principal axis
The unique principal axis is
always taken as the z-axis
C3 C2 In BF3 molecule, the C 3 axis is the z-axis

Each C2 axis passes and the molecular plane which is
through the B atom and perpendicular to the principal axis (Z) is
The C3 axis passes through
one of the F atoms. The the xy plane
the B atom and perpendicular
three C2 axes are in the
to the plane of the molecule In fact, in all planar molecules, with a unique
molecular plane
principal axis, the principal axis is the z-axis
and the molecular plane is xy plane
Ammonia NH3
The NH3molecule has pyramidal shape with the N atom at the apex
1200
There is only one C3 axis .
The C3 axis passes through the N atom and the

center of the triangular base formed by the 3 H atoms
C3

PtCl4- - ion The shape of this ion is square planar
Z
C2’’ ’
• One C4 axis
C2
900 C2 ’ --
-- • Four C2 axes separated
into 2 sets
C2’’
• Two C2’ axes
• Two C2’’ axes
The four C2 axes
C4
• The four C2 axes are in the plane of the molecule
The C4 axis passes through the Pt atom
and perpendicular to the plane of the • The C2’ axis passes through the Pt atom and
ion two diagonal Cl atoms
• The C2’’ axis passes through the Pt atom and
bisects the Cl-Pt-Cl bond angle
Cyclo penta dienyl anion C5H5 -
Shape of the ion: Pentagonal Planar
z
z
720 • One C5 axis perpendicular
720
to the molecular plane
- OR -
• Five C2 axes, all in the
molecular plane
C5 C2
C5
Benzene C6H6
Shape : Hexagonal planar
• One C6 axis
• Six C2 axes
• Three C2 axes of one type C2’
• Three C2 axes of another type C2’’
*Visualize these proper rotation axes of Benzene molecule

Symmetry operations associated with various Symmetry
elements
• An important note:
• In the application of group theory to molecular symmetry, the elements of the
‘group’ are the symmetry operations and not the symmetry elements.
• So it is very important to be familiar with the symmetry operations associated

with each symmetry element
• We have already seen that identity E can generate only one operation

Symmetry operations associated with

• Consider the following symmetry operations
2 Clockwise 1 3 2
1200
1 It is also evident that
1200 1200 1200
C34 = C3
1 3 3 2 2 1 1 3 3 2
C35 = C32
C3 C32 C33 = E C34 = C3
C36 = C33 = E
and so on
We find that C3 and C32 are unique operations but C33 = E

Therefore, the 3 operations generated by C3 axis are C3 , C32 and E

• In general, a Cn axis can generate n operations namely
Cn , Cn2, Cn3 … Cnn
• Also Cnn = E whether n is odd or even.
Cnn+1 = Cn
Cnn+2 = Cn2 and so on

Operations generated by some common Cn axes
C2 axis
2 Operations
C2 and C22 = E
C2

C3 axis
3 Operations
C3 , C32 and C33 = E
C3

C4 axis
4 Operations
C4 , C42 , C43 and C44 = E
900
C42 stands for rotation through 900 twice (90x2) which is
same as rotation through 1800 once. That is C2
C42 = C2
Therefore, the four operations of a C4 axis are
C4
C4 , C2 , C43 and C44 = E
VERIFY THIS DIAGRAMMATICALLY.

HINT: In the diagram, number the four Cl atoms, carry out C42 and C2 operations
separately and compare the two resulting configurations
• The four operations of a C4 axis are
C4 , C2 , C43 and C44 = E
• Of these 4 operations, C2 and E are operations of a C2 axis
• That means the C4 axis is also a C2 axis
• In other words, the C4 axis is coincident with a C2 axis

C5 axis
720
5 Operations
C5 , C52, C53, C54 and C55 = E
These operations cannot be written in any other way
C5

• 6 Operations
• C6 , C62, C63, C64, C65 and C66 = E
C6 axis • Some of these operations may be written in other simpler forms
• C62 stands for rotation through 600 twice (60x2) which is same as
rotation through 1200 once. That is C3
C62 = C3
• C63 stands for rotation through 600 three times (60x3) which is
same as rotation through 1800 once. That is C2
C63 = C2
• C64 stands for rotation through 600 four times (60x4) which is same
as rotation through 2400 once or rotation through 1200 twice (120x2)
That is C32
C64 = C32
Therefore, the six operations of a C6 axis are
C6 , C3 , C2, C32, C65 and C66 = E
VERIFY THIS DIAGRAMMATICALLY. Basic and Advanced Chemistry C Chitra Thomas
• The six operations of a C6 axis are
C6 , C3 , C2, C32, C65 and C66 = E
• Of these 6 operations, C3 , C32 and E are operations of a C3 axis
• That means the C6 axis is also a C3 axis
• In other words, the C6 axis is coincident with a C3 axis
• In general, if an even order Cn axis exists, then

a Cn/2 axis should exist independently
Note that the C6 axis is also coincident with a C2 axis

If you have any questions write to me at chitrathomasc@gmail.com
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• Mirror plane
• Inversion center


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GROUP THEORY AND CHEMISTRY

SYMMETRY ELEMENTS &

Proper rotation axis Cn

• Group Theory is a branch of the mathematical field of algebra

• Group Theory is one of the most important abstract theories in algebra

Basic and Advanced Chemistry C Chitra Thomas

(ii) Prediction of chirality of molecules

(iii) Derivation of symmetry selection rules for electronic, vibrational and

(i) Prediction of IR and Raman active vibrational modes in molecules

Basic and Advanced Chemistry C Chitra Thomas

(vii) Simplification of quantum mechanical calculations. Eg. Simplification of Huckel’s

(viii) Construction of energy level diagrams of coordination complexes in

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

Sphere Cube Rectangular Slab Stone

• In the geometric sense, symmetry can be defined more precisely in terms of

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

• For this reason, a molecule should never be translated during a symmetry

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

SYMMETRY ELEMENT SYMMETRY OPERATION

1. Identity E Doing nothing

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

• C stands for cyclic

• Cn is called a n- fold rotation axis and n is the order of the axis

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

1800 There is only one C2 axis

The C2 axis is in the plane of the molecule

Basic and Advanced Chemistry C Chitra Thomas

C3 C2 In BF3 molecule, the C 3 axis is the z-axis

The C3 axis passes through the N atom and the

Basic and Advanced Chemistry C Chitra Thomas

• Three C2 axes of one type C2’

• Three C2 axes of another type C2’’

*Visualize these proper rotation axes of Benzene molecule

Basic and Advanced Chemistry C Chitra Thomas

• So it is very important to be familiar with the symmetry operations associated

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

We find that C3 and C32 are unique operations but C33 = E

Basic and Advanced Chemistry C Chitra Thomas

• Also Cnn = E whether n is odd or even.

Cnn+2 = Cn2 and so on

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

Basic and Advanced Chemistry C Chitra Thomas

VERIFY THIS DIAGRAMMATICALLY.

• Of these 4 operations, C2 and E are operations of a C2 axis

• That means the C4 axis is also a C2 axis

• In other words, the C4 axis is coincident with a C2 axis

Basic and Advanced Chemistry C Chitra Thomas

These operations cannot be written in any other way

Basic and Advanced Chemistry C Chitra Thomas

• Of these 6 operations, C3 , C32 and E are operations of a C3 axis

• That means the C6 axis is also a C3 axis