Introduction to Group Theory

Eduardo Bed Barros

Universidade Federal do Cear
Summary
Symmetry and Groups

Representation Theory

Point Groups and their Representations

Basis Functions and Projection Operators

Direct Product and Selection Rules

Electronic States and Vibrations in Molecules

Translational Symmetry

Applications to Graphene and Carbon Nanotubes

What is Symmetry?
An object is symmetric under a certain
Operation if after the Operation takes place,
the object is inditinguishable from its initial
state.
a
Symmetry
We find Symmetry
EVERYWHERE!!!
Why is Symmetry important?
Simple Harmonic Oscilator
e
|
.
|

\
|
+ =
2
1
n E
n
n=0
n=1
n=2
n=3
x
) ( ) ( x x =
) ( ) ( x x = n even
n odd
) ( ) ( x V x V =
OPERATION: reflection
x -x
2 2
| ) ( | | ) ( | x x =
) ( ) ( x x =
The potential is SYMMETRIC
under this reflection
Point Operations
Point Operations are those in which at least one point is unchanged.
Rotation Axes
(2D)
reflection Planes
(1D)
Inversion Point
(3D)
SIMPLE POINT OPERATIONS
Rotation Axes
C
3
C
3
The rotational symmetry is usually denoted by a C
d
axis.
corresponding to a rotation by an angle 2/d

dC
d
=E
d=3
120
o
A molecule can have several different rotational axes. The axis (or
axes) with higher order (d) is called the principal axis.
Inversion symmetry

The inversion point is usually denoted by (i)
reflection planes
vertical planes contain the principal
axis

h
horizontal planes are
perpendicular to the principal
axis
Improper Axis
t/2
o
h
Improper Axis
t/2
o
h
S
4
=C
4
X o
h
Group Theory Formalism
Group Theory
A group is a set of elements for which a product of two
elements is always an element of the group.

Also, to form a group, the set of elements must follow 3
basic rules:
The produc is associative:

There exists an identity element (E):

For every element (A) there is an inverse element (A
-1
):

G e = C AB C
G , e B A
) ( ) ( BC A C AB =
A EA=
E A A =
1
But what is a product?
What we call PRODUCT is the result of an operation of
one elements upon the other.

Examples:

Sum: 1+2 =3

Multiplication: 2 x 4 = 8

Power: 2 ^ 6 (2
6
) =64
Do the Natural Numbers (0,1, 2,3,4...) form a group
with the product: SUM? Lets try...
1 Is the sum of two elements is an element of the
group?
YES, Ex.: 1+2=3
2 Is the sum associative?
YES, Ex.: (1+2)+3=1+(2+3) = 6
3 Is there a neutral element?
YES, Ex.: 0+4=4
4 Do all elements possess an inverse element
within the group?
NO!

The NATURAL numbers do not form a group
with respect to the sum!
PRODUCTS AND GROUPS
SUM Integer Numbers

MULTIPLICATION Rational Numbers

POWER Complex Numbers
N i N N i N i
N
e e e
/ ) ( / /
,... , ,
t t t 2 1 4 2
1 1

=
Form a group under multiplication
FINITE GROUP
Symmetry Operations as Group elements
C
6
C
3
C
6
X C
6
= C
3
So we just defined
THE PRODUCT of
two symmetry
operations!!
Which is another
symmetry operation
of the system.
So what?
So, the symmetry operations of an object form a
group
C
3
C
2
C
2
C
2 `
` `
D
3
Point Group
E C C
C E C
C C E
C C C
C C C
C C C
C C C
C C C
C C C
C E C
E C C
C C E
1
3
2
3
2
3
1
3
1
3
2
3
2 2 2
2 2 2
2 2 2
2 2 2
2 2 2
2 2 2
1
3
2
3
2
3
1
3
2
3
1
3
' ' '
' ' '
' ' '
' ' '
' ' '
' ' '
Some Important Deffinitions:
Order of a group (h):
Number of non-equivalent elements. Ex.:

Subgroups:
A set of elements within a group which form a group
among themselves

Order of an element:
Number of times an elements which needs to be
multiplied to itself in order to obtain the identity. Ex.:

C
3
order 3 C
3
xC
3
xC
3
= E

v
order 2
v
x
v
= E

Group of order 6

( )
2 2 2
2
3
1
3 3
C C C C C E D
' ' '
, , , , ,
( )
2
3
1
3 3
C C E C , ,
Subgroup of D
3
Other important information
Rearrangement Theory:
G= E,A
1
,A
2
,... A
h
A
k
E, A
k
A
1
, A
k
A
2
,... A
k
A
h
the product of A
k
and each element of the group:
contains each element of the group once and only once
Cosets
If B (E, B
1
, B
2
, ...) is a sub-group of G and x is an
element of B, the arrangement EX, EB
1
, EB
2
... is
known is the right coset of B.
Theorem: Each right coset of a sub-group either have the
exact same elements or do not have any elements in
common!

Theorem: The order of a sub-group is a divisor of the
order of the group
Conjugation and Classes
The element B is a conjugate of A if there is na
element X such that B=XAX
-1

All elements of an abelian group are self-conjugate

Self-conjugate, or invariant sub-groups

A sub-group is self-conjugate or invariant if for all X in the
group, the sub-group elements B=XBX
-1
belong to the
subgroup

Symmetry Group of Molecules
The symmetry operations of any given molecule form
a group. (Point Group)
There are 32 crystallographic point groups. These
groups have been studied and are indexed:
http://www.phys.ncl.ac.uk/staff/njpg/symmetry/index.ht
ml



Cubic
T, T
h
, O, T
d
, O
h
C
4
, S
4
, C
4h
, D
4
, C
4v
, D
2d
, D
4h

Tetragonal
D
2
, C
2v
, D
2h

Orthorombic
C
2
, C
s
, C
2h

Monoclinic
C
1
, C
i
C
3
, S
6
, D
3
, C
3v
, D
3d

triclinic trigonal hexagonal
C
6
, C
3h
, C
6h
, D
6
, C
6v
, D
3h
, D
6h

How do we find the Point Group of a
molecule?
Two ways:

1 Look at the molecule and try to find all of its symmetry
elements.


2 Follow down from the highest symmetry elements
using as shown in the next slide, and then look in the
indexes to find all the symmetry elements!
Some Useful Relations
Inversion commutes with all point symmetry
operations. (iA=Ai)
All rotations about the same axis commute.
All rotations about an arbitrary rotation axis commute
with reflections across a plane perpendicular to this
rotation axis.
Two twofold rotations about perpendicular axes
commute.
Two reflections in perpendicular planes will
commute.
Any two of the symmetry elements
h
, S
n
, C
n
(n =
even) implies the third
Molecule
linear?
YES
NO
inversion
center (i)?
Dh Dv
YES
NO
YES
NO
inversion
center(i)?
Linear
Groups
YES
C
s

symmetry
?
NO
Ih
Oh
YES
Td
are there
two or
more Cd
symmetries
with d>2?
Cubic
Groups
NO
go to the
next slide
Finding the Point
Group of a Molecule
Benzene
Continuatio
n
YES
NO
YES
YES
d
symmetry
?
select Cd with larger d.
are there C2 axes
perpendicular to Cd ?
Dnd
YES
NO
h symmetry?
NO
NO
v symmetry?
NO
S2n
symmetry?
Cn symmetry?
Dn Cn S2n
Cnv
YES
NO
YES
h symetry?
YES
symmetry?
NO
Cs
YES
inversion
center(i)?
NO
Ci
YES
C1
NO
Cnh
Dnh
D
6h
Problems for discussion
1. Find all the point operations of the
a) Benzene molecule
b) Methane molecule
c) Fullerene molecule.

2. Do integer numbers form a group regarding the
multiplication operation? Show why? What about the
Rational numbers?

3. Prove the rearrangement theorem.

4. What is the point group of the molecules in question1?

5. How many different conjugate classes are there in the D
6h

point group? Show schematically how these classes are
formed and the elements belonging to each of the classes.