Group Theory II

Group Theory II

Today

 Repetition
 Block matrices
 Character tables
 The great and little orthogonality theorems
 Irreducible representations
 Basis functions and Mulliken symbols
 How to find the symmetry species
Projection operator
 Applications
 Repetition

We already know…

 Symmetry operations obey the laws of group theory.

 Great, we can use the mathematics of group theory.

 A symmetry operation can be represented by a matrix operating on
a base set describing the molecule.
 Different basis sets can be choosen, they are connected by
similarity transformations.

 For different basis sets the matrices describing the

symmetry operations look different. However, their character
(trace) is the same!
 Repetition

We already know…

 Matrix representations of symmetry operations can often be

reduced into block matrices. Similarity transformations may help to
reduce representations further. The goal is to find the irreducible
representation, the only representation that can not be reduced
further.

 The same ”type” of operations (rotations, reflections etc)

belong to the same class. Formally R and R’ belong to the same
class if there is a symmetry operation S such that R’=S-1RS.
Symmetry operations of the same class will always have the
same character.
 Block Matrices

Block matrices are good

 A' 0 0 0  A' ' 0 0 0  A 0 0 0

 0 B ' 0 0  0 B ' ' 0 0  0 B 0 0
  
0 0  0 0  0 0 
 C’   C’’   C 
0 0  0 0  0 0 
A’A’’=A
B’B’’=B
C’C’’=C
 Block Matrices

If a matrix representing a symmetry operation is transformed

into block diagonal form then each little block is also a
representation of the operation since they obey the same
multiplication laws.

When a matrix can not be reduced further we have reached the

irreducible representation. The number of reducible
representations of symmetry operations is infinite but there is a
small finite number of irreducible representations.

The number of irreducible representations is always equal to

the number of classes of the symmetry point group.
 Group Theory II

Reducing big matrices to block diagonal form is always

possible but not easy. Fortunately we do not have to do this
ourselves.

As stated before all representations of a certain symmetry

operation have the same character and we will work with them
rather than the matrices themselves. The characters of different
irreducible representations of point groups are found in
character tables. Character tables can easily be found in
textbooks.
 Character Tables

The C3v character table

Symmetry operations

C3 v E C3 C32  v  v '  ' 'v

1 1 1 1 1 1 1
2 1 1 1 1 1 1
3 2 1 1 0 0 0

Irreducible The order h is 6

representations There are 3 classes
 Character Tables

Operations belonging to the same class will have the same

character so we can write: Classes

C3 v E 2C3 3 v
1 1 1 1
2 1 1 1
3 2 1 0

Irreducible representations
(symmetry species)
 The Great Orthogonality Theorem

”Consider a group of order h, and let D(l)(R) be the representative

of the operation R in a dl-dimensional irreducible representation
of symmetry species (l) of the group. Then

”
h
R Dij ( R) * Di ' j ' ( R)  d  ll ' ii' jj'
(l ) ( l ')

Read more about it in section 5.10.

 The Little Orthogonality Theorem

Here’s a smaller one,

R
 (l )
( R ) *  (l )
( R )  h ll '

where (l)(R) is the character of the operation (R). Or even

more simple if the number of symmetry operations in a class
c is g(c). Then

 g (c) 
c
(l )
( c ) *  ( c )  h ll '
(l )

since all operations belonging to the same class have the

same character.
 character Tables

There is a number of useful properties of character tables:

1. The sum of the squares of the dimensionality of all the irreducible
representations is equal to the order of the group
2. The sum of the squares of the absolute values of characters of any
irreducible representation is equal to the order of the group.
3. The sum of the products of the corresponding characters of any two
different irreducible representations of the same group is zero.

4. The characters of all matrices belonging to the operations in the same

class are identical in a given irreducible representation.
5. The number of irreducible representations in a C3 v E 2C3 3 v
group is equal to the number of classes of that 1 1 1 1
group.
2 1 1 1
3 2 1 0
 Irreducible representations

Each irreducible representation of a group has a label called a

symmetry species, generally noted . When the type of irreducible
representation is determined it is assigned a Mulliken symbol:

One-dimensional irreducible representations are called A or B.

Two-dimensional irreducible representations are called E.
Three-dimensional irreducible representations are called T (F).

The basis for an irreducible representation is said to span the

irreducible representation.
Don’t mistake the operation E for the Mulliken symbol E!
 Irreducible representations

The difference between A and B is that the character for a

rotation Cn is always 1 for A and -1 for B.
The subscripts 1, 2, 3 etc. are arbitrary labels.
Subscripts g and u stands for gerade and ungerade, meaning
symmetric or antisymmetric with respect to inversion.

Superscripts ’ and ’’ denotes symmetry or antisymmetry with

respect to reflection through a horizontal mirror plane.
 character Tables

Example: The complete C4v character table

C4 v E 2C4 C2 2 v 2 d
A1 1 1 1 1 1 z x2  y2 , z 2 z2
A2 1 1 1 1 1 Rz
B1 1 1 1 1 1 x2  y2 z( x 2  y 2 )
B2 1 1 1 1 1 xy xyz
E 2 0 2 0 0 ( x, y ), ( Rx , R y ) ( xz, yz) ( xz 2 , yz 2 ),[ x( x 2  3 y 2 ), y (3 x 2  y 2 )]

These are basis functions for the irreducible

representations. They have the same symmetry
properties as the atomic orbitals with the same
names.
 character Tables

Example: The complete C4v character table

C4 v E 2C4 C2 2 v 2 d
A1 1 1 1 1 1 z x2  y2 , z 2 z2
A2 1 1 1 1 1 Rz
B1 1 1 1 1 1 x2  y2 z( x 2  y 2 )
B2 1 1 1 1 1 xy xyz
E 2 0 2 0 0 ( x, y ), ( Rx , R y ) ( xz, yz) ( xz 2 , yz 2 ),[ x( x 2  3 y 2 ), y (3 x 2  y 2 )]

A1 transforms like z.
E does nothing, C4 rotates 90o about the z-axis, C2 rotates 180o
about the z-axis, v reflects in vertical plane and d in a diagonal
plane.
 character Tables
C4 v E 2C4 C2 2 v 2 d
A1 1 1 1 1 1 z x2  y2 , z 2 z2
A2 1 1 1 1 1 Rz
B1 1 1 1 1 1 x2  y2 z( x 2  y 2 )
B2 1 1 1 1 1 xy xyz
E 2 0 2 0 0 ( x, y ), ( Rx , R y ) ( xz, yz) ( xz 2 , yz 2 ),[ x( x 2  3 y 2 ), y (3 x 2  y 2 )]

A2 transforms like a rotation around z.

E v
+Rz -Rz
C2
+Rz
C4 d
+Rz -Rz
 Reducible to Irreducible representation

Given a general set of basis functions describing a molecule,

how do we find the symmetry species of the irreducible
representations they span?

( 1 ) ( 2 )
D( R)  D ( R)  D ( R )  ...
 Reducible to Irreducible representation

If we have an interesting molecule there is often a natural

choice of basis. It could be cartesian coordinates or something
more clever.

From the basis we can construct the matrix representations of

the symmetry operations of the point group of the molecule
and calculate the characters of the representations.
 Reducible to Irreducible representation

How do we find the irreducible representation?

Let’s use an old example from two weeks ago:
N
C3v in the basis (Sn, S1, S2, S3)
1 3 2

To find the characters of the symmetry operations we look at

how many basis elements ”fall onto themselves” (or their
negative self) after the symmetry operation.

E: =4 C3: =1 v: =2

 Reducible to Irreducible representation

N
So C3v in the basis (Sn, S1, S2, S3) will
have the following characters for the 1 3 2
different symmetry operations.

C3 v E 2C3 3 v
red 4 1 2
 Reducible to Irreducible representation

N
So C3v in the basis (Sn, S1, S2, S3) will
have the following characters for the 1 3 2
different symmetry operations.

C3 v E 2C3 3 v
Let’s add the red 4 1 2
character table of the
irreducible A1 1 1 1 By inspection we find
representation red=2A1+E
A2 1 1 1
E 2 1 0
 Reducible to Irreducible representation

The decomposition of any reducible representation into irreducible

ones is uniqe, so if you find combination that works it is right.

If decomposition by inspection does not work we have to use

results from the great and little orthogonality theorems
(unless we have an infinite group).
 Reducible to Irreducible representation

From LOT we can derive the expression (see section 5.10)

1
ai   g (c)  red (c) *  (c)
(l ) (l )

h l
where ai is the number of times the irreducible representation i
appears in red, h the order of the group, l an operation of the
group, g(c) the number of symmetry operations in the class of l,
red the character of the operation l in the reducible representation
and i the character of l in the irreducible representation.

red   ai i
i
 Reducible to Irreducible representation

1
ai   g (c)  red (c) *  (l ) (c)
(l )

h l
Let’s go back to our example again. C3 v E 2C3 3 v
1 red 4 1 2
a A1  1  4 1  2 1 1  3  2 1  2 A1 1 1 1
6 A2 1 1 1
1
a A2  1  4 1  2 1 1  3  2 1  0
E 2 1 0

6
1
aE  1  4  2  2 1 1  3  2  0   1
6
So once again we find red=2A1+E
 Projection Operator

Symmetry-adapted bases

The projection operator takes non-symmetry-adapted basis of a

representation and and projects it along new directions so that it
belongs to a specific irreducible representation of the group.

1
P    (l ) ( R )  Rˆ
ˆ l

h R
^
where Pl is the projection operator of the irreducible
representation l, (l) is the character of the operation R for the
representation l and R means ^ application of R to our original
basis component.
 Applications?

Can all of this actually be useful?

Yes, in many areas for example when studying electronic

structure of atoms and molecules, chemical reactions,
crystallography, string theory (Lie-algebra) etc…

Let’s look at one simple example concering molecular

vibrations. Martin Jönsson will tell you a lot more in a couple
of weeks.
 Molecular Vibrations

Water

Molecular vibrations can always

be decomposed into quite simple
components called normal modes.

Water has 9 normal modes of which 3 are translational, 3 are

rotational and 3 are the actual vibrations.

Each normal mode forms a basis for an irreducible

representation of the molecule.
 Molecular Vibrations

z3
First find a basis for the molecule. z1
Let’s take the cartesian coordinates y3
x3 z2
for each atom. y1
x1
y2
x2
Water belongs to the C2v group which
contains the operations E, C2, v(xz) and v’(yz).

The representation becomes

E C2 v(xz) v’(yz)
red 9 -1 1 3
 Molecular Vibrations

Character table for C2v.

C2 v E C2  v ( xz )  'v ( yz )
A1 1 1 1 1 z x2 , y2 , z 2
A2 1 1 1 1 R2 xy
B1 1 1 1 1 x, R y xz
B2 1 1 1 1 y , Rx yz

C2 v E C2  v ( xz )  v ' ( yz )
red 9 1 1 3

Now reduce red to a sum of irreducible representations. Use

inspection or the formula.
 Molecular Vibrations

C2 v E C2  v ( xz )  'v ( yz )
A1 1 1 1 1 z x2 , y2 , z2
A2 1 1 1 1 Rz xy
B1 1 1 1 1 x, R y xz
B2 1 1 1 1 y , Rx yz

The representation reduces to red=3A1+A2+2B1+3B2

trans= A1+B1+B2
rot=A2+B1+B2

vib=2A1+B2 Modes left for vibrations

 Molecular Vibrations

C2 v E C2  v ( xz )  'v ( yz )
A1 1 1 1 1 z x2 , y2 , z2
A2 1 1 1 1 Rz xy
B1 1 1 1 1 x, R y xz
B2 1 1 1 1 y , Rx yz

Modes with translational symmetry will be infrared active

while modes with x2, y2 or z2 symmetry are Raman active.

Thus water which has the vibrational modesvib=2A1+B2 will

be both IR and Raman active.
 Integrals

A last example…

Integrals of product functions often appear in for example

quantum mechanics and symmetry analysis can be helpful
with them to.

f i | Oˆ | f k

An integral will be non-zero only if the integrand belongs to

the totally symmetric irreducible representation of the
molecular point group.

fi f k  Oˆ
 Summary

 Molecules (and their electronic orbitals, vibrations etc) are

invariant under certain symmetry operations.

 The symmetry operations can be described by a

representation determined by the basis we choose to describe
the molecule.

 The representation can be broken up into its symmetry

species (irreducible representations).

 In character tables we find information about the

symmetry properties of the irreducible representations.
 More (and better) reading

The group theory chapter in Atkins is not very good (in my

opinion). More understandable descriptions can be found in:

Harris and Bertolucci, Symmetry and spectroscopy

Hargittai and Hargittai, Symmetry through the eyes of a chemist