Origin of Character Tables: These Show The Fundamental Rules of Group Theory (Completeness, Reciprocals, Associative Law)

Origin of Character Tables
• Symmetry operations obey the rules of group theory.

• Great! ? So we can use the mathematics of group theory:
completeness, associative law, reciprocals
 Symmetry operations combine according
the associative law of multiplication:
(RS)T = R(ST)
 If R and S are symmetry operations of an object,

then RS is also a symmetry operation.
 The inverse of each symmetry operation is also a

symmetry operation:
R-1R= RR-1 =E
• Any symmetry operation can be represented by a matrix
operating on some basis set (e.g., axes) describing the
molecule.
© K. S. Suslick, 2013
Group Multiplication Tables
These show the fundamental rules of Group Theory

(completeness, reciprocals, associative law)
i.e., they show the outcome of the different products in a group
C2v E C2 v  v’
E E C2 v  v’
C2 C2 E  v’ v
 v (xz) v  v’ E C2
 v’(yz)  v’ v C2 E
The number of elements = Group order (h)

here h = 4
1
Matrix Representations
For any symmetry operation,
we are just taking (x, y, z) to some new (x’, y’, z’)
(well, xyz for each atom of the molecule)
(x,y,z) is a vector, we’ll call it r .
The “taking” is called a transformation: for us, a sym op.

That transformation can be represented as a matrix.
The matrices of the sym ops must/will fulfill
the multiplication table of that point group.
So, what do these matrices look like?

2
Matrix Representations of Sym Ops
Identity Element, E
Er=r
1 0 0  x   x 
0 1 0   y    y 
    
0 0 1  z   z 
Inversion, i
i r = -r
 1 0 0   x    x 
 0  1 0   y    y 
    
 0 0  1  z    z 

Mirror Plane, h
σh (σxy i.e., x,y fixed, z to -z)
More generally:
1 0 0   x   x 
0 1 0   y    y 
    
0 0  1  z   z 
3
C2 rotation (z-axis)
x -> -x  1 0 0  x    x 
y -> -y  0  1 0  y     y 
    
z -> z  0 0 1  z   z 
Cn In general for rotations of 2/n

cos   sin    x1  x 2 
 sin  
 cos    y1  y 2

Sn improper rotation ( Cn followed by σh )
4
Matrix transformations will match
the multiplication tables of any group.
• 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.
5
Characters of Representation...
Even if the matrices have different basis (e.g., axes),
ICBST, the trace of the matrices are the same.
Character (trace) of the matrices 1 0 0
 ( R )   Dii ( R ) tr 0 1 0  3
i
0 0 1
The symmetry operations gives various classes that can be

distinguished by their characters.
In addition, there are only a certain number of distinct ways
in which a function can behave when subjected
to the symmetry operations of a particular point group.
These possibilities are called the irreducible representations:
the characters for each possible irr rep under each sym op
makes up the character table for each point group.
Characters / Traces

4.) tr(A•B•C) = tr(C•A•B) = tr(B•C•A) cyclic permutation

6
Characters and Classes
Definition:
R and R’ belongs to the same class if
there is some sym op (S) such that
R’ = S-1 R S
1 0 0
This implies that tr 0 1 0  3
tr(R’) = tr(R) 0 0 1
(R’) = (R)
 ( R)   Dii ( R)
i
Block Matrices
Block matrices are good!
icbst:
 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
That is, if two matrices are block diagonal, the corresponding
blocks of identical order can be multiplied individually.
7
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.
Block Matrices
• 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 (trace of
their matrix representation). So 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.
8
An Example…
 C3v in the basis {SN, S1, S2, S3} (S=sphere) N
i.e., a NH3 molecule
1 3 2
E, C3+, C3- 3 v are the sym ops.
matrix representations:
E =4 v =2 C3 =1 SN S1 S2 S3
1 0 1 0 0 0 1 0 0 0
 1  0 SN 1 0 0 0
1 0 0 0 0 1 0
   
S1
0 
 1  0 0 0 1 0 0 0 1  
     
0 1 0 1 0 0 0 1 0 0 S2 0 
 
C32 =1 v =2 v =2 S3
0 
1 0 0 0 1 0 0 0 1 0 0 0
0 0 0 1 0 0 0 1 0 0 1 0
  
0 1 0 0 0 0 1 0 0 1 0 0

0 0 1 0
 
0 1 0 0
 
0 0 0 1
 D ( 4 )  D (1)  D ( 3)
D(n) = blocks of n dim
Irreducible representations
 In principle, we can take any red. rep. and reduce it

to a block diagonal through similarity transformations.
In this example, we already have two blocks:
1 0 0 0 1 0 0 0
0 0 
0 0 1

0 0 1 0
 
0


   
0 1 0 0 0 
9
An Example…
N
 4-D basis {SN, S1, S2, S3} (S=sphere)
reduced to 1-D and 3-D 1 3 2
ICBST the3-D can be further reduced
(via a similarity transform. that separates z from x&y)
1 0 0 0
0 1 0 0

0 0  D ( 4 )  D (1)  D (1)  D ( 2 )
 
0 0 
No further reduction is possible

because the x & y axes transform into one another.
D(2) (the orange block) is now an irreducible representation
of the molecular point group.
Characters and Group Multiplication Tables

The characters of each Irr Rep must also fulfill the multiplication table.
Always must be true for the

totally symmetric Irr Rep!
10

E • σv = -1x1 = -1 ≠ σv
σv • C2 = 1x-1 = -1 ≠ σv'
11
Character Tables
There are a number of useful properties of character tables:
C3 v E 2C3 3 v
• The sum of the squares of the dimensionality of 1 1 1 1
all the irr reps is equal to the order of the group. 2 1 1 1
(normalization)
3 2 1 0
• The sum of (the squares of characters of any irr rep X the number of
elements in each class) is equal to the order of the group.
• The sum of the products of the corresponding characters of any two

different irr reps of the same group is zero. (orthogonality)
• The characters of all matrices belonging to the operations in the same

class are identical in a given irreducible representation. (similarity)
• The number of irreducible representations in a group is equal to the

number of classes of that group. (completeness)
Reducible to Irreducible Representation

From the orthonormalization of the IRRs (also known as the
”Grand Orthogonalization Theorem”), we can see that
1
ai  
h l
g ( c )  red ( c ) * 
(l ) (l )
(c )
where red   airr irr (i.e., the red. rep. is a lin comb.)
i  irr
where ai is the number of times the irreducible representation

irr appears in red , h the order of the group,
l an operation of the group, g(c) #of sym ops in class l,
red the character of the operation l in the red. rep., and
irr the character of l in the irreducible representation.
12
Reducible to Irreducible representation
As an example, in C3v (NH3), N
consider the following red. rep.
1 3 2
C3 v E 2C3 3 v
red 4 1 2
C3 v E 2C3 3 v
Here’s the
character table A1 1 1 1
of the irreducible A2 1 1 1
representations: E 2 1 0
By inspection we find red = 2A1 + E

BUT WE USUALLY CAN’T DO IT BY INSPECTION!
Reducible to Irreducible Representation

1
 g (c)  red (c) *  ( l ) (c)
(l )
ai 
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
a E  1  4  2  2 1 1  3  2  0   1
6
So once again we find red = 2A1 + E
13
Direct Products
• In many cases, we will want to know how a set
of product functions transform, already knowing how
the individual functions transform, within a pt gr.
• We could, of course, construct matrix reps for the

product basis functions under each sym op. Ugg.
• Easier: Products of functions transform as the

direct products of the irr rep of the initial functions!
• Direct products are simply the red. rep. generated by

multiplying each symmetry’s characters of the initial
functions.
Direct Products
• Consider C3v . Let’s find out how (x,y)  (x,y) behaves.
of course, in this case it’s obvious (x,y)  (x,y) = combined (xy, yx, x2, y2)
1
 g (c)  red (c) *  (l ) (c)
(l )
• So, (x,y)  (x,y) = E  E =  ai 
h l
 4 1 0
1
a A1  1 4  1  2 1 1  3  0 1  1 So,  = A1 + A2 + E
6
1
a A2  1 4  1  2  1  1  3  0  1  1
6
1
aE  1 4  2  2  1 1  3  0  0   1
6
14
Direct Product Shortcut Rules
Projection Operators
Symmetry-adapted bases:
The projection operator takes a non-symmetry-adapted basis

set of a representation and projects it along new directions,
so that it belongs to a specific irr. rep. of the group.
1
Pˆ l    ( l ) ( R )  Rˆ
h R
^
where P l is the projection operator of the irr rep l,
(l) is the character of the operation R for the rep l, and
R means application of R^ to our original basis component.
More later...
15
Integrals
A last example… (with more next time!)
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 irr. rep. of the 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.
16
Lagniappe: A Little Extra
Some Point Groups have complex characters:
specifically Cn and Cnh for n ≥ 3, S2n, T, and Th (all uncommon)
for n=3, 2cos2π/3 = -1
= 2 -1 -1
Realize, however, that the real number rep. is actually reducible!
e.g., for C3, h = 3, so Σ(χE)2 = 3 = 12 + 12 +12 ≠ 12 + 22 !
17
Double Rotation Groups
Within Dirac Equations (relativistic wave functions), the functions
that represent half-integer spins are treated as double valued
within a single 2 rotation (sorta like a Möbius strip), “spinors”.
So the usual identity element (C1) does not return the function,
but rather the negative of the function!
Solution:
In addition to the usual rotations, we add the rotation operation
R (= C2 = original E) and all the operations formed by taking
the product of R with the original sym ops.
For angular momentum basis functions with half-integer values
ONLY, these new sym ops, R (i.e., C2) can have characters
different than the “old” ops.
Twice the number of sym ops, but not twice as many classes.
This also give us a new identity element E = C4

Normal D4 Group
Double Rotation Group D4' adds the following

'
18
Double Rotation Group D4'
' or *
Adding R doubles the number of sym ops, but not the # of classes (7 vs. 5)

Double Group for Octahedral Field
19

Origin of Character Tables: These Show The Fundamental Rules of Group Theory (Completeness, Reciprocals, Associative Law)

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Origin of Character Tables: These Show The Fundamental Rules of Group Theory (Completeness, Reciprocals, Associative Law)

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Origin of Character Tables

• Symmetry operations obey the rules of group theory.

 If R and S are symmetry operations of an object,

 The inverse of each symmetry operation is also a

Group Multiplication Tables

These show the fundamental rules of Group Theory

The number of elements = Group order (h)

(x,y,z) is a vector, we’ll call it r .

The “taking” is called a transformation: for us, a sym op.

So, what do these matrices look like?

Matrix Representations of Sym Ops

Cn In general for rotations of 2/n

Matrix Representations of Sym Ops

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

The symmetry operations gives various classes that can be

4.) tr(A•B•C) = tr(C•A•B) = tr(B•C•A) cyclic permutation

• When a matrix can not be reduced further we have

• The number of irreducible representations is always

• Reducing big matrices to block diagonal form is

• As stated before, all representations of a certain

 In principle, we can take any red. rep. and reduce it

In this example, we already have two blocks:

No further reduction is possible

Characters and Group Multiplication Tables

Always must be true for the

Characters and Group Multiplication Tables

• The sum of the products of the corresponding characters of any two

• The characters of all matrices belonging to the operations in the same

• The number of irreducible representations in a group is equal to the

Reducible to Irreducible Representation

where ai is the number of times the irreducible representation

By inspection we find red = 2A1 + E

Reducible to Irreducible Representation

• We could, of course, construct matrix reps for the

• Easier: Products of functions transform as the

• Direct products are simply the red. rep. generated by

The projection operator takes a non-symmetry-adapted basis

A last example… (with more next time!)

Integrals of product functions often appear in for

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

• Molecules (and their electronic orbitals, vibrations etc)

• The symmetry operations can be described by a

• The representation can be broken up into its

• In character tables we find information about the

Lagniappe: A Little Extra

for n=3, 2cos2π/3 = -1

Lagniappe: A Little Extra

Double Rotation Group D4' adds the following

Lagniappe: A Little Extra

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