Irreducible Representations

and Character Tables

C734b

C734b Irreducible 1
Representations and Character
Tables

Irreducible Representations

Suppose {Γ(A), Γ(B), …} for an l-dimensional matrix representation of G.

Then if S is any non-singular lxl matrix (detS ≠ 0) the {Γ’(A), Γ’(B), …} also form a
l-dimensional representation of G where

~ ~
Γ' ( A) = S −1Γ( A)S
similarity transform
~ ~~ ~ ~ ~
Note: Γ' ( A)Γ(B ) = S −1Γ( A)S S −1Γ(B )S = S −1Γ( A)Γ(B )S
~ ~
= S −1Γ( AB )S = Γ' ( AB )
⇒ {Γ’(A), Γ’(B), …} is also a representation of G
Two representations related by a similarity transformation are said to be equivalent.
equivalent

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Suppose that Γ1 and Γ2 are matrix representations of G with dimensions l1 and l2,
respectively, and that for every operation A of G a (l1 + l2)-dimensional matrix is
defined by:

⎛ Γ1 ( A) 0 ⎞
Γ( A) = ⎜⎜ ⎟
⎟
⎝ 0 Γ 2
( A ) ⎠
⎛ Γ1 ( A) 0 ⎞⎛ Γ1 (B ) 0 ⎞
⇒ Γ( A)Γ(B ) = ⎜⎜ ⎟⎜ ⎟
⎝ 0 Γ ( A)⎟⎠⎜⎝ 0
2
Γ (B )⎟⎠
2

⎛ Γ1 ( A)Γ1 (B ) 0 ⎞ ⎛ Γ1 ( AB ) 0 ⎞
= ⎜⎜ ⎟=⎜ ⎟ = Γ( AB )
0 2 2 ⎟ ⎜
Γ ( A)Γ (B )⎠ ⎝ 0 Γ ( AB )⎟⎠
2
⎝

⇒ {Γ(A), Γ(B),…} as defined also form a representation of G

This representation of G is called the direct sum of Γ1 and Γ2

⇒ Γ = Γ1 ⊕ Γ 2
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Alternatively, we can regard Γ as reduced into Γ1 and Γ2

A representation of G is reducible if it can transformed by a similarity

transformation into an equivalent representation, each matrix which has the
same block diagonal form. Then each of the smaller representations Γ1, Γ2, Γ3
etc are also representations of G

A representation that can not be reduced any further is called an

irreducible representation, IR

of fundamental importance

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 Properties of Irreducible Representations

Great Orthogonality Theorem: (no proof)

∑ [Γ ( R) ][Γ ( R) ]
h
i mn j m 'n '
*
= δ ijδ mm 'δ nn '
R l il j

Interpretation: in a set of matrices constituting any one IR, and the set of
matrix elements, one from each matrix, behaves as the components of a vector
in a h-dimensional space. All these vectors are orthogonal and each is
normalized so the square of its length = h/ℓi.

a) ∑ Γ ( R)
R
i mn Γ j ( R) mn = 0 if i ≠ j

Vectors chosen from matrices of different representations are orthogonal.

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b) ∑ Γ ( R)
R
i Γ ( R) m 'n ' = 0 if m ≠ m' or n ≠ n'
mn i

Vectors chosen from the same representation but different matrix elements
are orthogonal.

h
c) ∑ Γ ( R)
R
i mn i Γ ( R) mn =
li
Vectors chosen from the same representation and same matrix elements
have a magnitude = h/li.

IRs, Γi and their characters, χi

Five important rules about IRs,
Rule 1.) the sum of the squares of the dimensions of the IRs of a group is equal to the
order of the group, h (no proof):

∑l
i
2
i = l 12 + l 22 + L = h

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 ∑ [χ ( E )]
2
Rule 1.) can be written as: i =h
i

since χi(E), the character of the representation of E in the ith IR = order of the
representation.

Rule 2.) The sum of the squares of the characters in any IR = h

∑ [χ ( R)]
2
i =h (simple test of irreducibility)
R

Rule 3.) the vectors whose components are the characters of two different IRs
are orthogonal:

∑ χ ( R) χ
R
i j ( R) = 0

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Rule 4.): In a given reducible or irreducible representation the character of all

matrices belong to the same class are identical.

Rule 5.): The number of IRs = number of classes in a group.

From rules 2.) and 3.): ∑ χ ( R) χ

R
i j ( R ) = hδ ij

Denote the number of elements in the mth class by gm, the number in the nth
class by gn, etc. and let there be k classes.

k
Then: ∑ χ (R
p
i p ) χ j ( R p ) g p = hδ ij

Here Rp is any one of the operations in the pth class.

This means the k χi(Rp) quantities in the Γi IR behave like components

of a k-dimensional vector which is orthogonal to the k-1 other vectors.

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Example: C3v {E, C3+, C3-, σa, σb, σ3}

defined w.r.t. the xz plane

y

-π/3
b
a
x
+π/3 c

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Representations and Character
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Matrix representations
⎛1 0 0⎞
⎜ ⎟
Γ(E ) = ⎜ 0 1 0 ⎟
⎜0 0 1⎟
⎝ ⎠

⎛ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎞ ⎛ 1 3 ⎞
⎜ cos⎜ ⎟ − sin ⎜ ⎟ 0⎟ ⎜ − − 0⎟
⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟ ⎜ 2 2 ⎟
+ ⎜ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎟ ⎜ 3 1 ⎟
Γ(C3 ) = ⎜ + sin ⎜ ⎟ cos⎜ ⎟ 0⎟ = ⎜ + − 0⎟
⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟ ⎜ 2 2 ⎟
⎜ 0 0 1⎟ ⎜ 0 0 1⎟
⎜ ⎟ ⎜ ⎟
⎝ ⎠ ⎝ ⎠

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 ⎛ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎞ ⎛ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎞
⎜ cos⎜ − ⎟ − sin ⎜ − ⎟ 0 ⎟ ⎜ cos⎜ ⎟ sin ⎜ ⎟ 0⎟
⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟ ⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟
⎜ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎟ ⎜ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎟
C3− = C32 = ⎜ sin ⎜ − ⎟ cos ⎜ − ⎟ 0 =
⎟ ⎜ − sin ⎜ ⎟ cos⎜ ⎟ 0 ⎟
⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟ ⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟
⎜ 0 0 1 ⎟ ⎜ 0 0 1 ⎟
⎜ ⎟ ⎜ ⎟
⎝ ⎠ ⎝ ⎠
⎛ 1 3 ⎞
⎜ − 0⎟
⎜ 2 2 ⎟
⎜ 3 1 ⎟
= ⎜− − 0⎟
⎜ 2 2 ⎟
⎜ 0 0 1⎟
⎜ ⎟
⎝ ⎠

⎛1 0 0⎞
⎜ ⎟
σ A = σ xz = ⎜ 0 − 1 0 ⎟
⎜0 0 1⎟
⎝ ⎠

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Representations and Character
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⎛ cos(2θ ) sin (2θ ) 0 ⎞

⎜ ⎟
σ B = ⎜ sin (2θ ) − cos(2θ ) 0 ⎟ θ = -π/3
⎜ 0 0 1 ⎟⎠
⎝

⎛ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎞ ⎛ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎞
⎜ cos⎜ − ⎟ sin ⎜ − ⎟ 0 ⎟ ⎜ cos⎜ ⎟ − sin ⎜ ⎟ 0⎟
⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟ ⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟
⎜ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎟ ⎜ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎟
∴σ B = ⎜ sin ⎜ − ⎟ − cos⎜ − ⎟ 0 ⎟ = ⎜ − sin ⎜ ⎟ − cos⎜ ⎟ 0⎟
⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟ ⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟
⎜ 0 0 1⎟ ⎜ 0 0 1⎟
⎜ ⎟ ⎜ ⎟
⎝ ⎠ ⎝ ⎠
⎛ 1 3 ⎞
⎜ − − 0⎟
⎜ 2 2 ⎟
⎜ 3 1 ⎟
= ⎜− 0⎟
⎜ 2 2 ⎟
⎜ 0 0 1⎟
⎜ ⎟
⎝ ⎠

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 Lastly:
⎛ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎞ ⎛ 1 3 ⎞
⎜ cos⎜ ⎟ sin ⎜ ⎟ 0⎟ ⎜ − 0⎟
⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟ ⎜ 2 2 ⎟
⎜ ⎛ 2π ⎞ ⎛ 2π ⎞ ⎟ ⎜ 3 1 ⎟
σ C = ⎜ sin⎜ ⎟ − cos⎜ ⎟ 0 ⎟ = ⎜ 0⎟
⎜ ⎝ 3 ⎠ ⎝ 3 ⎠ ⎟ ⎜ 2 2 ⎟
⎜ 0 0 1⎟ ⎜ 0 0 1⎟
⎜ ⎟ ⎜ ⎟
⎝ ⎠ ⎝ ⎠

Each matrix is block diagonal into two representations by inspection:

Γ1 ⊕ Γ 2

Χ(Γ1) = {E, C3+, C3-, σA, σB, σC}

={2, -1, -1, 0, 0, 0 } Point 4
= 1st class 2nd class 3rd class

Χ(Γ2) = {1 1, 1 1, 1, 1}

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∑ χ ( R)
2
i) Are Γ1 and Γ2 irreducible? Yes if i = h point 1.)
R

h=6

Γ1: (2)2 + (-1)2 +(-1)2 + 02 + 02 +02 irreducible

= 4 + 1+ 1 = 6

Γ2: (1)2 + (1)2 + (1)2 + (1)2 + (1)2 + (1)2 = 6 irreducible

ii) Is χ(Γ1) orthogonal to χ(Γ2)? point 3.)

(2)(1) + (-1)(1) +(-1)(1) +(0)(1) + (0)(1) + (0)(1)

=2–2=0 yes

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 iii) Are Γ1 and Γ2 the only irreducible representations?

No! There are 3 classes: E, {C3+, C3-}, {σA, σB, σC}

∴ There must be one more. point 5.)

Let that representation be Γ3

Q l 12 + l 22 + l 23 = 6 point 1.)
and l 1 = 2, l 2 = 1 ⇒ l 23 = 6 − 4 − 1 = 1

∴ χ(E) for Γ3 =1; the IR is 1-dimensional point 1.)

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Representations and Character
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∴ ∑ χ (Γ1 ) χ (Γ 3 ) = 0 and ∑ χ (Γ 2
) χ (Γ 3 ) = 0
R R

# in class

∴ (1)(2)(1) + (2)(-1)χ3(C3) +(3)(0)χ3(σ) = 0 (i)

and
(1)(1)(1) + (2)(1)χ3(C3) + (3)(1)χ3(σ) = 0 (ii)

∴ From (i): -2χ (C ) = -2 ⇒ χ(C ) = 1

3 3 3

∴ From (ii): 1+(2)(1)(1) + 3χ (σ) = 0 ⇒ 3 3χ3(σ) = -3

∴ Χ (σ) = -1 3

∴ χ(Γ ) = {1, 1, 1, -1, -1, -1}

3

Note: ∑ χ (Γ ) = 6 ⇒
R
3
IR point 2.)

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Will find that we will be constructing many reducible representations and therefore,
we will want to know how many IRs are within a reducible one.

A first glance might think we need to find a matrix similarity transformation to block
diagonalize the reducible matrix.

Yikes!

However: recall that the character of a matrix is not changed by a similarity

transformation. Therefore, we will only work with characters.

χ ( R) = ∑ a j χ j ( R)
j

Character of matrix representing # times block of jth IR Character of matrix representing

operation R in a reducible representation appears along diagonal operation R in jth IR

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∴ Multiply by χi(R) and sum over R

∑ χ ( R) χ ( R) = ∑∑ a χ
R
i
R j
j j ( R) χ i ( R)

but ∑ χ ( R) χ
R
i j ( R ) = hδ ij

⇒ ∑ χ ( R) χ i ( R ) = hai
R

1
∴ ai = ∑ χ ( R) χ i ( R)
h R

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 Character Tables
Tabulation by class the characters of the IRs of a point group

The Schonflies symbol is in the upper left-hand corner

Each column is headed by the number of elements in class x symbol for that
element. For example 2C3 for {C3+, C3-} in C3v

Each row ≡ Γ label for the IR given by Mulliken notation:

a) 1-D IRs symmetric to Cn rotation; that is, χ(Cn) = +1: A
otherwise if χ(Cn) = -1: B
b) Subscripts 1 or 2 are used depending on whether the IR is
symmetric or anti-symmetric, χ = +1 or -1, to a perpendicular C2
axis or σv
c) Prime or double prime superscripts to indicate IRs which are
symmetric or anti-symmetric to σh (if it exists).
d) g or u subscripts depending if IR is symmetric or anti-symmetric
with respect to I (if it exists). g ≡ gerade and u ≡ ungerade.

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e) 2-D or 3-D IRs are labelled by E and T, respectively.

(Don’t confuse this with R = E or T groups).

Right-hand side of character table tells how components of

r
r = eˆ1 x + eˆ2 y + eˆ3 z or how quadratic functions, xy, z2, etc. transform.

These will be useful down the road for understanding the IRs for p and d orbitals.

Rx, Ry, Rz tell how rotations about x, y, and z, transform, respectively.

The notation for the IRs of the axial groups C∞v and D∞h is different.

IRs are classified according to the magnitude of the z-component of angular

momentum Lz along the symmetry axis, z ≡ Λ

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 Λ = Lz = 0 1 2 3 ...
Σ Π Δ Φ ...

All IRs are 2-D except Σ. Subscripts g and u are the same but + or – superscripts
are used on Σ if χ(σv) = +1 or -1, respectively.

For Lz . 0, χ(C2`) and χ(σv) = 0.

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Note: by tradition the first IR listed in the character table is the totally symmetric one
where all the characters are +1 for every class of symmetry operator

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More on the RHS of the character table

As stated the table indicates the IRs for the functions x, y, z, x2, y2, xy, and cross products:
Rx =j x k; Ry =k x i and Rz = i x j (rotations about the axes).

z
Rz
Ry
y
Rx
x

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Should we care?
Yes because many important chemistry items share the same symmetry properties

What else behaves symmetry-

symmetry-wise as x, y, z?
The p-orbitals: px, py, pz
r
The components of the dipole moment: μˆ = −er : μ x = −ex μ y = −ey μ z = −ez

The dipole moment governs the strongest single-photon absorption and emission
transitions. Their IRs will help understand electronic spectroscopy

Bond lengths also behave as x, y, z. Their IRs come up in infrared spectroscopy

Translations of molecules behave as x, y, z

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What else behaves symmetry-

symmetry-wise as binary properties of x, y, z?

The d-orbitals: d z 2 d x 2 − y 2 d xy d xz d yz
Components of the electric quadrupole, Q

Qij ≡ ∫ ρ (3ri rj − r 2δ ij ) d 3 r

Important for weak electric quadrupole transitions; important in solid state NMR

Components of the polarizability tensor α. Their IRs come up in Raman spectroscopy

Binary products also show up as the operator for two-photon transitions

in molecules

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 What else behaves symmetry-
symmetry-wise as Rx Ry Rz?

The components of orbital angular momentum: Lx, Ly, Lz

r r
The components of the magnetic dipole: μm = −μ B L
Here μB is the Bohr magnetron constant.
Important for weak magnetic dipole transitions. Also important in NMR.

What about s-
s-orbitals?

s-orbitals look the same regardless of symmetry

operation. Hence their IR is the totally symmetric IR
of the point group under discussion.
This is always true and therefore, s is not labeled
in the character table.

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What about f-
f-orbitals?

There are seven: f z 3 f xz 2 f yz 2 f xyz f z (x2 − y 2 ) f x (x 2 −3 y 2 ) f y (3 x2 − y 2 )

Their IRs are not listed in character tables but if you know how
x, y, z, and the binary operators behave you can deduce the triple products by
taking direct products of the appropriate IRs.

What about electron spin?

Like every thing to do with electron spin, the behavior is weird. We’ll consider this later.

Point: You can learn a lot from a character table without doing a single calculation!

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