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Group Theory 3
Group Theory 3
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5.04, Principles of Inorganic Chemistry II
Prof. Daniel G. Nocera
Lecture 3: Irreducible Representations and Character Tables
A’ = v –1 ⋅ A ⋅ v
B’ = v –1 ⋅ B ⋅ v
C’ = v –1 ⋅ C ⋅ v
⎡
A
1 ⎤
⎡B1 ⎤
⎡C1 ⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥
A
′ =
⎢ A
2 ⎥ B′ =
⎢ B2 ⎥ C′ =
⎢ C
2 ⎥
⎢
A
3 ⎥
⎢
B ⎥
⎢
C
⎥
⎣
⎦ ⎣ 3⎦ ⎣ 3 ⎦
Matrices A, B, and C are reducible. Sub-matrices Ai, Bi and Ci obey the same
multiplication properties as A, B and C. If application of the similarity transform
does not further block-diagonalize A’, B’ and C’, then the blocks are irreducible
representations. The character is the sum of the diagonal elements of Γi.
As an example, let’s continue with our exemplary group: E, C3, C32, σv, σv’, σv” by
defining an arbitrary basis … a triangle
A
v'' v'
C B
The basis set is described by the triangles vertices, points A, B and C. The
transformation properties of these points under the symmetry operations of the
group are:
⎡A ⎤ ⎡B ⎤ ⎡0 1 0⎤ ⎡A ⎤ ⎡A ⎤ ⎡B ⎤ ⎡0 1 0⎤ ⎡A ⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥⎢ ⎥ ′ ⎢ ⎥ ⎢ ⎥ ⎢ ⎥⎢ ⎥
C3 ⎢B ⎥ = ⎢C ⎥ = ⎢0 0 1⎥ ⎢B ⎥ σ V ⎢B ⎥ = ⎢A ⎥ = ⎢1 0 0⎥ ⎢B ⎥
⎢C ⎥ ⎢A ⎥ ⎢1 0 0⎥ ⎢C ⎥ ⎢C ⎥ ⎢C ⎥ ⎢0 0 1⎥ ⎢C ⎥
⎣ ⎦ ⎣ ⎦ ⎣ ⎦⎣ ⎦ ⎣ ⎦ ⎣ ⎦ ⎣ ⎦⎣ ⎦
⎡A ⎤ ⎡C ⎤ ⎡0 0 1⎤ ⎡A ⎤ ⎡A ⎤ ⎡C ⎤ ⎡0 0 1⎤ ⎡A ⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥⎢ ⎥ ⎢ ⎥ ⎢ ⎥ ⎢ ⎥⎢ ⎥
σ V′′ ⎢B ⎥ = ⎢B ⎥ = ⎢0 1 0⎥ ⎢B ⎥
2
C3 ⎢B ⎥ = ⎢A ⎥ = ⎢1 0 0⎥ ⎢B ⎥
⎢C ⎥ ⎢B ⎥ ⎢0 1 0⎥ ⎢C ⎥ ⎢C ⎥ ⎢A ⎥ ⎢1 0 0⎥ ⎢C ⎥
⎣ ⎦ ⎣ ⎦ ⎣ ⎦⎣ ⎦ ⎣ ⎦ ⎣ ⎦ ⎣ ⎦⎣ ⎦
⎡
1 2
⎤ ⎡ 1 1 1
⎤
⎢ 0
⎥ ⎢ ⎥
⎢ 3 6
⎥ ⎢ 3 3 3
⎥
⎢ ⎥ ⎢ ⎥
1 1
1
⎥ 2 1
1
⎥
v =
⎢ −
; v
–1 =
⎢ −
−
⎢ 3 6 2
⎥ ⎢ 6 6 6
⎥
⎢ ⎥ ⎢ ⎥
⎢ 1 −
1
−
1
⎥ ⎢ 0
1
−
1
⎥
⎢
3 6 2
⎥
⎢ 2 2
⎥
⎣
⎦
⎣
⎦
⎡
1 1
1 ⎤
⎡ ⎡
1 2
⎤
⎢ ⎥ 0 1 0
⎤
⎢ 0
⎥
⎢ 3 3 3⎥ ⎢ ⎥ ⎢ 3 6
⎥
⎢ ⎥ ⎢ ⎥ ⎢ ⎥
2 1 1
⎥ ⎢ 1 1 1
⎥
v –1 ⋅
C3 ⋅ v =
⎢ −
−
⋅
0 0 1
⎥ ⋅
⎢ −
⎢ 6 6 6
⎥ ⎢ ⎥ ⎢ 3 6 2
⎥
⎢ ⎥ ⎢ ⎥ ⎢ ⎥
1 1 ⎥ ⎢ ⎢ 1 1
1
⎥
⎢ 0
−
⎣1 0 0
⎥
⎦
−
−
⎢ 2 ⎥
2 ⎦
⎢
3 6 2
⎥
⎣
⎣
⎦
⎡
1 1
1
⎤
⎡
1 1 1 ⎤
⎡
⎤
⎢ ⎥ ⎢ − ⎥ ⎢1 0 0⎥
⎢ 3 3 3
⎥ ⎢ 3 6 2
⎥ ⎢ ⎥
⎢ ⎥ ⎢ ⎥ ⎢
⎢ 2 −
1 1
⎥ ⎢ 1 1 1
⎥ 1 3⎥
−
⋅
−
−
=
⎢0 − ⎥ = C3*
⎢ 6 6 6
⎥ ⎢ 3 6 2
⎥ ⎢ 2 2 ⎥
⎢ ⎥ ⎢ ⎥ ⎢
1 1
⎥ ⎢ 1 2
3 1⎥
⎢ 0
−
0
⎥ ⎢0 − − ⎥
⎢
⎣
2 2
⎥⎦
⎢
⎣
3 6
⎥
⎦
⎣
2 2 ⎦
⎡ ⎤
⎢1 0 0
⎥
⎢ ⎥
⎡1 0 0
⎤
⎢ ⎥
⎢ ⎥ 1 3⎥
–1
v ⋅
E ⋅ v = E* = ⎢0 1 0
⎥ v –1 ⋅ C32 ⋅ v = C32* = ⎢0 − −
⎢ 2 2
⎥
⎢⎣0 0 1
⎥⎦
⎢ ⎥
⎢0 3 1 ⎥
−
⎢ 2 2
⎥
⎣
⎦
⎡ ⎤
⎢1 0 0
⎥
⎡1 0 ⎢ ⎥
0
⎤ ⎢ ⎥
⎢ ⎥ 1 3⎥
v –1 ⋅
σv ⋅ v = σv* = ⎢0 1 0
⎥ v –1 ⋅ σv” ⋅ v = σv”* = ⎢0 − −
⎢0 0 − 1⎥ ⎢ 2 2
⎥
⎣ ⎦
⎢ ⎥
⎢0 − 3 1 ⎥
⎢ 2 2
⎥
⎣ ⎦
⎡ ⎤
⎢1 0 0
⎥
⎢ ⎥ As above, the block-diagonalized
⎢ ⎥ matrices do not further reduce under re
1 3
⎥
v –1 ⋅ σv’ ⋅ v = σv’* = ⎢0 −
application of the similarity transform.
⎢ 2 2
⎥
⎢ ⎥ All are Γirrs.
⎢0 3 1
⎥
⎢ 2 2
⎥
⎣ ⎦
Γ1 1 1 1 1 1 1 Γ1 1 1 1
Γ2 2 –1 –1 0 0 0 Γ2 2 –1 0
Note: characters of
operators in the same
class are identical
The triangular basis set does not uncover all Γirr of the group defined by {E, C3, C32,
σv, σv’, σv’’}. A triangle represents Cartesian coordinate space (x,y,z) for which the
Γis were determined. May choose other basis functions in an attempt to uncover
other Γis. For instance, consider a rotation about the z-axis,
The transformation properties of this basis function, Rz, under the operations of the
group (will choose only 1 operation from each class, since characters of operators in
a class are identical):
E: Rz → Rz C3: Rz → Rz σv(xy): Rz → Rz
E 2C3 3σv
Γ1 1 1 1
from triangular basis, i.e. (x, y, z)
Γ2 2 –1 0
Γ3 1 1 –1 from Rz
Rule 1
2 2 2 2
∑ l i = l 1 + l 2 + l 3 + ... = h
i
Since the character under the identity operation is equal to the dimension of Γi
(since E is always the unit matrix), the rule can be reformulated as,
[
∑ xi(E)
i
] 2
= h
character under E
Rule 2
[
∑ xi(R)
R
] 2
= h
Rule 3
[ ][
∑ xi(R) x j(R) = 0
R
] for i ≠ j
Rule 4
Rule 5
2 2 2
Rule 1: l 1 + l 2 + l 3 = 6 ∴ l 1 = l 2 = 1, l 2 = 2
Rule 2: All character tables have a totally symmetric representation. Thus one of
the irreducible representations, Γi, possesses the character set χ1(E) = 1,
χ1(C3, C32) = 1, χ1(σv, σv’, σv”) = 1. Applying Rule 2, we find for the other
irreducible representation of dimension 1,
consequence of Rule 4
Since χ2(E) = 1,
2 + 2 ⋅ χ3(C3) + 3 ⋅ χ3(σv) = 0
However, application of Rule 2 to Γ3 gives us one equation for two unknowns. Have
several options to obtain a second independent equation:
E 2C3 3σv
Γ1 1 1 1
Γ2 2 –1 0
Γ3 1 1 –1
• Γis of:
l=1 A or B A is symmetric (+1) with respect to Cn
B is antisymmetric (–1) with respect to Cn
l=2 E
l=3 T