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Group Theory 1
Group Theory 1
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5.04, Principles of Inorganic Chemistry II
Prof. Daniel G. Nocera
Lecture 1: Symmetry Elements and Operations
There are five symmetry elements, which will be defined relative to point with
coordinate (x1, y1, z1 ) :
1) identity, E
E(x1, y1, z1 ) = (x1, y1, z1 )
2) plane of reflection, σ
σ (xz)(x1, y1,z1 ) = (x1,−y1,z1 )
2π
4) proper rotation axis, Cn (where θ = )
n
convention is a clockwise rotation of the point
C2 (z)(x1,y1,z1 ) = (− x1,−y1,z1 )
⎡
x1 ⎤ ⎡ ⎤ ⎡x1 ⎤
⎡
x1 ⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥ ⎢ ⎥
1) identity: E
⎢y1 ⎥ =
⎢ ?
⎥ ⎢y1 ⎥ =
⎢y1 ⎥
⎢⎣
z1 ⎥⎦
⎢⎣
⎥⎦ ⎢⎣ z1 ⎥
⎦ ⎢⎣ z1 ⎥⎦
⎡1 0 0
⎤
⎢ ⎥
matrix satisfying this condition is: ⎢0 1 0
⎥
⎢⎣0 0 1
⎥⎦
⎡1 0 0
⎤
⎢ ⎥
∴
E
=
⎢0 1 0
⎥ … E is always the unit matrix
⎢⎣0 0 1
⎥⎦
⎡
x1 ⎤
⎡
x1 ⎤
⎡1 0
0⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥
2) reflection: σ
(xy) ⎢y1 ⎥ =
⎢ y1 ⎥ ∴
σ
(xy) =
⎢0 1
0⎥
⎢⎣
z1 ⎥⎦
⎢⎣
−
z1 ⎥⎦
⎢⎣0 0 −
1⎥⎦
⎡1 0 0
⎤
⎡− 1 0 0⎤
⎢ ⎥
similarly σ (xz) =
⎢0 − 1 0
⎥ and σ (yz) =
⎢⎢ 0 1 0⎥⎥
⎢⎣0 0 1
⎥⎦
⎢⎣
0 0 1
⎥⎦
⎡
x1 ⎤ ⎡−
x1 ⎤ ⎡− 1 0
0⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥
3) inversion: i ⎢y1 ⎥ =
⎢−
y1 ⎥ ∴ i =
⎢ 0 − 1
0⎥
⎢⎣
z1 ⎥
⎦ ⎢⎣ −
z1 ⎥⎦
⎢⎣
0 0 −
1⎥⎦
projection into xy plane need only be considered… i.e., rotation of vector v(xi,yi)
through θ
v v v
x1 = v cos α Cn (θ ) x2 = v cos [− (θ − α )] = v cos (θ − α )
v ⎯⎯⎯ ⎯ ⎯→ v v
y1 = v sin α y2 = v sin [− (θ − α )] = – v sin (θ − α )
⎡
x1 ⎤
⎡
x1 cos θ + y1 sin θ ⎤
⎢ ⎥ ⎢ ⎥
Cn(θ )
⎢y1 ⎥ =
⎢− x1 sin θ +
y1 cos θ ⎥
⎢⎣
z1 ⎥⎦
⎢⎣
z1 ⎥⎦
⎡
cos θ sin θ 0⎤
⎢ ⎥ 2π
∴
Cn(θ ) =
⎢ − sin θ cos θ
0⎥ where θ
=
n
⎢⎣
0 0 1⎥⎦
Note… the rotation above is clockwise, as discussed by HB (pg 39). Cotton on pg.
73 solves for the counterclockwise rotation… and presents the clockwise result
derived above. To be consistent with HB (and math classes) we will rotate clockwise
as the convention.
Example: C3 , θ =
n
⎡
2π 2π
⎤
⎡
1 3 ⎤
⎢ cos sin 0
⎥ ⎢ − 0
⎥
⎢ 3 3
⎥ ⎢ 2 2
⎥
⎢ 2π 2π
⎥ ⎢ 3 1
⎥
C3 =
⎢ −
sin cos 0
⎥ =
⎢−
−
0
⎥
⎢ 3 3
⎥ ⎢ 2 2
⎥
⎢ ⎥ ⎢ ⎥
⎢ 0 0 1
⎥ ⎢ 0 0 1
⎥
⎢⎣
⎥⎦
⎢⎣
⎥
⎦
σh ⋅ Cn (θ ) = Sn (θ )
⎡1 0 0
⎤ ⎡ cos θ sin θ
0
⎤
⎡
cos θ sin θ
0⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥
⎢0 1 0
⎥ ⋅
⎢ −
sin θ cos θ
0
⎥ =
⎢ −
sin θ cos θ
0
⎥
⎢⎣0 0
−
1⎥⎦ ⎢⎣
0 0 1
⎥⎦
⎢⎣
0 0
−
1⎥⎦
Another example:
⎡1 0 0
⎤
⎡
−
1 0 0
⎤
⎡
−
1 0 0
⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥
⎢0 1 0⎥ ⋅
⎢ 0 − 1 0
⎥ =
⎢ 0
−
1 0⎥
⎢⎣0 0
−
1⎥⎦ ⎢⎣
0 0 1⎥⎦
⎢⎣
0 0
−
1⎥⎦
σ xy (≡ σ h ) ⋅ C2 (z) = i