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5.04 Principles of Inorganic Chemistry II ��

Fall 2008

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 5.04, Principles of Inorganic Chemistry II
Prof. Daniel G. Nocera
Lecture 1: Symmetry Elements and Operations

Consider the symmetry properties of an object (e.g. atoms of a molecule, set of

orbitals, vibrations). The collection of objects is commonly referred to as a basis set
J classify objects of the basis set into symmetry operations
J symmetry operations form a group
J group mathematically defined and manipulated by group theory

A symmetry operation moves an object into an indistinguishable orientation

A symmetry element is a point, line or plane about which a symmetry operation

is performed

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 )

5.04, Principles of Inorganic Chemistry II Lecture 1

Prof. Daniel G. Nocera Page 1 of 5
3) inversion, i
i (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 )

5) improper rotation axis, Sn

two step operation: Cn followed by σ through plane ⊥ to Cn

S4 (z)(x1, y1, z1 ) = σ (xy) C4 (z)(x1, y1, z1 ) = σ (xy)(y1,–x1, z1 ) = (y1,−x1 − z1 )

Note: rotation of pt is clockwise; Corollary is that axes rotate counterclockwise

relative to fixed point

In the example above, we took the direct product of two operators:

n n n
σ h ⋅ Cn = Sn for n even : Sn = Cn ⋅ σ h = E ⋅ E = E
n n n
for n odd: Sn = Cn ⋅ σ h = E ⋅ σ h = σ h
2n 2n 2n
Sn = Cn ⋅ σh = E ⋅ E = σh
Horizontal mirror plane
(normal to Cn)
m m m m
for m even: Sn = Cn ⋅ σh = Cn
m m m m m
for m odd: Sn = Cn ⋅ σh = Cn ⋅ σ h = Sn

5.04, Principles of Inorganic Chemistry II Lecture 1

Prof. Daniel G. Nocera Page 2 of 5
 v
Symmetry operations may be represented as matrices. Consider the vector v

Convention is that the principal

axis of rotation (rotation axis
with highest n) positioned to be
coincident with the z axis

⎡
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⎥⎦

5.04, Principles of Inorganic Chemistry II Lecture 1

Prof. Daniel G. Nocera Page 3 of 5
4) proper rotation axis:

because of convention, φ, and hence zi, is not transformed under Cn(θ) ∴

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 )

using identity relations:

v v v
x2 = v cos (θ − α ) = v cos θ cos α + v sinθ sin α = x1 cos θ + y1 sinθ
v v v
y2 = – v sin (θ − α ) = −[v sinθ cos α − v cos θ sinα ] = −x1 sinθ + y1 cosθ

Reformulating in terms of matrix representation:

⎡
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.

5.04, Principles of Inorganic Chemistry II Lecture 1

Prof. Daniel G. Nocera Page 4 of 5
The above matrix representation is completely general for any rotation θ…
2π

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
⎥
⎢⎣
⎥⎦
⎢⎣
⎥
⎦

5) improper rotation axis :

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⎥⎦

Like operators themselves, matrix operations may be manipulated with simple

matrix algebra…above direct product yields matrix representation for Sn.

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

5.04, Principles of Inorganic Chemistry II Lecture 1

Prof. Daniel G. Nocera Page 5 of 5