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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,

(xz)(x1, y1,z1 ) = (x1,y1,z1 )

5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera

Lecture 1 Page 1 of 5

3) inversion, i

i (x1,y1,z1 ) = ( x1,y1,z1 )
4) proper rotation axis, Cn (where =

2 ) 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 through plane to Cn

S4 (z)(x1, y1, z1 ) = (xy) C4 (z)(x1, y1, z1 ) = (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:

h Cn = Sn

for n even : Sn = Cn h = E E = E for n odd:

Sn = Cn h = E h = h
Sn
2n n n n

Horizontal mirror plane (normal to Cn)

= Cn = Cn

2n

h h

2n

= E E = h = Cn
m

for m even: Sn for m odd:

Sn

= Cn

= Cn

h = Sn

5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera

Lecture 1 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

x
1 1) identity: E
y1 =
z1

x x1

1
y1 =
y1 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

x
1

x1
2) reflection:
(xy) y1 =
y1 z1
z1

0 0

1 similarly (xz) =
0 1 0
0 0 1

1 0
0

(xy) =
0 1
0 0 0
1
1 0 0
(yz) =
0 1 0 0 0 1

and

x
1
x1 3) inversion: i y1 =

y1 z1

z1

0
0 1 i =
0 1
0 0 0
1

5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera

Lecture 1 Page 3 of 5

4) proper rotation axis:

because of convention, , and hence zi, is not transformed under Cn()
projection into xy plane need only be considered i.e., rotation of vector v(xi,yi)
through

v v v x1 = v cos x2 = v cos [ ( )] = v cos ( ) Cn ( ) v v v y1 = v sin y2 = v sin [ ( )] = v sin ( )

using identity relations:

v v v x2 = v cos ( ) = v cos cos + v sin sin = x1 cos + y1 sin v v v y2 = v sin ( ) = [v sin cos v cos sin ] = x1 sin + y1 cos
Reformulating in terms of matrix representation:

x
1

x1 cos + y1 sin
Cn( )
y1 =
x1 sin +
y1 cos z1 z1




cos
Cn( ) =
sin 0
0 cos
0 0 1
sin 2
n

where
=

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 Prof. Daniel G. Nocera

Lecture 1 Page 4 of 5

The above matrix representation is completely 2

Example: C3 , = n
2 2
3


1 sin 0
cos 3 3
2
2 2 2
3 1
C3 =

sin cos 0
=


3 3
2
2 0 0 0 1
0


5) improper rotation axis :

general for any rotation

0
0
1

h
1 0 0 0

Cn ( )

Sn ( )
0
cos
0
0

1 sin

0
cos 1 0


sin 0

1 0

sin
0


cos cos
0
=

sin 0 0 1

Like operators themselves, matrix operations may be manipulated with simple matrix algebraabove direct product yields matrix representation for Sn. Another example:

0

1 0 0

1 0 0
1 0




0
0 1 0
=
0

1 0 0 1 0 0

1 0 0 1 0 0

1

xy ( h )

C2 (z)

5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera

Lecture 1 Page 5 of 5