Symmetry and Properties of Crystals

(MSE638)
2D Point Groups

Somnath Bhowmick

Materials Science and Engineering, IIT Kanpur

January 16, 2015

Group theory
A set G is a group under an operation ? if it has the following properties:
1 Closure: For every a, b G, a ? b G

2 Associativity: a ? (b ? c) = (a ? b) ? c

3 Identity: There is an unit element 1 in G such that 1 ? a = a ? 1 = a

for every a in G
4 Inverse: There must be an inverse element a1 for every a, such that

a1 ? a = a ? a1 = 1
5 Commutativity: This is not compulsory, however if a ? b = b ? a, then

G is called a commutative or abelian group.

Example: real numbers form a abelian group under the operation of
addition
Example: set of counter clockwise vector rotations:
 
cos sin
R() =
sin cos
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Discrete group

Groups with finite number of elements

Let (1, a, b, c) be the elements of a group of rank 4, combined
according to multiplication table
1 a b c
1 1 a b c
a a b c 1
b b c 1 a
c c 1 a b
Let 1 = 1, a = i, b = 1, c = i; ? = ordinary multiplication
Group elements are complex numbers (1, i, 1, i)
Commutative or abelian group: a ? b = b ? a etc.
Cyclic group (all elements in successive powers of one element):
in , i = 0, 1, 2, 3
Group elements are successive 90 rotations in complex plane
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Discrete group

Let us examine the discrete group formed by R(), when

= 0, /2, , 3/2,
       
1 0 0 1 1 0 0 1
1=I= ,A = ,B = ,C =
0 1 1 0 0 1 1 0

Group elements are four matrices: (1, A, B, C); ? = matrix

multiplication
Check whether Abelian and cyclic
One to one correspondence between (1, i, 1, i) and (I, A, B, C) -
isomorphic representation
Elements of a group can be real/complex numbers, matrices ......
The operation ? that combines two elements of a group can be
addition, ordinary multiplication, matrix multiplication .....
Symmetry is defined as invariance of a system under a group of
transformations
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How to build a crystal

In four steps:
1 One step symmetry operation in 2D: T , m, 1, 2, 3, 4, 6
2 Point group: combination of symmetry operations without translation
3 Plane group: combination of symmetry operations with translation
4 Wyckoff positions: where to put atoms/molecules to get a crystal from
space group
There are 7 one step symmetry operations, 10 point groups and 17
plane groups in 2D

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Crystallographic point group

Example: combine successive 4-fold rotations about a fixed point

Do two 4-fold rotations and find out is there any one step operation
that can relate the first and third motif?
If they form a group, then there has to be a one step operation to
relate motif 1 and motif 3
For example: 4 ? 4 = 42 = 2, 4 ? 4 ? 4 = 43 = 41 , 4 ? 4 ? 4 ? 4 = 1
Symmetry elements of the point group {1, 2, 4, 41 } - rank is 4,
which is also equal to the number objects in the pattern
Point group: a group of geometric symmetries that keep one point
fixed
Representation: stereographic projection and multiplication table 6 / 20
Point group 1

It is a group of geometric symmetries that keep one point fixed

Point group 1 = {1} = I
Multiplication table
1
1 1
Rotation matrices: = 360
 
1 0
1=I=
0 1

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Point group 2

Point group 2 = {1, 2}

Multiplication table
1 2
1 1 2
2 2 1
Rotation matrices: = 180


1 0
2=
0 1

Remember that 2 = 21
Cyclic group 22 = 1

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Point group m

Point group m = {1, m}

Multiplication table
1 m
1 1 m
m m 1
Reflection matrix
 
cos 2 sin 2
m() =
sin 2 cos 2

Remember that m = m1

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Point group 3

Point group 3 = {1, 3, 31 }

Multiplication table
1 3 31
1 1 3 31
3 3 31 1
31 31 1 3

Rotation matrices: 3( = 120 ) and 31 ( = 120 )

   
1/2 3/2
1 1/2
3/2
3= ,3 =
3/2 1/2 3/2 1/2

Cyclic group 32 = 31 , 33 = 1
3 generates the other symmetry elements of the group

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Point group 4

Point group 4 = {1, 2, 4, 41 }

Multiplication table
1 2 4 41
1 1 2 4 41
2 2 1 41 4
4 4 41 2 1
41 41 4 1 2

Rotation matrices: 4( = 90 ) and 41 ( = 90 )

   
0 1 1 0 1
4= ,4 =
1 0 1 0

Cyclic group 42 = 2, 43 = 41 , 44 = 1
4 generates the other symmetry elements of the group

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Point group 6
Point group 6 = {1, 2, 3, 31 , 6, 61 }
Multiplication table
1 2 3 31 6 61
1 1 2 3 31 6 61
2 2 1 61 6 31 3
3 3 61 31 1 2 6
3 1 31 6 1 3 61 2
6 6 31 2 61 3 1
6 1 61 3 6 2 1 31
Rotation matrices: 6( = 60 ) and 61 ( = 60 )
   
1/2 3/2
1 1/2
3/2
6= ,6 =
3/2 1/2 3/2 1/2
Cyclic group 62 = 3, 63 = 2, 64 = 31 , 65 = 61 , 66 = 1
6 generates the other symmetry elements of the group
There are two subgroups: {1, 2} and {1, 3, 31 }
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Combine reflection with a rotation
How to combine two reflections at a common point?

Lm1 = , Lm2 = , m1 m2 = . Is there any symmetry

operation that takes the first L to third L directly?
m2 ? m1 = A2 , i.e., two reflections= one rotation
Values of compatible to the lattice: 30 , 45 , 60 , 90
Similarly, m2 ? A2 = m1 , where m1 m2 =
Conclusion: two mirror planes can intersect only at certain angles,
determined by allowed crystallographic rotation axes
Next: combine two mirrors at 90 , 45 , 30 , 60
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2mm

Two mirrors intersecting at 90 angle - there must be a rotation A2

Lets check the group multiplication table
1 m1 m2 2
1 1 m1 m2 2
m1 m1 1 2 m2
m2 m2 2 1 m1
2 2 m2 m1 1
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4mm

Two mirrors intersecting at 45 angle - there must be a rotation A 4

4-fold rotation gives the two other mirrors - for example start with
my , m45 and presence of A 4 gives two other mirrors mx , m45 .
Rank 8: {1, 2, 4, 41 , my , m45 , mx , m45 }
4, my , m45 generate all the other symmetry elements of the group
Thus the point group is called 4mm
Square - two types of mirror planes
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3m

Two mirrors intersecting at 60 angle - there must be a rotation A 3

3-fold rotation gives the third mirror - for example start with my , m30
& A 6 gives the third mirror m30
Rank 6: {1, 3, 31 , my , m30 , m30 }
3, my generate all the other symmetry elements of the group
Thus the point group is called 3m
Equilateral triangle - only one type of mirror plane
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6mm

Two mirrors intersecting at 30 angle - there must be a rotation A 6

6-fold rotation gives the four other mirrors - for example start with
my , m60 & A 6 gives four other mirrors m30 , mx , m30 , m60 .
Rank 12: {1, 2, 3, 31 , 6, 61 , my , m60 , m30 , mx , m30 , m60 }
6, my , m60 generate all the other symmetry elements of the group
Thus the point group is called 6mm
Hexagon - two types of mirror planes
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List of 2D point groups

Hermann-Mauguin Sch
onflies
1 1 C1
2 2 C2
3 m Cs
4 2mm C2v
5 4 C4
6 4mm C4v
7 3 C3
8 3m C3v
9 6 C6
10 6mm C6v

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Point group of ammonia molecule

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Point group of benzene molecule

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