Symmetry In Crystals

CH106| SYMMETRY AND GROUP THEORY IN CHEMISTRY

We understand……….

Lattice
Unit Cells
Crystal Systems
Bravais Lattice
 Symmetry Introduction
 Symmetry defines the order resulting from how atoms are arranged and
oriented in a crystal
 Study the 2-D and 3-D order crystals
 Dothis by defining symmetry operators (there are 13 total)  actions
which result in no change to the order of atoms in the crystal structure
 Combining different operators gives point groups – which are
geometrically unique units.
 Everycrystal falls into some point group, which are segregated into 7
major crystal systems
 2D
Lattice
1D
2-D Symmetry Operators

 Mirror Planes (m) – reflection along a plane

A line denotes mirror

planes
 2-D Symmetry Operators
 Rotation Axes (1, 2, 3, 4, or 6) – rotation of 360, 180, 120, 90, or 60º
around a rotation axis yields no change in orientation/arrangement

2-fold

3-fold

4-fold

6-fold
2-D Symmetry Operators

2-fold

3-fold

4-fold

6-fold
 2-D Point groups
 All possible combinations of the 5 symmetry operators: m, 2, 3, 4, 6, then combinations of the rotational
operators and a mirror yield 2mm, 3m, 4mm, 6mm
 Mathematical maximum of 10 combinations

4mm
2D Space Groups-----17
Two dimensional space symmetries
Two dimensional space symmetries
3-D Symmetry Operators

 Mirror Planes (m) – reflection along any plane in 3-D space

 3-D Symmetry Operators
 Rotation Axes (1, 2, 3, 4, or 6 a.k.a. A1, A2, A3, A4, A6) – rotation of
360, 180, 120, 90, or 60º around a rotation axis through any angle yields
no change in orientation/arrangement
5 or 8 fold axis of Symmetry!!!!!!!
3-D Symmetry Operators

 Inversion (i) – symmetry with respect to a point, called an inversion center

1
1
3-D Symmetry Operators

 Rotoinversion (1, 2, 3, 4, 6 a.k.a. A1, A2, A3, A4, A6) – combination of

rotation and inversion. Called bar-1, bar-2, etc.
 1,2,6 equivalent to other functions
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

1: Rotate 360/4
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

1: Rotate 360/4

2: Invert
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

1: Rotate 360/4

2: Invert
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

3: Rotate 360/4
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

3: Rotate 360/4

4: Invert
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

3: Rotate 360/4

4: Invert
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

5: Rotate 360/4
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

5: Rotate 360/4

6: Invert
 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

This is also a unique operation

 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

d. 4-fold rotoinversion ( 4 )

A more fundamental representative of the pattern

 3-D Symmetry
NEW SYMMETRY ELEMENTS
4. ROTOINVERSION

c. 3-fold rotoinversion ( 3 )
3
5 1
This is unique

4 2
6
3-D Symmetry Operators


Mirror planes
┴ rotation axes (x/m) – The combination of mirror planes and
rotation axes that result in unique transformations is represented as 2/m, 4/m, and
6/m
3-D Symmetry
3-D SYMMETRY ELEMENT COMBINATIONS
a. Rotation axis parallel to a mirror
Same as 2-D
2 || m = 2mm
3 || m = 3m, also 4mm, 6mm
b. Rotation axis  mirror
2  m = 2/m
3  m = 3/m, also 4/m, 6/m
c. Most other rotations + m are impossible
Point Groups
 Combinations of operators are often identical to other operators or combinations – there are 13
standard, unique operators
 I, m, 1, 2, 3, 4, 6, 3, 4, 6, 2/m, 4/m, 6/m
 These combine to form 32 unique combinations, called point groups
 Point groups are subdivided into 7crystal systems
 3-D Symmetry
Crystal System No Center Center
Triclinic 1 1
Monoclinic 2, 2 (= m) 2/m
Orthorhombic 222, 2mm 2/m 2/m 2/m
Tetragonal 4, 4, 422, 4mm, 42m 4/m, 4/m 2/m 2/m
Hexagonal 3, 32, 3m 3, 3 2/m
6, 6, 622, 6mm, 62m 6/m, 6/m 2/m 2/m
Isometric 23, 432, 43m 2/m 3, 4/m 3 2/m
Crystal family Crystal system Required symmetries of the Point Space Bravais l Lattice system
(6) (7) point group groups groups attices
Triclinic None 2 2 1 Triclinic
Monoclinic 1 twofold axis of rotation or 1  3 13 2 monoclinic
mirror plane
Orthorhombic 3 twofold axes of rotation or 1 3 59 4 Orthorhombic
twofold axis of rotation and 2
mirror planes
Tetragonal 1 fourfold axis of rotation 7 68 2 Tetragonal
Hexagonal Trigonal 1 threefold axis of rotation 5 7 1 Rhombohedral
18 1 Hexagonal
Hexagonal 1 sixfold axis of rotation 7 27
Cubic 4 threefold axes of rotation 5 36 3 Cubic
6 7 Total 32 230 14 7
 Hexagonal class

Rhombohedral
form Hexagonal
form
Glide plane
Glide plane