Lecture 4
Crystal Geometry
and
Structure Determination
Recap
Crystal = Lattice + Motif/basis
Unit cell: Size and shape can be characterized by
defining the lattice parameters
Primitive and non-primitive unit cell
Symmetry in lattice: Rotational symmetry, translation
symmetry and mirror symmetry
UNIT CELLS OF A LATTICE
Nonprimitive cell
Primitive
cell
If the lattice
points are only
at the corners,
the unit cell is
primitive
otherwise nonprimitive
A unit cell of a
lattice is NOT
unique.
Primitive
cell
Unit cell shape
CANNOT be the
basis for
classification of
Lattices
UNIT CELLS OF A LATTICE
Can we select a
triangular unit
cell? Since it can
give a very small
repeat unit
Primitive
cell
Unit cell is a small volume
of the crystal which by
periodic repetition
generates the entire
crystal (without overlaps
or gaps)
Symmetry of lattices
Lattices have
Translational symmetry
Rotational symmetry
Reflection symmetry
What is the basis for
classification of lattices
into
7 crystal systems
and
14 Bravais lattices?
Based on the complete symmetry, i.e.,
rotational, reflection and translational
symmetry
14 types of lattices
14 Bravais lattices
7 crystal Systems
Defining
symmetry
Crystal system
Conventional
unit cell
Cubic
a=b=c, ===90
Tetragonal
a=bc, ===90
Orthorhombic abc, ===90
Hexagonal
Rhombohedral a=b=c, ==90
Monoclinic
none
Triclinic
a=bc, == 90, =120
abc, ==90
abc,
8/87
Lets consider one by one each lattice
and its corresponding defining symmetry
1. Cubic Crystals
a = b= c
= = = 90
Simple cubic
Primitive cubic
Cubic P
Body-centred cubic
Cubic I
Face-centred cubic
Cubic F
Why end centred cubic is missing?? Will address later
Common Symmetry in Cube
3-4 fold
4-3 fold
6-2 fold
Cubic symmetry
4 triads: 4 body diagonals
12
2. Tetragonal Crystals
a=bc
= = = 90
Possible lattices
Simple Tetragonal
Body Centred Tetragonal BCT
Primitive
Body centred
Common Symmetry in Tetragonal
1-4 fold
2-2 fold
Tetragonal symmetry
1 tetrad
15
3. Orthorhombic Crystals
abc
= = = 90
All lattices are possible
Simple Orthorhombic
Body Centred Orthorhombic
Face Centred Orthorhombic
End Centred Orthorhombic
Common Symmetry in Orthorhombic
3-2 fold
4. Hexagonal Crystals
a=bc
= = 90
= 120
Only possible lattice
Simple Hexagonal
Note that unit cell of hexagonal lattice is 120 degree
Rhombic prism
Actual hexagonal lattice is the composite of three such
Lattices
We draw this to visualise the hexagonal symmetry
Common Symmetry in Hexagonal
1-6 fold
3-2 fold symmetry
5. Trigonal/Rhombohedral Crystals
a=b=c
= = 90
Only possible lattice
Rhombohedral (simple)
Pull the cubic lattice along body diagonal the distortion will
be such that it will satisfy trigonal condition
Common Symmetry in Trigonal
1-3 fold (along the diagonal where we pulled)
6. Monoclinic Crystals
abc
= = 90
Two possible variants
Simple Monoclinic
End Centred (base centered) Monoclinic
(A/C)
Squashing of Orthorhombic lattice can lead to formation
of monoclinic lattice
Common Symmetry in Monoclinic
1-2 fold (along b)
7. Triclinic Crystals
abc
Simple Triclinic
No symmetry
Why we do not have 28 (7x4=28)
Bravais lattices?? We only have
half of this!
Why some of them are missing??
25
To answer this
Two arguments can be put forth
Symmetry based
Size based
26
Missing Bravais lattices
Why C-centred
Cubic is missing
Crystal system
Bravais lattices
1. Cubic
2. Tetragonal
3. Orthorhombic
4. Hexagonal
5. Trigonal
6. Monoclinic
7. Triclinic
If you create end centred cubic then you
loose characteristic symmetry of cubic
system
You will also loose cubic 3-4 fold symmetry
The characteristic symmetry has been
destroyed so it can not be cubic lattice
28
End-centred cubic not in the Bravais list ?
Alternative
Choice of
Unit cell
Primitive cell
Smaller cell
End-centred cubic = Simple Tetragonal
14 Bravais lattices divided into seven crystal
systems
Crystal system
Bravais lattices
1. Cubic
2. Tetragonal
3. Orthorhombic
4. Hexagonal
5. Trigonal
6. Monoclinic
7. Triclinic
Missing Bravais lattices
Crystal system
Bravais lattices
1. Cubic
2. Tetragonal
3. Orthorhombic
4. Hexagonal
5. Trigonal
6. Monoclinic
7. Triclinic
Face centred tetragonal = Body centred
tetragonal
Smaller sized body centred tetragonal is
chosen
This choice of
unit cell is
smaller in size
32
14 Bravais lattices divided into seven crystal
systems
Crystal system
Bravais lattices
1. Cubic
2. Tetragonal
3. Orthorhombic
4. Hexagonal
5. Trigonal
6. Monoclinic
7. Triclinic
Missing Bravais lattices
Crystal system
Bravais lattices
1. Cubic
2. Tetragonal
3. Orthorhombic
4. Hexagonal
5. Trigonal
6. Monoclinic
7. Triclinic
?
C
Symmetry is not an issue here only the choice of unit
cell is important
End centred Tetragonal = Simple tetragonal
35
14 Bravais lattices divided into seven crystal
systems
Crystal system
Bravais lattices
1. Cubic
2. Tetragonal
3. Orthorhombic
4. Hexagonal
5. Trigonal
6. Monoclinic
7. Triclinic
F
C
F
Missing Bravais lattices
Crystal system
Bravais lattices
1. Cubic
2. Tetragonal
3. Orthorhombic
4. Hexagonal
5. Trigonal
6. Monoclinic
7. Triclinic
37
Why cant the FaceCentred Cubic lattice
(Cubic F) be considered
as a Body-Centred
Tetragonal lattice
(Tetragonal I) ?
14 Bravais lattices divided into seven crystal
systems
Crystal system
Bravais lattices
1. Cubic
2. Tetragonal
3. Orthorhombic
4. Hexagonal
5. Trigonal
6. Monoclinic
7. Triclinic
Face-centred cubic in the Bravais list ?
Cubic F = Tetragonal I ?!!!
Tetragonal symmetry
Cubic C = Tetragonal P
Cubic symmetry
41/87
Cubic F Tetragonal I
Summary
Crystal and crystal systems are defined based on
Symmetry not on unit cell geometry
For instance
Cubic crystal does not mean a=b=c, = = = 90
It implies the existence of 4-3 fold axis in the structure
The choice of unit cell is based on size and symmetry
42
