Different choices for the basis

Lattice +basis=crystal structure

Fourteen Bravais Lattices
 Exercise

Explain why there is no base-centered cubic lattice or face-

centered tetragonal lattice.

base-centered cubic lattice

face-centered tetragonal lattice
No base-centered cubic lattice

Consider it in another way :

No face-centered tetragonal lattice

A body-centered tetragonal lattice !

 • 2D Bravais lattices

Five Bravais lattices in two dimension

斜晶格 六角形晶格

正方形晶格 矩形晶格 中心矩形晶格

Primitive cell of BCC lattice
Primitive cell of FCC lattice
Primitive cell of HCP lattice
 Close packing (密堆积)

Close-packing of spheres is the arranging of an infinite lattice of spheres so

that they take up the greatest possible fraction of an infinite 2D or 3D space.

Primitive packing
(low space filling)

Close packing
(high space filling)
 Coordination Number (配位数)

Coordination number (CN) - the total number of neighbors of a central atom

CN = 4

CN = 6: the maximum possible for

2D packing.
From 2D to 3D lattice

simple cubic
sc (CN=6)

hexagonal close packing

hcp (CN=12)
 Crystal lattices commonly found in nature

body-centered cubic face-centered cubic

CN = 8 CN = 12 CN = 12 CN = 4

The diamond lattice is consist of two interpenetrating face

centered Bravais lattices.
Cubic crystals: SC, BCC, FCC
 Cubic crystals: SC, BCC, FCC

Unit Cell Net Number of Atoms CN

SC 1 6 Second neighbors are
BCC 2 8 important for BCC
FCC 4 12
Packing Fraction
• Packing Fraction (PF) is defined as the volume of
atoms within the unit cell divided by the volume of
the unit cell.

17
Packing Fraction of FCC

= V atoms = 0.74
PF FCC
V unit cell

4 (0.353a)

18
Characteristics of cubic lattices

aThe packing fraction is the maximum proportion of the available volume

that can be filled with hard spheres.
 Close packed structures

A plane

B plane

C plane

A plane

…ABCABCABC… packing …ABABAB… packing

 HCP and CCP (FCC) packing

Cubic close packed

Hexagonal close packed
Face-center close packed
ABABAB…
ABCABCABC…
Close-packed structures: hcp vs. fcc
HCP FCC
HCP and CCP (FCC)

hexagonal close packing (hcp)

(Be, Mg, Zn, Cd, Ti, Zr, Ru ...)

cubic close packing (ccp or fcc)

(Cu, Ag, Au, Al, Ni, Pd, Pt ...)
 Elementary solid in FCC, BCC, SC forms

FCC and BCC Bravais lattices are of great importance. An enormous variety of
solids crystallize in these forms.

• Elements with the monatomic FCC crystal structure:

Ar, Ag, Al, Au, Ca, Ce, Cu, La, Ne, Ni, Pb, …

• Elements with the monatomic BCC crystal structure:

Ba, Cr, Cs, Fe, K, Li, Mo, Na, Nb, W, …

• Only element with the monatomic SC crystal structure:

a-polonium (钋).
Crystal Structures of Elementary Metals
Metals usually have one of three structure types:
ccp=fcc, hcp or
bcc (body centred cubic)

Sc Ti V Cr Mn Fe Co Ni Cu Zn

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

La Hf Ta W Re Os Ir Pt Au Hg
hcp
ccp = fcc
bcc

The reasons why a particular metal prefers a particular

structure are still not well understood.
Open-access collection of crystal structures of organic, inorganic,
metal-organic compounds and minerals, excluding biopolymers.

http://www.crystallography.net/cod/
 3D close packing from 2D: HCP and FCC

Hexagonal close packed Cubic close packed (FCC)

28
 Primitive lattice vector

 a
a1 = (xˆ  yˆ)
2
 a
a2 = (yˆ  zˆ)
2
 a
a3 = (xˆ  zˆ)
2

Rhombohedral Primitive cell

The angle between two adjacent edges : 60o

Edge : 2
2
Zinc Sulfide structure

The diamond lattice is consist of two interpenetrating face

centered bravais lattices.
 a1 = a2 , with an included angle 1200
c = 1.633 a 1

a1, a2, and c do not construct a primitive

lattice
a1, a2, and a3 construct a primitive lattice

a1 = a2 = a3
12 nearest neighbors
Transition metals : Sc, Y, Ti, Zr, Co…
IIA metals : Be, Mg

Hexgonal lattice + basis of 2 atoms at (0,0,0) and (2/3,1/3,1/2)

 Chapter One
Crystal structure
• Periodic arrays of atom
• Fundamental types of lattices
• Index system for crystal planes
• Simple crystal structure
 Directions and planes in crystals

a. Crystal Directions
1. We choose one lattice point on the line
as an origin, say the point O. Choice of
origin is completely arbitrary, since
every lattice point is identical.
2. Then we choose the lattice vector joining O to
any point on the line, say point T. This vector can
be written as;
R = n1 a + n2 b + n3c
3. To distinguish a lattice direction from a lattice
point, the triple enclosed in square brackets [...]
is used. [n1 n2 n3] is the smallest reduced integer
of the same relative ratios. Fig. Shows [111]
direction
Examples

210

X=1,Y=½,Z=0 X=½ ,Y=½,Z=1

[1 ½ 0] [2 1 0] [½ ½ 1] [1 1 2]
Cubic has highest symmetric directions
Negative directions

• When we write the direction [n1 n2 n3]

depend on the origin, negative Z direction
directions can be written as

[n1n2 n3 ] - X direction
(origin) O
R = n1a + n2b + n3c - Y direction Y direction
[n1n 2n 3 ]
• Direction must be X direction
- Z direction
smallest integers.
Examples 1

X=1,Y=0,Z=0 [1 0 0] X = -1 , Y = -1 , Z = 0 [110]
X=1,Y=1,Z=0 [1 1 0]
 Example 2

X = -1 , Y = 1 , Z = -1/6
We can move vector to the origin. [-1 1 -1/6] [6 6 1]
A family of crystal directions
z

[1 0 0]、[0 1 0]、[0 0 1]
y [1̅ 0 0]、[0 1̅ 0]、[0 0 1̅ ]

x
<1 0 0>
Equivalent sets of crystal directions < > angular/angle brackets
b. Crystal planes
• Within a crystal lattice it is possible to identify sets of
equally spaced parallel planes. These are called lattice
planes.
• In the figure, density of lattice points on each plane of a
set is the same and all lattice points are contained on
each set of planes.

The set of
planes in
b b
2D lattice.
a a
Same lattice, two sets of crystal planes.
Miller Indices
Miller Indices are a symbolic vector representation for
the orientation of an atomic plane in a crystal lattice.
Notes:

1) Determine the intercepts of the

plane along each of the three
crystallographic directions.

2) Take the reciprocals of the

intercepts.

3) If fractions result, multiply each by

the denominator of the smallest
fraction.

( ) round brackets; parentheses

42
Example-1

Axis X Y Z
Intercept
points 1 ∞ ∞
Reciprocals 1/1 1/∞ 1/∞
Smallest
Ratio 1 0 0

(1,0,0)
Miller Indices (100)
Example-2

Axis X Y Z
Intercept
points 1 1 ∞
Reciprocals 1/1 1/1 1/∞
Smallest
Ratio 1 1 0
(0,1,0)

Miller Indices (110)

(1,0,0)
Example-3

Axis X Y Z
(0,0,1)
Intercept
points 1 1 1
Reciprocals 1/1 1/1 1/1
Smallest
(0,1,0) Ratio 1 1 1

(1,0,0) Miller Indices (111)

Example-4

Axis X Y Z
Intercept
points 1/2 1 ∞
Reciprocals 1/(½) 1/1 1/∞
Smallest
(0,1,0) Ratio 2 1 0
(1/2, 0, 0)
Miller Indices (210)
Example-5

Axis a b c
Intercept
points 2 ∞ 1
Reciprocals 1/2 1/∞ 1/1
Smallest
Ratio 1 0 2

Miller Indices (102)

Example-6
Six kinds of planes in cubic crystal
A family of lattice planes

(0ī0) (00ī)

Equivalent sets of Miller indices

{100} curly brackets

In cubic crystals the direction [hkl] is perpendicular to a plane (hkl) having

the same indices, but this is not generally true in other crystal systems.
Multiplicity of {hkl}

= # of (hkl) in {hkl}

For cubic systems

Mult {100} = 6

Mult {123} = 48 2
 Chapter One
Crystal structure
• Periodic arrays of atom
• Fundamental types of lattices
• Index system for crystal planes
• Simple crystal structure
IV. The MOST IMPORTANT
CRYSTAL STRUCTURES

1. Sodium Chloride Structure

• Sodium chloride
structure consists of
equal numbers of
sodium and chlorine
ions placed at alternate
points of a simple cubic
lattice.
• Each ion has six of the
other kind of ions as its
nearest neighbours.

CN = 6
SC Structure ?
 •LiF, NaBr, KCl, LiI, etc.

FCC Structure !
 2. Cesium Chloride Structure Cs+Cl-

• Cesium chloride crystallizes in a cubic

lattice. The unit cell may be depicted as
shown. (Cs+ is teal, Cl- is gold).

• Cesium chloride consists of equal numbers of

cesium and chlorine ions, placed at the points
of a body-centered cubic lattice so that each
ion has eight of the other kind as its nearest
neighbors.
CN = 8
BCC structure?
• The translational symmetry of this structure is that of
the simple cubic Bravais lattice, and is described as a
simple cubic lattice with a basis consisting of a
cesium ion at the origin 0 and a chlorine ion at the
cube center   
a / 2( x  y  z )

SC Structure !
3. Hexagonal Close-Packed lattice
1th step: Spheres are arranged
in a single closed-packed layer
A by placing each sphere in
contact with six others.

A
2th step: A second similar layerB
bottom B may be added by
placing each sphere of B in
contact with three spheres of
the bottom layer. HCP (-A-B-) FCC (A-B-C)

3th step: A third layer C may be

added in two way.
4. Diamond Structure
• The diamond lattice is consist of two interpenetrating
face centered bravais lattices.
• There are eight atom in the structure of diamond.
• Each atom bonds covalently to 4 others equally
spread about atom in 3D.
Some atoms form multiple stable structures:
for example, C→diamond or graphite (hexagonal)

An STM image of a graphite surface

clearly shows the interconnected 6-
membered rings of graphite.
graphite diamond
 Fullerene

Graphene
5. ZnS

cubic hexagonal

zincblende/sphalerite wurtzite
6. Perovskite structure CaTiO3 ABO3 BaTiO3

5 atom/Unit cell

67
BCC

SiF4 MoAl12, WAl12

 Summary

• A crystal structure is a unique arrangement of atoms in a crystal.

• A crystal structure is composed of a motif, a set of atoms arranged in a
particular way, and a lattice. Motifs are located upon the points of a lattice,
which is an array of points repeating periodically in three dimensions. The
points can be thought of as forming identical tiny boxes, called unit cells, that
fill the space of the lattice.
• The lengths of the edges of a unit cell and the angles between them are called
the lattice parameters.
• The symmetry properties of the crystal are embodied in its space group.
• A crystal’s structure and symmetry play a role in determining many of its
properties, such as cleavage, electronic band structure, and optical properties.
Homework
P22: 1, 2, 3.

75
 Point group and space group

• Symmetry and symmetry operation

• Point group
• Space group
Symmetry everywhere
 Symmetry operation (对称操作)

• An operation applied to an object is an act of doing something to it.

• Symmetry operation: object apparently unchanged upon operation.
• Different symmetry operations
 identity operation, E (doing nothing)
 rotation (旋转) operator, C (successive rotation about main axis)
 a reflection (镜像反射), s (one half of an object is the mirror
image of the other half)
 inversion (反演), i (reflection through the centre of the molecule
to an equal distance on the opposite site)
 improper rotation (反射旋转), S (combination of reflection and
rotation)
 Translation (平移), T (not for molecule, only in solid)
n-fold (Cn) rotation

1-Fold Rotation. A 1-fold (E) rotation

operation implies either a 0° rotation or a 360°
rotation, and is referred to as
the identity operation.

2-Fold Rotation. A 2-fold (C2) rotation

operation moves the object by (360/2) ° = 180 °.
The symbol used to designate a 2-fold axis is a
solid oval.

3-Fold Rotation. A 3-fold (C3) rotation operation

moves the object by (360/3) ° = 120 °. The
symbol used to designate a 3-fold axis is a solid
equilateral triangle.
4-Fold Rotation. A 4-fold (C4) rotation
operation moves the object by (360/4) °
= 90 °. The symbol used to designate a
4-fold axis is a solid square.

6-Fold Rotation. A 6-fold (C6) rotation

operation moves the object by (360/6) °
= 60 °. The symbol used to designate a
6-fold axis is a solid hexagon.
 Rotation operator, Cn

• n-fold rotation: rotate the object with a factor 2p/n

2 1

C2 1 = 2

5 4
1 4 5 3
C5 =
2 3 1 2
 Reflection, s
– Mirror plane (镜面)
sv Vertical plane
sh Horisontal plane
sd (dihedral plane)

C6

sv

C5

sh
 Inversion, i

• Centre of symmetry
– reflection through the centre of the
molecule to an equal distance on the
opposite site.

Point of inversion, i
 n-fold improper rotation (反射旋转), Sn
• “rotary-reflection”
– combination operation consisting of
 n-fold rotation
 horizontal reflection in a plane perpendicular to the n-fold axis

1 4

C4 1
3
4 2

2 Plane of reflection, s 3

4 S4
1
2 S1 = s
S2 = i
3
 Properties of Symmetry Operations

– Symmetry operations combine according to the associative

law of multiplication
• (RS)T=R(ST)

– If R and S are symmetry operations of an object then RS is

also a symmetry operation

– The inverse of each symmetry operation is also a symmetry

operation
• R-1R= RR-1 =E
 Definition of group

A group is a set with a binary operation that satisfies certain axioms (公理)
defined below.

A group (G) is a set G with a binary operation * that satisfies the four axioms:

• Closure (封闭性): For all a, b in G, the result of a*b is also in G.

• Associativity (结合律): For all a, b and c in G, (a*b)*c = a*(b*c).
• Identity element (幺元存在性): There exists an element e in G such that for all
a in G, e*a = a*e = a.
• Inverse element (逆元存在性): For each a in G, there exists an element b in G
such that a*b = b*a = e, where e is an identity element.
 Point group

• Point groups can exist in a Euclidean space of any dimension. A discrete point
group in 2D is sometimes called a rosette group, and is used to describe the
symmetries of an ornament. The 3D point groups are heavily used in
chemistry, especially to describe the symmetries of a molecule and of
orbitals forming covalent bonds, and in this context they are also called
molecular point groups (分子点群).

• There are infinitely many discrete point groups in each number of

dimensions. However, the crystallographic restriction theorem demonstrates
that only a finite number are compatible with translational symmetry. In 1D
there are 2, in 2D 10, and in 3D 32 such groups, called crystallographic point
groups (晶体学空间群).
 Point groups in 2D

Point groups in 2D fall into two distinct families, according to whether they consist of
rotations only, or include reflections. The cyclic groups, Cn, consist of rotations by
360°/n, and all integer multiples. For example, a swastika 卐 has symmetry group C4,
consisting of rotations by 0°, 90°, 180°, and 270°. The symmetry group of a square □
belongs to the family of dihedral groups, Dn, including as many reflections as rotations.
 Point groups in 3D

In geometry a point group in 3D is an isometry group in three dimensions that

leaves the origin fixed, or correspondingly, an isometry group of a sphere.

For point groups, being finite corresponds to being discrete. The set of finite 3D
point groups consists of

• 7 infinite series with at most one more-than-2-fold rotation axis; they are the
finite symmetry groups on an infinite cylinder, or equivalently, those on a
finite cylinder.
• 7 point groups with multiple 3-or-more-fold rotation axes; they can also be
characterized as point groups with multiple 3-fold rotation axes

A selection of point groups is compatible with discrete translational symmetry: 27

from the 7 infinite series, and 5 of the 7 others, the 32 so-called crystallographic
point groups
 The Schöefies notation

A point group in the Schöenflies convention is completely adequate to describe

the symmetry of a molecule; this is sufficient for spectroscopy.

• C: Cyclic
• D: Dihedral
• S: Spiegel (mirror)
• h: horizontal
• v: vertical
• d: diagonal
• O: octahedron
• T: tetrahedron
• I: icosahedron
 The Hermann-Mauguin notation

The Hermann-Maunguin notation (also known as the International notation) is

able to describe the space group of a crystal lattice, while the Schöenflies
notation isn’t. Thus the Hermann-Maunguin notation is used in crystallography.
The Hermann-Mauguin notation, compared with the Schöenflies notation, is
preferred in crystallography because it can easily be used to include translational
symmetry elements, and it specifies the directions of the symmetry axes.
The Hermann-Mauguin notation
The Hermann-Mauguin notation
 Seven infinite series of point group
The infinite series have an index n, which can be any integer; in each series, the nth
symmetry group contains n-fold rotational symmetry about an axis, i.e. symmetry
with respect to a rotation by an angle 360°/n. The terms horizontal (h) and vertical
(v) are used with respect to a vertical axis of rotation. The seven infinite series are:
• Cn (nn )
• Cnh (n* )
• Cnv (*nn )
• Dn (22n )
• Dnh (*22n )
• Dnd (-n2m )
• S2n (nx )
Seven infinite series of point group
Seven infinite series of point group
Seven infinite series of point group
 Seven point groups of very high or polyhedral symmetry

• T (332) - chiral tetrahedral symmetry: there are four C3 axes, each

through two vertices of a cube (body diagonals) or one of a regular
tetrahedron, and three C2 axes, through the centers of the cube's faces
• Td (*332) - full tetrahedral symmetry: has the same rotation axes as T,
but with six mirror planes, each containing two edges of the cube or
one edge of the tetrahedron, a single C2 axis and two C3 axes.
• Th (3*2) - pyritohedral symmetry: has the same rotation axes as T, with
mirror planes parallel to the cubes faces. The C3 axes become S6 axes,
and there is inversion symmetry
• O (432) - chiral octahedral symmetry: like T, but the C2 axes are now C4
axes, and additionally there are 6 C2 axes, through the midpoints of the
edges of the cube
• Oh (*432) - full octahedral symmetry: has the same rotation axes as O,
but with mirror planes, comprising both the mirror planes of Td and Th
• I (532) - chiral icosahedral symmetry: contains 10 versions of D3 and 6
versions of D5
• Ih (*532) - full icosahedral symmetry: contains 10 versions of D3d and 6
versions of D5d
Fivefold symmetry cannot repeat the entire space
 Aperiodic tiling and quasi-crystals

Penrose tiling
 Quasi-crystals and noble prize of chemistry 2011

Section perpendicular to decagonal axis of Al-Co-Ni

Electron diffraction pattern from an icosahedral quasicrystal

The Nobel Prize in Chemistry 2011 was awarded to Dan

Shechtman "for the discovery of quasicrystals".
http://www.nobelprize.org/nobel_prizes/chemistry/laureates/201
1/
 Quasi-crystals and noble prize of chemistry 2011

Polyhedral arrangement in the a) 1:1 and

b) 2:1 icosahedral quasicrystal
approximants in the system Ca-Cd

Structural model for i-YbCd5.7 showing

the two distinct clusters that build
structure
 32 crystallographic point groups

In crystallography, a crystallographic point group is a set of symmetry operations,

like rotations or reflections, that leave a point fixed while moving each atom of
the crystal to the position of an atom of the same kind. That is, an infinite crystal
would look exactly the same before and after any of the operations in its point
group. In the classification of crystals, each point group corresponds to a crystal
class.

There are infinitely many 3D point groups, however, in crystallography they are
restricted to be compatible with the discrete translation symmetries of a crystal
lattice. This crystallographic restriction of the infinite families of general point
groups results in 32 crystallographic point groups.
32 crystallographic point groups in 3D crystals
32 种三维空间点群的关系
(Hermann-Mauguin 记号)
 Point group: summary

The crystallographic point group or crystal class is the mathematical group

comprising the symmetry operations that leave at least one point
unmoved and that leave the appearance of the crystal structure
unchanged. These symmetry operations can include reflection, which
reflects the structure across a reflection plane, rotation, which rotates the
structure a specified portion of a circle about a rotation axis, inversion
which changes the sign of the coordinate of each point with respect to a
center of symmetry or inversion point and improper rotation, which
consists of a rotation about an axis followed by an inversion. Rotation axes
(proper and improper), reflection planes, and centers of symmetry are
collectively called symmetry elements. There are 32 possible crystal
classes. Each one can be classified into one of the seven crystal systems.
 Space group
The space group of a crystal is a mathematical description of the symmetry
inherent in the structure.
Space group = Point group + Translation
+ Screw axis (螺旋轴) & Glide planes (滑移面)

The space groups in 3D are made from combinations of the 32 crystallographic

point groups with the 14 Bravais lattices which belong to one of 7 crystal
systems. This results in a space group being some combination of the
translational symmetry of a unit cell including lattice centering, and the point
group symmetry operations of reflection, rotation and improper rotation.
Furthermore one must consider the screw axis and glide plane symmetry
operations. These are called compound symmetry operations and are
combinations of a rotation or reflection with a translation less than the unit
cell size. The combination of all these symmetry operations results in a total of
230 unique space groups describing all possible crystal symmetries.
 Glide planes and screw axes
• Two of the symmetry operations involved in the space groups are not contained in the
corresponding point group or Bravais lattice. These are the compound symmetry
operations called the glide plane and the screw axis.
• A glide plane is a reflection in a plane, followed by a translation parallel with that plane.
This is noted by a, b or c, depending on which axis the glide is along. There is also the n
glide, which is a glide along the half of a diagonal of a face, and the d glide, which is a
fourth of the way along either a face or space diagonal of the unit cell. The latter is
often called the diamond glide plane as it features in the diamond structure.
 Glide planes and screw axes
• A screw axis is a rotation about an axis, followed by a translation along the direction of
the axis. These are noted by a number, n, to describe the degree of rotation, where
the number is how many operations must be applied to complete a full rotation (e.g.,
3 would mean a rotation one third of the way around the axis each time). The degree
of translation is then added as a subscript showing how far along the axis the
translation is, as a portion of the parallel lattice vector. So, 21 is a twofold rotation
followed by a translation of 1/2 of the lattice vector.
 Notation of space group

• The International Union of Crystallography publishes a table of all space groups,

and assigns each a unique number.
• The Hermann-Mauguin (or international) notation is the one most commonly
used in crystallography, and consists of a set of four symbols.
• The first describes the centering of the Bravais lattice (P, A, B, C, I, R or F).
• The next three describe the most prominent symmetry operation visible when
projected along one of the high symmetry directions of the crystal. These
symbols are the same as used in point groups, with the addition of glide planes
and screw axis, described above.
• For example, the space group of quartz is P3121, showing that it exhibits
primitive centering of the motif (i.e., once per unit cell), with a threefold screw
axis and a twofold rotation axis. Note that it does not explicitly contain the
crystal system, although this is unique to each space group (in the case of
P3121, it is trigonal).
Space group
Space group
Summary of crystal system, groups and lattices

No. of No. of No. of

Crystal system Point Bravais Space
groups lattices groups
Triclinic 2 1 2
Monoclinic 3 2 13
Orthorhombic 3 4 59
Tetragonal 7 2 68
Trigonal 5 1 25
Hexagonal 7 1 27
Cubic 5 3 36
Total 32 14 230
Five types of 2D lattice

2D symmetry
Lattice type
group
p1
parallelogram
p2
pm
pmm
rectangular pg
pgg
pmg
cm
rhombic
cmm
p4
squar p4m
p4g
p3
p3m1
hexagonal p31m
p6
p6m
Elementary Bravais cells for 2D lattice
17 planar crystallographic groups in 2D
 Examples of planar symmetry groups

Egyptian design with group p4mm. Ceiling of Egyptian tomb with Indian metalwork at the Great
group p2 Exhibition with group pm.

Soffitt of arch, the Alhambra, Spain Mummy case stored in The Louvre with Overlaid patterns with group p4.
with group cm. group p2mm.