CHM 3301

Arrangement of
atoms in crystals
Lecture 1

Originated by Dr Haslina Ahmad

Edited. Dr. KB Tan

Objectives
At the end of this lecture you should be able to:1. Define the Terms
Lattice
Crystal Structure
Unit Cell
2. Interpret a Plan or Perspective structural diagram of a
Unit
Cell
3. Determine Lattice Type and number of atoms in unit cell

4. Determine the Miller Indices of a plane

Why study solids?

1. ALL compounds are solids under
suitable conditions of temperature
and pressure. Many exist only as
solids.
2. Solids are of immense technological
importance

Appearance - Precious and semi-precious

gemstones of many varieties, e.g Beryl,
jadeite and others

Why study solids?

Mechanical Properties
Metals/Alloys, e.g. Titanium for aircraft
Cement/Concrete Ca3SiO5
'Ceramics', e.g. clays, BN, SiC
Lubricants, e.g. Graphite
Abrasives, e.g. Diamond, Quartz (SiO2)

Electrical Properties
Semiconductors, e.g. Si, GaAs
Electrolytes, e.g. LiI in pacemaker batteries
Piezoelectrics, e.g. Quartz (SiO2) in watches

Why study solids?

Magnetic Properties
e.g. CrO2, Fe3O4 for recording technology

Optical Properties
Pigments, e.g. TiO2 in paints
Phosphors, e.g. Eu3+ in Y2O3 is red on TV

Some basic definitions

LATTICE = An infinite array of points in space, in which each point has
identical surroundings to all others.
CRYSTAL STRUCTURE = The periodic arrangement of atoms in the
crystal.
UNIT CELL = The smallest repeating unit which shows the full
symmetry of the crystal structure.
Unit Formula Z = The number of ions or atoms which found in a single
unit cell.
COORDINATION NUMBER = The atoms which are coordinated to a
particular atom within the unit cell, i.e. nearest neighbouring atoms

Lattice

The atoms in a crystal are in a regular

repeating pattern called the lattice
The lattice can influence on the properties of
material
Examples: crystals of graphite and diamond.
They contain only 1 kind of atom - carbon.
Different in structural arrangement having
same common composition- known as
Polymorph or allotrope!!!

Graphite

Diamond

Lattice points
lattice is an array of points.
Lattice points - an arbitrary point
But once chosen it is the same
throughout the crystal- repeating.

Unit Cell

A Unit Cell - simplest repeating unit of a

solid- The smallest repeating volume of a
solid.

The unit cell related to each other by

displacements without rotation, reflection,
or inversion pure translations.

Unit Cell
Each unit cell in a space lattice is identical
in size, shape and orientation to every other
unit cell.
It is the building block from which the
crystal is constructed by repetition in three
dimensions.

NaCl Structure

(a)

(b)

(c)

1 2

(d)
(e)
(f)
(a) Section through the NaCl structure, showing: (b) to (e) possible repeat u
(b)and (f) incorrect units

Bravais lattices
Combining 7 Crystal Classes with 4 possible unit cell types Symmetry
indicates that only 14 possible BRAVAIS LATTICES

Shapes of Unit Cells

All the possible shapes of a unit cell are defined by 7 crystal systems,
which are based on the relationship among a,b,c and , , ,

a b c ; 90

Cubic system

a b c ; 90

Tetragonal system

a b c ; 90

Orthorhombic system

a b c ; 90

Rhombohedral (trigonal) system

a b c ; 90; 120

Hexagonal system

a b c ; 90

Monoclinic system

a b c ; 90

Triclinic system

TEST
a = b c; = = = 90

a = b = c; = = = 90

Cubic

c
a

Tetragonal

a b c; = = = 90

a b c; = = 90, 90
c

Orthorhombic

Monoclinic

b
a

a = b = c; = = 90
a

Rhombohedral

a b c; 90
Triclinic

a
a

S im p le

F a c e -c e n te re d

b
a

B o d y -c e n te re d

S im p le

C U B IC

E n d fa c e -c e n te re d

Types of unit cells

M O N O C L IN IC

+
c
a

S im p le

E n d fa c e -c e n te r e d

B o d y -c e n te r e d

F a c e -c e n te re d

O R T H O R H O M B IC

Shapes of unit cell

S im p le
RHOM BOHEDRAL

14 Bravais lattices
c

c
a

120

S im p le

B o d y -c e n te re d

TETRAGONAL

HEXAGONAL

T R IC L IN IC

Bravais lattices define unit cells. When combined with translational

operations they give raise to 230 space groups, i.e there are 230 possible
space-filling patterns that atoms, ions or molecules can adopt in the 3D
space

Summary
There are seven crystal systems defined by unit cell parameters
a,b,c and , , and four bravais lattice types:
primitive (P), Body centered (I), face centred (F) and side centred (A, B, C,)
Combining these 14 Bravais lattices with all possible symmetry elements
230 different Space Groups- F d 3 m, C2/c

Cubic

a=b=c == =90 (P,F,I)

Tetragonal

a=bc == =90 (P, I)

Orthorhombic abc == =90 (P, F, I, A, B or C)

Hexagonal / trigonal
Monoclinic
Triclinic

Non-Orthogonal

Orthogonal

Lattice, Bravais Lattice

Lattice the manner of repetition of atoms,
ions or molecules in a crystal by an array of
points;
The points are called lattice points
Bravais lattice = derived from 7 crystal
systems and referred as a distinct lattice
type, e.g. P, C, I ,F

Cell B which has lattice

points only at the corner is
primitive, P.
Cell A which has additional
lattice points is centred.

Lattice, Bravais Lattice

The face centered cubic, F, contains additional

lattice points in the center of each face.
A side centered lattice contains extra lattice
points on only one pair of opposite faces.
C-centred lattice if the extra lattice pointson
the ab face
A-centred lattice has lattice points on the bc
face.
A body centred lattice, I has an extra point
at the body centre (c)

Types of Unit Cells

Primitive lattice: the unit cell has a lattice point at each

corner only (P)

Body centred lattice: the unit cell has a lattice point at

each corner and one in the centre (I)

Face-centered lattice: the unit cell has a lattice point at

each corner and one in the centres of one pair of
opposite faces (A), (B), (C)

All-face-centered lattice: the unit cell has a lattice

point at each corner and one in the centre of each face
(F)

Calculation of unit formula

Contribution of lattice point in unit formula
calculation- atom at different position
Corner- 1/8
center 1
Face 1/2
Edge 1/4
Example.
a) For Cu metal, which is fcc, the no. of atoms
= 4. The corner Cu counts as 1. The face
centre Cu atoms, of which there are 6, count
as each giving a total of 1 + (6 x ) = 4 Cu
in the unit cell.
b) NaCl is also fcc. How many Na and Cl
atoms?

= Na

= Cl

No. of Na
= (8 x 1/8) + (6 x )
= 4 Na
No. of Cl
= (12 x 1/4) +1
= 4 Cl

Lattice planes and Miller Indices

Lattice planes a concept introduced with

Braggs Law of diffraction and are entirely
imaginary and simply provide a reference
grid to which the atoms in the crystal
structure may be referred.

Lattice planes and Miller Indices

In 3D, these rows become lattice planes and adjacent

planes are separated by the interplanar d-spacing, d.

Lattice planes are labeled by assigning three numbers

known as Miller indices to each set.

Assigning Miller indices to a set of planes:

1. Find the intersection of this plane on the three axes of the cell.
2. If the intersection of the plane is fraction, take reciprocals of the
fractions.

A Miller index of 0 means that the plane is parallel to that

axis.

d-spacing and Braggs Law

Diffraction interference between waves

that occurs as a result of an object in their
path.

X-rays are scattered elastically (with no

change in energy) by the electrons in
atoms, and diffraction can occur for a
periodic array of scattering centers
separated by distances similar to the
wavelength of the radiation, such as exist in
a crystal.

d-spacing and Braggs Law

Bragg's Law refers to the simple equation:
n = 2d sin
derived to explain why the cleavage faces
of crystals appear to reflect X-ray beams at
certain angles of incidence (, ). The
variable d is the distance between atomic
layers in a crystal, and the variable lambda
is the wavelength of the incident X-ray
beam; n is an integer.

d-spacing and Braggs Law

Two X-ray beams, 1 and 2 are reflected from
adjacent planes, A and B, within the crystal.
1

1
2

z
B

d-spacing and Braggs Law

Beam 22 has to travel the extra distance

xyz as compared to beam 11, and for 1
and 2 to be in phase, the additional
distance travelled by the second wave is
equal to a whole number of the
wavelength,
1
1
n.
2

z
B

d-spacing and Braggs Law

The perpendicular distance between pairs of

adjacent planes, the d-spacing, d, and the
angle of the incidence, or Bragg angle, ,
are related to the distance xy by
xy = yz = d sin

Thus,
xyz = 2d sin

d-spacing and Braggs Law

But,

xyz = n
Therefore
2d sin = n

d-spacing and Braggs Law

When Braggs law is satisfied, the
reflected beams are in phase and interfere
constructively.
At angles other than the Bragg angle,
reflected beams are out of phase and
destructive interference or cancellation
occurs.

Two waves in phase

Two waves out of phase

DO IT YOURSELF
Miller Indices
What are the indices for
(a) Planes that pass
through opposite ab
faces of the unit cell
(b)Planes that are
parallel to b and c
which cut a at 0, , 1,
1 , etc.
(c) Planes that
perpendicular to a
unit cell body
diagonal, that cut a,
b, c at ( ), (111),
(1 1 1 ), etc.

DO IT YOURSELF
Miller Indices

(001)

(100)

(010)

(101)

(110)

(011)

(111)

Miller Indices: Example

Normalized intercepts:
1,2,3
Reciprocals:
1, 1/2, 1/3
Multiplier is 6
Miller indices for this
plane:
(6,3,2)

(1,0,0) planes (1,1,1) planes

Place a bar over negative

intercept.
Miller indices: (2,2,1)

When a plane does not intersect

an axis the intercept is infinity
and the miller index is zero.
Miller indices: (1,0,1)

Adapted from
http://www.ieong.net/ee3106/Lecture1.pdf

Summary
Lattice - regular repeating pattern of the
atoms in a crystal
Unit cell - The smallest repeating unit which
shows the full symmetry of the crystal
structure.
Atoms in a unit cell should be counted in a
proper way (body centre = 1 atom, face =
atom, edge = atom, corner = 1/8 atom); if
all corner, edge- and face-centre atoms are
simply counted as one each, then the
ludicrous answer is obtained.