Introduction

A solid composed of a closure collection of atoms. In solids atoms are very strongly held
together. Solids state maters may be crystalline or amorphous. A crystalline solid composed
of atoms, ions or molecule are arranged in long range of periodic order in three dimensions.
Examples of crystalline solid are metals, NaCl, KCl, diamond etc. A solid substance with its
atoms held apart at equilibrium spacing, but with no long-range periodicity in atom location
in its structure is an amorphous solid. Examples of amorphous solids are glass and some
types of plastic.










Types of bonding
A chemical bond is an attraction between atoms that allows the formation of chemical
substances that contain two or more atoms. The bond is caused by the electromagnetic force
of attraction between opposite charges, either between electrons and nuclei, or as the result of
a dipole attraction (dipole is an entity where two opposite kind of charges are separated by
some distance). The chemical bonds are classified into two groups based on the strength of
the bond i.e. primary bond and secondary bond. The Primary bonds are strong bonds and
have bond energies in the range of 0.1 to 10eV/bond. Ionic, covalent and metallic
bonding are the examples. Secondary bonding has energies in the range 0.01 to
0.5eV/bond. Hydrogen bonding and van der Waals bonding are the examples.
Ionic bonding
Ionic bond is the attractive force existing between a positive ion and a negative ion. These
ions are formed due to complete transfer of electron from one atom to another. Electro
positive elements readily give up electrons and are usually group I or II elements, e.g. Na, K
and Ba. Electro-negative elements readily take up electrons and are typically group VI and
VII elements e.g. Cl, Br and O. This bond is non directional bond. To understand the
formation of Ionic bonding, let us consider NaCl molecule. A sodium atom (Na) and a
chlorine atom (Cl) are shown below. A single circle represents the nucleus (protons and
neutrons) of the atoms. Dots represent the electrons. The sodium atom has a total of 11
electrons and one electron in its outer shell. Chlorine has a total of 17 electrons with seven in
its outer shell.







The outer valence electron of the sodium atom gets transferred to the chlorine atom to acquire
a stable electronic configuration fig.2. There exists an electrostatic attraction between
positively charged sodium cation and negatively charged chlorine anion and form NaCl
molecule.

Actually a positive charge attracts all negative charges in the neighborhood and vice versa.
Consequently in the crystalline solid, Na
+
ions are surrounded by Cl
-
ions and Cl
-
ions by Na
+

ions. The resulting NaCl structure is shown in Fig.3




Fig.1. Sodium and Chlorine atom
Fig.2. Sodium and Chlorine ions








Properties of Ionic solids
1. Ionic solids are made up of metallic and nonmetallic elements
2. Ionic solids are hard and brittle in nature
3. Ionic solids shows high melting points
4. Ionic solids are soluble in polar solvents like water and ammonia. This solids are
insoluble in non polar solvents.
5. Ionic solids are poor conductor of electricity because they do not have free electrons.
However, Ionic solids dissolve in water and the solution conducts electricity.
6. Ionic solids are transparent in visible radiation and exhibits characteristic absorption
peaks in IR regions.
7. In an ionic crystal, a anion is surrounded by as many cations as possible and vice-
versa. Because of this ionic bonds are non directional bond.

Covalent Bond
A covalent bond is formed when two similar or dissimilar atoms achieve stability by equal
sharing of valence electrons between themselves. This kind of bonding is possible whenever
sharing results in lowering the potential energy of the system.
The shared electrons are under the influence of nuclei of both combining atoms. A stable
covalent bond is formed at the separation (distance between two nuclei) where the repulsive
force between electrons of two combining atoms and two nuclei is balanced by attractive
force between nucleus and electrons.
Hydrogen atoms only need two electrons in their outer level to reach the noble gas structure
of helium. Once again, the covalent bond holds the two atoms together because the pair of
electrons is attracted to both nuclei
Fig.3. NaCl structure

In case of H
2
molecule the attractive and repulsive forces balance at 0.74
0
A and hence the
covalent bond exist with decrease in potential energy of the system. In order to break one H-
H bond 4.5eV of energy is required i.e.
H
2
+ 4.5ev H + H
Depending on the number of electrons shared, the covalent bonds may be single, double or
triple on sharing one two or three electrons per atom respectively.
Examples: H
2
, HCl, HF, O
2
, N
2
, Diamond , Si, Ge etc.
The number covelent bonds that can be formed by an element is determined by number of
electrons that can be added to the valence shell to get octet state. Therefore the maximum
number of covalent bond is (8-N). where N is number of valence electron.
Single covalent bond: H
2
,HCl, CH
4

Double covalent bond: O
2
molecule
Triple covalent bond: N
2
molecule
The important points about covalent bond formation are
1) Attainment of octet configuration is not essential
2) The essential feature of such bond is the fact that it involves the pairing of two
electrons with opposite spin
3) A covalent bond may be either polar or non polar depending on the fact that whether
the electrons pair is shared unequally (eg. HCl) or equally (O
2
, H
2
) between the two
atoms.


Properties of covalent bonded solids
1) The covalent bond exist in all three states of matter
a) Gases O
2
, H
2
etc.
b) Liquids CCl
4

c) Solids Diamond, Ge, Si and Sn
2) In solids they exist in crystalline state.
3) Covalent crystals are usually hard and brittle materials with high binding energies (eg.
Diamond =7.4eV)
4) The melting and boiling points of covalent solids are usually low as compared to
those of ionic solids (Diamond high melting point, tin low melting point)
5) Covalent bond is a directional bond
6) They generally dissolve in non polar solvents such as benzene, toluene and CCl
4
.
However some covalent compounds like, HCl, NH
4
, sugar, urea are soluble in water)
7) Basically all covalent crystals are insulators because of no free electrons available for
conduction. However Si, Ge are semiconductor and Sn is a conductor.
8) These crystals are transparent to long wavelength radiation and opaque to shorter
wavelength
9) Covalent bonds may be polar or non polar in nature, depending on the fact that
whether the electron pair is unequally shared (HCl) or equally shared ( O
2
, H
2
)
between two atoms.


Website : http://www.youtube.com/watch?NR=1&v=1wpDicW_MQQ

Metallic bond
Metallic bond is formed by partially showing of valance electrons by neighboring atoms,
sharing is not localized. Metallic bonds may also be considered as delocalized or unsaturated
covalent bond.


Free electrons
+ ve ion core
Fig.4. Atomic arrangement in metal crystal
In case of metal, the valance electrons are mobile and are not bound to any particular atom.
These are free to move throughout the volume of the metal. These free and mobile electrons
form a kind of electron cloud or electron gas. Thus a metal may be regarded as an array of
closely packed or positive ion core is immersed in a sea of electron gas. There exist
electrostatic force of attraction between the electron gas and +ve ion core.
A metallic bond is formed when the force of attraction between the +ve metal ions and
electron gas exceeds the mutual repulsion of the electrons in metal.
Examples : Na, Al, Cu, Au, Ag etc.
The binding energies of Na is 1.13eV, Al is 3.23eV
Properties of metallic bonded crystals:
1. The metallic bond is weaker than ionic or covalent bonds
2. Metallic crystals have crystalline structure
3. They have high thermal and electrical conductivities since metals posses a large no of
free electrons
4. The melting and boiling points of metallic solids are lower than ionic and covalent
solids
5. Metallic bond is a non directional bond
6. The metallic crystals are opaque to light
7. Metallic solids are not soluble in polar and non polar solvents
8. Metallic solids are soft and malleable and ductile



Dipole bond
Dipole bond is formed between molecules having permanent dipoles. The permanent
dipoles are arising due to unequal sharing of electrons between two atoms. Let us consider
the formation of HF molecule by electron sharing. The hydrogen atoms have only on electron
in its outermost energy level and fluorine atom has 7 electrons in its outermost energy level.
The hydrogen atom requires one more electron to acquire stable configuration and fluorine
atom also requires one more electron to acquire stable configuration. Therefore both the
hydrogen and fluorine atoms share a pair of electron to acquire stable configuration. This
leads formation of covalent bond and the resulting molecule is called as hydrogen fluoride.


In this covalent bond, the fluorine atom has high affinity than the hydrogen atom. Thus the
shared electron pair shifts towards the fluorine atom. This shifting of electron pair produces
an electric dipole. Similar dipoles are formed in adjacent molecule also. Adjacent HF
molecule therefore attract each other by means of electro static attraction between their
oppositely charged ends and the dipole bond is formed






Examples: HCl, SO
2
, NH
3
, H
2
O

Properties of dipole bonds:
1. Dipole bonds are much weaker than primary bonds but are stronger than Van dar
waals or dispersion bonds. Thus these are weakly bonded solids
2. These bonds have directional properties
3. Solids with dipole bonds are good insulators since there are no valance electrons


Hydrogen bond

A hydrogen bond is a particular type of dipole bond in which one atom is a hydrogen
atom. When a covalent bond is formed between a hydrogen atom and a highly
electronegative atom, such as an atom of oxygen, fluorine, chlorine etc. the shared electrons
pair gets attracted move towards the electronegative atom than the hydrogen atom. Thus the
electronegative atom acquires a slight negative charge and the hydrogen atom acquires an
equal amount of +ve charge. The molecule so formed is said to be polarized and behaves like
permanent dipole. A number of such dipoles get attracted to one another due to the columbic
force of attraction. This type of interaction between the oppositely charged ends of
permanently polarized molecules each containing a hydrogen atom is called the hydrogen
bond.

Dipole bond
134
0
Covalent bond

+










For example this bond is formed between ice or water molecules due to attraction between
the positively charged hydrogen end of a molecule and negatively charged oxygen of other
molecule as shown below.
Properties of hydrogen bonded solids
1. The hydrogen bonds are directional
2. The bonding is relatively strong as compared to other dipole-dipole interactions.
3. Hydrogen bonded solids have low melting points
4. Hydrogen bonded solids are good insulators since no valence electrons
5. They are soluble in both polar and non polar solvents
6. They are transparent to visible light
7. Since elements of low atomic numbers for such solids, they have low densities.



Van dar Waals bond
A relatively weak and temporary (fluctuating) kind of intermolecular bond that forms when
one side of a molecule develops a slight negative charge because a number of electrons have
temporarily moved to that side of the molecule. This negative charge attracts the nuclei of
the atoms of a neighboring molecule. The side of the molecule with fewer electrons develops
a slight positive charge that attracts the electrons of the atoms of neighboring molecules.
Van dar waals bonding arise from the fluctuating dipole nature of an atom with all
occupied electron shell filled .This bond is non directional.
If the symmetrical distribution of electrons around the nucleus is disturbed, the centre of
positive and negative charges may not coincide at that moment giving rise to weak
fluctuating dipole.
Hydrogen bond in Water molecules












A weak attractive force exists between the opposite ends of the dipoles in the neighboring
atoms. This force only allows inert gas atoms to condense at low temperatures. Van der
Waals bonding is typically an order of magnitude weaker than the hydrogen bonding.
Properties of solids with van der waals bonding

1. Van der waals bonds are non directional
2. Solids with van der waals bonds are insulators since no valence electrons are
available.
3. Solids are soluble in polar and nonpolar solvent
4. They are transparent to light
5. Van der waals bonded solids has low melting point
6. Van der waals bonding is weaker than hydrogen bond

Examples: solid Argon, solid neon.



Interatomic forces

The attractive forces between the atoms bring them close together until a strong repulsive
force arises due to overlap of electron shells. When two atoms approach each other, the
negatively charged electron shells come much closer than their positive nuclei. At a certain

-

=0
(a)
(b)
(c)
Van der
waals bond
(a) Symmetric distribution of electrons in a
nobel gas atom
(b) Asymmetric distribution
(c) Formation of van der waals bond
separation, called the equilibrium separation, r
0
the attractive and repulsive forces are equal.
The two atoms come to a stable condition and have minimum potential energy. At
equilibrium the bonding force F is
( ) M N > =
N M
r
B
r
A
r F
Where r is the inter atomic distance, A, B, M, N are constant depend on the type of bond. The
first term represents the force of attraction and the second term represents force of repulsion.
The value of M is 2. The value of N is 7-10 for metallic bond and 10 to 12 for ionic and
covalent bond. At equilibrium spacing r
0
the net force is zero . The value of r
0
is of the
order of 10
-10
m. i.e. 1A
0
.
M N
B
A
r

|
.
|

\
|
=
1
0

Estimation of cohesive energy

To calculate the cohesive energy, let us consider the general situation of two identical atoms.
As the atoms approach, the attractive forces increase. Since the atoms do the work during
attraction, the energy of attraction is Ve. Hence the potential energy decreases. When the
separation decreases to the order of few atomic diameters, repulsive forces begin to act. Since
external work must be done to bring the two such atom close together, the repulsive force is
positive and hence the Potential Energy increase. At equilibrium position the potential energy
of the either atom is given by
U= decrease in Potential energy due to attraction + increase in potential energy due to
repulsion
Since the work done on the system is stored as potential energy it can be calculated by
integrating F(r)
The work done in moving through a small distance dr is
dU(r)=F(r)dr
The potential energy of the atom
} }
= = dr r F r du r U ) ( ) ( ) (
}
|
.
|

\
|
= dr
r
B
r
A
N M

( ) ( )
C
r N
B
r M
A
N M
+
|
.
|

\
|

+
|
.
|

\
|

=
1 1
1
1
1
1

C
r
b
r
a
n m
+ +

=
Where a and b are new constants related to A and B as
1
=
M
A
a ,
1
=
N
B
b
When r=, U=0
Hence C=0
Therefore
n m
r
b
r
a
r U +

= ) (
All the stable arrangements of atoms in solids are such that the potential energy U(r) is a
minimum. This happens at equilibrium position (r=r
0
)
m n
m
n
a
b
r

(

=
1
0

The energy corresponding to the equilibrium position is called the bonding energy or energy
of cohesion of the molecule.
Calculation of cohesive energy of ionic solids
Cohesive energy of ionic crystals is mainly due to electrostatic interaction. The cohesive
energy of an ionic crystal is the energy that would be liberated by the formation of the crystal
from individual neutral atoms. Cohesive energy is usually expressed in eV/atom or
eV/molecule or in kJ/kmol.
The binding energy of ionic crystals are about 5-10eV per molecule. This is the energy
required to dissociate the lattice into +ve and ve ions at infinite separation. The common
types of structures found in ionic crystals are NaCl-FCC and CsCl-BCC.
In classical Born-Madelung theory it is assumed that the e
-
s are transferred from electro +ve
atoms(Na, K, Mg) to electronegative atoms (O,F,Cl). The stability of the ionic crystal
depends on the balancing of at least three forces.
1) Coulombs forces between the ions
2
1
r

2) Van der waals forces
7
1
r

3) Inter ionic repulsive forces falling off still more rapidly with distance.
The resultant of attractive and repulsive forces is to lead an equilibrium position of
minimum potential energy. i.e. of greatest stability
Consider two ions of charge Z
1
e and Z
2
e are separated by a distance r
r
e Z Z
0
2
2 1
4
energy attractive The
tc

=
For the whole crystal the coulomb potential energy may be written as
r
e Z AZ
0
2
2 1
4tc

This term represent the net coulomb potential energy of any one ion due to the present of
all other similar and dissimilar ions present in the crystal
The minus sign shows that net coulomb energy is attractive
The Constant A is known as Madelung constant, it differs with crystal structures. It is
1.748 for NaCl crystal.
The repulsive energy of this ion, due to all the other ions present in the crystal is
n
r
B

where n is called born repulsive exponent.
Therefore the total energy of one ion due to the presence of all other ions is given by
( )
n
r
B
r
e Z AZ
r U +

=
0
2
2 1
4tc

The total energy per kmol of the crystal is
( )
(

=
n
A
r
B
r
e Z AZ
N r U
0
2
2 1
4tc

Where N
A
is the Avogadro number
If Z
1
= Z
2
= 1 then
( )
(

=
n
A
r
B
r
Ae
N r U
0
2
4tc

The potential energy will be minimum at equilibrium spacing r
0
0
4
1
0
2
0 0
2
0
=
(

=
(

+
=
n A
r r
r
Bn
r
Ae
N
dr
dU
tc

n
r Ae
B
n
0
1
0
2
4tc

=
Substituting this value of B along with r = r
0
we get total equilibrium energy per kmol of
the crystal.
| |
(

= =

= n
n
A r r
nr
r Ae
r
Ae
N U U
0 0
1
0
2
0 0
2
0
4 4
0
tc tc

Rearranging the above equation for lattice energy per kmol of ionic crystal
|
.
|

\
|

=
n r
Ae N
U
A
1
1
4
0 0
2
0
tc

Then the expression for the lattice energy that is released in the process when the
constituent ions are placed in their respective positions in the crystal lattice
|
.
|

\
|

=
n r
Ae
U
1
1
4
0 0
2
0
tc

The cohesive energy and lattice are equal and opposite in sign.
The expression for cohesive energy of a molecule



Bond formation energy is ve and bond breaking energy is +ve.
Note: the cohesive energy is the energy required to separate the crystal into positive
and negative ions







|
.
|

\
|
=
n r
Ae
U
1
1
4
0 0
2
0
tc


Problems
1) Calculate the cohesive energy of NaCl from the following data
Equilibrium separation between the ion pair = 0.281nm
Born repulsive exponent = 9
Madelung constant = 1.748
Solution:
Cohesive energy per molecule is


e = 1.602x10
-19
C

0
=8.854x10
-12
F/m
Then cohesive energy per molecule of NaCl is
=-0.12755x10
-17
Jouls
=-7.96eV
2) The madelung constant of KCL is 1.75. Its neighbor separation is 0.314nm. Find
the cohesive energy per atom ( given that the repulsive exponent value = 5.77;
Ionisation energy of potassium = 4.1eV; Electron affinity of chlorine = 3.6eV).
Solution:
Potential energy per pair of ions is


e = 1.602x10
-19
C

0
=8.854x10
-12
F/m
Then bond energy per molecule of NaCl is
=- 0.12755x10
-17
Jouls
=- 6.63eV
Potential energy per ions is (6.63/2) = - 3.315eV
|
.
|

\
|

=
n r
Ae
U
1
1
4
0 0
2
0
tc
0 0
2
0
4 r
e
U
tc

=
The average energy needed to create an ion( K
+
or Cl
-
) from pair of K and Cl atom is
(4.1-3.6)/2=0.25eV
The cohesive energy per atom is = -3.315+0.25 = -3.065eV
3) Estimate the bond energy for the NaCl molecule as formed from sodium and
chlorine atoms. The inter ionic equilibrium distance is 236pm. The ionization
energy(IP) of sodium is 5.14eV and electron affinity(EA) of Cl is 3.65eV.
Solution:
Potential energy

= - 6.1eV
The bond energy is given by
= (U) + (IP - EA )
= -6.1+ (5.14-3.65)
= -4.61eV














0 0
2
4 r
e
U
tc
=
Crystal structure
Matter consisting of one or more elements or their chemical compounds, exists in nature in
the solid, liquid and gases. As the atom or molecules in solids are attached to one another
with strong forces of attraction, the solid maintains a definite volume and shape.
On the basis of arrangement of constituent particles solids are divided into
1) Crystalline solids
2) Amorphous ( non crystalline solids)
Crystalline solids
The crystalline state of solid is characterized by regular and periodic arrangement of atoms or
molecules. Most of the solids are crystalline in nature since the energy released during the
formation of an ordered structure is more, than that released during the formation of
disordered structure, i.e. the crystalline state is a low energy state.
The crystalline solid may be further divided into
1) Single crystal (eg. Diamond, quartz, mica etc.)
2) Poly crystalline solids ( eg. Metals, ceramics etc.)
In single crystal, the periodicity of atoms extends throughout the crystal (Diamond, Quartz)
A poly crystalline material is an aggregate of number of small crystallites with random
orientations separated by well defined boundaries. The smallest crystallites are known as
grains and the boundaries are grain boundaries.
It may be noted that although the periodicity of individual crystallites in interrupted at grain
boundaries. Yet the polycrystalline form of the material may be more stable compared to the
crystal form. Most of metals and ceramics exhibit poly crystalline structure.
Amorphous solids:
Amorphous solids are characterized by the complete random arrangement of atoms or
molecules. The periodicity if at all present, extends upto a distance of a few atomic diameters
only. In other words, these solids exhibit short range order.
Amorphous solids are formed when the atoms do not get sufficient time to undergo a periodic
arrangement. Eg. Glass, plastics, rubber, wood etc.





Difference between crystalline and amorphous solids
Crystalline Amorphous
The constituent particles
(atoms/molecules/ions) are arranged in
regular fashion containing short range as well
as long range order.
The constituent particles are not arranged in
any regular fashion, short range order.
They are anisotropic They are isotropic
They show elastic behavior They do not show elastic behavior
They are ductile in nature They are brittle in nature
They have sharp melting point i.e. all the
bonds are broken at particular temperature as
they are of equal strength
They melt over a range of temperature as all
bonds are of not equal strength.

Crystallography
The branch of science, which deals with the study of geometrical form and physical
properties of crystalline solids, is called crystallography.
Lattice points and space lattice
A crystal is a 3 dimensional body, which is made up of regular and periodic arrangement of
atoms or molecules in space. The periodicity in the arrangement generally varies in different
directions. It is very convenient to imagine points in space about which these atoms are
located. Such points in space are called lattice points and totality of such points form a
crystal lattice or space lattice. If all the atoms at the lattice points are identical, the lattice is
called Bravias lattice.
A space lattice may be defined as an infinite array of points in three-dimensions in which
every point has surroundings or environments identical to that of every other point in
the array.







Let us consider the case of a two dimensional square array of points as shown in figure. By
repeated translation of the two vectors a and b on the plane of the paper, we can generate the
square array.
The magnitudes of a and b are equal and can be taken to be unity. The angle between them is
90
0
. A and b are called the fundamental translation vectors that generate the square array. Let
us choose any arbitrary point O as origin. If we choose a lattice point P at position r it can be
represented by translation vectors as
b m a l r + =
Where l and m are integers. In the figure l=2 and m=1


Similarly for three dimensional lattice
c n b m a l r + + =

Thus a three dimensional space lattice is generated by repeated translation of three
noncoplaner vectors a, b and c.

A crystal lattice refers to the geometry of a set of points in space, where as the structure of
crystal refers to actual ordering of its constituent atom, ions, or molecules in space.
Lattice points: - Lattice points denote the position of atoms or molecules in the crystals.
It is an Infinite array of points in space, in which each point has identical surroundings to all
others
a
O
P
b
r
Space lattice:- An infinite three dimensional array of points showing how atoms are
molecules are arranged in a crystal is known as space lattice or simply lattice.
The Basis and Crystal structure
In order to obtain a crystal structure, an atom or group of atoms must be placed on each
lattice point in a regular fashion such an atom or group of atoms is called the basis or the
pattern. When the basis is repeated with correct periodicity in all directions it gives the actual
crystal structure. The crystal structure is real, while the lattice is imaginary. Mathematically it
is expressed as
Space lattice + basis ----------- Crystal structure

-The number of atoms in a basis varies from one to several thousands
- In crystalline solids like Cu and Na the basis is Single atom, In NaCl & CsCl the basis in
diatomic, where as in crystals, like CaF
2
the basis in tri-atomic.
Complex basis are found in biological materials.
Unit cell and lattice parameters
The unit cell is the smallest block or geometrical figure from which the entire crystal is built
up by repetition in three dimensions.
The unit cell may also be defined as the fundamental elementary pattern of minimum number
of atoms, molecules which represents fully all the characteristics of the crystal
Unit cell may be defined as that volume of a solid from which entire crystal may be
constructed by translation repetitions in three dimensions.
It should be noted that the choice of a unit cell is not unique but can be constructed in number
of ways. The unit cell should be chosen in such a way that it conveys the symmetry of the
crystal lattice and makes the mathematical calculations easy.

Space Lattice + Basis = Crystal Structure
=




Let us consider a unit cell of a three dimensional crystal lattice. Unit cell can be completely
described by three vectors a , b, c when the length of the vectors and the angle between
them , , or specified.
The lines drawn parallel to the lines of intersection of any three faces of the unit cell which
do not lie in the same plane are called crystallographic axes. An arbitrary arrangement of
crystallographic axes marked x,y and z defining the unit cell is shown in fig below.





The angles between the three crystallographic axes are known as interfacial angles or
interaxial angles
The angle between the axes y and z is
The angle between the axes z and x is
The angle between the axes x and y is
Thus the above angles , and are the interfacial angles.
The intercepts a, b, and c defines the dimensions of a unit cell and are known as its primitives
or characteristics intercept on the axes or fundamental translational vectors.
The primitives a, b and c and interfacial angles , , and are the basic lattice parameter and
they determine the form and actual size of the unit cell and hence the space lattice. But if we
do not know actual values of primitives but only their ratio and the value of interfacial
angles, then we can only determine the form of the unit cell but not its actual size.
The vectors a , b, c may or may not be equal. Also the angles , and may or may not be
right angles. Based in these conditions, there are seven crystal systems. If the existing of
atoms is only at the corners of the unit cell the seven crystal systems yield seven types of
lattices.
We have seen that a three dimensional space lattice is generated by repeated translation of
three non coplanar vectors a, b and c. there are only fourteen distinguishable ways of
arranging points in three dimensional space. These 14 space lattices are known as Bravais
lattices.
Primitive cell
Primitive cell in the smallest volume cell, all the lattice points belong to a primitive cell lies
at its corners. Therefore effective number of lattice points in a primitive cell is one.
Non primitive cell
A non primitive cell many have the lattice points at the corner as well as other locations both
inside and on the surface of the cell. Therefore the effective number of lattice points in a non-
primitive cell in greater than one.




















Crystal systems
On the basis of the length and directions of the axes of the symmetry all the crystals may be
classified into following seven systems








.




Important crystal structure terms

1. Coordination number (N): The coordination number is defined as the number of equidistant
neighbours that an atom has in the given lattice.
2. Nearest neighbour distance (2r): The distance between the centers of two nearest
neighbouring atoms is called the nearest neighbour distance.
3. Atomic radius (r) : Atomic radius is defined as half the distance between nearest neibours in
a crystal of pure element.
4. Unit cell volume (V): The volume of unit cell is given by
( )
1/2
2 2 2
cos cos cos cos cos cos 1 abc V | =
If a = b = c and = = =90
o
then
V= a
3
(cubic unit cell)
5. Atomic packing factor(APF): The fraction of space occupied by atoms in a unit cell is known
as atomic packing factor or packing factor or density of packing. It is the ratio of volume
occupied by the atoms in unit cell (v) to the volume of the unit cell relating to that structure.
V
v
cell unit the of volume
cell unit atoms by occupied volume
factor packing Atomic = =


cell unit the of volume
atom each of volume cell) atoms/unit of (number
(APF) factor packing Atomic

=
6. Void space: The void space in the unit cell is the vacant space left unutilized in the cell. It is
equal to (1-APF). It is often expressed in percentage.
Void space = (1-APF) 100
The void space is most commonly known as Interstitial space.
7. Density : As the unit cell posses all the structural properties of a bulk material. The density
of unit cell must be equal to that of the bulk crystal. Then,

A
VN
zM
V
zw
volume
mass
Density = = =
Where w is mass of each atom =M/N
A
, z is number of atoms per unit cell, M is molecular
weight and N
A
is Avagadro number.

Simple cubic (BCC) structure :

The unit cell of a simple cubic lattice, there is one lattice point (atom) at each of the eight
corners of unit cell. Only polonium at certain temperature region exhibits this type of structure.





Coordination number:
In this structure for every one corner atom there are four nearest neighbours in the same
plane plus two nearest neighbours, one exactly above and the other exactly below that corner atom.
Thus, the coordination number is (4+1+1) six.

Number of atoms per unit cell:
This unit cell as eight corner atoms. Each corner atom is shared by eight adjacent unit cells.

The total number of atoms per unit cell 1
8
1
8 =
|
.
|

\
|
=
Atomic radius:
In this structure the atoms touches each other along cube edges. Hence the nearest
neighbour distance
a = 2r
Atomic radius
2
a
r =
Atomic packing factor:

Volume of all atoms in unit cell, v =
3
r
3
4
1
v
3
3
a
6
1
2
a

3
4
1 =
|
.
|

\
|
=
Volume of the unit cell, V= a
3

V
v
cell unit the of volume
cell unit atoms by occupied volume
factor packing Atomic = =
6

a
a
6
1
V
v
APF
3
3
= = =
% 2 5 0.52
6

APF = = =
Void space :

Void space = (1-APF) 100 = (1-0.52) 100
=48%

Body centered cubic (BCC) structure :
In this structure in a unit cell there are eight atoms at the eight corners and one atom at the
body center. The unit cell of the body center cubic structure is shown in fig.
Iron (at room temperature), chromium, tungsten, sodium etc. have BCC structure.


















Coordination number:
In body centered cubic structure the corner atoms do not touch each other but each corner
atom touches the body center atom along body diagonal. Hence the coordination number this
structure is eight.

Number of atoms per unit cell:
This unit cell as eight corner atoms and one body centered atom. As body centered atom is
contained with in the unit cell and it is not shared by and surrounding unit cell.

The total number of atoms per unit cell of BCC 2 1
8
1
8 = +
|
.
|

\
|
=
Atomic radius:
For calculation of r in case of BCC, consider the fig
2 2 2 2
2a a a AC = + =
2 2 2 2 2
a 2a CD AC AD + = + =
2 2
3 AD a =
Body diagonal AD = r+ 2r + r = 4r
2 2
a 3 ) 4 ( = r
Lattice parameter
3
4r
a =
Nearest neighbor distance
2
3 a
2r =
Atomic radius
4
3 a
r =
Atomic packing factor:

Volume of all atoms in unit cell, v =
3
r
3
4
2
v
3
3
a
8
3
a
4
3

3
4
2 =
|
|
.
|

\
|
=
Volume of the unit cell, V= a
3

V
v
cell unit the of volume
cell unit atoms by occupied volume
factor packing Atomic = =

8
3
a
a
8
3
V
v
APF
3
3
= = =
68% 0.68
8
3
APF = = =
Void space :

Void space = (1-APF) 100 = (1-0.68) 100
= 32%

Face centered cubic (FCC) structure:
In the case of FCC lattice, there are eight atoms at eight corners and six atoms at the six face
centers of the unit cell. Copper, aluminum, argon, gold, platinum, lead, thorium etc. are of FCC
structure.








Coordination number:
In this case the nearest neighbors of any corner atom are the four face centered atoms of
surrounding unit cells. The corner atom will have four face centered nearest neighbor atoms in it
own plane, four in a plane above it and four in a plane below it. Thus the coordination number is
(4+4+4) twelve.

Number of atoms per unit cell:
This unit cell as eight corner atoms and six face center atoms. Each of these face centered
atom is shared by the two adjacent unit cells
The total number of atoms per unit cell of FCC 4
2
1
6
8
1
8 =
|
.
|

\
|
+
|
.
|

\
|
=
Atomic radius:
For calculation of r in case of FCC, consider the fig
2 2 2 2
2a a a AC = + =
Body diagonal AC = r+ 2r + r = 4r
2 2
a 2 ) 4 ( = r
Lattice parameter
2
4r
a =
Nearest neighbor distance
2
2 a
2r =
Atomic radius
4
2 a
r =
Atomic packing factor:

Volume of all atoms in unit cell, v =
3
r
3
4
4
v
3
3
a
6
2
a
4
2

3
4
4 =
|
|
.
|

\
|
=
Volume of the unit cell, V= a
3

V
v
cell unit the of volume
cell unit atoms by occupied volume
factor packing Atomic = =

6
2
a
a
6
2
V
v
APF
3
3
= = =
% 4 7 0.74
6
2
APF = = =
Void space :

Void space = (1-APF) 100 = (1-0.74) 100
= 26%

Hexagonal close packed structure:
The lattice parameter of simple hexagonal structure are a=bc and == 90
o
; =120
o
. It contains
one lattice point at each corner of hexagonal face and one in the center of hexagonal faces. Each
corner atom is shared by six other unit cells and each central atom is shared by two unit cells.
Hence number of atoms per unit cell 3
2
1
6
6
1
2 =
|
.
|

\
|
+ =
The total number of atoms in a unit cell is only 3, its packing fraction is low hence metals do not
crystallize in this simple hexagonal structure. The atoms attain a lower energy and more stable
configuration only by forming hexagonal close packed (HCP) structure. The unit cell of HCP is shown
in the fig.















HCP structure belongs to hexagonal Bravias lattice with a basis of two atoms associated with
each lattice point. In HCP there are three atoms at interstices between two hexagonal faces.
Example of metals that crystallize in HCP structure are Zn, Co, Mg, Cd, Ti etc.

Number of atoms per unit cell:

The total number of atoms per unit cell in HCP structure is six calculated as below.
The total number of atoms per unit cell 6 3
2
1
6
6
1
2 = +
|
.
|

\
|
+ =

Coordination number:
Consider the bottom layer, the central atom has 6 nearest neighboring atoms in the same
plane. Further at a distance of c/2 from this plane there are two layers one above and another below
it containing three atoms in each layer. Thus there are 12 nearest neighboring atoms.

The coordination number = 6+3+3= 12


Atomic radius:
The atoms are in contact along the edges of hexagon. The nearest neighbor distance
a 2r =
Atomic radius
2
a
r =

c/a ratio:

In HCP structure the three body atoms lie in a horizontal plane at a height c/2 from the orthocenter
of alternate equilateral triangles in the base or at top of the hexagonal cell. From the fig.

( )
2
2 2
2
c
x 2r
|
.
|

\
|
+ =
But
2
3
a
3
2
cos30 a
3
2
AN
3
2
x
o
= = =
3
a
x =
and 2r =a
( )
4
c
3
a
2
c
3
a
a
2 2
2
2
2
+ =
|
.
|

\
|
+
|
|
.
|

\
|
=
3
2a
3
a
a
4
c
2 2
2
2
= =
3
8
=
a
c


Atomic packing factor:

Volume occupied by atoms in a unit cell v =
3
r
3
4
6
v
3
3
a
2
a

3
4
6 =
|
.
|

\
|
=
Volume of the unit cell may be determined by calculating the area of the base of the unit cell and
then multiplying it by the height of the unit cell.

Area of the base of the unit cell = 6 (area of triangle ABO)

2 o
a
2
3 3
2
3
a a
2
1
6 asin60 a
2
1
6 = = =
the volume of the unit cell = c a
2
3 3
2

Substituting the value of a
3
8
c = we get,
volume of the unit cell =
3 2
a 2 3 a
3
8
a
2
3 3
=
V
v
cell unit the of volume
cell unit atoms by occupied volume
factor packing Atomic = =
6
2
2 3

a 2 3
a
V
v
APF
3
3
= = = =
% 74 74 . 0
6
2
APF = = =
Void space :

Void space = (1-APF) 100 = (1-0.74) 100
= 26%
Density of unit cell:
The density of HCP cell is given by

( )
3
A
3
A A
a N
M 2
.a 2 3 N
6M
V N
zM
= = =






Diamond structure:
In crystalline form diamond is one of the most important precious stone, it crystallizes in
cubic as well as in hexagonal structures. The diamond cubic (DC) structure is very important
structure as besides diamond, the semiconductors Ge and Si crystallizes in this structure. The unit of
diamond cubic is shown in fig. The diamond structure is a FCC structure with basis of two carbon
atoms one located at (0,0,0) and other at (1/4,1/4,1/4) associated with each lattice point.








The diamond lattice can be considered to be formed by the interpenetrating two FCC sub-
lattices along the body diagonal by 1/4th cube edge. If one sub-lattice has its origin at a point (0,0,0)
and the other at point quarter of the way along the body diagonal i.e. at (a/4,a/4,a/4).

Unit cell of diamond structure contains 18 atoms. Of these atoms 14 carbon atoms are
situated at 8 corners and 6 face centers of the cube, apart from those occupying the FCC lattice
points the other four carbon atoms are situated along the two body diagonals at a height of 1/4 of
the lattice parameter for the bottom and 3/4 of the lattice parameter from the bottom on the other
two body diagonals which are opposite to each other. The coordinates of four body diagonal atoms
in the unit cell are |
.
|

\
|
|
.
|

\
|
|
.
|

\
|
|
.
|

\
|
4
3
,
4
3
,
4
3
and
4
1
,
4
3
,
4
3
,
4
3
,
4
3
,
4
1
,
4
1
,
4
1
,
4
1
.

Coordination number:

Each carbon atom has four nearest neighbors in the tetrahedral coordination with a bond
angle 109.5
o
. Hence the coordination number in diamond cubic structure is four.


Number of atoms per unit cell:

This unit cell consists of eight corner atoms, six face centered atoms and four atoms inside
the cube along body diagonal
Hence the number of atoms per unit cell = 8 4 6
2
1
8
8
1
= +
|
.
|

\
|
+
|
.
|

\
|

Atomic radius:
From the figure, the nearest neighbour distance,

2 2 2
4
a
0
4
a
0
4
a
0 2r
|
.
|

\
|
+
|
.
|

\
|
+
|
.
|

\
|
=

2 2 2
4
a
4
a
4
a
2r
|
.
|

\
|
+
|
.
|

\
|
+
|
.
|

\
|
=
therefore
4
a 3
2r =
Atomic radius
8
a 3
r =

Atomic packing factor:

Volume occupied by atoms in a unit cell v =
3
r
3
4
8
v
3
3
a
16
3
a
8
3

3
4
8 =
|
|
.
|

\
|
=
Volume of the unit cell, V= a
3

V
v
cell unit the of volume
cell unit atoms by occupied volume
factor packing Atomic = =

16
3
a
a
16
3
V
v
APF
3
3
= = =
% 4 3 0.34
16
3
APF = = =
Void space :

Void space = (1-APF) 100 = (1-0.34) 100
= 76%

- Diamond cubic structure is loosely packed structure because the atomic packing factor is
only 34%.
- If the two atoms in the basis are identical, the structure is called diamond. Semiconductors
such as Ge, Si fall in this category. If the two atoms are different, the structure is called zinc
blende (ZnS) and examples are GaAs, AlAs, CdS, InSb etc.


Zinc Blende or cubic zinc sulphide structure:
Zinc Blende structure belongs to FCC Bravias lattice with a basis of two atoms (Zn and S). The
structure of ZnS is similar to diamond cubic structure except that the two atoms belonging to the
basis are not same. This structure can be considered to be formed by the two interpenetrating FCC
lattices (one sublattice with Zn atoms other with S atoms), which are displaced by one quarter of the
cube edge, along the body diagonal.







There are four molecules of ZnS per unit cell. Each atom there are four equidistant nearest
neighbouring atoms of opposite king arranged in a regular tetrahedral configuration. The
coordination number, APF and other parameters in this structure would be same as in the case of
diamond structure. The materials that crystallizes in zinc blende structure are InSb, Cds,CuF, AgI, SiC,
BeO, ZnTe, CdTe, GaAs etc.
The coordination number, APF and other parameters in this structure would be same as in the
case of diamond structure.
Because of covalent nature of the bonds the material which crystallize with these structures
(i.e. Diamond and ZnS) have very high hardness and are used as abrasives.
NaCl structure
NaCl and many other ionic solids crystallize in the rock salt structure which is also known as
sodium chloride structure. It belongs to the FCC Bravias lattice with two ions, one anion and
one cation forming a basis. The two ions are separated by a distance of a/2. Where a is the
lattice parameter.
The larger anions are in FCC packing with all octahedral interstitial positions filled with the
small cations. The octahedral interstitial(voids) are at the body center and at midpoint of cube
edges as shown in fig.






The structure can be thought of as two interpenetrating mono-atomic FCC lattices along the
cube edge by of the cube edges. If the corner of one FCC is located at (0,0,0), the other
corner of the other is located at (1/2,0,0)
Each ion in NaCl lattice has six nearest neighbor ions at a distance of a/2 i.e. its coordination
number is six. The ionic radius of Cl is about 1.81
0
A and for sodium it is about 0.98
0
A.
Number of NaCl molecules per unit cell
1) Number of Cl
-
ions per unit cell
(1/8) x8+(1/2)x6 = 4
2) Number of Na
+
ions per unit cell
(1/4) x12+1 = 4
Thus there are 4 molecules in each unit cell
The crystal having NaCl structure are KCl, KBr, AgBr, LiH




Cesium chloride
CsCl structure belongs to the simple cubic Bravias lattice with two atoms forming a basis.
The two atoms of a basis which are unidirectional are at positions (0,0,0) and (1/2,1/2,1/2)






In CsCl structure the Cs and Cl ions have the same size approximately. The
structure can be viewed as a BCC lattice with atoms of on type at the corners and
the atoms of the other type at the body centers. This structure is considered to be
formed by interpenetrations of two simple cubic lattices such that the corner of one
sub lattice is at the center of other sub lattice.

Each Cs ions is surrounded by eight Cl ions. Thus its coordination number is 8
Number of Cl ions per unit cell is (1/8)x8 = 1
Number of Cs ions per unit cell is =1
Number of CsCl molecules per unit cell is = 1
The crystals having CsCl structure are RbCl, LiHg, TiBr etc.