Interatomic Forces: Solid State Physics by S.O.Pillai)

LECTURE 1
INTERATOMIC FORCES
(Solid State physics by S.O.Pillai)
Q: What kind of force holds the atoms
together in a solid?
The bonds are made of attractive and repulsive forces
that tend to hold the adjacent atoms, this process of
holding atoms together is known as BONDING.
http://202.141.40.218/wiki/index.php/Unit-
3:_Atomic_Cohesion_and_Crystal_Binding#FORCE_BETWEEN_
ATOMS
Types of Bonding Mechanisms
It is conventional to classify the bonds between
atoms into different types as

Ionic,
Covalent, Primary (interatomic)
Metallic,

Van der Waals,
Hydrogen. Secondary (intermolecular)

1 - Ionc Bondng
Ionic bonding is the electrostatic force of attraction between positively
and negatively charged ions (between non-metals and metals).

These ions have been produced as a result of a transfer of electrons
between two atoms with a large difference in electro negativities.

Na Cl
Notice that when sodium loses its one valence electron it gets smaller in size,
while chlorine grows larger when it gains an additional valance electron. After
the reaction takes place, the charged Na+ and Cl- ions are held together by
electrostatic forces, thus forming an ionic bond.
Bond Energy of NaCl molecule
Na+5.1eVNa
+
+e
-
Cl+e
-
Cl
-
+ 3.6eV

Na+Cl+1.5 eVNa
+
+Cl
-

What happens when the electrostatic attraction between Na
+
and Cl
-
ions
brings them together to the equilibrium spacing r
o
=0.24nm?
At the equilibrium potential energy will be the min.

and the energy released in the formation of NaCl molecule is called the bond energy
of the molecule.
2
o o
e
V 6eV
4 r
= =
tc
Electron
affinity
Ionization
potential
Thus energy released in the formation of NaCl molecule starting from neutral
Na and Cl atoms having zero potential energies is (5.1-3.6-6)=-4.5eV.

Na
+
+Cl
-
Na + Cl NaCl +4.5eV

0.24nm

Energy released
Calculation of Lattice Energy of Ionic Crystal

BOND ENERGY for particular molecule(making bond),
Energy liberated by the formation of the crystal from
individual neutral atom.

LATTICE ENERGY for particular crystal. (chain of
molecules with bond)

Cl
Na NaCl
Bond Energy
Lattice energy
For two ions Z
1
e and Z
2
e
separated by a distance r, the
attractive energy is

For the whole crystal , the
Coulomb potential energy
may be written as
2
1 2
4
o
Z Z e
r tc
2
1 2
4
o
AZ Z e
r tc
The minus sign shows that the net Coulomb energy is attractive. The
constant A is MADELUNG constt.
Now the total energy of one ion due to presence of all others ,
2
1 2
( )
4
n
o
AZ Z e B
U r
r r tc
= +
Repulsive energy of this ion
due to presence of all other
ions in the crystal.
n repulsive exponent.
For univalent alkali halides

The total energy per kmol of
the crystal is

The potential energy is the
min. at the equilibrium
spacing r
o
. Thus,

2
( )
4
n
o
A e B
U r
r r tc
= +
2
( )
4
A
n
o
B A e
U r N
r r tc
(
=
(

2
2 1
2
2 1
2 1
( )
0
4
4
4
o
A
n
r r o o o
n
o o o
n
o
o
dU r A e Bn
N
dr r r
A e Bn
r r
e r A
B
n
tc
tc
tc
+
=
+
(
(
= =
(
(

=
=
| |
2 2
1 2
( )
4 4
o
o A
r r
o o o o
o
A e A e
U r U N
r nr
U U U
tc tc
=
(
= = +
(

= +
Where U
1
and U
2
represent the net
coulomb attractive energy and repulsive
energy.
Thus,
2
1
4
A
o
o o
Ae N n
U
r n tc
(

(
=
(
(

2
1
4
A
o
o o
Ae N n
U
r n tc
(

(
=
(
(

This equilibrium energy U
o
is called the lattice energy . This is defined as
the energy released in the process when the constituent ions are placed in
their respective positions in the crystal lattice or this is the amount of energy
which is spent to separate the solid ionic crystal into its constituent ions.

Example: In a NaCl crystal , the equilibrium distance r
o
between ions is
0.281 nm. Find the cohesive energy in NaCl. Given A=1.748 and n=9.
Solution:

Energy spent in ionization ( atomion) =1.53 eV
Cohesive energy (in crystal) per NaCl molecule=(-7.96+1.53)=-6.42 eV
And, Cohesive energy (in crystal)per atom=-6.42/2=-3.21 eV

Experimental value=-3.28 eV

2
1
7.96 eV
4
A
o
o o
Ae N n
U
r n tc
(

(
= =
(
(

Calculation of Madelung constt. of Ionic Crystal
Madelung constant (A) represents the effect of a specific geometrical
array of ions on the electrostatic potential energy. It is a property of the
crystal structure and depends on the lattice parameters, anion-cation
distances, or molecular volume of the crystal.

Madelung constant (A) in a linear chain of ions of alternateive signs

The attractive Coulomb energy due
to nearest neighbors is

The repulsive energy due to the two positive ions at a distance of 2r
o
is

The attractive Coulomb energy due to two next neighbors at a distance 3r
o

is
And so on.
2 2 2
2
4 4 4
o o o o o o
e e e
r r r tc tc tc
(
+ =
(

2
2
4 (2 )
o o
e
r tc
2
2
4 (3 )
o o
e
r tc
Thus the total energy due to all the ions in the linear array is

Thus (2 log 2 ) is the Madelung constt. per molecule of the ionic
solid. Hence (2N
A
log 2) is the Madelung constt per kmol of the ionic
solid.
| |
| |
2 2 2
2
2
2
2 2 2
...
4 4 (2 ) 4 (3 )
1 1 1
2 1 ...
4 2 3 4
2log(1 1)
4
2log2
4
o o o o o o
o o
o o
o o
e e e
r r r
e
r
e
r
e
r
tc tc tc
tc
tc
tc
+ +
(
| |
= + +
|
(
\ .

= +
=
Madelung constant in 3D
Na
+
is coordinated by 6 Cl
-
ions at a distance r
0
.
Therefore ,
Attractive potential energy

Similarly , repulsive energy due to
12 Na
+
at \2 r
0

and due to 6 Na
+
at 2 r
0

2
6
4
o o
e
r tc
2
12
4 2
o o
e
r tc
2
6
4 2
o o
e
r tc
r
o
a
A
Madelung constant in 3D
Thus the Coulomb energy of this Na
+
at A in the field of other ions is

For kmol of the crystal , the total Coulomb energy is

AMadelung constant and A=1.75 for NaCl structure
2 2 2 2
2
6 12 8 6
...
4 4 2
4 2 4 3
12 8 6
6 ...
4
2 3 4
o o o o o
o o o
o o
e e e e
U
r r
r r
e
U
r
tc tc
tc tc
tc
= + + +
(
= + +
(

2
12 8 6
6 ...
4
2 3 4
A
o o
N e
U
r tc
(
= + +
(

2
4
A
o o
N e A
U
r tc
=
2 - COVALENT BONDING
Covalent bonding takes place between atoms with small
differences in electronegativity which are close to each
other in periodic table (between non-metals and non-
metals).
The covalent bonding is formed by sharing of outer shell
electrons (i.e., s and p electrons) between atoms rather
than by electron transfer.
This bonding can be attained if the two atoms each
share one of the others electrons.
So the noble gas electron configuration can be attained.

Each electron in a shared pair is attracted to both nuclei
involved in the bond. The approach, electron overlap, and
attraction can be visualized as shown in the following
figure representing the nuclei and electrons in a hydrogen
molecule.
e
e
Comparison of Ionic and
Covalent Bonding

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LECTURE 1

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