LECTURE 1&2&3

INTERATOMIC FORCES
(Solid State physics S.O.Pillai)
http://202.141.40.218/wiki/index.php/Unit-
3:_Atomic_Cohesion_and_Crystal_Binding#FORCE_BETWEEN_ATOMS
 Matter:
 Solid State Gaseous State
 Liquid State  Plasma (99% of universe)
Few centuries ago: few metals/alloys
Since last century: a large no. of new materials/crystal/alloys

Different physical/chemical/electrical properties ??

Solid/crystal Molecules Atoms Basic Particles

 physical/chemical/electrical properties depends on
Arrangement and interaction of atoms/molecules
Definite pattern governed by bonding

Bonding is governed by interaction

Q: What kind of force holds the atoms together in 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.
 Interatomic Binding
 All of the mechanisms which cause bonding between the atoms derive
from electrostatic interaction between nuclei and electrons. Magnetic
interaction is weak and gravitational is negligible

 The differing strengths and differing types of bond are determined by the
particular electronic structures of the atoms involved.

 Type of Bonding decides the physical, chemical and electrical properties .

 Bonds are made due to the resultant force of attraction and repulsion
b/w atoms.

 This force hold the adjacent atoms together at particular

spacing/position/pattern.
 Forces Between Atoms
Forces between atoms  Attractive ( keep the atoms together)
Repulsive ( when solid is compressed)

Suppose two atoms, exert attractive and repulsive forces on each other
such that the bonding force is

Due to attractive Due to repulsive

force
force

A B
F(r)  M  N with N>M
r r

Where, r centre to centre spacing

between the atoms.
A, B, M and N are constants
characteristics of the molecule.
 Potential Energy
A B
F(r)  M
 N U=0 when r=  C=0 and
r r
Thus,
a b
A B U(r)   m  n
U(r)=  F(r)dr   ( M
 N )dr r r
r r
Ar1M Br1N r : distance between the centers of
  C
1 M 1 N the atoms
a b n and m are +ve numbers
U(r)   m  n  C a: +ve constant
r r b: +ve constant
A B
where a= , b= , m=M-1, n=N-1
M 1 N 1
• Potential energy due to attraction is –ve , since the atoms do the work of
attraction.
• Potential energy due to repulsion, energy is +ve, since external work must
be done to bring the atoms together
• Potential energy is inversely proportional to some power of inter-atomic
spacing ‘r’.
 Energies of Interactions Between Atoms
 The energy of the crystal is lower than that of the free atoms by
an amount equal to the energy required to pull the crystal apart
into a set of free atoms. This is called the binding (cohesive)
energy of the crystal.

 NaCl is more stable than a collection of free Na and Cl.

Cl Na NaCl

The potential energy of either atom will be given by:

U= decrease in potential energy+increase in potential energy
(due to attraction) (due to repulsion)

a b
or simply: U (r )  m  n
r r
 This typical curve has a minimum at
equilibrium distance r0 V(R)
 r > r0 ;
 the potential increases gradually,
approaching 0 as R∞ Repulsive
 the force is attractive
 r < r0 ;
 the potential increases very 0 r0
rapidly, approaching ∞ at small r
separation.
 the force is repulsive
Attractive

 At equlibrium, repulsive force

becomes equals to the attractive
part.

The potential energy of either atom will be given by:

a b Potential Energy Curve
or simply: U (r )  m  n
r r
Quest: Determine Umin, value of r = r0=?
 Potential Energy  Cohesive Energy
The energy corresponding to the equilibrium position ( r=ro) denoted by U(ro) is called
the bonding energy or the energy of cohesion of the molecule. This is the energy
required to dissociate the two atoms of the molecule (AB) into an infinite separation.
This energy is also known as the energy of dissociation.

a b
U(r)   m  n a  a  m  1
r r U min    b    m
U(r) is mimimum at r=ro rom  b  n  ro
a b a m  a 
Thus , U(r)   m  n U min  m   m 
ro ro ro  n   ro 
 dU  ma nb
a  m
Hence,    m1  n 1 =0
 dr  r ro ro ro U min   m 1  
ro  n
 b  n  
ron  rom    
 a  m  
 Potential Energy
Let ro be the distance between the atoms for this minimum U( r) to occur.
r o  equillibrium spacing of the system. U(r=ro)min  –ve
a b
U(r)   m  n
r r V(R)
U(r) is mimimum at r=ro
 dU 
Thus ,   0 Repulsive
 dr  r ro
1
 b  n   n m 0 r0
ro     
 a  m  
Attractive
d U 
2
am(m  1) bn(n  1)
 2    m 2
+ n 2
>0
 dr  r ro ro ro
bn(n  1)  am(m  1)ron m
 b  n 
bn(n  1)  am(m  1)   
 a  m  The minimum for U(r) occur only if
n>m
(n  1)  (m  1)
 The attractive force should vary more
nm
slowly with r than repulsive force.
Problem: 1
a b
 Given Potential energy function is U(r)    9 ...
r r
1/8
 9b 
(a) Show that r  ro    in stable situation
a 
(b) Show that potential energy of the two particles in the stable
configuration is
 a  8
U(r)min     
 ro   9 
Problem:2
Assume the energy of two particles in the field of each other is given by
the following function of the distance ‘r’ between the centers of the
particles: a b
U(r)    8
r r
a) Show that the two particles from a stable compound for
1/7
 8b 
r  ro   
a 
b) Show that the P.E. of the two particles in the stable configuration is
equal to 
7
(a / r )
 8  o

c) Show that if the particles are pulled apart, the molecule will break a
soon as 1/7
 36b 
r
 a 
and that the minimum force required to break the molecule is

a 9/7  8
(36b) 2/7 1  36 
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 - Ionıc Bondıng
 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
 Bond Energy of NaCl molecule
 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.
Electron
affinity
Cl+e-Cl- + 3.6eV

Na+5.1eVNa++e-
Ionization
potential
Na+Cl+1.5 eVNa++Cl-
What happens when the electrostatic attraction between Na+ and Cl- ions
brings them together to the equilibrium spacing ro=0.24nm?
At the equilibrium potential energy will be the min. e2
V  6eV
4o ro
and the energy released in the formation of NaCl molecule is called the bond energy
of the molecule.
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

Cohesive or Dissociation 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
Calculation of Lattice Energy of Ionic Crystal
For two ions Z1e and Z2e
separated by a distance r, the
attractive energy is
Z1Z 2 e2

4 o r
For the whole crystal , the
Coulomb potential energy
may be written as
AZ1Z 2 e2

4 o r
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 ,

AZ1Z 2 e2 B Repulsive energy of this ion

U (r )    n due to presence of all other
4 o r r ions in the crystal.
n  repulsive exponent.
Calculation of Lattice Energy of Ionic Crystal
For univalent alkali halides
A e2 B
U (r )    n
4 o r r
The total energy per mol of
the crystal is
B A e2 
U (r )  N A  n  
 r 4 o r 
The potential energy is the NA= 6.022140857 × 1023
min. at the equilibrium  A e2 A e2 
U (r )r ro  U o  N A   
spacing ro . Thus,  4 r
o o 4 o nro

 dU (r )   A e 2 Bn  U o  U1  U 2
 dr   N A  4 r 2  r n 1   0 Where U1 and U2 represent the net
r  ro  o o o  coulomb attractive energy and repulsive
A e 2 Bn energy.  Ae2 N A   n  1
 n 1 Thus, Uo    
4 o ro ro 
 4 o ro   n 
2

A e 2 ron 1 This equilibrium energy Uo is

B
4 o n lattice energy
  Ae2 N A   n  1
Uo     
 4 o o  n 
r

This equilibrium energy Uo 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 ro between ions is

0.281 nm. Find the cohesive energy in NaCl. Given A=1.748 and n=9.
Solution:
 Ae N A   n  1
2
Uo       7.96 eV
 4 o ro   n 
Energy spent in ionization ( atomion) =5.13eV-3.6 0eV= 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

NA= 6.022140857 × 1023

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
e2  e2  2e2
   
4 o ro  4 o ro  4 o ro
The repulsive energy due to the two positive ions at a distance of 2ro is
2e2
4 o (2ro )
The attractive Coulomb energy due to two next neighbors at a distance 3ro
is 2e 2

4 o (3ro ) And so on….
Thus the total energy due to all the ions in the linear array is
2e2 2e2 2e2
    ...
4 o ro 4 o (2ro ) 4 o (3ro )
e2   1 1 1 
 2  1     ... 
4 o ro   2 3 4 
e2
  2 log(1  1)
4 o ro
e2
  2 log 2
4 o ro
Thus (2 log 2 ) is the Madelung constt. per molecule of the ionic
solid. Hence (2NA log 2) is the Madelung constant per mol of the
ionic solid.
Madelung constant in 3D

A
ro
 Na+ is coordinated by 6 Cl- ions at a distance r0.

 Attractive potential energy

6e 2

4 o ro
 Similarly, repulsive energy due  Na+ is coordinated by 8 Cl- ions
to 12 Na+ at 2 r0 at a distance (body diagonal ) 3r0 .
Attractive potential energy
12e 2 8e 2

4 o 2ro 40 3r0
 Similarly, repulsive energy due to 6 Na+ at 2r0

6e2
4 o 2ro
Madelung constant in 3D
Thus the Coulomb energy of this Na+ at A in the field of other ions is
6e2 12e2 8e2 6e2
U      ...
4 o ro 4 2 o ro 4 o 3ro 4 o 2ro
e2  12 8 6 
U  6     ...
4 o ro  2 3 4


For mol of the crystal , the total Coulomb energy is
N Ae 2  12 8 6 
U   6     ...
4 o ro  2 3 4 
N Ae 2 A
U 
4 o ro
AMadelung constant and A=1.75 for NaCl structure

NA= 6.022140857 × 1023