Physics

Paper No. : Solid State Physics

Module : Thermal Expansion and Lindemann Melting Formula

Development Team
Prof. Vinay Gupta, Department of Physics and Astrophysics,
Principal Investigator
University of Delhi, Delhi

Dr. A.B. Bhattacherjee, Professor, School of Physical Sciences,

Paper Coordinator
Jawaharlal Nehru University, New Delhi

Content Writer Dr. A.B. Bhattacherjee, Professor, School of Physical Sciences,

Jawaharlal Nehru University, New Delhi

Dr. Poonam Silotia, Department of Physics and Astrophysics,

Content Reviewer
University of Delhi, Delhi

Solid State Physics

Physics
Thermal Expansion and Lindemann Formula
Description of Module
Subject Name Physics
Paper Name Solid State Physics
Module Name/Title Thermal Expansion and Lindemann Melting Formula

Module Id

Solid State Physics

Physics
Thermal Expansion and Lindemann Formula
Contents of this Unit

1. Introduction
2. Thermal Expansion
3. Lindemann Melting formula
4. Summary

Learning Outcomes

After studying this module, you shall be able to

• Learn about the one dimensional model to explain the expansion of the solid.
• Know that crystal expands as temperature increases.
• Able to derive expression for Lindemann formula.
• To know that melting occurs when lattice vibration is too long.

Solid State Physics

Physics
Thermal Expansion and Lindemann Formula
 THERMAL EXPANSION AND LINDEMANN MELTING FORMULA

INTRODUCTION

While dealing with lattice vibrations, we had approximated the interatomic potential in a
Crystal by

1   2V 
V ( R1 , R2 .....RN )  V ( R10 , R20 ,....RN 0 )  
2! ij ( ,  x, y , z )
 Ri , 
 Ri , , R j ,   R j , 
  Ri ,0 R j ,0
higher terms
(5.1)
This we had referred to as the harmonic approximation which was used with much success to
discuss lattice vibrations. However there are number of physical phenomena such as (a)
Thermal Expansion (b) Melting of Solids (c) Thermal Conductivity (d) Temperature
dependence of Elastic Constants, which cannot be explained on the basis of harmonic
approximation. The reason of the inability of the harmonic approximation in explaining the
above mentioned phenomena lies in the fact that
(1) It is not always true that vibrations of atoms can be treated as small oscillations and;
(2) The potential cannot always be approximated by the quadratic term alone.
Figure 5.1 illustrates these points

Solid State Physics

Physics
Thermal Expansion and Lindemann Formula
 Figure5.1

In the figure 5.1, the actual potential felt by one atom and the corresponding harmonic
approximation is shown for comparison. Clearly, as the interatomic separation increases, the
harmonic approximation breaks down. The validity of harmonic approximation is questionable
at high temperatures where the amplitude of atomic vibrations is large. As examples of
anharmonic effects, we now in the next two sections deal with

(a) Thermal Expansion (b) Melting of Solids

Thermal Expansion

We will now give a simple one–dimensional model to explain the expansion of solids. We can
write Rx  Rxo   Rx where Rxo the equilibrium separation between two atoms is and

 Rx  Rx  Rxo is the deviation from equilibrium. In this situation, we can model the one-
dimensional potential shown in fig. 5.1 as

V ( Rx )  V ( Rxo )  C Rx2  g Rx3  f  Rx4 (5.2)

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Solid State Physics

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Thermal Expansion and Lindemann Formula
 Here, g and f are positive constants. The term c Rx2 is the usual harmonic component.

The asymmetry in the potential around  Rx  0 is accounted for by the term g Rx3 . When

 Rx is negative,  g Rx3 is positive and hence makes the short range repulsion larger. When
 Rx is positive,  g Rx3 is negative and hence makes the interatomic repulsion smaller for large
Rx . The term f  Rx4 represents the softening of the vibration at large amplitudes.
We now move ahead and evaluate the expectation value   Rx  as a function of temperature T


 d ( R ) R e
 V
x x

  Rx  
 (5.3)


d ( Rx )e  V

Taking into account, equation (5.2) we find,

e V  e  [V ( Rxo )C Rx ] (1   g Rx3   f  Rx4 )

2

(5.4)

We now evaluate the integrals in the numerator and denominator as

 

 d ( Rx )e  d ( Rx )e x (1   g Rx   f  Rx )
 V  V ( Rxo )   c R
e
2
2 4
(5.5)
 

The odd function  g Rx3 vanishes while the contribution of  f  Rx4 is negligible, Hence

 1/2
  
 d ( R )e
 V  V ( Rxo )
e  
 C 
x (5.6)


Solid State Physics

Physics
Thermal Expansion and Lindemann Formula
 Similarily,
 

 d ( Rx ) R x e  d ( Rx ) R x e x (1   g Rx   f  Rx )
 V  V ( Rxo )   c R
e
2
2 4
(5.7)
 

In the above integral only  g Rx3 contribute and hence


3 

 d ( Rx ) R x e V ≃ e V ( Rxo )
4
3g (  C )5/2 (5.8)

Finally we get,

1 3g 3g
  Rx   k BT
 4c 2
4c 2 (5.9)

The above expression equation. 5.9 shows that as the temperature increases the crystal expands
since   Rx  T .

Lindemann Melting Formula

Let us now determine the melting temperature of a solid. To this end, we will be using quantum
concepts. A solid melts because the vibrations of the atoms about their equilibrium positions

become too large. Hence we have calculated the mea n-square amplitude of vibration   R j 
2

at a certain temperature. We can make a preliminary guess that a solid will melt if   R j  Ro
2 2

(square of the interatomic spacing).

A parameter which can quantify melting of a solid is
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Solid State Physics

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Thermal Expansion and Lindemann Formula
   R 2j 
r (5.10)
R02

Now since from module 2 we have

1
 Rj   ˆ
iK . R
K ,
qˆ K , e j 0
N K,

(5.11)

1
 qˆ

i ( K  K ). R j ,0
 R 2j  ˆ
q †

K , K ,  e 
ˆ .
K ,
ˆ K , 
N K,
(5.12)
K , 

We will only retain the term for which K  K ,     since other terms for which

K  K and     describe transitions between states with different nK (phonon occupation

number).

Consequently,

1
  R 2j  
N K ,
 qˆK† , qˆK ,  (5.13)

We now express   R j  in terms of the phonon operators

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Solid State Physics

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Thermal Expansion and Lindemann Formula
 1
  R 2j  
2MN K , K ,
 (aˆK† ,  aˆ K , )(aˆK ,  aˆ† K , )  (5.14)

1  1
  R 2j  
MN  
 nK ,    (5.15)
K , 
K, 2

1  EK ,  
  R 2j 
MN

K, K2 , (5.16)

Where  nK ,  and  E K ,  are the average number and average energy of phonons in mode

K ,  . This will now help us to write the expression for r,

 EK ,  
r
K , MN K2 , R02 (5.17)

We will now take the help of Debye approximation i.e K ,  v k .

Therefore, we have for low temperatures taking into account only the zero-point vibrations

3 1
rlow    
K , 2MNK , R02 2MNv R02 K K (5.18)

Solid State Physics

Physics
Thermal Expansion and Lindemann Formula
 KD
3 L3
rlow 
2 MNv R02 (2 )3  4 KdK
0
(5.19)

3 K D2 L3
rlow 
8 2 MNv R02 (5.20)

K D3 3 v K
Using N   and D   D
6 2
4 R0
3
kB

0.4k B D
rlow  (5.21)
Mv2

For high temperatures using the equipartition of energy,  EK ,  kBT , we have

1.6 2 K D2
rhigh  k BT (5.22)
M  D2

Now if T   D , then we can write down a relation between melting temperature Tm and D as

1/2
 1.6 
1/2
 2  2.4  
2

D     kBTm    (5.23)
 rm   M  0  
R

Where rm is critical value of r for which melting will occur

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Solid State Physics

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Thermal Expansion and Lindemann Formula
 Metal Tm (o K)  D (0 K )
Experime ntal
Li 459 400
Na 370 160
K 355 100
Table 5.1

Table 5.1 shows clearly when T   D , melting occurs and that implies melting occurs when

lattice vibrations become too large.

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Solid State Physics

Physics
Thermal Expansion and Lindemann Formula