Unit-I

Quantum theory
 Success and Failure of Classical Model

◆ Gives explanation for both electrical and thermal conduction

◆ Wiedemann-Franz law can be derived
◆ Ohm’s law can be verified

Failure
◆ Does not explain electrical resistivity with Temperature
◆ Lorentz number obtained from C.T differs from experimental
value
◆ Specific heat capacity of electron is higher than the actual
value
◆ Photoelectric, Compton effect, Black body radiation
can’t be explained
◆ Not distinguish metal, semiconductor, insulator
◆ Not explain ferromagnetic and paramagnetic susceptibility
 Quantum Theory of Free Electron

◆ Failure of classical free electron –Another theory –

◆ Sommerfeld (1928) –QUANTUM CONCEPTS

◆ From CFET
✓ Free electron – responsible for conduction
✓ Totally free to move with in the crystal
✓ Electrostatic interaction between e-  e- and e-  lattice
ion
✓ In applied filed, e- moves away from the field with
constant velocity (drift velocity)
◆ According to QFET –electrons are like wave
◆ Velocity and the energy distribution of electron
◆ By Fermi Dirac function
◆ Pauli’s exclusion principle is applicable
 Quantum Theory of Free Electron

◆ Electrons are quantum particles (fitting Quantum Theory)

– Sommerfeld theory
◆ Metals – treat as 3D Potential Box
– Electron move freely
– Potential within the box is ZERO (U=0)

– At end of the box (U=)

– Pauli’s exclusion principle is applicable
– System of Free electrons –Fermi gas (since e-e- is neglected)

◆ Motion of electron by Schrödinger wave eq.

  + 2 (E − U ) = 0
2 2m

0  x  a

0  y  b for U ( x, y, z ) = 0
0  z  c 
 2m Since U=0
  + 2 E = 0
2

Height - 

U(x)=  U(x) = 

U(x) = 0

x=0 x=a
 d 2
2
+ k 2
 =0 Total derivative is the same as partial
Derivative becs,  is the function only
dx
Of x
2m
where k = 2 E 2


 ( x) = A sin kx + B cos kx

A and B are constants to be determined from boundary conditions

At x = 0, =0

0 = A sin k 0.0 + B cos k 0.0

0=B -> (x) = A sin kx

And At x = a then =0 => 0 = A sin ka

A = 0 is meaning less, ie it means that no wave

ka = n ; where n = 1,2,3…..
k = n / a

(2mE/ ħ2 ) = n / a

Energy of particle can not be any arbitrary values,

It can have only certain discrete values

2m n 2 2
En = 2
 2
a
n 2 2  2
En = 2
where n = 1,2,3.... ; are energy eigen values
2ma
n  (h / 2 )
2 2 2
n2h2
or ⎯⎯→ En = 2
=
2ma 8ma 2
N=0 is excluded since E0=0 then  become ‘Zero’ which
not permissible physically and quantum mechanically

It s energy is quantized.
Wave function of particle in a box whose energy En with B=0

2mEn
 ( x) = A sin x

n
 ( x) = A sin x
a

For each n,  is a finite, single valued function of ‘x’

n and dn/dx are continuous

Integral of | n |2 for over all space is finite.

To normalize  we have assign the value of A



  ( x) dx = 1
2

−
a

  ( x) dx = 1
2

 n 
a
A  sin 
2
x dx = 1
2

0  a 
A   n  
2 a a

  dx −  cos 2 x dx = 1 ; from trignametry;

2 0 0  a  
L
A   a   2n 
2
1
 x −  sin x  = 1 sin  = (1 - cos2 )
2

2   2n   a  0 2
2
A
a = 1 →→→ A = 2
2 a
 The normalized wave function of the particle

2 n
n = sin x n = 1,2,3....
a a
0.4 0.4
0.2 0.2
0.0 4 |4|2 0.0
-0.2 -0.2
-0.4 -0.4
0.4 0.4
0.2 0.2
0.0
-0.2 3 |3| -0.2
2 0.0
-0.4 -0.4
0.4 0.4
0.2 0.2
0.0
-0.2 2 |2|2-0.2
0.0

-0.4 -0.4
0.4 0.4
0.2 0.2
0.0 1 |1|20.0
-0.2 -0.2
-0.4 -0.4
0 2 4 6 8 10 0 2 4 6 8 10
A A
For metal, we have to extend to 3-dimensions
(while box dimension is a x b x c

2 2 2 nx n y n z
n n n = sin x sin y sin z n = 1,2,3....
x y z
a b c a b c
   n x n y n z 
2
2 2 2 2
En x n y n z =  2
+ 2 + 2 
2m  a b c 
nx, ny nz take 1,2, 3… independently

For cubic ie a=b=c

En x n y n z =
 2 2
2ma 2
(n x
2
+n y +n z
2 2
)
For ground state
 2 2
E111 = 2
3
2ma
In terms of wave vector
2 2
Ek = k
2m

k2 =
2
a 2
(n x
2 2
)
+n y +n z = k x + k y + k z
2 2 2 2

K specifies the state of the electron

The corresponding momentum of electron p=ħk

2 2
Ek = kx + k y + kz
2 2

2m
1
Ep = px + p y + pz
2 2 2

2m

px = nx
a
This theory treats the electron as quantum particles
rather than classical.

It explains the electrical conductivity, thermal

conductivity specific heat capacity of metal and
electron, photoelectric effect Compton effect, Etc.

Even though it explains most of the physical properties

of metals it fails to prove the distinction between metal
semiconductor And insulator.

It also fails to explain the positive value of hall

coefficient and some transport properties of metals.