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Quantum free electron theory

Particles of micro dimension like the electrons are studied under

quantum physics

moving electrons inside a solid material can be associated with

waves with a wave function ψ(x) in one dimension (ψ(r) in 3D)

Hence its behaviors can be studied with the Schrödinger's

equation (1D)

2

( x )

x

2

2 m

2

(
E V
)
(
x
)
0

For a free particle V=0, hence the equation reduces to

2

( x )

x

2

k

2

E
E f

K

( x ) 0,

2

k

2

2

mE

With

k

2

o r E

,

2 ,

2

m

,

h

2

Sommerfield’s model

As the freely moving electrons can not escape the surface of the

material, they may be treated as particles confined (trapped)in a

box

. e-
V(x)
0
L
x
0

Hence, V(x) =0,

for

0<x<L

x=0 & x=L

= ∞, for

Sch’s equation ,

2

( x )

2 mE

( x )

x

2

2

Solution of the equation can be obtained as

ψ(x) = A sin kx + B cos kx

From boundary conditions , at x=o & x=L , ψ(x)=0,

we can get

B=0 and

k= ± nπ / L ,

Putting the normalization condition we get A= √2/L

Substituting all the values

Ψ n (x) = (√ 2/L) sin nπx /L

&

This shows that energy of the electrons inside the material is quantized and hence

E n (x) = ħ 2 k 2 / 2m = ħ 2 π 2 n 2 / 2m L 2 = h 2 n 2 / 8mL 2

is discrete
ψ3
ψ2
ψ1

n=3

n=2

n=1

E3
E2
E1

In 3D,

Ψ n (r) = (√ 8/L 3 ) sin n x πx /L sin n y πx /L sin n z πx /L

Fermi Level and Fermi Energy:

Electrons are fermions or Fermi particles, which obey Pauli’s

exclusion principle

At

0K temperature the highest filled energy level is called the

Fermi Level” & the energy possessed by the electrons in that

level is “Fermi EnergyE f = ħ 2 k f 2 / 2m

In 3D electrons will fill up the k-space with one state

k f = (2mE f / ħ 2 ) 1/2

or

accommodating

2 electrons each ( ↑↓)

N is the total no. of electrons & is large , electrons will occupy a sphere of radius k f , then highest occupied state n f = N/2

If

From uncertainty principle ∆x ∆p =h or, ∆x ħ∆k = h

Or, L (h/2π) ∆k = h

or, ∆k = 2π / L

k
y
k f
k x

electron states

Size of each state in k-space of radius kf

3
4
k f
3
3
2
L

=

K f 3 L 3 / 6π 2

Hence no. of electrons ‘N’ = 2 X ( K f 3 L 3 / 6π 2 )

N = k f 3 V / 3π 2

So, k f = {3π 2 (N/ V) } 1/3

k f = (3π 2 n) 1/3

where n = electron density = N/V = 1/ V (k f 3 V / 3π 2 )

Or, n=

1

2

3

2 m

2

3

2

E

3

2

f

Hence at

Ef (0) = ħ 2 k f 2 / 2m

= ħ 2 / 2m ( 3π 2 n) 2/3

= h 2 / 8m (3n/ π ) 2/3

Fermi velocity

0K, the fermi energy

v f = ħk f / m = ħ /m (3π 2 n) 1/3

Density of States

No. of free electrons within energy value ‘E’

= no. of states within the sphere of radius ‘k’ in k-space

= N(E) = Vk 3 / 3π 2 = V/ 3π 2 ( 2mE/ ħ 2 ) 3/2

Density of state = no. of states per unit energy range per unit volume

of the metal

or ,

Z(E) =

 1 d N E ( ) V d E

d

d E

3
k
2
3
d
1
2
d E
3
3
2 mE
2
2

=

1

2

3

2 m

2

3

2
1
2 m
• Or, Z(E)=
2
2
2
Z(E)
T=0
0

E

3

2

3

2

or,

1

2

1

2

E

E

Z(E)

α

E ½

Fermi Dirac distribution function

Distribution of electrons in different energy states is given by Fermi-Dirac statistics.

Fermi Dirac distribution function F(E) gives the probability of

occupation of an energy level ‘E’, by an electron at temperature ‘T’

F(E) =

1

(
E
)
E f

e

k

T

1

If

If

At

T= 0 K

E

E >

< E f

E f

, then F(E)=1 , then F(E)= 0

F(E)

T=0
E f

E

At

Some states below E f are unoccupied and some above are occupied For E= E f , F(E) = ½ *This is applicable in an energy range k β T

T > 0 K

F(E)
E

Average energy of free electrons

Av. Energy =

total energy of all the electrons in the metal no. of electrons per unit volume

(

E

)

F

(

E dE

)

E Z

.

< E >

=

0

n

( In a metal some states above fermi level are occupied at T > 0K

At T = 0 K : upper limit of integration is

E f0 and F(E) is

1

<E 0 >

=

3

E
f
1
0
1
2
m
2
1
2
E .
E
d E
2
2
E
E
2
f
0
e
1
k
T
3
1
1
2 m
2
2
E
2
2
3

As, n= N(E)/ V = k f 3 /3π 2

=

1

2

3

2 m

2

3

2

3

E 2

5
1
E
2
f
0
2
<E 0 >
=
3
5
1
.
E
2
f
0
2
3
<E 0 > =
3/5 E f0
so,
1
For
T > 0 K
3
2
1
1
2 m
2
E dE
< E T > =
2
2
E
E f
n
2
0
k T
e
1
2
2
5
k T
=
E
1
0
1 2
E
f
0
2
2
k T
As , E f (T) =
E
1
f
0
1 2
E
f
0

Specific heat and Lorenz no. in quantum theory

As per classical theory , Specific heat ‘C’ of the electron gas

= (dE / dT) = d/dT (3/2 k β T) =

= 3/2 k β

C =

n C = 3/2 n k β

Molar specific heat =

Hence, thermal conductivity K = 1/3 C v th λ But according to quantum theory, av. Energy of a free electron,

E

3

5

E

f

0

For an electron density ‘n’

1

2

5

1 2

2
2
k
T
2
E
f
0

C = n d<E>/ dT = π 2 nk β 2 T / 2E f0

specific heat =

So, thermal conductivity K = 1/3 (π 2 nk β 2 T / 2E f0 ) v th 2 τ

π 2 k β 2 nTτ / 3m (as ½ mv th 2 = E f0 ) Thus, Weidman Franz law K/σ =

=

π 2 k β 2 T/ 3e 2 = LT L= Lorenz no. =

π 2 k β 2 / 3e 2 = 2.45X 10 -8 WΩ / K2, which agrees well with exptl. result