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 (x) in one dimension ((r) in 3D) Hence its behaviors can be studied with the Schrdinger's equation (1D)
2

( x) x2

2m ( E V ) ( x) 0 2
2

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

( x) 2 k ( x) 2 x

0,

Ef

With

2mE 2k 2 h , or, E , 2 2m 2

Sommerfields 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 Hence, V(x) =0, for 0<x<L . e= , for x=0 & x=L V(x) 0 L x

Schs equation ,

( x) x2

2mE 2

( x)

Solution of the equation can be obtained as (x) = A sin kx + B cos kx From boundary conditions , at x=o & x=L , (x)=0, we can get B=0 and k= n / L , Putting the normalization condition we get A= 2/L

 Substituting all the values n (x) = ( 2/L) sin nx /L & En (x) = 2 k2 / 2m = 22n2 / 2m L2 = h2n2/ 8mL2 This shows that energy of the electrons inside the material is quantized and hence is discrete

n=3

E3

n=2

E2

n=1

E1

In 3D, n (r) = ( 8/L3) sin nxx /L sin nyx /L sin nzx /L & En (r) = 2 k2 / 2m = (nx2+ny2+nz2) 22 / 2m L2

Fermi Level and Fermi Energy:

Electrons are fermions or Fermi particles, which obey Paulis 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 Energy Ef = 2 kf2 / 2m or kf = (2mEf / 2 )1/2 In 3D electrons will fill up the k-space with one state accommodating 2 electrons each ( ) If N is the total no. of electrons & is large , electrons will occupy a sphere of radius kf , then highest occupied state nf = N/2 ky
kf

From uncertainty principle x p =h or, x k = h Or, L (h/2) k = h or, k = 2 / L

electron states

kx

 Size of each state in k-space of radius kf

4 kf 3 2 L
3

= Kf3 L3 / 62 Hence no. of electrons N = 2 X ( Kf3 L3 / 62 )

N = kf3 V / 32

So, kf = {32 (N/ V) }1/3 kf = (32 n) 1/3

where n = electron density = N/V = 1/ V (kf3 V / 32 )

1 3
2

Or, n=

2m 2

3 2

3 2 f

 Hence at 0K, the fermi energy Ef (0) = 2 kf2 / 2m = 2 / 2m ( 32n)2/3 = h2/ 8m (3n/ ) 2/3 Fermi velocity vf = kf / m = /m (32n) 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) = Vk3 / 32 = V/ 32 ( 2mE/ 2)3/2 Density of state = no. of states per unit energy range per unit volume of the metal

1 dN ( E ) or , Z(E) = V dE

d k3 dE 3 2

d 1 2mE dE 3 2 2

3 2

 =
Or, Z(E)=

1 3
2

2m 2
1
2

3 2

3 E 2
3 2

1 2

2m 2

1 2

Z(E) 0
E

T=0

or,

Z(E)

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 Ef )

k T

1
F(E) T=0

At T= 0 K If E < Ef , then F(E)=1 If E > Ef , then F(E)= 0

Ef

At T > 0 K Some states below Ef are unoccupied and some above are occupied F(E) For E= Ef , F(E) = *This is applicable in an energy range k T
E

 Average energy of free electrons

Av. Energy = total energy of all the electrons in the metal no. of electrons per unit volume
E.Z ( E ) F ( E ) dE

<E> =

( In a metal some states above fermi level are occupied at T > 0K At T = 0 K : upper limit of integration is Ef0 and F(E) is 1
E f0

E.
0

1 2
2

2m 2 1 3
2

3 2

1 2

<E0 > =
2m 2
1 3
2

e
3 2

E
1 2

1 Ef

dE 1

k T E

As, n= N(E)/ V = kf3 /32

2m 2

3 2

3 2

<E0> =

5 1 E f0 2 2 3 5 1 . E f0 2 2 3

so,

<E0> = 3/5 Ef0

For T > 0 K < E T> =

1 1 n 2 2

2m 2
2

3 2 0

E dE
E Ef

1 2

k T

E0

5 12

k T E f0
2

As , E f(T) =

E f0 1

k T E f0

12

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 T) = = 3/2 k Molar specific heat = C = n C = 3/2 n k Hence, thermal conductivity K = 1/3 C vth But according to quantum theory, av. Energy of a free electron, 2 2 2 k T 3 5 E E f0 1 5 12 E 2 f 0 For an electron density n C = n d<E>/ dT = 2nk2T / 2Ef0 specific heat = So, thermal conductivity K = 1/3 (2nk2T / 2Ef0 ) vth 2 = 2k2nT / 3m (as mvth2 = Ef0 ) Thus, Weidman Franz law K/ = 2k2T/ 3e2 = LT L= Lorenz no. = 2k2/ 3e2 = 2.45X 10 -8 W / K2, which agrees well with exptl. result