Homework 2

João Felipe Chaves e Silva

Sep 2021
Calculating Electrical
Conductivity from
Boltzmann Equation

Starting from the Boltzmann equation:

 
∂f ∂k ∂f
+ v · ∇r f + · ∇k f =
∂t ∂t ∂t coll

Consider a homogeneous (∇r f = 0, ∂f /∂t = 0) free electron gas subject

to an external electric field E such that ∂k/∂t = −eE. The collision term and
the equilibrium distribution are assumed to take the form:

 
∂f f (k) − f0 (k) 2
=− , f0 (k) = ,
∂t coll τ (k) ek −µ/kb T + 1
with a factor of 2 in the Fermi distribution due to spin. Using k = k 2 /2m,
we have:

E · k ∂f
f (k) ≈ f0 (k) + eτ (k)E · ∇k f (k) = f0 (k) + eτ (k)
m ∂k
The electric current in the presence of an electric field is then calculated by

d3 k d3 k
Z Z  
k ∂f
J = −ehvi = −e 3
f (k) = e2 τ (k)vk (vk · E) −
(2π) m (2π)3 ∂k
Note that the integration of f0 (k) does not contribute to the above integral.
At low temperature limit −∂f /∂k = 2δ(k − f ) and choosing the electric field
to be along x direction, show that the current in the same direction is:

!
e2 Ex ne2 τf
J x = σ xx Ex = (2mf )3/2 τf = Ex
3π 2 m m

1
 from which it follows that the longitudinal conductivity is σ xx = ne2 τf /m,
where τf = τ (f )

Solution
First, let’s write the electric current equation:

d3 k
Z  
∂f
J = e2 τ (k)v k (v k · E) −
(2π)3 ∂k
Considering that E is along the x direction, we will have:
!
π 2π ∞
e2 k2
Z Z Z 
∂f
J= dθsinθ dφ τ (k) E · 2 − k 2 dk
8π 3 0 0 0 m ∂k
!
π 2π ∞
e2 k2
Z Z Z 
∂f
J= dθsinθ dφ τ (k) E · 2 − k 2 dk
8π 3 0 0 0 m ∂k
2 Z π Z 2π Z ∞  
e Ex 2 ∂f
J= dθsinθ dφ τ (k)k x − k 2 dk
8π 3 m2 0 0 0 ∂k

But kx = kcosθ, so:

π 2π ∞
e2 Ex
Z Z Z  
2 4 ∂f
J= dθcos θsinθ dφ τ (k)k − dk
8π 3 m2 0 0 0 ∂k
√ 1
Considering now that k = 2k m, and dk = (2k m3 )− 2 dk :

π 2π ∞
e2 Ex
Z Z Z 
∂f 1
J= dθcos sinθ 2
dφ (2k m) − m (2k m)− 2 τ (k )dk
2
8π 3 m2 0 0 0 ∂ k

Z ∞
e2 Ex π
Z Z 2π  
2 3 ∂f
J= dθcos sinθ dφ (2k m) 2 − τ (k )dk
8π 3 m 0 0 0 ∂k
Z ∞
e2 E x π
Z Z 2π
3
2
J= 3
dθcos sinθ dφ (2k m) 2 2δ(k − f )τ (k )dk
8π m 0 0 0
3 Z π
2
(2f m) 2 τ (f )e Ex
J= 4π dθcos2 sinθ
m 8π 3 0

This integral value is equal to 2/3, so:

3
(2f m) 2 τ (f )e2 Ex
J= 8π


m 3 · 8
π 3
e2 Ex 3
J= 2
(2f m) 2 τ (f )
3π m
J = σ xx Ex

2
Arriving at the result that we wanted to prove!

3
Classical Paramagnet

A collection of N classical paramagnet in a magnetic field is described by the

Hamiltonian:

N
X
H=− mi H
i=1

where the magnetic moment takes only two values mi = ±m, and H is the
magnetic field. Now the fundamental thermodynamic relation for this system
is:

T dS = dU + M dH
because it has to take into account the energy to build up the magnetic
moment. The magnetization is M = nm and the internal energy U = −Hnm
where n = n+ − n− and N = n+ + n− , i.e., n± = (N ± n)/2
(1) In the kinetic theory approach, we consider the number of ways to realize
a configuration that has magnetic moment M is W = N !/n+ !n− !. Use this and
the Stirling formula lnN ! ≈ N lnN − N to show that the entropy is:
"       #
N kb n n n n
S = kb lnW = N kb ln2 − 1+ ln 1 + + 1− ln 1 −
2 N N N N
(2) Use the Maxwell relations:
       
1 ∂S ∂n ∂S ∂S ∂n ∂S
= = , M =T =T
T ∂U H ∂U H ∂n ∂H U ∂H U ∂n
to show that the inverse of temperature, internal energy, and magnetization
are:
 
1 kb N Hm + U Hm
=− ln , U = −N Hmtanh ,
T 2Hm N Hm − U kb T
U Hm
M = − = N mtanh
H kb T

4
 At high temperature and small field, M ≈ N Hm2 /kb T , gives a susceptibility
χ = ∂M/∂H ≈ N m2 /kb T that is inversely proportional to temperature, called
Curie’s law.
(3) In the Gibbsian ensemble approach, use the partition function and the
Helmholtz free energy:

 
N
Y X 1
QN =  e−βHmσ  , A = − lnQN ,
i=1 σ=±
β

and the identities

∂A ∂
M =− , U =− lnQN
∂H ∂β
to obtain the same magnetization M and the internal energy U as in (2)

Solutions
(1) First, writting the number of states we have:

N!
W =
n+ !n− !
↓
lnN !
lnW = = lnN ! − lnn+ ! − lnn− !
ln(n+ !n− !)
Now, using Stirling’s formula:

lnW = N lnN − N − n+ lnn+ + n+ − n− lnn− + n−

↓
           
N +n N +n N −n N −n N −n N
(+ (n((
= N lnN − − (−
(
ln ln + (N +
( (
2 2 2 2 ((( 2 ( 2
       
N +n N +n N −n N −n
= N lnN − ln − ln
2 2 2 2
       
N +n N −n N −n N +n
= N lnN − ln(N + n) − ln(N − n) + ln2 + ln2
2 2 2 2
       
N +n n N −n n
= N lnN + N ln2 − lnN 1 + − lnN 1 −
2 N 2 N
"       #
N n n n n
lnW = NlnN + N ln2 − 
 N lnN −
 1+ ln 1 + + 1− ln 1 −
2 N N N N

5
 And calculating the entropy, we will get:

"       #
N kB n n n n
S = kB lnW = N kB ln2 − 1+ ln 1 + + 1− ln 1 −
2 N N N N

As we wanted to show!
(2) Let’s first calculate the temperature:

 " 
        #
1 ∂n ∂  N kB n n n n
= N kB ln2 − 1+ ln 1 + + 1− ln 1 − 
T ∂U H ∂n 2 N N N N
         1    
∂n N kB 1 n n N 1 n
= 0− ln 1 + + 1+ n

+ − ln 1 − + ...
∂U H 2 N N N 1+ N N N
− N1
  
n
+ 1− n


N 1− N
           
∂n N kB 1 n 1 n 1  1
= − ln 1 + − ln 1 − +  −
∂U H 2 N N N N N N
! 
     n
∂n N
kB
 1 1+ N
= − ln n
∂U H 2 N

 1− N
!
    n 
∂n kB 1+ N
= − ln n
∂U H 2 1− N

But we have that n = −U/Hm so:

! 
  n
1 1 kB 1+ N
== − − ln n
T Hm 2 1− N
 U

 − Hm 
1 kB 1+ N
= ln  −U

T 2Hm 1 − Hm
N
 
1 kB N Hm − U
= ln
T 2Hm N Hm + U
↓
 
1 kB N Hm + U
=− ln
T 2Hm N Hm − U

Now, let’s calculate internal energy from what we found:

6
 2Hm N Hm + U
− = ln
kB T N Hm − U
− 2Hm N Hm + U
e kB T =
N Hm − U
− 2Hm
(N Hm − U )e k T
B = N Hm + U
− 2Hm − 2Hm
U + Ue = N Hme kB T − N Hm
kB T

 2Hm
  
− − 2Hm
U 1 + e kB T = −N Hm 1 − e kB T
 
Hm
− kHm
e kB T
− e BT
U = −N Hm  Hm 
− Hm
e kB T + e kB T
↓
Hm
U = −N Hmtanh
kB T
and finally, from that, we acquire the magnetization:

U Hm
M =− = N mtanh
H kB T
(3) Using the Gibbsian approach, we first calculate the partition function:

 
N
Y X Hmσ
QN =  e kB T 
i=1 σ=±
N h i
Hm
− kHm
Y
QN = e kB T + e B T

i=1
N  
Y Hm
QN = 2cosh
i=1
kB T
 N
Hm
QN = 2cosh
kB T

Now, Helmholtz free energy:

 
Hm
A = −N kB T ln 2cosh
kB T

and using that to calculate the magnetization, we get:

7
 ∂A 1 Hm m
M =− = N
kB
T
 2
sinh
∂H 2
cosh kHm
BT
k BT 
kB
T

Hm
M = N mtanh
kB T
Finally, the internal energy will be:

∂ ∂  
U =− lnQN = − N ln (2coshHmβ)
∂β ∂β
 
1
= −N 2sinh(Hmβ)Hm
2cosh(Hmβ)
Hm
U = −N Hmtanh( )
kB T
Which are the same results we got on (2)!