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Brennan 5.4
ECE6451-1
Maxwell-Boltzmann Distribution
Scottish physicist James Clerk Maxwell developed his kinetic theory of gases in 1859.
Maxwell determined the distribution of velocities among the molecules of a gas. Maxwell's
finding was later generalized in 1871 by a German physicist, Ludwig Boltzmann, to
express the distribution of energies among the molecules.
[1] McEnvoy, J.P. and Zarate, Oscar; “Introducing Quantum Theory;” 2004 ECE6451-2
[2] http://www.hk-phy.org/contextual/heat/tep/trans01_e.html
Maxwell-Boltzmann Distribution
The diameter of the molecules The collisions
are much smaller than the distance between molecules
between them conserve energy
x
D D
Maxwell’s
Four Assumptions[1]
[1] McEnvoy, J.P. and Zarate, Oscar; “Introducing Quantum Theory;” 2004
ECE6451-4
Maxwell-Boltzmann Distribution
Why use statistical mechanics to predict molecule behavior? Why not just
calculate the motion of the molecules exactly?
Even if we were only dealing with one mole of gas, we would still have to
determine characteristics of 6x1023 molecules!!
ECE6451-5
Maxwell-Boltzmann Distribution
In Section 5.3, it was determined that the thermal equilibrium is established
when the temperatures of the subsystems are equal. So…
First, we’ll need to determine the number of microstates within any given
configuration, i.e. the number of ways in which N objects can be arranged
into n distinct groups, also called the Multiplicity Function.
ECE6451-6
Maxwell-Boltzmann Distribution
The Multiplicity Function - determine the number of ways in which N objects
can be arranged into n containers.
abcdefghijkl
For the 1st slot, there are 12 possibilities. |c__| |____| |_____|
For the 2nd slot, there are 11 possibilities. |ch_| |____| |_____|
For the 3rd slot, there are 10 possibilities. |chk| |____| |_____|
etc…
There are 12! possible arrangements if the containers are ignored.
ECE6451-7
Maxwell-Boltzmann Distribution
(cont.) The Multiplicity Function - determine the number of ways in which N objects can
be arranged into n containers
Since we care about the containers but we don’t care about the order of the letters within
each container, we divide out the number of arrangements within each given
container, resulting in:
The Multiplicity N! N!
Q ( N 1 , N 2 ,..., N i ,..., N n ) = =
Function: N 1!⋅ N 2 !⋅... ⋅ N i !⋅... ⋅ N n ! n
∏N !
i =1
i
ECE6451-8
Maxwell-Boltzmann Distribution
Physically, each container corresponds to a state in which each particle can be put.
• In the classical case, there are no restrictions on how many particles that can be
put into any one container or state
• See Section 5.7 for the quantum case where there are restrictions for some
particles
R R R G
G
B G B B G B R
G R R R
G
R B G B B G B
Ni
In general, the possible arrangements of Ni
particles into gi subcontainers is:
g i
Therefore, if our system has a particular state that has a particular degeneracy, there is
an additional multiplicity of g iN i for that particular state.
ECE6451-11
Maxwell-Boltzmann Distribution
(cont.) Therefore, the total Multiplicity Function for a collection of classical particles is:
N! n
Q( N 1 , N 2 ,..., N i ,..., N n ) = n ∏ g iN i
i =1
∏ i N !
i =1
The equilibrium configuration corresponds to the most probable (most likely)
configuration of the system, i.e. the configuration with the greatest multiplicity! To
find the greatest multiplicity, we need to maximize Q subject to constraints.
∂ ∂φ ∂ψ
ln Q + α −β =0
∂N j ∂N j ∂N j
Taking the derivative, noting that N is constant and the only terms that are nonzero are
when i = j:
1
ln g j − 1 ⋅ ln N j + N j ⋅ + 1 + α − βE j = 0
Nj
ln g j − ln N j + α − βE j = 0
ECE6451-14
Maxwell-Boltzmann Distribution
From previous slide:
ln g j − ln N j + α − βE j = 0
Nj
ln = α − βE j
gj What are α and β?
Nj α − βE j
f (E j ) = =e
gj
To find β, we need to determine the total number of particles, N, in the system and the
total energy, E, of the system.
If the states are closely spaced in energy, they form a quasi-continuum and the total
number of particles, N, is given by:
∞
N = ∫ f ( E ) D( E )dE
0
ECE6451-15
Maxwell-Boltzmann Distribution
From previous slide: ∞
N = ∫ f ( E ) D( E )dE
0
3
Nj α − βE m 2
2E
f (E) = =e D( E ) =
gj h 3π 2
3 ∞
m 2 2 α
N = 3 2 e ∫ E e − βE dE
hπ 0
3
3 Γ
m 2 2 α 2
N= 3 e
hπ 2
β
3
2
ECE6451-16
Maxwell-Boltzmann Distribution
The total energy, E, of the system can be found by:
∞
E = ∫ Ef ( E ) D( E )dE
0
3
Nj α − βE m 2
2E
f (E) = =e D( E ) =
gj
3
h 3π 2
∞
m 2 2 α 3
E = 3 2 e ∫ E 2 e − βE dE
hπ 0
5
3 Γ
m 2 2 α 2
E= 3 e
hπ 2 5
β 2
ECE6451-17
Maxwell-Boltzmann Distribution
The average energy per particle is given as:
E 3
= k BT k B = 8.6175 × 10 −5 eV
N 2 K
Where kB is the Boltzmann constant.
Equating the average energy per particle with the ratio of our equations for E and N:
5
3 Γ
m 2 2 α 2
e
E h 3π 2
β
5
2 3 E
= = k BT =
N 3 2 N
3 Γ
m 2 2 α 2
e
h 3π 2
β
3
2
5
Γ 3
2 ⋅ β 2 = 3k T
B
β
5
2 3 2
Γ
2 ECE6451-18
Maxwell-Boltzmann Distribution
From previous slide:
5
Γ 3
2
⋅ β 2
3
Use the relationship[1]: = k BT
β 2 Γ 3 2
5
3 3
⋅ Γ
2 2 3
= k BT
3 2
β ⋅ Γ
2
3 3
= k BT
2β 2
1
β=
k BT
µ
α= (Eq. 5.7.26)
k BT
Where µ is the chemical potential. In Section 5.8, we will find out that the chemical
potential, µ, is exactly equal to the Fermi Energy, EF — Leaving us with an α of:
EF
α=
k BT
From previous slides:
Nj α − βE j 1
f (E j ) = =e β=
gj k BT
EF − E j
Nj
f (E j ) = =e k BT
gj
ECE6451-20
Maxwell-Boltzmann Distribution
From previous slide: EF − E j
Nj
f (E j ) = =e k BT
gj
It’s intuitive! For a given
Reversing terms in the numerator of the exponent:
temperature, the chance of higher
Maxwell-Boltzmann (
− E j − EF ) energy states being occupied
Distribution Nj decreases exponentially.
f (E j ) = =e k BT
gj
This distribution gives the number of particles in the jth state, where the jth state has a
degeneracy, gj.
If we want to find the probability of finding the particle in the jth state, we need to
normalize. We’ll start by dividing the number of particles in the jth state, Nj, by the
total number of particles, N.
j =1 j =1
ECE6451-21
Maxwell-Boltzmann Distribution
From previous slide: −E j
n n
N = ∑Nj = e α
∑g j e k BT
j =1 j =1
∑g
j =1
j e k BT
−E j
Substituting eα into f(Ej):
f ( E j ) = N j = g j eα e k BT
−E j
k BT
Ng j e
Nj = n −E j
∑g
j =1
je
k BT
Normalizing: −E j
k BT
Nj g je
= −E j
N n
∑g
j =1
j e k BT
ECE6451-22
Maxwell-Boltzmann Distribution
From previous slide: −E j
k BT
Nj g je
= −E j
N n
∑g
j =1
j e k BT
This normalized distribution is the probability, Pj, of finding the particle in the jth state
with energy Ej:
−E j
k BT
Nj g je
Pj = = −E j
N n
∑g
j =1
j e k BT
Since j is just a dummy index, the probability of finding of a particle having an energy Er
is: −E r
k BT
gre
Pr = n −E j
∑g
j =1
j e k BT
ECE6451-23
Maxwell-Boltzmann Distribution
If the degeneracy factor is 1, i.e. no repeatable arrangements, the probability becomes:
− Er
k BT
e
Pr = n −E j
∑e
j =1
k BT
If we want to find out the mean value of a physical observable, y, we can make use of
the following equation derived in Chapter 1:
∑P y r r
y= r
∑P r
r
∑E e r
k BT
E= r
− Er
∑e r
k BT
ECE6451-24
Maxwell-Boltzmann Distribution
From previous slide: − Er This denominator occurs very often—
∑E e r
k BT every time a mean value is calculated in
the Maxwell-Boltzmann Distribution.
E= r
− Er Since it occurs so often, it is given a
∑e r
k BT special name, the classical Partition
Function, Z.
We can use the classical partition function to easily calculate the mean value of the
energy.
∂ − βEr
∑ E r e − βEr = −∑
r r ∂β
e
∂ − βEr ∂ ∂
−∑ e =− ∑ e − βEr = − Z
r ∂β ∂β r ∂β
ECE6451-25
Maxwell-Boltzmann Distribution
From previous slide: − Er ∂
∑E e r
k BT
∑ E r e − βEr = −
r ∂β
Z
E= r
− Er
∑e r
k BT
Z = ∑ e − βEr
r
1 ∂
E = − Z
Z
∂β
The mean energy equation
∂
E =− (ln Z )
∂β
ECE6451-26
Maxwell-Boltzmann Distribution
Summarizing:
(
− E j − EF )
Nj EF
f (E j ) = =e k BT α=
gj k BT
− ( E − EF ) 1
β=
f (E) = e k BT
k BT
− Er
gre
− Er
k BT ∑E e r
k BT
Pr = n −E j E= r
− Er
∑g
j =1
j e k BT
∑e r
k BT
∂
Z = ∑ e − βEr E =− (ln Z )
r ∂β
ECE6451-27
Maxwell-Boltzmann Distribution
Summarizing:
− Er
− ( E − EF ) k BT
∂ gre
f (E) = e k BT E =− (ln Z ) Pr = −E j
∂β n
∑g
j =1
j e k BT