Maxwell-Boltzmann statistics

• Let us now be very specific about what we mean by the sum over all possible states
R of the gas.
• Maxwell-Boltzmann statistics: Here one must sum over all possible numbers of
particles in each state

nr = 0, 1, 2, 3, . . . for each r

• But the particles have also to be considered as distinguishable. Thus any

• Therefore, it is not enough to specify how many particles are in each single-particle
state, but it is necessary to specify which particular particle is in which state.
• The partition function of Maxwell-Boltzmann statistics.

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• Summing over all possible values of the numbers nr, and taking into account the
distinguishability of the particles. If there is a total of N molecules, there are for
given values of (n1, n2, . . . )

• Possible ways in which the particles can be put into the given single-particle states,
so that there are nl particles in state 1, n2 particles in state 2,…, etc.

• Each of these possible arrangements corresponds then to a distinct state for the
whole gas. Hence

• where one sums over all values nr, = 0, 1, 2, . . .for each r, subject to the restriction

• Now Z can be written

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• By virtue of (N=constant), it is just the result of expanding a polynomial. Thus

• Or simply

• From this partition function we can calculate the thermodynamic functions of the gas

• By differentiating the partition function with respect to the one term involving r, one
obtains,

Thus the mean number of particles in a given single-particle state r can

• This is called the Maxwell-Boltzmann distribution

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 The quantum distribution functions
• We begin by noting that there is a profound difference between quantum
gases obeying
– FD statistics and
– those obeying BE statistics
• This difference becomes most striking in the limit as T → 0,
– when the gas as a whole is in its state of lowest energy.
• Consider a gas consisting of a fixed number N of particles,
• For Fermions
• For Bosons
• Fermi-Dirac statistics: Here the particles are to be as indistinguishable, so
that mere specification of the numbers [n1, n2, . . . ] is enough to specify
the state of the gas.

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• Thus it is necessary only to sum over all possible numbers of particles in each
single-particle state, i.e., over all possible values
• But nr = 0, 1 for each r

• In Fermi,
• The restriction implies that if one particle is in state r, the sum ∑(r) in this eq extends
only over the remaining (N - 1) particles which can be put into the states other than
s. Let us then introduce for the sum r, extended over all states except r, the
convenient abbreviation

• If N particles are to be distributed over these remaining states, if

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• By performing explicitly the sum over = 0 and 1, the expression of mean numbers
becomes

• This can be simplified by relating Zr(N - 1) to Z(N). When ∆N << N, we can expand

ln Zr(N - ∆N) with Taylor expansion and after some algebra and With ∆N = 1
approximation, we will get that

• In macroscopic systems:  ln Z r
ln Z r  N  1 ln Z r  N  
N

  ln Z r 
Z r  N  1 Z r  N  exp   
 N 
 ln Z r  ln Z
~  
N N
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• Then the result of the mean number ns becomes then

• This is called the “Fermi-Dirac distribution."

• The μ chemical potential and at T=0 it is called the Fermi energy(level) or for free
electron gas, the Fermi energy EF. And K = Boltzmann constant = 1.38 1023 J/K

= 8.6  105 eV/K , T = absolute temperature in K

exp   r Z r ( N  1) 1
 nr  
Z r ( N )  exp   r Z r ( N  1) exp    r     1

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 Properties of Fermi-Dirac distribution

• At T = 0 K, FD distribution is a
step function and the
chemical potential defines
the Fermi surface
– Electrons in metals
• When  r   , kT
FD
distribution can be
approximated by the classical
MB distribution
– Electrons in the
conduction band of
semiconductors or
insulators 8
 Bose-Einstein (BE) statistics
• Bose-Einstein and photon statistics: Here the particles are to be as indistinguishable, so that
mere specification of the numbers [n1,n2, . . . ] is enough to specify the state of the gas.
• Thus it is necessary only to sum over all possible numbers of particles in each single-particle
state, i.e., over all possible values
• nr = 0, 1, 2, 3, . . . for each r
• Note N is fixed, but N is not fixed, example when one considers the particles to be photons
enclosed in a container of volume V, since the photons can be readily absorbed and emitted
by the walls. The mean number of particle in state r
0  exp   r Z r ( N  1)  2 exp  2  r Z r ( N  2)  ...
nr 
Z r ( N )  exp   r Z r ( N  1)  exp  2  r Z r ( N  2)  ...
Z r ( N )  0  exp   r     2 exp  2  r  2    ...

Z r ( N )  0  exp   r     exp  2  r  2    ...

 n exp  n     r
1
 n

 exp  n    
n
r exp    r     1
Chemical potential µ is determined by  nr  N
For a system comprised of conservative Bosons,
r
m is always lower than any single-particle
energy level
Partition function: ln Z  N  
ln  1  exp    r 
r 9
 Photon statistics
• Photons are Bosons
• The partition function is given by
• Here the sum is over all the possible states R of the whole gas, i.e., essentially over all the
various possible values of the numbers nl, n2 n3, . . . .
• Z depends on the total number N of particles in the system which is fixed no of particles. But
note that N is not fixed for photons, hence

• Since each sum is just an infinite geometric series

• Then
• Finally
• By applying differentiation with respect to the one term involving r/s, yields

• Hence
• This is called the Planck distribution- Planck statistics
• Note that the condition µ = 0 only applies to photons in thermal equilibrium with a blackbody!

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 Quantum statistics in the classical limit
• The quantum statistics of ideal gases can be summarized by the
statements
• For bosons distribution function + and
• For fermions the distribution function -
• Remember, bosons are particles with integral spins. There is no limit
on the number of bosons which may occupy any particular state
(typically the ground state).
• Do these different distribution relate one another?
• In a dilute ideal gas, << 1 the case of a gas with some fixed number N
of particles and when its temperature is made sufficiently large, i.e.
when β is made sufficiently small.
>> 1

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• The mean equation for all states r.
 nr exp     r   
  nr  exp     r    exp   exp   r   N
r r r
N
  kT ln
 exp   r 
r
exp   r 
 nr  N 
 exp   
r
r
Maxwell-Boltzmann distribution

Therefore, It follows that in the classical limit of

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