Chapter 24: Quantum Statistics

Mahdi Pourfath
pourfath@ece.ut.ac.ir

Quantum Physics

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Why Statistical Mechanics ?

When we know completely the initial condition of a physical system, one may predict exactly its future. If the system is only partially known, however, we can still make predictions on its future behavior. The lack of maximum knowledge of the initial condition of the system is often due to the extremely large number of degrees of freedom. Statistical physics is the branch of physics that deals with systems only partially known. Statistical mechanics provides a framework for relating the microscopic properties of individual atoms and molecules to the macroscopic bulk properties of materials that can be observed in everyday life.

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A Classical System

Consider a system composed of 4 distinguishable particles. Each particle can have an integer number of energy quanta. Two units of energy is given to this system. All possible ways of distributing this energy on this system is given in the following table.

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Classical Statistics
Micro-State Macro-State 1 2 3 4

2 0 0 0 1 1 1 0 0 0
6 10 ,

0 2 0 0 1 0 0 1 1 0

0 0 2 0 0 1 0 1 0 1
6 10

0 0 0 2 0 0 1 0 1 1
3 10 ,

The probabilities of nding a particle with 2, 1, and 0 units of energy: p(0) =

4 10 6 3 + 10 1 = 4 2

p(1) =

1 2 =

p(2) =

4 10

1 = 4

1 10

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Classical Statistics: Distribution Function

The essential problem in statistical mechanics is to calculate the distribution of a given amount of energy E over N identical systems. In classical systems, where particles are distinguishable, the distribution function is given by the Maxwell-Boltzmann statistics f (E ) = A exp E kB T

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Classical Statistics: Distribution Function

The microstates into which the particles are arranged are classied in terms of their energy Ei and the degeneracy they have gi . Therefore, each level has gi degenerate states into which Ni particles can be arranged. The system is assumed to have n independent levels. The total multiplicity function for this system is given by Q(N1 , N2 , . . . , Nn ) = N! n i =1 Ni !
n

giNi
i =1

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Classical Statistics: Boltzmann Statistics

There are two physical constraints on the system: the total number of particles and the total energy of the system must be conserved:
n

Ni = N
i =1 n

Ei Ni = U
i =1

The equilibrium corresponds to the most probable conguration of the system. Mathematically, this entails maximizing the multiplicity function Q subject to the above constraints.

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Multivariate functions
Consider a function of n variables dened as f (x1 , x2 , . . . , xn ), where (x1 , x2 , . . . , xn ) is held constant. The condition of is the system constraint. An extremum of f is found when df = 0. If is constant then d = 0. Therefore, one can write df + d = 0 is called a Lagrange multiplier and is simply a multiplicative factor. The complete dierentials can be expanded out in terms of partial derivatives of the coordinate system f + x1 x1 dx1 + . . . + f + xn xn dxn = 0

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Classical Statistics: Boltzmann Statistics

It is easier to use ln Q rather than Q
n n

ln Q(N1 , N2 , . . . , NN ) = ln N! +
i =1

Ni ln gi

ln Ni !
i =1

Using the Stirlings approximation in the form ln x! x ln x x for large values of x:

n n n

ln Q = ln N! +
i =1

Ni ln gi

Ni ln Ni +
i =1 i =1

Ni Ni = N and

One can maximize ln Q subject to the conditions that Ei Ni = U as ln Q + =0 Nj Nj Nj

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Classical Statistics: Boltzmann Statistics

Nj Ni ln gi Ni
i

Ni ln Ni +
i i

Ni Ei Ni

+ =0

Nj

Nj

ln gi ln Nj 1 + 1 + Ej = 0

ln Nj = ln gi + Ej Nj = Ej ln gi Nj = gi e e Ej

The Lagrange multiplier is equal to 1/kB T . kB = 8.62 105 eV/K is Boltzmanns constant.
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Quantum Statistics: Indistinguishablity

If there is an appreciable overlapping of the wavefunctions of two identical particles in a system, non-classical eects arise from indistinguishablity of the identical particles:
Measurable results can not depend on the assignment of the labels to identical particles. In the presence of one in a particular quantum state inuences the chance that another identical particle will be in that state.

Indistinguishablity requires that |(r1 , , ri , rj , , rn )|2 = |(r1 , , rj , ri , , rn )|2 Particles with symmetric wavefunctions are called Bosons (r1 , , ri , rj , , rn ) = +(r1 , , rj , ri , , rn ) Particles with anti-symmetric wavefunctions are called Fermions (r1 , , ri , rj , , rn ) = (r1 , , rj , ri , , rn )
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Quantum Statistics: Indistinguishablity

In a system without interaction, particles move independently. For a system with two particles one obtains: T (r1 , r2 ) = (r1 ) (r2 ) T does not satisfy the symmetry or antisymmetry conditions. To satisfy these relations one can write the wavefunction of the system as 1 S = [ (r1 ) (r2 ) + (r1 ) (r2 )] 2 1 A = [ (r1 ) (r2 ) (r1 ) (r2 )] 2 Two identical particles with antisymmetric wavefuntions (Fermions) can not occupy the same state.
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Quantum Statistics: Multiplicity Functions

In classical mechanics particles are distinguishable. Q(N1 , N2 , . . . , Nn ) = N! n i =1 Ni !
n

giNi
i =1

In quantum mechanics particles are indistinguishable. Particles with antisymmetric wavefunctions (Fermions) obey Pauli exclusion principle.
n

Q(N1 , N2 , . . . , Nn ) =
i =1

Particles with symmetric wavefunctions (Bosons) do not obey Pauli exclusion principle.
n

gi ! Ni ! (gi Ni )

Q(N1 , N2 , . . . , Nn ) =
i =1
Pourfath (ECE UT) Quantum Statistics

(gi + Ni 1)! Ni ! (gi 1)!

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Quantum Statistics: Distribution Functions

f (E ) give the proability that a state of energy E is occupied: distinguishable f (E ) = Ae E /kB T 1 indistinguishable f (E ) = (E )/k T Quantum: Fermi-Dirac B e +1 1 Quantum: Bose-Einstein indistinguishable f (E ) = E /k T e B 1 Classic: Boltzmann

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