Sri Shivaji Science College,

Nagpur

Roshni Pahuja

Quantum MechanicsII

Unit III
System of Identical
particles
 Identical Particles

By identical particles we mean the particles like electrons which cannot be

distinguished by means of any inherent property, since otherwise they would
not be identical in all respects.

In Classical Mechanics,
Identical particles do not loose their identity despite the identity of their
physical properties due to the existence of sharply definable trajectories for
individual particles.

Each particle can be followed during the courseof an experiment.

As the molecules in gas are much smaller than the volume available to it,
every molecule of the gas can be identified . Hence the classical particles
are distinguishable.
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 Identical particles

In Quantum Mechanics

Aparticle is described by a wave packet of finite size and spread.

The exact specification of the position and momentum of the particle

simultaneously is restricted by Heisenberg’s Uncertainity Principle
∆x ∆p ≈h.
Therefore there is no way of keeping track of the individual particles separately,
specifically if they interact with each other to an appreciable extent.
Wavefunctions of the particles overlap considerably and hence a quantum
mechanical particle cannot bedistinguished.

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 Identical Particles

Thus, there are two general categories of particles

1) Classicalparticles which are identical but distiguishable.

2) Quantum particles which are identical and indistinguishable.

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 Physical meaning of Identical

1) Identical or indistinguishable particles are those particles in a system

for which there will be no change in system by inter changing theparticles.
2) These particles can be distinguished from one another, only when their wave
packets do not overlap.
3) If the particles have spin which are alligned in different positions during
interaction, they can be identified from one another due to different spin
components.

4) Thus, the word ‘identical’ in quantum mechanics mean that if the

position and spin coordinates of two of them are interchanged, there is no
physical way of measuring that a change has been made in the system.

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 Hamiltonian of identical particles
For example, Consider Hamiltonian for the system of two particles.
H = 1/2m (p 2 + p 2) + V(1,2) ……….. (1)
1 2

Where p 2= p 2 + p 2 + p 2
i ix iy iz

m = mass of eachparticle

V = potential energy of the system containing twoparticles.

Corresponding Operator for the system of two particles is
Ĥ (1,2) = -ħ2 /2m (▼ 2 + ▼ 2) + V(1,2) ……….. (2)
1 2

On changing the coordinates weget,

Ĥ (2,1) = -ħ2 /2m (▼ 2 + ▼ 2) + V(2,1) ………..(3)
2 1

= -ħ2/2m(▼ 2+▼ 2) + V(1,2), since the particles are identical their

2 1

potential energy must be same and they behave identically in every respect.
Ĥ (1,2) =Ĥ (2,1) ……….. (4)
Thus, Hamiltonian is symmetric with respect to the interchange of any pair of
particles 6
 Exchange Degeneracy.
The Schrodinger equation now becomes
Ĥ(1,2) Ѱ(1,2) = E Ѱ(1,2) ……….. (5)
where Ѱ(1,2) is the solution of Schrodinger equation and
E is the eigenvalues of the operator Ĥ(1,2) .
Interchanging the particles
Ĥ(2,1) Ѱ(2,1) = E Ѱ(2, 1) ……….. (6)
which can be written as
Ĥ(1,2) Ѱ(2,1) = E Ѱ(2, 1) , since Ĥ (1,2) = Ĥ (2,1)
So that Ѱ(2,1) is also the solution of Schrodingerequation
In other words, Ѱ(1,2) and Ѱ(2,1) are eigenfunctions of the operator Ĥ
belonging to the same eigenvalue E.
The system is saidto be degenerate and any linear combination
Ѱ’(1,2) = AѰ(1,2) + B Ѱ(2,1) is also an eigenfunction belonging to E.
The type of degeneracy occuring here is known as exchange degeneracy.
 Hamiltonian of n identical particles

For example,
n electrons are indistinguishable. As their positions can’t be specified.,
interchanging the coordinates of any two electrons does not change the
Hamiltonian of the system.

In other words,
Hamiltonian of the system is symmetric in the coordinates of
the n particles.

Mathematically, it is written as

H(1,2,3,…….n) = H( 2,1,3,…….n) ………..(7)

Where each number represents all the cordinates, both position and spin, of
one of the particles 8
 Particle Exchange Operator

Consider a two-particle system. Its energy eigen value equationbe

H(1,2) Ѱ(1,2) = E Ѱ(1,2) ……….. (8)

Since the particles are identical, interchanging 1 and2
H (2,1) Ѱ(2,1) = E Ѱ(2,1) ……….. (9)
Since hamiltonian is symmetric

Applying equation (4), above equation can be writtenas

H(1,2)) Ѱ(2,1) = E Ѱ(2,1) ……….. (10)
We define a particle exchange operator P12 such that when it operates ona
state, interchanges all coordinates of particles 1 and 2.

Thus, P12 Ѱ(1,2) = Ѱ(2,1) ……….. (11)

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Particle Exchange Operator : Constant of motion

Equation (10) H(1,2) Ѱ(2,1) = E Ѱ(2,1) can be written as

H(1,2) P12 Ѱ(1,2) = E P12 Ѱ(1,2)

= P12 E Ѱ(1,2)

= P12 H(1,2)Ѱ(1,2)
It follows that
H(1,2) P12 = P12 H(1,2)or
P12 H(1,2) - H(1,2) P12 =0

[P12 H(1,2) ] = 0

In general [P,H] = 0 ……….. (12)

Particle Exchange Operator is a constant of motion.
Since particles are indtisntiguishable, any operator representing a physical
property of the system must be symmetric with respect to particleinterchange.
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 Eigen value of Particle Exchange Operator
Any operator representing physical property commutes with the particle
exchange operator.
Eigen functions of physical variables will also be eigen functions of the particle
exchange operator.

Consider a function Ѱ(1,2) which is an eigen function of P12with eigen value α.

P12 Ѱ(1,2) = α Ѱ(1,2)

Ѱ(2,1) = α Ѱ(1,2)
Operating both sides byP12
P12 Ѱ(2,1) = P12 α Ѱ(1,2)
Ѱ(1,2) = α P12 Ѱ(1,2)

Ѱ(1,2) = α α Ѱ(1,2)

Ѱ(1,2) = α2 Ѱ(1,2) → α2 =1, α =±1

P12 Ѱ(1,2) = ±1 Ѱ(1,2) ………..(13)
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 Eigen value of Particle Exchange Operator
Equation 13 could as well be extended to the system of n particles

Consider a system of n particles described by the wavefunction

Ѱ(1, 2,…….r,…. s,…. n) where 1 stands for position and spin coordinates of
particle 1 and similarly 2,…….r….s and n. The wavefunction is now subjected to
the exchange operator Prs defined as

PrsѰ(1,2,…..r,….s…n) = Ѱ(1,2,…..s,….r…n) ……….. (14)

Eigen value equation for the operator Prs is

PrsѰ(1,2,…..r,….s…n) = α Ѱ(1,2,…..r,….s…n), where α is the eigen value of the
operator. Operating on both sides by Prs and applying eq 14, we get

Prs Prs Ѱ(1,2,…..r,….s,…n) = Prs α Ѱ(1,2,…..r,….s,…n)

Prs Ѱ(1,2,…..s,….r…n) = α Prs Ѱ(1,2,…..r,….s…n)

Ѱ(1,2,…..r,….s…n)= α αѰ(1,2,…..r,….s…n) )

Ѱ (1,2,…..r,….s…n) = α2 (1,2,…..r,….s…n) → α2 =1, α = ±1

Prs (1,2,…..r,….s…n) =±1 (1,2,…..r,….s…n) ………..(15) 12
Symmetric and Anti-symmetric wave functions
The Schrodinger equation for a particle is given by

H Ѱ(t)= iЋ ∂ Ѱ / ∂t
The Schrodinger equation for n particles can be written as

H(1, 2, …….n) Ѱ(1, 2,…….n, t) = iЋ ∂ Ѱ(1, 2,…….n, t) / ∂t ………..(16)

Where each of the numbers represents all the co-ordinates i.e. position and spin of
one of the particles

The Hamiltonian H is symmetric due to the identity of particles.

There are two kinds of solutions of wave function Ѱ of equation 8
1) Symmetric wave function Ѱs : A wave function is symmetric if the interchange
of any pair of particles among its arguments leaves the wave function
unchanged.
2) Antisymmetric wave function Ѱ A :A wave function is antisymmetric if the
interchange of any pair of particles among its arguments changes the sign of
the wave function. 13
 Symmetry character of a wave function

If Ѱs is symmetric at a particular time tthen

HѰ s is also symmetric and hence according to the equation

H(1, 2, …….n) Ѱ(1, 2,…….n, t) = iЋ ∂ Ѱ(1, 2,…….n, t) / ∂t
∂ Ѱ / ∂t is also symmetric at time t.
Since Ѱs and ∂ Ѱ / ∂t are symmetric at timet,
Ѱs at infinitesimally later time t+dt given by Ѱ s + ∂ Ѱ / ∂t is also symmetric .

Such a step by step integration of the wave function can be continued for
large time intervals and Ѱs is seen to remain symmetricalways.

Similarly, Ѱ A is always antisymmetric.

Thus the symmetry character of a wave function does not change
with time.

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Construction of symmetric and antisymmetric wave
functions
We know that the number of ways in which the indices can be interchanged will give
a number of solutions of the Schrodinger equation of the system.
Lets consider two and three particle systems
Schrodinger equation for a two particles wavefunction is
Ĥ (1,2) Ѱ(1,2) = E Ѱ(1,2)

whose two degenerate solutions are Ѱ(1,2) and Ѱ(2,1)

Now the symmetric wavefunction will be givenby

Ѱ S = Ѱ(1,2) + Ѱ(2,1) ……….. (17)

And antisymmetric wavefunction is given by

Ѱ A = Ѱ(1,2) - Ѱ(2,1) ……….. (18)
Ѱ(1,2) and Ѱ(2,1) are unnormalised wavefunction

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Construction of symmetric and antisymmetric wave
functions
Similarly in case of three particle system, there are six ways of interchanging the
indices of the particle

i.e. Ѱ(1,2,3), Ѱ(2,3,1), Ѱ(3,1,2), Ѱ(1,3,2), Ѱ(3,2,1) and Ѱ(2,1,3)

Now the symmetric wavefunction will be givenby
Ѱ S = Ѱ(1,2,3) + Ѱ(2,3,1) + Ѱ(3,1,2) +Ѱ(1,3,2)+Ѱ(3,2,1) +Ѱ(2,1,3) ……….. (19)
And antisymmetric wavefunction is given by

Ѱ A = Ѱ(1,2,3) + Ѱ(2,3,1) + Ѱ(3,1,2) – {Ѱ(1,3,2)+Ѱ(3,2,1)+Ѱ(2,1,3)} ...….….. (20)

Antisymmetric wavefunction can be built by adding all the functions with even
number of interchanges and substracting the sum of all those with odd number of
interchanges

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If P is an exchange operator then

P Ѱ S (1,2) = Ѱ S (2,1) ……….. (21)

P Ѱ A (1,2) = -Ѱ A (2,1) ……….. (22)
This symmetry property of the wave function has close relationship with the
spin of the particle.
Postulate 1: The identical particles having an integral spin quantum number
are describedby symmetric wavefunction i.e.

P Ѱ S (1,23,…….n) = +Ѱ S (1,2,3,……n) ……….. (23)

These particles are k/a bosonsand obey Bose-EinsteinStatistics.
Eg : photons( spin 1) and helium atoms in normal state(s=0).

Postulate 2: The identical particles having half odd spin quantum number are
described by antisymmetric wavefunctioni.e.

P ѰA(1,23,…….n) = -Ѱ A (1,2,3,……n) ……….. (24)

These particles are k/a fermionsand obey Fermi-Dirac Statistics.
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Eg: electrons, protons, neutrons ( all with spin ½)
 Distinguishability of Identical Particles
Two particles will be distinguishable from each other if the sum of the probabilities
of the individual wavefunctions in two states is equal to the probability derived by
the symmetrized wavefunctions given by
Ѱ S = Ѱ(1,2) + Ѱ(2,1) and
Ѱ A = Ѱ(1,2) - Ѱ(2,1)
|Ѱ(1,2)|2 + |Ѱ(2,1) | 2 = |Ѱ(1,2) ± Ѱ(2,1) | 2
= |Ѱ(1,2)|2 + |Ѱ(2,1) |2 ± 2Re Ѱ(1,2) Ѱ(2,1) ……….. (25)
Where Re stands for the real part of {Ѱ(1,2) Ѱ(2,1)}
This is possible if the overlap of wavefunctions Ѱ(1,2) and Ѱ(2,1) is zero or
2Re Ѱ(1,2) Ѱ(2,1) = 0
In this way when the coordinates ( space and spin) of two particles are not the same
between exchange degenerate functions, the interferenceterms 2Re Ѱ(1,2) Ѱ(2,1)
Becomes zero and particle co-ordinatesdo not overlap.
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