Chapter 8

Identical Particle Symmetry

Systems containing identical particles are often encountered in physics. The consequences of requiring that the system has the appropriate symmetry under the exchange of particles is explored in this chapter.

8.1

Pair exchange operator

Suppose we have a system containing two particles, such as a Helium atom. The Hamiltonian is given by p2 p2 2e2 2e2 e2 p2 + H= N + 1 + 2 2mN 2me 2me 40 |r1 rN | 40 |r2 rN | 40 |r1 r2 | (8.1)

where the rst term is the nuclear kinetic energy, the second the kinetic energy of electron 1, the third the kinetic energy of electron 2, the fourth and fth the attraction of the electrons and the nucleus, and the last the repulsion between the two electrons. The energy of the system is unchanged when we swap the labels 1 and 2 i.e. H(1, 2) = H(2, 1). This is an expression of identical particle symmetry. We dene a particle exchange operator that swaps the two particles around P 12 (1, 2) = (2, 1) (8.2)

This operator is Hermitian, so is an observable, and commutes with the Hamiltonian operator, so exchange symmetry should be a constant of the motion. The eigenstates of this operator can be found as follows P 12 (1, 2) = (1, 2) = (1, 2) 12 P 2 (1, 2) = P 12 (2, 1) = 2 (1, 2) (8.3) (8.4)

so = 1. Wavefunctions corresponding to = 1 are symmetric under particle exchange, and those with = 1 are antisymmetric. If we have a state that is not an eigenstate of P 12 then we can make the eigenstates as follows (8.5) = [(1, 2) (2, 1)] / 2 Note that no measurement can distinguish between identical particles so we must always have this symmetry in the wavefunction. 65

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CHAPTER 8. IDENTICAL PARTICLE SYMMETRY

8.2

Spin-Statistics theorem

If two particles have integer spin quantum numbers s1 = 0, 1, 2, . . . and s2 = 0, 1, 2, . . . then the wavefunction for a state containing these two particles is symmetric under exchange of particles. These particles are known as bosons. If instead we have two particles with half integer spin e.g. 3 s1 = 1 , 3 , . . . and s2 = 1 , 2 , . . ., then the wavefunction must be antisymmetric under their exchange, 2 2 2 and they are known as fermions. This is the contents of the spin-statistics theorem that links the spin of the particles to their exchange symmetry, and hence to their statistical mechanics (they either obey Bose-Einstein or Fermi-Dirac statistics).

8.3

Two particle case

We now consider the case where we have two particles that do not interact. The position of particle 1 is r1 and that of particle 2 is r2 . We have two single particle wavefunctions a and b , so we could write the wavefunction of the system as (r1 , r2 ) = a (r1 )b (r2 ) If we symmetrise this state then we obtain (r1 , r2 ) = (a (r1 )b (r2 ) a (r2 )b (r1 ))/ 2 for fermions and (r1 , r2 ) = (a (r1 )b (r2 ) + a (r2 )b (r1 ))/ 2 (8.7) (8.6)

(8.8)

for bosons. Note that for the fermionic state (r1 , r2 ) = 0 i.e. we cannot have two fermions occupying the same quantum state, which is the Pauli-exclusion principle.

Two particles in a square well

By way of a more concrete example consider the familiar 1-D square well. Suppose we have two single-particle wavefunctions a (x) b (x) = = x 2 sin a a 2x 2 sin a a (8.9) (8.10)

The wave function for the case of two distinguishable particles, indistinguishable fermions, and indistinguishable bosons respectively are Distinguishable (x1 , x2 ) Indistinguishable Fermions (x1 , x2 ) Indistinguishable Bosons (x1 , x2 ) = = = x1 2x2 2 sin sin a a a 2x2 x2 2x1 x1 2 sin sin sin sin a a a a a 2x2 x2 2x1 x1 2 sin + sin sin sin a a a a a (8.11) (8.12) (8.13)

A contour plot of the probability density in each of these cases is shown in g. 8.1.

8.4. SPIN AND SPACE WAVEFUNCTIONS

67

Distinguishable

Fermions

Bosons

x2

x2

x2

x1

x1

x1

Figure 8.1: Contour plots of the probability density of nding particle 1 at x1 and particle 2 at x2 for wavefunctions of dierent symmetry as explained in the text. Note there is a zero line in x1 = x2 for the fermionic case.

8.4

Spin and space wavefunctions

In the last couple of examples we have ignored the spin part of the wavefunction for simplicity. However, the exchange operator applies to the whole of the wavefunction so will also swap around the 1 particle in the spin states. If we consider the whole wavefunction for spin- 2 fermions = space (r1 , r2 )spinS S,m (8.14)

when we exchange the two electrons then the whole wavefunction must change sign. This can be achieved in two ways: either the space wavefunction is symmetric and the spin wavefunction antisymmetric, or the space wavefunctionis antisymmetric and the spin wavefunction symmetric. We have met the symmetric triplet state, and the antisymmetric singlet state in the previous chapter. Here we see that the singlet state must be paired with a symmetric space wavefunction, and the triplet state with an antisymmetric space wavefunction. If the particles we are considering do not interact then there will be no dierence in the energy of the triplet and singlet spin states. However, if they interact say via coulomb repulsion as is the case for electrons then the triplet state will have higher energy than the singlet state because the electrons on average are closer together. This energy dierence between symmetric and antisymmetric wavefunctions is referred to as the exchange interaction, and it produces a preference for symmetric spins.

Example: Helium atom

There are two electrons in the Helium atom, and the lowest energy state has the electronic conguration 1s2 , meaning that both the electrons are in the = 0, m = 0 orbital. Since the space wavefunction in this case is symmetric, then the spin wavefunction must be antisymmetric, i.e. the singlet state. If we consider an excited state e.g. 1s1 2s1 then we have two dierent orbitals to put the electron in. Consequently we can make both symmetric and anti-symmetric space wavefunctions, and pair them with the symmetric (triplet) and antisymmetric (singlet) spin wavefunctions. The antisymmetric space wavefunction has lower energy here since the electrons are on average farther apart. Thus the triplet spin wavefunction that must be paired with the antisymmetric space wavefunction has the lower energy in comparison the the symmetric (singlet) spin wavefunction.

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CHAPTER 8. IDENTICAL PARTICLE SYMMETRY

Example: Hydrogen molecule

The hydrogen molecule consists of two identical protons. The wavefunction of the molecule must obey particle exchange symmetry. Exchanging the two particles is the same as inverting space r r. The rotational states of the hydrogen molecule can be labelled using the angular momentum operator L2 . As was shown at the end of the angular momentum chapter, the symmetry of these states is given by (1) . Consequently the rst rotational state is odd, the second even etc. We can only pair the singlet spin state with even and the triplet spin state with odd as illustrated in the table below. S, 0, 0 1, 1 0, 2 1, 3 Energy h2 ( + 1)/2I 0 h 2 /I 3 2 /I h 6 2 /I h Degeneracy (2S + 1)(2 + 1) 1 9 5 21

8.5

Slater Determinant

If we have an N -particle wavefunction then an antisymmetric wavefunction can be built up from single particle orbitals by using the slater determinant, which is dened as follows 1 (r1 ) 1 (r2 ) . . . 2 (r1 ) 2 (r2 ) . . . ... N (r1 ) ... N (r2 ) . .. . . . . . . N (rN 1 ) ... N (rN )

1 (r1 , r2 , . . . , rN ) = N!

(8.15)

1 (rN 1 ) 2 (rN 1 ) 1 (rN ) 2 (rN )

This is antisymmetric under the exchange of any two particles because the determinant is antisymmetric under the exchange of any two rows. In the case of just two particles this reduces to the example we considered earlier in the chapter 1 (r1 , r2 ) = 2 a (r1 ) a (r2 ) b (r1 ) b (r2 ) 1 = (a (r1 )b (r2 ) a (r2 )b (r1 )) 2 (8.16)

8.6
1A.

Problems
What are the consequences in quantum mechanics of indistinguishability of particles? Include 1 discussion of singlet and triplet states for two spin- 2 particles. Explain why for helium (a) there is no triple state corresponding to the lowest singlet state; and (b) for excited states of given n and l the triplet level always lies below the corresponding singlet level. Consider the nuclear spin and space wavefunction of a rotating H2 molecule, and explain why the degeneracies of the two lowest states of the molecule are 1 and 9.

2B.

3B.