11.2 Single-Particle versus System States

The purpose of this section is to describe the generic form of the energy eigenfunctions of a system of weakly interacting particles.

The total number of particles will be indicated by . If the interactions between the particles are ignored, any energy eigenfunction of the complete system of particles can be written in terms of single-particle energy eigenfunctions .

The basic case is that of noninteracting particles in a box, like
discussed in chapter 6.2. For such particles the
single-particle eigenfunctions take the spatial form

where , , and are constants, called the

wave number components.Different values for these constants correspond to different single-particle eigenfunctions, with single-particle energy

The single-particle energy eigenfunctions will in this chapter be numbered as . Higher values of index correspond to eigenfunctions of equal or higher energy .

The single-particle eigenfunctions do not always correspond to a particle in a box. For example, particles caught in a magnetic trap, like in the Bose-Einstein condensation experiments of 1995, might be better described using harmonic oscillator eigenfunctions. Or the particles might be restricted to move in a lower-dimensional space. But a lot of the formulae you can find in literature and in this chapter are in fact derived assuming the simplest case of noninteracting particles in a roomy box.

The details of the single-particle energy eigenfunctions are not really that important in this chapter. What is more interesting are the energy eigenfunctions of complete systems of particles. It will be assumed that these system eigenfunctions are numbered using a counter , but the way they are numbered also does not really make a difference to the analysis.

As long as the interactions between the particles are weak, energy
eigenfunctions of the complete system can be found as products of the
single-particle ones. As an important example, at absolute zero
temperature, all particles will be in the single-particle ground state
, and the system will be in its ground state

where is the total number of particles in the system. This does assume that the single-particle ground state energy is not degenerate. More importantly, it assumes that the particles are not identical fermions. According to the exclusion principle, at most one fermion can go into a single-particle state. (For spin fermions like electrons, two can go into a single spatial state, one in the spin-up version, and the other in the spin-down one.)

Statistical thermodynamics, in any case, is much more interested in
temperatures that are not zero. Then the system will not be in the
ground state, but in some combination of system eigenfunctions of
higher energy. As a completely arbitrary example of such a system
eigenfunction, take the following one, describing 36 different
particles:

This system eigenfunction has an energy that is the sum of the 36 single-particle eigenstate energies involved:

To understand the arguments in this chapter, it is essential to visualize the system energy eigenfunctions as in figure 11.1. In this figure the single-particle states are shown as boxes, and the particles that are in those particular single-particle states are shown inside the boxes. In the example, particle 1 is inside the box, particle 2 is inside the one, etcetera. It is just the reverse from the mathematical expression above: the mathematical expression shows for each particle in turn what the single-particle eigenstate of that particle is. The figure shows for each type of single-particle eigenstate in turn what particles are in that eigenstate.

To simplify the analysis, in the figure single-particle eigenstates of
about the same energy have been grouped together on
shelves.

(As a consequence, a subscript to a
single-particle energy may refer to either a single-particle
eigenfunction number or to a shelf number , depending on
context.) The number of single-particle states on a shelf is intended
to roughly simulate the density of states of the particles in a box as
described in chapter 6.3. The larger the energy, the
more single-particle states there are at that energy; it increases
like the square root of the energy. This may not be true for other
situations, such as when the particles are confined to a lower-dimensional
space, compare chapter 6.12. Various formulae given here
and in literature may need to be adjusted then.

Of course, in normal nonnano applications, the number of particles will be astronomically larger than 36 particles; the example is just a small illustration. Even a millimol of particles means on the order of 10 particles. And unless the temperature is incredibly low, those particles will extend to many more single-particle states than the few shown in the figure.

Next, note that you are not going to have something like 10 different types of particles. Instead they are more likely to all be helium atoms, or all electrons or so. If their wave functions overlap nontrivially, that makes a big difference because of the symmetrization requirements of the system wave function.

Consider first the case that the particles are all identical
bosons, like plain helium atoms. In that case the wave function must
be symmetric, unchanged, under the exchange of any two of the bosons,
and the example wave function above is not. If, for example,
particles 2 and 5 are exchanged, it turns the example wave function
from

into

and that is simply a different wave function, because the states are different, independent functions. In terms of the pictorial representation figure 11.1, swapping the numbers

2” and “5in the particles changes the picture.

As chapter 5.7 explained, to eliminate the problem that exchanging particles 2 and 5 changes the wave function, the original and exchanged wave functions must be combined together. And to eliminate the problem for any two particles, all wave functions that can be obtained by merely swapping numbers must be combined together equally into a single wave function multiplied by a single undetermined coefficient. In terms of figure 11.1, we need to combine the wave functions with all possible permutations of the numbers inside the particles into one. And if all permutations of the numbers are equally included, then those numbers no longer add any nontrivial additional information; they may as well be left out. That makes the pictorial representation of an example system wave function for identical bosons as shown in figure 11.2.

For identical fermions, the situation is similar, except that the different wave functions must be combined with equal or opposite sign, depending on whether it takes an odd or even number of particle swaps to turn one into the other. And such wave functions only exist if the single-particle wave functions involved are all different. That is the Pauli exclusion principle. The pictorial representation figure 11.2 for bosons is totally unacceptable for fermions since it uses many of the single-particle states for more than one particle. There can be at most one fermion in each type of single-particle state. An example of a wave function that is acceptable for a system of identical fermions is shown in figure 11.3.

Looking at the example pictorial representations for systems of bosons
and fermions, it may not be surprising that such particles are often
called “indistinguishable.“ Of course, in classical
quantum mechanics, there is still an electron 1, an electron 2,
etcetera; they are mathematically distinguished. Still, it is
convenient to use the term distinguishable

for
particles for which the symmetrization requirements can be ignored.

The prime example is the atoms of an ideal gas in a box; almost by definition, the interactions between such atoms are negligible. And that allows the quantum results to be referred back to the well-understood properties of ideal gases obtained in classical physics. Probably you would like to see all results follow naturally from quantum mechanics, not classical physics, and that would be very nice indeed. But it would be very hard to follow up on. As Baierlein [4, p. 109] notes, real-life physics adopts whichever theoretical approach offers the easiest calculation or the most insight. This book’s approach really is to formulate as much as possible in terms of the quantum-mechanical ideas discussed here. But do be aware that it is a much more messy world when you go out there.