Bound States

Electrons are at their most interesting when they're in atoms, that is, when they are bound within a small region of space. We can understand a great deal about atoms and molecules based on simple arguments about such bound states, without going into any of the realistic details of atom. The simplest model of a bound state is known as the particle in a box: like a ball on a pool table, the electron feels zero force while in the interior, but when it reaches an edge it encounters a wall that pushes back inward on it with a large force. In particle language, we would describe the electron as bouncing off of the wall, but this incorrectly assumes that the electron has a certain path through space. It is more correct to describe the electron as a wave that undergoes 100% reflection at the boundaries of the box.

f / Three possible standingwave patterns for a particle in a box.

Like a generation of physics students before me, I rolled my eyes when initially introduced to the unrealistic idea of putting a particle in a box. It seemed completely impractical, an artificial textbook invention. Today, however, it has become routine to study electrons in rectangular boxes in actual laboratory experiments. The "box" is actually just an empty cavity within a solid piece of silicon, amounting in volume to a few hundred atoms. The methods for creating these electron-in-a-box setups (known as "quantum dots") were a by-product of the development of technologies for fabricating computer chips.

For simplicity let's imagine a one-dimensional electron in a box, i.e., we assume that the electron is only free to move along a line. The resulting standing wave patterns, of which the first three are shown in the figure, are just like some of the patterns we encountered with sound waves in musical instruments. The wave patterns must be zero at the ends of the box, because we are assuming the walls are impenetrable, and there should therefore be zero probability of finding the electron outside the box. Each wave pattern is labeled according to n, the number of peaks and valleys it has. In quantum physics, these wave patterns are referred to as "states" of the particle-in-the-box system.

The following seemingly innocuous observations about the particle in the box lead us directly to the solutions to some of the most vexing failures of classical physics:

The particle's energy is quantized (can only have certain values). Each wavelength corresponds to a certain momentum, and a given momentum implies a definite kinetic energy, E = p²/2m. (This is the second type of energy quantization we have encountered. The type we studied previously had to do with restricting the number of particles to a whole number, while assuming some specific wavelength and energy for each particle. This type of quantization refers to the energies that a single particle can have. Both photons and matter particles demonstrate both types of quantization under the appropriate circumstances.)

The particle has a minimum kinetic energy. Long wavelengths correspond to low momenta and low energies. There can be no state with an energy lower than that of the n = 1 state, called the ground state.

The smaller the space in which the particle is confined, the higher its kinetic energy must be. Again, this is because long wavelengths give lower energies.

Spectra of thin gases

The stability of atoms

Chemical bonds in hydrogen molecules

Discussion Questions

A

Neutrons attract each other via the strong nuclear force, so according to classical physics it should be possible to form nuclei out of clusters of two or more neutrons, with no protons at all. Experimental searches, however, have failed to turn up evidence of a stable two-neutron system (dineutron) or larger stable clusters. Explain based on quantum physics why a dineutron might spontaneously fly apart.

B

The following table shows the energy gap between the ground state and the first excited state for four nuclei, in units of picojoules. (The nuclei were chosen to be ones that have similar structures, e.g., they are all spherical in shape.) Explain the trend in the data.