Atkins_4e_Ch01_p56 4/24/07 2:12 PM Page 21

21

1.8 THE PRINCIPAL QUANTUM NUMBER

SELF-TEST 1.8A Use the same model for helium but suppose that the box is 100. pm
long, because the atom is smaller. Estimate the wavelength of the same transition.
[Answer: 11.0 nm]

The probability density for a particle at a location is proportional to the square

of the wavefunction at that point; the wavefunction is found by solving the
Schrdinger equation for the particle. When the equation is solved subject to the
appropriate boundary conditions, it is found that the particle can possess only
certain discrete energies.

THE HYDROGEN ATOM

We are now ready to build a quantum mechanical model of a hydrogen atom. Our
task is to combine our knowledge that an electron has wavelike properties and is
described by a wavefunction with the nuclear model of the atom, and explain the
ladder of energy levels suggested by spectroscopy.

1.8 The Principal Quantum Number

An electron in an atom is like a particle in a box, in the sense that it is confined
within the atom by the pull of the nucleus. We can therefore expect the electrons
wavefunctions to obey certain boundary conditions, like the constraints we
encountered when fitting a wave between the walls of a container. As we saw for a
particle in a box, these constraints result in the quantization of energy and the existence of discrete energy levels. Even at this early stage, we can expect the electron
to be confined to certain energies, just as spectroscopy requires.
To find the wavefunctions and energy levels of an electron in a hydrogen atom,
we must solve the appropriate Schrdinger equation. To set up this equation,
which resembles the equation in Eq. 9 but allows for motion in three dimensions,
we use the expression for the potential energy of an electron of charge e at a

or 2

Another surprising implication of Eq. 11 is that a particle in a container cannot

have zero energy. Because the lowest value of n is 1 (corresponding to a wave of onehalf wavelength fitting into the box), the lowest energy is E1  h2/8mL2. This lowest
possible energy is called the zero-point energy. The existence of a zero-point energy
means that, according to quantum mechanics, a particle can never be perfectly still
when it is confined between two walls: it must always possess an energyin this
case, a kinetic energyof at least h2/8mL2. This result is consistent with the uncertainty principle. When a particle is confined between two walls, the uncertainty in its
position cannot be larger than the distance between the two walls. Because the position is not completely uncertain, the linear momentum must be uncertain, too, and
so we cannot say that the particle is completely still. The particle must therefore have
some kinetic energy. The zero-point energy is a purely quantum mechanical phenomenon and is very small for macroscopic systems. For example, a billiard ball on a
pool table has a completely negligible zero-point energy of about 1067 J.
Finally, the shapes of the wavefunctions of a particle in a box also reveal some
interesting information. Lets look at the two lowest energy wavefunctions, corresponding to n  1 and n  2. Figure 1.27 shows, by the density of shading, the
likelihood of finding a particle: we see that when a particle is described by the
wavefunction 1 (and has energy h2/8mL2), then it is most likely to be found in
the center of the box. Conversely, if the particle is described by the wavefunction
 2 (and has energy h2/2mL2), then it is most likely to be found in regions between
the center and the walls and is unlikely to be found in the middle of the box.
Remember that the wavefunction itself does not have any direct physical significance: we have to take the square of  before we can interpret it in terms of the
probability of finding a particle somewhere.

1
Location, x/L

n=1

or 2

SELF-TEST 1.8B Use the same model for hydrogen and estimate the wavelength for the
transition from the n  3 energy level to the n  2 level.

n=2

1
Location, x/L

FIGURE 1.27 The two lowest energy

wavefunctions (, orange) for a particle in
a box and the corresponding probability
densities ( 2, blue). The probability
densities are also shown by the density of
shading of the bands beneath each
wavefunction.