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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]
or 2
n=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.
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.
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.
0 Location, x/L
n=1
or 2
0 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.