10.3.
EXAMPLES 7
This isn’t possible classically, and it is one of the many ways in which quantum mechanics
diverges from classical mechanics. We’ll talk more about this when we discuss the finite
square well in Section 10.3.3.
If E = V0 , then this is the one case where the strategy of guessing an exponential function
doesn’t work. But if we go back to Eq. (9) we see that E = V0 implies ∂ 2 ψ/∂x2 = 0, which
in turn implies that ψ is a linear function,
ψ(x) = Ax + B. (14)
In all of these cases, the full wavefunction (including the time dependence) for a particle
with a specific value of E is given by
ψ(x, t) = e−iωt ψ(x) = e−iEt/h̄ ψ(x) (15)
Again, we’re using the letter ψ to stand for two different functions here, but the meaning of
each is clear from the number of arguments. Any general wavefunction is built up from a
superposition of the states in Eq. (15) with different values of E, just as the general motion
of a string is built of from various normal modes with different frequencies ω. The fact that a
particle can be in a superposition of states with different energies is another instance where
quantum mechanics diverges from classical mechanics. (Of course, it’s easy for classical
waves to be in a superposition of normal modes with different energies, by Fourier analysis.)
The above E > V0 and E < V0 cases correspond, respectively, to being above or below
the cutoff frequency in the string/spring system we discussed in Section 6.2.2. We have an
oscillatory solution if E (or ω) is above a particular value, and an exponential solution if
E (or ω) is below a particular value. The two setups (quantum mechanical with constant
V0 , and string/spring with springs present everywhere) are exactly analogous to each other.
The spatial parts of the solutions are exactly the same (well, before taking the real part
in the string/spring case). The frequencies, however, are different, because the dispersion
relations are different (h̄ω = h̄2 k 2 /2m + V0 and ω 2 = c2 k 2 + ωs2 , respectively). But this
affects only the rate of oscillation, and not the shape of the function.
The above results hold for any particular region where V (x) is constant. What if the
region extends from, say, x = 0 to x = +∞? If E > V0 , the oscillatory solutions are fine,
even though they’re not normalizable. That is, the integral of |ψ|2 is infinite (at least for any
nonzero coefficient in ψ; if the coefficient were zero, then we wouldn’t have a particle). So
we can’t make the total probability equal to 1. However, this is fine. The interpretation is
that we simply have a stream of particles extending to infinity. We shouldn’t be too worried
about this divergence, because when dealing with traveling waves on a string (for example,
when discussing reflection and transmission coefficients) we assumed that the sinusiodal
waves extended to ±∞, which of course is impossible in reality.
If E < V0 , then the fact that x = +∞ is in the given region implies that the coefficient
A in Eq. (13) must be zero, because otherwise ψ would diverge as x → ∞. So we are left
with only the Ba−κx term. (It’s one thing to have the integral of |ψ|2 diverge, as it did in
the previous paragraph. It’s another thing to have the integral diverge and be dominated
by values at large x. There is then zero probability of finding the particle at a finite value
of x.) If the region where E < V0 is actually the entire x axis, from −∞ to ∞, then the B
coefficient in Eq. (13) must also be zero. So ψ(x) = 0 for all x. In other words, there is no
allowed wavefunction. It is impossible to have a particle with E < V0 everywhere.
10.3.2 Infinite square well
Consider the potential energy,
½
0 (0 ≤ x ≤ L)
V (x) = (16)
∞ (x < 0 or x > L).
8 CHAPTER 10. INTRODUCTION TO QUANTUM MECHANICS
This is called an “infinite square well,” and it is shown in Fig. 1. The “square” part of the
V= V= name comes from the right-angled corners and not from the actual shape, since it’s a very
8
8 (infinitely) tall rectangle. This setup is also called a “particle in a box” (a 1-D box), because
the particle can freely move around inside a given region, but has zero probability of leaving
V=0 the region, just like a box. So ψ(x) = 0 outside the box.
-a a
The particle does indeed have zero chance of being found outside the region 0 ≤ x ≤ L.
Figure 1 Intuitively, this is reasonable, because the particle would have to climb the infinitely high
potential cliff at the side of the box. Mathematically, this can be derived rigorously, and
we’ll do this below when we discuss the finite square well.
We’ll assume E > 0, because the E < 0 case makes E < V0 everywhere, which isn’t
possible, as we mentioned above. Inside the well, we have V (x) = 0, so this is a special
case of the constant potential discussed above. We therefore have the oscillatory solution
in Eq. (12) (since E > 0), which we will find more convenient here to write in terms of trig
functions,
√
h̄2 k 2 2mE
ψ(x) = A cos kx + B sin kx, where E = =⇒ k = . (17)
2m h̄
The coefficients A and B may be complex.
We now claim that ψ must be continuous at the boundaries at x = 0 and x = L. When
dealing with, say, waves on a string, it was obvious that the function ψ(x) representing
the transverse position must be continuous, because otherwise the string would have a
break in it. But it isn’t so obvious with the quantum-mechanical ψ. There doesn’t seem
to be anything horribly wrong with having a discontinuous probability distribution, since
probability isn’t an actual object. However, it is indeed true that the probability distribution
is continuous in this case (and in any other case that isn’t pathological). For now, let’s just
assume that this is true, but we’ll justify it below when we discuss the finite square well.
Since ψ(x) = 0 outside the box, continuity of ψ(x) at x = 0 quickly gives A cos(0) +
B sin(0) = 0 =⇒ A = 0. Continuity at x = L then gives B sin kL = 0 =⇒ kL = nπ, where
n is an integer. So k = nπ/L, and the solution for ψ(x) is ψ(x) = B sin(nπx/L). The full
solution including the time dependence is given by Eq. (15) as
³ nπx ´ h̄2 k 2 n2 π 2 h̄2
ψ(x, t) = Be−iEt/h̄ sin where E= = (18)
L 2m 2mL2
We see that the energies are quantized (that is, they can take on only discrete values) and
indexed by the integer n. The string setup that is analogous to the infinite square well is
a string with fixed ends, which we discussed in Chapter 4 (see Section 4.5.2). In both of
these setups, the boundary conditions yield the same result that an integral number of half
n=4 wavelengths fit into the region. So the k values take the same form, k = nπ/L.
The dispersion relation, however, is different. It was simply ω = ck for waves on a
string, whereas it is h̄ω = h̄2 k 2 /2m for the V (x) = 0 region of the infinite well. But as
n=3 in the above case of the constant potential, this difference affects only the rate at which
the waves oscillate in time. It does’t affect the spatial shape, which is determined by the
wavenumber k. The wavefunctions for the lowest four energies are shown in Fig. 2 (the
n=2
vertical separation between the curves is meaningless). These look exactly like the normal
modes in the “both ends fixed” case in Fig. 24 in Chapter 4.
n=1
x=0 x=L
Figure 2
Energy in units of
π2h2/2mL2
10.3. EXAMPLES 9
E
16 n=4
The corresponding energies are shown in Fig. 3. Since E ∝ ω = (h̄2 /2m)k 2 ∝ n2 , the
gap between the energies grows as n increases. Note that the energies in the case of a string
are also proportional to n2 , because although ω = ck ∝ n, the energy is proportional to ω 2
(because the time derivative in Eq. (4.50) brings down a factor of ω). So Figs. 2 and 3 both
√
apply to both systems. The difference between the systems is that a string has ω ∝ E,
where as the quantum mechanical system has ω ∝ E. 9 n=3
There is no n = 0 state, because from Eq. (18) this would make ψ be identically zero.
That wouldn’t be much of a state, because the probability would be zero everywhere. The
lack of a n = 0 state is consistent with the uncertainty principle (see Section 10.4 below), n=2
4
because such a state would have ∆x∆p = 0 (since ∆x < L, and ∆p = 0 because n = 0 =⇒
k = 0 =⇒ p = h̄k = 0), which would violate the principle.
1 n=1
10.3.3 Finite square well Figure 3
Things get more complicated if we have a finite potential well. For future convenience, we’ll
V = V0
let x = 0 be located at the center of the well. If we label the ends as ±a, then V (x) is given
by
½
0 (|x| ≤ a) V=0
V (x) = (19) -a a
V0 (|x| > a).
This is shown in Fig. 4. Given V0 , there are two basic possibilities for the energy E: Figure 4
• E >p V0 (unbound state): From Eq. (11),√ the wavenumber k takes thep general form
of 2m(E − V (x))/h̄. This equals 2mE/h̄ inside the well and 2m(E − V0 )/h̄ E
outside. k is therefore real everywhere, so ψ(x) is an oscillatory function both inside V0
and outside the well. k is larger inside the well, so the wavelength is shorter there. A
possible wavefunction might look something like the one in Fig. 5. It is customary to -a a
draw the ψ(x) function on top of the E line, although this technically has no meaning
because ψ and E have different units. Figure 5
The wavefunction extends infinitely on both direction, so the particle can be anywhere.
Hence the name “unbound state.” We’ve drawn an even-function standing wave in
Fig. 5, although in general we’re concerned with traveling waves for unbound states.
These are obtained from superpositions of the standing waves, with a phase thrown
in the time dependence. For traveling waves, the relative sizes of ψ(x) in the different
regions depend on the specifics of how the problem is set up.
√
• p
0 < E < V0 (bound state): The wavenumber k still equals 2mE/h̄ inside the well and
2m(E − V0 )/h̄ outside, but now that latter value is imaginary. So ψ is an oscillatory
function inside the well, but an exponential function outside. Furthermore, it must
be an exponentially decaying function outside, because otherwise it would diverge at
x = ±∞. Since the particle has an exponentially small probability of being found
far away from the well, we call this a “bound state.” We’ll talk more below about
the strange fact that the probability is nonzero in the region outside the well, where
E < V (x).
There is also the third case were E = V0 , but this can be obtained as the limit of the
other two cases (more easily as the limit of the bound-state case). The fourth case,
E < 0, isn’t allowed, as we discussed at the end of Section 10.3.1.
In both of these cases, the complete solution for ψ(x) involves solving the boundary
conditions at x = ±a. The procedure is the same for both cases, but let’s concentrate on
the bound-state case here. The boundary conditions are given by the following theorem.
10 CHAPTER 10. INTRODUCTION TO QUANTUM MECHANICS
Theorem 10.1 If V (x) is everywhere finite (which is the case for the finite square well),
then both ψ(x) and ψ 0 (x) are everywhere continuous.
Proof: If we solve for ψ 00 in Eq. (9), we see that ψ 00 is always finite (because V (x) is always
finite). This implies two things. First, it implies that ψ 0 must be continuous, because if ψ 0
were discontinuous at a given point, then its derivative ψ 00 would be infinite there (because
ψ 0 would make a finite jump over zero distance). So half of the theorem is proved.
Second, the finiteness of ψ 00 implies that ψ 0 must also be finite everywhere, because if
ψ were infinite at a given point (excluding x = ±∞), then its derivative ψ 00 would also be
0
infinite there (because ψ 0 would make an infinite jump over a finite distance).
Now, since ψ 0 is finite everywhere, we can repeat the same reasoning with ψ 0 and ψ that
we used with ψ 00 and ψ 0 in the first paragraph above: Since ψ 0 is always finite, we know
that ψ must be continuous. So the other half of the theorem is also proved.
Having proved this theorem, let’s outline the general strategy for solving for ψ in the
E < V0 case. The actual task of going through the calculation is left for Problem 10.2. The
calculation is made much easier with the help of Problem 10.1 which states that only even
and odd functions need to be considered. p
If we let k ≡ iκ outside the well, then we have κ = 2m(V0 − E)/h̄, which is real and
positive since E < V0 . The general forms of the wavefunctions in the left, middle, and right
regions are
x < −a : ψ1 (x) = A1 eκx + B1 e−κx ,
−a < x < a : ψ2 (x) = A2 eikx + B2 e−ikx ,
x>a: ψ3 (x) = A3 eκx + B3 e−κx , (20)
where √ p
2mE 2m(V0 − E)
k= , and κ= . (21)
h̄ h̄
We’ve given only the x dependence in these wavefunctions. To obtain the full wavefunction
ψ(x, t), all of these waves are multiplied by the same function of t, namely e−iωt = e−iEt/h̄ .
We now need to solve for various quantities. How many unknowns do we have, and how
many equations/facts do we have? We have seven unknowns: A1 , A2 , A3 , B1 , B2 , B3 , and
E (which appears in k and κ). And we have seven facts:
• Four boundary conditions at x = ±a, namely continuity of ψ and ψ 0 at both points.
• Two boundary conditions at x = ±∞, namely ψ = 0 in both cases.
R∞
• One normalization condition, namely −∞ |ψ|2 dx = 1.
As we mentioned at the end of Section 10.3.1, the boundary conditions at ±∞ quickly
tell us that B1 and A3 equal zero. Also, in most cases we’re not concerned with the overall
normalization constant (the usual goal is to find E), so we can ignore the normalization
condition and just find all the other constants in terms of, say, A1 . So were’re down to
four equations (the four boundary conditions at x = ±a), and four unknowns (A2 , B2 , B3 ,
and E). Furthermore, the even/odd trick discussed in Problem 10.1 cuts things down by a
factor of 2, so we’re down to two equations and two unknowns (the energy E, along with
one of the coefficients), which is quite manageable. The details are left for Problem 10.2,
but let’s get a rough idea here of what the wavefunctions look like.
