Griffiths Quantum Mechanics 3e: Problem 2.

48 Page 1 of 5

Problem 2.48
Consider a particle of mass m in the potential

∞
 x < 0,
V (x) = −32~2 /ma2 0 ≤ x ≤ a,

0 x > a.


(a) How many bound states are there?

(b) In the highest-energy bound state, what is the probability that the particle would be found
outside the well (x > a)? Answer: 0.542, so even though it is “bound” by the well, it is
more likely to be found outside than inside!

Solution

The governing equation for the wave function Ψ(x, t) is the Schrödinger equation.
∂Ψ ~2 ∂ 2 Ψ
i~ =− + V (x, t)Ψ(x, t), −∞ < x < ∞, t > 0
∂t 2m ∂x2
Split it up over the intervals where the given potential is finite and infinite.
∂Ψ ~2 ∂ 2 Ψ ∂Ψ ~2 ∂ 2 Ψ
i~ =− + (∞)Ψ(x, t), x < 0, t > 0; i~ =− + V (x)Ψ(x, t), x > 0, t > 0
∂t 2m ∂x2 ∂t 2m ∂x2
The only solution for the PDE over x < 0 is Ψ(x, t) = 0. Because the wave function is continuous,
Ψ(0, t) = 0 becomes a boundary condition for the remaining PDE on x > 0.
∂Ψ ~2 ∂ 2 Ψ
i~ =− + V (x)Ψ(x, t), x > 0, t > 0
∂t 2m ∂x2
Ψ(0, t) = 0
Ψ(∞, t) = 0

Since information about the eigenstates and their corresponding energies is desired, the method of
separation of variables is opted for. This method works because Schrödinger’s equation and its
associated boundary conditions are linear and homogeneous. Assume a product solution of the
form Ψ(x, t) = ψ(x)φ(t) and plug it into the PDE
∂ ~2 ∂ 2
i~ [ψ(x)φ(t)] = − [ψ(x)φ(t)] + V (x)[ψ(x)φ(t)]
∂t 2m ∂x2
~2 00
i~ψ(x)φ0 (t) = − ψ (x)φ(t) + V (x)ψ(x)φ(t)
2m
and the boundary conditions.

Ψ(0, t) = 0 → ψ(0)φ(t) = 0 → ψ(0) = 0

Ψ(∞, t) = 0 → ψ(∞)φ(t) = 0 → ψ(∞) = 0

Divide both sides of the PDE by ψ(x)φ(t) in order to separate variables.

φ0 (t) ~2 ψ 00 (x)
i~ =− + V (x)
φ(t) 2m ψ(x)

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Griffiths Quantum Mechanics 3e: Problem 2.48 Page 2 of 5

The only way a function of t can be equal to a function of x is if both are equal to a constant E.

φ0 (t) ~2 ψ 00 (x)
i~ =− V (x) = E
φ(t) 2m ψ(x)
As a result of using the method of separation of variables, the Schrödinger equation has reduced
to two ODEs, one in x and one in t.
φ0 (t)

i~ = E

φ(t) 
~2 ψ 00 (x) 
− + V (x) = E 

2m ψ(x)
Values of E for which the boundary conditions are satisfied are called the eigenvalues (or
eigenenergies in this context), and the nontrivial solutions associated with them are called the
eigenfunctions (or eigenstates in this context). The ODE in x is known as the time-independent
Schrödinger equation (TISE) and can be written as

d2 ψ 2m
2
= 2 [V (x) − E]ψ, x > 0.
dx ~
Split it up over the intervals that V (x) is defined on.

d2 ψ 2m 32~2 d2 ψ
 
2m
=− 2 + E ψ, 0 ≤ x ≤ a; = 2 (−E)ψ, x>a
dx2 ~ ma2 dx 2 ~

Bound states have energy −32~2 /(ma2 ) < E < 0, or 32~2 /(ma2 ) + E > 0, as illustrated below.

The general solution for ψ can be written as

(
C1 cos `x + C2 sin `x if 0 ≤ x ≤ a
ψ(x) = ,
C3 e−κx + C4 eκx if x > a

where √ s
32~2
 
−2mE 2m
κ= and ` = +E .
~ ~2 ma2

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Griffiths Quantum Mechanics 3e: Problem 2.48 Page 3 of 5

Apply the boundary condition at x = 0 to determine one constant.

ψ(0) = C1 = 0.

To satisfy the boundary condition at x = ∞, set C4 = 0.

(
C2 sin `x if 0 ≤ x ≤ a
ψ(x) =
C3 e−κx if x > a

Use the fact that the wave function [and consequently ψ(x)] must be continuous at x = a to
determine another constant.

lim ψ(x) = lim ψ(x) : C2 sin `a = C3 e−κa (1)

x→a− x→a+

Finally, integrate both sides of the TISE with respect to x from a −  to a + , where  is a really
small positive number.
ˆ a+ 2 ˆ a+
d ψ 2m
2
dx = 2
[V (x) − E]ψ(x) dx
a− dx a− ~
ˆ a ˆ a+
dψ a+ 32~2
 
2m 2m
= 2
− 2
− E ψ(x) dx + (−E)ψ(x) dx
dx a− a− ~ ma a ~2
ˆ a ˆ a+
32~2
 
2m 2m
= 2 − − E ψ(a) dx + 2 (−E)ψ(a) dx
~ ma2 a− ~ a
32~2
 
2m 2m
= 2 − 2
− E ψ(a) + 2 (−E)ψ(a)
~ ma ~

Take the limit as  → 0.

a+
dψ
=0
dx a−
It turns out that ∂Ψ/∂x is also continuous at x = a.

dψ dψ
lim = lim : C2 ` cos `a = −C3 κe−κa (2)
x→a− dx x→a+ dx

Substitute equation (1) into equation (2).

C2 ` cos `a = −C2 κ sin `a

To avoid the trivial solution, assume that C2 6= 0.

` cos `a = −κ sin `a

Multiply both sides by a.

`a cot `a = −κa (3)
Note that
32~2
 
2 2−2mE 2m 2mE 64 2mE 64
κ +` = + 2 +E =− + 2 + 2 = 2.
~2 ~ ma2 ~2 a ~ a

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Griffiths Quantum Mechanics 3e: Problem 2.48 Page 4 of 5

Multiply both sides by a2 and then solve for κa.

κ2 a2 + `2 a2 = 64

κ2 a2 = 64 − `2 a2
p
κa = 64 − `2 a2
As a result, equation (3) becomes
p
`a cot `a = − 64 − `2 a2
r
64
− cot `a = − 1.
`2 a2
Plot the functions on both sides versus `a.

Since there are three intersections, there are three bound states. These intersections occur at
approximately
s
2m 32~2 28.1194~2
 
`a ≈ 2.78590 → + E1 a ≈ 2.78590 → E1 ≈ −
~2 ma2 ma2
s
2m 32~2 16.7568~2
 
`a ≈ 5.52145 → + E2 a ≈ 5.52145 → E2 ≈ −
~2 ma2 ma2
s
2m 32~2 0.340529~2
 
`a ≈ 7.95732 → + E3 a ≈ 7.95732 → E3 ≈ − .
~2 ma2 ma2

For the highest energy,

√
−2mE3 0.825263 7.95732
κ= ≈ and ` ≈ .
~ a a

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Griffiths Quantum Mechanics 3e: Problem 2.48 Page 5 of 5

The eigenfunction associated with the highest energy is

(
C2 sin `x if 0 ≤ x ≤ a
ψ(x) =
C3 e−κx if x > a
(
C2 sin `x if 0 ≤ x ≤ a
= κa −κx
(C2 e sin `a)e if x > a
(
C2 sin `x if 0 ≤ x ≤ a
= −κ(x−a)
(C2 sin `a)e if x > a

C2 sin 7.95732x if 0 ≤ x ≤ a
a
≈ .
(C sin 7.95732) exp −0.825263 x − 1
 if x > a
2 a

C2 is arbitrary and is chosen so that the integral of [ψ(x)]2 over the half-line is 1.
ˆ ∞
1= [ψ(x)]2 dx
0
ˆ a ˆ ∞n
7.95732x 2
 h x io2
= C2 sin dx + (C2 sin 7.95732) exp −0.825263 −1 dx
0 a a a
= 1.10587aC22

Solve for C2 .
0.950930
C2 = √
a
Therefore, the eigenstate with the highest energy is

 0.950930
√ sin 7.95732x
a if 0 ≤ x ≤ a
a
ψ(x) = .
 0.945857
√

exp −0.825263 x
−1


if x > a
a a

The probability that the particle is outside the well is 1 minus the probability that it’s inside the
well.
ˆ a ˆ a
7.95732x 2

2 0.950930
1− [ψ(x)] dx = 1 − √ sin dx
0 0 a a
≈ 0.542

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