120 Chapter 3 I The SchrOdinger Equation and a Particle in a Box

Problems
3-1. Evaluate g = Af, where Aand fare given below:

A f
(a) SQRT x4

d3
(b) - 3 + x3 e-ax
dx

(c) lo 1
dx x 3 - 2x +3
a2 a2 a2
(d) - +- +- x 3 y2z4
ox2 oy
2 oz2
3-2. Determine whether the following operators are linear or nonlinear:

(a) Af (x) = SQRf (x) [square f(x)]

(b) Af(x) = f*(x) [form the complex conjugate of f(x)]

(c) Af(x) = 0 [multiply f (x) by zero]

(d) Af(x) = [f(x)]- 1 [take the reciprocal of f(x)]

(e) Af(x) = f(O) [evaluate f(x) at x = 0)

(f) Af(x) = In f(x) [take the logarithm of f(x)]

3-3. In each case, show that f (x) is an eigenfunction of the operator given. Find the eigenvalue .

.4 f(x)
d2
(a) - coswx
dx 2

(b) !!_ ei(J)t

dt
d2 d etJX
(c) - +2- + 3
dx2 dx

(d) i_ x2e6y
ay
3-4. Show that (cos ax) (cos by) (cos cz) is an eigenfunction of the operator,

2 a2 a2 a2
v =- + - + -
ax2 oy2 oz2
which is called the Laplacian operator.
Problems 121

3- 5. Write out the operator A2 for A=

d2 d d2 d
(a) - 2 (b) - +x (c) - - 2x - +l
dx dx dx 2 dx
Hint: Be sure to include f (x ) before carrying out the operations.

3- 6. Determine whether or not the following pain of operators commute.

A 8
d d2 d
(a) - + 2-
dx dx2 dx
d
(b) x
dx
(c) SQR SQRT

(d)
a a
ax ay

3- 7. In ordinary algebra, ( P + Q) ( P - Q) = P 2 - Q 2. Expand (P + Q)(P - Q). Under what

conditions do we find the same result as in the case of ordinary algebra?

3-8. Ifwe operate on the particle- in-a-box wave functions (Equations 3.27) with the momentum
operator (Equation 3. l I), we find

PAB S111
. -nTCX
- ' " Ba
= - In - (. nTCX)
Sill - -
a ax a

= _ ilinTC B cos nTCx

a a

Note that this is not an eigenvalue equation, and so we say that the momentum of a particle
in a box does not have a fixed, definite value. Although the particle does not have a definite
momentum, we can use the classical equation E = ri /2m to define formally some sort
of effective momentum. Using Equation 3.2 l for E, show that p = nh /2a and that the
de Broglie wavelengths associated with these momenta are A. = h / p = 2a / n. Show that
this last equation says that an integral number of half-wavelengths fit into the box or that
Figure 3.2 corresponds to standing de Broglie waves or matter waves.

3-9. In Section 3.5, we applied the equations for a particle in a box to the TC electrons in
butadiene. This simple model is called the free-electron model. Using the same argument,
show that the length of hexatriene can be estimated to be 867 pm. Show that the first
electronic transition is predicted to occur at 2.8 x 104 cm- 1. (Remember that hexatriene
has six TC electrons.)

3-10. Prove that if 1/f (x) is a solution to the Schrodinger equation, then any constant times 1/1 (x)
is also a solution.

3-11 . In this problem, we will prove that the form of the Schrodinger equation imposes the
condition that the first derivative of a wav·e function be continuous. The Schrodinger
equation is

2
-ddx21{! + -2m
;,,2 [E - V(x)]1/f (x) = 0
122 Chapter 3 I The SchrOdinger Equation and a Particle in a Box

If we integrate both sides from a - E to a + E, where a is an arbitrary value of x and E is

infinitesimally small, then we have

I
-di/I - di/I
- I = 2m
- 1"+€
[V (x) - E]1/f(x)dx
dx x=att dx x=a- € Ji,2 a- €

Now show that di/I/ dx is continuous if V (x) is continuous.

Suppose now that V(x) is not continuous at x = a, as in

vr _____

Show that

-di/I I - di/I
- I = 2m
- (Vi + V,. - 2£)1/f (a)E
dx x=att dx x=t1- € Ii,2

so that d1{!/dx is continuous even if V(x) has a.finite discontinuity. What if V(x) has an
infinite discontinuity, as in the problem of a particle in a box? Are the first derivatives of
the wave ftmctions continuous at the boundaries of the box?

3-12. Show that the probability associated with the state 1/1,, for a particle in a one-dimensional

I
box of length a obeys the following relationships:

n even
Prob(O < x < a/4) = Prob(3a/4 < x <a) = n- 1
- - - - I (- 1)2
n odd
4 27rn

I
and

n even
Prob(a/4 ::: x ::: a / 2) = Prob(a/2 ::: x ::: 3a/4) = (-1) ";'
- + --- n odd
4 27rn

3-1 3. What are the units, if any, for the wave function of a particle in a one-dimensional box?

3-1 4. Using a table of integrals, show that

l
a n7rx a
sin 2 - -dx = -
o a 2

a2
l
a n7rx
x sin2 - -dx = -
a 4
Problems 123

and

" nrrxd X -_ ( -a- )

X. 2 Sill
. 2 --
3
(4rr n
3 3
2n 7r)
loo a 2rrn
--- -
3

All of these integrals can be evaluated from

nnx
l
a
I ({J) = efix sin 2 - dx
a

Show that the above integrals are given by I (0), I' (0), and ! " (0), respectively, where the
primes denote differentiation with respect to {J. Using a table of integrals, evaluate I ({J)
and then the above three integrals by differentiation.

3-1 5 . Show that

a
{x) = -
2

for all the states of a particle in a box. Is this result physically reasonable?

3-16. Show that {p) = 0 for all states of a one-dimensional box oflength a.

3-1 7. Show that

for a particle in a box is less than a, the width of the box, for any value of n. If Cfx is the
tmcertainty in the position of the particle, could Cfx ever be larger than a?

3-18. A classical particle in a box has an equi-likelihood of being found anywhere within the
region 0 ::: x ::: a. Consequently, its probability distribution is

dx
p(x)dx = -
a

Show that {x) = a/2 and {x 2) = a 2/3 for this system. Now show that {x 2) (Equation 3.32)
and Cfx (Equation 3.33) for a quantum-mechanical particle in a box take on the classical
values as n oo. This result is an example of the correspondence principle.

3-19. Using the trigonometric identity

sin 28 = 2 sine cos e

show that

l o
a . nnx
Sill - -
a
nrrx d
cos - - x =
a
()

3-20. Prove that

124 Chapter 3 I The SchrOdinger Equation and a Particle in a Box

3-21. Using the trigonometric identity

. . . I (
sm a Sill f3 = - cos a - fJ) - -l cos(a + ,., )
R
2 2

show that the particle-in-a-box wave functions (Equations 3.27) satisfy the relation

t 1{!* (x)1{!
lo II
111
(x)dx =0 m =I= n

(The asterisk in this case is superfluous because the functions are real.) Ifa set offtlllctions
satisfies the above integral condition, we say that the set is orthogonal and, in particular,
that 1{!111 (x) is ort.hogonal to 1{!11 (x). If, in addition, the functions are normalized, then we say
that the set is orthonormal.

3-22. Prove that the set of functions

n = 0, ± I, ± 2, ...

is orthonormal (cf. Problem 3-21) over the interval - a x a. A compact way to express
orthonormality in the 1{111 is to write

! 1/r,;,
-a (x )1/111 (x )dx = 811111

The symbol 811111 is called a Kronecker delta and is defined by

ifm = n
8,,,,, = {
if m =I= n

3- 23. In problems dealing with a particle in a box, we often need to evaluate integrals of the
type

ll
. nrrx . mrrx d ll nrrx mrrx d
loo Sill - -
a
sm - - x
a
and
loo cos -a- cos -a- x
Integrals such as these are easy to evaluate if you convert the trigonometric functions to
complex exponentials by using the identities (see MathChapter A)

eifl + e-i8 e;e _ e-ifl

cosB = - - - - and sinB = - - - -
2 2i

and then realize that the set offunctions

1/r 11
(x) = a-l/2ei11rrx /a n = 0, ± 1, ± 2, ...

is orthonormal on the interval - a x (Problem 3-22). Show that

a . nrrx . mrrx !o a nrrx mrrx a

sm - - sm - -dx = cos - - cos - -dx = - 811111
!oo a a o a a 2
Problems 125

where 811111 is the Kronecker delta (defined in Problem 3-22). Also show that

l
a nrcx mrcx
cos - - sin - -dx = 0
o a a

3- 24. Show that the set of functions

is orthonormal (Problem 3-2 1).

3- 25 . In going from Equation 3.34 to 3.35, we multiplied Equation 3.34 from the left by 1/f*(x)
and then integrated over all values of x to obtain Equation 3.35. Does it make any difference
whether we multiplied from the left or the right?

3-26. Calculate (x} and (x 2} for the n = 2 state of a particle in a one-dimensional box of
length a. Show that

erx = !!.._ (4rc2 - 2) 1/2

4rc 3

3- 27. Calculate (p) and (p 2} for the n = 2 state of a particle in a one-dimensional box of
length a. Show that

h
er,, = -
a

3- 28. Consider a particle of mass m in a one-dimensional box of length a. Its average energy
is given by

I (p2}
(£ } = _
2m

Because (p } = 0, (p 2 } = where er,, can be called the uncertainty in p. Using the

uncertainty principle, show that the energy must be at least as large as !i2 /8ma 2 because erx,
the uncertainty in x., cannot be larger than a.

3-29. Discuss the degeneracies of the first few energy levels of a particle in a three-dimensional
box when a f= b f= c.

3- 30. Show that the normalized wave function for a particle in a three-dimensional box with
sides of length a, b, and c is

8 ) 112 . nrcx . n ,rcy . n ,rcz

1/f(x, y, z) = ( - sm _x_ sm _ )_ sm - --
abc a b c

3-3 1. Show that (p} = 0 for the ground state of a particle in a three-dimensional box with sides
of length a, b, and c.

3-32. What are the degeneracies of the first four energy levels for a particle in a three-
dimensional box with a = b = 1.5 c?
126 Chapter 3 I The SchrOdinger Equation and a Particle in a Box

3-33. The Schrodinger equation for a particle of mass m constrained to move on a circle of
radius a is

where I = rna 2 is the moment of inertia and e is the angle that describes the position of the
particle around the ring. Show by direct substitution that the solutions to this equation are

1/1 (B) = Ae;"o

where n = ± (2/ E) 112 /It Argue that the appropriate boundary condition is 1/1 (B) =
1/1 (B + 21r) and use this condition to show that

n = 0, ± 1, ± 2, ...

Show that the normalization constant A is (2rr )- 112 . Discuss how you might use these results
for a free-electron model of benzene.

3-34. Set up the problem of a particle in a box with its walls located at - a and + a. Show that
the energies are equal to those of a box with walls located at 0 and 2a. (These energies may
be obtained from the results that we derived in the chapter simply by replacing a by 2a.)
Show, however, that the wave functions are not the same and are given by

l
l . 111rx
l /2 Sill - - n even
a 2a
1/111(x) = 1
nnx
l / 2 cos - - n odd
a 2a

Does it bother you that the wave functions seem to depend upon whether the walls are
located at ± a or 0 and 2a'! Surely the particle "knows" only that it has a region of length 2a
in vvhich to move and cannot be affected by where you place the origin for the two sets of
wave functions. What does this tell you? Do you think that any experimentally observable
properties depend upon where you choose to place the origin of the x axis? Show that
axerP > n/2, exactly as we obtained in Section 3 .8.

3-35. The quantized energies ofa particle in a box result from the boundary conditions, or from
tl1e fact that the particle is restricted to .a finite region. In this problem, we investigate the
quantum-mechanical problem of a free particle, one that is not restricted to a finite region.
The potential energy V(x) is equal to zero and the Schrodinger equation is

2
d 1/I + 2mE 1/J(x) = 0 - OO < X < OO
dx2 ri2

Note that the particle can lie anywhere along the x axis in this problem. Show that the two
solutions of this Schrodinger equation are
Problems 127
and

where

(2mE) 112
k =----
h

Show that if E is allowed to take on negative values, then the wave ftmctions become
tmbounded for large x . Therefore, we will require that the energy, E , be a positive quantity.
To get a physical interpretation of the states that 1/1 1(x) and ifi2 (x) describe, operate on
1/11(x) and 1/12 (x) with the momentum operator P(Equation 3.11 ), and show that

and

' d i/12
Pi/12 = - i Ii- = - n,ki/12
dx

Notice that these are eigenvalue equations. Our interpretation of these two equations is that
1/11 describes a free particle with fixed momentum l'ik and that i/12 describes a particle with
fixed momentum - hk. Thus, i/1 1 describes a particle moving to the right and 1/12 describes
a particle moving to the left, both with a fixed momentum. Notice also that there are no
restrictions on k, and so the particle can have any val ue of momentum. Now show that

Notice that the energy is not quantized; the energy of the particle can have any positive
value in this case because no boundaries are associated with this problem.
Last, show that ifir(x)ifi 1(x) = ATA 1 = IAtl2 = constant, and that 1/12(x)ifi2(x) =
Ai,A2 = IA212 = constant. Discuss this result in terms of the probabilistic interpretation
of 1/1*1/f. Also discuss the application of the tmcertainty principle to this problem. What are
aP and a/!

3-36. Derive the equation for the allowed energies of a particle in a one-dimensional box by
assuming that the particle is described by standing de Broglie waves within the box.

3- 37. In Chapter 4, we will encounter the time-dependent Schri:idinger equation

HW(x, t) = i Ii o'll (x, t)

or
where '!I is now a ftmction ofboth position and time. Show that if the Hamiltonian operator
does not contain time explicitly [ H = H(x) ]. then tllis partial differential equation can be
separated into two ordinary differential equations by setting '!I (x, t) = if! (x)f (t). What is
the separation constant in t11is problem? Generalize this result to three dimensions. What is
the function f (t)?
128 Chapter 3 I The SchrOdinger Equation and a Particle in a Box

3-38. Using the result of Problem 3- 37, what is the time-dependent wave function for the
ground state of a particle in a one-dimensional box of length a? Use this wave ftmction to
evaluate the average value of x. Are you surprised?

3- 39. We can use the wave functions of Problem 3-34 to illustrate some fundamental symmetry
properties of wave functions. Show that the wave functions are alternately symmetric and
antisymmetric or even and odd with respect to the operation x - x, which is a reflection
through the x = 0 line. This symmetry property of the wave function is a consequence of
the symmetry of the Hamiltonian operator, as we shall now show. The Schrodinger equation
may be written as

ii (x )1/1
11
(x) = £ 11 1/111 (x)

Reflection through the x = 0 line gives x - x, and so

il(- x)l/1,,(- x) = £ 11 1/111 (- x)

Now show that il(x) = il(- x) (i.e., that ii is symmetric), and so show that

il(x)l/111 (- x) = £ 11 1{!11 ( - x)

Thus, we see that 1{!11 (- x) is also an eigenfunction of fl belonging to the same eigenvalue £ 11 •
Now, if there is only one eigenfunction associated with each eigenvalue (we call this a
nondegenerate case), then argue that 1/1,.(x) and 1{111 ( - x) must differ by a multiplicative
constant [i.e., that 1{!11 ( - x) = c1{!11 (x)]. By applying the inversion operation again to this
equation, show that c =± I and that all the wave fm1ctions must be either even or odd with
respect to reflection through the x = 0 line because the Hamiltonian operator is symmetric.
Thus, we see that the symmetry of the Hamiltonian operator influences the symmetry of the
wave functions.

References
Moore, W. J. Schrodinger: Life and Thought. Cambridge University Press: New York, 1992.
Greenspan, N. The End ofthe Certain World: The Life and Science o.f Max Born. Basic Books: New
York, 2005.