Chapter 13: The Schrödinger Equation

Problem numbers in italics indicate that the solution is included in the

Student’s Solutions Manual.
Questions on Concepts

Q13.1) By discussing the diffraction of a beam of particles by a single slit, justify the
statement that there is no sharp boundary between particle-like and wave-like behavior.

For a low particle energy, corresponding to a long wavelength, the diffraction

pattern is clearly resolved. As the energy increases, the wavelength decreases, the
diffraction peak moves closer to the central peak and its intensity decreases. The
diffraction peak does not disappear with increasing energy; it simply becomes
difficult to observe.

Q13.2) Why does a quantum mechanical system with discrete energy levels behave as if
it has a continuous energy spectrum if the energy difference between energy levels ∆ E
satisfies the relationship ∆ E << kT ?

If the difference in energy between levels becomes small compared to kT, the
levels become “smeared out” and overlap. When this happens, the levels can no
longer be distinguished, and from the viewpoint of the observer, the system has a
continuous energy spectrum.

Q13.3) Why can we conclude that the wave function ψ ( x, t ) = ψ ( x)e− i ( E
)t represents a
standing wave?

It represents a standing wave because it can be written as the product of a function

that depends only on time with a function that depends only on the spatial
coordinate. Therefore the nodes do not move with time.

Q13.4) Why is it true for any quantum mechanical problem that the set of wave
functions is larger than the set of eigenfunctions?

The set of all wave functions must satisfy the boundary conditions as well as
satisfy the conditions that allow us to interpret the square of the magnitude of the
wave function in terms of probability. The set of eigenfunctions must satisfy an
additional condition given by the eigenvalue equation. Because some wave
functions won’t satisfy the eigenvalue equation, the set of wave functions is larger
than the set of eigenfunctions.

Q13.5) Is it correct to say that because the de Broglie wavelength of a H2 molecule at

300 K is on the order of atomic dimensions that all properties of H2 are quantized?

13-1
Chapter 13/The Schrödinger Equation

No. The system must be treated using quantum mechanics if the characteristic
size is comparable to the wavelength. For a H2 molecule moving in a one liter
container, the wavelength is much smaller than the characteristic dimension of the
container. In this case, the translational energy levels are so closely spaced that
they can be described classically. Therefore, the pressure exerted by the H2
molecules on the walls of the container can be described classically.

Q13.6) In Figure 13.6 the extent to which the approximate and true functions agree was
judged visually. How could you quantify the quality of the fit?

∫  f ( x ) − g ( x ) dx , where f(x) and g(x) are the

2
You could use a function like
functions to be compared, as a quantitative measure of how alike the functions
are. The value of the integral goes to zero as the two functions become identical.

Q13.7) If ψ ( x, t ) = A sin(kx − ωt ) describes a wave traveling in the plus x direction, how

would you describe a wave moving in the minus x direction?

Consider the nodes in the function ψ ( x, t ) = A sin(kx + ωt ). The wave amplitude

x t
is zero for 2π  +  = nπ where n is an integer. Solving for x, we obtain the
λ T 
n t 
location of the nodes. x = λ  −  . We see that x decreases as t increases,
2 T 
showing that the wave is moving in the direction of negative x.

Q13.8) A traveling wave with arbitrary phase φ can be written as

ψ ( x, t ) = A sin(kx − ωt + φ ). What are the units of φ? Show that φ could be used to
represent a shift in the origin of time or distance.

The units of φ are radians. We can rewrite this equation either as

 φ  φ
ψ ( x, t ) = A sin(k  x +  − ωt ) or ψ ( x, t ) = A sin(kx − ω t −  ) . The first of
 k  ω
these equations suggests a shift in x, and the second suggests a shift in t.

Q13.9) One source emits spherical waves and another emits plane waves. For which
source does the intensity measured by a detector of fixed size fall off more rapidly with
distance? Why?

The intensity of the spherical source falls off more rapidly. The total intensity is
the same for all spheres centered at the source. Larger spheres correspond to
larger distances, and for a given detector area, the fraction of the intensity in the
A
area A is , where r is the radius of the sphere, which is equal to the distance
4π r 2

13-2
 Chapter 13/The Schrödinger Equation

from the source to the detector. Therefore the measured intensity for the spherical
source decreases as 1/r2. There is no decrease in intensity for the source emitting
plane waves. A well collimated light source, such as a laser, is an approximation
to a plane wave source.

Q13.10) Distinguish between the following terms applied to a set of functions:

orthogonal, normalized, and complete.

Two functions φi(x) and φj(x) are orthogonal if ∫ φi* ( x ) φ j ( x ) dx = 0 , normalized

if ∫ φi* ( x ) φi ( x ) dx = ∫ φ *j ( x ) φ j ( x ) dx = 1 , and complete if any well behaved

∞
function ψ(x) can be expanded in terms of the φi(x), ψ ( x ) = ∑ bmφm ( x ) .
m =1

Problems

P13.1) Assume that a system has a very large number of energy levels given by the
formula ε = ε 0l 2 with ε 0 = 2.34 ×10−22 J, where l takes on the integral values 1, 2, 3, … .
Assume further that the degeneracy of a level is given by gl = 2l . Calculate the ratios
n5 / n1 and n10 / n1 for T = 100 K and T = 650 K, respectively.
n5 g5  − ( ε 5 − ε1 )  2 × 5  − ( 52 ε 0 − ε 0 ) 
= exp  = exp  
n1 g1  kT  2 ×1  kT 
n5 10  −2.34? 0−22 J × ( 25 − 1) 
(100 K) = exp  −23 −1  = 0.086
n1 2  1.381× 10 J K × 100 K 
n5 10  −2.34? 0−22 J × ( 25 − 1) 
(650 K) = exp  −23 −1  = 2.67
n1 2  1.381×10 J K × 650 K 
n10 20  −2.34 ×10−22 J × (100 − 1)  −7
(100 K ) = exp  −23 −1  = 5.2 ×10
n1 2  1.381×10 J K × 100 K 
n10 20  −2.34 ×10−22 J × (100 − 1) 
(650 K) = exp  −23 −1  = 0.757
n1 2 1.381×10 J K × 650 K 

P13.2) Consider a two-level system with ε1 = 3.10 × 10−21J and ε 2 = 6.10 × 10−21J. If
g2 = g1, what value of T is required to obtain n2 / n1 = 0.150? What value of T is required
to obtain n2 / n1 = 0.999?

13-3
Chapter 13/The Schrödinger Equation

n2 g 2  − ( ε 5 − ε1 ) 
= exp  
n1 g1  kT 
n   g  (ε − ε )
ln  2  = ln  2  − 5 1
 n1   g1  kT
1 k   g2   n2  
= ln   − ln   
T ( ε 5 − ε1 )   g1   n1  

T=
( ε 5 − ε1 )
 g   n 
k ln  2  − ln  2  
  g1   n1  
3.00? 0−21J
for n2 n1 = 0.150 T = = 115 K
1.381×10−23J K −1 × ln (1) − ln ( 0.150 ) 
3.00 × 10−21J
for n2 n1 = 0.999 T = = 2.17 × 105 K
1.381 × 10−23J K −1 ×  ln (1) –ln ( 0.999) 

P13.3) To plot Ψ( x , t ) = A sin( kx − ωt ) as a function of one of the variables x and t, the

Ψ( x0 ,0)
other variable needs to be set at a fixed value, x0 or t0. If = –0.280, what is the
Ψmax
Ψ(0, t0 )
constant value of x0 in the upper panel of Figure 13.3? If = –0.309, what is the
Ψmax
constant value of t0 in the lower panel of Figure 13.3? (Hint: The inverse sine function
has two solutions within an interval of 2π. Make sure that you choose the correct one.)
x t  x t 
For the traveling wave Ψ ( x, t ) = A sin 2π  −  = A sin 2π  − −3 
λ T   1.46 1.00 x 10 
Ψ ( x0 , 0)  x0   x0 
= sin 2π   = −0.284; 2π  
Ψ max  1.46 m   1.46 m 
= −0.28 radians or π − ( −0.28 ) = 3.43 radians
x = −6.4 ×10−2 m or 0.79 m

Ψ (0, t0 )  −t0   −t0 

= A sin 2π  −3 
= − 0.309; 2π  −3 
Ψ max  1.00 x 10 s   1.00 x 10 s 
= −0.31 radians or π − ( −0.31) = 3.45 radians
t0 = 5.0 ×10−5s or − 5.5 ×10−4s
To decide which of the two values best fits the data in Figure 13.2, it is necessary to plot
the data.

13-4
 Chapter 13/The Schrödinger Equation

It is seen that the data are fit by x0 = 0.79 m and t0= –5.5 × 10–4 s. Adding any positive or
negative integral multiple of λ to x0 or T to t0 will give equally good agreement.

P13.4) A wave traveling in the z direction is described by the wave function

Ψ ( z, t ) = A1 x sin( kz − ωt + φ1 ) + A2 y sin( kz − ωt + φ2 ) where
x and y are vectors of unit length along the x and y axes, respectively. Because the
amplitude is perpendicular to the propagation direction, Ψ( z , t ) represents a transverse
wave.
a) What requirements must A1 and A2 satisfy for a plane polarized wave in the x-z plane?
b) What requirements must A1 and A2 satisfy for a plane polarized wave in the y-z plane?
c) What requirements must A1 and A2 and φ 1 and φ 2 satisfy for a plane polarized wave in a
plane oriented at 45º to the x-z plane?
d) What requirements must A1 and A2 and φ 1 and φ 2 satisfy for a circularly polarized wave?

a) The amplitude along the x axis must oscillate, and the amplitude along the y axis must
vanish. Therefore A1 ≠ 0 and A2 = 0.

b) The amplitude along the y axis must oscillate, and the amplitude along the x axis must
vanish. Therefore A1 = 0 and A2 ≠ 0.

c) The amplitude along both the x and y axes must oscillate. Therefore A1 ≠ 0 and A2 ≠ 0 .
Because they must oscillate in phase, φ1 = φ2 .

13-5
Chapter 13/The Schrödinger Equation

d) The amplitude along both the x and y axes must oscillate with the same amplitude.
Therefore A1 = A2 ≠ 0 . For circularly a polarized wave, the x and y components must be
π
out of phase by π/2. Therefore φ1 =φ2 ± . This can be seen by comparing the x and y
2
amplitudes for the positive sign.
π
Ψ ( z , t ) = A1 x sin(kz − ωt + φ1 ) + A1 y sin(kz − ωt + φ1 + )
2
let kz + φ = kz ′
π
Ψ ( z , t ) = A1 x sin(kz ′ − ωt ) + A1 y sin(kz ′ − ωt + )
2
 π π
= A1 x sin(kz ′ − ωt ) + A1 y sin(kz ′ − ωt ) cos + cos(kz ′ − ωt )sin 
 2 2
= A1 x sin(kz ′ − ωt ) + A1 y cos(kz ′ − ωt )
The x and y amplitudes are π/2 out of phase and the sum of the squares of their
amplitudes is a constant as required for a circle.

P13.5) Show that

b
a + ib ac + bd + i bc − ad
=
g
c + id c2 + d 2

a + ib  a + ib   c − id  ac + bd + ibc − iad ac + bd + i ( bc − ad )
=  = =
c + id  c + id   c − id  c2 + d 2 c2 + d 2

P13.6) Does the superposition ψ ( x , t ) = A sin( kx − ω t ) + 2 A sin( kx + ω t ) generate a

standing wave? Answer this question by using trigonometric identities to combine the
two terms.

ψ ( x, t ) = A sin( kx − ω t ) + 2 A sin( kx + ω t )
Using the identities
sin (α ± β ) = sin α cos β ± cos α sin β
cos (α ± β ) = cos α cos β ∓ sin α sin β

the previous equation can be simplified to

ψ ( x, t ) = A sin kx cos ω t − A cos kx sin ω t + 2 A sin kx cos ω t + 2 A cos kx sin ω t
= 3A sin kx cos ω t + A cos kx sin ω t

Because the wave function cannot be written as a single product of a function that is
periodic in length with one that is periodic in time, the nodes will not be stationary.
Therefore it is not a standing wave.

P13.7) Express the following complex numbers in the form reiθ .

13-6
 Chapter 13/The Schrödinger Equation

3+i 8+i
a) 2 − 4i b) 6 c) d)
4i 2 − 4i

 Re z 
In the notation reiθ , r = z = a 2 + b 2 and θ = cos −1 
 z 
.
 
 1 
a) 2 − 4i = 2 5 exp  i cos −1  = 2 5 exp ( 0.352iπ )
 5
b) 6 = 6 exp ( i cos −1 1) = 6 exp ( 0 )
3 + i 1 3i 10  1  10
c) = − = exp  i cos −1  = exp ( 0.398iπ )
4i 4 4 4  10  4
8+i 3 17i 13  6  13
d) = + = exp  i cos −1  = exp ( 0.392iπ )
2 − 4i 5 10 2  5 13  2

P13.8) Express the following complex numbers in the form a + ib.

iπ − iπ 3 2 iπ 4
a) 2e 2
b) 2 5 e 2 c) eiπ d) e
5+ 3

To convert to the form a + ib, we use the equations Re z = z cos θ and Im z = z sin θ
iπ  π
π
a) 2e 2
= 2 cos
+  2 sin  i = 2i
2  2
− iπ −π  −π 
b) 2 5 e 2 = 2 5 cos +  2 5 sin  i = −2 5i
2  2 
c) e = cos π + ( sin π ) i = −1
iπ

3 2 iπ 4 3 2 π  3 2 π 3 2 2 π  3 2 2
e = cos +  sin  i = cos +  i
d) 5 + 3 5+ 3 4  5+ 3 4  5+ 3 2 4  5 + 3 2 

3
= (1 + i)
5+ 3

P13.9) Using the exponential representation of the sine and cosine functions
cos θ =
2
(
1 iθ
e + e − iθ ) and sin θ = ( eiθ − e − iθ ) , show that
1
2i
a) cos 2 θ + sin 2 θ = 1

b)
b
d cos θ g = − sin θ
dθ

c) sin θ +
FG πIJ = cos θ
H 2K

13-7
Chapter 13/The Schrödinger Equation

a)
2 2
1  1 
cos2 θ + sin 2 θ =  ( eiθ + e − iθ )  +  ( eiθ − e − iθ )
 2   2 i 
= ( 2 + e2iθ + e −2iθ ) − ( −2 + e2iθ + e −2 iθ ) = 1
1 1
4 4
b)
1 
d  ( eiθ + e − iθ ) 
d ( cos θ )
=   = 1 ieiθ − ie − iθ = − 1 eiθ − e − iθ = − sin θ
( ) 2−( )
2
dθ dθ 2
c)
 π  π
 π  1  i θ +  − i θ +   1  i π π
 i
sin  θ +  =  e  2  − e  2   =  e 2 eiθ − e 2 e − iθ  = ( eiθ + e − iθ ) = cos θ
−i

 2  2i   2i 
  2i

P13.10) Determine in each of the following cases if the function in the first column is an
eigenfunction of the operator in the second column. If so, what is the eigenvalue?
∂
a) sin θ cos φ
∂φ
−x
2
1 d
b) e 2
x dx
sin θ d
c) sin θ
cosθ dθ

∂
a) sin θ cos φ
∂φ
∂
sin θ cos φ = − sin θ sin φ . Not an eigenfunction
∂φ
− 1 x2 1 d
b) e 2
x dx
1 d − 1 2 x2 − 1 x2
e = −e 2 Eigenfunction with eigenvalue –1
x dx
sin θ d
c) sin θ
cos θ dθ
sin θ d
sin θ = sin θ Eigenfunction with eigenvalue +1
cos θ dθ

P13.11) Determine in each of the following cases if the function in the first column is an
eigenfunction of the operator in the second column. If so, what is the eigenvalue?

13-8
 Chapter 13/The Schrödinger Equation

d3
a) x 3
d x3
∂ ∂
b) x y x +y
∂x ∂y
∂ 2
c) sin θ cos φ
∂θ 2

d
a) x 3
d x3
d x3
=6 Not an eigenfunction
d x3
∂ ∂
b) x y x +y
∂x ∂y
∂ xy ∂ xy
x +y = 2 xy Eigenfunction with eigenvalue +2
∂x ∂y
∂2
c) sin θ cos φ
∂θ 2
∂2
( sin θ cos φ ) = − sin θ cos φ Eigenfunction with eigenvalue –1
∂θ 2

P13.12) Determine in each of the following cases if the function in the first column is an
eigenfunction of the operator in the second column. If so, what is the eigenvalue?
1 d  d 
a) 3cos 2 θ − 1  sin θ 
sin θ d θ  dθ 
−x
2
d2
b) e 2
− x2
dx 2
d2
c) e −4iφ
dφ 2

1 d  d 
a) 3cos2 θ − 1  sin θ 
sin θ d θ  dθ 
1 d  d ( 3cos2 θ − 1) 
sin θ d θ 
 sin θ
dθ
=
1 d
 sin θ d θ
( −6 cos θ sin 2 θ )
 
=
1
sin θ
( 6 sin3 θ − 12 cos2 θ sin θ ) = 6 sin 2 θ − 12 cos2 θ
= 6 − 18 cos 2 θ = −6 ( 3cos2 θ − 1)
Eigenfunction with eigenvalue –6.

13-9
Chapter 13/The Schrödinger Equation

− 12 x2 d2
b) e − x2
d x2
− 1 x2
d 2e 2 1 2
2 − 2x − 1 x2
− x e = − e 2
d x2
Eigenfunction with eigenvalue –1.

d2
c) e −4iφ
dφ 2
d 2 e −4iφ
= −16e −4iφ
dφ 2

Eigenfunction with eigenvalue –16.

P13.13) Determine in each of the following cases if the function in the first column is an
eigenfunction of the operator in the second column. If so, what is the eigenvalue?
∂2
a) e − i b 3 x + 2 y g
∂ x2
∂
b) x 2 + y 2
x
(
1 2
x + y2 )
∂x
d  d 
c) sin θ cos θ sin θ  sin θ  + 6sin θ
2

dθ  dθ 

−i(3x +2 y ) ∂2
a) e
∂ x2
∂2e (
−i 3 x +2 y )
− i (3 x + 2 y )
= −9e Eigenfunction with eigenvalue –9.
∂ x2
∂
b) x2 + y 2
x
(
1 2
x + y2 )
∂x
∂ x2 + y2
x
(
1 2
x + y2 )
∂x
= x2 + y2 Eigenfunction with eigenvalue +1.

d  d 
c) sin θ cos θ sin θ  sin θ  + 6 sin θ
2

dθ  d θ 

d  d sin θ cos θ 
sin θ  sin θ
dθ  dθ
 + 6 sin θ cos θ = sin θ

3 d
dθ
( )
sin θ 1 − 2 sin 2 θ  + 6 sin 3 θ cos θ

= sin θ ( cos θ − 6 sin 2 θ cos θ ) + 6 sin 3 θ cos θ = sin θ cos θ

Eigenfunction with eigenvalue +1.

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 Chapter 13/The Schrödinger Equation

P13.14) Which of the following wave functions are eigenfunctions of the operator d/dx?
If they are eigenfunctions, what is the eigenvalue?
2
a) a e −3 x + b e −3i x b) sin 2 x c) e −i x d) cosa x e) e − i x

d ( a e −3 x + b e −3i x )
a) = −3 a e −3 x − 3 i b e −3ix Not an eigenfunction
dx
d sin 2 x
b) = 2 sin x cos x Not an eigenfunction
dx
d e−i x
c) = −i e − i x Eigenfunction with eigenvalue –i
dx
d cos a x
d) = −a sin a x Not an eigenfunction
dx
2
d e −i x 2
e) = −2i x e − i x Not an eigenfunction
dx

P13.15) Which of the following wave functions are eigenfunctions of the operator
d 2 dx 2 ? If they are eigenfunctions, what is the eigenvalue?

2
a) a e−3 x + b e−3i x b) sin 2 x c) e − i x d) cosa x e) e −i x

d 2 ( a e −3 x + b e −3i x )
a) = 9 a e −3 x − 9 b e −3i x Not an eigenfunction
d x2

d 2 sin 2 x
b) = −2 sin 2 x + 2 cos2 x Not an eigenfunction
d x2

d 2 e −i x
c) 2
= −e −i x Eigenfunction with eigenvalue –1
dx
d 2 cos a x
d) = −a 2 cos a x Eigenfunction with eigenvalue –a2
d x2
2
d 2 e −i x 2 2
e) 2
= −2i e −i x − 4 x 2 e −i x Not an eigenfunction
dx

  f x , it is important
P13.16) If two operators act on a wave function as indicated by AB bg
to carry out the operations in succession with the first operation being that nearest to the
function. Mathematically, AB   f b x g = A d B f b x gi and A f b x g = A d A f b x gi . Evaluate the
2

13-11
Chapter 13/The Schrödinger Equation

bg
  f x . The operators A and B are listed in the first
following successive operations AB
bg
and second columns and f x is listed in the third column.
d d 2
a) x 2 + ea x
dx dx
∂ 2
∂
b) (cos 3 y ) sin 2
∂y 2
∂x
∂ ∂2 cos φ
c)
∂θ ∂φ 2
sin θ

a)
 (
d d x + e
2 a x2 
)
 = d  2 x + 2a x e a x 2  = 2 + 4a 2 x 2 e a x 2 + 2a e a x 2
dx dx  dx 
 
∂ 2  ∂ ( cos 3 y sin x ) 
2
∂2
b)   = [2 cos 3 y sin x cos x ] = −18 cos 3 y sin x cos x
∂ y2  ∂x  ∂ y2
 
 2  cos φ  
∂
∂   sin θ   ∂  cos φ  cos φ cos θ
c)  = −  = sin 2 θ
∂θ  ∂ φ 2  ∂θ  sin θ 
 

  f x , it is important
P13.17) If two operators act on a wave function as indicated by AB bg
to carry out the operations in succession with the first operation being that nearest to the
function. Mathematically, AB   f b x g = A d B f b x gi and A f b x g = A d A f b x gi . Evaluate the
2

following successive operations AB   f b x g . The operators A and B are listed in the first
two columns and f b x g is listed in the third column.
d 2
a) x x e−a x
dx
d 2
b) x x e−a x
dx
∂ ∂ e
−a x2 + y2 j
c) y x e
∂x ∂y

Note that your answers to parts (a) and (b) are not identical. As we will learn in Chapter
18, the fact that switching the order of the operators x and d dx changes the outcome of
the operation AB bg
  f x is the basis for the Heisenberg uncertainty principle.

a)
d 
dx
(  )
x x e−a x  = 2 x e− a x − 2 a x3 e− a x
2 2 2

13-12
 Chapter 13/The Schrödinger Equation

 d 2 
b) x 
d x
( ) 2
x e− a x  = x e−a x − 2 a x3 e−a x

2

y
∂ 
 x
(
 ∂ e− a ( x2 + y2 ) 


)
=y
∂ 
−2 a x y e
− a ( x2 + y2 ) 
=
c) ∂ x  ∂y  ∂ x  
 
−a (x + y )
2 2
− a ( x2 + y 2 )
= −2 a y 2 e + 4 a2 x2 y2e

d2 2
P13.18) Find the result of operating with 2 − 4 x 2 on the function e − ax . What must
dx
the value of a be to make this function an eigenfunction of the operator?
2
d 2 e − ax
− 4 x 2 e − ax = −2ae − ax − 4 x 2 e − ax + 4a 2 x 2 e − ax = −2ae − ax + 4 ( a 2 − 1) x 2 e − ax
2 2 2 2 2 2

2
dx
2
For the function to be an eigenfunction of the operator, the terms containing x 2 e − ax must
vanish. This is the case if a = ±1 .

1 d 2 d 2
P13.19) Find the result of operating with 2
r + on the function Ae − br . What
r dr dr r
must the values of A and b be to make this function an eigenfunction of the operator?
1 d 2 dAe − br 2 Ae − br 2 Ae − br
r 2 dr
r
dr
+
r
= 2
1 d
r dr
( −bAr e ) + r
2 − br

2 Ae − br
= 2 ( −2brAe − br + b2 r 2 Ae − br ) +
1
r r
− br
2 Ae
= ( 2 − 2b ) + b2 Ae − br
r
Ae − br
To be an eigenfunction of the operator, the terms in must vanish. This requires
r
that b = 1. There are no restrictions on the value of A.

d2 d2 d2
P13.20) Find the result of operating with 2 + 2 + 2 on the function x 2 + y 2 + z 2 .
dx dy dz
Is this function an eigenfunction of the operator?
 d2 d2 d2  2
 2 + 2 + 2  ( x + y + z ) = 6 . Therefore, the function is not an eigenfunction of
2 2

 dx dy dz 
the operator.

13-13
Chapter 13/The Schrödinger Equation

P13.21) Show that the set of functions φn (θ ) = ei nθ , 0 ≤ θ ≤ 2π , are orthogonal if n and

m are integers. To do so, you need to show that the integral
2π

∫ φ (θ ) φ (θ ) dθ = 0 for m ≠ n if n and m are integers.

*
m n
0
2π
2π 2π 2π
 1 i ( n − m )θ 
i ( n − m )θ
∫0 φ (θ ) φn (θ ) dθ = ∫0 e e dθ = ∫0 e dθ =  i ( n − m ) e 
* − imθ inθ
m
 0
1 1
 ei ( n −m )2π − e0  =
=
i (n − m)   i ( n − m ) cos ( n − m ) 2π + sin ( n − m ) 2π − 1
Because n and m are integers, ( n − m ) is an integer and the arguments of the
sine and cosine functions are integral multiples of 2π .
2π
1
∫ φ (θ ) φ (θ ) dθ = i ( n − m ) [1 + 0 − 1] = 0
*
m n
0

P13.22) Show by carrying out the integration that sin ( mπ x/a ) and cos ( mπ x/a ) , where
m is an integer, are orthogonal over the interval 0 ≤ x ≤ a . Would you get the same result
if you used the interval 0 ≤ x ≤ 3a / 4? Explain your result.
a
 mπ x   mπ x  2  mπ x  
a
 a a
∫0 cos  a  sin  a  d x =  2mπ sin  a  0 = 2mπ sin ( mπ ) − 0 = 0
2

3a 3a

 mπ x   mπ x   mπ x   mπ x 
4 4

∫ cos 
0
a 
 sin 
 a 
d x = ∫ cos 
0
a 
 sin 
 a 
d x
3a
 a  mπ x   a  2  3mπ  
4
= sin 2   = sin   − 0 ≠ 0
 2mπ  a 0 2mπ   4  
3m
except for the special case = n where n is an integer. The length of the integration
4
interval must be n periods (for n an integer) to make the integral zero.

P13.23) Normalize the set of functions φn (θ ) = ei nθ , 0 ≤ θ ≤ 2π . To do so, you need to

multiply the functions by a so-called normalization constant N so that the integral

z
2π

NN *
bg bg
φ *m θ φ n θ dθ = 1 for m = n
0
2π 2π
1
∫e ∫ dθ = 2π N N
− i nθ i nθ
NN *
e dθ = N N * *
= 1 This is satisfied for N = and the
0 0 2π
1 i nθ
normalized functions are φn (θ ) = e , 0 ≤ θ ≤ 2π .
2π

13-14
 Chapter 13/The Schrödinger Equation

P13.24) In normalizing wave functions, the integration is over all space in which the
wave function is defined. The following examples allow you to practice your skills in
two- and three-dimensional integration.
 nπ x   mπ y 
a) Normalize the wave function sin   sin   over the range
 a   b 
0 ≤ x ≤ a, 0 ≤ y ≤ b . The element of area in two-dimensional Cartesian coordinates is
dx dy ; n and m are integers and a and b are constants.
−r
b) Normalize the wave function e a cosθ sin φ over the interval
0 ≤ r < ∞, 0 ≤ θ ≤ π , 0 ≤ φ ≤ 2π . The volume element in three-dimensional spherical
coordinates is r 2 sin θ dr dθ dφ .

a)
 nπ x  2  mπ y 
a b
1 = N 2 ∫ ∫ sin 2   sin  d xd y
0 0  a   b 
nπ x mπ y adu bdw
Let u = ,w = ; then dx = and dy =
a b nπ mπ
nπ mπ
a b
nπ mπ ∫0 ∫0
1 = N2 sin 2 u sin 2 w d u d w

mπ
a b    nπ 2 
=N  ∫ sin u d u  x  ∫ sin w d w 
2 2

nπ mπ  0  0 
Using the standard integral ∫ ( sin 2 ax ) dx = x −
1 1
sin 2ax
2 4a
a b  mπ 1 1    nπ 1 1 
1 = N2   − sin 2mπ − 0 − sin 0   ×  − sin 2nπ − 0 − sin 0  
nπ mπ  2 4 4    2 4 4 
a b nπ mπ ab
= N2 = N2
nπ mπ 2 2 4
2
N=
ab

13-15
Chapter 13/The Schrödinger Equation

b)
2π π ∞ 2π π ∞
−2 r −2 r
1= N ∫ d φ ∫ dθ ∫ e cos θ sin φ r sin θ d r = N ∫ sin φ dφ ∫ cos θ sin θ dθ ∫ r e
2 a 2 2 2 2 2 2
2 a
dr
0 0 0 0 0 0
∞
n!
Using the standard integral ∫ x n e − ax dx = ( a > 0, n positive integer)
0
a n +1
 2π 1  1  2! a 3  π
− sin 2π − 0 − sin 0  × ( cos3 0 − cos π ) ×  3  = N 2 a 3
1
1 = N2 
 2 4 4  3  2  6
6
N=
π a3

P13.25) Show that the following pairs of wave functions are orthogonal over the
indicated range.
1 1
and ( 2α x 2 − 1) e
− α x2 − α x2
a) e 2 2
, −∞ ≤ x < ∞ where α is a constant that is greater than
zero.

 r  r − r / 2 a0
b)  2 −  e − r / 2 a0 and e cosθ over the interval 0 ≤ r < ∞, 0 ≤ θ ≤ π , 0 ≤ φ ≤ 2π
 a0  a0

a)

∞ 1 1 ∞ ∞ ∞
− α x2 − α x2
∫ ( 2α x − 1) e ∫ ( 2α x − 1) e d x = 2α ∫ x e ∫
−α x 2 −α x 2
e −α x d x
2
2 2
e 2
dx= 2 2
d x−
−∞ −∞ −∞ −∞
∞ ∞
= 4α ∫ x 2 e −α x d x − 2 ∫ e −α x d x because the integrand is an even function of x.
2 2

0 0
∞
1 ⋅ 3 ⋅ 5 ⋅ ⋅ ⋅ ( 2n − 1) π
Using the standard integrals ∫ x 2 n e − ax dx =
2
(a > 0, n positive integer)
0
2n +1 a n a
∞ 1
π  2

∫
2
and e − ax dx =  
0  4a 
∞ 1
− α x2
1
− α x2 π π
∫ ( 2α x − 1) e
1
2 2
e 2
d x = 4α − =0
−∞
2α α
2
α

13-16
 Chapter 13/The Schrödinger Equation

b)
2π π ∞
 r  r − r / 2 a0 2
∫
0
dφ ∫ cos θ sin θ dθ ∫  2 −  e − r / 2 a0
0 0
a0  a0
e r dr

π ∞ r  r − r / 2 a0 2 
= 2π  ∫ cos θ sin θ dθ   ∫  2 −  e − r / 2 a0 e r d r
0  0  a0  a0 
∞ r  r − r / 2 a0 2   1 1 
= 2π  ∫  2 −  e − r / 2 a0 e r d r   cos2 0 − cos2 π  = 0
0 a0  a0  2 2 

d nπ x   mπ x 
P13.26) Because 0∫cos 
 d 
 cos 
 d 
d x = 0, m ≠ n , the functions
cos ( nπ x/d ) for n = 1, 2, 3, ... form an orthogonal set. What constant must these functions
be multiplied by to form an orthonormal set?
d
d  mπ x   mπ x  2 x d  2mπ x  
1 = N 2 ∫ cos   cos  d x = N  + sin  
0
 d   d   2 4mπ  d  0

where we have used the standard integral ∫ ( cos2 ax ) dx = x +

1 1
sin 2ax
2 4a
d d 0 d  d
1 = N2  + sin ( 2mπ ) − − sin ( 0 )  = N 2 = 1
 2 4mπ 2 4mπ  2
2
N=
d

P13.27) Use a Fourier series expansion to express the function f ( x) = x, − b ≤ x ≤ b in

m
 nπ x   nπ x 
the form f ( x ) = d 0 + ∑ cn sin   + d n cos   . Obtain d0 and the first five
n =1  b   b 
coefficients cn and dn.

13-17
Chapter 13/The Schrödinger Equation

b b
1 1
d0 = ∫
2 b −b
f ( x ) dx =
2 b −∫b
x dx = 0

 nπ x   nπ x 
b b
1 1
dn = ∫
b −b
f ( x ) cos 
 b 
 dx = ∫ x cos 
b −b  b 
 dx

cos ax x sin ax
Using the standard integral ∫ x cos ax = +
a2 a
1  b   nπ ( −b )   b   nπ ( −b )  
2 2
 nπ b   b   nπ b   b 
dn =   cos  +  b sin  −  cos  −  ( −b ) sin   = 0
b  nπ   b   nπ   b   nπ   b   nπ   b  
All the d n = 0 because f ( x ) is an odd function of x.
 nπ x   nπ x 
b b
1 1
b −∫b
cn = f ( x ) sin   dx = ∫ x sin   dx
 b  b −b  b 
x cos ax sin ax
Using the standard integral ∫ x sin ax = − +
a a2
b
1  b   nπ x  
2
 nπ x   b 
cn =    sin  −  x cos  
b   nπ   b   nπ   b   − b

1  b   nπ ( −b )   b   nπ ( −b )  
2 2
 nπ b   b   nπ b   b 
cn =   sin  −  b cos  −  sin  +  ( −b ) cos  
b   nπ   b   nπ   b   nπ   b   nπ   b  
2  b  
2
b2
cn =   sin ( nπ ) − cos ( nπ ) 
b   nπ  nπ 
 2b  2b n +1
cn =   cos nπ = ( −1)
 nπ  nπ
2b b 2b b 2b
Therefore, d 0 = 0 and d1 − d 5 = 0. c1 = , c2 = − , c3 = , c4 = − , and c5 =
π π 3π 2π 5π

P13.28) Carry out the following coordinate transformations.

a) Express the point x = 3, y = 2, and z = 1 in spherical coordinates.
π 3π
b) Express the point r = 5, θ = , and φ = in Cartesian coordinates.
4 4
a) r = x 2 + y 2 + z 2 = 32 + 22 + 1 = 14
z 1
θ = cos−1 = cos −1 = 1.30 radians
x +y +z
2 2 2
14
y 2
φ = tan −1 = tan −1 = 0.588 radians
x 3
π 3π
b) x = r sin θ cos φ = 5sin cos = −2.5
4 4
π 3π
y = r sin θ sin φ = 5sin sin = 2.5
4 4
π 5
z = r cos θ = 5cos =
4 2

13-18
 Chapter 13/The Schrödinger Equation

P13.29) Operators can also be expressed as matrices and wave functions as column
α β  a
vectors. The operator matrix   acts on the wave function   according to the
δ ε  b
 α β  a   α a + β b 
rule    =   . In words, the 2 × 2 matrix operator acting on the two-
 δ ε  b   δ a + ε b 
element column wave function generates another two-element column wave function. If
the wave function generated by the operation is the original wave function multiplied by
a constant, the wave function is an eigenfunction of the operator. What is the effect of the
0 1  1   0   1  −1 
operator   on the column vectors   ,   ,   and   ? Are these wave
1 0  0   1   1 1
functions eigenfunctions of the operator? See the Math Supplement for a discussion of
matrices.

0 1 1 0 0 1  0 1

1 0  0 = 1 1 0 1 = 0
         

 0 1   1  1  0 1   −1   1   −1 
 1 0   1 =  1  1 0   1  =  −1 = ( −1)  1 
           

 1  −1
Only   and   are eigenfunctions with the eigenvalues 1 and –1, respectively.
 1 1

FG 1IJ and FG 0IJ represent the unit vectors along the x and y directions,
P13.30) Let
H 0K H 1K
 cos θ − sin θ 
respectively. The operator   effects a rotation in the x-y plane. Show that
 sin θ cos θ 
a 1 0
the length of an arbitrary vector   = a   + b   , which is defined as a 2 + b 2 , is
b 0 1
unchanged by this rotation. See the Math Supplement for a discussion of matrices.

 cos θ − sin θ   a   a cos θ − b sin θ 

 sin θ cos θ   b  =  a sin θ + b cos θ 
    
The length of the vector is given by

( a cos θ − b sin θ ) + ( a sin θ + b cos θ ) = ( a 2 cos2 θ + b2 sin 2 θ − 2ab sin θ cos θ

2 2

+ a 2 sin 2 θ + b2 cos2 θ + 2ab sin θ cos θ )1 2

= a 2 ( cos2 θ + sin 2 θ ) + b2 ( cos2 θ + sin 2 θ ) = a 2 + b2
This result shows that the length of the vector is not changed.

13-19