Physical Chemistry II

1-1
Chapter 1: From Classical to Quantum Mechanics

Problem numbers in italics indicate that the solution is included in the
Students Solutions Manual.
Questions on Concepts

Q1.1) How did Planck conclude that the discrepancy between experiments and classical
theory for blackbody radiation was at high and not low frequencies?

The experimental results and the classical theory agree in the limit of low
frequencies and diverge at high frequencies.

Q1.2) The inability of classical theory to explain the spectral density distribution of a
blackbody was called the ultraviolet catastrophe. Why is this name appropriate?

The divergence between the classical theory and the experimental results is very
pronounced in the UV region. In particular, because the classical theory predicts
that the spectral density increases as
2
, the total energy radiated by a blackbody
is predicted to be infinite. This prediction was clearly wrong, and the lack of
agreement with the experimental results was viewed by scientists of the time as a
catastrophe.

Q1.3) Why does the analysis of the photoelectric effect based on classical physics
predict that the kinetic energy of electrons will increase with increasing light intensity?

In the classical theory, more light intensity leads to more energy absorption by the
solid and the electrons. At equilibrium, as much energy must leave the surface as
is absorbed. Therefore, the electrons will have a greater energy. Classical
physicists thought that the greater energy would manifest as a higher speed. In
fact, it appears as a larger number of electrons leaving the surface with a
frequency determined by the photon energy and the work function of the surface.

Q1.4) What did Einstein postulate to explain that the kinetic energy of the emitted
electrons in the photoelectric effect depends on the frequency? How does this postulate
differ from the predictions of classical physics?

Einstein postulated that the energy of light depends on the frequency, whereas in
classical theory, the energy depends only on the intensity and is independent of
the frequency. He further postulated that the energy of light could only be an
integral multiple of . hv

Q1.5) Which of the experimental results for the photoelectric effect suggests that light
can display particle-like behavior?

Chapter 1/From Classical to Quantum Mechanics

1-2
The fact that at very low intensity the incident light is still able to eject electrons,
if its frequency is above the threshold frequency, suggests that the energy of the
light can be concentrated in a region of atomic dimensions at the surface of the
solid. This suggests particle-like behavior.

Q1.6) In the diffraction of electrons by crystals, the volume sampled by the diffracting
electrons is on the order of 3 to 10 atomic layers. If He atoms are incident on the surface,
only the topmost atomic layer is sampled. Can you explain this difference?

Whereas electrons can penetrate through the topmost layer into the solid, He
atoms are too large to allow penetration at thermal energies. Therefore electrons
sample a number of atomic layers below the surface, and He atoms are only
sensitive to the outermost layer.

Q1.7) In the double-slit experiment, researchers found that an equal amount of energy
passes through each slit. Does this result allow you to distinguish between purely
particle-like or purely wave-like behavior?

No. This result would be expected for both waves and particles. In the case of
particles, the same number would pass through each slit for a large number of
incident particles. For a wave, the fraction of the intensity of the wave that passes
through each slit would be the same.

Q1.8) Is the intensity observed from the diffraction experiment depicted in Figure 1.6
the same for the angles shown in parts (b) and (c)?

Yes. For all minima in a graph of intensity versus frequency, the intensity is zero
as seen in Figure 1.5.

Q1.9) What feature of the distribution depicted as Case 1 in Figure 1.7 tells you that the
broad distribution arises from diffraction?

The intensity goes through a minimum and increases again on both sides of the
maximum. This can only occur through wave interference.

Q1.10) Why were investigations at the atomic and subatomic levels required to detect
the wave nature of particles?

The wavelength of particles with greater mass is so short that particle diffraction
could not be observed experimentally. Therefore, the wave-particle duality
present even in heavier particles was not observed.


1-3
Problems

P1.1) The distribution in wavelengths of the light emitted from a radiating blackbody is
a sensitive function of the temperature. This dependence is used to measure the
temperature of hot objects, without making physical contact with those objects, in a
technique called optical pyrometry. In the limit ( ) 1, hc k T >> the maximum in a plot of
( ) , versus T is given by
max
/ 5 . hc kT = At what wavelength does the maximum in
( ) ,T occur for T = 450, 1500, and 4500 K?

According to Example Problem 3.1,
max
5
h c
k T
= .
34 8 1
6
max 23 1
6.626 10 J s 2.998 10 m s
6.40 10 m
5 1.381 10 J K 450 K

= =

at 450 K.
max
for 1500 K and
4500 K is 1.9210
6
m and 6.3910
7
m, respectively.

P1.2) For a monatomic gas, one measure of the average speed of the atoms is the root
mean square speed,
1
2 2
3
v v ,
rms
kT
m
= = in which m is the molecular mass and k is the
Boltzmann constant. Using this formula, calculate the de Broglie wavelength for He and
Ar atoms at 100 and at 500 K.

34
23 1 27 1
rms
10
6.626 10 J s
v
3
3 1.381 10 J K 100 4.003amu 1.661 10 kgamu
1.26 10 m
h h
m
k T m
K
= = =

=

for He at 100 K. =5.6510
11
m for He at 500 K. For Ar, = 4.00 10
11
m and
1.7910
11
m at 100 K and 500 K, respectively.

P1.3) Using the root mean square speed,
1
2 2
3
v v ,
rms
kT
m
= = calculate the gas
temperatures of He and Ar for which = 0.20 nm, a typical value needed to resolve
diffraction from the surface of a metal crystal. On the basis of your result, explain why Ar
atomic beams are not suitable for atomic diffraction experiments.

For He,
( )
( )
2
2
2
34
2
23 1 27 1 9
3
6.626 10 J s
40 K
3 1.381 10 J K 4.003amu 1.661 10 kgamu 0.20 10 m
h
T
k m
= =

For Ar, T = 4.0 K.

1-4
The argon temperature is well below its liquifaction temperature at 4 K. It will not be
possible to make an atomic beam of Ar atoms with this wavelength with conventional
means.

P1.4) Electrons have been used to determine molecular structure by diffraction.
Calculate the speed of an electron for which the wavelength is equal to a typical bond
length, namely, 0.150 nm.
34
6 1
31 9
6.626 10 J s
v 4.85 10 m s
9.109 10 kg 0.150 10 m
p h
m m
= = = =

P1.5) Calculate the speed that a gas-phase oxygen molecule would have if it had the
same energy as an infrared photon ( = 10
4
nm), a visible photon ( = 500 nm), an
ultraviolet photon ( = 100 nm), and an X-ray photon ( = 0.1 nm). What temperature
would the gas have if it had the same energy as each of these photons? Use the root mean
square speed,
1
2 2
3
v v ,
rms
kT
m
= = for this calculation.
( )
34 8 1
1
1
27 9
2 2 2 6.626 10 Js 2.998 10 m s
v 864 ms
32.0amu 1.661 10 kg amu 10000 10 m
E h c
m m

= = = =

for
= 10
4
nm.The results for 500 nm, 100 nm and 0.1 nm are 3.8710
3
m s
1
, 8.6510
3
m
s
1
, and 2.7310
5
m s
1
.

We calculate the temperature using the formula
( )
2
1 1
2
1 1
32.0kg mol 864m s
v
958K
3 3 8.314 J mol K
rms
M
T
R

= = =

= 10
4
nm. The results for 500 nm, 100 nm and 0.1 nm are 1.9210
4
K, 9.6010
4
K,
and 9.5610
7
K.

P1.6) Pulsed lasers are powerful sources of nearly monochromatic radiation. Lasers that
emit photons in a pulse of 10-ns duration with a total energy in the pulse of 0.10 J at 1000
nm are commercially available.
a) What is the average power (energy per unit time) in units of watts (1 W = 1 J/s)
associated with such a pulse?
b) How many 1000-nm photons are emitted in such a pulse?

a)
7 1
8
0.10 J
1.0 10 J s
1.0 10 s
E
P
t

= = =

b)
17
8 1
34 1
6
0.10 J
5.0 10
2.998 10 m s
6.626 10 J s
1.000 10 m
pulse pulse
photon
E E
N
c
E
h

= = = =


1-5
P1.7) Assume that water absorbs light of wavelength 3.00 10
6
m with 100%
efficiency. How many photons are required to heat 1.00 g of water by 1.00 K? The heat
capacity of water is 75.3 J mol
1
K
1
.
,
1 1 6
, 19
1 34 8 1
1.00g 75.3J K mol 1.00K 3.00 10 m
6.31 10
18.02g mol 6.626 10 J s 2.998 10 ms
p m
p m
hc
E Nh N nC T
C T
m
N
M hc

= = =

= = =

P1.8) A 1000-W gas discharge lamp emits 3.00 W of ultraviolet radiation in a narrow
range centered near 280 nm. How many photons of this wavelength are emitted per
second?
1 1 1 1
18 1
34 8 1
9
3.00W 1J s W 3.00W 1J s W
4.23 10 s
6.626 10 J s 2.998 10 ms
280 10 m
total
photon
E
n
hc
E

= = = =

P1.9) A newly developed substance that emits 225 W of photons with a wavelength of
225 nm is mounted in a small rocket such that all of the radiation is released in the same
direction. Because momentum is conserved, the rocket will be accelerated in the opposite
direction. If the total mass of the rocket is 5.25 kg, how fast will it be traveling at the end
of 365 days in the absence of frictional forces?

The number of photons is given by
1 1
20 1
34 8 1
9
1 J s 1 J s
3.00W 225W
W W
2.547 10 s
6.626 10 J s 2.998 10 ms
225 10 m
total
photon
E
n
hc
E

= = = =

The momentum of one photon is
34
27 1
9
6.626 10 J s
2.945 10 kg ms
225 10 m
h
p
= = =

The force is given by the rate of change of momentum.
( )
27 1 20 1 7 2
2.945 10 kg ms 2.547 10 s 7.501 10 kg ms
d n p
F
dt

= = =

The final speed is given by
7 2
1
0
7.501 10 kg ms 86400s
v v 365days = 4.51ms
5.25kg day
F
at t
m

= + = =

P1.10) What speed does a H
2
molecule have if it has the same momentum as a photon of
wavelength 280 nm?


1-6
( )
2 2
2
2
34
1
1
27 9
v
6.626 10 J s
v 0.707ms
2.016amu 1.661 10 kg amu 280 10 m
H H
H
H
h
p m
h
m

= =
= = =

P1.11) The following data were observed in an experiment of the photoelectric effect
from potassium:
10
19

Kinetic
Energy (J)
4.49 3.09 1.89 1.34 7.00 3.11
Wavelength
(nm)
250 300 350 400 450 500

Graphically evaluate these data to obtain values for the work function and Plancks
constant.

2.510
6
310
6
3.510
6
410
6
110
-19
210
-19
310
-19
410
-19
E (J)
1

The best-fit line is given by
19 25
1
3.97362 10 2.11171 10 . E

= +
Because the slope is hc,
25
34
8 1
2.11171 10 J m
7.0 10 J s.
2.998 10 m s
h

The work function is

given by the intercept of the line with the x axis at y = 0.
0
hc
E
= where
25
7
0
19
2.117110 J m
= =5.3010 m.
3.9736210 J
This gives
19
4.0 10 J or 2.5eV.

P1.12) Show that the energy density radiated by a blackbody
( )
( )
3
3 /
0 0
8 1
,
1
total
hv kT
E T
h
T d d
V c e

= =

depends on the temperature as T
4
.
(Hint: Make the substitution of variables / . x h kT = ) The definite integral
3 4
0
.
1 15
x
x
dx
e

Using your result, calculate the energy density radiated by a blackbody

at 800 and 4000 K.

1-7

3
3
0
8 1
.
1
total
h
kT
E h
d
V c
e

Let
h
x
kT
= ;
h
dx d
kT
=

3 4 4 3 5 4 4
3 3 3 3 3
0 0
8 1 8 8
1 15
1
h x
kT
h k T x k T
d dx
c h c e h c
e

= =

At 800 K,
( ) ( )
5 4 4 5 23 1 4 4
4 3
3 3 3 3
34 8 1
8 8 (1.381 10 J K ) (800 K)
3.10 10 J m
15
15 6.62610 J s 2.998 10 m s
total
E k T
V h c

= = =

At 4000,
( ) ( )
5 23 1 4 4
3
3 3
34 8 1
8 (1.381 10 J K ) (4000 K)
0.194 J m
15 6.626 10 J s 2.998 10 m s
total
E
V

= =

P1.13) The power per unit area emitted by a blackbody is given by
4 8 2 4
with 5.67 10 Wm K . P T

= = Calculate the energy radiated by a spherical
blackbody of radius 0.500 m at 1000 K per second. What would the radius of a blackbody
at 2500 K be if it emitted the same energy as the spherical blackbody of radius 0.500 m at
1000 K?
( ) ( )
2 4
4 8 1 2 4 5 1
=4 0.500m 5.67 10 J s m K 1000 K 1.78 10 J s E A T

= =

Because the total energy radiated by the spheres must be equal,
( ) ( )
( )
2 4 2 4
1 1 2 2
2 4
2 4
1 1
2 4 4
2
4 =4
0.500m 1000 K
= 0.0800 m
2500 K
r T r T
r T
r
T

= =

P1.14) In our discussion of blackbody radiation, the average energy of an oscillator
1
osc
h
kT
h
E
e

was approximated as
( )
1 1
osc
h
E kT
h
kT
= =
+
for 1
h
kT
<< .
Calculate the relative error =
approx
E E
E
in making this approximation for

= 4 10
12
s
1
at temperatures of 6000, 2000, and 500 K. Can you predict what the sign
of the relative error will be without a detailed calculation?


1-8
exp 1
Relative Error =
exp 1
approx
h
kT
h
E E
kT
E
h
h
kT
| |
|
|
| |
|
| |
\ . \ .
=
| |
|
|
| |
|
| |
\ . \ .

34 12 1
23 1
34 12 1
23 1
34
6.626 10 J s 4.00 10 s
1.381 10 J K 6000K
6.626 10 J s 4.00 10 s
exp 1
exp 1
1.381 10 J K 6000K
6.626 10 J
exp 1
h
kT
h
kT
h
h
kT
| |
| |
|
|

|

|
|
| |
| |
|

|
|
| | |

\ . \ . \ . \ .
=
| |
|

|
| |
|
| |
\ . \ .
12 1
34 12 1
23 1
s 4.00 10 s
1
6.626 10 J s 4.00 10 s
exp
1.381 10 J K 6000K

| |
|

|
|
| |
| |
|

\ . \ .
Relative Error = 0.0162
approx
E E
E
= for T = 6000 K.
The results for 2000 K, and 500 K are 0.0496 and 0.219.
Because E
approx
= kT > E, the relative error =
approx
E E
E
is always a negative number.

P1.15) The power (energy per unit time) radiated by black body per unit area of surface
expressed in units of W m
2
is given by
4
P T = with
8 2 4
5.67 10 W m K .

= The
radius of the sun is 7.00 10
5
km and the surface temperature is 6000 K. Calculate the
total energy radiated per second by the sun. Assume ideal blackbody behavior.
( ) ( )
4 2
2
4
8 2 4 8
26
4
5.67 10 W m K 6000 K 4 7.00 10 m
4.52 10 W
E PA T r

= =
=
=

P1.16) A more accurate expression for Eosc would be obtained by including additional
terms in the Taylor-Mclaurin series. The Taylor-Mclaurin series expansion of f(x) in the
vicinity of x
0
is given by (see Math Supplement)
0
0 0
2 3
2 3
0 0 0 0
2 3
( ) 1 ( ) 1 ( )
( ) ( ) ( ) ( ) ( ) ...
2! 3!
x x
x x x x
d f x d f x d f x
f x f x x x x x x x
d x d x d x
=
= =
| | | |
| |
= + + + +
| | |
\ .
\ . \ .
Use this formalism to better approximate Eosc by expanding
h
kT
e

in powers of h kT out
to ( )
3
h kT in the vicinity of 0. h kT = Calculate the relative error,
E kT
E
osc
osc
, if you

1-9
had not included the additional terms for = 1.00 10
12
s
1
at temperatures of 800, 500,
and 250 K.
The Taylor series expansion of
h
kT
e

is
2 3
1 1
1 ...
2 6
h h h
kT kT kT

| | | |
+ + + +
| |
\ . \ .
. Therefore
including terms up to
( )
3
h
kT
,
2 3
1 1
2 6
osc
h
E
h h h
kT kT kT

=
| | | |
+ +
| |
\ . \ .

2 3 2 3
1 1 1 1
2 6 2 6
osc
osc
E kT h h
kT
E
h h h h h h
kT kT kT kT kT kT

=

| | | | | | | |
+ + + +
| | | |
\ . \ . \ . \ .

2
34 12 1 34 12 1
23 1 23 1
34 12 1
34 12 1
23 1
6.626 10 J s 1.00 10 s 1 6.626 10 J s 1.00 10 s
1.381 10 J K 800K 2 1.381 10 J K 800K
6.626 10 J s 1.00 10 s
1 6.626 10 J s 1.00 10 s
6 1.381 10 J K 800K
osc
osc
E kT
E

| |
+
|

\ .
=
| |
+

\
23 1
3
2
34 12 1 34 12 1
23 1 23 1
34 12 1
3
1.381 10 J K 800K
6.626 10 J s 1.00 10 s 1 6.626 10 J s 1.00 10 s
1.381 10 J K 800K 2 1.381 10 J K 800K
6.626 10 J s 1.00 10 s
1 6.626 10
6

`

|
. )
| |
+
|

\ .

+
3
4 12 1
23 1
J s 1.00 10 s
1.381 10 J K 800K

`
| |
|

\ . )

0.0306
osc
osc
E kT
E
= for 800 K. The corresponding values for 500 K and 250 K are
0.0495 and 0.102.

P1.17) The observed lines in the emission spectrum of atomic hydrogen are given by
( ) ( )
1 1 1
1 2 2
1
1 1
cm cm cm ,
H
R n n
n n

| |
= >
|
\ .
. In the notation favored by spectroscopists,
1 E
hc
= = and
1
109, 677cm .
H
R

= The Lyman, Balmer, and Paschen series refers to
n
1
= 1, 2, and 3, respectively, for emission from atomic hydrogen. What is the highest
value of and v E in each of these series?
The highest value for corresponds to
1
n
0. Therefore
1 1
2
1
cm 109, 677cm
1
H
R
| |
= =
|
\ .
or E
max
= 2.1810
18
J for the Lyman series.
1 1
2
1
cm 27419cm
2
H
R
| |
= =
|
\ .
or E
max
= 5.4510
19
J for the Balmer series, and

1-10
1 1
2
1
cm 12186cm
3
H
R
| |
= =
|
\ .
or E
max
= 2.4210
19
J for the Paschen series

P1.18) A beam of electrons with a speed of 3.50 10
4
m/s is incident on a slit of width
200 nm. The distance to the detector plane is chosen such that the distance between the
central maximum of the diffraction pattern and the first diffraction minimum is 0.500 cm.
How far is the detector plane from the slit?

The diffraction minima satisfy the condition sin , 1, 2, ...
n
n
a
= = and the first

minimum is at sin .
a
= We choose the plus sign (the minus sign gives the distance
from the slit in the opposite direction) giving
34
31 4 1 9
6.626 10 J s
sin 0.10392
v 9.109 10 kg 3.50 10 ms 200 10 m
5.97 degrees
h
a m a
= = = =

=

The distance d from the screen and the position of the first minimum s are related by
0.500cm
4.78cm.
tan 0.1045
s
d
= = =

P1.19) If an electron passes through an electrical potential difference of 1 V, it has an
energy of 1 electron-volt. What potential difference must it pass through in order to have
a wavelength of 0.100 nm?
( )
( )
2
2
2
2
2
34
17
2 19
31 10
1 1
v
2 2 2
6.626 10 J s
1eV
2.41 10 J 150.4 eV
1.602 10 J
2 9.109 10 kg 10 m
e e
e e
h h
E m m
m m

| |
= = =
|
\ .
= = =

The electron must pass through an electrical potential of 150.4 V.

P1.20) What is the maximum number of electrons that can be emitted if a potassium
surface of work function 2.40 eV absorbs 3.25 10
3
J of radiation at a wavelength of
300 nm? What is the kinetic energy and velocity of the electrons emitted?
34 8 1 19
19
9
6.626 10 J s 2.998 10 ms 1.602 10 J
2.40eV 2.77 10 J
300 10 m eV
c
E h

= = =

19
5 1
31
2 2 2.77 10 J
v 7.80 10 ms
9.109 10 kg
E
m

= = =

( )
3
15
34 8 1 9
3.25 10 J
4.91 10
6.626 10 J s 2.998 10 m s 300 10 m
total total
photon
E E
n
E hc
= = = =

electrons.

1-11

P1.21) The work function of platinum is 5.65 eV. What is the minimum frequency of
light required to observe the photoelectric effect on Pt? If light with a 150-nm wavelength
is absorbed by the surface, what is the velocity of the emitted electrons?

a) For electrons to be emitted, the photon energy must be greater than the work function
of the surface.
19
19
19
15 1
34
1.60210 J
5.65 eV 9.05 10 J
eV
9.05 10 J
1.37 10 s
6.626 10 J s
E h
E
h
= =

b) The outgoing electron must first surmount the barrier arising from the work function,
so not all the photon energy is converted to kinetic energy.

34 8 1
19 19
9
19
5 1
31
6.626 10 J s 2.998 10 m s
9.05 10 J 4.19 10 J
150 10 m
2 2 4.19 10 J
v = 9.59 10 m s
9.11 10 kg
e
e
e
hc
E h
E
m

= =

= =

= =

P1.22) X-rays can be generated by accelerating electrons in a vacuum and letting them
impact on atoms in a metal surface. If the 1000-eV kinetic energy of the electrons is
completely converted to the photon energy, what is the wavelength of the X-rays
produced? If the electron current is 1.50 10
5
A, how many photons are produced per
second?
34 8 1
19
6.626 10 J s 2.998 10 ms
1.24nm
1.602 10 J
1000eV
eV
hc
E

= = =

5 1
13 1
19
current 1.50 10 Cs
9.36 10 s .
charge per electron 1.602 10 C
n

= = =

P1.23) When a molecule absorbs a photon, both the energy and momentum are
conserved. If a H
2
molecule at 300 K absorbs an ultraviolet photon of wavelength 100
nm, what is the change in its velocity v ? Given that its average speed is
v 3 /
rms
kT m = , what is v / v ?
rms

Because momentum is conserved,

34
27 1
9
6.626 10 J s
6.626 10 kg m s
100 10 m
photon
h
p
= = =


1-12
All this momentum is transferred to the H
2
molecule
2
2
27 1
27 1
1
27
1 1
3
1 1
3 1
= 6.626 10 kg m s v
6.626 10 kg m s
v 1.98 m s
2.016 amu 1.661 10 kg/amu
v 1.98 ms 1.98 ms
1.03 10
v 3
3 8.314J mol K 298K
2.016 10 kg mol
H
H
p m
RT
M

= =

= = =

2-1
Chapter 2: The Schrdinger Equation

Q2.1) 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.

Q2.2) 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.

Q2.3) Why can we conclude that the wave function
( )
( , ) ( )
i E t
x t x e

=
h
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.

Q2.4) 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 wont satisfy the eigenvalue equation, the set of wave functions is larger
than the set of eigenfunctions.

Q2.5) Is it correct to say that because the de Broglie wavelength of a H
2
molecule at
300 K is on the order of atomic dimensions that all properties of H
2
are quantized?
Chapter 2/The Schrdinger Equation
2-2

No. The system must be treated using quantum mechanics if the characteristic
size is comparable to the wavelength. For a H
2
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 H
2

molecules on the walls of the container can be described classically.

Q2.6) In Figure 2.6 the extent to which the approximate and true functions agree was
judged visually. How could you quantify the quality of the fit?

You could use a function like ( ) ( )
2
f x g x dx

, where f(x) and g(x) are the
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.

Q2.7) If ( , ) sin( ) x t A kx t = 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 ( , ) sin( ). x t A kx t = + The wave amplitude
is zero for 2
x t
n
T

+ =

where n is an integer. Solving for x, we obtain the
location of the nodes.
2
n t
x
T

=

. We see that x decreases as t increases,
showing that the wave is moving in the direction of negative x.

Q2.8) A traveling wave with arbitrary phase can be written as
( , ) sin( ). x t A kx t = + What are the units of ? Show that could be used to
represent a shift in the origin of time or distance.

The units of are radians. We can rewrite this equation either as
( , ) sin( ) x t A k x t
k

= +

or ( , ) sin( ) x t A kx t

=

. The first of
these equations suggests a shift in x, and the second suggests a shift in t.

Q2.9) 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
area A is
2
4
A
r
, where r is the radius of the sphere, which is equal to the distance
2-3
from the source to the detector. Therefore the measured intensity for the spherical
source decreases as 1/r
2
. 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.

Q2.10) Distinguish between the following terms applied to a set of functions:
orthogonal, normalized, and complete.

Two functions
i
(x) and
j
(x) are orthogonal if ( ) ( )
*
0
i j
x x dx =
, normalized
if ( ) ( ) ( ) ( )
* *
1
i i j j
x x dx x x dx = =

, and complete if any well behaved
function (x) can be expanded in terms of the
i
(x), ( ) ( )
1
m m
m
x b x
=
=
.
Problems

P2.1) Assume that a system has a very large number of energy levels given by the
formula
2 22
0 0
with 2.34 10 J, l

= = where l takes on the integral values 1, 2, 3, .
Assume further that the degeneracy of a level is given by g l
l
= 2 . Calculate the ratios
5 1 10 1
/ and / n n n n for T = 100 K and T = 650 K, respectively.
( ) ( )
( )
( )
2
0 0
5 1
5 5
1 1
22
5
23 1
1
22
5
23 1
1
10
1
5
2 5
exp exp
2 1
2.3410 J 25 1
10
(100 K) exp 0.086
2 1.381 10 J K 100 K
2.3410 J 25 1
10
(650 K) exp 2.67
2 1.381 10 J K 650 K
(100 K
n g
n g k T k T
n
n
n
n
n
n

= =

= =

= =

( )
( )
22
7
23 1
22
10
23 1
1
2.34 10 J 100 1
20
) exp 5.2 10
2 1.381 10 J K 100 K
2.34 10 J 100 1
20
(650 K) exp 0.757
2 1.381 10 J K 650 K
n
n

= =

= =

P2.2) Consider a two-level system with
21 21
1 2
= 3.10 10 J and 6.10 10 J.

= If g
2
= g
1
, what value of T is required to obtain
2 1
/ n n = 0.150? What value of T is required to
obtain
2 1
/ n n = 0.999?

2-4
( )
( )
( )
( )
( ) ( )
5 1
2 2
1 1
5 1
2 2
1 1
2 2
5 1 1 1
5 1
2 2
1 1
21
2 1
23 1
exp
ln ln
1
ln ln
ln ln
3.0010 J
for 0.150 1
1.381 10 J K ln 1 ln 0.150
n g
n g k T
n g
n g k T
k g n
T g n
T
g n
k
g n
n n T

=

=

=

= = =

15K

( ) ( )
21
5
2 1 23 1
3.00 10 J
for 0.999 2.17 10 K
1.381 10 J K ln 1 ln 0.999
n n T

= = =

P2.3) To plot ( , ) sin( ) x t A kx t = as a function of one of the variables x and t, the
other variable needs to be set at a fixed value, x
0
or t
0
. If
( , )
max
x
0
0
= 0.280, what is the
constant value of x
0
in the upper panel of Figure 2.3? If
( , )
max
0
0
t
= 0.309, what is the
constant value of t
0
in the lower panel of Figure 2.3? (Hint: The inverse sine function has
two solutions within an interval of 2. Make sure that you choose the correct one.)
For the traveling wave
3
( , ) sin 2 sin 2
1.46 1.00 10
x t x t
x t A A
T x

= =

( )
0 0 0
max
2
( , 0)
sin 2 0.284; 2
1.46m 1.46m
0.28 radians or 0.28 = 3.43 radians
6.4 10 m or 0.79 m
x x x
x

= =

=
=

( )
0 0 0
3 3
max
5 4
0
(0, )
sin 2 0.309; 2
1.00 10 1.00 10
0.31 radians or 0.31 3.45 radians
5.0 10 s or 5.5 10 s
t t t
A
x s x s
t

= =

= =
=

To decide which of the two values best fits the data in Figure 2.2, it is necessary to plot
the data.

2-5

It is seen that the data are fit by x
0
= 0.79 m and t
0
= 5.5 10
4
s. Adding any positive or
negative integral multiple of to x
0
or T to t
0
will give equally good agreement.

P2.4) A wave traveling in the z direction is described by the wave function
1 1 2 2
( , ) sin( ) sin( ) z t A kz t A kz t = + + + x y 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, ( , ) z t represents a transverse
wave.
a) What requirements must A
1
and A
2
satisfy for a plane polarized wave in the x-z plane?
b) What requirements must A
1
and A
2
satisfy for a plane polarized wave in the y-z plane?
c) What requirements must A
1
and A
2
and

1 2
and satisfy for a plane polarized wave in a
plane oriented at 45 to the x-z plane?
d) What requirements must A
1
and A
2
and
1 2
and 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
1 2
0 and 0. A A =

b) The amplitude along the y axis must oscillate, and the amplitude along the x axis must
vanish. Therefore
1 2
0 and 0. A A =

2-6
c) The amplitude along both the x and y axes must oscillate. Therefore
1 2
0 and 0 A A . Because they must oscillate in phase,
1 2
= .

d) The amplitude along both the x and y axes must oscillate with the same amplitude.
Therefore
1 2
0 A A = . For circularly a polarized wave, the x and y components must be
out of phase by /2. Therefore
1 2
=
2
. This can be seen by comparing the x and y

amplitudes for the positive sign.
1 1 1 1
1 1
1 1
1 1
( , ) sin( ) sin( )
2
let
( , ) sin( ) sin( )
2
sin( ) sin( ) cos cos( ) sin
2 2
sin( ) c
z t A kz t A kz t
kz kz
z t A kz t A kz t
A kz t A kz t kz t
A kz t A
= + + + +
+ =
= + +

= + +

= +
x y
x y
x y
x y os( ) kz t

The x and y amplitudes are /2 out of phase and the sum of the squares of their
amplitudes is a constant as required for a circle.

P2.5) Show that
a ib
c id
ac bd i bc ad
c d
+
+
=
+ +
+
b g
2 2

( )
2 2 2 2
ac bd i bc ad
a ib a ib c id ac bd ibc iad
c id c id c id c d c d
+ +
+ + + +

= = =

+ + + +

P2.6) Does the superposition ( , ) sin( ) sin( ) x t A kx t A kx t = + + 2 generate a
standing wave? Answer this question by using trigonometric identities to combine the
two terms.

( , ) sin( ) 2 sin( ) x t A kx t A kx t = + +
Using the identities
( )
( )
sin sin cos cos sin
cos cos cos sin sin

=
= m

the previous equation can be simplified to
( ) , sin cos cos sin 2 sin cos 2 cos sin
= 3 sin cos cos sin
x t A kx t A kx t A kx t A kx t
A kx t A kx 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.
2-7

P2.7) Express the following complex numbers in the form .
i
re

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

In the notation ,
i
re

2 2 1
Re
= and = cos
z
r z a b
z

= +

.
a) ( )
1
1
2 4 2 5 exp cos 2 5 exp 0.352
5
i i i

= =

b)
( ) ( )
1
6 6exp cos 1 6exp 0 i

= =
c) ( )
1
3 1 3 10 1 10
exp cos exp 0.398
4 4 4 4 4
10
i i
i i
i

+
= = =

d) ( )
1
8 3 17 13 6 13
exp cos exp 0.392
2 4 5 10 2 2
5 13
i i
i i
i

+
= + = =

P2.8) Express the following complex numbers in the form a + ib.
a)
2
2
i
e
b) 2 5
2
e
i
c) e
i
d)
3 2
5 3
4
+
e
i

To convert to the form a + ib, we use the equations Re cos and Im sin z z z z = =
a)
2
2 2cos 2sin 2
2 2
i
e i i

= + =

b)
2
2 5 2 5 cos 2 5 sin 2 5
2 2
i
e i i

= + =

c) ( ) cos sin 1
i
e i
= + =
d)
4
3 2 3 2 3 2 3 2 2 3 2 2
cos sin cos
4 4 2 4 2 5 3 5 3 5 3 5 3 5 3

i
e i i

= + = +

+ + + + +

( )
3
1
5 3
i = +
+

P2.9) Using the exponential representation of the sine and cosine functions
( ) ( )
1 1
cos and sin
2 2
i i i i
e e e e
i

= + = , show that
a) cos sin
2 2
1 + =
b)
d
d
cos
sin

b g
=
2-8
c) sin cos

+
F
H
G
I
K
J
=
2

a)

( ) ( )
( ) ( )
2 2
2 2
2 2 2 2
1 1
cos sin
2 2
1 1
2 2 1
4 4
i i i i
i i i i
e e e e
i
e e e e

+ = + +

= + + + + =

b)

( )
( )
( ) ( )
1
cos
1 1 2
sin
2 2
i i
i i i i
d e e
d
ie ie e e
d d

+

= = = =

c)
( )
2 2
2 2
1 1
sin cos
2 2 2 2
i i
i i
i i i i
i
e e e e e e e e
i i i

+ +

+ = = = + =

P2.10) 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 cos

b)
2
2
x
e

1
x
d
d x

c) sin
sin
cos

d
d

a) sin cos

sin cos sin sin .
Not an eigenfunction
b)
2
1
2
x
e

1 d
x d x

2 2
1 1
2 2
1 x x d
e e
x d x

= Eigenfunction with eigenvalue 1
c) sin
sin
cos
d
d

sin
sin sin
cos
d
d

= Eigenfunction with eigenvalue +1

2-9
a) x
3

3
3
d
d x

b) x y x
x
y
y

c) sin cos
2
2

a)
3
x
3
d
d x

3
3
6
d x
d x
= Not an eigenfunction
b) x y x y
x y

+

2
xy xy
x y xy
x y

+ =

Eigenfunction with eigenvalue +2
c) sin cos
2
2

( )
2
2
sin cos sin cos
Eigenfunction with eigenvalue 1

a)
2
3cos 1
1
sin
sin
d d
d d

b)
2
2
x
e

2
2
2
d
x
dx

c) e
i 4

d
d
2
2

a)
2
3cos 1
1
sin
sin
d d
d d

( )
( )
( )
( )
2
2
3 2 2 2
2 2
3cos 1
1 1
sin 6cos sin
sin sin
1
6sin 12cos sin 6sin 12cos
sin
6 18cos 6 3cos 1
d
d d
d d d
=

= =
= =

2-10
Eigenfunction with eigenvalue 6.

b)
2
1
2
x
e

2
2
2
d
x
d x

2
2 2
1
2
2
1 1
2
2 2
2
x
x x d e
x e e
d x

=

c)
4i
e

2
2
d
d

2 4
4
2
16
i
i
d e
e
d
=

a) e
i x y + 3 2 b g

2
2
x

b) x y
2 2
+
( )
2 2
1
x y
x x

c) sin cos
2
sin sin 6sin
d d
d d

+

a)
( ) 3 2 i x y
e
+

2
2
x

( )
( )
3 2 2
3 2
2
9
i x y
i x y
e
e
x
+
+

b)
2 2
x y +
( )
2 2
1
x y
x x

( )
2 2
2 2 2 2
1 x y
x y x y
x x
+
+ = +
Eigenfunction with eigenvalue +1.

c) sin cos
2
sin sin 6sin
d d
d d

+

( )
( )
3 2 3
2 3
sin cos
sin sin 6sin cos sin sin 1 2sin 6sin cos
sin cos 6sin cos 6sin cos sin cos
d d d
d d d

+ = +

= + =

2-11
Eigenfunction with eigenvalue +1.

P2.14) Which of the following wave functions are eigenfunctions of the operator d/dx?
If they are eigenfunctions, what is the eigenvalue?

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

a)
( )
3 3
3 3
3 3
x i x
x ix
d a e b e
a e i be
d x

+
b)
2
sin
2sin cos
d x
x x
d x
c)
i x
i x
d e
i e
d x
= Eigenfunction with eigenvalue i

d)
cos
sin
d a x
a a x
d x
e)
2
2
2
i x
i x
d e
i x e
d x

P2.15) Which of the following wave functions are eigenfunctions of the operator
2 2
d dx ? If they are eigenfunctions, what is the eigenvalue?

a)
3 3

x i x
ae be

+ b) sin
2
x c) e
i x
d) cosa x e) e
i x
2

a)
( )
2 3 3
3 3
2
9 9
x i x
x i x
d a e b e
a e be
d x

+

b)
2 2
2 2
2
sin
2sin 2cos
d x
x x
d x
= + Not an eigenfunction

c)
2
2
i x
i x
d e
e
d x
= Eigenfunction with eigenvalue 1

d)
2
2
2
cos
cos
d a x
a a x
d x
= Eigenfunction with eigenvalue a
2
e)
2
2 2
2
2
2
2 4
i x
i x i x
d e
i e x e
d x


P2.16) If two operators act on a wave function as indicated by
$ $
AB f x b g , it is important
to carry out the operations in succession with the first operation being that nearest to the
2-12
function. Mathematically,
$ $ $ $
AB f x A B f x b g b g d i
= and
$ $ $
A f x A A f x
2
b g b g d i
= . Evaluate the
following successive operations
$ $
AB f x b g . The operators
$
A and
$
B are listed in the first
and second columns and f x b gis listed in the third column.
a)
d
d x

d
d x
x e
a x 2
2
+
b)
2
2
y

x

2
(cos3 ) sin y
c)
2
2

cos
sin

a)
( )
2
2 2 2
2
2 2
2 2 2 4 2
a x
a x a x a x
d x e
d d
x a x e a x e a e
d x d x d x

+

= + = + +

b)
( )
[ ]
2
2 2
2 2
cos 3 sin
2cos 3 sin cos 18cos 3 sin cos
y x
y x x y x x
y x y

= =

c)
2
2 2
cos
cos cos cos sin
sin sin

= =

P2.17) If two operators act on a wave function as indicated by
$ $
AB f x b g , it is important
to carry out the operations in succession with the first operation being that nearest to the
function. Mathematically,
$ $ $ $
AB f x A B f x b g b g d i
= and
$ $ $
A f x A A f x
2
b g b g d i
= . Evaluate the
following successive operations
$ $
AB f x b g . The operators
$
A and
$
B are listed in the first
two columns and f x b gis listed in the third column.
a)
d
d x
x x e
a x
2

b) x
d
d x
x e
a x
2

c) y
x
x
y
e
a x y +
2 2
e j

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

2-13
a)
( )
2 2 2
3
2 2
a x a x a x
d
x x e x e a x e
d x

=

b)
( )
2 2 2
3
2
a x a x a x
d
x x e x e a x e
d x

=

c)
( )
( )
( )
( ) ( )
2 2
2 2
2 2 2 2
2 2 2 2
2
2 4
a x y
a x y
a x y a x y
e
y x y a x y e
x y x
a y e a x y e
+
+
+ +

= =

= +

P2.18) Find the result of operating with
2
2
2
4
d
x
dx
on the function
2
.
ax
e
What must the

value of a be to make this function an eigenfunction of the operator?
( )
2
2 2 2 2 2 2
2
2 2 2 2 2 2
2
4 2 4 4 2 4 1
ax
ax ax ax ax ax ax
d e
x e ae x e a x e ae a x e
dx

= + = +

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

( )( )( )
2 2
1 2 r d dr r d dr r + on the function
br
Ae
. What must the values of A and b be to make this function an eigenfunction of the
operator?
( )
( )
( )
2 2
2 2
2 2
2
2
1 2 1 2
1 2
2
2
2 2
br br br
br
br
br br
br
br
d dAe Ae d Ae
r bAr e
r dr dr r r dr r
Ae
brAe b r Ae
r r
Ae
b b Ae
r

+ = +
= + +
= +

To be an eigenfunction of the operator, the terms in
br
Ae
r
must vanish. This requires

that b = 1. There are no restrictions on the value of A.

2 2 2
2 2 2
d d d
dx dy dz
+ + on the function
2 2 2
. x y z + +
Is this function an eigenfunction of the operator?
( )
2 2 2
2 2 2
2 2 2
6
d d d
x y z
dx dy dz

+ + + + =

. Therefore, the function is not an eigenfunction of
the operator.
2-14

P2.21) Show that the set of functions ( ) , 0 2 ,
i n
n
e

= are orthogonal if n and
m are integers. To do so, you need to show that the integral
( ) ( )
2
*
0
0 for
m n
d m n
if n and m are integers.

( ) ( )
( )
( )
( )
( )
( )
( )
( ) ( )
( )
2
2 2 2
*
0 0 0
0
2 0
1
1 1
cos 2 sin 2 1
Because and are integers, is an integer and the argume
i n m i n m im in
m n
i n m
d e e d e d e
i n m
e e n m n m
i n m i n m
n m n m

= = =

= = +

( ) ( )
( )
[ ]
2
*
0
nts of the
sine and cosine functions are integral multiples of 2 .
1
1 0 1 0
m n
d
i n m
= + =

P2.22) Show by carrying out the integration that ( ) ( ) sin / and cos / , m x a m 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 3 / 4? x a Explain your result.
( )
2 2
0 0
cos sin sin sin 0 0
2 2
a
a
m x m x a m x a
d x m
a a m a m

= = =

3 3
4 4
0 0
3
4
2 2
0
cos sin cos sin
3
sin sin 0 0
2 2 4
a a
a
m x m x m x m x
d x d x
a a a a
a m x a m
m a m

=

= =

except for the special case
3
4
m
n = where n is an integer. The length of the integration
interval must be n periods (for n an integer) to make the integral zero.

P2.23) Normalize the set of functions ( ) , 0 2 .
i n
n
e

= To do so, you need to
multiply the functions by a so-called normalization constant N so that the integral
N N d m n
m n
* *

b g b g
0
2
1
z
= = for
2 2
* * *
0 0
2 1
i n i n
N N e e d N N d N N

= = =

This is satisfied for
1
2
N
= and the
normalized functions are ( )
1
, 0 2 .
2
i n
n
e

=
2-15
P2.24) 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.
a) Normalize the wave function sin sin
n x m y
a b

over the range
0 , 0 x a 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.
b) Normalize the wave function e
r
a
cos sin over the interval

0 , 0 , 0 2 . r < The volume element in three-dimensional spherical
coordinates is r dr d d
2
sin .

a)

( )
2 2 2
0 0
2 2 2
0 0
2 2 2
0 0
2
1 sin sin
Let , ; then and
1 sin sin
sin sin
Using the standard integral sin
a b
n m
m n
n x m y
N d x d y
a b
n x m y adu bdw
u w dx dy
a b n m
a b
N u wd u d w
n m
a b
N u d u x wd w
n m
ax

=

= = = =
=

=

2
2 2
1 1
sin 2
2 4
1 1 1 1
1 sin 2 0 sin 0 sin 2 0 sin 0
2 4 4 2 4 4

2 2 4
2
dx x ax
a
a b m n
N m n
n m
a b n m ab
N N
n m
N
ab

=

=

= =
=

2-16
b)
( )
2 2
2 2
2 2 2 2 2 2 2 2
0 0 0 0 0 0
1
0
2 3
1 cos sin sin sin cos sin
!
Using the standard integral ( 0, positive integer)
2 1 1 1 2!
1 sin 2 0 sin 0 cos 0 cos
2 4 4 3
r r
a a
n ax
n
N d d e r d r N d d r e d r
n
x e dx a n
a
a
N

+
= =
= >

=

3
2 3
3
3
2 6
6
N a
N
a

=

=

P2.25) Show that the following pairs of wave functions are orthogonal over the
indicated range.
a) e
x
1
2
2
and
( )
2
1
2
2
2 1 ,
x
x e

< x where is a constant that is greater than
zero.

b)
0
/ 2
0
2
r a
r
e
a

and
r
a
e
r a
0
2
0
/
cos over the interval 0 , 0 , 0 2 r <

a)

( ) ( )
2 2
2 2 2
2 2
2
1 1
2 2 2
2 2
2
0 0
2
0
2 1 2 1 2
4 2 because the integrand is an even function of .
1 3 5 2
Using the standard integrals
x x
x x x
x x
n ax
x e e d x x e d x x e d x e d x
x e d x e d x x
x e dx

= =
=

=

( )
( )
2
2 2
1
1
2
ax
0
1 1
2
2 2
2
1
( 0, positive integer)
2
and e dx
4
1
2 1 = 4 0
2
n n
x x
n
a n
a a
a
x e e d x

>

=

=

2-17

b)

0 0
0 0
0 0
2
/ 2 / 2 2
0 0 0 0 0
/ 2 / 2 2
0 0 0 0
/ 2 / 2 2 2 2
0 0 0
cos sin 2
2 cos sin 2
1 1
2 2 cos 0 cos 0
2 2
r a r a
r a r a
r a r a
r r
d d e e r d r
a a
r r
d e e r d r
a a
r r
e e r d r
a a

=

= =

P2.26) Because
0
cos cos 0,
d
n x m x
d x m n
d d

=

, the functions
( ) cos / for 1, 2, 3, ... n x d n = form an orthogonal set. What constant must these functions
be multiplied by to form an orthonormal set?
( )
( ) ( )
2 2
0
0
2
2 2
2
1 cos cos sin
2 4
1 1
where we have used the standard integral cos sin 2
2 4
0
1 sin 2 sin 0 1
2 4 2 4 2
2
d
d
m x m x x d m x
N d x N
d d m d
ax dx x ax
a
d d d d
N m N
m m
N
d

= = +

= +

= + = =

=

P2.27) Use a Fourier series expansion to express the function ( ) , f x x b x b = in
the form ( )
0
1
sin cos .
m
n n
n
n x n x
f x d c d
b b

=

= + +

Obtain d
0
and the first five
coefficients c
n
and d
n
.

2-18
0
2
2 2
1 1
( ) 0
2 2
1 1
( ) cos cos
cos sin
Using the standard integral cos
1
cos sin cos
b b
b b
b b
n
b b
n
d f x dx x dx
b b
n x n x
d f x dx x dx
b b b b
ax x ax
x ax
a a
n
b n b b n b b
d b
b n b n b n

= = =

= =

= +

= +

( )
( )
( )
( )
2
sin 0
All the = 0 because is an odd function of .
1 1
( ) sin sin
cos sin
n
b b
n
b b
n
b n b
b
b
b n b
d f x x
n x n x
c f x dx x dx
b b b b
x ax ax
x ax
a a
c

=

= =

= +
=

( )
( )
( )
( )
2
2 2
2
2
1
sin cos
1
sin cos sin cos
2
sin cos
b
b
n
n
b n x b n x
x
b n b n b
n b n b b n b b n b b b
c b b
b n b n b n b n b
b b
c n n
b n n

= +

=

( )
( )
1
0 1 5 1 2 3 4 5
2 2
cos 1
2 2 2
Therefore, 0 and 0. , , , , and
3 2 5
n
n
b b
c n
n n
b b b b b
d d d c c c c c

+

= =

= = = = = = =

P2.28) Carry out the following coordinate transformations.
a) Express the point x = 3, y = 2, and z = 1 in spherical coordinates.
b) Express the point r = = = 5
4
3
4
, ,

and in Cartesian coordinates.
a)
2 2 2 2 2
3 2 1 14 r x y z = + + = + + =

1 1
2 2 2
1
cos cos 1.30 radians
14
z
x y z

= = =
+ +

1 1
2
tan tan 0.588 radians
3
y
x

= = =
b)
3
sin cos 5sin cos 2.5
4 4
x r

= = =

3
sin sin 5sin sin 2.5
4 4
y r

= = =
5
cos 5cos
4
2
z r

= = =
2-19
P2.29) Operators can also be expressed as matrices and wave functions as column
vectors. The operator matrix

acts on the wave function
a
b

according to the
rule
a a b
b a b

+
=

+

. In words, the 2 2 matrix operator acting on the two-
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
operator
0 1
1 0

on the column vectors
1
0

,
0
1

,
1
1

and
1
1

? Are these wave
functions eigenfunctions of the operator? See the Math Supplement for a discussion of
matrices.

0 1 1 0
1 0 0 1

=

0 1 0 1
1 0 1 0

=

0 1 1 1
1 0 1 1

=

( )
0 1 1 1 1
1
1 0 1 1 1

= =

Only
1
1

and
1
1

are eigenfunctions with the eigenvalues 1 and 1, respectively.

P2.30) Let
1
0
F
H
G
I
K
J
and
0
1
F
H
G
I
K
J
represent the unit vectors along the x and y directions,
respectively. The operator
cos sin
sin cos

effects a rotation in the x-y plane. Show that
the length of an arbitrary vector
1 0
0 1
a
a b
b

= +

, which is defined as
2 2
, a b + is
unchanged by this rotation. See the Math Supplement for a discussion of matrices.

( ) ( )
2 2
2 2 2 2
cos sin cos sin
sin cos sin cos
The length of the vector is given by
cos sin sin cos ( cos sin 2 sin cos

a a b
b a b
a b a b a b ab

=

+

+ + = +
( ) ( )
2 2 2 2 1 2
2 2 2 2 2 2 2 2
sin cos 2 sin cos )
cos sin cos sin
a b ab
a b a b

+ + +
= + + + = +

This result shows that the length of the vector is not changed.
4-1
Chapter 4: Using Quantum Mechanics on Simple Systems
Problem numbers in italics indicate that the solution is included in the Students
Solutions Manual.


Q4.1) Why are standing-wave solutions for the free particle not compatible with the classical
result
0 0
v x x t = + ?

Because the particle is moving, we must represent it by a traveling wave, for which the
nodes move with time. This is not possible using a standing wave, because the nodes do
not move with time.

Q4.2) Why is it not possible to normalize the free-particle wave functions over the whole
range of motion of the particle?

This is the case because ( ) ( )
*
2
L L
ik x ik x
L L
x x dx A A e e dx A A L
+
+ + + +

= =

diverges as
L.

Q4.3) Show that for the particle in the box total energy eigenfunctions,
( )
2
sin
n
n x
x
a a
| |
=
|
\ .
, ( ) x is a continuous function at the edges of the box. Is
( ) d x
d x
a
continuous function of x at the edges of the box?

( )
2
sin 0
n
n x
x
a a
| |
= =
|
\ .
at x = 0 and x = a. Because the wave function is zero
everywhere outside the box, it has the value zero at x = 0 and x = a. Therefore, ( ) x is a
continuous function of x because there is no abrupt change in the function at x = 0 or
x = a.

( ) 2 2
sin cos 1 at 0
cos 1 for zero or even and 1 for odd at .
d x
d n x n n x
x
d x d x a a a a a
n n n x a
| | | |
= = = =
| |
\ . \ .
= =

Chapter 4/Using Quantum Mechanics on Simple Systems

4-2

( ) d x
d x
= 0 everywhere outside the box because (x) = 0 outside the box.

Because
( ) d x
d x
can be one when approaching x = a from inside the box, and is always
equal to zero outside of the box,
( ) d x
d x
is not a continuous function at x = a.

Q4.4) Can the particles in a one-dimensional box, a square two-dimensional box, and a cubic
three-dimensional box all have degenerate energy levels?

The two and three dimensional boxes can have degenerate energy levels if the lengths
along the x and y or x, y, and z directions are the same or if any of the quantities

2
2 2
2 2 2
, , or
y
x z
n
n n
a b c
are equal. The one dimensional box levels have only one state per level.

Q4.5) We set the potential energy in the particle in the box equal to zero and justified it by
saying that there is no absolute scale for potential energy. Is this also true for kinetic energy?

Yes.
2
1
v ,
2
kinetic
E m = and the velocity is measured relative to the frame of reference. The
same is true if we express the kinetic energy as
2 2
2
kinetic
k
E
m
=
=
, because the value of
p k = = depends on the frame of reference if the observer is moving relative to the source.

Q4.6) Why are traveling-wave solutions for the particle in the box not compatible with the
boundary conditions?

The nodes in traveling waves move with time. This is incompatible with the boundary
conditions for the particle in the box.

Q4.7) Why is the zero point energy lower for a He atom in a box than for an electron?

The zero point energy
2
2
8
h
E
ma
= varies inversely with the mass, and the mass of a He
atom is much greater than the mass of an electron.

Q4.8) Invoke wave-particle duality to address the following question: How does a particle get
through a node in a wave function to get to the other side of the box?

The question poses a problem only if we try to see the particle as a pure particle rather
than as a wave-particle. The essence of particle-wave particle duality is that some
properties are more easily addressed in a wave picture, and some properties are more

4-3
easily addressed in a particle picture. Address this question by looking at the particle as
a wave. We can easily make a guitar string vibrate over its whole length and still have
nodes by holding a finger at the fifth fret. The wave-like properties of the particle
allow it to have a nonzero probability of being found within any interval dx throughout
the box, even if the amplitude of the wave function is zero at a number of special points.

Q4.9) What is the difference between probability and probability density?

Probability is expressed as ( ) ( )
*
d and is the probability density ( ) ( )
*

integrated over the interval . d

Q4.10) Explain using words, rather than equations, why if ( ) ( ) ( ) ( ) , , ,
x y z
V x y z V x V y V z + +
the total energy eigenfunctions cannot be written in the form ( ) ( ) ( ) ( ) , , . x y z X x Y y Z z =

If the potential has the form ( ) ( ) ( ) ( ) , , ,
x y z
V x y z V x V y V z = + + then the total energy can
be written in the form E = E
x
+ E
y
+ E
z
. This allows the Schrdinger equation to be
separated into separate equations for x, y and z and the wave functions to be written in the
form ( ) ( ) ( ) ( ) , , x y z X x Y y Z z = . However, if ( ) ( ) ( ) ( ) , ,
x y z
V x y z V x V y V z + + , this
separation into three separate Schrdinger equations is not possible, and ( ) , , x y z
cannot be factored into three terms, each of which depends only on one variable.

Problems

P4.1) Show by examining the position of the nodes that Re A e A e
i kx t i kx t
+
b g b g
and Re
represent plane waves moving in the positive and negative x directions, respectively. The
notation Re[ ] refers to the real part of the function in the brackets.
( )
( )
( )
( )
Re = cos . The nodes of this function occur at
2 1
2
2 1
2
i kx t
A e kx t
kx t n
x n t
+

= +
= + +

Because the position of the nodes is increasing as t increases, this function represents a plane
wave moving in the positive x direction.
( )
( ) ( )
( )
( )
Re cos cos . The nodes of this function occur at
2 1
2
2 1
2
i kx t
A e kx t kx t
kx t n
x n t

= = +

+ = +
= +

Because the position of the nodes is decreasing as t increases, this function represents a plane
wave moving in the negative x direction.

4-4
P4.2) Show that the energy eigenvalues for the free particle, E
k
m
=
=
2 2
2
, are consistent with
the classical result
2
1
v .
2
E m =
2
2
2
2 2
1
v
2 2
From the de Brogliie relation,
1
, showing consistency between the classical and quantum result.
2 2
p
E m
m
h
p
h k
E
m m
= =
=
| |
= =
|
\ .
=

P4.3) Are the total energy eigenfunctions for the free particle in one dimension,
( ) ( )
2 2
2 2
and ,
mE mE
i x i x
x A e x A e
+
+
+
= =
= =
eigenfunctions of the one-dimensional linear
momentum operator? If so, what are the eigenvalues?
( )
2 2
2 2
2
2
2

mE mE
i x i x
ikx
d mE
i A e i A e k A e
d x
+ +
+
+ + +
= =
= =
= = =
=

Eigenfunction with eigenvalue k +=
( )
2 2
2 2
2
2
2

mE mE
i x i x
ikx
d mE
i A e i A e k A e
d x

= =
= =
= = =
=

Eigenfunction with eigenvalue k =

P4.4) Is the superposition wave function for the free particle
+
+
+
= + x A e A e
i
mE
x i
mE
x
b g
2 2
2 2
= =
an eigenfunction of the momentum operator? Is it an
eigenfunction of the total energy operator? Explain your result.

( ) ( )
2 2 2 2
2 2
2 2 2 2
2 2
2 2
2 2
2 2

mE mE mE mE
i x i x i x i x
mE mE
i x i x
d mE mE
i A e A e i A e i A e
d x
k A e k A e
+ +
+ +
+
+
| |
| + = +
|
\ .
=
= = = =
= =
= = =
= =
= =

This function is not an eigenfunction of the momentum operator, because the operation does
not return the original function multiplied by a constant.
( ) ( )
2 2 2 2
2 2
2 2 2 2
2 2 2 2
2 2
2 2 2
2 2
2 2
-
2 2 2
mE mE mE mE
i x i x i x i x
mE mE
i x i x
d mE mE
A e A e i A e i A e
m d x m m
E A e A e
+ +
+ +
+
+
| |
| + =
|
\ .
| |
| = +
|
\ .
= = = =
= =
= = =
= =

This function is an eigenfunction of the total energy operator. Because the energy is

4-5
proportional to p
2
, the difference in sign of the momentum of these two components does not
affect the energy.

P4.5) Consider a particle in a one-dimensional box defined by
( ) ( ) 0, 0 and , , 0. V x a x V x x a x = > > = Explain why each of the following
unnormalized functions is or is not an acceptable wave function based on criteria such as being
consistent with the boundary conditions, and with the association of
*
x x dx b g b g with
probability.
a) A
n x
a
cos

b) B x x +
2
c h
c) C x x a
3
b g d)
D
n x
a
sin

a) cos
n x
A
a
is not an acceptable wave function because it does not satisfy the boundary
condition that ( ) 0 0. =

b)
( )
2
B x x + is not an acceptable wave function because it does not satisfy the boundary
condition that ( ) 0. a =

c) ( )
3
C x x a is an acceptable wave function. It satisfies both boundary conditions and can
be normalized.
d)
sin
D
n x
a
is notan acceptable wave function. It goes to infinity at x = 0 and cannot be

normalized in the desired interval.

P4.6) Evaluate the normalization integral for the eigenfunctions of
H for the particle in the

box ( ) sin
n
n x
x A
a
| |
=
|
\ .
using the trigonometric identity
2
1 cos 2
sin
2
y
y

= .
( )
2 2
0
2 2 2 2
0 0 0
2 2 2
1 sin
let = ;
1 cos 2 sin 2
1 sin
2 2 4
sin 2 sin 0
2 2 2
2
a
n n n
n x
A dx
a
n x a
y dx dy
a n
a a y a y y
A y dy A dy A
n n n
A a A a A a
n n
n n
A
a

| |
=
|
\ .
=

= = =

= =
=


4-6
P4.7) Use the eigenfunction ( ) +
ikx ikx
x A e B e
+
= rather than x A kx B kx b g = + sin cos to
apply the boundary conditions for the particle in the box.
a) How do the boundary conditions restrict the acceptable choices for and A B and for k?
b) Do these two functions give different probability densities if each is normalized?

a)

( ) ( ) ( ) ( )
( )
( )
( ) ( )
( )
+ cos cos sin sin
cos cos sin sin
0 0, giving . Therefore
cos cos sin sin 2 sin
2 sin 0
ik x ik x
x A e B e A k x B k x i A k x B k x
A k x B k x i A k x B k x
A B A B
x A k x A k x i A k x A k x iA k x
a iA k a
+
= = + + +
= + +
= + = =
= + + =
= =

This leads to the same condition on k, namely . k a n = The amplitude is now 2iA rather than
A.

b) The wave function after the imposition of the boundary conditions is
( ) ( )
2 sin .
ik x ik x
x A e e iA k x
+
= = After the normalization condition is imposed,
( ) ( )
2
2 2 iA iA
a
= . Therefore functions are indistinguishable, because both will give the same
probability densities when normalized.

P4.8) Calculate the probability that a particle in a one-dimensional box of length a is found
between 0.31a and 0.35a when it is described by the following wave functions:
a)
2
sin
x
a a
| |
|
\ .

b)
2 3
sin
x
a a
| |
|
\ .

What would you expect for a classical particle? Compare your results in the two cases with the
classical result.

a)

( ) ( )
( ) ( )
( ) ( )
2
0.35
0.35
2
0.31 0.31
1
Using the standard integral sin sin 2
2 4
2 2
sin sin
2 4
2 0.35 0.31
sin 0.70 sin 0.62
2 4 2 4
1
0.04 sin 0.62 sin 0.70 0.059
2
a
a
a a
y
by dy by
b
x x a x
P dx
a a a
a a a a
a

=

| | | |
= =
| |
\ . \ .

= +

= + =


4-7
b)

( ) ( )
( ) ( )
( ) ( )
2
0.35
2
0.31
1
2 4
2 3 2 0.35 0.31
sin sin 2.10 sin 1.86
2 12 2 12
1
0.04 sin 1.86 sin 2.10 0.0010
6
a
a
y
by dy by
b
x a a a a
P dx
a a a
=
| |
= = +
|

\ .
= + =

Because a classical particle is equally likely to be in any given interval, the probability will be
0.04 independent of the energy. In the ground state, the interval chosen is near the maximum
of the wave function so that the quantum mechanical probability is greater than the classical
probability. For the n = 3 state, the interval chosen is near a node of the wave function so that
the quantum mechanical probability is much less than the classical probability.

P4.9) Are the eigenfunctions of
H for the particle in the one-dimensional box also

eigenfunctions of the position operator x? Calculate the average value of x for the case where
n = 3. Explain your result by comparing it with what you would expect for a classical particle.
Repeat your calculation for n = 5 and, from these two results, suggest an expression valid for
all values of n. How does your result compare with the prediction based on classical physics?

No, they are not eigenfunctions because multiplying the function by x does not return the
function multiplied by a constant.

For n = 3,
( ) ( )
( )
( ) ( )
( ) ( )
* 2
0 0
2
2
2
2
2
0
2
2
2 3
sin
cos 2 sin 2
4 8 4
6 6
cos sin
2
3 4
3
4
8
cos 6 sin 6 c
2
4 72 12
a a
a
x
x x x x d x x d x
a a
bx x bx
x
x b x d x
b b
x x
x
x a a
x
x a
x
a
a
a
a
x
a

| |
= =
|
\ .
=

| | | |

| |
\ . \ .

=
| |
| |
|
|
\ .
\ .
= +

( ) ( )
2
2 2 2
os 0 0sin 0
2 1 1
0 0
72 12 4 72 72 2
a a
a

= + =

For n = 5,

4-8
( ) ( )
( )
( ) ( )
( ) ( )
* 2
0 0
2
2
2
2
2
0
2
2
2 5
sin
cos 2 sin 2
4 8 4
10 10
cos sin
2
5 4
5
4
8
cos 10 sin 10
2
4 200
a a
a
x
x x x x d x x d x
a a
bx x bx
x
x b x d x
b b
x x
x
x a a
x
x a
x
a
a
a
a
x
a
| |
= =
|
\ .
=

| | | |

| |
\ . \ .

=
| |
| |
|
|
\ .
\ .
=

( ) ( )
2
2 2 2
cos 0 0sin 0
2 1 1
0 0
20 200 20 4 200 200

2
a
a
a

+ = +

=

The general expression valid for all states is
2
a
x = . Classical physics gives the same result
because the particle is equally likely to be at any position. The average of all these values is
the midpoint of the box.

P4.10) Are the eigenfunctions of
H for the particle in the one-dimensional box also

eigenfunctions of the momentum operator p
x
? Calculate the average value of p
x
for the case
n = 3. Repeat your calculation for n = 5 and, from these two results, suggest an expression
valid for all values of n. How does your result compare with the prediction based on classical
physics?

For n = 3,
( ) ( )
( ) ( )
( )
( ) ( )
*
0 0
2
2 2
2 3 3 3
sin cos
cos
Using the standard integral sin cos
2
cos 3 cos 0
2 3 2 3 1 1
0
2 2 2 2
a a
d i x x
p x i x d x d x
d x a a a a
bx
b x b x d x
b
i i
p
a a b b a a b b

| |
| | | |
= =
| | |
\ . \ .
\ .
=

= = =

=
=
= =

For n = 5,
( ) ( )
( ) ( )
( )
( ) ( )
*
0 0
2
2 2
2 5 5 3
sin cos
cos
Using the standard integral sin cos
2
cos 5 cos 0
2 5 2 5 1 1
0
2 2 2 2
a a
d i x x
p x i x d x d x
d x a a a a
bx
b x b x d x
b
i i
p
a a b b a a b b

| |
| | | |
= =
| | |
\ . \ .
\ .
=

= = =

=
=
= =


4-9
This is the same result that would be obtained using classical physics. The classical particle is
equally likely to be moving in the positive and negative x directions. Therefore the average of
a large number of measurements of the momentum is zero for the classical particle moving in a
constant potential.

P4.11) It is useful to consider the result for the energy eigenvalues for the one-dimensional
box E
h n
ma
n
n
= =
2 2
2
8
1 2 3 , , , ,... as a function of n, m, and a.
a) By what factor do you need to change the box length to decrease the zero point energy by a
factor of 400 for a fixed value of m?
b) By what factor would you have to change n for fixed values of a and m to increase the
energy by a factor of 400?
c) By what factor would you have to increase a at constant n to have the zero point energies of
an electron be equal to the zero point energy of a proton in the box?

a)
( )
2
2
, 400; 20
n
n
a E a
E a a

= = =
b)
( )
2
2
, 400; 20
n
n
E n n
E n
n
= = =

c)

2 2
27
31
1 1
1.673 10 kg
42.9
9.109 10 kg
e e p p
p
e
p e
m a m a
m
a
a m
= = =

P4.12) Is the superposition wave function ( )
2
sin sin
n x m x
x
a a a

| | | |
= +
| |
\ . \ .
an
eigenfunction of the total energy operator for the particle in the box?
( )
2 2
2
2 2 2 2
2 2
2 2
sin sin
2
2 2
sin sin
8 8
d n x m x
H x
m d x a a a a
h n n x h m m x
ma a a ma a a

| | | |
= +
| |
\ . \ .

| | | |
= +
| |
\ . \ .
=

Because the result is not the wave function multiplied by a constant, the superposition wave
function is not an eigenfunction of the total energy operator.


4-10
P4.13) The function ( ) 1
x
x Ax
a
| |
=
|
\ .
is an acceptable wave function for the particle in the
one dimensional infinite depth box of length a. Calculate the normalization constant A and the
expectation values
2
and x x .
2
4 3
2 2 2
2
0 0
5 4 3 3 3 3 3
2 2 2
2
0 0
3
1 1 2
1
5 2 3 5 2 3 30
30
a a
a a
x x x
A x dx A x dx
a a a
x x x a a a a
A A A
a a
A
a
| |
= = +
|
\ .

= + = + =

=

( ) ( )
( ) ( )
2
*
3
0 0
4 5 6 4 4 4 4
3 2 3 3
0
2
2 * 2 2
3
0 0
5 6 7 5 5 5
3 2 3
0
30
1
30 2 30 2 30
4 5 6 6 5 4 60 2
30
1
30 30
5 3 7 5 3 7
a a
a
a a
a
x
x x x x dx x x dx
a a
x x x a a a a a
a a a a a
x
x x x x dx x x dx
a a
x x x a a a
a a a a

| |
= =
|

\ .

= + = + = =

| |
= =
|

\ .

= + = + =

5 2
3
30 2
105 7
a a
a
=

P4.14) Derive an equation for the probability that a particle characterized by the quantum
number n is in the first quarter ( 0
4
a
x ) of an infinite depth box. Show that this probability
approaches the classical limit as . n
( ) ( )
( )
2
0.25
0.25
2
0 0
1
2 4
2 2 2
sin sin
2 4
2 0 1 1
sin sin 0 sin
8 4 2 2 4 4 2 2
As , the second term goe
a
a
y
b y d y b y
b
n x x a n x
P dx
a a a n a
a a n a n
a n n n
n

=

| | | |
= =
| |
\ . \ .

| | | |
= + =
| |

\ . \ .

1
s to zero, and the probability approaches .
4

This is the classical value, because the particle is equally likely to be found anywhere in the
box.


4-11
P4.15) What is the solution of the time-dependent Schrdinger equation ( ) , x t for the total
energy eigenfunction

4
2 4
x
a
x
a
b g =
F
H
G
I
K
J
sin in the particle in the box model? Write
E
=
=

explicitly in terms of the parameters of the problem.
( ) ( ) ( )
( )
2
2 2 2
2 2
4
,
16
Because ,
8 8
2 4
, sin
Et
i
i t
ht
i
ma
x t x e x e
n h h
E
ma ma
x
x t e
a a
= =
= =
| |
=
|
\ .
=

P4.16) For a particle in a two-dimensional box, the total energy eigenfunctions are
( ) , sin sin
x y
y
x
n n
n y
n x
x y N
a b
= .
a) Obtain an expression for
,
x y
n n
E in terms of n
x
, n
y
, a, and b by substituting this wave function
into the two-dimensional analog of Equation (4.19).
b) Contour plots of several eigenfunctions are shown here. The x and y directions of the box lie
along the horizontal and vertical directions, respectively. The amplitude has been displayed as
a gradation in colors. Regions of positive and negative amplitude are indicated. Identify the
values of the quantum numbers n
x
and n
y
for plots af.

+
+ +
+
+
+
+
+
+
+
+
+
-
-
-
-
-
- -
-
-
-
-
-
a
b
c
d e
f


4-12
a)
2 2 2
2 2 2 2
2
2
2 2
2 2
4 4
sin sin sin sin
2
4 4
sin sin sin sin
2 2
y y
x x
y y y
x x x
n y n y
n x n x
m x a a a y a a a
n y n x n y
n x n x n x
m a a a a m a a a a

| |
| | | | | | | |
+
|
| | | |
|

\ . \ .
\ . \ . \ .

| | | | | |
| | | | | |
= +
| | | | | |
\ . \ . \ .
\ . \ . \ .

=
= =
( )
2 2 2
2 2
4
sin sin
8
x y y
x
h n n
n y
n x
ma a a a

+

| |
| |
=
| |
\ .
\ .

Because application of the total energy operator returns the wave function multiplied by a
constant, ( ) , sin sin
x y
y
x
n n
n y
n x
x y N
a b
= is an eigenfunction of the total energy operator.

b) From the result of part (a),
( )
2 2 2
, 2
8
x y
x y
n n
h n n
E
ma
+
=
a: n
x
= 1 n
y
= 1
b: n
x
= 2 n
y
= 3
c: n
x
= 3 n
y
= 1
d: n
x
= 2 n
y
= 2
e: n
x
= 1 n
y
= 5
f: n
x
= 2 n
y
= 1

P4.17) Normalize the total energy eigenfunction for the rectangular two-dimensional box,
( )
,
, sin sin
x y
y
x
n n
n y
n x
x y N
a b
| |
| |
=
| |
\ .
\ .

in the interval 0 , 0 . x a y b
( ) ( )
( )
( )
* 2 2 2
0 0 0 0
2
2 2 2
0 0
2
1 , , sin sin
sin 2
2 4
sin sin
sin sin 0 sin s
2 4 2 4
a b a b
y
x
a b
y
x
x y
x y
n y
n x
x y x y d x d y N d x d y
a b
x
x
x d x
n y
n x
N d x d y
a b
a a b a
N n n
n n

| |
| |
= =
| |
\ .
\ .
=
| |
| |
| |
\ .
\ .

=

( )
( )
2
in 0
4
4 4
and , sin sin
y
x
ab
N
n y
n x
N x y
ab ab a b

=

| |
| |
= =
| |
\ .
\ .

P4.18) Consider the contour plots of Problem P4.16.
a) What are the most likely area or areas dxdy to find the particle for each of the eigenfunctions
of
Hdepicted in plots af?


4-13
b) For the one-dimensional box, the nodes are points. What form do the nodes take for the
two-dimensional box? Where are the nodes located in plots af? How many nodes are there in
each contour plot?

a) What is the most likely point to find the particle for each of the eigenfunctions of
H depicted in plots ae?

The most likely location of the particle is the set of points at which the wave function has its
largest positive or negative value as indicated by the gray scale. There are 1, 6, 3, 4, 5, and 2
equivalent points in plots ae respectively.

b) For the one-dimensional box, the nodes are points. What form do the nodes take for the
two-dimensional box? Where are the nodes located in plots ae? How many nodes are there in
each contour plot?

The nodes are lines that lie between values at which the absolute magnitude of the wave
function reaches its maximum value. There are 0, 3, 2, 2, 4, and 1 nodes in plots ae,
respectively.

P4.19) Show by substitution into Equation (4.19) that the eigenfunctions of
H for a box with

lengths along the x, y, and z directions of a, b, and c, respectively, are
( )
, ,
, , sin sin sin
x y z
y
x z
n n n
n y
n x n z
x y z N
a b c
| |
| | | |
=
| | |
\ . \ .
\ .

b) Obtain an expression for
, ,
x y z
n n n
E in terms of n
x
, n
y
, n
z
and a, b, and c.

a)
2 2 2 2
2 2
2 2
2
sin sin sin sin sin sin
2 2
sin sin sin
2
y y
x x z z
y
x z
n y n y
n x n x n z n z
N N
m x a b c m y a b c
n y
n x n z
N
m z a b c

| | | | | | | | | | | |

| | | | | |

\ . \ . \ . \ .
\ . \ .
| | | | | |
| | |
\ . \ .
\ .
=
= =
=
2
2
2 2
2
2
sin sin sin sin sin sin
2 2
sin sin sin
2
y y y
x x x z z
y
x z z
n y n x n y
n x n x n x n z n z
N N
m a a b c m b a b c
n y
n x n x n z
N
m c a b c

| | | | | |
| | | | | | | | | |
+
| | | | | | | |
\ . \ . \ . \ . \ .
\ . \ . \ .
| |
| | | | | |
+
| | |
\ . \ \ .
\ .
= =
=
2
2 2 2
2 2 2
sin sin sin
8
y y
x x z z
n n y
n n x n n z h
N
m a b c a b c

|
.
| |
| |
| | | |
= + +
|
| | |
|
\ . \ .
\ .
\ .


4-14
Because application of the total energy operator returns the wave function multiplied by a
constant, ( )
, ,
, , sin sin sin
x y z
y
x z
n n n
n y
n x n z
x y z N
a b c
| |
| | | |
=
| | |
\ . \ .
\ .
is an eigenfunction of the
total energy operator.
b) Based on the result from part (a),
2
2 2 2
, , 2 2 2
8
x y z
y
x z
n n n
n
h n n
E
m a b c
| |
= + +
|
\ .

P4.20) Normalize the total energy eigenfunctions for the three-dimensional box in the interval
0 , 0 , 0 . x a y b z c
( ) ( )
( )
*
0 0 0
2 2 2 2
0 0 0
2
2 2 2 2
0 0
1 , , , ,
sin sin sin
sin 2
2 4
1 sin sin sin
a b c
a b c
y
x z
a b
y
x z
x y z x y z d x d y d z
n y
n x n z
N d x d y d z
a b b
x
x
x d x
n y
n x n z
N d x d y
a b b

=
| |
| | | |
=
| | |
\ . \ .
\ .
=
| |
| | | |
=
| |
\ . \ .
\ .

( ) ( ) ( )
( )
0
2 2
1 sin sin 0 sin sin 0 sin sin 0
2 4 2 4 2 4 8
8 8
and , sin sin sin
c
x y z
x y
y
x z
d z
a a b a c a abc
N n n n N
n n r
n y
n x n z
N x y
abc abc a b c

|

= =

| |
| | | |
= =
| | |
\ . \ .
\ .

P4.21) In discussing the Boltzmann distribution in Chapter 2, we used the symbols g
i
and g
j
to
indicate the degeneracies of the energy levels i and j. By degeneracy, we mean the number of
distinct quantum states (different quantum numbers) all of which have the same energy.
a) Using your answer to Problem P4.16a, what is the degeneracy of the energy level
5
8
2
2
h
ma
for
the square two-dimensional box of edge length a?
b) Using your answer to Problem P4.19b, what is the degeneracy of the energy level
9
8
2
2
h
ma
for
a three-dimensional cubic box of edge length a?

a) What is the degeneracy of the energy level
2
2
5
8
h
ma
for the square two-dimensional box?
The only pairs n
x
, n
y
that satisfy the equation
2 2
5
x y
n n + = are 2, 1 and 1, 2. Therefore the
degeneracy of this energy level is 2.
b) What is the degeneracy of the energy level
2
2
9
8
h
ma
for a three-dimensional cubic box of edge
length a?

4-15

The only trios of nonzero numbers n, q, r that satisfy the equation
2 2 2
9
x y z
n n n + + = are 2, 2, 1;
2, 1, 2; and 1, 2, 2. Therefore the degeneracy of this energy level is 3.

P4.22) This problem explores under what conditions the classical limit is reached for a
macroscopic cubic box of edge length a. An argon atom of average translational energy 3/2 kT
is confined in a cubic box of volume V = 0.500 m
3
at 298 K. Use the result from
Equation (4.25) for the dependence of the energy levels on a and on the quantum numbers n
x
,
n
y
, and n
z
.
a) What is the value of the reduced quantum number
2 2 2
x y z
n n n = + + for T = 298 K?
b) What is the energy separation between the levels a and a + 1? (Hint: Subtract E
a+1
from E
a

before plugging in numbers.
c) Calculate the ratio
E E
k T
+

1
and use your result to conclude whether a classical or
quantum mechanical description is appropriate for the particle.
( )
( )
( )
( )
( )
2
2 2 2
, , 2
2
, ,
2 2 2
2
2
, ,
2 2 2
2
2
27 1 3 23 1 3
2
34
10
8
8
8
839.95amu 1.661x10 kg(amu) 0.500m 1.5 1.381 10 J K 298 K
6.626 10 J s
6.86 10
x y z
x y z
x y z
n n n x y z
n n n
x y z
n n n
x y z
h
E n n n
ma
ma E
n n n
h
ma E
n n n
h
= + +
+ + =
= + + =

=
=

b) What is the energy separation between the levels and + 1? (Hint: Subtract E
+1
from E

before plugging in numbers.
[ ]
( )
( )
( ) ( )
( )
2
2
2
2
1
2 2
2
34 10
31
2
27 1 3 3
2 1
1
8 8
6.626 10 Js 2 6.86 10 +1
= 1.80 10 J
8 39.95amu 1.661 10 kg(amu) 0.500m
h
h
E E
ma ma

+
= + =

=

c) Calculate the ratio
1
E E
k T
+

and use your result to conclude whether a classical or quantum
mechanical description is appropriate for the particle.

31
7 1
23 1
1.80 10 J
4.44 10
1.361 10 J K 298 K
E E
k T

+

= =


4-16
Because E<<kT, a classical description is appropriate.

P4.23) Generally, the quantization of translational motion is not significant for atoms because
of their mass. However, this conclusion depends on the dimensions of the space to which they
are confined. Zeolites are structures with small pores that we describe by a cube with edge
length 1 nm. Calculate the energy of a H
2
molecule with n
x
= n
y
= n
z
= 10. Compare this
energy to kT at T = 300 K. Is a classical or a quantum description appropriate?
( )
( ) ( )
( )
2
2 2 2
, ,
2
2
34 2 2 2
21
2
27 1 9
8
6.626 10 J s 10 10 10
4.92 10 J
82.016amu 1.661x10 kg(amu) 10 m
x y z
n n n x y z
h
E n n n
ma

= + +
+ +
= =

Using the results of P4.22, the ratio of the energy spacing between levels and kT determines if
a classical or quantum description is appropriate.
[ ]
( )
( )
( )
( ) ( )
( )
2
2
2
2 2 2 2
1
2 2
2
34
22
2
27 1 9
22
1
23 1
2 1
1 where
8 8
6.626 10 Js 300+1
= 3.00 10 J
8 2.016amu 1.661 10 kg(amu) 10 m
3.00 10 J
0.073
1.361 10 J K 298 K
x y z
h
h
E E n n n
ma ma
E E
kT

+

+
= + = = + +
=

= =

Because this ratio is not much smaller than one, a quantum description is appropriate.

P4.24) Two wave functions are distinguishable if they lead to a different probability density.
Which of the following wave functions are distinguishable from sin cos ? i +
a) ( )
2 2
sin cos
2 2
i i
| |
+ +
|
\ .
b) ( ) sin cos i i +
c) ( ) sin cos i + d) ( )
2 2
sin cos
2 2
i i
| |
+ +
|
\ .

e) ( ) sin cos i f)
i
e

Two wave functions
1 2
and are indistinguishable if
1 2
* *
1 2
. = For the wave function in
the problem, ( )( ) ( )
2 2
sin cos sin cos sin cos 1 i i + = + = .

a) ( ) ( ) ( )
2 2
2 2 2 2
sin cos sin cos sin cos 1
2 2 2 2
i i i i
| | | |
+ + = + =
| |
\ . \ .

indistinguishable.


4-17
b) ( ) ( ) ( )
2 2
sin cos sin cos sin cos 1 i i i i + = + =

indistinguishable

c) ( ) ( ) ( )
2 2
sin cos sin cos sin cos 1 i i + = + =

indistinguishable

d) ( ) ( ) ( )
2 2
2 2 2 2
sin cos sin cos sin cos 1
2 2 2 2
i i i i
| | | |
+ + = + =
| |
\ . \ .

indistinguishable

e) ( ) ( ) ( )
2 2
sin cos sin cos sin cos 1 i i + = + =
indistinguishable

f) 1
i i
e e

= indistinguishable

P4.25) Suppose that the wave function for a system can be written as
x x x
i
x b g b g b g b g = + +
+ 1
2
1
4
3 2
4
1 2 3
and that
1 2 3
x x x b g b g b g , and are normalized
eigenfunctions of the operator
E
kinetic
with eigenvalues E
1
, 3E
1
, and 7E
1
, respectively.
a) Verify that ( ) x is normalized.
b) What are the possible values that you could obtain in measuring the kinetic energy on
identically prepared systems?
c) What is the probability of measuring each of these eigenvalues?
d) What is the average value of E
kinetic
that you would obtain from a large number of
measurements?

a) We first determine if the wave function is normalized.
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) ( ) ( ) ( )
( ) ( ) ( )
1 2 3
1 1 3
2 3
* * * *
1 2 3
* * *
2 3 1 1
* *
3 2
1 1 3 2 3 2
4 16 4 4
1 3 2 3 2 1

4 16 16 2
3 2 3 2

8 8
i i
x x dx x x dx x x dx x x dx
i i
x x dx x x dx x x dx x
i i
x x dx x

| | | |
+
= + +
| |
\ . \ .
+
+ + +
+
+ +

( ) x dx

All but the first three integrals are zero because the functions ( ) ( ) ( )
1 2 3
, , and x x x are
orthogonal. The first three integrals have the value one, because the functions are normalized.
Therefore,
( ) ( )
*
1 1 3 2 3 2 1 1 11
1
4 16 4 4 4 16 16
i i
x x dx
| | | |
+
= + + = + + =
| |
\ . \ .


4-18
b) The only possible values of the observable kinetic energy that you will measure are those
corresponding to the finite number of terms in the superposition wave function. In this case,
the only values that you will measure are E
1
, 3E
1
, and 7E
1
.

c) For a normalized superposition wave function, the probability of observing a particular
eigenvalue is equal to the square of the magnitude of the coefficient of that kinetic energy
eigenfunction in the superposition wave function. These coefficients have been calculated
above. The probabilities of observing E
1
, 3E
1
, and 7E
1
are , 1/16, and 11/16, respectively.

d) The average value of the kinetic energy is given by
1 1 1 1
1 1 11
3 7 5.25
4 16 16
i i
E PE E E E E = = + + =

7-1
Chapter 7: A Quantum Mechanical Model for the Vibration
and Rotation of Molecules


Q7.1) What is the functional dependence of the total energy of the quantum harmonic
oscillator on the position variable x?

It is independent of x. Both the kinetic and potential energy depend on x, but the
total energy is independent of x.

Q7.2) The two linearly independent total energy eigenfunctions for rotation in two
dimensions are
+

= =

b g b g
1
2
1
2
e e
im im
l l
and . What is the difference in
motion for these two solutions? Explain your answer.

From Section 7.4, the angular momentum operator for rotation in two dimensions
is
l i
h if we apply this operator to the two eigenfunctions

+

= =

b g b g
1
2
1
2
e e
im im
l l
and ,
( ) ( ) ( )
( ) ( ) ( )
= and
2
=
2
l
l
im l
l
im l
l
m
l i e m
m
l i e m

+ + +
= =

= =
h
h h
h
h h

Therefore, the direction of rotation is opposite for these two eigenfunctions.

Q7.3) Spatial quantization was discussed in Supplemental Section 7.8. Suppose that we
have a gas consisting of atoms, each of which has a nonzero angular momentum. Are all
of their angular momentum vectors aligned?

No. Only the application of an eternal field that makes the energy depend on the
component of the angular momentum will lead to spatial quantization. Even in
this case, not all molecules will have the same component of angular momentum
along the field direction. The number of molecules with a particular value for the
component of angular momentum along the field direction will be determined by
the Boltzmann distribution.

Chapter 7/A Quantum Mechanical Model for the Vibration and Rotation of Molecules

7-2
Q7.4) Why can the angular momentum vector lie on the z axis for two-dimensional
rotation in the x-y plane but not for rotation in three-dimensional space?

For rotation in two dimensions, the angular momentum vector has only one
component, and the vector is perpendicular to the plane of rotation. For rotation
in three dimensions, the angular momentum vector has three components.
Because the corresponding angular momentum operators do not commute, all
three components of the angular momentum cant be known simultaneously.
Therefore, the angular momentum vector cant lie on the z axis, because this
requires that the x and y components are known to be zero, and the z component is
known through the value of L
2
.

Q7.5) The zero point energy of the particle in the box goes to zero as the length of the
box approaches infinity. What is the appropriate analogue for the quantum harmonic
oscillator?

The force constant k goes to zero. This corresponds in a diatomic molecule to a
very weak bond, such as for Ar
2
.

Q7.6) Explain in words why the amplitude of the total energy eigenfunctions for the
quantum mechanical harmonic oscillator increases with |x| as shown in Figure 7.4.

The velocity of the particle goes through zero at the classical turning point.
Therefore, it spends more time near the turning point than in the same interval
near x = 0. Therefore, the probability density must be highest at the classical
turning point.

Q7.7) Why does the energy of a rotating molecule depend on l, but not on m
l
?

The energy depends only on the frequency of rotation, and not on the orientation
of the rotation axis. The quantum number l determines the speed, and m
l

determines the orientation of the rotational axis.

Q7.8) Are the real functions listed in Equations (7.34) and (7.35) eigenfunctions of l
z
?
Justify your answer.

No. They are formed by the combination of and .
l l
m m
l l
Y Y Therefore, the
functions are eigenfunctions of
2

and , H l but not of
.
z
l

Q7.9) Why is only one quantum number needed to characterize the eigenfunctions for
rotation in two dimensions, whereas two quantum numbers are needed to characterize the
eigenfunctions for rotation in three dimensions?

For rotation in two dimensions, the angular momentum vector is perpendicular to
the plane of rotation, and therefore has only one component. Only one quantum

7-3
number is needed to describe this vector. By contrast, the angular momentum
vector for 3-D rotation has three components. However, the commutation
relations say that we can only know the magnitude of the vector and one of its
components simultaneously. Two quantum numbers are needed to describe this
vector.

Q7.10) What makes the z direction special so that we say that
2
l ,
$
H , and
z
l commute,
whereas the individual angular momentum operators
z
l ,
y
l and
x
l dont commute?

There is nothing special about the z direction. We choose the z direction because the
angular momentum operator for this component has a simple form. We can rotate our
coordinate system to make any direction that we choose to lie along the z axis. The
important point is that we can know the magnitude of the angular momentum and only
one of its components.

Problems

P7.1) The force constant for a H
19
F molecule is 966 N m
1
.
a) Calculate the zero point vibrational energy for this molecule for a harmonic potential.
b) Calculate the light frequency needed to excite this molecule from the ground state to
the first excited state.

a)
1
34
1
27 1
19
1
20
0 1
1 3 966 N m
1+ = 1.055 10 J s
1.0078 18.9984
2 2
1.66x10 kgamu
1.0078+18.9984
1.23 10 J
1 1
4.10 10 J
2 3

=

=

= = =

h
k
E h
E
k
E E

b)
19 20
14 1 1 0
34
1.23 10 J 4.10 10 J
= 1.24 10 s
6.626 10 J s

= =
E E
h

P7.2) By substituting in the Schrdinger equation for the harmonic oscillator, show that
the ground-state vibrational wave function is an eigenfunction of the total energy
operator. Determine the energy eigenvalue.


7-4
( )
( ) ( )
2
2
2 2
2 2
2
2 2
2
1 4
1
1 4
1
2
2
2
1 4 1 4
1 1 2 2 2 2
2 2
2
1 4 1 4
1 1 2 2
2 2
2 2
2 2
2 2 2 2
2 2
n
n n n
x
x
x x
x x
d x
k x
x E x
d x
d x e
d e
k x k x
e e
d x d x
k x
e x e

+ =

+ = +

= +

h
h h
h
( )
2
2 2 2 2
2 2
1 4
1
2
1 4 1 4 1 4 1 4
1 1 1 1 2 2 2 2 2
2 2
2 2 2 2
1 4 1 4
1 1 2
2 2
1 1 1 2
2 2 2
with
2 2 2
x
x x x x
x x
e
x
e x e e e
k k k
e e E x E

= + =

= = = =

h h h
h h h
h

P7.3) Show by carrying out the appropriate integration that the total energy
eigenfunctions for the harmonic oscillator ( )
2
1 4
1
2
0
x
x e

=

and

2
1 4
2
1
2
4
2 1
2
x x e
x
b g c h
=
F
H
G
I
K
J

are orthogonal over the interval < < x and that
2
x b g is normalized over the same interval. In evaluating integrals of this type,
f x d x b g
z
= 0 if f(x) is an odd function of x and f x d x f x d x b g b g

z z
= 2
0
if f(x) is an
even function of x.
2
2
2
1
0
1
2
0
1 3 5 (2 1)
We use the standard integrals and
2
4
n a x
n n
ax
n
x e d x
a a
e dx
a
=

=

( ) ( ) ( )
( ) ( )
2 2
2 2
1 4 1 4
1 1
* 2
2 2
2 0
1 4 1 4
2 2
2 2
2 2
0
1 4
2
2
2 1
4
2 1 2 2 1
4 4
1 1
2 0
4 4 2
x x
x x
x x d x x e e d x
x e d x x e d x

=

= =

= =


7-5
( ) ( ) ( ) ( )
( )
2 2
2
1 4 1 4
1 1
* 2 2
2 2
2 2
1 2
2 4 2
0
1 2 1 2
2
3 2 2
2 1 2 1
4 4
2 4 4 1
4
3 1 1 3 1
2 4 4 2 1 1
4 2 2 2 4 2 2
x x
x
x x d x x e x e d x
x x e d x

=

= +

= + = + =

P7.4) Evaluate the average kinetic and potential energies, E E
kinetic potential
and , for the
ground state (n = 0) of the harmonic oscillator by carrying out the appropriate
integrations.
2
2
2
1
0
1
2
0
1 3 5 (2 1)
2
4
n a x
n n
ax
n
x e d x
a a
e dx
a
=

=

( ) ( )
2 2
* 2
0 0
1 2 1 2
2 2
0
1 2
1
2
1

2
1 1
=
4 4 4
potential
x x
E x k x x dx
k x e dx k x e dx
k
k k

=

= =

= =

h

( ) ( )
( )
2 2
2
2 2
*
0 0 2
1 4 1 4
1 1 2 2
2 2
2
1 2
2
2
0
2

2

kinetic
x x
x
E x x dx
x
e e dx
x
e x dx

h
h
h

1 2
2 2
2
2

4 2 4

4 4

k k

= =

= =
h h
h h
h


7-6
P7.5) Evaluate the average kinetic and potential energies, E E
kinetic potential
and , for the
second excited state (n = 2) of the harmonic oscillator by carrying out the appropriate
integrations.
2
2
2
1
0
1
2
0
1 3 5 (2 1)
2
4
n a x
n n
ax
n
x e d x
a a
e dx
a
=

=

( ) ( ) ( )
( ) ( )
( )
2 2
2
*
2 2
1 4 1 4
1 1
2 2 2
2 2
1 2
2
2 2
1
2 1 2 1
4 2 4
1
2 1
2 4
potential
x x
x
E x V x x dx
x e k x x e dx
k x x e dx

=

=

=

( )
2
1 2
2 6 4 2
0
1 2
2
4 3 3 2 2
4 4
4
15 3 1
4 4
4 2 2 2
5 5
=
4 4
x
k x x x e dx
k
k k

= +

= +

=
h

( ) ( )
( ) ( )
( ) ( )
2 2
2 2
2 2
*
2 2 2
1 4 1 4
1 1 2 2
2 2
2 2
2
1 4 1 4
1 1 2
2 2 4 2
2 2
2
2 1 2 1
4 2 4
2 1 2 11 5
4 2 4
kinetic
x x
x x
E x x dx
x
x e x e dx
x
x e x x e dx

= +

h
h
h

( )( )
( )
2
2
1 2
2
2 2 4 2
0
1 2
2
3 6 2 4 2
0
2 1 2 11 5
4
4 24 21 5
4
x
x
x x x e dx
x x x e dx

= +

= +

h
h

1 2
2
3 2
4 3 3 2 2
2
15 3 21 1
4 24 5
4 2 2 2 2
5 5
4 4
k

= +

= =
h
h
h


7-7
P7.6) Evaluate the average vibrational amplitude of the quantum harmonic oscillator
about its equilibrium value, x , for the ground state (n = 0) and first two excited states
(n = 1 and n = 2). Use the hint about evaluating integrals in Problem P7.3.

( ) ( )
2
*
n n n
x x x d x x d x

= =

. Because
( )
2
n
is an even function of x for
all n, the product
( )
2
n
x is an odd function of x. Therefore, x = 0 for all n.

P7.7) Evaluate the average linear momentum of the quantum harmonic oscillator, p
x
,
for the ground state (n = 0) and first two excited states (n = 1 and n = 2). Use the hint
about evaluating integrals in Problem P7.3.
2
2
2
1
0
1
2
0
1 3 5 (2 1)
2
4
n a x
n n
ax
n
x e d x
a a
e dx
a
=

=

( )
( )
2 2
2
*
1 4 1 4
1 1
2 2
1 2
for 0,
x n n
x x
x
x
x
d
p x i d x
d x
d
n p e i e d x
d x
p i x e d x

=

= =

=

h
h
h

Because the integrand is an odd function of , 0 for 0.
x
x p n = =
( ) ( )
2 2
2
1 4 1 4
1 1 3 3
2 2
1 2
3
2
4 4
for 1,
4
1
x x
x
x
x
d
n p x e i x e d x
d x
p i x x e d x

= =

=

h
h

x
x p n = =
( ) ( )
( ) ( ) ( )
( ) ( )
2 2
2
2
1 4 1 4
1 1
2 2
2 2
1 2
2 2 3
1 2
3 5 2 3
for 2, 2 1 2 1
4 4
2 1 2 4
4
4 12 5
4
x x
x
x
x
x
x
d
n p x e i x e d x
d x
p i x e x x x d x
p i e x x x d x

= =

= + +

= +

h
h
h

x
x p n = =
The result is general. 0 for all values of .
x
p n =

7-8

P7.8) Evaluate the average of the square of the vibrational amplitude of the quantum
harmonic oscillator about its equilibrium value,
2
, x for the ground state (n = 0) and
first two excited states (n = 1 and n = 2). Use the hint about evaluating integrals in
Problem P7.3.
2
2
2
1
0
1
2
0
1 3 5 (2 1)
2
4
n a x
n n
ax
n
x e d x
a a
e dx
a
=

=

( )( )
( )
2 2
2 2
2 * 2
1 4 1 4
1 1
2 2
2 2
1 2 1 2
2 2 2
0
for 0,
2
n n
x x
x x
x x x d x
n x e x e d x
x x e d x x e d x

=

= =

= =

x
k
2
1 2
2
2
1
2
1
2
2
=
F
H
G
I
K
J
= =

h

( )
2 2
2 2
1 4 1 4
1 1 3 3
2 2
2 2
1 2 1 2
3 3
2 4 4
0
1 2
3
2
3 2
4 4
for 1,
4 4
2
4 3 3 3
2
2 2 2
x x
x x
n x x e x x e d x
x x e d x x e d x
x
k

= =

= =

= = =

h

( ) ( ) ( )
( ) ( )
2 2
2 2
1 4 1 4
1 1
2 2 2 2
2 2
1 2 1 2
2 2 6 4 2 2 6 4 2
0
for 2, 2 1 2 1
4 4
4 4 2 4 4
4 4
x x
x x
n x x e x x e d x
x x x x e d x x x x e d x

= =

= + = +

x
k
2
1 2
2
4 3 3 2 2
2
4
4
15
2
4
3
2
1
2
5
2
5
2
=
F
H
G
I
K
J
+
F
H
G
I
K
J
= =

h

P7.9) Evaluate the average of the square of the linear momentum of the quantum
harmonic oscillator
2
,
x
p for the ground state (n = 0) and first two excited states (n = 1
and n = 2). Use the hint about evaluating integrals in Problem P7.3.


7-9
2
2
2
1
0
1
2
0
1 3 5 (2 1)
2
4
n a x
n n
ax
n
x e d x
a a
e dx
a
=

=

( ) ( )
( )
2 2
2
2
2 * 2
0 0 2
1 4 1 4
1 1 2
2
2 2
2
1 2
2 2
0

For = 0

x
x x
x
d
p x x dx
d x
n
d
e e dx
d x
e x dx

=

=

=

h
h
h

=
F
H
G
I
K
J

F
H
G
I
K
J
= = h h h
2
1 2
2
4 2 2
1
2

k

( ) ( )
( )
2 2
2
2
2 * 2
1 1 2
1 4 1 4
1 1 3 2 3
2
2 2
2
1 2
3
2 2 4 2
For = 1
4 4

4
3
x
x x
x
n
p x x dx
x
xe xe dx
x
x x e dx

h
h
h

=
F
H
G
I
K
J

=
F
H
G
I
K
J
L
N
M
O
Q
P

L
N
M
O
Q
P
F
H
G
I
K
J
= =
z
h
h
h h
2
3
1 2
2 4 2
2
3
1 2
2
2
2
4
3
4 3
4
3
1
2
3
2
3
2
2
x x e dx
k
x
c h


7-10
( ) ( )
( ) ( )
( ) ( )
2 2
2
2
2
1 4 1 4
1 1 2
2 2 2 2
2 2
2
1 2
2 2 2 4 2
1 2
2 2 2 4 2
0
1 2
2
0
For = 2,
2 1 2 1
4 4
2 1 2 11 5
4
2 2 1 2 11 5
4
2 4
4
x x
x
x
x
x
n
p x e x e dx
x
x e x x dx
x e x x dx
e

= +

= +

=

h
h
h
h
( )
4 6 3 4 2 2
24 21 5 x x x dx +

1 2
2 3 2
4 3 3 2 2
2
15 3 21 1
2 4 24 5
4 2 2 2 2
5 5
2 2
k

= +

= =
h
h h

P7.10) Using your results for Problems P7.6 through P7.9, calculate the uncertainties in
the position and momentum
p x
p p x x
2 2
2
2 2
2
= = and for the ground state
(n = 0) and first two excited states (n = 1 and n = 2) of the quantum harmonic oscillator.
Compare your results with the predictions of the Heisenberg uncertainty principle.
2 2
2 2 2 2
2
2
2 2
and
1 1
For = 0, 0
2 2
0
2 2
1 1
2 2
p x
p
x
p x
p p x x
n k k
k k
p x

= =
= =
= =
= =
h h
h h
h h

2
2
2 2
3 3
For = 1, 0
2 2
3 3
0
2 2
3 1
2 2
p
x
p x
n k k
k k
p x

= =
= =
= =
h h
h h
h h


7-11
2
2
2 2
5 5
For = 2, 0
2 2
5 5
0
2 2
5 1
2 2
p
x
p x
n k k
k k
p x

= =
= =
= =
h h
h h
h h

P7.11) The vibrational frequency of
1
H
35
Cl is 8.963 x 10
13
s
1
. Calculate the force
constant of the molecule. How large a mass would be required to stretch a classical
spring with this force constant by 1.00 cm? Use the gravitational acceleration on Earth at
sea level for this problem.
( )
2 2
27
2
2 13 1
2
2 2
2
1
; 4
2
1.008 34.969 1.661 10 kg
4 amu 8.963 10 s
1.008 34.969 amu
516 kg s
516 kg s 10 m
0.525 kg
9.81 m s
k
k
k
k
F kx mg
kx
m
g

= =

=
+
=
= =
= = =

P7.12) Two 1.00-g masses are attached by a spring with a force constant k = 500 kg s
2
.
Calculate the zero point energy of the system and compare it with the thermal energy kT.
If the zero point energy were converted to translational energy, what would be the speed
of the masses?
3 1 2
1 2
34 2
32
0 3
32
11 0
23 1
2 32
32
15 1
3
0.500 10 kg
2
1.055 10 J s 500 kg s
5.28 10 J
2 2 0.500 10 kg
5.28 10 J
1.27 10
300 K 1.381 10 J K
1
v 5.28 10 J
2
2 5.28 10 J
v = 7.27 10 m s
2.00 10 kg
m m m
m m
k
E
E
kT
m
= = =
+
= = =
= =

=

=
h

P7.13) Use x
2
as calculated in Problem P7.8 as a measure of the vibrational
amplitude for a molecule. What fraction is x
2
of the 127-pm bond length of the HCl

7-12
molecule for n = 0, 1, and 2? The force constant for the
1
H
35
Cl molecule is 516 N m
1
.
Use your results from Problem P7.8 in this problem.

For n = 0,
1
2
1
34 2
2 12
1 27 1
2
12
2
12
1.055 10 J s
7.59 10 m
2 1.0078 34.9688
2 516 N m 1.66 10 kgamu
1.0078 + 34.9688
7.59 10 m
= 5.97 10
bondlength 127 10 m
x
k
x

= = =

h

For n = 1
1
2
1
2 34
2 11
1 27 1
2
11
12
3 3 1.055 10 J s
1.31 10 m
2 1.0078 34.9688
2 516 N m 1.66 10 kgamu
1.0078 + 34.9688
1.31 10 m
0.103
bondlength 127 10 m
x
k
x

= = =
= =
h

For n = 2
1
2
1
2 34
2 11
1 27 1
2
11
12
5 5 1.055 10 J s
1.70 10 m
2 1.0078 34.9688
2 516 N m 1.66 10 kgamu
1.0078 + 34.9688
1.70 10 m
0.134
bondlength 127 10 m
x
k
x

= = =
= =
h

P7.14)
1
H
35
Cl has a force constant k = N m
1
and a moment of inertia of 2.644 10
47

kg m
2
. Calculate the frequency of the light corresponding to the lowest energy pure
vibrational and pure rotational transitions. In what regions of the electromagnetic
spectrum do the transitions lie?

7-13
2
13 1
27
1 1 516 kg s
8.963 10 s
1.008 34.969 1.661 10 kg 2 2
amu
1.008 34.969 amu
This frequency lies in the infrared region of the eletromagnetic spectrum.
The lowest energy transition is = 0 = 1.
k
J J
= = =

( )
( )
2
34
2 2
22
2 2 47 2
0 0
11 1
1.055 10 J s
2 1 4.20 10 J
2 2.644 10 kg m
6.35 10 s
This frequency lies in the microwave region of the eletromagnetic spectrum.
rot
rot
E J
r r
E
h

= + = = =
= =
h h

P7.15) The vibrational frequency for N
2
expressed in wave numbers is 2358 cm
1
. What
is the force constant associated with the N N triple bond? How much would a classical
spring with this force constant be elongated if a mass of 1.00 kg were attached to it? Use
the gravitational acceleration on Earth at sea level for this problem.
( )
( )
2
27
2
10 1 1
1
1
2
so 2
14.01amu 14.01amu 1.661 10 kg
2 2.998x10 cm s 2358cm
2 14.01amu amu
2299 Nm
k
c
k c
k
k

= =
=

=
=
%
%

2
3
1
1.00kg 9.81ms
= 4.28 10 m
2299 Nm
F mg
x
k k
= = =

P7.16) The force constant for the
1
H
35
Cl molecule is 516 N m
1
. Calculate the
vibrational zero point energy of this molecule. If this amount of energy were converted to
translational energy, how fast would the molecule be moving? Compare this speed to the
root mean square speed from the kinetic gas theory,
3
rms
kT
m
= v for T = 300 K.
1
34 20
27 1
1 1 516 N m
1.055 10 J s = 2.97 10 J
1.0078 34.9688
2 2
1.66 10 kgamu
1.0078 + 34.9688
k
E

= =

h
The speed if converted to translational energy would be
( )
20
1
27 1
2 2 2.97 10 J
v = 997 ms
1.0078 + 34.9688 1.66x10 kgamu
E
m

= =

The average speed from the kinetic gas theory is

7-14
( )
23 1
1
rms
27 1
1
1
rms
3 3 1.381 10 J K 300 K
v = 456ms
1.0078 + 34.9688 1.66 10 kgamu
v
997ms
2.19
v 456ms
kT
m

= =

= =

P7.17) A gas-phase
1
H
19
F molecule, with a bond length of 91.7 pm, rotates in a three-
dimensional space.
a) Calculate the zero point energy associated with this rotation.
b) What is the smallest quantum of energy that can be absorbed by this molecule in a
rotational excitation?

a) There is no zero point energy because the rotation is not constrained.

b) The smallest energy that can be absorbed is
( )
( )
2
34
2 2
2
27 1 12
22
2 1.055x10 J s
( 1) 1(1 1)
1.0078 18.9984
2 2
2 1.66 10 kgamu 91.7 x10 m
1.0078 + 18.9984
8.33 10 J
E J J
I I
E
= + = + =

=
h h

P7.18) A
1
H
19
F molecule, with a bond length 91.7 pm, absorbed on a surface rotates in
two dimensions.
a) Calculate the zero point energy associated with this rotation.
b) What is the smallest quantum of energy that can be absorbed by this molecule in a
rotational excitation?

a) There is no zero point energy because the rotation is not constrained.

b) The smallest energy that can be absorbed is
( )
( )
2
34
2 2 2
2
27 1 12
22
1.055 10 J s
1.0078 18.9984
2 2
2 1.66 10 kgamu 91.7 10 m
1.0078 + 18.9984
4.17 10 J
l
m
E
I I
E
= = =

=
h h

P7.19) The moment of inertia of
1
H
35
Cl is 2.64410
47
kg m
2
. Calculate
rot
E
kT
for
J = 0, 5, 10, and 20 at 298 K. For which of these values of J is 1
rot
E
kT
?


7-15
( )
2
34
2 2
22
47 2
0
22 21
5
21
5
23 1
22
10
1.055 10 J s
( 1) 1(1 1) ( 1) 2.089 10 ( 1)
2 2 2 2.664 10 kg m
0
30 2.089 10 J = 6.267 10 J
6.267 10 J
1.51
1.381 10 J K 298 K
110 2.089 10 J = 2.297 10
J
J
J
J
E J J J J J J
I I
E
E
E
kT
E
=

=
= + = + = + = +

=
=
= =

=
h h
20
20
10
23 1
22 20
20
20
20
23 1
J
2.528 10 J
5.55
1.381 10 J K 298 K
20 21 2.089 10 J = 8.774 10 J
8.774 10 J
21.2
1.381 10 J K 298 K
J
J
J
E
kT
E
E
kT
=

=
= =

=
= =

1
rot
E
kT
for J = 5.

P7.20) Using the Boltzmann distribution, calculate
0
J
n
n
for
1
H
35
Cl for the J values of
Problem P7.19 at T = 298 K. Does
0
J
n
n
go through a maximum as J increases? If so, what
can you say about the value of J corresponding to the maximum?

( )
( )
( ) [ ]
( ) ( )
( ) ( )
( ) ( )
0
0
0
0
21 23 1 5
0
20 23 1 10
0
20 23 1 20
0
2 1 2 1 exp
1
2 5 1 exp 6.267 10 J 1.381 10 J K 298 K 2.42
2 10 1 exp 2.297 10 J 1.381 10 J K 298 K 0.082
2 20 1 exp 8.774 10 J 1.381 10 J K 2
J
E E kT
J
J
n
J e J E kT
n
n
n
n
n
n
n
n
n

= + = +
=

= + =

= + =

= +
8
98 K 2.60 10

=

0
J
n
n
goes through a maximum because it has a value greater than one for J = 5. You can
only conclude that J
max
< 10.


7-16
P7.21) By substituting in the Schrdinger equation for rotation in three dimensions,
show that the rotational wave function
( )
1/ 2
2
5
3cos 1
16

is an eigenfunction of the
total energy operator. Determine the energy eigenvalue.

( ) ( )
( )
( ) ( )
2
2
2 2 2
0
1/ 2 1/ 2
2 2 2
2
2 2 2
0
2
2
0
, ,
1 1
sin ,
2 sin sin
5 5
3cos 1 3cos 1
16 16
1 1
sin
2 sin sin
5
2 16
Y Y
EY
r
r
r

+ =

+

=
h
h
h
( ) ( ) ( )
{ } ( ) ( ) ( )
1/ 2 1/ 2
2
2 3 2
2
0
1/ 2 1/ 2 1/ 2
2 2 2
2 2 2 2
2 2 2
0 0 0
1 5 1
6cos sin 6sin 12cos sin
sin 2 16 sin
5 5 6 5
6 1 cos 12cos 6 18cos 3cos 1
2 16 2 16 2 16
The energy
r
r r r

= = =

h
h h h
2 2
2
0
3
eigenvalue is , corresponding to ( 1) with = 2.
2
l
E l l l
r I
= +
h h

P7.22) Show by carrying out the necessary integration that the eigenfunctions of the
Schrdinger equation for rotation in two dimensions,
1 1
and ,
2 2
l l
im in
l l
e e m n

are
orthogonal.
1
2
2 1 2 0
2
0
2
0
2

F
H
G
I
K
J
= +
= + =
z z
e e d m n i m n d
m n i m n
m n
im in
l l l l
l l l l
l l
l l

1
2
1
2
because is an integer
cos sin
cos sin
b g b g c h
b g b g c h
b g

P7.23) In this problem you will derive the commutator

, .
x y z
l l i l

=

h
a) The angular momentum vector in three dimensions has the form
x y z
l l l = + + l i j k
where the unit vectors in the x, y, and z directions are denoted by , , and i j k.
Determine l
x
, l
y
, and l
z
by expanding the 3 3 cross product l r p. = The vectors
and r p are given by r k x y z = + + i j and .
x y z
p p p = + + p i j k
b) Substitute the operators for position and momentum in your expressions for l
x
and l
y
.
Always write the position operator to the left of the momentum operator in a simple
product of the two.
c) Show that

, .
x y z
l l i l

=

h

7-17
a)

( ) ( ) ( )
( ) ( ) ( )
y z x y x z
x y z
z y z x y x
z y x z y x
y z x y x z
x y z
p p p p p p
p p p
y p z p x p z p x p y p
y p z p z p x p x p y p
= =
+
= + +
i j k
l i j + k
= i j k
i j k

b)

x y z
l i y i z i z i x i x i y
z y x z y x
l i y z l i z x l i x y
z y x z y x

= + + + + +

= = =

i j k h h h h h h
h h h

c)

2 2
2 2 2 2
2

,
x y x y y x
l l l l l l
f f f f
y z x z x z y z
z y z x z x z y
f f f f f f f f
y x z z x z x y z z y z
z z x y z x z z y x z y
y x

= =

+

= + +

=
h h
h h h h
h
2 2 2 2
2 2 2 2 2
2
2 2 2 2
2 2 2 2 2 2
2
2 2
2

,
x y z
f f f f f
y yz zx z
z x z x y z y x
f f f f f
xy xz x yz z
z y z y z x y x
f f
y x
x y
l l x y i i y x i l
y x x y

+ + +

+ + =

= = =

h h h h
h h h h h
h h
h h h h

P7.24) For molecular rotation, the symbol J rather than l is used as the quantum number
for angular momentum. A
1
H
35
Cl molecule whose bond length and force constant are
127 pm and 516 N m
1
, respectively, has the rotational quantum number l = 10 and
vibrational quantum number n = 0.
a) Calculate the rotational and vibrational energy of the molecule. Compare each of these
energies with kT at 300 K.

7-18
b) Calculate the period for vibration and rotation. How many times does the molecule
rotate during one vibrational period?

a)
( ) ( )
( )
2
34
2
27 2
2
10
20
20
23 1
10 11 1.055 10 J s
1
1.0078amu 34.9688amu 1.661 10 kg 2
2 1.275 10 m
1.0078amu 34.9688amu amu
2.55 10 J
2.55 10 J
6.15
1.381 10 J K 300 K
rot
rot
rot
J J
E
r
E
E
kT

+
= =

+
=
= =

h
1
34
27
20
20
23 1
1 1 516 N m
1.055 10 J s
1.0078amu 34.9688amu 1.661 10 kg 2 2
1.0078amu 34.9688amu amu
2.97 10 J
2.97 10 J
7.17
1.381 10 J K 300 K
vib
vib
vib
k
E n
E
E
kT

= + =

+
=
= =

h

b) Calculate the period for vibration and rotation. How many times does the molecule
vibrate during one rotational period?
( )
2
13
20
27
2
10
1 2
; 2
2
2 2

2
2
= = 1.43 10 s
2 2.55 10 J
1.0078amu 34.9688amu 1.661 10 kg
1.275 10 m
1.0078amu 34.9688amu amu
1.0078amu 34.9688amu 1.
1 1.0078amu 34.9688amu
2 2
rot
rot
rot
rot
vib
E I
T
T
E
I
T
k
= = =
= =

+
= = =
27
14
1
661 10 kg
amu
= 1.12 10 s
516 N m

It vibrates
13
14
1.43 10 s
12.8
1.12 10 s
rot
vib
T
T
= =
times in one rotational period.

P7.25) At what values of does ( ) ( )
1/ 2
0 2
2
5
, 3cos 1
16
Y

=

have nodes? Are the
nodes points, lines, planes, or other surfaces?

7-19

Y
2
0
, b g has nodes when 3 1
2
cos
c h
has nodes. This occurs for
0.955 and 0.955 radians or 54.7 and 125.3 degrees. = These surfaces are cones.

P7.26) The wave functions p
x
and d
xz
are linear combinations of the spherical harmonic
functions, which are eigenfunctions of the operators
, H
2
, l and
z
l for rotation in three
dimensions. The combinations have been chosen to yield real functions. Are these
functions still eigenfunctions of
?
z
l Answer this question by applying the operator to the
functions.
$
sin cos sin sin L p i i
z x
=

= h h

3
4
3
4
. This shows that p
x
is not an
eigenfunction of
.
z
L
$
sin cos cos sin cos sin L d i i
z xz
=

= h h

15
4
15
4
. This shows that d
xz
is
not an eigenfunction of
.
z
L

P7.27) Show that the function ( ) ( )
1/ 2
0 2
2
5
, 3cos 1
16
Y

=

is normalized over the
interval 0 0 2 and .
( ) ( ) ( )
( )
2
2 2
0 2
2
0 0
4 2
0
5
, sin 3cos 1
16
5
2 sin 9cos 6cos 1
16
Y d d d
d

=

= +

( ) ( ) ( )
( )
2
2 2
0 2
2
0 0
4 2
0
5 3
0
5
, sin 3cos 1
16
5
2 sin 9cos 6cos 1
16
5 9 5 18
cos 2cos cos 4 2 1
8 5 8 5
Y d d d
d

=

= +

= + = + =

P7.28) Is it possible to know simultaneously the angular orientation of a molecule
rotating in a two dimensional space and its angular momentum? Answer this question by
evaluating the commutator , i

h .

7-20
( )
( ) ( )
( ) ,
,
d f df
i f i i i f
d d
i i

= + =

h h h h
h h

Because the commutator is not equal to zero, it is not possible to simultaneously know
the angular orientation of a molecule rotating in a two-dimensional space and its angular
momentum.

P7.29) At 300 K, most molecules are in their ground vibrational state. Is this also true
for their rotational degree of freedom? Calculate
1 5
0 0
and
J J
J J
n n
n n
= =
= =
for the H
35
Cl molecule
whose bond length is 1.2710
10
m. Make sure that you take the degeneracy of the
levels into account.
( )
( ) ( )
( )
( )
2
2
1
-
2 1
0
2
34
2
27 1 10 23 1
1
0
1
-
2 5
0
2 1
= e
1
1.055 10 J s 1 1+1
3 exp
1.0078 34.9688
2 amu 1.66 10 kgamu 1.27 10 m 1.381 10 J K 300 K
1.0078 + 34.9688
= 2.708
2 1
= e
1
J J
I kT J
J
J
J
J J
I kT J
J
n J
n
n
n
n J
n
+
=
=

=
=
+
=
=
+

+
=
h
h
( ) ( )
( )
2
34
2
27 1 10 23 1
5
0
1.055 10 J s 5 5+1
11 exp
1.0078 34.9688
2 amu 1.66x10 kgamu 1.27 10 m 1.381 10 JK 300 K
1.0078 +34.9688
= 2.369
J
J
n
n

=
=

P7.30) Draw a picture (to scale) showing all angular momentum cones consistent with
l = 5. Calculate the half angles for each of the cones.


7-21
m
l
= +5
m
l
= +4
m
l
= +3
m
l
= +2
m
l
= +1
m
l
= 0
m
l
= -1
m
l
= -2
m
l
= -3
m
l
= -4
m
l
= -5

The half angles of the cones measured from the positive and negative z axis are
( )
1
5
5
cos 0.420radians
5 5 1
l
m

=

= =

+

( )
1
4
4
cos 0.752 radians
5 5 1
l
m

=

= =

+

( )
1
3
3
cos 0.991radians
5 5 1
l
m

=

= =

+

( )
1
2
2
cos 1.20radians
5 5 1
l
m

=

= =

+

( )
1
1
1
cos 1.39 radians
5 5 1
l
m

=

= =

+

( )
1
0
0
cos 1.57 radians
5 5 1
l
m

=

= =

+

as well as minus these values for the negative values of m
l
.

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Physical Chemistry II

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1-1

Chapter 1: From Classical to Quantum Mechanics

The work function is

Using your result, calculate the energy density radiated by a blackbody

in making this approximation for

is always a negative number.

= = and the first

. This can be seen by comparing the x and y

Eigenfunction with eigenvalue 1

Eigenfunction with eigenvalue 9.

Eigenfunction with eigenvalue +1.

= Eigenfunction with eigenvalue i

= Eigenfunction with eigenvalue 1

What must the

must vanish. This requires

if n and m are integers.

cos sin over the interval

= 0 everywhere outside the box because (x) = 0 outside the box.

is not a continuous function at x = a.

is notan acceptable wave function. It goes to infinity at x = 0 and cannot be

H for the particle in the

H for the particle in the one-dimensional box also

H for the particle in the one-dimensional box also

= is an eigenfunction of the total energy operator.

Hdepicted in plots af?

H depicted in plots ae?

H for a box with

h if we apply this operator to the two eigenfunctions

times in one rotational period.

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