159

Chapter 37
Molecules

Conceptual Problems

1 • [SSM] Would you expect NaCl to be polar or nonpolar?

Determine the Concept Yes. Because the center of charge of the positive Na ion
does not coincide with the center of charge for the negative Cl ion, the NaCl
molecule has a permanent dipole moment. Hence, it is a polar molecule.

2 • Would you expect N
2
to be polar or nonpolar?

Determine the Concept Because a N
2
molecule has no permanent dipole
moment, it is a non-polar molecule.

3 • Does neon naturally occur as Ne or Ne
2
? Explain your answer.

Determine the Concept No. Neon naturally occurs as Ne, not Ne
2
. Neon is a rare
gas atom with a closed shell electron configuration.

4 • What type of bonding mechanism would you expect for atoms of
(a) HF, (b) KBr, (c) N
2
, (d) Ag in solid silver?

Determine the Concept

(a) Because an electron is transferred from the H atom to the F atom, the bonding
mechanism is ionic.

(b) Because an electron is transferred from the K atom to the Br atom, the bonding
mechanism is ionic.

(c) Because the atoms share two electrons, the bonding mechanism is covalent.

(d) Because each valence electron is shared by many atoms, the bonding
mechanism is metallic bonding.

5 •• [SSM] The elements on the far right column of the periodic table are
sometimes called noble gases, both because they are gasses under a wide range of
conditions, and because atoms of these elements almost never react with other
atoms to form molecules or ionic compounds. However, atoms of noble gases
can react if the resulting molecule is formed in an electronic excited state. An
example is ArF. When it is formed in the excited state, it is written ArF* and is
called an excimer (for excited dimer). Refer to Figure 37-13 and discuss how a
Chapter 37

160
diagram for the electronic, vibrational, and rotation energy levels of ArF and
ArF* would look in which the ArF ground state is unstable and the ArF* excited
state is stable. Remark: Excimers are used in certain kinds of lasers.

Determine the Concept The diagram would consist of a non-bonding ground
state with no vibrational or rotational states for ArF (similar to the upper curve in
Figure 37-4) but for ArF* there should be a bonding excited state with a definite
minimum with respect to inter-nuclear separation and several vibrational states as
in the excited state curve of Figure 37-13.

6 • Find other atoms that have the same subshell electron configurations in
their two highest energy orbitals as carbon atoms do. Would you expect the same
type of hybridization for these orbitals as for carbon?

Determine the Concept Elements similar to carbon in outer shell configurations
are silicon, germanium, tin, and lead. We would expect the same hybridization
for these as for carbon, and this is indeed the case for silicon and germanium
whose crystal structure is the diamond structure. Tin and lead, however, are
metallic and here the metallic bond is dominant.

7 • How does the value of the effective force constant calculated for a CO
molecule in Example 37-4 compare with the value of the force constant of the
suspension springs on a typical automobile, which is about 1.5 kN/m?

Determine the Concept The effective force constant from Example 37-4 is
1.85×10
3
N/m. This value is about 25% larger than the given value of the force
constant of the suspension springs on a typical automobile.

8 • Explain why the moment of inertia of a diatomic molecule increases
slightly with increasing angular momentum.

Determine the Concept As the angular momentum increases, the separation
between the nuclei also increases (the effective force between the nuclei is similar
to that of a stiff spring). Consequently, the moment of inertia also increases.

9 • Why would you expect the separation distance between the two
protons to be larger in a

H
2
+
ion than in a H
2
molecule?

Determine the Concept For H
2
, the concentration of negative charge between the
two protons holds the protons together. In a
+
2
H ion, there is only one electron that
is shared by the two positive charges such that most of the electronic charge is
again between the two protons. However, the negative charge in a
+
2
H ion is not
as effective as the larger charge in a H
2
molecule, and the protons should be
Molecules

161
farther apart. The experimental values support this argument. For H
2
,
r
0
=0.074 nm, while for
+
2
H , r
0
=0.106 nm.

10 • At room temperature an atom typically absorb radiation only from the
ground state, whereas a diatomic molecule typically absorbs radiation from many
different rotational states. Why?

Determine the Concept The energy of the first excited state of an atom is orders
of magnitude greater than kT at ordinary temperatures. Consequently, practically
all atoms are in the ground state. By contrast, the energy separation between the
ground rotational state and nearby higher rotational states is less than or roughly
equal to kT at ordinary temperatures, and so these higher states are thermally
excited and occupied.

11 •• The vibrational energy levels of diatomic molecules are described by a
single vibrational frequency f that is the frequency of vibration of the two atoms
of the molecule along the line through their centers. Would you expect to see one,
or more than one, vibrational frequency in molecules that have three or more
atoms? Consider in particular a water molecule H
2
O (Figure 37-9).

Determine the Concept With more than two atoms in the molecule there will be
more than just one frequency of vibration because there are more possible relative
motions. In advanced mechanics these are known as normal modes of vibration.

Estimation and Approximation

12 •• The potential energy for a diatomic molecule has a minimum as shown
in Figure 37-13. Near this minimum, the graph for the energy as a function of
distance between the atoms may be approximated as a parabola, leading to the
harmonic oscillator model for the vibrating molecule. An improved
approximation is called the anharmonic oscillator and leads to a modification of
the expression for the energy E
ν
= ν +
1
2
( )
hf , where ν =0, 1, 2, …(Equation 37-
18). The modified expression for energy is E
ν
= ν +
1
2
( )
hf − ν +
1
2
( )
2
hf α , where
ν =0, 1, 2, …. For a O
2
molecule, the constants have the values f =4.74 × 10
13
s
–1

and α =7.6 × 10
–3
. Use this formula to estimate the smallest value of the quantum
number ν for which the modified expression differs from the original expression
by 10 percent.

Picture the Problem We can estimate the value of the quantum number ν for
which the improved formula corrects the original formula by 10 percent by setting
the ratio of the correction term to the first term equal to 10 percent and solving for
ν.

Chapter 37

162
Express the ratio of the correction
term to the first term of the
expression for E
ν
and simplify to
obtain:

( )
( )
( )α ν
ν
α ν
2
1
2
1
2
2
1
+ =
+
+
hf
hf

For a correction of 10 percent:

( ) 10 . 0
2
1
= + α ν ⇒
2
1
10
1
− =
α
ν

Substitute numerical values and
evaluate ν :
( )
13 7 . 12
2
1
10 6 . 7 10
1
3
≈ = −
×
=

ν

13 •• To understand why quantum mechanics is not needed to describe
many macroscopic systems, estimate the rotational energy quantum number

and
spacing between adjacent energy levels for a baseball (m ∼ 300 g, r ∼ 3 cm)
spinning about its own axis at 20 rev/min. Hint: Pick

so the quantum energy
formula ( ) ( ) I E 2 1
2

+ = , where =0, 1, 2, ..., (Equation 37-12) gives the
correct energy for the given system. Then find the energy increase for the next
highest energy level.

Picture the Problem We can solve Equation 37-12 for and substitute for the
moment of inertia and rotational kinetic energy of the baseball to estimate the
quantum number and spacing between adjacent energy levels for a baseball
spinning about its own axis.

The rotational energy levels are
given by Equation 37-12:

( )
I
E
2
1
2

+
=
where =0, 1, 2, … is the rotational
energy quantum number and I is the
moment of inertia of the ball.

Solving for (+1) yields:
( )
2
2
1

IE
= +

Factoring from the parentheses
gives:

2
2
2 1
1

IE
=






+

The result of our calculation of
will show that >>1. Assuming for
the moment that this is the case:

2
2
2

IE
≈ ⇒
2
2

IE

Because the energy of the ball is
rotational kinetic energy:

2
2
1
rot
ω I K E = =

Molecules

163
Substitute for

E in the expression
for and simplify to obtain:
( ) ( )

ω ω ω
I I I I
= = ≈
2 2 2
2
1
2


The moment of inertia of a ball about
an axis through its diameter is (see
Table 9-1):

2
5
2
mr I =
Substituting for I gives:

5
2
2
ω mr


Substitute numerical values and evaluate :

( )( )
( )
30
34
2
10 2
s J 10 055 . 1 5
s 60
min 1
rev
rad 2
min
rev 20
cm 3 kg 300 . 0 2
× ≈
⋅ ×








× ×


π


Set =0 to express the spacing
between adjacent energy levels:

2
2 2
r 0
4
5
2 mr I
E

= =
Substitute numerical values and
evaluate E
0r
:

( )
( )( )
J 10 5
cm 0 . 3 g 300 4
s J 10 055 . 1 5
65
2
2
34
r 0


× ≈
⋅ ×
= E


Remarks: Note that our value for justifies our assumption that >> 1.

14 •• Estimate the quantum number ν and spacing between adjacent energy
levels for a 1.0-kg mass attached to spring. The spring has a force constant equal
to 1200-N/m and the mass-spring system is vibrating with an amplitude of 3.0 cm.
Hint: Pick ν so that the quantum energy formula E
ν
= ν +
1
2
( )
hf , where ν =0, 1,
2, … (Equation 37-18) gives the correct energy for the given system. Then find the
energy increase for the next highest energy level.

Picture the Problem We can solve Equation 37-18 for ν and substitute for the
frequency of the mass-and-spring oscillator to estimate the quantum number ν and
spacing between adjacent energy levels for this system.

The vibrational energy levels are
given by Equation 37-18:
( )hf E
2
1
+ = ν
ν

where ν =0, 1, 2, …
Chapter 37

164

Solve for ν to obtain:
2
1
− =
hf
E
ν
ν
or, because ν >>1,
hf
E
ν
ν ≈

The vibrational energy of the object
attached to the spring is:

2
2
1
kA E =
ν

where A is the amplitude of its motion.

Substitute for E
ν
in the expression for
ν to obtain:

hf
kA
2
2
= ν
The frequency of oscillation f of the
mass-and-spring oscillator is given
by:

m
k
f
π 2
1
=
Substitute for f in the expression for
ν and simplify to obtain:
mk
h
A
k
m
h
kA
2 2
π π
ν = =

Substitute numerical values and evaluate ν :

( )
( )( )
32
34
2
10 1 N/m 1200 kg 0 . 1
s J 10 626 . 6
cm 0 . 3
× ≈
⋅ ×
=

π
ν

Set ν =0 in Equation 37-18 to
express the spacing between adjacent
energy levels:

m
k h
hf E
π
ν
4 2
1
0
= =
Substitute numerical values and
evaluate E

:

J 10 8 . 1
kg 1.0
N/m 1200
4
s J 10 626 . 6
33
34
0


× =
⋅ ×
=
π
ν
E


Remarks: Note that our value for ν justifies our assumption that ν >> 1.

Molecular Bonding

15 • Calculate the separation of of Na
+
and Cl

ions for which the potential
energy of a single ionic unit (one Na
+
ion and one Cl

ion) is –1.52 eV.


Molecules

165
Picture the Problem The electrostatic potential energy with U
e
with ions
separated a distance r is given by .
2
r ke U − =

Relate the electrostatic potential
energy of the ions to their separation:
r
ke
U
2
e
− = ⇒
e
2
U
ke
r − =

Substitute numerical values and evaluate r:

( )
( )
nm 0.947
eV
J
10 602 . 1 eV 52 . 1
C 10 602 . 1
C
m N
10 988 . 8
19
2
19
2
2
9
=






× −
×







⎛ ⋅
×
− =


r

16 • The equilibrium separation of the atoms in a HF molecule is
0.0917 nm and the measured electric dipole moment of the molecule is
6.40 × 10
–30
C⋅m. What percentage of the HF bond is ionic?

Picture the Problem The percentage of the bonding that is ionic is given by
( ). 100
100 meas
p p

Express the percentage of the
bonding that is ionic:








=
100
meas
bonding ionic
100 Percent
p
p


Express the dipole moment for
100% ionic bonding:

er p =
100

Substituting for p
100
gives:







=
er
p
meas
bonding ionic
100 Percent

Substitute numerical values and evaluate the percent ionic bonding:

( )( )
% 6 . 43
nm 0917 . 0 C 10 602 . 1
m C 10 40 . 6
100 Percent
19
30
bonding ionic
=






×
⋅ ×
=




17 •• The dissociation energy of RbF is 5.12 eV, and the equilibrium
separation of RbF is 0.227 nm. The electron affinity of a fluorine atom is
–3.40 eV and the ionization energy of rubidium is 4.18 eV. Determine the core-
repulsion energy of RbF.


Chapter 37

166
Picture the Problem If we choose the potential energy at infinity to be ΔE, the
total potential energy is U
tot
=U
e
+ΔE +U
rep
, where U
rep
is the energy of
repulsion, which is found by setting the dissociation energy equal to −U
tot
.

Express the total potential energy of
the molecule:

rep e tot
U E U U + Δ + =
The core-repulsive energy is :

( )
d e rep
E U E U + + Δ − = (1)
Calculate the energy ΔE needed to
form Rb
+
and F

ions from neutral
rubidium and fluorine atoms:

eV 78 . 0 eV 3.40 eV 18 . 4 = − = ΔE
The electrostatic potential energy
is given by:

r
ke
U
2
e
− =
Substitute numerical values and evaluate U
e
:


( )
( )
eV 34 . 6
eV
J
10 602 . 1 nm 227 . 0
C 10 602 . 1
C
m N
10 988 . 8
19
2
19
2
2
9
e
− =






×
×







⎛ ⋅
×
− =


U

Substitute numerical values in
equation (1) and evaluate U
rep
:
( )
eV 44 . 0
eV 12 . 5 eV 34 . 6 eV 78 . 0
rep
=
+ − − = U


18 •• The equilibrium separation of the K
+
and Cl

ions in KCl is about
0.267 nm. (a) Calculate the potential energy of attraction of the ions. Assume that
the ions are point charges at this separation. (b) The ionization energy of
potassium is 4.34 eV and the electron affinity of chlorine is –3.62 eV. Calculate a
value for the dissociation energy under the assumption that the energy of
repulsion is negligible. (See Figure 37-1) (c) The measured dissociation energy is
4.49 eV. What is the energy due to repulsion of the ions at the equilibrium
separation?

Picture the Problem The potential energy of attraction of the ions is
.
2
e
r ke U − = We can find the dissociation energy from the negative of the sum of
the potential energy of attraction and the difference between the ionization energy
of potassium and the electron affinity of chlorine.

Molecules

167
(a) The potential energy of
attraction of the ions is given by:
r
ke
U
2
e
− =
where ke
2
=1.44 eV⋅nm

Substitute numerical values and
evaluate U
e
:

eV 39 . 5
nm 267 . 0
nm eV 44 . 1
e
− =

− = U
(b) Express the total potential energy
of the molecule:

rep e tot
U E U U + Δ + =
or, neglecting any energy of repulsion,
E U U Δ + =
e tot


The dissociation energy is the
negative of the total potential
energy:

( ) E U U E Δ + − = − =
e tot calc d,

ΔE is the difference between the
ionization energy of potassium and
the electron affinity of Cl:

eV 0.72 eV 3.62 eV 34 . 4 = − = ΔE
Substitute numerical values and
evaluate E
d,calc
:
( )
eV 67 . 4
eV 72 . 0 eV 39 . 5
calc d,
=
+ − − = E


(c) The energy due to repulsion of
the ions at equilibrium separation is
given by:

meas d, calc d, rep
E E U − =
Substitute numerical values and
evaluate U
rep
:
eV 18 . 0 eV 49 . 4 eV 67 . 4
rep
= − = U

19 •• Indicate an approximate value for the average value of the separation
distance r for two vibrational levels on the potential energy curve for a diatomic
molecule (one of the curves in Figure 37-13). Your teacher claims that the
increase in r
av
with increases in vibration energy explains why solids expand
when heated. Do you agree? If so, give an argument supporting this claim. If not,
give an argument opposing this claim.

Picture the Problem You should agree. The potential energy curve is shown in
the following diagram. The turning points for vibrations of energy E
1
and E
2
are
at the values of r where the energies equal U(r). The average value of r for the
vibrational levels E
1
and E
2
are labeled r
1 av
and r
2 av
. Note that the estimate of r
1 av

is midway between r
1 min
and r
1 max
. The potential is like a special spring that has a
Chapter 37

168
greater spring constant for compressions than it has for extensions. The period of
a spring-and-mass oscillator is inversely proportional to the square root of the
spring constant, so our ″special spring″ spends more time in extension than in
compression. As a result, r
1 av
will be greater than the equilibrium radius.

( ) r U
r 0

2
E

1
E

av 1
r
av 2
r

This argument can be extended to explain why r
2 av
is greater than r
1av
. It is
because the ″spring constant″ for extension, which can be estimated by taking the
average slope of the potential energy curve in the region to the right of the
equilibrium position, is greater for E =E
2
than for E =E
1
. It is also because the
″spring constant″ for compression is greater for E =E
2
than for E =E
1
. It follows
that r
2 av
is greater than r
1 av
. Because r
2,av
is greater than r
1 av
, it follows that as the
vibrational energy of a diatomic molecule increases, the average separation of the
atoms of the molecule increases and, hence, the solid expands with heating.

20 •• Calculate the potential energy of attraction between the Na
+
and Cl


ions at the equilibrium separation r
0
=0.236 nm. Compare this result with the
dissociation energy given in Figure 37-1. What is the energy due to repulsion of
the ions at the equilibrium separation?

Picture the Problem We can use
0
2
e
r ke U − = to calculate the potential energy
of attraction between the Na
+
and Cl

ions at the equilibrium separation
r
0
=0.236 nm. We can find the energy due to repulsion of the ions at the
equilibrium separation from ( ) E E U U Δ + + − =
d e rep
.

The potential energy of attraction
between the Na
+
and Cl

ions at
the equilibrium separation r
0
is
given by:

0
2
e
r
ke
U − =
where ke
2
=1.44 eV⋅nm.

Molecules

169
Substitute numerical values and
evaluate U
e
:

eV 10 . 6
nm 236 . 0
nm eV 44 . 1
e
− =

− = U
From Figure 37-1:

eV 27 . 4
d
= E
The ratio of the magnitude of the
potential energy of attraction to
the dissociation energy is:

43 . 1
eV 4.27
eV 10 . 6
d
e
= =
E
U

U
rep
is related to U
e
, E
d
, and ΔE
according to:

( ) E E U U Δ + + − =
d e rep

From Figure 37-1:

eV 52 . 1 = ΔE

Substitute numerical values and
evaluate U
rep
:
( )
eV 31 . 0
eV 52 . 1 eV 27 . 4 eV 10 . 6
rep
=
+ + − − = U


21 •• The equilibrium separation of the K
+
and F

ions in KF is about
0.217 nm. (a) Calculate the potential energy of attraction of these ions. Assume
that the ions are point charges at this separation. (b) The ionization energy of
potassium is 4.34 eV and the electron affinity of fluorine is –3.40 eV. Find the
dissociation energy by neglecting any energy of repulsion. (c) The measured
dissociation energy is 5.07 eV. Calculate the energy due to repulsion of the ions at
the equilibrium separation.

Picture the Problem The potential energy of attraction of the ions is
.
2
e
r ke U − = We can find the dissociation energy from the negative of the sum of
the potential energy of attraction and the difference between the ionization energy
of potassium and the electron affinity of fluorine.

(a) The potential energy of
attraction between the K
+
and F


ions at the equilibrium separation
r
0
is given by:

0
2
e
r
ke
U − =
where ke
2
=1.44 eV⋅nm.

Substitute numerical values and
evaluate U
e
:

eV 64 . 6
nm 217 . 0
nm eV 44 . 1
e
− =

− = U
Chapter 37

170

(b) Express the total potential energy
of the molecule:

rep e tot
U E U U + Δ + =
or, neglecting any energy of repulsion,
E U U Δ + =
e tot


The dissociation energy is the
negative of the total potential
energy:

( ) E U U E Δ + − = − =
e tot calc d,

ΔE is the difference between the
ionization energy of potassium and
the electron affinity of fluorine:

eV 0.94 eV 3.40 eV 34 . 4 = − = ΔE
Substitute numerical values and
evaluate E
d,calc
:
( )
eV 70 . 5
eV 94 . 0 eV 64 . 6
calc d,
=
+ − − = E


(c) The energy due to repulsion of
the ions at equilibrium separation is
given by:

meas d, calc d, rep
E E U − =
Substitute numerical values and
evaluate U
rep
:
eV 63 . 0 eV 07 . 5 eV 70 . 5
rep
= − = U

Energy Levels of Spectra of Diatomic Molecules

22 • The characteristic rotational energy E
0r
for the rotation of a N
2

molecule is 2.48 × 10
–4
eV. Using this value, find the separation distance of the 2
nitrogen atoms.

Picture the Problem We can relate the characteristic rotational energy E
0r
to the
moment of inertia of the molecule and model the moment of inertia of the N
2

molecule as two point objects separated by a distance r.

The characteristic rotational energy
of a molecule is given by:
I
E
r
2
2
0

=

The moment of inertia of the
molecule is given by:

2
N 2
1
2
N
2
2 r M
r
M I =






=
Substitute for I to obtain:

( )
2
p
2
2
N
2
2
N 2
1
2
0
14 2 r m r M r M
E
r

= = =
Molecules

171
Solving for r gives:
p 0
14
1
m E
r
r
=

Substitute numerical values and evaluate r:

( )
( )( )( )
nm 109 . 0
kg 10 673 . 1 J /eV 10 602 . 1 eV 10 48 . 2 14
1
s J 10 055 . 1
27 19 4
34
=
× × ×
⋅ × =
− − −

r


23 • [SSM] The separation of the two oxygen atoms in a molecule of O
2

is actually slightly greater than the 0.100 nm used in Example 37-3. Furthermore,
the characteristic energy of rotation E
0r
for O
2
is 1.78 × 10
–4
eV rather than the
result obtained in that example. Use this value to calculate the separation distance
of the two oxygen atoms.

Picture the Problem We can relate the characteristic rotational energy E
0r
to the
moment of inertia of the molecule and model the moment of inertia of the O
2
molecule as two point objects separated by a distance r.

The characteristic rotational energy
of a molecule is given by:
I
E
r
2
2
0

=

The moment of inertia of the
molecule is given by:

2
O 2
1
2
O
2
2 r M
r
M I =






=
Substitute for I to obtain:

( )
2
p
2
2
O
2
2
O 2
1
2
0
16 2 r m r M r M
E
r

= = =

Solving for r yields:
p 0
1
4 m E
r
r

=

Substitute numerical values and evaluate r:

( )( )( )
nm 121 . 0
kg 10 673 . 1 J /eV 10 602 . 1 eV 10 78 . 1
1
4
s J 10 055 . 1
27 19 4
34
=
× × ×







⎛ ⋅ ×
=
− − −

r


Chapter 37

172
24 •• Show that the reduced mass of a diatomic molecule is always smaller
than the mass of the molecule. Calculate the reduced mass for (a) H
2
, (b) N
2
, (c)
CO, and (d) HCl. Express your answers in unified atomic mass units.

Picture the Problem We can use the definition of the reduced mass to show that
the reduced mass is smaller than either mass in a diatomic molecule.

Express the reduced mass of a two-
body system:

2 1
2 1
m m
m m
+
= μ
Divide the numerator and
denominator of this expression
by m
2
to obtain:

2
1
1
1
m
m
m
+
= μ (1)
Divide the numerator and
denominator of this expression by m
1

to obtain:
1
2
2
1
m
m
m
+
= μ (2)

Because the denominator is greater
than 1 in equations (1) and (2):

1
m < μ and
2
m < μ
(a) For H
2
, m
1
=m
2
=1 u:

( )( )
u 500 . 0
u 1 u 1
u 1 u 1
2
H
=
+
= μ

(b) For N
2
, m
1
=m
2
=14 u:

( )( )
u 00 . 7
u 14 u 14
u 14 u 14
2
N
=
+
= μ

(c) For CO, m
1
=12 u and m
2
=16 u:

( )( )
u 86 . 6
u 16 u 12
u 16 u 12
CO
=
+
= μ

(d) For HCl, m
1
=1 u and
m
2
=35.5 u:
( )( )
u 973 . 0
u 5 . 35 u 1
u 5 . 35 u 1
HCl
=
+
= μ

25 •• A CO molecule has a binding energy of approximately 11 eV. Find the
vibrational quantum number ν that corresponds to 11 eV. (If a CO molecule
actually had this much vibrational energy, it would ″shake″ apart.)

Picture the Problem We can solve Equation 37-18 for ν and substitute for the
frequency of the CO molecule (see Example 37-4) and its binding energy to
estimate the quantum number ν .

Molecules

173
The vibrational energy levels
are given by Equation 37-18:

( )hf E
2
1
+ = ν
ν

2
1
− =
hf
E
ν
ν

where ν =0, 1, 2, …, k

Substitute numerical values and
evaluate ν :
( )( )
41
2
1
Hz 10 42 . 6 s J 10 626 . 6
eV
J 10 1.602
eV 11
13 34
19


× ⋅ ×
×
×
=


ν

26 •• Derive the equation I = μr
0
2
(Equation 37-14) for the moment of
inertia in terms of the reduced mass of a diatomic molecule.

Picture the Problem Let the origin of coordinates be at the point mass m
1
and
point mass m
2
be at a distance r
0
from the origin. We can express the moment of
inertia of a diatomic molecule with respect to its center of mass using the
definitions of the center of mass and the moment of inertia of point particles.

Express the moment of inertia of a
diatomic molecule:

2
2 2
2
1 1
r m r m I + = (1)
The r coordinate of the center of
mass is:

0
2 1
2
CM
r
m m
m
r
+
=
The distances of m
1
and m
2
from the
center of mass are:

CM 1
r r =
and
0
2 1
1
0
2 1
2
0 CM 0 2
r
m m
m
r
m m
m
r r r r
+
=
+
− = − =


Substitute for r
1
and r
2
in equation
(1) to obtain:
2
0
2 1
1
2
2
0
2 1
2
1








+
+








+
= r
m m
m
m r
m m
m
m I

Simplifying this expression leads
to:

2
0
2 1
2 1
r
m m
m m
I
+
= ⇒
2
0
r I μ = 37-14
where
2 1
2 1
m m
m m
+
= μ

Chapter 37

174
27 •• [SSM] The equilibrium separation between the atoms of a LiH
molecule is 0.16 nm. Determine the energy separation between the =3 and =2
rotational levels of this diatomic molecule.

Picture the Problem We can use the expression for the rotational energy levels
of the diatomic molecule to express the energy separation ΔE between the 3 =
and 2 = rotational levels and model the moment of inertia of the LiH

molecule
as two point objects separated by a distance r
0
.

The energy separation between the
3 = and 2 = rotational levels of
this diatomic molecule is given by:

2 3 = =
− = Δ

E E E
Express the rotational energy levels
E

=3
and E

=2
in terms of E
0r
:

( )
r r
E E E
0 0 3
12 1 3 3 = + =
=

and
( )
r r
E E E
0 0 2
6 1 2 2 = + =
=


Substitute for E

=3
and E

=2
to
obtain:

r r r
E E E E
0 0 0
6 6 12 = − = Δ

The characteristic rotational energy
of a molecule is given by
I
E
r
2
2
0

= .
Hence:

I I
E
2 2
3
2
6

=








= Δ

The moment of inertia of the
molecule is given by:

2
0
r I μ =
where μ is the reduced mass of the
molecule.

Substituting for I yields:

( )
2
0 H Li
H Li
2
2
0
H Li
H Li
2
2
0
2
3
3 3
r m m
m m
r
m m
m m
r
E
+
=
+
= = Δ

μ


Substitute numerical values and evaluate ΔE:

( ) ( )
( )( )( ) ( )( )
meV 6 . 5
kg/u 10 661 . 1 J /eV 10 602 . 1 nm 16 . 0 u 1 u 94 . 6
u 1 u 94 . 6 s J 10 055 . 1 3
27 19 2
2
34
=
× ×
+ ⋅ ×
= Δ
− −

E
Molecules

175

28 •• The equilibrium separation of the K
+
and Cl

ions in KCl is about
0.267 nm. Use this value together with the reduced mass of KCl to calculate the
characteristic rotational energy E
0r
(Equation 37-13) of KCl.

Picture the Problem We can relate the characteristic rotational energy E
0r
to the
moment of inertia of the molecule and model the moment of inertia of the KCl

molecule as two point objects of reduced mass μ separated by a distance r.

The characteristic rotational energy
of a molecule is given by:
I
E
r
2
2
0

=

Express the moment of inertia of
the molecule:

2
0
r I μ =
where
Cl K
Cl K
m m
m m
+
= μ

Substituting for I and simplifying
gives:

( )
2
0 Cl k
Cl K
2
2
0
2
0
2 2 r m m
m m
r
E
r
+
= =

μ


Substitute numerical values and evaluate E
0r
:

( ) ( )
( )( )( ) ( )
meV 0158 . 0
J /eV 10 1.602
1
J 10 53 . 2
kg/u 10 661 . 1 nm 267 . 0 u 35.5 u 1 . 39 2
u 35.5 u 1 . 39 s J 10 055 . 1
19
24
27 2
2
34
0
=
×
× × =
×
+ ⋅ ×
=




r
E


29 •• The central frequency for the absorption band of HCl shown in Figure
37-14 is at 8.66 × 10
13
Hz, and the absorption peaks to either side of the central
frequency are separated by about 6 × 10
11
Hz. Use this information to find (a) the
lowest (zero-point) vibrational energy for HCl, (b) the moment of inertia of HCl,
and (c) the equilibrium separation of the two atoms.

Picture the Problem We can use the expression for the vibrational energies of a
molecule to find the lowest vibrational energy. Because the difference in the
vibrational energy levels depends on both Δf and the moment of inertia I of the
molecule, we can relate these quantities and solve for I. Finally, we can use
2
r I μ = , with μ representing the reduced mass of the molecule, to find the
equilibrium separation of the atoms.

(a) The vibrational energy levels are
given by:
( ) ... , 2 , 1 , 0
2
1
= + = ν ν
ν
hf, E
Chapter 37

176

The lowest vibrational energy
corresponds to ν =0:

hf E
2
1
0
=
Substitute numerical values and evaluate E
0
:

( )( )
eV 179 . 0
J /eV 10 1.602
1
J 10 87 . 2 Hz 10 66 . 8 s J 10 626 . 6
19
20 13 34
2
1
0
=
×
× × = × ⋅ × =

− −
E


(b) For Δ =±1:
f h
I
E Δ = = Δ

2


Solving for I and simplifying gives:

f
h
f h
h
f h
I
Δ
=
Δ
=
Δ
=
2 2
2 2
4 4 π π

Substitute numerical values and
evaluate I:
( )
2 47
2 47
11 2
34
m kg 10 3
m kg 10 80 . 2
Hz 10 6 4
s J 10 626 . 6
⋅ × ≈
⋅ × =
×
⋅ ×
=



π
I


(c) The moment of inertia of a HCL
molecule is given by:

2
r I μ =
Replace μ by the reduced mass of a
HCl molecule and r by r
0
to obtain:

2
0
Cl H
Cl H
r
m m
m m
I
+
= ⇒ I
m m
m m
r
Cl H
Cl H
0
+
=

Substitute numerical values and evaluate r
0
:

( )( )
( )
nm 0.1
kg/u 10 661 . 1
m kg 10 80 . 2
u 453 . 34 u 1
u 453 . 34 u 1
27
2 47
0
=
×
⋅ ×





⎡ +
=


r

30 •• Calculate the effective force constant for HCl from its reduced mass
and from the fundamental vibrational frequency obtained from Figure 37-14.

Picture the Problem Let the numeral 1 refer to the H
+
and the numeral 2 to the
Cl

ion. For a two-mass and spring system on which no external forces are acting,
the center of mass must remain fixed. We can use this condition to express the net
force acting on either the H
+
or Cl

ion. Because this force is a linear restoring
Molecules

177
force, we can conclude that the motion of the object whose mass is m
1
will be
simple harmonic with an angular frequency given by
1 eff
m k = ω .

If the particle whose mass is m
1

moves a distance r
1
from (or toward)
the center of mass, then the particle
whose mass is m
2
must move a
distance:

1
2
1
2
r
m
m
r Δ = Δ from (or toward) the
center of mass.
Express the force exerted by the
spring:

( )
2 1
r r k r k F Δ Δ Δ + − = − =
Substitute for Δr
2
to obtain:

1
2
2 1
1
2
1
1
r
m
m m
k
r
m
m
r k F
Δ
Δ Δ







⎛ +
− =








+ − =


A displacement Δr
1
of m
1
results in a
restoring force:

1 eff 1
2
2 1
r k r
m
m m
k F Δ Δ − =







⎛ +
− =
where







⎛ +
=
2
2 1
eff
m
m m
k k

Because this is a linear restoring
force, we know that the motion will
be simple harmonic with the angular
frequency given by:

1
eff
m
k
= ω ⇒
1
eff
2
m
k
f = π

Substitute for k
eff
and simplify to
obtain: ⎟






⎛ +
=
2 1
2 1
2
m m
m m
k f π
or, because
Cl H
Cl H
2 1
2 1
m m
m m
m m
m m
+
=
+
= μ is
the reduced mass of the two-particle
system,
μ
π
k
f = 2

Solving for k yields:

Cl H
Cl H 2 2 2 2
4 4
m m
m m
f f k
+
= = π μ π

Chapter 37

178

Substitute numerical values and evaluate k:

( ) ( )( )( )
( )
N/m 478
u 453 . 35 u 1
kg/u 10 661 . 1 u 453 . 35 u 1 Hz 10 66 . 8 4
27
2
13 2
=
+
× ×
=

π
k

31 •• [SSM] The equilibrium separation between the atoms of a CO
molecule is 0.113 nm. For a molecule, such as CO, that has a permanent electric
dipole moment, radiative transitions obeying the selection rule
Δ = ±1 between
two rotational energy levels of the same vibrational level are allowed. (That is, the
selection rule
Δν = ±1 does not hold.) (a) Find the moment of inertia of CO and
calculate the characteristic rotational energy E
0r
(in eV). (b) Make an energy-level
diagram for the rotational levels from

= 0 to

= 5 for some vibrational level.
Label the energies in electron volts, starting with E =0 for 0 = . Indicate on your
diagram the transitions that obey

Δ = −1, and calculate the energies of the
photons emitted. (c) Find the wavelength of the photons emitted during each
transition in (b). In what region of the electromagnetic spectrum are these
photons?

Picture the Problem We can find the reduced mass of CO and the moment of
inertia of a CO molecule from their definitions. The energy level diagram for the
rotational levels from 0 = to 5 = can be found using . 2
0 1 , r
E E

= Δ

Finally,
we can find the wavelength of the photons emitted for each transition using
r
E
hc
E
hc
0 1 ,
1 ,
2 Δ
=
Δ
=

λ .

(a) Express the moment of inertia
of CO:
2
0
r I μ =
where μ is the reduced mass of the CO
molecule.

The reduced mass of the CO molecule
is given by:
O C
O C
m m
m m
+
= μ

Substituting for μ gives:
O C
2
0 O C
m m
r m m
I
+
=

Molecules

179

Substitute numerical values (r
0
=0.113 nm) and evaluate I:

( )( )
( )( )
2 46
2 46 2 27
m kg 10 45 . 1
m kg 10 454 . 1 nm 113 . 0 kg/u 10 661 . 1
u 16 u 12
u 16 u 12
⋅ × =
⋅ × = ×








+
=

− −
I


The characteristic rotational energy
E
0r
is given by:

I
E
r
2
2
0

=
Substitute numerical values and evaluate E
0r
:

( ) ( )
( )
meV 0.239 meV 0.2385
m kg 10 454 . 1 2
J /eV 10 602 . 1 s eV 10 58 . 6
2 46
19
2
16
0
= =
⋅ ×
× ⋅ ×
=

− −
r
E

(b) The energy level diagram is
shown to the right. Note that ΔE

,

−1
,
the energy difference between
adjacent levels for Δ =−1, is
. 2
0 1 , r
E E

= Δ




meV 76 . 4 , 4 = = E l
meV 86 . 2 , 3 = = E l
meV 43 . 1 , 2 = = E l
meV 476 . 0 , 1 = = E l
0 , 0 = = E l
meV 14 . 7 , 5 = = E l

Chapter 37

180

The energies of the photons emitted
in each transition are given by
1 , −
Δ

E . Hence:

meV 38 . 2
meV 76 . 4 meV 14 . 7
4 , 5
=
− = ΔE

meV .90 1
meV 86 . 2 meV 76 . 4
3 , 4
=
− = ΔE

meV .43 1
meV 43 . 1 meV 86 . 2
2 , 3
=
− = ΔE

meV .25 1
meV 476 . 0 meV 43 . 1
1 , 2
=
− = ΔE

meV 476 . 0
0 meV 476 . 0
0 , 1
=
− = ΔE


(c) Express the energy difference
1 . −
Δ

E between energy levels in
terms of the frequency of the emitted
radiation:

1 , 1 , − −
= Δ

hf E
Because :
1 , 1 , − −
=

λ f c
r
E
hc
E
hc
0 1 ,
1 ,
2 Δ
=
Δ
=

λ

Substitute numerical values to obtain:

( )( )
( )

m 2600
meV 2385 . 0 2
m/s 10 998 . 2 s eV 10 136 . 4
8 15
1 ,
μ
λ =
× ⋅ ×
=




For =1:
m 2600
1
m 2600
0 , 1
μ
μ
λ = =

For =2:
m 1300
2
m 2600
1 , 2
μ
μ
λ = =

For =3:
m 867
3
m 2600
2 , 3
μ
μ
λ = =

For =4:
m 650
4
m 2600
3 , 4
μ
μ
λ = =

Molecules

181
For =5:
m 520
5
m 2600
4 , 5
μ
μ
λ = =

These wavelengths fall in the microwave region of the electromagnetic spectrum.

32 •• Two objects, one of mass m
1
and the other of mass m
2
, are connected
to opposite ends of a spring of force constant k
F
. The objects are released from
rest with the spring compressed. (a) Show that when the spring is extended and
the object of mass m
1
is a distance Δr
1
from its equilibrium position in the center-
of-mass reference frame, the force exerted by the spring is given by
( )
1 1 F
r m k F Δ − = μ , where μ is the reduced mass. (b) Show that the frequency of
oscillation f is related to k and μ by μ π
F
2 k f = .

Picture the Problem For a two-mass and spring system on which no external
forces are acting, the center of mass must remain fixed. We can use this condition
to express the net force acting on either object. Because this force is a linear
restoring force, we can conclude that the motion of the object whose mass is m
1

will be simple harmonic with an angular frequency given by
1 eff
m k = ω .
Substitution for k
eff
will lead us to the result given in (b).

(a) If the particle whose mass is m
1

moves a distance Δr
1
from (or
toward) the center of mass, then the
particle whose mass is m
2
must
move a distance:

1
2
1
2
r
m
m
r Δ = Δ from (or toward) the
center of mass.
Express the force exerted by the
spring:

( )
2 1 F F
r r k r k F Δ + Δ − = Δ − =
Substitute for Δr
2
and simplify to
obtain:

1
1
F 1
2 1
2 1
1
F
1
2
2 1
F
1
2
1
1 F
r
m
k r
m m
m m
m
k
r
m
m m
k
r
m
m
r k F
Δ








− = Δ












+
− =
Δ







⎛ +
− =








Δ + Δ − =
μ
where
2 1
2 1
m m
m m
+
= μ is the reduced mass
of the spring and mass oscillator.
Chapter 37

182
(b) A displacement Δr
1
of m
1
results
in a restoring force given by:

1 eff 1
2
2 1
F
r k r
m
m m
k F Δ − = Δ







⎛ +
− =
where







⎛ +
=
2
2 1
F eff
m
m m
k k

Because this is a linear restoring
force, we know that the motion will
be simple harmonic with an angular
frequency given by:

1
eff
m
k
= ω ⇒
1
eff
2
1
2 m
k
f
π π
ω
= =

Substitute for k
eff
and simplify to
obtain: ⎟






⎛ +
= =
2 1
2 1
F
2
1
2 m m
m m
k f
π π
ω

or, because
2 1
2 1
m m
m m
+
= μ is the reduced
mass of the two-particle system,
μ
π
F
2
k
f = .

33 ••• Calculate the reduced masses for H
35
Cl and H
37
Cl molecules and the
fractional difference Δμ/μ. Show that the mixture of isotopes in HCl leads to a
fractional difference in the frequency of a transition from one rotational state to
another given by Δf/f =–Δμ/μ. Compute Δf/f and compare your result with Figure
37-17.

Picture the Problem We can use the definition of the reduced mass to find the
reduced mass for the H
35
Cl and H
37
Cl molecules and the fractional difference
μ μ Δ . Because the rotational frequency is proportional to 1/I, where I is the
moment of inertia of the system, and I is proportional to μ, we can obtain an
expression for f as a function of μ that we differentiate implicitly to show that
μ μ Δ − = Δ f f .

For H
35
Cl:

( )( )
u 972 . 0 u
36
35
u 1 u 35
u 1 u 35
Cl H
35
= =
+
= μ

For H
37
Cl:

( )( )
u 974 . 0 u
38
37
u 1 u 37
u 1 u 37
Cl H
37
= =
+
= μ

Molecules

183

The fractional difference is:

( )( )
00150 . 0
u
38 36 2
37 36 38 35
u
38 36
38 35 37 36
u
38
37
u
36
35
2
1
u
36
35
u
38
37
=
× + ×
×
× − ×
=






+

=
Δ
μ
μ


The rotational frequency is
proportional to I
−1
, where I is the
moment of inertia of the system.
Because I is proportional to μ:

μ
C
f =
and
μ μ d C df
2 −
− =

Divide df by f to obtain:
μ
μ d
f
df
− = and
μ
μ Δ
− ≈
Δ
f
f


From Figure 37-17: Hz 10 1 Hz 10 01 . 0
11 13
× = × ≈ Δf

For f =8.40×10
13
Hz:
001 . 0
Hz 10 40 . 8
Hz 10 1
13
11
=
×
×

Δ
f
f


This result is in fair agreement (about 20% difference) with the calculated result.
Note that Δf is difficult to determine precisely from Figure 37-17.

General Problems

34 • Show that when one atom of a diatomic molecule is much more
massive than the other the reduced mass is approximately equal to the mass of the
lighter atom.

Picture the Problem We can use the definition of the reduced mass to show that
when one atom in a diatomic molecule is much more massive than the other the
reduced mass is approximately equal to the mass of the lighter atom.

Express the reduced mass of a two-
body system:

2 1
2 1
m m
m m
+
= μ
Divide the numerator and
denominator of this expression by m
2

to obtain:

2
1
1
1
m
m
m
+
= μ
Chapter 37

184
If m
2
>>m
1
, then:
1
2
1
<<
m
m
and
1
m ≈ μ

35 •• The equilibrium separation between the nuclei of a CO molecule is
0.113 nm. Determine the energy difference between the

= 2 and

= 1 rotational
energy levels of this molecule.

Picture the Problem The rotational energy levels are given by
( )
. ... , 2 , 1 , 0 ,
2
1
2
=
+
=

I
E

Express the energy difference
between these rotational energy
levels:

1 2 2 , 1
E E E − = Δ

Express E
2
and E
1
:

( )
I I
E
2 2
2
3
2
1 2 2
=
+
=
and
( )
I I
E
2 2
1
2
1 1 1
=
+
=

Substitute to obtain:

I I I
E
2 2 2
2 , 1
2 3
= − = Δ

The moment of inertia of the
molecule is given by:

2
0
r I μ =
where μ is the reduced mass of the
molecule.

Substituting for I yields:
( )
2
0 O C
O C
2
2
0
O C
O C
2
2
0
2
2 , 1
2
2 2
r m m
m m
r
m m
m m
r
E
+
=
+
= = Δ

μ


Substitute numerical values and evaluate ΔE
1,2
:

( ) ( )
( )( )( ) ( )( )
meV 955 . 0
J /eV 10 1.602 kg/u 10 661 . 1 nm 113 . 0 u 12 u 16
u 16 u 12 s J 10 055 . 1 2
19 27 2
2
34
2 , 1
=
× ×
+ ⋅ ×
= Δ
− −

E

Molecules

185
36 •• The effective force constant for a HF molecule is 970 N/m. Find the
frequency of vibration for this molecule.

Picture the Problem We can use the result of Problem 32 to find the frequency
of vibration of the HF molecule.

In Problem 32 it was established
that:

μ π
k
f
2
1
= where μ is the reduced
mass of the HF molecule.

The reduced mass of the HF
molecule is given by:
F H
F H
m m
m m
+
= μ

Substitute for μ and simplify to
obtain:

( )
F H
F H
F H
F H
2
1
2
1
m m
m m k
m m
m m
k
f
+
=
+
=
π π


Substitute numerical values and evaluate f:

( )( )
( )( )( )
Hz 10 25 . 1
kg/u 10 661 . 1 u 19 u 1
u 19 u 1 N/m 970
2
1
14
27
× =
×
+
=

π
f

37 •• The frequency of vibration of a NO molecule is 5.63 × 10
13
Hz. Find
the effective force constant for NO.

Picture the Problem We can use the result of Problem 32 to find the effective
force constant for NO.

In Problem 32 it was established
that:

μ π
k
f
2
1
= ⇒ μ π
2 2
4 f k = where μ is
the reduced mass of a NO molecule.

The reduced mass of the NO
molecule is given by:
O N
O N
m m
m m
+
= μ

Substituting for μ gives:

O N
O N
2 2
4
m m
m m f
k
+
=
π


Chapter 37

186

Substitute numerical values and evaluate k:

( ) ( )( )( )
kN/m 55 . 1
u 16 u 14
kg/u 10 661 . 1 u 16 u 14 s 10 63 . 5 4
27
2
1 13 2
=
+
× ×
=
− −
π
k

38 •• The effective force constant of the hydrogen bond in a H
2
molecule is
580 N/m. Obtain the energies of the four lowest vibrational levels of the H
2
, HD,
and D
2
molecules, where H is protium and D is deuterium, and find the
wavelengths of photons resulting from transitions between adjacent vibrational
levels for each of these molecules.

Picture the Problem We can use the expression for the vibrational energy levels
of a molecule and the expression for the frequency of oscillation from Problem 32
to find the four lowest vibrational levels of the given molecules.

The vibrational energy levels are
given by:

( ) ... , 2 , 1 , 0 where
2
1
= + = ν ν
ν
hf, E
In Problem 32 we showed that the
frequency of oscillation is:

μ π
k
f
2
1
= where
2 1
2 1
m m
m m
+
= μ

Substitute for f and μ to obtain:
( ) ( )
( ) ( )
2 1
2 1 2
1
2 1
2 1 2
1
2
2
m m
m m
k
h
m m
k m m h
E
+ +
=
+ +
=
π
ν
π
ν
ν


Substitute numerical values to obtain:

( )( ) ( )
( )( )
( )
2 1
2 1
2
1
2 1
2 1
27
15
2
1
u eV 389 . 0
kg/u 10 661 . 1
N/m 580
2
s eV 10 136 . 4
m m
m m
m m
m m
E
+
⋅ + =
+
×
⋅ × +
=


ν
π
ν
ν


Substitute for m
1
and m
2
and evaluate E
0
for H
2
:

( )
( )
( )( )
eV 275 . 0
u 1 u 1
u 1 u 1
u eV 389 . 0
2
1
0
=
+
⋅ = E

Molecules

187
Proceed similarly to complete the
table to the right:
H
2
HD D
2

(eV) (eV) (eV)
0
275 . 0 238 . 0 195 . 0
1
825 . 0 715 . 0 584 . 0
2
375 . 1 191 . 1 973 . 0
3
925 . 1 667 . 1 362 . 1


The energies of the photons resulting
from transitions between adjacent
vibrational levels of these molecules
are given by:

λ
hc
hf E = = Δ ⇒
E
hc
Δ
= λ
Evaluate λ(H
2
):
( ) m 25 . 2
eV 550 . 0
nm eV 1240
H
2
μ λ =

=

Evaluate λ(HD):
( ) m 60 . 2
eV 477 . 0
nm eV 1240
HD μ λ =

=

Evaluate λ(D
2
):
( ) m 19 . 3
eV 389 . 0
nm eV 1240
D
2
μ λ =

=

39 •• The potential energy between two atoms in a molecule separated
by a distance r can often be described rather well by the Lenard–J ones (or 6-12)
potential function, which can be written as


U = U
0
a
r






12
− 2
a
r






6









where U
0
and a are constants. Find the equilibrium separation r
0
in terms of a.
Hint: At the equilibrium separation the potential energy is a minimum. Find U
min
,
the value of U when r =r
0
. Use Figure 37-4 to obtain numerical values of r
0
and
U
0
for a H
2
molecule, and express your answers in nanometers and electron volts.

Picture the Problem We can set the derivative of the potential energy function
equal to zero to find the value of r for which it is either a maximum or a
minimum. Examination of the second derivative of this function at the value for r
obtained from setting the first derivative equal to zero will establish whether the
function is a relative maximum or relative minimum at this point.

Chapter 37

188
Differentiate the potential energy
function with respect to r:





















− =































=
5 11
0
6 12
0
12 12
2
r
a
r
a
r
U
r
a
r
a
U
dr
d
dr
dU


Set the derivative equal to zero for
extrema:
0 12 12
5
0
11
0 0
0
=

























− =
r
a
r
a
r
U
dr
dU


Solve for r
0
to obtain a candidate
for r that minimizes the Lenard-
J ones potential:

a r =
0

To show that r
0
=a corresponds to a
minimum, differentiate U a second
time to obtain:





















=































− =
4 10
2
0
5 11
0
2
2
60 132
12 12
r
a
r
a
r
U
r
a
r
a
r
U
dr
d
dr
U d


Evaluate this second derivative of
the potential at r
0
=a:
[ ] 0
72
60 132
2
0
2
0
2
2
> = − =
=
a
U
a
U
dr
U d
a r

Therefore, we can conclude that
a r =
0
minimizes the potential function.

Evaluate
min
U :
( )
0
6 12
0 min
2
U
a
a
a
a
U a U U
− =





















= =


From Figure 37-4:
nm 074 . 0
0
= r
and
eV 52 . 4
0
= U

40 •• In this problem, you are to determine how the van der Waals force
between a polar molecule and a nonpolar molecule depends on the distance
between the molecules. Let the polar molecule be at the origin and let its dipole
moment be in the +x direction. In addition, let the nonpolar molecule be on the x
axis a distance x away. (a) How does the electric field strength due to an electric
Molecules

189
dipole vary with the distance from the dipole in a given direction? (b) Use (1) that
the potential energy U of an electric dipole of dipole moment

p in an electric
field

E can be expressed as

U = −

p ⋅

E , and (2) that the induced dipole moment
' p

of the nonpolar molecule is in the direction of

E , and that p′ is proportional to
E, to determine how the potential energy of interaction of the two molecules
depends on the separation distance x. (c) Using F
x
= −dU/ dx , determine how the
force between the two molecules depends on distance.

Picture the Problem We can use Equation 21-10 to establish the dependence of
E on x and the dependence of an induced dipole on the field that induces it to
establish the dependence of p and U on x.

(a) In terms of the dipole moment,
the electric field on the axis of the
dipole at a point a great distance x
away has the magnitude (see
Equation 21-10):

3
2
x
kp
E = ⇒
3
1
x
E ∝

(b) Because the induced dipole
moment is proportional to the field
that induces it:

3
1
x
p ∝ and
6
1
x
U ∝ ⋅ − = E p

(c) Differentiate U with respect to x
to obtain:
7
1
x dx
dU
F
x
∝ − =

41 •• Find the dependence of the force on the separation distance between
the two polar molecules described in Problem 40.

Picture the Problem For the case of two polar molecules, p does not depend on
the field E. The dependence of F on the separation distance x can be found from
dU/dx.

Because p does not depend on the
electric field in which the polar
molecules find themselves:

3
1
x
U ∝
Differentiate U with respect to x to
obtain:
4
1
x dx
dU
F
x
∝ − =

Chapter 37

190
42 •• Use the infrared absorption spectrum of HCl in Figure 37-17 to obtain
(a) the characteristic rotational energy E
0r
(in eV) and (b) find vibrational
frequency f and the vibrational energy hf (in eV).

Picture the Problem (a) Except for a gap of 4E
0r
/h at the vibrational frequency f,
the absorption spectrum contains frequencies equally spaced at 2E
0r
/h. We can
measure this spacing of the absorption peaks to obtain E
0r
. (b) We can use the
expression for the vibrational and rotational energies of a molecule, in
conjunction with Figure 37-17 to find f and hf.

(a) Letting Δf represent the
frequency gap, we have:

h
E
f
r 0
2
= Δ ⇒ f h E
r
Δ =
2
1
0



Estimating from Figure 37-17, the
frequency gap is approximately:

Hz 10 0 . 7
11
× = Δf
where the peaks at 8.40 × 10
13
Hz and
8.61 × 10
13
Hz were used.

Substitute numerical values and evaluate E
0r
:

( )( ) meV 4 . 1 Hz 10 0 . 7 s eV 10 136 . 4
11 15
2
1
0
= × ⋅ × =

r
E

(b) The vibrational energy levels are
given by:

( ) ... , 2 , 1 , 0
2
1
= + = ν ν
ν
hf, E
The lowest vibrational energy
corresponds to ν =0:

hf E
2
1
0
= ⇒
0
2E hf = (1)

Determine f from Figure 37-17:
Hz 10 66 . 8
13
× = f

Substitute for f and h and evaluate E
0
:

( )( ) eV 179 . 0 Hz 10 66 . 8 s eV 10 136 . 4
13 15
2
1
0
= × ⋅ × =

E

Substitute in equation (1) and
evaluate hf:
( ) eV 358 . 0 eV 179 . 0 2 = = hf

43 • The dissociation energy is sometimes expressed in kilocalories per
mole (kcal/mol). (a) Find the relation between the units eV/molecule and
kcal/mol. (b) Find the dissociation energy of NaCl in kcal/mol.

Molecules

191
Picture the Problem We can use conversion factors to convert eV/molecule into
kcal/mol.

(a)

kcal/mol 0 . 23
eV
J 10 602 . 1
mole
molecules 10 022 . 6
J 4184
kcal 1
molecule
eV
1
molecule
eV
1
19 23
=
×
×
×
× × =



(b) The dissociation energy of NaCl,
in eV/molecule, is 4.27 eV/molecule.
Using the conversion factor in (a),
express this energy in kcal/mol:
kcal/mol 2 . 98
mol
kcal 0 . 23
molecule
eV 27 . 4
= ×

Chapter 37

192