1225

Chapter 37
Molecules

Conceptual Problems

*1
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
Determine the Concept Because a N
2
molecule has no permanent dipole moment, it is a
non-polar molecule.

3
Determine the Concept No. Neon occurs naturally as Ne, not Ne
2
. Neon is a rare gas
atom with a closed shell electron configuration.

4
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
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
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
Chapter 37


1226
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
Determine the Concept The effective force constant from Example 37-4 is 1.8510
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
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
Determine the Concept For H
2
, the concentration of negative charge between the two
protons holds the protons together. In the
+
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 the
+
2
H ion is not as effective as the larger
charge in the H
2
molecule, and the protons should be 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
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
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
Picture the Problem We can estimate the value of the quantum number 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 .

Molecules


1227
Express the ratio of the correction
term to the first term of the
expression for E

and simplify to
obtain:

( )
( )
( )

2
1
2
1
2
2
1
+ =
+
+
hf
hf

For a correction of 10 percent:

( ) 1 . 0
2
1
= +
Solve for to obtain:

2
1
10
1
=

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

=



13
Picture the Problem We can solve Equation 37-12 for l and substitute for the moment
of inertia and rotational kinetic energy of the baseball to estimate the quantum number l
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
h l l +
=
where l =0, 1, 2, is the rotational
quantum number and I is the moment of
inertia of the ball.

Solve for l(l+1):
( )
2
2
1
h
l l
IE
= +

Factor l from the parentheses to
obtain:

2
2
2 1
1
h l
l
IE
=

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

2
2
2
h
l
IE
and
h
l
IE 2

Because the energy of the ball is
rotational kinetic energy:

2
2
1
rot
I K E = =
Substitute for E in the expression for
l to obtain:

( ) ( )
h h h
l

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 =
Substitute for I to obtain:

h
l
5
2
2
mr


Chapter 37


1228
Substitute numerical values and evaluate l:

( )( )
( )
30
34
2
10 15 . 2
s J 10 05 . 1 5
s 60
min 1
rev
rad 2
min
rev 20
m 03 . 0 kg 3 . 0 2
=

l

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

2
2 2
r 0
4
5
2 mr I
E
h h
= =
Substitute numerical values and
evaluate E
0r
:

( )
( )( )
J 10 10 . 5
m 03 . 0 kg 3 . 0 4
s J 10 05 . 1 5
65
2
2
34
r 0

=

= E


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

*14
Picture the Problem We can solve Equation 37-18 for and substitute for the
frequency of the mass-and-spring oscillator to estimate the quantum number and
spacing between adjacent energy levels for this system.

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

( )hf E
2
1
+ =

where =0, 1, 2,

Solve for :
2
1
=
hf
E

or, because >>1,
hf
E

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

2
2
1
kA E =

where A is the amplitude of its motion.
Substitute for E

in the expression
for to obtain:

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

m
k
f
2
1
=

mk
h
A
k
m
h
kA
2 2

= =

Molecules


1229

Substitute numerical values and evaluate :

( )
( )( )
32
34
2
10 64 . 1 N/m 1500 kg 5
s J 10 63 . 6
m 02 . 0
=

=

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

m
k h
hf E

4 2
1
0
= =
Substitute numerical values and
evaluate E
0
:

J 10 14 . 9
kg 5
N/m 1500
4
s J 10 63 . 6
34
34
0

=

=

E


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

Molecular Bonding

15
Picture the Problem The electrostatic potential energy with U at infinity is given by
.
2
r ke U =

Relate the electrostatic potential
energy of the ions to their
separation:

r
ke
U
2
e
=
Solve for r:

e
2
U
ke
r =

Substitute numerical values and evaluate r:

( )( )
( )( )
nm 0.946
J /eV 10 6 . 1 eV 52 . 1
C 10 6 . 1 C / m N 10 99 . 8
19
2
19 2 2 9
=


=

r

16
Picture the Problem We can find the energy absorbed or released per molecule by
computing the difference between dissociation energy of Cl and the binding energy of
NaCl.

Chapter 37


1230
Noting that the dissociation energy
per Cl atom is 1.24 eV, express the
net energy change per molecule
E:

NaCl binding,
eV 24 . 1 E E =
The binding energy of NaCl is (see
page 1210):

4.27 eV
Substitute and evaluate E:
eV 03 . 3 eV 27 . 4 eV 24 . 1 = = E

. is reaction The released. is energy 0, Because exothermic E <

17
Picture the Problem We can use conversion factors to convert eV/molecule into
kcal/mol.

(a)
kcal/mol 0 . 23
eV
J 10 60 . 1
mole
molecules 10 02 . 6
J 4184
kcal 1
molecule
eV
1
molecule
eV
1
19 23
=

=



(b) The dissociation energy of
NaCl, in eV/molecule, is (see page
1205):

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
=

*18
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
100 bonding ionic Percent
p
p

Express the dipole moment for
100% ionic bonding:

er p =
100

Molecules


1231
Substitute to obtain:

=
er
p
meas
100 bonding ionic Percent

Substitute numerical values and evaluate the percent ionic bonding:

( )( )
% 6 . 43
nm 0917 . 0 C 10 60 . 1
m C 10 40 . 6
100 bonding ionic Percent
19
30
=

19
Picture the Problem If we choose the potential energy at infinity to be E, the total
potential energy is U
tot
=U
e
+E +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 + + =
The core-repulsive energy is :

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

ions from neutral

rubidium and fluorine atoms:

eV 78 . 0 eV 3.40 eV 18 . 4 = = E
Express the electrostatic potential
energy is:

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


( )( )
( )( )
eV 34 . 6
J /eV 10 60 . 1 nm 227 . 0
C 10 60 . 1 C / m N 10 99 . 8
19
2
19 2 2 9
e
=

U

Substitute numerical values and
evaluate U
rep
:

( )
eV 44 . 0
eV 12 . 5 eV 34 . 6 eV 78 . 0
rep
=
+ = U


20
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
Chapter 37


1232
affinity of chlorine.

(a) The potential energy of attraction
of the ions is given by:
r
ke
U
2
e
=
where ke
2
=1.44 eVnm

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


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

( ) E U U E + = =
e tot calc d,

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

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


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

21
Picture the Problem Assume that U(r) is of the form given in Problem 24 with
n =6.

Molecules


1233
The potential energy curve is shown in the
figure. The turning points for vibrations of
energy E
1
and E
2
are at the values of r,
where the energies equal U(r). It is
apparent that the average value of r
depends on the energy and that r
2,av
is
greater than r
1,av
.


22
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 + + =
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 eVnm.

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 E
according to:

( ) E E U U + + =
d e rep

From Figure 37-1:

eV 52 . 1 = E

Substitute numerical values and
evaluate U
rep
:
( )
eV 310 . 0
eV 52 . 1 eV 27 . 4 eV 10 . 6
rep
=
+ + = U


23
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
Chapter 37


1234
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 eVnm.

Substitute numerical values and
evaluate U
e
:

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

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

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


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

( ) E U U E + = =
e tot calc d,

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

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


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

*24
Picture the Problem U(r) is the potential energy of the two ions as a function of
separation distance r. U(r) is chosen so U() =E, where E is the negative of the
energy required to form two ions at infinite separation from two neutral atoms also at
infinite separation. U
rep
(r) is the potential energy of the two ions due to the repulsion of
the two closed-shell cores. E
d
is the disassociation energy, the energy required to separate
the two ions plus the energy E required to form two neutral atoms from the two ions at
Molecules


1235
infinite separation. The net force acting on the ions is the sum of F
rep
and F
e
. We can find
F
rep
from U
rep
and F
e
from Coulombs law and then use dU/dr =F
net
=0 at r =r
0
to solve
for n.

Express the net force acting on the
ions:

e rep net
F F F + = (1)
Find F
rep
from U
rep
:

[ ]
1
1 rep
rep
+

=
= = =
n
n n
r
nC
nCr Cr
dr
d
dr
dU
F


The electrostatic potential energy of
the two ions as a function of
separation distance is given by:

r
ke
U
2
e
=
Find the electrostatic force of
attraction F
e
from U
e
:

2
2 2
e
e
r
ke
r
ke
dr
d
dr
dU
F =

= =

Substitute for F
rep
and F
e
in equation
(1) to obtain:

2
2
1 net
r
ke
r
nC
F
n
+ =
+

Because dU/dr =F
net
=0 at
r =r
0
:

2
0
2
1
0
0
r
ke
r
nC
n
+ =
+


Multiply both sides of this equation
by r
0
to obtain:

( ) ( )
0 e 0 rep
0
2
0
0 r U r nU
r
ke
r
nC
n
+ = + =
Solve for n to obtain:

( )
( )
0 rep
0 e
r U
r U
n =

25
Picture the Problem U
rep
at r =r
0
is related to U
e
, E
d
, and E through
( ) E E U U + + =
d e rep
. The net force is the sum of F
rep
and F
e
. We can find F
rep
from
U
rep
and F
e
from Coulombs law. Because F
net
=0 at r =r
0
, we can obtain simultaneous
equations in C and n that we can solve for each of these quantities.

(a) U
rep
is related to U
e
, E
d
, and E
according to:

( ) E E U U + + =
d e rep

where E
NaCl
=1.52 eV
Chapter 37


1236
U
e
(r
0
) is given by:

0
2
e
r
ke
U =
where ke
2
=1.44 eVnm

Substitute numerical values and
evaluate U
e
:
eV 10 . 6
nm 236 . 0
nm eV 44 . 1
e
=

= U

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


(b) Express the net force acting on
the Na
+
and Cl

ions:

e rep net
F F F + = (1)
Find F
rep
from U
rep
:

[ ]
1
1 rep
rep
+

=
= = =
n
n n
r
nC
nCr Cr
dr
d
dr
dU
F


The electrostatic force of attraction
is:

2
2
e
r
ke
F =
Substitute for F
rep
and F
e
in equation
(1) to obtain:

2
2
1 net
r
ke
r
nC
F
n
+ =
+

Because F
net
=0 at r =r
0
:

2
0
2
1
0
0
r
ke
r
nC
n
+ =
+

or
( ) ( )
0 rep
0
0 e
r nU
r
C
n r U
n
= =

Solve for n and C to obtain:

( )
( )
0 rep
0 e
r U
r U
n =
and
( )
n
r r U C
0 0 rep
=

From (a):
( ) eV 10 . 6
0 e
= r U
( ) eV 31 . 0
0 rep
= r U
and, from Figure 37-1,
Molecules


1237
nm 236 . 0
0
= r

Substitute for U
e
(r
0
) and U
rep
(r
0
) and
evaluate n and C:
7 . 19
eV 31 . 0
eV 10 . 6
= = n
and
( )( )
19.7 13
7 . 19
nm eV 10 37 . 1
nm 236 . 0 eV 31 . 0
=
=

C


Energy Levels of Spectra of Diatomic Molecules

26
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
h
=

Express the moment of inertia of the
molecule:

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
h h h
= = =

Solve for r:
p 0
14
1
m E
r
r
h =

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


*27
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.

Chapter 37


1238
The characteristic rotational energy
of a molecule is given by:
I
E
r
2
2
0
h
=

Express the moment of inertia of the
molecule:

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
h h h
= = =

Solve for r:
p 0
1
4 m E
r
r
h
=

Substitute numerical values and evaluate r:

( )( )( )
nm 121 . 0
kg 10 67 . 1 J /eV 10 6 . 1 eV 10 78 . 1
1
4
s J 10 055 . 1
27 19 4
34
=

r


28
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
+
=
Divide the numerator and
denominator of this expression by
m
2
to obtain:

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

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

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

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

Molecules


1239
(b) For N
2
, m
1
=m
2
=14 u:

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

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

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

(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
=
+
=

29
Picture the Problem We can solve Equation 37-18 for and substitute for the
frequency of the CO molecule (see Example 37-4) and its binding energy to estimate the
quantum number .

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

( )hf E
2
1
+ =

where =0, 1, 2,

Solve for :
2
1
=
hf
E

Substitute numerical values and
evaluate :
( )( )
41 8 . 40
2
1
Hz 10 42 . 6 s J 10 63 . 6
eV
J 10 1.60
eV 11
13 34
19
=

*30
Picture the Problem We can use the expression for the rotational energy levels of the
diatomic molecule to express the energy separation E between the 3 = l and
2 = l 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 = l and 2 = l rotational levels of
this diatomic molecule is given by:

2 3 = =
=
l l
E E E
Express the rotational energy levels
E
l =3
and E
l =2
in terms of E
0r
:

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

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


Substitute for E
l =3
and E
l =2
to
r r r
E E E E
0 0 0
6 6 12 = =
Chapter 37


1240
obtain:

or
E E
r
=
6
1
0


The characteristic rotational energy
of a molecule is given by:
E
I
E
r
= =
6
1
2
0
2
h

I
E
2
3h
=

Express the moment of inertia of the
molecule:

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

Substitute for I to obtain:

( )
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
+
=
+
= =
h
h h

Substitute numerical values and evaluate E:

( ) ( )
( )( )( ) ( )( )
meV 61 . 5
kg/u 10 660 . 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
=

+
=

E

*31
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
+
=
+
= =

Molecules


1241
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
+
=
or
2
0
r I = 36-14
where
2 1
2 1
m m
m m
+
= 36-15

32
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 separated by a distance r.

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

Express the moment of inertia of the
molecule:

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

Substitute for I to obtain:

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

Substitute numerical values and evaluate E
0r
:

( ) ( )
( )( )( ) ( )
meV 0158 . 0
J /eV 10 1.602
1
J 10 53 . 2
kg/u 10 660 . 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


33
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 f 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 = , with representing
Chapter 37


1242
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
= + =

hf, E
The lowest vibrational energy
corresponds to =0:

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

( )( )
eV 179 . 0
J /eV 10 1.6
1
J 10 87 . 2 Hz 10 66 . 8 s J 10 63 . 6
19
20 13 34
2
1
0
=

= =


E


(b) For l =1:
f h
I
E = = l
lh
l
2


Solve for I:

f
h
f h
h
f h
I

=
2 2
2 2
4 4
h


Substitute numerical values and
evaluate I:
( )
2 47
11 2
34
m kg 10 80 . 2
Hz 10 6 4
s J 10 63 . 6
=


=

I


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

2
r I =
Replace 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
+
=

Solve for r
0
:

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

Substitute numerical values and evaluate r
0
:

( )( )
( )
nm 0.132
kg/u 10 66 . 1
m kg 10 80 . 2
u 453 . 34 u 1
u 453 . 34 u 1
27
2 47
0
=

+
=

r

Molecules


1243
34
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 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 = . Substitution for K
eff
will lead us to the result given
in (b).

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 = from (or toward) the center
of mass.
Express the force exerted by the
spring:

( )
2 1
r r K r K F + = =
Substitute for r
2
to obtain:

1
2
2 1
1
2
1
1
r
m
m m
K
r
m
m
r K F

+
=

+ =


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

1 eff 1
2
2 1
r K r
m
m m
K F =

+
=
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:

1
eff
m
K
=
or
1
eff
2
1
2 m
K
f

= =

Substitute for K
eff
and simplify to
obtain:

+
= =
2 1
2 1
2
1
2 m m
m m
K f

or, because
2 1
2 1
m m
m m
+
= is the reduced
Chapter 37


1244
mass of the two-particle system,

K
f
2
1
=

Solve for K:

Cl H
Cl H 2 2 2 2
4 4
m m
m m
f f K
+
= =

Substitute numerical values and evaluate K:

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

=

K

35
Picture the Problem

Were given the population of rotational
states function:
( ) ( ) 1 2
/kT E
l
e f

+ = l l
where
r
E E
0
) 1 ( + = l l
l
and
I
E
2
2
r 0
h
=

The moment of inertia I of an
oxygen molecule is given by:
2
0 2
1
mr I =
where m is the reduced mass and r
0
is the
separation of the atoms in a molecule.

Well assume, as in Example
37-3, that:

nm 1 . 0
0
= r
A spreadsheet program to plot f(l) is shown below. The formulas used to calculate the
quantities in the columns are as follows:

Cell Formula/Content Algebraic Form
B1 1.00E10 r
0

B2 16 m (u)
B3 2.66E26 m (kg)
B4 1.05E34 h
B5 1.38E23 k
B6 4.15E23 E
0r

B7 100 T (K)
B8 200 T (K)
B9 300 T (K)
B10 500 T (K)
A13 0
l
Molecules


1245
B13 A13*(A13+1)*$B$6
( )
0r
1E + l l
C13 (2*A13 +1)*EXP(B13/($B$5*$B$7)) f(l, T =100 K)
D13 (2*A13 +1)*EXP(B13/($B$5*$B$8)) f(l, T =200 K)
E13 (2*A13 +1)*EXP(B13/($B$5*$B$9)) f(l, T =300 K)
F13 (2*A13 +1)*EXP(B13/($B$5*$B$10)) f(l, T =500 K)

A B C D E F
1 r_0= 1.00E10 m
2 m= 16 u
3 m= 2.656E26 kg
4 h_bar= 1.05E34 J .s
5 k= 1.38E23 J /K
6 E_0r= 4.15E23 eV
7 T= 100 K
8 T= 200 K
9 T= 300 K
10 T= 500 K
11
12 l E_l E_100 K E_200 K E_300 K E_500 K
13 0.0 0.00E+00 1.00 1.00 1.00 1.00
14 0.5 3.11E23 1.96 1.98 1.99 1.99
15 1.0 8.30E23 2.82 2.91 2.94 2.96
16 1.5 1.56E22 3.57 3.78 3.85 3.91
17 2.0 2.49E22 4.17 4.57 4.71 4.82

29 8.0 2.99E21 1.95 5.76 8.26 11.02
30 8.5 3.35E21 1.59 5.34 8.01 11.07
31 9.0 3.74E21 1.27 4.91 7.71 11.06
32 9.5 4.14E21 1.00 4.46 7.36 10.98
33 10.0 4.57E21 0.77 4.02 6.97 10.83

Chapter 37


1246

The following graph shows f(l) as a function of temperature.
0
2
4
6
8
10
12
0 2 4 6 8 10
rotational quantumnumber l
f
(
l
)
T =100 K
T =200 K
T =300 K
T =500 K


*36
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
= . 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 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 = from (or toward) the center
of mass.
Express the force exerted by the
spring:

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

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

+
=

+ =

Molecules


1247
(b) A displacement r
1
of m
1
results
in a restoring force:

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

+
=
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:

1
eff
m
k
=
or
1
eff
2
1
2 m
k
f

= =

Substitute for k
eff
and simplify to
obtain:

+
= =
2 1
2 1
2
1
2 m m
m m
k f

or, because
2 1
2 1
m m
m m
+
= is the reduced
mass of the two-particle system,

k
f
2
1
= .

37
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 . Because the
rotational frequency is proportional to 1/I, where I is the moment of inertia of the system,
and I is proportional to , we can obtain an expression for f as a function of that we
differentiate implicitly to show that = f f .

For H
35
Cl:

( )( )
u 9722 . 0 u
36
35
u 1 u 35
u 1 u 35
= =
+
=

For H
37
Cl:

( )( )
u 9737 . 0 u
38
37
u 1 u 37
u 1 u 37
= =
+
=

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
=
+


=

Chapter 37


1248
The rotational frequency is
proportional to 1/I, where I is the
moment of inertia of the system.
Because I is proportional to :

C
f =
and
d C df
2
=
Divide df by f to obtain:

d
f
df
= and

f
f


From Figure 36-17: Hz 10 Hz 10 01 . 0
11 13
= f

For f =8.4010
13
Hz:
00119 . 0
Hz 10 40 . 8
Hz 10
13
11
=

f
f


17. - 36 Figure from precisely determine to difficult is that Note result.
calculated with the ) difference 21% (about agreement fair in is result This
f


General Problems

38
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
+
=
Divide the numerator and
denominator of this expression by
m
2
to obtain:

2
1
1
1
m
m
m
+
=
If m
2
>>m
1
, then:
1
2
1
<<
m
m
and
1
m

39
Picture the Problem The rotational energy levels are given by
( )
. ... , 2 , 1 , 0 ,
2
1
2
=
+
= l
h l l
I
E

Express the energy difference
between these rotational energy
1 2 2 , 1
E E E =

Molecules


1249
levels:

Express E
2
and E
1
:

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

Substitute to obtain:

I I I
E
2 2 2
2 , 1
2 3 h h h
= =

The moment of inertia of the
molecule is:

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

Substitute for I to obtain:
( )
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
+
=
+
= =
h
h h

Substitute numerical values and evaluate E
1,2
:

( ) ( )
( )( )( ) ( )
meV 955 . 0
J /eV 10 1.6
J 10 53 . 1
kg/u 10 66 . 1 nm 113 . 0 u 12 u 16
u 16 u 12 s J 10 055 . 1 2
19
22
27 2
2
34
2 , 1
=


=

+
=

E


*40
Picture the Problem We can use the result of Problem 36 to find the frequency of
vibration of the HF molecule.

In Problem 36 it was established
that:


k
f
2
1
=

The reduced mass is:
F H
F H
m m
m m
+
=

Chapter 37


1250
Substitute for 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
+
=
+
=



Substitute numerical values and evaluate f:

( )( )
( )( )( )
Hz 10 25 . 1
kg/u 10 66 . 1 u 19 u 1
u 19 u 1 N/m 970
2
1
14
27
=

+
=

f

41
Picture the Problem We can use the result of Problem 36 to find the effective force
constant for NO.

In Problem 36 it was established
that:


k
f
2
1
=

Solve for k:


2 2
4 f k =
The reduced mass is:
O N
O N
m m
m m
+
=

Substitute for to obtain:

O N
O N
2 2
4
m m
m m f
k
+
=



Substitute numerical values and evaluate k:

( ) ( )( )( )
kN/m 55 . 1
u 16 u 14
kg/u 10 66 . 1 u 16 u 14 s 10 63 . 5 4
27
2
1 13 2
=
+

=

k

42
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 36 to find the
four lowest vibrational levels of the given molecules.

The vibrational energy levels are
given by:

( ) ... , 2 , 1 , 0
2
1
= + =

hf, E
In Problem 36 we showed that the
frequency of oscillation is:

k
f
2
1
=
Molecules


1251
where
2 1
2 1
m m
m m
+
=

Substitute for f and 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
+ +
=
+ +
=

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
+
+ =
+

+
=

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

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:

hc
hf E = =
Solve for :
E
hc

=

Chapter 37


1252
Evaluate (H
2
):
( ) m 25 . 2
eV 550 . 0
nm eV 1240
H
2
=

=

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

=

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

=

43
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.

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:
extrema for 0
12 12
5
0
11
0 0
0
=

=
r
a
r
a
r
U
dr
dU


Solve for r
0
to obtain, as our
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 r
0
= a
Molecules


1253
minimizes the potential function.

Evaluate U
min
:
( )
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

44
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 =
or
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
r
r


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

45
Picture the Problem the case of two polar molecules, p does not depend on the field E.

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

3
1
x
U
Chapter 37


1254
Differentiate U with respect to x to
obtain:
4
1
x dx
dU
F
x
=

46
Picture the Problem We can use the expression for the vibrational and rotational
energies of a molecule, in conjunction with Figure 37-17 to find E
0r
, f, and hf.

(a) Except for a gap of 4E
0r
/h at the
vibrational frequency f, the
absorption spectrum contains
frequencies equally spaced at:

h
E
f
r 0
2
=


Solve for E
0r
:

hf E
r 2
1
0
=
From Figure 37-17: Hz 10 66 . 8
13
= f

Substitute numerical values and evaluate E
0r
:

( )( )
eV 179 . 0
J /eV 10 1.6
1
J 10 87 . 2 Hz 10 66 . 8 s J 10 63 . 6
19
20 13 34
2
1
0
=

= =


r
E


(b) The vibrational energy levels are
given by:

( ) ... , 2 , 1 , 0
2
1
= + =

hf, E
The lowest vibrational energy
corresponds to =0:
hf E
2
1
0
=
and
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
J /eV 10 1.6
1
J 10 87 . 2 Hz 10 66 . 8 s J 10 63 . 6
19
20 13 34
2
1
0
=

= =


E


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

Molecules


1255
*47
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 for
0 = l to 5 = l can be found using . 2
0 1 , r
E E l
l l
=

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

l
l l
l l
.

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

Find :
( )( )
u 86 . 6
u 16 u 12
u 16 u 12
O C
O C
=
+
=
+
=
m m
m m


In Problem 39 it was established that r
0
=0.113 nm. Use this result to evaluate I:

( )( )( )
2 46 2 27
m kg 10 45 . 1 nm 113 . 0 kg/u 10 66 . 1 u 86 . 6 = =

I

The characteristic rotational energy
E
0r
is given by:

I
E
r
2
2
0
h
=
Substitute numerical values and evaluate E
0r
:

( ) ( )
( )
meV 0.239
m kg 10 45 . 1 2
J /eV 10 6 . 1 s eV 10 58 . 6
2 46
19
2
16
0
=


=


r
E

Chapter 37


1256
(b) The energy level diagram is
shown to the right. Note that E
l,l1
,
the energy difference between
adjacent levels for l =1, is
. 2
0 1 , r
E E l
l l
=




(c) Express the energy difference
1 .

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

1 , 1 ,
=
l l l l
hf E
Because :
1 , 1 ,
=
l l l l
f c
r
E
hc
E
hc
0 1 ,
1 ,
2
=

l
l l
l l


Substitute numerical values to obtain:

( )( )
( ) l l
l l
m 2596
meV 239 . 0 2
m/s 10 3 s eV 10 136 . 4
8 15
1 ,

=

=

For l =1:
m 2596
1
m 2596
0 , 1

= =

For l =2:
m 1298
2
m 2596
1 , 2

= =

For l =3:
m 865
3
m 2596
2 , 3

= =

Molecules


1257
For l =4:
m 649
4
m 2596
3 , 4

= =

For l =5:
m 519
5
m 2596
4 , 5

= =

spectrum. the of region microwave in the fall hs wavelengt These

*48
Picture the Problem The wavelength resulting from transitions between adjacent
harmonic oscillator levels of a LiCl molecule is given by .
2

c
= We can find an
expression for by following the procedure outlined in the problem statement.

The wavelength resulting from
transitions between adjacent
harmonic oscillator levels of this
molecule is given by:

c hc
E
hc 2
= =

=
h
(1)
From Problem 24 we have:

( )
n
r
C
r
ke
r U + =
2
, where E is constant.

The Taylor expansion of U(r)
about r =r
0
is:

( ) ( ) ( )
( ) ...
2
1
2
0 2
2
0 0
0
0
+

+ =
r r
dr
U d
r r
dr
dU
r U r U
r
r


Because U(r
0
) is a constant, it can
be dropped without affecting the
physical results and because
: 0
0
=

r
dr
dU


( ) ( )
2
0 2
2
0
2
1
r r
dr
U d
r U
r

(2)
DifferentiateU(r) twice to obtain:

( )
2 3
2
2
2
1 2
+
+ =
n
r
C
n n
r
ke
dr
U d

Because dU/dr =F
net
=0 at
r =r
0
:

2
0
2
1
0
0
r
ke
r
nC
n
+ =
+


Chapter 37


1258
Solving for C yields:

n
r ke
nr
r ke
C
n n 1
0
2
2
0
1
0
2 +
= =

Substitute for C and evaluate
0
2
2
r
dr
U d

to obtain:

( )
( )
( ) 1
1
1 2
3
0
2
1
0
2
2
0
3
0
2
2
2
0
=

+ =

+
n
r
ke
n
r ke
r
n n
n
r
ke
dr
U d
n
n
r


Substitute for
0
2
2
r
dr
U d

in
equation (2):

( ) ( ) ( )
2
0 3
0
2
1
2
1
r r n
r
ke
r U

Because the potential energy of a
simple harmonic oscillator is given
by ( ) :
2
0
2
2
1
SHO
r r m U =

( ) ( ) ( )
2
0 3
0
2
2
0
2
1
2
1
2
1
r r n
r
ke
r r m

Solve for to obtain:

( )
3
0
2
1
mr
ke n


Substitute
LiCl
for m to obtain:

( )
( )( )
3
0 Cl Li
2
Cl Li
3
0
Cl Li
Cl Li
2
1
1
r m m
ke m m n
r
m m
m m
ke n
+
=
+

(3)

From Problem 24:

) (
) (
0 rep
0 e
r U
r U
n = (4)

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

( ) E E U U + + =
d e rep
(5)

The energy needed to form Li
+
and
Cl

from neutral lithium and

chlorine atoms is:

eV 1.77 eV 3.62 eV 39 . 5
affinity electron ionization
= =
= E E E

U
e
(r
0
) is given by:

0 0
2
e
nm eV 44 . 1
r r
ke
U

= =
Molecules


1259

Substitute r
0
and evaluate U
e
:
eV 13 . 7
nm 202 . 0
nm eV 44 . 1
e
=

= U

Substitute numerical values in
equation (5) and evaluate U
rep
:
( )
eV 500 . 0
eV 77 . 1 eV 86 . 4 eV 13 . 7
rep
=
+ + = U


Substitute for U
rep
(r
0
) and U
e
(r
0
) in
equation (4) and evaluate n:
3 . 14
eV 500 . 0
eV 13 . 7
=

= n

Substitute numerical values in equation (3) and evaluate :

( )( )( )( )
( )( )( )( )
1 14
3 27
19
s 10 96 . 1
nm 202 . 0 kg/u 10 66 . 1 u 453 . 35 u 941 . 6
J /eV 10 60 . 1 nm eV 44 . 1 u 453 . 35 u 941 . 6 1 3 . 14

=

+



Substitute numerical values in
equation (1) and evaluate :
( )
m 62 . 9
s 10 96 . 1
m/s 10 3 2
1 14
8

=























Chapter 37


1260